WO2000063278A1 - Composition de résine thermoplastique et procédé de production - Google Patents

Composition de résine thermoplastique et procédé de production Download PDF

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Publication number
WO2000063278A1
WO2000063278A1 PCT/JP2000/002540 JP0002540W WO0063278A1 WO 2000063278 A1 WO2000063278 A1 WO 2000063278A1 JP 0002540 W JP0002540 W JP 0002540W WO 0063278 A1 WO0063278 A1 WO 0063278A1
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Prior art keywords
thermoplastic resin
resin composition
fibrous
coupling agent
zonolite
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PCT/JP2000/002540
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English (en)
Japanese (ja)
Inventor
Shin-Ichi Yamamoto
Kaoru Takazaki
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Ube Material Industries, Ltd.
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Application filed by Ube Material Industries, Ltd. filed Critical Ube Material Industries, Ltd.
Priority to AU38393/00A priority Critical patent/AU3839300A/en
Priority to JP2000612362A priority patent/JP4718015B2/ja
Publication of WO2000063278A1 publication Critical patent/WO2000063278A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • thermoplastic resin composition Description Method for producing thermoplastic resin composition and thermoplastic resin composition
  • the present invention relates to a thermoplastic resin composition that can be advantageously used for producing a resin molded product having improved properties such as impact resistance and bending strength, and a method for producing the same.
  • Thermoplastic polyamide resins, polyester resins, polyolefin resins, etc. are easy to mold using their thermoplasticity, and the resulting resin molded products have good properties such as elasticity and rigidity. Used in the manufacture of molded products. In particular, it is widely used in the manufacture of automotive parts, electrical and electronic parts, precision machine parts, and so on.
  • fibrous calcium silicate hydrate such as zonolite is treated with a surfactant and Z or a force-pulverizing agent.
  • Kneaded thermoplastic resin compositions have been proposed (e.g., Japanese Patent Application Laid-Open No. Hei 6-12841, Japanese Patent Laid-open No. Hei 7-21613, Japanese Patent Laid-open No. Hei 8-16653) No. 7 publication).
  • the fibrous zonolite is easily crushed into fine particles in the major axis and minor axis directions to form fine particles. It has the effect of improving various properties such as impact resistance and bending strength of the molded article of the thermoplastic resin composition.
  • thermoplastic resin molded products can be improved by adding the above-mentioned surface treated zonolite to thermoplastic resin.
  • thermoplastic resin molded products In the technical fields such as parts and precision machinery parts, there is a tendency for thermoplastic resin molded products to have higher properties such as higher impact resistance and bending strength.
  • the demand for further improvement of the mechanical properties of such resin molded articles cannot be sufficiently satisfied by the zonotrite-containing thermoplastic resin compositions known so far.
  • an object of the present invention is to provide a thermoplastic resin composition containing a zonotrite, which has improved properties such as impact resistance and flexural strength, and is more suitable for producing a resin molded product than before.
  • a main object is to provide a plastic resin composition.
  • the present invention also provides a method capable of advantageously producing a thermoplastic resin composition suitable for producing a resin molded article having improved properties such as impact resistance and bending strength. Aim.
  • the present invention provides a thermoplastic resin, a BET ratio surface area of which surface is previously coated with a surfactant, a surface area of 21 n ⁇ Zg or more, an average fiber length of 1 to 5 ⁇ m, and an average fiber diameter of 0 ⁇ m.
  • a fibrous zonolite in the range of 1 to 0.5 ⁇ m is mixed at a weight ratio of 99.5: 0.5 to 20:80, and the resulting mixture is mixed with the fiber.
  • the present invention provides a method for producing a thermoplastic resin composition, comprising heating and kneading in the presence of a force coupling agent in an amount in the range of 0.2 to 10% by weight based on the weight of the zonotralate. .
  • the present invention also provides a thermoplastic resin and a fibrous material having an average fiber length in the range of 0.1 to 0.7 / xm and an average fiber diameter in the range of 0.01 to 0.05 / m.
  • thermoplastic resin composition containing a force coupling agent.
  • the present invention also resides in a thermoplastic resin composition obtained by the above method for producing a thermoplastic resin composition of the present invention.
  • the present invention further comprises the step of heating and melting the above-mentioned thermoplastic resin composition of the present invention.
  • thermoplastic resin molded product obtained by molding it into a desired shape.
  • the present invention also provides a thermoplastic resin composition of the present invention described above as a master batch, to which the thermoplastic resin 1: 1 to 1: 1 6 0 weight ratio were mixed in (the former the latter), then heated There is also a method for producing a thermoplastic resin composition characterized by kneading.
  • the present invention further provides a thermoplastic resin composition obtained by the above-described production method of the present invention as a masterbatch, and a thermoplastic resin in a weight ratio of 1: 1 to 1: 160 (former: latter). And then heating and kneading, there is also a method for producing a thermoplastic resin composition.
  • thermoplastic resin composition obtained by adding a conventional fibrous zonolite having a surface treated with a surfactant to a thermoplastic resin and kneading the resin
  • the dispersibility of the fibrous zonolite is excellent, the adhesiveness between the resin component and the fibrous zonolite inside the molded product is insufficient in the resin molded product obtained by molding the resin composition.
  • the conventional fibrous zonolite whose surface has been treated with a coupling agent is added to a thermoplastic resin and kneaded.
  • the fibrous zonolite is hard to be crushed by the coupling agent bonded to the surface thereof and is hard to be dispersed in the resin composition, so that it is difficult to form fine particles. , That It has been found that a resin molded product obtained by molding the resin composition of the above does not easily obtain the required high impact resistance and bending strength.
  • the present inventor continued research and found that fibrous zonotrite, which had been surface-treated with a surfactant in advance, was treated with a resin component (thermoplastic resin component) without being subjected to a coupling agent treatment. Then, after adding a coupling agent to the mixture, the mixture is heated and kneaded, or the coupling agent is added when the mixture is heated and kneaded.
  • a force coupling agent that is not bound to fibrous zonolite enables the fibrous zonolite to be finely divided and improves the dispersion of the finely divided zonolite in the resin composition. And found that the binding between the finely divided zonolite and the resin component is also improved, and arrived at the present invention.
  • the average aspect ratio represented by the average fiber length and average fiber diameter of the fibrous zonolite used in the method for producing the thermoplastic resin composition of the present invention is 10 to 35 (particularly, 10 to 20). Be in the range.
  • thermoplastic resin used in the thermoplastic resin composition of the present invention is selected from the group consisting of polyamide resin, polyester resin, polyolefin resin, polyacetal resin, polyphenylene sulfide resin, and polycarbonate resin. Is also a kind of thermoplastic resin.
  • the surfactant used for coating the fibrous zonolite is a nonionic surfactant.
  • the BET specific surface area of the fibrous zonolite used in the method for producing a thermoplastic resin composition of the present invention is 30 m 2 / g or more and 60 m 2 / g or less.
  • the amount of the surfactant coated on the fibrous zonolite should be in the range of 0.1 to 10% by weight based on the weight of the fibrous zonolite.
  • the coupling agent is at least one kind of force coupling agent selected from the group consisting of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent.
  • thermoplastic resin composition the thermoplastic resin and the fibrous zonolite should be mixed at a weight ratio of 99.5: 0.5 to 30:70.
  • thermoplastic resin composition the thermoplastic resin and the fibrous zonolite are mixed at a weight ratio of 55:45 to 20:80.
  • the average fiber length of the fibrous zonolite contained in the thermoplastic resin composition is in the range of 1 ° to 35 (especially, 10 to 20) represented by the average fiber diameter. .
  • thermoplastic resin mixed with the master batch and heated and kneaded is selected from the group consisting of polyamide resin, polyester resin, polyolefin resin, polyacetal resin, polyphenylene sulfide resin, and polycarbonate resin. It must be a kind of thermoplastic resin.
  • thermoplastic resin mixed with the master batch and heated and kneaded is It must be in the range of 2 to 50 parts by weight, especially in the range of 3 to 30 parts by weight, per part by weight of the terbatch.
  • thermoplastic resin composition The thermoplastic resin composition, the method for producing the thermoplastic resin composition, and the thermoplastic resin molded article of the present invention will be described in detail.
  • the fibrous Zono trie you want to blended in the thermoplastic resin composition of the present invention Zono tri Doo (rational formula: C ai ⁇ (OH), I ⁇ formula: 6 C a O ⁇ 6 S i 0 2 ⁇ H 2 0, the term needle crystals substances known Kei calcium hydrate can be generally represented).
  • the value of the specific surface area of the fibrous Zono tri preparative is very important, it must be at 2 1 m 2 Zg or more, good Mashiku 30 m 2 It is Zg or more (however, it is a measured value by the BET method by nitrogen adsorption).
  • the shape of the raw material fibrous zonolite (the fibrous zonolite in a state before kneading) to be blended in the thermoplastic resin composition of the present invention is, particularly, an average fiber length.
  • the fibrous zonolite used in the present invention can be produced, for example, by a production method described in Japanese Patent Application Laid-Open No. 6-128412, that is, a hydrothermal synthesis by mixing a calcareous raw material and a siliceous raw material at a specific ratio. It can be produced by a reaction.
  • the fibrous zonolite used in the present invention is treated with a surfactant before mixing with the thermoplastic resin. It is considered that the surfactant improves the affinity of the fibrous zono-lite with the thermoplastic resin as a matrix, and promotes the dispersion of the zono-lite granules into the primary particles in the initial stage of kneading.
  • any of anionic, cationic, amphoteric and nonionic surfactants can be used.
  • anionic surfactants include alkyl ether sulfate, dodecylbenzene sulfonate, and stearate.
  • examples of the cationic surfactant include tetradecylamine acetate and alkyltrimethylammonium chloride.
  • Examples of the amphoteric surfactant include dimethyl alkyl lauryl pentane.
  • Nonionic surfactants include polyoxyethylene octadecylamine, polyepoxy Tylene lauryl ether can be mentioned. Particularly preferred are nonionic surfactants, which can be used in combination with other types of surfactants, if desired.
  • An amount in the range from 1 to 1 0 weight 0/0, preferably 0. 5 8 is an amount in the range of weight 0/0. If the added amount is less than 0.1% by weight, the above-mentioned effects are hardly exhibited, and if the added amount exceeds 10% by weight, the above-mentioned effects are significantly improved even if the added amount is increased. do not do.
  • a slurry of fibrous zonolite obtained by a hydrothermal synthesis reaction is extracted from an autoclave, and then the surface of the fibrous zonolite with a surfactant is directly used. Processing can be performed.
  • the surface treatment method is not limited.For example, a surfactant is added to the fibrous zonolite slurry as it is or after adding an appropriate amount of water, and the slurry is mixed and stirred in an appropriate apparatus in a slurry state. Then, excess water is filtered and separated by a centrifugal dehydrator or a filter press to obtain a cake-like surfactant-treated fibrous zonolite.
  • This surface treatment with a surfactant may be carried out using a surfactant dissolved in a small amount of water or a solvent after drying the fibrous zonolite.
  • the fibrous zonolite treated with the surfactant is granulated in a granular form in order to easily mix and stir the thermoplastic resin and the coupling agent.
  • Granular zonolite can be obtained by forming the above-mentioned surfactant-treated cake-like fibrous zonolite into granules having a diameter of 1 to 8 mm using a granulator and drying. Can be.
  • a known granulator such as a rotary vertical granulator, a rotary drum granulator, a rotary dish granulator, a screw extrusion granulator, and a roll extrusion granulator can be used.
  • Drying at the time of granulation is performed using a known dryer such as a hot air circulating dryer or an infrared heating dryer at a temperature of 100 to 180 ° C for 1 to 30 hours. It is desirable to carry out until the water content of the try becomes 1% by weight or less.
  • a known dryer such as a hot air circulating dryer or an infrared heating dryer at a temperature of 100 to 180 ° C for 1 to 30 hours. It is desirable to carry out until the water content of the try becomes 1% by weight or less.
  • thermoplastic resin to be mixed with the fibrous zonolite treated with a surfactant in the present invention examples include polyethylene having various densities and molecular weights, and linear low density.
  • Polyethylene ethylene copolymer (ethylene'vinyl acetate copolymer, ethylene.propylene copolymer, etc.), polypropylene homopolymer, polypropylene copolymer (ethylene'propylene block copolymer, etc.), modified polypropylene, polybutene 1 and poly 4 —Polyolefin resin such as methylpentene, polyvinyl alcohol copolymer, polystyrene, high-impact polystyrene, acrylonitrile-butadiene-styrene (ABS) resin, polyvinyl chloride resin, acrylonitrile-styrene ( AS) Resin, maleic anhydride-styrene resin, polcapamide (nylon 6), polytetramethylene adipamide (
  • Examples of the coupling agent used in the production of the thermoplastic resin composition of the present invention include a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent, and a silane coupling agent is preferable.
  • the coupling agent may be partially hydrolyzed in advance and modified to partially have a silanol group before use.
  • the silane coupling agent has an organic functional group such as an amino group, a diamino group, a butyl group, a chloro group, a methacryloxy group, a cyclic epoxy group, a glycidoxy group, a mercapto group, a ureide group, and a ketimide group.
  • organic functional group such as an amino group, a diamino group, a butyl group, a chloro group, a methacryloxy group, a cyclic epoxy group, a glycidoxy group, a mercapto group, a ureide group, and a ketimide group.
  • silane-based coupling agents having an inorganic functional group such as a methoxy group, an ethoxy group, and an ethoxy group can be used.
  • silane coupling agent examples include vinyl trichlorosilane, vinyl tris (i3-methoxyethoxy) silane, vinyl triethoxy silane, ⁇ - (methacryloyloxypropyl) triethoxy silane, ⁇ — (3, 4 —Epoxycyclyl hexyl) ethi ⁇ / trimethoxysilane, ⁇ -glycidinoleoxypropyltrimethoxysilane, ⁇ —glycidoxypropylmethyljetoxysilane, ⁇ — (aminoethyl) ⁇ -aminoaminopropyltrimethoxysilane, N—] 3 (aminoethyl) ⁇ —aminopropyltrimethyldimethoxysilane, ⁇ —aminopropyltriethoxysilane, ⁇ -phenyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -methylcaptopropyltri
  • thermoplastic resin when a polyamide resin is used as the thermoplastic resin, an amino-based, chloro-based, or cationic silane coupling agent can be advantageously used, but an amino-based resin is particularly desirable.
  • thermoplastic resin is a polyester resin
  • amino-, epoxy-, or Lol-based or cationic silane coupling agents can be advantageously used, and epoxy-based compounds are particularly desirable.
  • thermoplastic resin is a polyolefin resin, particularly when it is modified and polar, an amino-based, epoxy-based, chloro-based, cationic-based silane coupling agent is advantageously used, but an amino-based resin is particularly preferred. .
  • thermoplastic resin is a polyphenylene sulfide resin
  • a mercapto-based silane coupling agent is desirable.
  • thermoplastic resin composition of the present invention may optionally contain various auxiliary materials added for improving the properties of the resin composition and improving the production, such as a heat stabilizer and a light stabilizer.
  • auxiliary materials such as a heat stabilizer and a light stabilizer.
  • Plasticizers, crosslinkers, antioxidants, flame retardants, reinforcements, pigments, dyes, lubricants, antistatic agents, release agents, fragrances, rubber or thermoplastic elastomers, thermoplastics modified with rubber A resin or the like can be blended.
  • the weight percentage of the addition ratio of the coupling agent to the fibrous zonolite is preferably at least 0.2% by weight and less than 10% by weight, particularly preferably. Is not less than 0.5% by weight and not more than 5% by weight.
  • thermoplastic resin composition of the present invention can be produced, for example, using the following method.
  • thermoplastic resin composition of the present invention comprising a surfactant-treated fibrous zonolite, a thermoplastic resin, and a coupling agent includes, for example, a fibrous zonolite, a thermoplastic resin, and a coupling agent. Simultaneously or sequentially, they can be put into a kneader, and then melt-kneaded under heating to produce the compound. Alternatively, the thermoplastic resin and any one of the components can be mixed in advance, and then the other components can be added during heating and melting.
  • thermoplastic resin and the coupling agent can be arbitrarily selected as described above, but preferably, the fibrous zonolite is preferably used. It is desirable to supply the extruder to the hopper of the extruder. For example, prior to melt-kneading, it may be mixed with a thermoplastic resin and a coupling agent and then supplied to a hopper of an extruder.
  • the fibrous zonolite and the thermoplastic resin are double-feed, and the coupling agent is Liquid addition may be used.
  • cutlet It is also possible to supply only a part of the pulling agent from the middle of the extruder.
  • the above-mentioned various auxiliary materials can be added at the same time, if necessary.
  • the temperature most suitable for the thermoplastic resin used select the temperature most suitable for the thermoplastic resin used.
  • the thermoplastic resin is a crystalline resin
  • a temperature higher by 10 to 60 ° C than the melting point of the resin preferably 10 to 40 ° C higher than the melting point of the resin is used.
  • the thermoplastic resin is an amorphous resin
  • the temperature is 110 to 160 ° C higher than the glass transition point of the resin, preferably 110 to 140 ° C higher than the glass transition point of the resin. Temperature is used.
  • Examples of the kneading machine used include extruders such as a single-screw extruder and a twin-screw extruder, a twin-screw continuous mixer, a non-variable mixer, a super mixer, a mixing groonole, a kneader, a brabender plastograph, and the like.
  • the composition is generally obtained as a pellet.
  • extruders are preferred, and twin-screw extruders are particularly preferred.
  • the fibrous zonolite is broken in the longitudinal direction of the fiber due to the shearing treatment in the molten resin, but is also split vertically. Is expressed. By adding and kneading a coupling agent, this longitudinal tearing phenomenon is further promoted.
  • the initially added zonotrite fiber has an average fiber length (L) of 1111 ⁇ 5 / 111, an average fiber diameter of 0.1 ⁇ 0.5 ⁇ ⁇ and an aspect ratio of Even if the ratio (L ⁇ D) is 10 ⁇ LZD ⁇ 20, the dispersed primary particles of zonolite in the kneaded resin composition have an average fiber length (L) of 0.2 Az m ⁇ L ⁇ 0.7 / im, average fiber diameter is 0.Ol / m D ⁇ 0.05 // m, and aspect ratio (L / D) is 5 ⁇ L, D ⁇ 35 (particularly 5 ⁇ L / D ⁇ 20 and 7 ⁇ L / D ⁇ 15 5) and dispersed.
  • the physical properties of the resin composition are remarkably improved, That balance can be greatly improved.
  • the effect of suppressing line changes and warpage due to molding shrinkage and temperature changes is also improved, so the range of application as a structural material can be expanded, and especially as a material in the fields of automobiles, electricity, electronics, precision machinery, etc. It can be used to advantage.
  • the composition obtained in this way has improved fluidity as compared with conventional compositions, it can be molded by various known molding methods such as injection molding, extrusion molding, compression molding, and hollow molding. You.
  • thermoplastic resin composition obtained by kneading and blending the surfactant-treated fibrous zonolite of the present invention in the presence of a coupling agent can be used as it is for the production of a resin molded product.
  • a thermoplastic resin composition containing a large amount of the agent-treated fibrous zonolite is produced, then used as a masterbatch, and mixed (diluted) with the same type of thermoplastic resin.
  • a thermoplastic resin composition in which the amount of the zonolite in the form of a mixture is adjusted can also be used.
  • the measurement was performed using Tensilon UTM-5T manufactured by Orientec. After molding the desired thermoplastic resin composition, it was conditioned for 48 hours at 23 ° C and a relative humidity of 50% (hereinafter abbreviated as “50% RHJ”). The test was performed at 23 ° C and 50% RH in accordance with STM D 790. In the case of a composition containing a polyamide resin as a main component, the condition was adjusted in a desiccator at 23 ° C for 48 hours. Flexural strength and flexural modulus were measured according to ASTM D790 at 23 ° C in a completely dry state.
  • the measurement was performed using an Izod impact tester manufactured by Toyo Seiki Co., Ltd.
  • the notched Izod impact strength was determined in accordance with ASTM D256 under the same temperature and humidity conditions as in the above item (1), using the test specimen whose condition was adjusted in the same manner as in the above item (1).
  • the measurement was performed using a Toyo Seiki load deflection tester. The value was determined under the stress of 1.82 MPa in accordance with ASTM D648 using a test piece which had been subjected to the same condition control as in the above (1). In the case of a composition containing a polypropylene resin as a main component, the value was obtained under a stress of 0.45 MPa.
  • the measurement was performed using a melt indexer YA2072-0000 manufactured by Takara Kogyo Co., Ltd. According to ASTM D 1 238, using a test piece with the same condition adjustment as in the above (1), in the case of a composition containing nylon 6 as a main component, at a temperature of 250 ° C, In the case of a composition containing propylene resin as a main component, the value was determined at a temperature of 230 ° C.
  • the thickness of the kneading strand was set to 0.1 / m using a microtome with a cryo-apparatus, manufactured by Raike Co., Ltd., targeting the center of the kneading strand.
  • a slice sample parallel to the direction was produced.
  • the dimensions of the Zono Tritoe secondary particles were measured. After measuring the fiber length and diameter of 500 to 1,000 particles, the average aspect ratio was calculated.
  • This granular fibrous Zono tri DOO each was subjected to measurement of the average fiber ⁇ and average fiber diameter by the measurement and scanning electron micrograph of the BET specific surface area by nitrogen adsorption, 4 8 m 2 / g, It was confirmed that they were 3 / m and 0.2 / m (therefore, the aspect ratio: 15).
  • the obtained fibrous zonolite is hereinafter referred to as “surfactant-treated fibrous zonolite A”.
  • the production of granular fibrous zonolite was carried out in exactly the same manner as in Reference Example 1, except that the holding temperature for the hydrothermal synthesis reaction was 240 ° C instead of 220 ° C in Reference Example 1.
  • a fibrous zonolite with a BET specific surface area of 24 m 2 / g, an average fiber length of 4 ⁇ m and an average fiber diameter of 0.2 ⁇ m (hence the aspect ratio of 20) was used. Obtained.
  • this is referred to as “surfactant-treated fibrous zonolite B”.
  • Granular zonolite was produced in the same manner as in Reference Example 1 except that the nonionic surfactant as a surface treatment agent was not added, and the BET specific surface area was 39 n ⁇ Zg. : 3 m and an average fiber diameter of 0.2 m (accordingly, an aspect ratio: 15), a fibrous zonolite untreated with a surfactant was obtained.
  • Treated fibrous Zonotry E 14
  • Nonionic surfactant (trade name: Nymein 204) is replaced with silane coupling agent—Aminopropyl Triethoxyethoxylan, a product of Nippon Tunica Co., Ltd., trade name: A—110) 46 g (fibrous Zono tri fed versus except the E strange to 5 weight 0/0) solids, reference example 1 and row production of exactly the same way Zono tri preparative surface treatment Le ,, 8 £ Ding specific surface area 45 111 2 8 Thus, a fibrous zonolite having an average fiber length of 3 ⁇ m and an average fiber diameter of 0.2 ⁇ m (accordingly, an aspect ratio of 15) was obtained. Hereinafter, this is referred to as “Fibrous Zonotri F treated with coupling agent F”.
  • Nylon 6 as thermoplastic resin (trade name: UBE Nylon 1013B) manufactured by Ube Industries, Ltd. 99.5 parts by weight, aminosilane-based coupling agent as coupling agent (trade name, manufactured by Nippon Tunicar Co., Ltd.) : A—1 100) 0.5 part by weight of a mixture consisting of 0.5 part by weight and 20 parts by weight of the surfactant-treated fibrous zonolite A obtained in Reference Example 1 as fibrous zonolite in a proportion of 80 parts by weight. Parts were previously mixed using a V-type blender.
  • the cylinder temperature (however, the temperature of the nozzle head, the same applies hereinafter) 260 ° C and the mold temperature 1
  • the pellet was injection-molded at 00 ° C to prepare a molded article (test piece) for a physical property test.
  • Table 1 shows the results of the physical property test.
  • the melt flow index (MF I) was 43%.
  • Example 2 Except that an epoxy silane coupling agent (trade name: A-187, manufactured by Nippon Tunicer Co., Ltd.) was used in place of the aminosilane-type jj agent A-110 of Example 1. Was performed in exactly the same manner as in Example 1. Table 1 shows the physical property test results of the obtained test pieces.
  • an epoxy silane coupling agent trade name: A-187, manufactured by Nippon Tunicer Co., Ltd.
  • Example 1 Except that the aminosilane type coupling agent A-110 of Example 1 was replaced with a mercapto-based silane coupling agent (trade name: A-197, manufactured by Nippon Tunicer Co., Ltd.), The same operation as in Example 1 was performed. The test results of physical properties of the obtained test piece were as shown in Table 1.
  • Example 1 The same operation as in Example 1 was performed, except that the surfactant-treated fibrous zono-lite A in Example 1 was changed to the surfactant-treated fibrous zono-lite B.
  • Table 1 shows the physical property test results of the obtained test pieces.
  • Example 1 The pellet obtained in Example 1 was used as a master batch, and 25 parts by weight of the pellet and 75 parts by weight of nylon 6 alone were pre-blended using a V-type blender. By performing the same operation as above, the molded product for heat melting and physical property evaluation
  • Table 1 shows the physical property test results of the obtained test pieces.
  • Example 1 Using the pellet obtained in Example 1 as a master batch, 5 parts by weight thereof and 95 parts by weight of nylon 6 alone were previously blended using a V-type blender, and then completely blended as in Example 1. Molding for heat melting and physical property evaluation
  • coupling agent 98.988 parts by weight: 1 part by weight: 0.02 parts by weight
  • Example 1 the amount of the aminosilane-based coupling agent was (The same operation was performed except that the amount was changed to 1% by weight based on the surfactant-treated fibrous zonolite A.)
  • the physical property test results of the obtained test piece are as shown in Table 1.
  • the melt flow index (MF I) was 44%.
  • Example 1 The same operation as in Example 1 was performed except that the amount of the aminosilane-based coupling agent was changed to 0.8 parts by weight (4% by weight based on the surfactant-treated fibrous zonolite A). Table 1 shows the physical property test results of the obtained test pieces.
  • the melt flow index (MF I) was 42%.
  • Example 1 Except that the surfactant-treated fibrous zono-lite A in Example 1 was changed to coarse surfactant-treated fibrous zono-lite C, the same operation as in Example 1 was performed. Physical test results of the obtained test pieces are as shown in Table 1. Melt flow index (MFI) was 39%.
  • Example 1 Except that the surfactant-treated fibrous zonolite A in Example 1 was changed to untreated fibrous zonolite E, the same operation as in Example 1 was performed. Physical test results of the obtained test pieces are as shown in Table 1.
  • Example 1 Except that the amount of the aminosilane-based coupling agent (A-1100) used in Example 1 was set to 0.01 part by weight (0.05% by weight based on the surfactant-treated fibrous zonolite A). Was performed in exactly the same manner as in Example 1. Physical test results of the obtained test piece are as shown in Table 1.
  • Example 1 The same operation as in Example 1 was performed, except that the aminosilane-based coupling agent (A-110) in Example 1 was not used at all. Physical test results of the obtained test piece are as shown in Table 1. The melt flow index (MFI) was 38%.
  • Example 1 The surfactant-treated fibrous zonolite A in Example 1 was treated with a coupling agent. Except for changing to the fibrous zonolite F, the same operation as in Example 1 was carried out. C The physical property test results of the obtained test pieces were as shown in Table 1. Table 1 Example I z Impact strength Falling weight impact strength Flexural strength Flexural modulus Load deflection
  • Example 4 1 02 3 8 1 6 1 2 7 0 2 29 Example 5 6 7 1 1 4 1 1 1 1 5 2 1 56 Example 6 6 5 1 1 3 1 0 9 1 3 3
  • Example 7 8 9 1 7 1 6 3 2 5 9 2 2 7
  • Example 8 1 1 3 1 6 1 6 5 2 5 9 2 27 Comparative Example 1 60 5 1 5 8 24 8 208 Comparative Example 2 Surface withstanding evaluation 3 5 6 5 1 5 9 2 3 7
  • Example 9 The same operation as in Example 9 was performed, except that the blending amount of the fibrous zonolite A treated with surfactant was changed to 5 parts by weight. Physical test results of the obtained test pieces are as shown in Table 2.
  • Example 9 the same operation as in Example 9 was performed except that no coupling agent was used. Physical test results of the obtained test piece are as shown in Table 2.
  • Example 9 The same operation as in Example 9 was performed, except that the fibrous zonolite A treated with a surfactant in Example 9 was changed to the fibrous zonolite F treated with a coupling agent. Physical test results of the obtained test pieces are as shown in Table 2. Table 2 Example I Z impact strength Drop weight impact strength Flexural strength Flexural modulus Load deflection
  • Nylon 6 was changed to polybutylene terephthalate (PBT resin) (manufactured by Ube Industries, Ltd., trade name: UBE PBT 100), and the coupling agent was amino.
  • the coupling agent was changed from an aminosilane-based coupling agent to a mercapto-based silane coupling agent (A-197, manufactured by Nippon Tunicer Co., Ltd.).
  • the melting and kneading temperature was changed to 250 ° C. 300 ° C, cylinder temperature of injection molding machine changed from 260 ° C to 300 ° C, and mold temperature of injection molding machine changed from 100 ° C to 130 ° C Except for this, the same operation as in Example 1 was performed. Table 3 shows the physical property test results of the obtained test pieces.
  • Example 4 shows the physical property test results of the obtained test pieces. Table 4 Example Iz impact strength Falling weight impact strength Flexural strength Flexural modulus Load deflection
  • thermoplastic resin composition produced by the method of the present invention has a high impact resistance because the fibrous zonolite is finely divided and uniformly dispersed in the resin composition and shows a strong bond with the thermoplastic resin. It has particularly excellent properties and bending strength, and can be used particularly advantageously in the production of resin moldings for automobile parts, electric and electronic parts, precision machined parts, and the like.
  • fibrous zonolite is dispersed in a resin composition at a high concentration as a master patch and using a method of diluting with a thermoplastic resin, the fibrous zonolite is formed at a desired concentration.
  • the melt-kneading temperature was changed to 240 ° C instead of 250 ° C, and the cylinder temperature of the injection molding machine was changed from 260 ° C to 27 ° C.
  • the same operation as in Example 1 was performed except that the temperature was changed to 0 ° C, and the mold temperature of the injection molding machine was changed from 100 ° C to 110 ° C.
  • Table 3 shows the physical property test results of the obtained test pieces.
  • Example 11 was completely different from Example 11 except that the amount of the epoxy silane coupling agent was changed to 0.2 part by weight (1% by weight based on the surfactant-treated fibrous zonolite A). A similar operation was performed. Table 3 shows the physical property test results of the obtained test pieces.
  • Example 9 the same operation as in Example 11 was performed, except that no coupling agent was used.
  • Table 3 shows the physical property test results of the obtained test pieces.
  • Example I Z impact strength Falling weight impact strength Flexural strength Flexural modulus Load deflection
  • Nylon 6 was changed to Polyphenylene Sulfide (PPS resin) (manufactured by Kureha Corporation, trade name: FORTRON KPS Compound PF-200A). Can also be manufactured.
  • PPS resin Polyphenylene Sulfide

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

On produit cette composition de résine thermoplastique en mélangeant une résine thermoplastique à de la xonotlite fibreuse, dont la surface a été au préalable enduite d'un tensioactif, dont la surface spécifique BET est égale ou supérieure à 21 m2/g, dont la longueur moyenne des fibres est comprise entre 1 et 5 νm et dont le diamètre moyen des fibres est compris entre 0'1 et 0,5 νm, puis en malaxant le mélange résultant tout en le chauffant en présence de 0,2 à 10 % en poids d'un agent couplant à base de xonotlite fibreuse. Dans cette composition de résine, la xonotlite fibreuse a été réduite en fines particules, uniformément dispersée et fermement liée à la résine thermoplastique. Cette composition possède, de ce fait, de remarquables propriétés de résistance au choc et à la flexion. Elle peut, notamment, être avantageusement utilisée pour produire des résines moulées pour pièces d'automobile, pièces pour les domaines de l'électricité/électronique, pièces pour travaux de précision, etc.
PCT/JP2000/002540 1999-04-19 2000-04-19 Composition de résine thermoplastique et procédé de production WO2000063278A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU38393/00A AU3839300A (en) 1999-04-19 2000-04-19 Process for producing thermoplastic resin composition and thermoplastic resin composition
JP2000612362A JP4718015B2 (ja) 1999-04-19 2000-04-19 熱可塑性樹脂組成物の製造方法

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JP11133499 1999-04-19
JP11/111334 1999-04-19

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WO2000063278A1 true WO2000063278A1 (fr) 2000-10-26

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015048468A (ja) * 2013-09-04 2015-03-16 旭化成ケミカルズ株式会社 ポリアセタール樹脂組成物

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07216133A (ja) * 1994-02-04 1995-08-15 Ube Ind Ltd 強化された有機高分子組成物
EP0717072A1 (fr) * 1994-12-16 1996-06-19 Ube Industries Limited Composition de polymère organique renforcé de xénolite

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Publication number Priority date Publication date Assignee Title
JPH0816179B2 (ja) * 1987-05-28 1996-02-21 株式会社クラレ 樹脂組成物
JP2777762B2 (ja) * 1992-05-28 1998-07-23 東洋紡績 株式会社 ポリアミド樹脂組成物
JPH08170022A (ja) * 1994-12-20 1996-07-02 Ube Ind Ltd 熱可塑性樹脂組成物
JPH08165377A (ja) * 1994-12-16 1996-06-25 Ube Ind Ltd 熱可塑性樹脂組成物
JPH08165376A (ja) * 1994-12-16 1996-06-25 Ube Ind Ltd 熱可塑性樹脂組成物
JP3646737B2 (ja) * 1995-03-17 2005-05-11 大日本インキ化学工業株式会社 反応性に富むポリアリーレンスルフィド
JP3341974B2 (ja) * 1996-12-26 2002-11-05 東洋紡績株式会社 難燃性ポリアミド樹脂組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07216133A (ja) * 1994-02-04 1995-08-15 Ube Ind Ltd 強化された有機高分子組成物
EP0717072A1 (fr) * 1994-12-16 1996-06-19 Ube Industries Limited Composition de polymère organique renforcé de xénolite

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015048468A (ja) * 2013-09-04 2015-03-16 旭化成ケミカルズ株式会社 ポリアセタール樹脂組成物

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