WO1999048973A1

WO1999048973A1 - Resin composition reinforced with polyamide fibers and process for producing the same

Info

Publication number: WO1999048973A1
Application number: PCT/JP1998/001216
Authority: WO
Inventors: Shinji Yamamoto; Hideo Kurihara; Kimio Nakayama; Yukihiko Asano
Original assignee: Ube Industries, Ltd.
Priority date: 1998-03-20
Filing date: 1998-03-20
Publication date: 1999-09-30

Abstract

100 parts by weight of a polyolefin resin (a) is melt-kneaded together with a mixture comprising 10 to 400 parts by weight of a rubbery polymer (b) having a glass transition temperature of 0 °C or lower, 10 to 400 parts by weight of a thermoplastic polyamide (c) containing a phyllosilicate, and a silane coupling agent (d). The product is extruded and then stretched or rolled at a temperature lower than the melting point of the ingredient (c) to disperse the same in the form of fibers. The resin composition reinforced with polyamide fibers thus obtained is excellent in strength, rigidity, and frictional performance.

Description

Description Polyamide fiber reinforced resin composition and method for producing the same

The present invention relates to a polyamide fiber reinforced resin composition and a method for producing the same. More specifically, the present invention provides a resin matrix containing a polyolefin resin and a rubbery polymer, in which a fibrous polyamide containing a layered silicate is dispersed and captured. The present invention relates to a polyamide fiber reinforced resin composition and a method for producing the same. Background art

Rubber-like polymers have been used as various rubber products because of their high recovery elastic modulus and low elastic modulus. However, the demands have become increasingly higher, such as those with a higher recovery modulus but a slightly higher modulus, and those with a higher modulus and higher durability. Even in the resin field, a material with high elastic modulus, light strength, and high impact resistance has been required.

A fiber reinforced composition in which fine polyamide fibers are dispersed in a polyolefin and a rubber-like polymer is disclosed in JP-A-7-238189. Since it is obtained in the form of pellets with an average fiber diameter of 1 / m or less, it is easy to handle and is suitably used as a reinforcing agent for resins and rubber-like polymers. However, in fields such as tires, rolls, and footwear, friction performance is also required. Disclosure of the invention

The present invention solves the above-mentioned problems of the prior art, and has excellent rigidity and strength. Another object of the present invention is to provide a polyamide fiber reinforced resin composition having excellent friction performance and a method for producing the same.

The polyamide fiber reinforced resin composition of the present invention comprises the following components mixed with each other;

(a) 100 parts by weight of polyolefin resin,

(b) 10 to 400 parts by weight of a rubbery polymer having a glass transition temperature of 0 ° C or less,

(c) 10 to 400 parts by weight of fibrous thermoplastic polyamide containing layered silicate, and

(d) Silane coupling agent

It contains.

The method for producing the polyamide fiber reinforced resin composition of the present invention comprises the steps of (a) 100 parts by weight of a polyolefin resin, and (b) 100 to 400 parts by weight of a rubbery polymer having a glass transition temperature of 0 ° C. or less. And (d) the silane coupling agent is melt-kneaded to form a molten matrix, and the molten matrix is mixed with (c) the layered silicate-containing thermoplastic polyamide. 10 to 400 parts by weight are mixed at a temperature equal to or higher than the melting temperature of the thermoplastic polymer, and the molten mixture is extruded to a temperature lower than the melting point of the thermoplastic polymer (c). In the matrix comprising the mixture of the other components (a) and (b), the layered silicate-containing thermoplastic polyamide is dispersed in a fibrous form. Including this.

In the polyamide fiber reinforced resin composition and the method for producing the same according to the present invention, the silane coupling agent (d) is used based on a total of 100 parts by weight of the components (a), (b) and (c). However, it is preferable that the content is 0.1 to 5.5 parts by weight.

Also, the polyamide fiber reinforced resin composition of the present invention and a method for producing the same In the above, it is preferable that the layered silicate is blended at a ratio of 0.05 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic polymer. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the polyamide fiber reinforced resin composition of the present invention and a method for producing the same will be specifically described.

(a) The polyolefin resin preferably has a melting point in the range of 80 to 250 ° C, more preferably 50 ° C or more, and particularly preferably 50 to 50 ° C. Those having a vicat softening point of 200 ° C can also be used. Preferable examples of the polyolefin resin (a) include homopolymers and copolymers of olefins having 2 to 8 carbon atoms, for example, olefins having 2 to 8 carbon atoms and styrene, Copolymers with aromatic vinyl compounds such as chlorostyrene and monomethylstyrene; copolymers of C2 to C8 olefins with vinyl acetate; C2 to C8 olefins and acrylates Copolymers of acrylic acid or its esters, copolymers of C2 to C8 olefins and methacrylic acid or its esters, and C2 to C8 olefins and vinyl Copolymers with a lucirane compound are exemplified.

(a) Specific examples of the polyolefin resin used as the component include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, and ethylene-propylene block. Copolymer, ethylene-propylene random copolymer, poly (4-methylpentene-11), polybutene-11, polyhexene-11, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer Copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid propylene copolymer, ethylene-acrylic acid Acid butyl copolymer, ethylene-acrylate 2-ethylhexyl acrylate copolymer, ethylene-hydroxyhexyl acrylate copolymer, ethylene-vinyl trimethoxy silane copolymer, ethylene-vinyl triethoxy silane copolymer, ethylene-vinyl silane Copolymers, ethylene-styrene copolymers, and propylene-styrene copolymers. As another specific example of the polyolefin resin used as the component ( _a ), there may be mentioned a polyolefin resin such as chlorinated polyethylene, brominated polyethylene, and chlorosulfonated polyolefin. Is mentioned.

Among the above-mentioned polyolefin resins, particularly preferred are high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and polypropylene (LPE). PP), ethylene-propylene block copolymer, ethylene-propylene random copolymer, poly4-methylpentene 1 (P4MP1), ethylene-vinyl acetate copolymer (EVA), and ethylene-vinyl acetate Alcohol-copolymers, and among them, those having a Menoletov Mouth Index (MFI) force of 0.2 to 50 g / 10 minutes are the most preferable. No. The component (a) may be composed of one kind of polyolefin resin, or may be used in combination of two or more kinds of polyolefin resins.

As the component (b), the glass transition temperature is 0 ° C or less, preferably —2

A rubbery polymer of 0 ° C or less is used. (B) Specific examples of the rubbery polymer for components include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene'butadiene rubber (SBR), and acrylonitrile. Nore butadiene rubber (NBR), butyl rubber (

1 IR), chlorinated butyl rubber, brominated butyl rubber, chlorobrene rubber (CR), acrylonitrile monocrop copolymer rubber, acrylonitrile copolymer rubber, acrylyl Tobutage Rubbers such as ethylene copolymer rubber, vinyl pyridine-butadiene copolymer rubber, vinyl pyridine-styrene copolymer rubber, etc. Rubber (EPR), Ethylene propylene copolymer rubber (EPDM), Ethylene butene copolymer rubber, Ethylene butene copolymer rubber, Chlorinated polyethylene rubber, Polyolefin rubbers such as chlorosulfonated polyethylene rubber (CSM), acryl rubber, ethylene acryl rubber, polychlorinated trifluorinated rubber, and fluorinated rubber Rubbers having oxygen atoms in the main chain, such as rubbers having a polymethylene-type main chain, such as rubber, epichlorohydrin rubber, and ethyleneoxy-epichlorohydrin copolymer rubber. Rubber In the main chain, such as silicone rubber such as polyvinylmethylsiloxane rubber and polymethylethylsiloxane rubber, dinitro rubber, polyester urethane rubber, and polyether urethane rubber. Rubbers having nitrogen atoms and oxygen atoms in addition to carbon atoms are included. Epoxy-modified, silane-modified, or maleated rubbers of these rubbers may be used as component (b).

(b) Another specific example of the rubbery polymer constituting the component is a thermoplastic elastomer. For example, styrene-butadiene-styrene block copolymer, styrene-ethylene block styrene-styrene block copolymer, styrene-isoprene-styrene block copolymer Polymers, styrene-ethylene-propylene-styrene-block copolymers, polyolefin-based thermoplastic elastomers, chlorinated polyolefin-based thermoplastic elastomers, Thermoplastic elastomer, Polyester thermoplastic elastomer 1, 1, 2 —Polybutadiene thermoplastic elastomer, Transform 1,4,1-Polyisoprene thermoplastic Plastic elastomers, polyamide thermoplastic elastomers, polyvinyl chloride thermoplastic elastomers and the like can be mentioned. (C) The layered silicate-containing thermoplastic polyamide constituting the component contains the layered silicate uniformly dispersed therein, and the thermoplastic polyamide is tough by extrusion and stretching or rolling. It is formed in a fibrous form. The melting point of the thermoplastic polyamide is preferably in the range of 135 to 350 ° C, particularly preferably in the range of 160 to 265 ° C.

(c) Specific examples of the thermoplastic polyamide for the component include Nylon 6, Nylon 66, Nylon 6-Nylon 66 copolymer, and Nylon 610. , Nylon 61 2, Nylon 46, Nylon 11, Nylon 12, Nylon MXD 6, Polycondensate of xylylenediamine and adipic acid, xylylenediamine Polycondensate of xylylenediamine and sperinic acid, polycondensate of xylylenediamine and azearic acid, xylylenediamine Polycondensate of terephthalene diamine and terephthalic acid, polycondensate of hexamethylene diamine and terephthalic acid, polycondensate of octamethylenediamine and terephthalic acid, trimethyl Hexamethylenediamine and terephthalic acid polycondensate Polycondensate of decamethylenediamine and terephthalic acid, polycondensate of dexamedecylenediamine and terephthalic acid, polycondensate of dodecamethylenediamine and terephthalic acid, polycondensation of tetramethylenediamine and isophthalic acid Isomers, polycondensates of hexamethylene diamine and isophthalic acid, polycondensates of octamethylenediamine and isophthalic acid, polycondensates of trimethyl hexamethylene diamine and isophthalic acid, decame Examples include polycondensates of tylenediamine and isophthalic acid, polycondensates of pendecamethylenediamine and isophthalic acid, and polycondensates of dodecamethylenediamine and isophthalic acid.

Of the above thermoplastic polyamides, particularly preferred ones have a melting point higher than that of the constituent polyolefin resin by 30 ° C or more. To be specific, Nylon 6 (PA 6) 66 (PA66), Nylon 6—Nylon 66 copolymer, Nylon 61, Nylon 61, Nylon 46, Nylon 11 and Nylon 1 and 2 are particularly preferred. These thermoplastic polyamides may be used alone or in combination of two or more. It is also preferable that these thermoplastic polyamides have a molecular weight in the range of 100,000 to 200,000.

(c) The layered silicate uniformly dispersed and contained in the component is effective in imparting excellent mechanical properties and frictional properties to the polyamide resin composition. The phyllosilicate particles preferably have a thickness of usually 0.6 to 2 nm and a length of 2 to 1,000 nm. The component (c) of the present invention is characterized in that the layered silicate is uniformly dispersed in the thermoplastic polyamide while maintaining an average interlayer distance of 2 nm or more. The term “inter-brows distance” as used herein refers to the distance between the plate-shaped centers of gravity of the silicate layer, and “uniformly dispersed” refers to 50% or more, preferably 70% or more of the layered silicate. A state in which both parallel and random are dispersed parallel to each other and to Z or random without forming aggregates. Therefore, the layered silicate is a fine layer having a length of 2 to 100 nm and a thickness of 0.6 to 2 nm. Examples of such a layered silicate include a layered phyllosilicate mineral composed of layered particles of magnesium silicate or aluminum silicate. Layered silicates include, specifically, smectite clay minerals such as montmorillonite, savonite, nontronite, hectrite, and stevensite, as well as bamiyucurite and harasite. Is included. These layered silicates may be natural products or synthetic ones. Of these, it is preferable to use the Montmori mouth. The method of uniformly dispersing such layered silicate particles in a polyamide resin is not limited, but the method of the present invention is not limited. When the raw material of the silicate particles is a multi-layered clay mineral, it is brought into contact with a swelling agent to expand the layers in advance to make it easy to take in the monomers between the layers, and then to form the monomer for forming the polyamide. And a method of polymerizing this monomer (Japanese Patent Publication No. 08-222946). In addition, using a polymer compound as a swelling agent, the interlayer is spread to 10 nm or more in advance, and this is melt-kneaded with a polyamide resin or a resin containing the same to be uniformly dispersed. A method may be used. The mixing ratio of the layered silicate is preferably 0.05 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the polyamide component. Department. If the compounding ratio of the layered silicate is less than 0.05 parts by weight, the rigidity and heat resistance of the obtained molded article will be small, and if it exceeds 30 parts by weight, the flow of the resin composition will increase. It is not preferable because sex is extremely reduced.

The silane coupling agent used as the component (d) is a binder that binds the components (a), (b) and (c) to each other. Specific examples of this silane coupling agent include vinyl trimethoxysilane, vinyl triethoxy silane, vinyl tris (^ -methoxetoxy) silane, vinyl tri Acetylsilane, amethacryloxyprovir trimethoxysilane, / 5— (3,4-epoxycyclohexyl) ethyl trimethoxysilane, aglycidoxypropyltrimethoxy Silane, α-glycidoxypropylmethyldimethoxysilane, aglycidoxypropylmethylethylethoxysilane, γ-glycidoxypropylpyrethyldimethoxysilan, α-glycidoxypropylpropylethylethoxysilane, Ν—; 5_ ( Aminoethyl) Aminop mouth Bitrimethoxysilane, ン — 3 — (Aminoethyl Tyl) aminopropyltriethoxysilane, Ν — /? — (Aminoethyl) aminopropyl tyldimethoxysilane, N—S— (aminoethyl) aminopro Pyrethyldimethoxysilane, N— / 3 — (Aminoethyl) Aminove Mouth pilletyl jetoxirane, a-aminoprovir triethoxysilane, N-vinylaminopropyl trimethoxysilane, 7- [N _ (; S-meth (Tacryloxyshethyl) -N, N-dimethylammonium (chloride)] propylmethoxy silane, and styrene diamino silane. Among these, a group which easily desorbs a hydrogen atom from an alkoxy group or the like, and a group having Z or a polar group and a vinyl group are particularly preferably used.

The amount of the silane coupling agent is preferably 0.1 to 5.5 parts by weight based on 100 parts by weight of the total of the components (a), (b) and (c). Particularly preferred is 0.2 to 3.0 parts by weight. When the content of the silane coupling agent is less than 0.1 part by weight, the mutual bonding of the components (a), (b) and (c) becomes insufficient, so that a composition having high strength can be obtained. May not be possible. On the other hand, if it exceeds 5.5 parts by weight, it becomes difficult for the polyamide in the component (c) to form a fine fiber structure, so that it is difficult to obtain a composition having excellent elastic modulus. There is power.

(d) An organic peroxide can be used in combination with the silane coupling agent used as the component. When the organic peroxide is used in combination, a radical is formed on the molecular chain of the component (a), component (b), and component (c), and this reacts with the silane coupling agent to form the component (a). , (B) component and (c) component resin are promoted to bond with each other. In this way, (a) component, (b) component and (c) component are mutually bonded at the interface. . As the organic peroxide, the half-life temperature for 1 minute is from the same temperature as the melting point of component (a) or the melting point of component (c), whichever is higher, to a temperature 30 ° C higher than this temperature. Those within the range are preferably used. More specifically, as an organic peroxide, the half-life temperature of one minute is about 110 to 250 ° C. Things are preferably used. The amount of organic peroxide used at this time is

(a) It is preferably in the range of 0.01 to 1.0 part by weight based on 100 parts by weight of the component.

Specific examples of the organic peroxide used in the present invention include 1,1-di-t-butylperoxy-1,3,5, -trimethylcyclohexane, 1,1-di-t-butylperoxy. Oxycyclohexane, 2, 2-di-t-butyl-butoxy-butane, n-butyl- 4,4--g-t-butyl-l-oxy-sino << relinate, 2, 2-bis (4, 4—Di-t-butylbutyloxane) propane, 2,2,4-trimethylpentyl-peroxyneodecanate, a—Li-minoleoxyneodeneate, t—butyl-peroxide Xineohexanate, t-butyl peroxypivalate, t-butyl peroxy acetate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxybenzoate G In the resin composition of the present invention, the majority of the layered silicate-containing thermoplastic polyamide of the component (c) forms a fine fibrous form and is mainly composed of the components (a) and ( b) It is uniformly dispersed in the matrix composed of the components. More specifically, 70% by weight or more, preferably 80% by weight or more, and particularly preferably 90% by weight or more of the thermoplastic polyamide are dispersed in the form of fine fibers. I have. The average fiber diameter of the polyamide fiber is preferably 1 zm or less, and the average fiber length is preferably 1,000 m or less. The aspect ratio expressed by the ratio of the average fiber length to the average fiber diameter is preferably 20 or more, more preferably 20 or more and 1,000 or less. . Component (a), component (b) and component (c) are bonded to each other at their respective interfaces, and this bond is strengthened by the silane coupling agent forming component (d). Have been.

The proportions of component (a), component (b) and component (c) are 100 to 400 parts by weight of component (a), 100 to 400 parts by weight of component (b), and 100% by weight of component (c). ~ 400 parts by weight. Preferably, the component (b) is 20 to 250 parts by weight, and the component (c) is 20 to 300 parts by weight. More preferably, the component (b) is 50 to 200 parts by weight, and the component (c) is 50 to 300 parts by weight. If the amount of the component (b) is less than 100 parts by weight based on 100 parts by weight of the component (a), the resulting composition will have insufficient impact resistance, and will exceed 400 parts by weight. The resulting composition has insufficient creep resistance. If the amount of the component (c) is less than 100 parts by weight relative to 100 parts by weight of the component (a), the resulting composition has insufficient creep resistance. If the amount exceeds 400 parts by weight, the proportion of polyamide fibers present as fine fibers in the composition becomes too large, and the dispersion of the fibers becomes poor. The appearance of the molded product obtained by this is poor.

A filler may be added to the resin composition of the present invention as long as the physical properties are not impaired. As the filler, carbon fibers, glass fibers, metal fibers, glass beads, talc, kaolin, cres, mica, montmorillonite, basic magnesium carbonate, walazite, etc. can be used. . In addition, antioxidants, ultraviolet absorbers, softeners, flame retardants, softeners, lubricants, tackifiers, and the like can be appropriately added to the resin composition of the present invention.

Next, a method for producing the polyamide fiber reinforced resin composition of the present invention will be described. First, the method for producing a thermoplastic polyamide for component (c) in which layered silicate particles are uniformly dispersed will be described. This dispersion method is not particularly limited as long as the layered silicate can be uniformly dispersed. For example, when the raw material of the layered silicate is a multilayer clay mineral, the layered silicate is ionized with hydrochloric acid. Reacts with a swelling agent, for example, 12-aminododecanic acid, to expand the layers in advance, to facilitate the incorporation of monomers between the layers, and to form a polyamide for the component (c). By mixing the monomers and polymerizing this monomer (Japanese Patent Publication No. 8-229496), the layered silicate and the polyamide are mixed to make the layered silicate uniform. It is possible to manufacture thermoplastic polyamide dispersed and contained.

Examples of the swelling agent include aminoic acid and nitric acid salt, and specific examples thereof are ω-amino-decanoic acid, ω-amino-dodecanoic acid, and diamin. And equimolar salts of dicarboxylic acids, such as tetramethylammonium adipate, hexamethylene diammonium diagedate, and hexamethylene diammonium sebague toka and so on.

The method for producing a polyamide fiber reinforced resin composition includes the following steps (1) to (4).

(1) A reactive matrix is prepared by melt-kneading the (a) component polyolefin resin and the (b) component rubbery polymer together with the (d) component silane coupling agent. Process,

(2) The reactive molten matrix and the composite of the layered silicate of the component (c) and the thermoplastic polyamide are melted at a temperature equal to or higher than the melting point of the polyamide. Kneading to produce a chemically modified composition,

(3) extruding the molten chemically modified composition from a die at a temperature higher than the melting point of the polyamide of component (c) (preferably higher than 10 ° C);

(4) A step of stretching or rolling the extrudate while drafting at a temperature lower than the melting point of the thermoplastic polyamide in the component (c) and at which the thermoplasticity is exhibited. The stretching or rolling temperature at this time may be equal to or higher than the melting point of the components (a) and (b). Each step of the production method of the present invention will be described more specifically.

Step (1): Melt and knead the polyolefin of component (a) and the rubbery polymer of component (b) with the silane coupling agent of component (d), and mix the components (a) and (b) with each other. A) a step of preparing a reactive matrix between the component (d) and the component (d).

This melting is performed at a temperature higher than the melting point of the polyolefin of component (a), and preferably at a temperature higher by at least 10 ° C than this melting point. If kneaded at a temperature higher than the melting point by 10 ° C. or more, the (a) component and the (d) component silane coupling agent react to form a reactive matrix.

Melt kneading can be carried out by a device usually used for resin and rubber. As such a device, a kneading mixer, a kneader, a kneader extruder, an open roll, a single-screw kneader, a twin-screw kneader, and the like are used. Among these apparatuses, it is most preferable to use a twin-screw kneader in that melt kneading can be performed in a short time and continuously.

Step (2): The above-mentioned reactive matrix is treated with a composite of the layered silicate of the component (c) and the thermoplastic polyamide at a temperature not lower than the melting point of the thermoplastic polyamide. A step of producing a chemically modified composition by melt-kneading in step (b). This melting is performed at a temperature equal to or higher than the melting point of the polyamide (c). That is, the components are mutually chemically denatured at a temperature higher than the melting point of the polyamide. If the melting temperature is lower than the melting point of the polyamide, kneading cannot be performed, and dispersing cannot be performed. Accordingly, the component (c) is melt-kneaded at a temperature higher than the melting point of the polyamide of the component (c), particularly preferably at a temperature higher than the melting point by 10 ° C or more, and the component (c) is added to the matrix. Disperse to prepare a chemically modified composition.

Step (3): applying the above-mentioned molten chemically modified composition to the polyamide of the component (c) Extruding from a die at a temperature higher than the melting point (1 o ° c or more) In this extrusion process, the chemically modified composition is extruded from a spinneret or T-die. Both spinning and extrusion are preferably performed at a temperature higher than the melting point of the component (c), preferably at a temperature higher than the melting point by 10 ° C or more. If the extrusion is performed at a temperature lower than the melting point of the polyamide, the polyamide cannot be further finely divided in the matrix. For this reason, the polyamide fibers formed by drawing or rolling the composition may become coarse.

Step (4): a step of drawing or rolling the above extrudate while drafting at a temperature lower than the melting point of the polyamide in the component (c) but exhibiting thermoplasticity. The stretching or rolling temperature at this time may be lower than the melting point of the components (a) and (b).

The melt-extruded string, thread, or tape obtained in step (3) is continuously cooled and stretched or rolled. The stretching or rolling treatment is performed at a temperature lower than the melting point of the polyamide. This temperature is such that the mixture of components (a), (b) and (d) and component (c) exhibit thermoplasticity. By drawing or rolling, stronger polyamide fibers are formed, so that the performance as a fiber reinforced composition is further improved. The stretching or rolling treatment is, for example, a method in which the kneaded composition is extruded from a spinneret and spun into a string or a thread, and this is stretched and wound while being drafted, or cut and collected as a pellet. It will be implemented in. The draft ratio when the extrudate is stretched is preferably 1.5 to 100, more preferably 2 to 50, and most preferably 3 to 30. The draft ratio means the ratio of the winding speed to the speed of the extrudate passing through the extrusion die. Thus, a polyimide fiber reinforced resin composition is obtained. As described above, the process has been described separately for (1), (2), (2) and (4), but the components (a), (b), (c) and (d) A supply port capable of supplying an organic peroxide or the like; a kneading zone having a first supply port, a second supply port, a third supply port, a fourth supply port, a fifth supply port, and the like, and a supply port corresponding to each supply port; It is also possible to carry out by a continuous process using a twin-screw extruder having a 1 kneading zone, a 2nd kneading zone, a 3rd kneading zone, a 4th kneading zone and a 5th kneading zone. This results in an economical and stable manufacturing method. Example

The present invention will be described more specifically with reference to the following Examples and Comparative Examples, but these do not limit the scope of the present invention. In Examples and Comparative Examples, the physical properties of the polyamide fiber reinforced resin composition were measured by the following methods.

Average fiber diameter and fiber shape: The sample polymer fiber reinforced resin composition was dissolved in hot xylene to separate and collect the fiber, which was observed with a scanning electron microscope. The dispersibility was evaluated by checking whether the fibers were fine. For fibers with good dispersibility, the fiber diameters of 200 fibers were measured, and the average was determined as the average fiber diameter.

Surface appearance: Sheets were prepared from the test resin composition at 180 ° C using a hot press, and the smoothness of the sheet surface was visually observed, evaluated and indicated as follows.

◎ Very smooth and excellent.

〇 Almost smooth.

X Rough or sticky, unsuitable for molding.

Tensile properties: Tensile strength, tensile elongation at break and tensile modulus were measured at a temperature of 23 ° C and a tensile speed of 5 O mm Z according to ASTMD 638. Dynamic friction: According to JISK 7125, the gravitational friction coefficient between a 0.2 mm thick x 80 mm wide x 200 mm long sample and a transparent glass plate as the mating material The measurement was performed at 200 g and a pulling speed of 100 mm / min. The coefficient of gravitational friction is a measure of the difficulty of slipping on the surface of an article.

Reference example 1

At atmospheric pressure, a 20 liter Hastelloy reactor equipped with a stirrer and temperature controller was used as a layered silicate, with an average width of 0.95 nm and a length of phyllosilicate. About 10 O nm of montmorillonite 10 Og and 10 liters of distilled water were added to disperse montmorillonite particles in water. While maintaining the dispersion at 35 ° C., 51.2 g of 12-aminododecanic acid and 24 milliliters of concentrated hydrochloric acid were added thereto, followed by stirring for 5 minutes. The particles were collected by filtration. Further, the particles were washed with water until the filtrate became neutral, and then collected by filtration and vacuum-dried at 80 ° C for 48 hours. By this procedure, a complex of 12-amino dodecanoate ion and montmorillonite (hereinafter, montmorillonite complex) was prepared. The content of layered silicate in the composite was about 80%. Next, 10 kg of ε-caprolactam, 1 kg of distilled water and 180 g of the above monomorillonite complex were placed in the reactor, and nitrogen gas was introduced to replace the air. The mixture was stirred at 100 ° C. so that the reaction system became uniform. The temperature was further increased to 260 ° C., and the mixture was stirred for 1 hour under a pressure of 15 kg Z cm ² (pressurized with nitrogen). Thereafter, the reaction mixture was returned to normal pressure and reacted at 260 ° C. for 3 hours. The reaction mixture was taken out from the lower nozzle of the reaction vessel in the form of a strand, cooled with water, cut, and mixed with a polyamid. (Average molecular weight: 15,000), montmorillonite and strength were obtained. This pellet was immersed in hot water at 90 ° C to remove unreacted monomers and oligomers. Was extracted and removed, followed by vacuum drying at 90 ° C for 48 hours. The obtained layered silicate-containing polyamide (monmorillonite composite nylon 6) was ignited at 65 ° C, and the content of organic composite monmorillonite was determined from the residual weight of the burning. The measured value was 2.0%. Table 1 shows the results.

Reference Examples 2 to 4

In each of Reference Examples 2 to 4, a layered silicate-containing polyamide was prepared in the same manner as in Reference Example 1. However, as shown in Table 1, the amount of the same monomorillonite complex used in Reference Example 1 was set to 270 g, 36008 or 720, and this was set to 1 Monomorillonite composite Nylon 6 was produced in the same manner as in Reference Example 1 using 0 kg of one-strength prolactam and 1 liter of water. The content of monmorillonite in the mixed montrinite composite mouth 6 was 3.0%, 4.1% and 7.9%, respectively. Table 1 shows the results.

table 1

Example 1

(a) low-density polyethylene (available from Ube Industries, trade name: F522, melting point: 110 ° C, MFI = 5 g / 10 minutes) as a component: 100 parts by weight, b) 100 parts by weight of natural rubber (SMR-L) as a component, and 1.0 parts by weight of 7-methacryloxyprovir trimethoxysilane as a silane coupling agent of component (d). Of the component (a) at a temperature (150 ° C) or higher than the melting point of the component (a), A run-modified matrix was prepared, which was dumped at 170 ° C and pelleted. This matrix was mixed with 50 parts by weight of the monomoronilonite composite nylon 6 of Reference Example 1 as the component (c) in a twin-screw extruder heated to 250 ° C. The mixture was kneaded, extruded in a strand shape through a nozzle attached to the tip of a twin-screw extruder, and stretched at a draft ratio of 20 in the air and at room temperature, and pelletized. This pellet was pressed at 180 ° C. to form a sheet. A dumbbell-shaped test piece was punched out of the sheet to measure desired physical properties. The results are shown in Table 2 . The low-density polyethylene of component (a) and the natural rubber of component (b) are extracted and removed from the obtained sheet with hot xylen, and the ammonium nitrate composite nylon of component (c) is extracted. The fine fiber composed of No. 6 was collected and observed with a scanning electron microscope. The average fiber diameter was 0.2 μm.

Examples 2 to 6

In each of Examples 2 to 6, a polyimide fiber reinforced resin composition sheet was produced in the same manner as in Example 1. However, the type of the monmorillonite composite nylon 6 of the component (c) and the draft ratio were as shown in Table 2. Table 2 shows the measurement results of the physical properties of the obtained sheet.

Table 2

[Note] (a) Polyolefin resin Tsukitsuki! Dashi (b): rubbery polymer

(c) Monmoronite composite PA 6

(d) Silane cupping agent

Examples 7 to 12

Example ? In each of Examples 1 to 12, a polyimide fiber reinforced composition sheet was produced in the same manner as in Example 1. However, as shown in Table 3, as the component (a), PP (manufactured by Grand Polymer Co., Ltd., trademark: J105W, melting point 165-170 ° MFI = 9 gZlO ], HDPE (manufactured by Maruzen Polymer Co., Ltd., trademark: Chemretz, melting point: 125 to 135 ° C, MF 1 = 5 g X 10 minutes), and Z or EVA (Ube Industries, Ltd., trademark: V

(B) The natural rubber (NR) and EPDM (Japan) were used as the rubbery polymer of the component (b) with a melting point of 107 ° C and MFI = 5 g / 10 min. Made by Synthetic Rubber Co., Ltd., Trade name: EP-22, Mu-viscosity = 42) or NBR (manufactured by Nippon Synthetic Rubber Co., Ltd., Trademark: N230SL, Mu-viscosity = 42, Akryloni (Trile content: 35%) and peroxides of 4,

4-Gee t-butyl butoxy butyl valerate, a monomole-containing night compound composite nylon 6 described in Reference Example 1 was used, and the draft ratio was set as shown in Table 3. . The physical properties of the obtained sheet were measured, and the results are shown in Table 3.

Table 3

[Note] (a): Polyolefin resin, (b) Rubbery polymer

(c): Night mouth composite compound PA 6

(d): Silane force printing agent

Comparative Example 1

(d) Matrix of low-density polyethylene and natural rubber in the same manner as in Example 1 except that a silane coupling agent is not used as a component. This was kneaded and extruded with the monomole mouth composite nylon 6 described in Reference Example 1. The strand fluctuated the discharge, and by adjusting the draft, it could barely be turned into a winding pellet. From the pellets, the heat xylene insolubles in the sheet obtained in the same manner as in Example 1 were in the form of a film (thickness of 10 to 30 am) or spherical. A sheet was prepared from this pellet in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 4.

Comparative Examples 2 to 4

In each of Comparative Examples 2 to 4, as shown in Table 4, any one of (a) component LDPE, (b) component NR, and (c) component montmorillonite composite nylon 6 was used. A sheet was prepared in the same manner as in Example 1 except that one component was not added. Table 4 shows the measurement results.

Comparative Examples 5 and 6

In each of Comparative Examples 5 and 6, a resin composition was prepared in the same manner as in Example 1. However, Nylon 6 (manufactured by Ube Industries, trade name: 1022B, melting point: 2115 to 220 ° C) is shown in place of the montmorillonite composite nylon 6 of the component (c). The amounts described in 4 were used. The results of physical properties are not shown in Table 4. "

Table 4

[Note] (a) Polyolefin resin (b): rubbery polymer (c) Montmorillonite composite PA 6

(d) Silane coupling agent Industrial applicability

The polyamide fiber reinforced resin composition obtained by the present invention is preferably used in a matrix comprising a polyolefin and a rubber-like polymer, preferably having an average fiber diameter of 1 m or less. In addition, natural polyamide fibers are dispersed, and layered silicate particles are uniformly dispersed in the polyamide fibers. The structure is such that polyolefin, rubbery polymer and polyamide fiber are bonded to each other at their respective interfaces. For this reason, the polyamide fiber reinforced resin composition of the present invention can be easily dispersed in various resins and rubbers, and is excellent in strength, elastic modulus, and friction performance. It is useful as a suitable reinforcing material for floor materials and footwear.

Claims

The scope of the claims

1. The following components mixed with each other:

(a) 100 parts by weight of polyolefin resin,

(c) 10 to 400 parts by weight of a fibrous thermoplastic polyamide containing a layered silicate, and

(d) Silane coupling agent

A polyamide fiber reinforced resin composition containing:

2. The component according to claim 1, wherein the component (d) is blended in a ratio of 0.1 to 5.5 parts by weight with respect to a total of 100 parts by weight of the components (a), (b) and (c). The polyamide fiber reinforced resin composition according to the above.

3. The polyamide fiber reinforced resin composition according to claim 1, wherein the layered silicate-containing thermoplastic polyimide fiber has an average fiber diameter of 1 m or less.

4. In the layered silicate-containing thermoplastic polyimide fiber, the layered silicate is blended in a ratio of 0.05 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic polyamide. 2. The polyamide fiber reinforced resin composition according to item 1.

5. Melt and knead (a) 100 parts by weight of polyolefin resin, (b) 100 to 400 parts by weight of rubbery polymer having a glass transition temperature of 0 ° C. or less, and (d) silane coupling agent To form a molten matrix, and the molten matrix and (c) 10 to 400 parts by weight of the layered silicate-containing thermoplastic polymer are mixed with the thermoplastic polymer. Mixing at a temperature equal to or higher than the melting temperature of the mid, extruding the molten mixture, and stretching or rolling at a temperature lower than the melting point of the thermoplastic polyamide (c); Thereby, a polyamide fiber reinforced resin including dispersing the layered silicate-containing thermoplastic polyamide in a fibrous form in the matrix comprising the components (a) and (b). A method for producing the composition.

6. The silane coupling agent (d) is blended in a ratio of 0.1 to 5.5 parts by weight with respect to a total of 100 parts by weight of the components (a), (b) and (c). 6. A method for producing the polyimide fiber reinforced resin composition according to claim 5.

7. The poly according to claim 5, wherein the layered silicate-containing thermoplastic polyamide is dispersed in the drawing or rolling step into a fiber having an average fiber diameter of 1 m or less. A method for producing a mid-fiber reinforced resin composition.

8. In the layered silicate-containing thermoplastic polyamide, the layered silicate is blended in a ratio of 0.05 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic polyamide. 6. The method for producing a polyamide fiber reinforced resin composition according to claim 5, wherein: