JPH07314444A - Long fiber-reinforced thermoplastic resin structure and its production - Google Patents

Abstract

PURPOSE:To eliminate fuzzing of fibers and enhance an adhesion of long fibers to a matrix by a method wherein a structure contains a predetermined percentage by weight of reinforcing fibers oriented in parallel to the longitudinal direction of the structure with the same length as the structure, and the length of the structure is specified. CONSTITUTION:While a plurality of continuous fiber bundles 1 are oriented, the fiber bundles 1 are each opened by a plurality of opening means, such as opening rollers 2 and bars. Next, the opened fiber bundles 1 are impregnated with a themoplastic resin melted in a melting and extruding machine 5 or the like by a cross head die 4 or the like. At this time, the structure contains 10-80wt.% reinforcing fibers oriented in parallel to the longitudinal direction of the structure with the same length as the structure, and the length of the structure is determined to 3-100mm. Furthermore, fibers separated from the structure are 1000ppm or less in a shaking test wherein a container loaded with the structure in the amount of 10vol.% is rotated 500 times through 180 deg. alternately at a speed of 60/min.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber-reinforced thermoplastic resin structure useful for obtaining a molded product by a molding method such as injection molding, and particularly to a long-fiber-reinforced thermoplastic resin structure and its production. Regarding the method.

[0002]

2. Description of the Related Art Among pellet-like structures containing reinforcing fibers and thermoplastic resins, structures containing a high concentration of fibers and having good dispersibility during injection molding are useful for obtaining molded products. Is. Such a structure is usually produced by a pultrusion method in which a cross-head is impregnated with a melt of a thermoplastic resin while a continuous reinforcing fiber bundle is taken in and is shaped by a shaping die (pultrusion method). Has been done.

However, as the concentration of the reinforcing fiber increases, the impregnation property of the resin and the dispersibility of the fiber decrease, and fluffing and breakage of the fiber occur. Therefore, the fibers are easily aggregated inside the structure, the reinforcing fibers cannot be maintained at a predetermined fiber length in injection molding, and it is difficult to enhance the reinforcing property of the molded product. Also, the fluffy pellet-like structure not only impairs the appearance and commercial value, but also
A bridging phenomenon is likely to occur in the hopper, which makes it difficult to supply the molding machine smoothly. Further, the broken fiber may block the shaping die, which makes it difficult to continuously obtain the structure.

Japanese Unexamined Patent Publication (Kokai) No. 3-7307 contains 30 to 80% by weight of a thermoplastic resin and 70 to 20% by weight of reinforcing fibers having a fiber length of 3 to 20 mm and uniformly dispersed in the thermoplastic resin. A pellet structure is disclosed. However, this structure, by the same manufacturing method or papermaking method as the non-woven fabric,
Since a sheet containing a thermoplastic resin and a reinforcing fiber is prepared, hot pressed and pelletized, there is a limit to increase productivity.

Japanese Unexamined Patent Publication (Kokai) No. 3-188131 discloses a fiber reinforced molded article containing 30% by weight or more of filaments extending in the length direction of pellets, and at least 50% by weight of the filaments having a length of 2 mm or more. ing.

However, in order to wet the filament, it is necessary that the melt viscosity of the thermoplastic resin is 30 Ns / m ² or less, preferably 1 to 10 Ns / m ² . Therefore, when a thermoplastic resin having a high melt viscosity is used, not only it is necessary to melt the thermoplastic resin at a high temperature to reduce the melt viscosity, but also the thermoplastic resin decomposes and deteriorates.

Further, in Japanese Patent Laid-Open No. 1-214408, 50-90 continuous fiber reinforcements are provided that are substantially parallel to the axial direction.
Disclosed is a molding material containing 90% by weight or more and 90% or more of the surfaces of single fibers coated with a thermoplastic resin.

The molding material is obtained by sandwiching a fibrous sheet between a lower belt coated with a molten resin and an upper belt, passing it between rollers to form a sheet-like composite, and cutting the composite. To be However, as the fiber sheet, a sheet in which a large number of rovings made of a large number of short fibers are aligned in one direction is passed between a pair of belts to impregnate the molten resin, so that the impregnation efficiency of the molten resin is not so high.

Further, in order to improve the method of impregnating the melt of the thermoplastic resin in the crosshead die while taking in the continuous reinforcing fiber, the applicant of the present invention has disclosed that in Japanese Patent Laid-Open No.
No. 272830 proposes a pultrusion method in which a reinforcing fiber bundle is impregnated with a melt of a first thermoplastic resin and then covered with a melt of a second thermoplastic resin. Further, the present applicant has filed in Japanese Patent Application No. 3-230128,
Impregnating the molten resin into the roving of the reinforcing fiber, squeezing the excess resin with a nozzle, pressing the strand obtained in this step into a ribbon, and passing the pressed strand through a shaping nozzle. A manufacturing method including a step of adjusting the shape was proposed.

The present invention further improves on these methods,
It is intended to obtain a composite having excellent properties.

[0011]

That is, the object of the present invention is to provide a homogeneous long-fiber-reinforced heat which does not cause fiber fluffing and has high adhesion between long fibers and a matrix even if the content of reinforcing fibers is large. To provide a plastic resin structure.

Another object of the present invention is to improve the impregnation efficiency of a molten resin even if it is a thermoplastic resin having a high melt viscosity, and to efficiently provide a long fiber reinforced thermoplastic resin structure having the above-mentioned excellent properties. It is to provide a method that can be manufactured.

[0013]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that when a fiber bundle is opened to a specific degree of opening and impregnated with a molten resin, a reinforcing fiber is contained. Even if the amount is 40% by weight or more, it is possible to enhance the impregnation efficiency of the molten resin without damaging the filament, to obtain a homogeneous structure with no fluffing and high adhesion between the fiber and the matrix. Found and completed the present invention.

That is, the present invention comprises 10 to 80% by weight of reinforcing fibers arranged substantially parallel to the longitudinal direction of the structure and having substantially the same length as the structure, and a length of 3 to.
A container having a fiber-reinforced structure of 100 mm and containing the structure at a filling rate of 10% by volume was used at a rate of 60 times / min.
Provided is a long fiber reinforced thermoplastic resin structure having 1000 ppm or less of fibers dissociated from the structure in a shaking test in which it is alternately rotated 180 times for 180 °.

In the method of the present invention, the weight per 1000 m is 50 to 4400 g, that is, 50 to 4400 T.
A method of making a composite by contacting with a molten resin while pulling out a fiber bundle of EX, and bringing the molten resin into contact with the fiber bundle opened to a width / thickness ratio of 35 to 750 to obtain a long fiber reinforced thermoplastic resin. A resin structure is manufactured.

In the present specification, the "longitudinal direction" of the structure means the take-up direction of the fiber bundle. The term "impregnation" is used not only to impregnate a fiber bundle with a resin but also to cover the surface of the fiber.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings as needed. The attached drawings are
1 illustrates an example of the method of the present invention, and the present invention is not limited by the method of the accompanying drawings.

Examples of the thermoplastic resin include olefin polymers such as polyethylene, polypropylene and ethylene-propylene copolymer; polystyrene, rubber-reinforced polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer and the like. Styrene-based polymers; polyesters such as polyethylene terephthalate and polybutylene terephthalate;
Nylon 6, Nylon 66, Nylon 11, Nylon 1
2. Polyamide such as nylon 610 and nylon 612; thermoplastic polyurethane; polyether resin such as polyphenylene oxide and modified polyphenylene oxide, polyacetal, polycarbonate, polyphenylene sulfide, polysulfone, polysulfone, polyether ether ketone, polyether sulfone, polyether amide And heat-resistant resins such as polyetherimide. These thermoplastic resins may be used alone or in combination of two or more.

Of these thermoplastic resins, olefin polymers, polyesters, polyamides, polyethers, polycarbonates, polyphenylene sulfides, etc. are often used.

As the reinforcing fiber, a fiber having a higher elastic modulus than the thermoplastic resin is used. As such a fiber, depending on the type of thermoplastic resin, for example,
Inorganic fiber such as glass fiber, carbon fiber, ceramic fiber, mineral fiber; metal fiber such as stainless steel; ultra high molecular weight polyethylene, polyvinyl alcohol, aromatic polyester, polyethylene terephthalate, polyester such as polybutylene terephthalate, aromatic polyamide, polyacrylonitrile Can be appropriately selected from polymer fibers such as. The reinforcing fibers may be used alone or in combination of two or more.

Of these reinforcing fibers, glass fibers, carbon fibers, inorganic fibers such as ceramic fibers, metal fibers, fibers having a high melting point or a high softening point such as aromatic polyester or aromatic polyamide fibers are often used. .

The fiber diameter of the reinforcing fiber can be appropriately selected,
For example, it is about 5 to 30 μm. The form of the reinforcing fiber is not particularly limited, and may be short fiber (staple), long fiber (filament), roving, or yarn. Reinforcing fibers are often used as fiber bundles such as rovings and yarns. The number of filaments in the roving is, for example, 1,000 to 50,000, preferably 2,000 to 30,000.

The fibers may be surface-treated with a conventional surface-treating agent such as a silane coupling agent or an alkyl titanate.

The length of the structure of the present invention is usually 3 to 10.
It is about 0 mm, preferably about 5 to 50 mm, and the reinforcing fibers are arranged substantially in parallel with the longitudinal direction of the structure and substantially the same length as the structure. In the structure, the fibers may be arranged substantially in parallel, and the fibers may be partially curved or entangled. The length of the structure is often about 5 to 30 mm.

The ratio between the reinforcing fiber and the thermoplastic resin is, for example, reinforcing fiber / thermoplastic resin = 10 to 80/90.
20 (wt%), preferably 20-70 / 80-30
(Wt%), more preferably 30-70 / 70-30
(% By weight). 10% by weight of reinforcing fibers
If it is less than 80, high reinforcing properties may not be imparted, and 80
When the content exceeds the weight%, the dispersibility of the fibers is lowered, the fibers are easily aggregated, and inconvenience may occur in the molding process. The structure of the present invention is characterized in that it is homogeneous even if the content of the reinforcing fiber is 40% by weight or more based on the entire structure. The content of the reinforcing fiber is 40 to 80% by weight, preferably 50 to 80% by weight based on the whole structure.
It is often about 80% by weight.

The structure may contain various additives, if necessary, such as antioxidants, deterioration inhibitors such as ultraviolet absorbers, and fillers, as long as they do not impair molding processability and mechanical properties. , Antistatic agent, lubricant, wetting agent, plasticizer, release agent,
It may contain a flame retardant, a flame retardant aid, a crystallization accelerator, a coloring agent such as a dye or a pigment, and the like.

The structure of the present invention is characterized in that the reinforcing fibers are highly dispersed, the surface smoothness is high, the fluffing, and the breakage of the fibers are significantly suppressed even when the structure of the present invention contains a large amount of long fibers. is there. Therefore, the structure has high mechanical properties and impact strength. The characteristics of such a structure can be evaluated in a strength shaking test. Note that, conventionally, the characteristics of the structure have been evaluated by crushing strength, slipperiness, etc., but the structure of the present invention is microscopic even if there is a defective portion, and therefore In such an evaluation method, the variation is large.

In the shaking test, the structure was housed in a container at a filling rate of 10% by volume, and 180 ° alternately at a speed of 60 times / minute 500 times centered on the midpoint in the longitudinal direction of the container.
It can be performed by rotating. In this test, the container has an inner diameter of 50 mmφ and a length of 350 m.
m containers are used.

In such a shaking test, the proportion of fibers dissociated from the structure is 1000 ppm or less, preferably 500 ppm or less, more preferably 300 ppm or less, and particularly 100 ppm or less. Further, when a pellet-like structure having a reinforcing fiber content of 40% by weight is subjected to a shaking test, the number of fibers dissociated from the structure is 500 ppm or less, preferably 300 ppm or less.

The shape of the structure of the present invention is not particularly limited as long as the fibers can be arranged in one direction, and for example, a surface shape such as a ribbon shape, a tape shape, a sheet shape, a strand shape, a prism shape, or a column shape. It may be rod-shaped, and is usually a prismatic column or a cylindrical pellet in many cases.

The structure of the present invention can be prepared in various ways, for example by:
It can be manufactured by a pultrusion molding method in which a molten thermoplastic resin is impregnated while a continuous reinforcing fiber bundle is being drawn.

As the reinforcing fiber bundle, a bundle of fibers obtained by treating a large number of single fibers from the bushing with a treating agent such as a sizing agent or an aqueous emulsion can be used. As such a fiber bundle, a wound body of a bundle of fibers which is bundled and wound into a cylindrical shape and dried (a package of direct roving), and a wound body of a bundle of fibers which is wound into a shape having substantially no end face and dried. (Cake winding body) and the like. The number of fiber bundles is not particularly limited,
Usually, a plurality of fiber bundles are often used.

In a preferred method, the weight per 1000 m is 50 to 4400 g (50 to 4400 TEX), preferably 100 to 4000 TEX, more preferably 150.
The method of the present invention is included in which a fiber bundle of about 3500 TEX is drawn and brought into contact with molten resin to form a composite. In this method, the width / thickness ratio (W / T = openness) is set to 3
When the fiber bundle opened to 5 to 750, preferably 40 to 500, and more preferably about 50 to 300 is brought into contact with the molten resin, the impregnation efficiency of the molten resin can be improved without damaging the filament, and fluffing occurs. A homogeneous structure with no cracks is obtained. The degree of opening of the fiber bundle is 35 to 2
Even if it is 50 (for example, about 35 to 100 or about 40 to 75), it is often possible to sufficiently impregnate the molten resin. In the fiber bundle, the impregnation efficiency of the molten resin varies depending on the melt viscosity of the molten resin and the affinity with the fiber, but the thickness of the fiber bundle is, for example, 0.2 mm or less, preferably 0.15 mm or less. As a result, the impregnation efficiency of the resin can be significantly improved.

In the method of impregnating the molten resin with a fiber-spreading roller or the like, it is considered that increasing the fiber-spreading degree is useful for increasing the impregnation efficiency of the molten resin. However, if the degree of openness is too large, the filaments and fiber bundles will be damaged, and the homogeneity will deteriorate, and the amount of fibers dissociated or dropped from the structure will increase.

FIG. 1 is a schematic process diagram for explaining the method of the present invention. In this method, the fiber bundle 1 is opened by a plurality of fiber opening means such as a fiber opening roller 2 and a bar while aligning a plurality of continuous fiber bundles 1, and is melted by a melt extruder 5 or the like. The method includes an impregnation step of impregnating the thermoplastic resin with the crosshead die 4 or the like.

Further, in order to improve the impregnation efficiency of the molten thermoplastic resin, a preheating step of preheating the fiber bundle and / or the opened fiber bundle 1 by the preheating part 3 or the like is provided prior to the impregnation step. preferable. Further, in order to uniformly impregnate the resin, it is preferable to employ a drawing step after the above-mentioned impregnation step, in which an excessive amount of the resin is continuously drawn while being drawn by the shaping die 6 or the like by the drawing means. The fiber bundle 1 is taken up by a take-up belt 7 while applying tension to the fiber bundle 1, and cut into a predetermined size by a cutting machine 8 such as a pelletizer.

In the opening step, the opening means is various means for opening the fiber bundle, such as a plurality of tension rollers or bars arranged in a direction intersecting with the traveling direction of the fiber bundle. It may be an opening roller (or a bar). The opening roller is usually regulated or non-rotatable. Therefore, when the fiber bundle is wound around a plurality of opening rollers and the fiber bundle is pulled while applying tension, the fiber bundle is sequentially expanded and opened as the fiber bundle progresses, and finally becomes a strip shape. Become.

The fiber-spreading roller 2 may have a cylindrical cross-section, but it is preferably a fiber-spreading roller or bar in which axially scattered projections are formed. 2 is a schematic front view showing another example of the fiber opening roller, FIG. 3 is a schematic side view showing a fiber opening state by the fiber opening roller shown in FIG. 2, and FIG. 4 is a fiber opening state by the fiber opening roller shown in FIG. It is a schematic plan view showing.

The fiber-spreading rollers 12 are formed with projections 13 scattered in the axial direction. In addition, a plurality of opening rollers 12 are arranged in parallel in a direction intersecting the traveling direction of the fiber bundle 11 (for example, a direction orthogonal to each other), and the convex portion 13 of the adjacent opening roller 12 has an axial direction. The positions are different from each other. In this example, the convex portion 13 of the one opening roller 12
The convex portion 13 of the other fiber-spreading roller 12 is formed in a position where the convex portion 13 partially overlaps. Further, in the adjacent fiber-opening roller 12, one roller 12 has a convex portion 13 formed on an upper portion thereof, and the other roller 12 has a convex portion 13 formed on a lower portion thereof.

A plurality of continuous fiber bundles 11 are supplied to the opening roller 12 while being aligned and in contact with each other. That is, the fiber bundles 11 are alternately suspended and supplied to the plurality of opening rollers 12. With such a method, the fibers forming the fiber bundle 11 can be moved and expanded along the inclined surfaces on both sides of the convex portion 13. Moreover, since the axial positions of the convex portions 13 formed on the plurality of fiber-spreading rollers 12 are different, the fiber bundle 11 can be sequentially spread at different positions in the width direction, and the fiber-spreading efficiency is high.

The shape of the convex portion formed on the fiber-spreading roller is not particularly limited as long as it can prevent yarn breakage, and for example, it may have a triangular cross-section with a sharp top.
A curved surface is formed on the top like a mountain shape or a bulge,
It is preferable that inclined surfaces are formed on both side portions extending from the top with respect to the traveling direction of the fiber bundle. Further, the convex portions may be formed at the contact portion with the fiber bundle, may be scattered at predetermined intervals in the axial direction of the roller, and may be formed on the peripheral surface.

The axial width of the convex portion can be appropriately selected depending on the axial density of the convex portion, the width of the roving, and the like. For example, the width of the roving is 0.3 to 5 times, preferably 0.5.
It is about 2.5 times, more preferably about 0.7 to 1.5 times. Further, in the adjacent opening roller, it is preferable that the position of the convex portion is different in the axial direction, and the convex portion of the succeeding opening roller is located at a portion corresponding to the intermediate portion of the convex portion of the former opening roller. May be formed. The height of the top of the convex portion may be the same or different in the plurality of opening rollers, and the tops of the following opening rollers are sequentially increased,
The opening efficiency may be increased.

Further, the fiber opening means may be a plurality of comb-tooth-shaped members arranged in a direction intersecting with the traveling direction of the fiber bundle. The comb-shaped member is formed on a plurality of supporting members arranged in a direction intersecting the traveling direction of the aligned plurality of fiber bundles, and is formed on the supporting member, and is capable of penetrating or penetrating into the fiber bundle. It can be configured with comb teeth formed of a plurality of pins or the like. At that time, if a supporting member having different positions, for example, a plurality of comb-tooth-shaped members in which adjacent supporting members are formed with comb teeth at different positions in the axial direction,
The fibers can be efficiently opened as the fiber bundle progresses.

The plurality of comb-shaped members may be movable back and forth with respect to the surfaces of the plurality of aligned fiber bundles. By simultaneously or sequentially advancing and retracting the plurality of comb-tooth-shaped members with respect to the surfaces of the plurality of aligned fiber bundles, the fibers can be spread more efficiently while suppressing the transfer resistance of the fiber bundle.

The opening means may be arranged in a direction intersecting with the traveling direction of the fiber bundle, and is usually arranged in a direction orthogonal to the traveling direction of the fiber bundle.

To open the fiber bundle, at least one opening means may be used.
For example, it is preferable to use about 3 to 10 opening means, and usually about 3 to 7 opening means are often used.
When using multiple opening means, different types of opening means,
For example, a comb tooth-shaped member and an opening roll having a convex portion may be combined.

In the preheating step of preheating the fiber bundle and / or the opened fiber bundle in the preheating section 3, the preheating temperature can be appropriately selected according to the type of fiber and the melting temperature of the thermoplastic resin. 75-350 ° C, preferably 10
It is about 0 to 300 ° C. In the preheating step, it is preferable to preheat at least the opened fiber bundle. In order to suppress the cooling of the fiber bundle that has been opened during the transition to the impregnation step, for example, a roll in which a heater is embedded may be used as the open roll.

In the impregnation step, the opened fiber bundle can be impregnated with the molten thermoplastic resin by a conventional method, for example, a method using a crosshead die 4 or an impregnation bath. A preferable method includes a method using the crosshead die 4 which has high work efficiency.

The opened fiber bundle is fed to the crosshead die 4
It is introduced inside and impregnated with the molten resin supplied from the melt extruder 5. In the crosshead die, as disclosed in JP-A-3-272830,
It is also possible to provide a plurality of ridge barriers that alternately project in a direction that intersects with the take-up direction of the fiber bundle, and use these barriers to open the fiber bundle in the die to further increase the resin impregnation efficiency.
The ridge barrier often has a curved surface in contact with the fiber bundle.

The fiber bundle impregnated with the resin is continuously drawn and shaped while squeezing an excessive amount of the resin by the shaping die 6 in the drawing step. In the drawing step, the resin-impregnated fiber bundle may be drawn from a nozzle of the shaping die 6 that is smaller than the apparent cross-sectional area of the band-shaped fiber bundle. When the fiber bundle is taken out from such a nozzle, a shearing force acts on the fiber bundle and the impregnated resin in the process of passing through the nozzle, and the impregnation efficiency of the resin may increase.

The shape of the nozzle of the shaping die 6 can be appropriately selected according to the shape of the shaped fiber bundle, and for example, circular cross section, elliptical cross section, polygonal cross section, irregular cross section, slit shape. And so on. When the slit nozzle is used, the fiber bundle can be smoothly drawn from the nozzle while suppressing damage to the fiber. The shape of the fiber bundle formed by the drawing step may be any of a strand shape, a rod shape, a ribbon shape, a tape shape, a sheet shape and the like.

The long fiber reinforced thermoplastic resin structure of the present invention is used in various molded articles such as general sundries, automobiles, electric appliances,
It is useful for producing molded products for a wide range of applications such as housings and casings for electronic components.

[0053]

INDUSTRIAL APPLICABILITY The long fiber reinforced thermoplastic resin structure of the present invention has a remarkably small proportion of dissociated fibers in the shaking test, and even if the content of the reinforcing fibers is large, the fibers do not fluff and the long fibers And the adhesion to the matrix is high and homogeneous.

According to the method of the present invention, the fiber bundle is highly opened and impregnated with the molten thermoplastic resin. Therefore, even if the thermoplastic resin has a high melt viscosity, the impregnation efficiency of the molten resin is increased. It is possible to efficiently manufacture the structure having the excellent characteristics as described above.

[0055]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples.

The degree of opening in the examples and comparative examples was measured as follows. That is, by measuring the width and thickness of the roving of the reinforcing fiber before use,
The apparent cross-sectional area of roving was calculated in advance. Further, at the time of resin impregnation, the width W of the roving immediately before entering the crosshead die was measured, and the thickness T was calculated from the value of the apparent cross-sectional area, and the degree of opening = width W / thickness T was calculated.

Example 1 Using the apparatus shown in FIG. 1, a glass fiber (GF) roving (2200TEX) was hung on a columnar opening roller and continuously taken over to open to a degree of opening 43, A polypropylene (PP) melt (2
(65 ° C.). Next, the pellet-like structure having a glass fiber content of 60% by weight and a length of 12 mm was obtained by passing it through a shaping die and collecting it as a strand.

Comparative Example 1 A pellet-like structure was obtained in the same manner as in Example 1 without passing the glass roving on the fiber opening roller. The degree of opening of the roving was 12.5.

Example 2 In place of the fiber-spreading roller of Example 1, a fiber-spreading roller in which a plurality of convex portions were formed in the axial direction was used, and the glass roving was spread to a fiber-spreading degree of 57. Similarly, a pellet-shaped structure was obtained.

Example 3 A pellet-shaped structure was obtained in the same manner as in Example 1 except that polyethylene terephthalate (PET) was used instead of polypropylene (PP). Roving degree is 41
Met.

Comparative Example 2 A pellet-shaped structure was obtained in the same manner as in Comparative Example 1 except that polyethylene terephthalate (PET) was used instead of polypropylene (PP). Roving degree is 1
It was 2.5.

Example 4 Instead of polypropylene (PP), polyamide 66 (P
A66) was used to obtain a pellet-shaped structure in the same manner as in Example 1 except that the fiber was opened by the opening roller of Example 2.
The opening degree of roving was 55.

Comparative Example 3 Instead of polypropylene (PP), polyamide 66 (P
A66) was used, and the roving was opened at a degree of opening of 1100 using the opening roller of Example 2 to obtain a pellet-shaped structure having a glass fiber content of 58% by weight in the same manner as in Example 1.

Then, the pellet-shaped structures obtained in the above-mentioned Examples and Comparative Examples were accommodated in a cylindrical container (inner diameter 50 mmφ, length 350 mm) at a filling rate of 10% by volume, and the central portion in the longitudinal direction of the container. The shaft was alternately rotated 180 ° at a speed of 60 times / min for 500 times and shaken. Then
Separate the separated glass fibers and pellets while washing with water, dry the separated glass fibers, weigh,
The ratio of the open glass fiber to the weight of the pellet structure before the shaking test was calculated. The results are shown in the table.

[0065]

[Table 1] As is clear from the table, the pellet-shaped structures obtained in the examples have a very small content of reinforcing fibers despite the large content of reinforcing fibers.

[Brief description of drawings]

FIG. 1 is a schematic process diagram for explaining a method of the present invention.

FIG. 2 is a schematic front view showing another example of the opening roller.

FIG. 3 is a schematic side view showing an opened state by the opening roller shown in FIG.

FIG. 4 is a schematic plan view showing an opened state by the opening roller shown in FIG.

[Explanation of symbols]

 1, 11 ... Fiber bundle 2, 12 ... Spreading roller 3 ... Preheating part 4 ... Crosshead die 5 ... Extruder 6 ... Shaping die 13 ... Convex part

Claims (10)

[Claims] 1. A fiber reinforced having a length of 3 to 100 mm, containing 10 to 80% by weight of reinforcing fibers arranged substantially parallel to the longitudinal direction of the structure and having substantially the same length as the structure. A structure, which is a container containing the structure at a filling rate of 10% by volume, is alternated 180 times at a rate of 60 times / minute and 500 times.
A long-fiber-reinforced thermoplastic resin structure in which 1000 ppm or less of fibers are dissociated from the structure in a shaking test in which the product is rotated. 2. The long fiber reinforced thermoplastic resin structure according to claim 1, wherein the content of the reinforcing fiber is 30 to 80% by weight based on the entire structure. 3. A fiber reinforced structure having a length of 5 to 50 mm, containing 40 to 80% by weight of reinforcing fibers, wherein the fiber dissociated from the structure in a shaking test is 500 ppm or less. Plastic resin structure. 4. A long-fiber-reinforced thermoplastic resin structure in which, when a pelletized structure having a reinforcing fiber content of 40% by weight is subjected to a shaking test, the number of fibers dissociated from the structure is 300 ppm or less. 5. The weight per 1000 m is 50 to 4400.
A method of making a composite by contacting with a molten resin while taking a fiber bundle of g, wherein the molten resin is brought into contact with a fiber bundle having a width / thickness ratio of 35 to 750 opened. Method of manufacturing resin structure. 6. The fibers are spread by a plurality of opening means while aligning a plurality of continuous fiber bundles, impregnated with a molten thermoplastic resin, and an excessive amount of the resin is squeezed by a squeezing means. The method for producing a long fiber-reinforced thermoplastic resin structure according to claim 5, wherein the bundle is continuously drawn. 7. A plurality of rollers or bars arranged in parallel in a direction intersecting with the traveling direction of the fiber bundle and having a convex portion having a curved surface at a different position in the axial direction and continuous to a plurality of rollers or bars. 7. The method for producing a long fiber reinforced thermoplastic resin structure according to claim 6, wherein the fiber bundle is opened while the fiber bundle is aligned and hung and taken over. 8. The production of a long fiber reinforced thermoplastic resin structure according to claim 7, wherein the fiber bundle is impregnated with a molten thermoplastic resin to obtain a pellet-like structure having a reinforcing fiber content of 40 to 80% by weight. Method. 9. The weight per 1000 m is 100 to 400.
While aligning a plurality of 0 g fiber bundles, the width / thickness ratio is opened to 40 to 500 by a plurality of opening means, the opened fiber bundles are impregnated with the molten resin, and the excess amount is drawn by a drawing means. The fiber bundle is continuously taken up while squeezing the resin of 40 to 80% by weight of the reinforcing fiber and the length of 5 to 5
In a shaking test in which a container having a structure of 0 mm and containing the structure at a filling rate of 10% by volume was alternately rotated 180 ° at a speed of 60 times / min for 500 times, fibers dissociated from the structure were 500 ppm. A method for producing a long fiber reinforced thermoplastic resin structure for obtaining the following fiber reinforced structure. 10. The long fiber according to claim 9, wherein when a pelletized structure having a reinforcing fiber content of 40% by weight is subjected to a shaking test, a fiber-reinforced structure having 300 ppm or less of fibers dissociated from the structure is obtained. A method for manufacturing a reinforced thermoplastic resin structure.