JP2005060547A - Resin structure of long fiber-reinforced polymer alloy and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin capable of replacing a metal by improving mechanical strengths of a polyamide resin, especially a fiber-reinforced polyamide resin. <P>SOLUTION: The subject resin structure of the long fiber-reinforced polymer alloy comprises 40-90 pts. wt. matrix resin (C) comprising 50-90 wt.% polyamide resin (A) homogeneously dispersed in a modified polyolefin resin (B) so that the deviation rate of the polyamide resin (A) may be within ±10%, and the 10-50 wt.% modified polyolefin resin (B), and 60-10 pts. wt. fibrous reinforcing material nearly parallelly arranged in the length direction and having 3-50 mm length. A deviation rate represents the homogeneity of the composition distribution of the polyamide resin in the matrix resin (C), and is a percentage obtained by dividing the difference between the maximum value and the minimum value of the content (a measured value) of the polyamide resin, by its average value. A molded article thereof is also provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a long-fiber reinforced polymer alloy resin structure and a molded article that are excellent in impact strength reinforced with long fibers using a polymer alloy composed of a polyamide resin and a modified polyolefin resin as a matrix resin.

  Polyamide resins have applications as various engineering plastics due to their good mechanical strength, and are used in large quantities for automobiles and vehicles. In addition, it has been studied for a long time as a fiber reinforced resin reinforced with fibers as a weight-reducing material instead of metal. Among them, the strength is dramatically improved by reinforcing with long fibers. However, it is known that the water resistance is inferior as a drawback of polyamide. As a countermeasure, mixed use with modified polyolefins has been proposed. It is also known that modified polyolefins react easily with polyamides and cover the disadvantages of polyamides. Various long-fiber reinforcement technologies using such a polymer alloy as a matrix resin have been proposed in the past. As examples, JP-A-7-330918 and JP-A-2002-234998 are known, and further, for example, JP-A-5-320504, JP-A-6-207064 and the like which have been improved in function by the third component are known. ing.

In recent years, the study of weight reduction of automobiles and vehicles has been spurred, and further improvement in mechanical properties is demanded for the resin as the material.
JP-A-7-330918 JP 2002-234998 A Japanese Patent Laid-Open No. 5-320504 JP-A-6-207064

  An object of the present invention is to provide a resin that can improve the mechanical strength of a polyamide resin, particularly a fiber reinforced polyamide resin, and can replace a metal.

  As a result of intensive studies to solve the above problems, the present inventors have made a long-fiber reinforced material that exceeds the mechanical properties of a polyamide resin and a modified polyolefin resin as a polymer alloy under specific conditions and uses it as a matrix resin. The present invention was completed by finding.

  That is, in the present invention, in the matrix resin (C) containing 50 to 90% by weight of the polyamide resin (A) and 10 to 50% by weight of the modified polyolefin resin (B), the polyamide resin (A) has a deviation rate within ± 10%. A long fiber reinforced polymer alloy resin structure comprising 40 to 90 parts by weight of a uniformly dispersed matrix resin (C) and 60 to 10 parts by weight of a 3 to 50 mm fibrous reinforcing material arranged substantially parallel to the length direction (in the text) The deviation rate indicates the uniformity of the composition distribution of the polyamide resin in the matrix resin (C), and the difference between the maximum value and the minimum value of the polyamide resin content (measured value) and the average value is divided by the average value. Provide percentages).

  The present invention also provides a matrix resin in which the matrix resin (C) is melt-mixed after mechanically mixing a resin containing 50 to 90% by weight of the polyamide resin (A) and 10 to 50% by weight of the modified polyolefin resin (B). The long-fiber-reinforced polymer alloy resin structure described above is provided.

  The present invention further provides the long fiber reinforced polymer alloy resin structure described above, wherein the modified polyolefin resin (B) is a polyolefin resin modified with an unsaturated carboxylic acid or an anhydride thereof.

  The present invention also provides the long fiber reinforced polymer alloy resin structure as described above, wherein the particle sizes of the polyamide resin (A) and the modified polyolefin resin (B) do not differ from each other by 5 times or more in the average weight of the particles. I will provide a.

  The present invention also provides the long fiber reinforcement as described above, wherein the polyolefin of the modified polyolefin resin (B) is a block copolymer of polyethylene, polypropylene, or polyethylene and a poly α-olefin having 3 to 6 carbon atoms. A polymer alloy resin structure is provided.

  In the present invention, the long-fiber-reinforced polymer alloy resin structure containing the matrix resin (C) and the fibrous reinforcing material is used to extract the melted matrix resin (C) into the opened fiber while drawing the continuous fiber roving. After the impregnation, the long fiber reinforced polymer alloy resin structure described above is cut into 3 to 50 mm.

  In the matrix resin (C) further comprising 50 to 90% by weight of the polyamide resin (A) and 10 to 50% by weight of the modified polyolefin resin (B), the polyamide resin (A) is uniform with a deviation rate within ± 10%. Formed from a long fiber reinforced polymer alloy resin structure containing 40 to 90 parts by weight of the matrix resin (C) dispersed in the resin and 60 to 10 parts by weight of a 3 to 50 mm fibrous reinforcing material arranged substantially parallel to the length direction. A molded product of a long fiber reinforced polymer alloy resin, characterized in that the weight average fiber length of the contained fiber is 1 mm or more (in the text, the deviation rate is the composition of the polyamide resin in the matrix resin (C)) It shows the uniformity of distribution, and provides the percentage obtained by dividing the difference between the maximum and minimum values of polyamide resin content (measured values) and the average value by the average value. .

  In the matrix resin (C) containing 50 to 90% by weight of the polyamide resin (A) and 10 to 50% by weight of the modified polyolefin resin (B), the polyamide resin (A) has a deviation rate within ± 10%. A long fiber reinforced polymer alloy resin structure comprising 40 to 90 parts by weight of a uniformly dispersed matrix resin (C) and 60 to 10 parts by weight of a 3 to 50 mm fibrous reinforcing material arranged substantially parallel to the length direction; and The long-fiber reinforced polymer alloy resin molded article described above, which is molded from a composition to which a matrix resin (C) is added.

  The present invention also provides a matrix resin in which the matrix resin (C) is melt-mixed after mechanically mixing a resin containing 50 to 90% by weight of the polyamide resin (A) and 10 to 50% by weight of the modified polyolefin resin (B). The long fiber reinforced polymer alloy resin molded article described above is provided.

  The present invention also provides the long fiber reinforced polymer alloy resin molded article described above, wherein the modified polyolefin resin (B) is a polyolefin modified with an unsaturated dicarboxylic acid or an anhydride thereof.

  The present invention further provides the long fiber reinforced polymer alloy resin molding described above, wherein the particle sizes of the polyamide resin (A) and the modified polyolefin resin (B) are not different from each other by 5 times or more in the average weight of the particles. Provide goods.

  The present invention also provides the long fiber reinforcement as described above, wherein the polyolefin of the modified polyolefin resin (B) is a block copolymer of polyethylene, polypropylene, or polyethylene and a poly α-olefin having 3 to 6 carbon atoms. A polymer alloy resin molded article is provided.

  Furthermore, the present invention provides a fiber in which a melted matrix resin (C) is opened while a continuous fiber reinforced polymer alloy resin structure including a matrix resin (C) and a fibrous reinforcing material is drawn out of a continuous fiber roving. After the impregnation, the long fiber reinforced polymer alloy resin molded product described above is cut into 3 to 50 mm.

  The present invention also provides the above-described long fiber reinforced polymer alloy resin molded product, wherein the molding method is injection molding.

  The present invention further provides the long fiber reinforced polymer alloy resin molded article as described above, wherein injection molding as a molding method is a method capable of preventing wasteful fiber breakage.

  The long-fiber-reinforced polymer alloy resin structure and molded product according to the present invention are obtained by mechanically mixing and homogenizing a polyamide resin and a modified polyolefin resin, and then melt-mixing them to uniformly disperse the polyamide in the matrix resin. It has been improved and expanded as a lightweight material that can replace metals such as automobiles.

  The polyamide resin (A) used in the present invention is not particularly limited. For example, nylon 6, nylon 6,6, nylon 4,6, nylon 11, nylon 12, nylon 6,10, nylon 6, Nylon to which an aliphatic polyamide resin such as 12 and an aromatic, alicyclic or side chain substituted aliphatic monomer is applied is also useful. Examples thereof include terephthalic acid hexamethylene amide, isophthalic acid hexamethylene amide, adipic acid trimethyl hexamethylene amide, metaxylene adipamide, and the like. An aliphatic polyamide resin is preferable, and nylon 6 and nylon 6,6 are particularly preferable.

  The polyolefin used as the base of the modified polyolefin resin (B) to be added to the polyamide resin is not particularly limited. For example, polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, etc. , Polypropylene, polybutene-1, polymethylpentene-1, and copolymers of ethylene and α-olefins having 3 to 6 carbon atoms (ethylene-propylene copolymer, ethylene-butene-1 copolymer, etc.), ethylene -Propylene-diene terpolymer, copolymer of ethylene and vinyl compound (ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester polymer, ethylene-methacrylic acid copolymer) Polymer, ethylene-methacrylic acid ester copolymer, ethylene- (meth) acrylate Le acid (ester)-.alpha., beta-unsaturated carboxylic acid (derivative) terpolymer, ethylene - vinyl chloride copolymer) or a mixture thereof.

  As a method for modifying these base polyolefins, a method in which a modifier is graft polymerized to the base polyolefin is preferable. As the modifier, an unsaturated carboxylic acid or its anhydride is used. Examples of unsaturated carboxylic acids or anhydrides thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid, crotonic acid and other unsaturated carboxylic acids, maleic anhydride, itaconic anhydride and the like. Anhydrides are mentioned. Preferred are anhydrides such as maleic anhydride and itaconic anhydride. The amount of the modifier added to the base polyolefin is usually 0.01 to 5.0% by weight, preferably 0.05 to 3.0% by weight. When the addition amount is less than 0.01% by weight, the amount of reaction between the polyamide resin and the modified polyolefin resin is decreased, and the strength is decreased. Moreover, when it exceeds 5.0 weight%, the water resistance and chemical-resistance of the added polyolefin will be impaired.

  The method for modifying the polyolefin is not particularly limited. Graft polymerization can be performed by melt-mixing a base polyolefin, a modifier and an organic peroxide with an extruder. It is also preferable to uniformly mix the three kinds of materials with a mixer or the like before charging into the extruder. The organic peroxide used in the present invention is not particularly limited, and has a half-life of 1 minute, and the decomposition temperature for obtaining the half-life is not lower than the melting point of the raw crystalline polypropylene and not higher than 250 ° C. If it is a thing. If the necessary decomposition temperature exceeds 250 ° C., the amount of radicals generated at the time of graft modification decreases, so that the graft reaction may not be carried out efficiently. Examples of such organic peroxides are hydroperoxides, dialkyl peroxides, peroxyesters, and the like, such as t-butyl peroxide, cyclohexanenon peroxide, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t -Butyl peroxyacetate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl 2,5-di (t-butylperoxy) hexane and the like.

  The mixing ratio of the polyamide resin (A), which is the matrix resin of the present invention, and the modified polyolefin resin (B) is 50 to 90% by weight of the polyamide resin (A) and 10 to 50% by weight of the modified polyolefin resin (B). Preferably, it is 55 to 85% by weight of the polyamide resin (A) and 15 to 45% by weight of the modified polyolefin resin (B). If the modified polyolefin is less than 10% by weight, there is no effect of adding the modified polyolefin, and the strength is the same as 100% of the polyamide resin. On the other hand, if the modified polyolefin exceeds 50% by weight, the mechanical strength characteristic of the polyamide resin cannot be maintained.

  The method for mixing the polyamide resin (A) and the modified polyolefin resin (B) for preparing the matrix resin is not particularly limited as long as it is a method capable of mixing solid substances. Solid substance mixers include a container rotation type, a mechanical stirring type, an airflow mixing type, and combinations thereof. In this invention, it is normal to use a pellet as resin, and a container rotation type is preferable. For example, a mixer tumbler is preferable. In the case of mixing, the polyamide resin (A) and the modified polyolefin resin (B) having a particle size that does not differ by 5 times or more from the average weight of the particles is used. Further, it is preferable that the difference is not more than 3 times, and it is particularly preferable that the difference is not more than 2 times. It means that the average weight of each particle is preferably similar in order to mix uniformly. It is also possible to mix with powder instead of pellets. There are various methods for measuring the average particle size, but in the present invention, 5 g is sampled from each material resin, the number of particles is counted, the resin weight is divided by the number of particles, and the weight per particle is indicated. It was.

  Elemental analysis is appropriate as a method for evaluating the uniformity of the polyamide resin (A) and the modified polyolefin resin (B) in the mixed and adjusted matrix resin (C). The polyamide resin (A) contains nitrogen atoms, but the modified polyolefin resin (B) does not contain any nitrogen atoms. Therefore, the nitrogen content obtained by elemental analysis indicates the content of the polyamide resin (A) in the sample (matrix resin). For example, a pure product of nylon 6 (100% is nylon 6) has a nitrogen content of approximately 12.4%, 70% polyamide resin (A) and 30% modified polyolefin resin (B). One mixture theoretically has a nitrogen content of 8.68%, which is 70% of 12.4%. Table 1 to be described later describes the measured values of nitrogen content. Further, from the measured values, Table 2 shows the difference between the average value and the maximum value among the 10 times measured, and the difference between the minimum value, The difference was divided by the average value, and further multiplied by 100 and expressed in%, expressed as a deviation rate. The deviation rate for the maximum value was the maximum deviation rate, and the deviation rate for the minimum value was the minimum deviation rate. When the mixture is completely mixed, the deviation rate becomes 0%, and this value becomes larger as the uniformity becomes worse. Further, the minimum value difference and the minimum deviation rate are displayed as minus values in order to subtract the average value from the minimum value. The deviation rate in the matrix resin (C) prepared from the polyamide resin (A) and the modified polyolefin resin (B) is preferably within ± 10%. Particularly preferably, it is within ± 8%.

  The method for producing a long fiber reinforced polymer alloy resin structure is characterized in that melted matrix resin (C) is impregnated into opened fibers and then cut to 3 to 50 mm while drawing rovings of continuous fibers. It is. More specifically, an apparatus having a configuration as shown in FIG. 1 is used. The fiber bundle is heated while continuously roving the fiber bundle, and then the fiber is opened to obtain a polyamide resin (A) and a modified polyolefin resin (B ) Prepared from the matrix resin (C) is impregnated and taken as a strand through a shaping die (an exit die of a crosshead die) and cut into 3 to 50 mm. The long fiber reinforced polymer alloy resin structure produced above is cut to a length of 3 to 50 mm, the fibers are arranged substantially parallel to the length direction of the pellet, and the length (fiber length) is less than 3 mm. Then, since the fiber is further shortened at the stage of forming into a molded product, the effect on the mechanical strength of the fiber is diminished. If it exceeds 50 mm, handling as a pellet becomes difficult, and if it is longer than necessary, there is a possibility of causing a problem of blockage in the resin flow path during molding.

  The reinforcing fiber of the long fiber reinforced polymer alloy resin structure used in the present invention is not limited to the fibers listed below as long as it has a higher elastic modulus than the matrix resin used. Any fiber can be used as the reinforcing fiber. For example, glass fibers such as E-glass and D-glass; carbon fibers such as polyacrylonitrile, pitch and rayon; inorganic fibers such as boron fibers and mineral fibers; metal fibers such as stainless steel and brass; ultrahigh molecular weight polyethylene Fiber, polyoxymethylene fiber, polyvinyl alcohol fiber, liquid crystalline aromatic polyester fiber, polyethylene terephthalate fiber, poly-p-phenylene terephthalamide fiber, poly-m-phenylene isophthalamide fiber, aramid fiber, polyacrylonitrile fiber, cotton, Examples thereof include organic fibers such as cellulose fibers such as jute. Particularly preferred fibers to which the present invention is applied are glass fibers or carbon fibers.

Since the long fiber reinforced polymer alloy resin structure of the present invention is excellent in mechanical properties, it is useful as a material for various molded products. The molding method is not particularly limited, and examples thereof include extrusion molding, injection molding, blow molding, extrusion blow molding, injection blow molding, inflation molding, stamping molding, compression molding, and bead molding. Extrusion molding, injection molding and the like can be said to be preferable methods. As the extruder used at the time of molding, a single screw extruder or a twin screw extruder is useful. It can be said that a twin screw extruder with good mixing property is preferable. Further, since the long fiber reinforced polymer alloy resin structure as a molding material contains long fibers, it is useful to select a method that can prevent wasteful breakage of fibers during melt mixing for molding. As a method for preventing wasteful fiber breakage, it is preferable that the depth of the screw groove of the extruder is 5 mm or more over the entire length, and the depth of the screw groove is 7 mm or more at least in the feed portion. It is also preferred that the screw length / diameter ratio is 7-30. Furthermore, it is also preferable that the compression ratio of the screw is smaller than 1.8. In particular, injection molding under the condition of a back pressure of 0 to 50 kg / cm ² is a particularly preferable method.

  Furthermore, when molding, it is preferable to mold only with the long fiber reinforced polymer alloy resin structure, but it is also possible to mold by adding other resins. Examples of other resins include aliphatic polyamide resins such as nylon 6, nylon 6,6, nylon 4,6, nylon 11, nylon 12, nylon 6,10, nylon 6,12, and aromatic and alicyclic Alternatively, nylon using a side chain substituted aliphatic monomer is also useful. Examples thereof include terephthalic acid hexamethylene amide, isophthalic acid hexamethylene amide, adipic acid trimethyl hexamethylene amide, metaxylene adipamide, and the like. Also, polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, polybutene-1, polymethylpentene-1, and co-use of ethylene and α-olefin having 3 to 6 carbon atoms. Polymer (ethylene-propylene copolymer, ethylene-butene-1 copolymer, etc.), ethylene-propylene-diene terpolymer, copolymer of ethylene and vinyl compound (ethylene-vinyl acetate copolymer, Ethylene-acrylic acid copolymer, ethylene-acrylic acid ester polymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene- (meth) acrylic acid (ester) -α, β-unsaturated Polyolefins such as carboxylic acid (derivative) terpolymers and ethylene-vinyl chloride copolymers) Can be mentioned. Furthermore, mixtures of these can also be used.

  In addition, as other resins, matrix resin (C) which is a material for producing the long fiber reinforced polymer alloy resin structure of the present invention, that is, polyamide resin (A) 50 to 90% by weight and modified polyolefin resin (B) It is particularly preferable to mechanically mix a resin comprising 10 to 50% by weight and then melt and mix, and add the melt-mixed matrix resin (C).

  When two or more different resin materials are mixed and molded, it is preferable that the average value of the particle size of the material resin is relatively close in consideration of the mixing property. The average value of the particle size in each resin material used for molding is usually 5 times or more different from each other, but preferably 3 times or more, preferably 2 times or more. preferable. When three or more types of resin materials are used, it is reasonable to compare the material with the heaviest average weight with the lightest material. The average particle size is measured by the method described above.

  In addition, in order to impart desired characteristics according to the purpose at the time of molding, generally known substances that are added to thermoplastic resins, such as stabilizers such as antioxidants, heat stabilizers, UV absorbers, antistatic agents, difficulty It is also possible to add a flame retardant, a flame retardant aid, a colorant such as a dye or pigment, a lubricant, a plasticizer, a crystallization accelerator, a crystal nucleating agent, or the like. Further, plate-like and powdered inorganic compounds such as glass flakes, mica, glass powder, glass beads, talc, clay, alumina, carbon black and wollastonite, whiskers and the like may be used in combination.

  Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the examples. The elemental analysis used to determine the composition ratio of the resin in the present invention was measured by “Yanako Analytical Industry MT-5”. The strength of the molded product was measured according to IZOT impact strength according to JIS K7110.

Synthesis example 1
Synthesis of modified polypropylene resin 10 kg of polypropylene resin with a melt flow index of 1.5 g / 10 min, 60 g of maleic anhydride, and 8 g of dicumyl peroxide, an organic peroxide as a radical generator, are thoroughly mixed using a mixer tumbler. After that, using a twin screw extruder with a screw diameter of 30 mmφ and L / D = 30, the mixture was melted and mixed at 200 ° C., a strand with a diameter of 2 mm was extruded and air-cooled at a screw rotation speed of 100 rpm, and the length was 3 mm by a pelletizer. The pellets were cut into pellets of acid-modified polypropylene resin.

Synthesis example 2
Synthesis of modified polyolefin resin 10 kg of polyethylene-polypropylene block copolymer resin with a melt flow index of 0.7 g / 10 min, 60 g of maleic anhydride, and 8 g of dicumyl peroxide as an organic peroxide as a radical generator were mixed with a mixer tumbler. Then, using a twin screw extruder with a screw diameter of 30 mmφ and L / D = 30, melt and mix at 200 ° C., and extrude a strand with a diameter of 2 mm at a screw speed of 100 rpm and air-cool. The pellet was cut into pellets having a length of 3 mm by a pelletizer to obtain a pellet-like acid-modified polyolefin resin.

  In addition, as a material for producing a long fiber reinforced resin molded body, polyamide is nylon 6 (manufactured by Toyobo Co., Ltd.) (2 mm diameter strand cut into 2 mm length), polypropylene resin (manufactured by Sumitomo Mitsui Polyolefin Co., Ltd.) , Sumitomo Mitsui Polypropylene) and polyethylene-polypropylene block copolymer resin (Mitsui Chemicals, trade name Mitsui Nobren BJS-G) were used.

  7 kg of nylon 6 resin obtained by cutting a strand having a diameter of 2 mm into a length of 2 mm and 3 kg of the modified polypropylene resin synthesized in Synthesis Example 1 were mixed in a mixer tumbler for 15 minutes. The mixed resin was supplied to the resin supply port of the twin screw extruder and kneaded. The twin screw extruder used had a cylinder diameter of 47 mm and an L / D of 31.5. The cylinder temperature was 240 ° C., and the screw rotation speed was set to 200 rpm. The extruded strand had a diameter of 2 mm and was cut into a length of about 12 mm by a pelletizer to obtain a matrix resin composed of nylon 6 resin and modified polypropylene resin. From the obtained pellets, the pellets were randomly sampled from 10 locations and subjected to elemental analysis. Next, the step of impregnating the fiber was shown below.

  Using an apparatus having a structure as shown in FIG. 1 and heating while continuously drawing the roving of the glass fiber bundle, the fibers are opened, impregnated with the melt of the matrix resin synthesized above, and shaped It was cut as a strand through a die (exit die of a crosshead die) to obtain a pellet having a glass fiber content of 40% (in the composition) and a length of 12 mm (approximately 2 mm in diameter).

The obtained long fiber reinforced resin pellets were fed into an extruder having a feed portion groove depth of 10.5 mm, other groove depth of 7.7 mm, and a screw length (L) / diameter (D) ratio of 21. Injection molding was performed with the injection molding machine provided. At this time, the injection speed was 0.5 m and the back pressure was 0 kg / cm ³ . The molded sample was subjected to strength measurement and fiber length analysis.
Comparative Example 1

  The same operation as in Example 1 was carried out except that the nylon 6 resin and the modified polypropylene resin synthesized in Synthesis Example 1 were not mixed with a mixer tumbler.

The same operation as in Example 1 was performed except that 3 kg of the modified polyolefin resin synthesized in Synthesis Example 2 was used instead of 3 kg of the modified polypropylene resin synthesized in Synthesis Example 1.
Comparative Example 2

  The same operation as in Example 2 was performed, except that the nylon 6 resin and the modified polyolefin resin synthesized in Synthesis Example 2 were not mixed with a mixer tumbler.

  7 kg of nylon 6 resin obtained by cutting a strand having a diameter of 2 mm into a length of 2 mm and 3 kg of the modified polypropylene resin synthesized in Synthesis Example 1 were mixed in a mixer tumbler for 15 minutes. The mixed resin was supplied to the resin supply port of the twin screw extruder and kneaded. The twin screw extruder used had a cylinder diameter of 47 mm and an L / D of 31.5. The cylinder temperature was 240 ° C., and the screw rotation speed was set to 200 rpm. The extruded strand had a diameter of 2 mm and was cut into a length of about 12 mm by a pelletizer to obtain a matrix resin composed of nylon 6 resin and modified polypropylene resin. From the obtained pellets, the pellets were randomly sampled from 10 locations and subjected to elemental analysis. Next, the step of impregnating the fiber was shown below.

  Using an apparatus having a structure as shown in FIG. 1 and heating while continuously drawing the roving of the glass fiber bundle, the fibers are opened, impregnated with the melt of the matrix resin synthesized above, and shaped It was cut as a strand through a die (exit die of a crosshead die) to obtain a pellet having a glass fiber content of 40% (in the composition) and a length of 12 mm (approximately 2 mm in diameter).

Using a mixture of 100 parts by weight of the obtained long fiber reinforced resin pellets and 300 parts by weight of the matrix resin used for impregnation of the fibers with a mixer tumbler, the groove depth of the feed part is 10.5 mm, other Injection molding was performed by an injection molding machine equipped with an extruder having a groove depth of 7.7 mm and a screw length (L) / diameter (D) ratio of 21. At this time, the injection speed was 1 m / min and the back pressure was 0 kg / cm ³ . The molded sample was subjected to strength measurement and fiber length analysis.
Comparative Example 3

The same operation as in Example 3 was performed, except that the nylon 6 resin and the modified polypropylene resin synthesized in Synthesis Example 1 were not mixed with a mixer tumbler.
The strength of the molded product obtained in the above examples and comparative examples, the fiber length contained, and the elemental analysis value of the matrix resin and the impact strength of the molded product, the weight average fiber length of the contained fiber and its content It is shown in Table 1. The deviation rate derived from the nitrogen content is shown in Table 2. In contrast to the example in which the polyamide resin and the modified polyolefin resin were mixed with a mixer tumbler, the comparative example in which the mixing was not performed had a poor impact strength and a large deviation rate of nitrogen.

  By improving mechanical properties such as impact strength, it is expected to be used as an alternative to metal materials aimed at weight reduction of automobiles and the like.

It is a conceptual diagram for demonstrating the flow which manufactures the long fiber reinforced polymer alloy resin structure of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Continuous fiber 2 Heating device 3 Crosshead die 4 Extruder 5 Take-off roll 6 Pelletizer 7 Heating roll 8 Thermal insulation cover

Claims (15)

In the matrix resin (C) containing 50 to 90% by weight of the polyamide resin (A) and 10 to 50% by weight of the modified polyolefin resin (B), the matrix resin in which the polyamide resin (A) is uniformly dispersed within a deviation rate of ± 10% (C) A long fiber reinforced polymer alloy resin structure comprising 40 to 90 parts by weight and 60 to 10 parts by weight of a 3 to 50 mm fibrous reinforcing material arranged substantially parallel to the length direction. (In the text, the deviation rate indicates the uniformity of the composition distribution of the polyamide resin in the matrix resin (C). The average value is the difference between the maximum and minimum values of the polyamide resin content (measured value) and the average value. Indicates the percentage divided by.) The matrix resin (C) is a matrix resin obtained by mechanically mixing a resin containing 50 to 90% by weight of a polyamide resin (A) and 10 to 50% by weight of a modified polyolefin resin (B) and then melt-mixing the resin. The long fiber reinforced polymer alloy resin structure according to claim 1. The long fiber reinforced polymer alloy resin structure according to claim 1, wherein the modified polyolefin resin (B) is a polyolefin resin modified with an unsaturated carboxylic acid or an anhydride thereof. The long fiber reinforced polymer alloy resin structure according to claim 1, wherein the particle size of the polyamide resin (A) and the modified polyolefin resin (B) are not different from each other by 5 times or more in terms of the average weight of the particles. The long fiber reinforced polymer alloy resin according to claim 1, wherein the polyolefin of the modified polyolefin resin (B) is polyethylene, polypropylene, or a block copolymer of polyethylene and a poly α-olefin having 3 to 6 carbon atoms. Structure. A long fiber reinforced polymer alloy resin structure containing a matrix resin (C) and a fibrous reinforcing material impregnates the melted matrix resin (C) into the opened fiber while pulling out the continuous fiber roving, The long fiber reinforced polymer alloy resin structure according to claim 1, which is cut to 50 mm. In the matrix resin (C) containing 50 to 90% by weight of the polyamide resin (A) and 10 to 50% by weight of the modified polyolefin resin (B), the matrix resin in which the polyamide resin (A) is uniformly dispersed within a deviation rate of ± 10% (C) A molded product formed from a long fiber reinforced polymer alloy resin structure including 40 to 90 parts by weight and 60 to 10 parts by weight of a 3 to 50 mm fibrous reinforcement arranged substantially parallel to the length direction. A long fiber reinforced polymer alloy resin molded product, wherein the weight average fiber length of the contained fibers is 1 mm or more. (In the text, the deviation rate indicates the uniformity of the composition distribution of the polyamide resin in the matrix resin (C). The average value is the difference between the maximum and minimum values of the polyamide resin content (measured value) and the average value. Indicates the percentage divided by.) In the matrix resin (C) containing 50 to 90% by weight of the polyamide resin (A) and 10 to 50% by weight of the modified polyolefin resin (B), the matrix resin in which the polyamide resin (A) is uniformly dispersed within a deviation rate of ± 10% (C) A long fiber reinforced polymer alloy resin structure containing 40 to 90 parts by weight and 60 to 10 parts by weight of a 3 to 50 mm fibrous reinforcement arranged substantially parallel to the length direction, and further a matrix resin (C) The long fiber reinforced polymer alloy resin molded product according to claim 7, wherein the molded product is molded from the added composition. The matrix resin (C) is a matrix resin melt-mixed after mechanically mixing a resin containing 50 to 90% by weight of the polyamide resin (A) and 10 to 50% by weight of the modified polyolefin resin (B). The long fiber reinforced polymer alloy resin molded article according to claim 7 or 8. The long fiber reinforced polymer alloy resin molded article according to claim 7 or 8, wherein the modified polyolefin resin (B) is a polyolefin modified with an unsaturated dicarboxylic acid or an anhydride thereof. The long fiber reinforced polymer alloy resin molded article according to claim 7 or 8, wherein the polyamide resin (A) and the modified polyolefin resin (B) have a particle size that does not differ by 5 times or more from the average weight of the particles. The long fiber reinforced polymer according to claim 7 or 8, wherein the polyolefin of the modified polyolefin resin (B) is polyethylene, polypropylene, or a block copolymer of polyethylene and a poly α-olefin having 3 to 6 carbon atoms. Alloy resin molded product. The long fiber reinforced polymer alloy resin structure containing the matrix resin (C) and the fibrous reinforcing material is impregnated with the melted matrix resin (C) into the opened fiber while drawing the continuous fiber roving, The long fiber reinforced polymer alloy resin molded product according to claim 7 or 8, which is cut to 50 mm. 14. The long fiber reinforced polymer alloy resin molded article according to claim 7, wherein the molding method is injection molding. 15. The long fiber reinforced polymer alloy resin molded article according to claim 14, wherein the injection molding, which is a molding method, is a method that can prevent useless fiber breakage.

Images