WO2000063278A1

WO2000063278A1 - Process for producing thermoplastic resin composition and thermoplastic resin composition

Info

Publication number: WO2000063278A1
Application number: PCT/JP2000/002540
Authority: WO
Inventors: Shin-Ichi Yamamoto; Kaoru Takazaki
Original assignee: Ube Material Industries, Ltd.
Priority date: 1999-04-19
Filing date: 2000-04-19
Publication date: 2000-10-26
Also published as: AU3839300A; JP4718015B2

Abstract

A thermoplastic resin composition which is produced by mixing a thermoplastic resin with fibrous xonotlite the surface of which has been coated beforehand with a surfactant and which has a BET specific surface area of 21 m2/g or larger, an average fiber length of 1 to 5 νm, and an average fiber diameter of 0.1 to 0.5 νm in a weight ratio of 99.5/0.5 to 20/80 and kneading the resultant mixture with heating in the presence of 0.2 to 10 wt.% coupling agent based on the fibrous xonotlite. In the resin composition, the fibrous xonotlite has been reduced to fine particles, is evenly dispersed, and strongly bonds to the thermoplastic resin. The composition is hence excellent especially in impact resistance and flexural strength. It is advantageously usable especially in producing molded resins for automotive parts, electrical/electronic parts, precision work parts, etc.

Description

Description Method for producing thermoplastic resin composition and thermoplastic resin composition

[Technical field]

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.

[Background technology]

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.

In recent years, high impact resistance has been required for resin molded products used for automobile parts, electric / electronic parts, precision machine parts, and the like. For this reason, the use of a resin composition in which a rubber, a thermoplastic elastomer, a thermoplastic resin modified with a rubber component, or the like was mixed as a modifier with a thermoplastic resin was studied. However, the addition of such a rubber component tends to decrease the strength, elastic modulus, and heat resistance of the obtained resin molded product. Cannot be enough.

In order to solve the above problems, 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). During heating and kneading with a resin component, 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. [Disclosure of the Invention]

Various properties such as impact resistance and elasticity of thermoplastic resin molded products can be improved by adding the above-mentioned surface treated zonolite to thermoplastic resin. 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. On the other hand, 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.

Accordingly, 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 μm, and an average fiber diameter of 0 μm. A fibrous zonolite in the range of 1 to 0.5 μm 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. A kneaded product containing zono-lite in a weight ratio of 99.5: 0.5 to 20:80, and 0.2 to 10% by weight based on the weight of the fibrous zono-lite. There is also a 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. There is also a 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.

That is, according to the research of the present inventor, in a 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, Although 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. As a result, it is difficult to obtain the required high impact resistance and bending strength.On the other hand, the conventional fibrous zonolite whose surface has been treated with a coupling agent is added to a thermoplastic resin and kneaded. In the plastic resin composition, 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.

Based on the above findings, 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. The presence of 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. [Best Mode for Carrying Out the Invention] ⁴

(1) 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.

(2) The 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.

(3) The surfactant used for coating the fibrous zonolite is a nonionic surfactant.

(4) 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.

(5) 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.

(6) 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.

(7) In producing the 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.

(8) In the production of the thermoplastic resin composition, the thermoplastic resin and the fibrous zonolite are mixed at a weight ratio of 55:45 to 20:80.

(9) 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. .

(10) at least a 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.

(11) The amount of 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.

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 βθιτ (OH), I匕学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). When blending the thermoplastic resin composition of the present invention, 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). Further, 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.

(L) Force S 1 m ≤ L ≤ 5 m, average fiber diameter 0. l Ai m ≤ D ≤ 0.5 / zm, and aspect ratio (LZD) 10 ≤ 0 ≤ 0 ≤ 35, especially Those satisfying the condition of 10 ≤ LZD ≤ 20 at the same time can be suitably used.

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.

As the surfactant, any of anionic, cationic, amphoteric and nonionic surfactants can be used. Examples of 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. Normal amount of these surfactants, for the fibrous Zono tri preparative (dry basis), 0. 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.

For surface treatment of fibrous zonolite with a surfactant, for example, 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.

Further, it is desirable that 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. There is no particular limitation on the granulator to be used, and 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. 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.

Examples of the thermoplastic resin to be mixed with the fibrous zonolite treated with a surfactant in the present invention 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 (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebaca (Nylon 610), polyhexamethylene dodecanoamide (nylon 612), polyhexamethylene terephthalamide (6 nylons), polyhexamethylene phthalamide (nylon 6I), polydecanamide (Nylon 11), Polydodecaneamide (Nylon 12), Nylon 96, Nylon 912, Nylon 91, Nylon 9T, Nylon 666, Nylon 6Ζ11, Nylon 612, Nylon 6 610, nylon 6 6 6 12, nylon 6 6 6 10, nylon 6 66 6 10, nylon 6Ζ66 / 12, nylon 6 6Τ, nylon 6 61, nylon 6 9 Nylon 6 9 1, Nylon 6 6Ζ9 Τ, Nylon 66/91 1, Nylon δΖδ δΖθ Τ Nylon 6Z1 2 9 Τ, Nylon 6 6 / \ 2/9 Nylon 6 6 6 1 \ Nylon 6 6 6 1, Nylon 6 1 1/6 Τ, nylon 6 1 2Ζ6 Τ, Niro β δ / Ι ΐ / δ Τ Nylon 6 6/1 2/6 Τ, Nylon 1 1Z6 Tno 6 I and Nylon 1 2/6 TZ6 I, etc.Polyamide resin, polybutylene terephthalate, polyethylene terephthalate And other polyester resins such as aromatic polyesters, polycarbonate, polyacetal resins (including homopolymers and copolymers), polyphenylene ether, modified polyphenylene ether, polyether ketone, polysulfone, poloethersulfone , Polyphenylene sulfide resin, Polyetherimide, Thermoplastic polyimide, Thermoplastic polyimide, Polytetrafluoroethylene, Tetrafluoroethylene-hexafluoropropylene copolymer, Te Trifluoroethylene-ethylene copolymer, tetrafluoroethylene Pafunoreoroa To mention, for example, alkyl vinyl ether copolymers, trifluoromethyl ethylene copolymers, polyvinylidene fluoride, tetrafluoronoreoethylene-hexaphnoleo-propylene-perphnoleo-alkylbule ether copolymers, and mixtures thereof. Can be done. Among these, a polyamide resin, a polyester resin, a polyolefin resin, a polyacetal resin, a polyphenylene sulfide resin, and a mixture thereof are mentioned as particularly preferred specific examples.

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. Various silane-based coupling agents having an inorganic functional group such as a methoxy group, an ethoxy group, and an ethoxy group can be used.

Specific examples of the silane coupling agent include vinyl trichlorosilane, vinyl tris (i3-methoxyethoxy) silane, vinyl triethoxy silane, γ- (methacryloyloxypropyl) triethoxy silane, β— (3, 4 —Epoxycyclyl hexyl) ethi ^ / trimethoxysilane, γ-glycidinoleoxypropyltrimethoxysilane, γ—glycidoxypropylmethyljetoxysilane, Ν— (aminoethyl) γ-aminoaminopropyltrimethoxysilane, N—] 3 (aminoethyl) γ—aminopropyltrimethyldimethoxysilane, γ—aminopropyltriethoxysilane, 、 -phenyl-γ-aminopropyltrimethoxysilane, γ-methylcaptopropyltrimethoxysilane, Provir trimethoxysilane It is.

In particular, 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.

When the 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.

When the 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. .

When the thermoplastic resin is a polyphenylene sulfide resin, a mercapto-based silane coupling agent is desirable.

In addition to the coupling agent, the 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. , 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.

Next, the weight percentage of the addition ratio of the coupling agent to the fibrous zonolite (which has been treated with a surfactant) 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.

The thermoplastic resin composition of the present invention can be produced, for example, using the following method.

That is, the 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.

The addition and mixing order of these components when melt-kneading the fibrous zonolite, the 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. Also, cutlet It is also possible to supply only a part of the pulling agent from the middle of the extruder. In the production of the above-mentioned composition, the above-mentioned various auxiliary materials can be added at the same time, if necessary.

For the melt-kneading temperature, select the temperature most suitable for the thermoplastic resin used. When 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. When 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. Among these, extruders are preferred, and twin-screw extruders are particularly preferred.

In the production of the thermoplastic resin composition of the present invention, in the above-mentioned kneading step, 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. As a result, the initially added zonotrite fiber has an average fiber length (L) of 1111≤≤≤5 / 111, an average fiber diameter of 0.1 μτη≤Ό≤0.5 μππ ^ 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. By strengthening the bond at the interface between the thermoplastic resin used in the present invention and the zonolite by a coupling reaction, the physical properties of the resin composition, particularly rigidity, heat resistance and impact resistance, are remarkably improved, That balance can be greatly improved. At the same time, 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. Since 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.

The 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. Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The methods for evaluating physical properties of molded articles described in Examples and Comparative Examples were performed according to the following methods.

(1) Bending characteristics

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.

(2) Izod impact strength

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).

(3) Instrumented falling weight impact strength

The measurement was performed using Orientec's instrumented impact tester UTM-5 at a speed of 4.5 seconds, a temperature of 23 ° C, and a humidity of 50%. (4) Deflection temperature under load

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.

(5) Melt flow index (may be abbreviated as MFI)

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.

(6) Measurement of fiber length and fiber diameter of zonolite in the composition

In order to understand the morphology of the zono-lite fibers in the composition, 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. Based on the 60,000-times TEM observation image shown in some of the reference figures, 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.

[Reference Example 1]

Quicklime as calcareous material (Ube Material Co., C a O Purity: 9 8%) 430 g, agricultural silica powder as siliceous material (Japan General Corporation product, blur over down specific surface area: 7000 cm ² zg, S I_〇 ₂ purity: 9 7%) 4 70 g , and water Michisui 1 8 liters was charged to SUS 3 1 with 6 made stirrer Otokure over blanking the internal volume 30 Li Tsu torr. Then, while stirring at a rotation speed of 80 rpm, the temperature was raised at a holding temperature of 220 ° C at a rate of 2 ° C / Z, and held at a holding temperature of 220 ° C for 5 hours to perform a hydrothermal synthesis reaction. Thereafter, the mixture was allowed to cool over 10 hours or more with stirring to obtain a fibrous zono trie slurry. When the slurry X-ray diffraction was measured, only zonotrite was identified. Subsequently, about 180 g of tap water and a nonionic surfactant (polyoxyethylene octadecylamine, Nippon Oil & Fats Co., Ltd.) were added to 920 g of the fibrous zono trit slurry (based on the fixed amount). Product, trade name: Nymein 204) 46 g (5% by weight based on the solid content of fibrous zonolite) was added, and the surface was treated with a homogenizer while dispersing. The slurry is dehydrated by Nutsche to form a cake, then formed into a diameter of 0.3 mm by a granulator, and dried at about 100 to obtain a surface-treated granular fibrous zono. Got a try. This granular fibrous Zono tri DOO, each was subjected to measurement of the average fiber維長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”.

[Reference Example 2]

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 μm and an average fiber diameter of 0.2 μm (hence the aspect ratio of 20) was used. Obtained. Hereinafter, this is referred to as “surfactant-treated fibrous zonolite B”.

[Reference Example 3]

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 changed to 260 ° C instead of 220 ° C in Reference Example 1. The BET specific surface area: 16 m ² / g, average fiber length 10 μπι and average fiber diameter ◦. 2 / m (Accordingly, aspect ratio: 50) were obtained. Was. Hereinafter, this is referred to as “surfactant-treated fibrous zonolite coarse particles C”.

[Reference Example 4]

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. Hereafter, Treated fibrous Zonotry E ”. ¹⁴

[Reference Example 5]

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 μm and an average fiber diameter of 0.2 μm (accordingly, an aspect ratio of 15) was obtained. Hereinafter, this is referred to as “Fibrous Zonotri F treated with coupling agent F”.

[Example 1]

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. Subsequently, using a co-rotating twin-screw screw extruder with a cylinder diameter of Φ3 Omm (PCM30, manufactured by Ikegai Iron Works Co., Ltd.), the temperature was set to 250 ° C (where the temperature of the nozzle was The same procedure was followed by melt-kneading to prepare a pellet composed of 79.6 parts by weight of the nylon, 0.4 part by weight of the coupling agent, and 20 parts by weight of the fibrous zonolite. However, the nylon 6, aminosilane-based coupling agent and fibrous zono triit A were supplied from the supply port using a screw feeder, and deaeration was performed from the second vent port.

Next, using an injection molding machine (N100 manufactured by Japan Steel Works, Ltd.), 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.

[Example 3]

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 4]

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 5]

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

(Test piece, nylon 6: surfactant-treated fibrous zonolite A _: coupling agent = 94.9 parts by weight: 5 parts by weight: 0.1 part by weight) was obtained. Table 1 shows the physical property test results of the obtained test pieces.

[Example 6]

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

(Test piece, nylon 6: surfactant treated fibrous zonolite A _: coupling agent = 98.988 parts by weight: 1 part by weight: 0.02 parts by weight) was obtained. Physical test results of the obtained test pieces are as shown in Table 1.

[Example 7]

In 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 8]

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%.

[Comparative 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%.

[Comparative Example 2]

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.

[Comparative Example 3]

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.

[Comparative Example 4]

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%.

[Comparative Example 5]

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 1 1 08 40 1 6 3 2 7 0 232 Example 2 1 08 1 5 0 26 7 2 1 7 Example 3 1 08 1 4 9 26 7

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

Comparative Example 4 6 0 5 1 6 0 24 1 2 1 1 Comparative Example 5 5 6 4 1 44 22 6

[Example 9]

Nylon 6, polypropylene (ethylene 'propylene block copolymer, manufactured by Grand Polymer Co., Ltd., trade name: Grand Polypro J815K) 90 parts by weight and modified polypropylene (manufactured by Grand Polymer Co., Ltd., trade name: Grand Polyp) Mouth (block-based modified polypropylene) ZP 648) Changed to a mixture with 10 parts by weight, and changed the melt-kneading temperature to 240 ° C instead of 250 ° C, and the injection molding machine Except that the mold temperature was changed from 100 ° C to 80 ° C, the same operation as in Example 1 was performed. Physical test results of the obtained test pieces are as shown in Table 2.

[Example 10]

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.

[Comparative Example 6]

In 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.

[Comparative Example 7]

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

(%) (%) (%) (%) (%) Example 9 05 47 1 2 7 1 38

Example 1 0 9 7 5 2 1 1 0 1 1 9 Comparative Example 6 8 6 42 08 1 3

Comparative Example 7 8 6 2 7 3 8

[Example 11]

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.

[Comparative Example 9]

The same operation as in Example 13 was performed, except that the coupling agent was not used in Example 13. Table 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

(%) (%) (%) (%) (%) Example 1 3 1 4 3 1 3 7 2 1 0 Comparative example 9 1 2 3 1 22 2 1 0

[Industrial applicability]

The 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. In addition, by using a method in which 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. Highly uniformly dispersed resin composition 19

From silane-based coupling agents to epoxy-based silane-based coupling agents

A-187), 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 12]

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.

[Comparative Example 8]

In 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. Table 3 Example I Z impact strength Falling weight impact strength Flexural strength Flexural modulus Load deflection

(%) (%) (%) (%) (%) Example 1 1 1 8 62 2 3 9 283 Example 1 2 9 5 49 2 3 9 28 2 Comparative example 8 9 3 39 23 2 28

[Example 13]

Nylon 6 was changed to Polyphenylene Sulfide (PPS resin) (manufactured by Kureha Corporation, trade name: FORTRON KPS Compound PF-200A). Can also be manufactured.

Claims

The scope of the claims

1. a thermoplastic resin, and coating treatment beforehand surface with a surfactant, B ET specific surface area of 2 1 m ² Zg above, the range of the average fiber length. 1 to 5 / m, and an average fiber diameter of 0.1: ~ 0.5 zm in the range of 99.5: 0.5 to 20:80 by weight, and the resulting mixture is mixed with the fibrous zonolite. A method for producing a thermoplastic resin composition, comprising heating and kneading in the presence of a coupling agent in an amount in the range of 0.2 to 10% by weight based on the weight of zonolite.

2. The thermoplastic resin composition according to claim 1, wherein an average fiber specific force represented by an average fiber length represented by an average fiber diameter is in a range of from 10 to 20. Method of manufacturing a product.

3. at least one thermoplastic resin selected from the group consisting of polyamide resins, polyester resins, polyolefin resins, polyacetal resins, polyphenylene sulfide resins, and polycarbonate resins; 3. The method for producing a thermoplastic resin composition according to claim 1, wherein the method is characterized in that:

4. The method for producing a thermoplastic resin composition according to any one of claims 1 to 3, wherein the surfactant is a nonionic surfactant.

5. fibrous Zono BET specific surface area of the tri bets is 3 Om ^ g or more, thermoplastic according to any one of the paragraphs within the range 1 to 4 claims characterized in that it is a 60 m ² / g hereinafter A method for producing a resin composition.

6. The amount of the surfactant coated on the fibrous zonolite is in the range of 0.1 to 10% by weight based on the weight of the fibrous zonolite. 6. The method for producing a thermoplastic resin composition according to any one of items 5.

7. The coupling agent according to claim 1, wherein the coupling agent is at least one kind of coupling agent selected from the group consisting of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent. Method for producing a thermoplastic resin composition according to any one of-

8. The composition according to any one of claims 1 to 7, wherein the weight ratio of the thermoplastic resin to the fibrous zonolite is in the range of 99.5: 0.5 to 30:70. The method for producing a thermoplastic resin composition according to any one of the above items.

9. The method according to any one of claims 1 to 7, wherein the weight ratio of the thermoplastic resin to the fibrous zonolite is in the range of 55:45 to 20:80. 13. A method for producing a thermoplastic resin composition according to the above item.

1 0. Thermoplastic resin and fibrous zonolite having an average fiber length in the range of 0.1 to 0.7 im and an average fiber diameter in the range of 0.01 to 0.05 m A kneaded product containing a weight ratio of 99.5: 0.5 to 20:80, containing 0.2 to 10% by weight of a coupling agent with respect to the weight of the fibrous zonolite. Thermoplastic resin composition.

11. The thermoplastic resin according to claim 10, wherein the average fiber length of the fibrous zonotrites is in the range of 5 to 35, which is the average flux ratio represented by the average fiber diameter. Resin composition.

1 2. The thermoplastic resin is at least one kind of thermoplastic resin selected from the group consisting of polyamide resin, polyester resin, polyolefin resin, polyacetal resin, polyphenylene sulfide resin, and polycarbonate resin. The thermoplastic resin composition according to any one of claims 11 to 12, characterized in that:

1 3. The coupling agent, wherein 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. 13. The thermoplastic resin composition according to any one of items 1 to 12.

1 4. The claims 10 to 13 wherein the weight ratio of the thermoplastic resin to the fibrous zonolite is in the range of 99.5: 0.5 to 30:70. The thermoplastic resin composition according to any one of the above.

1 5. The method according to any one of claims 10 to 13, wherein the weight ratio between the thermoplastic resin and the fibrous zonolite is in the range of 55:45 to 20:80. Item 10. The thermoplastic resin composition according to Item 1.

1 6. A thermoplastic resin composition obtained by the production method according to any one of claims 1 to 9.

1 7. A thermoplastic resin molded article obtained by heating and melting the thermoplastic resin composition according to any one of claims 10 to 16 and then molding the same into a desired shape.

1 8. The thermoplastic resin composition according to any one of claims 10 to 16 and the thermoplastic resin are mixed at a weight ratio of 1: 1 to 1: 160, and then A method for producing a thermoplastic resin composition, comprising heating and kneading.

1 9. The weight ratio of the thermoplastic resin composition and the thermoplastic resin obtained by the production method according to any one of claims 1 to 9 is 1: 1 to 1: 1. And then heating and kneading the mixture. 2. A method for producing a thermoplastic resin composition, comprising: