WO1998043807A1

WO1998043807A1 - Long fiber-reinforced thermoplastic resin composite body

Info

Publication number: WO1998043807A1
Application number: PCT/JP1998/001316
Authority: WO
Inventors: Rikio Yonaiyama; Masanori Ishikawa; Koichi Saito; Susumu Arase; Hiroyoshi Asakuno; Takashi Shimpuku; Yasuhiro Sakai
Original assignee: Chisso Corporation
Priority date: 1997-04-02
Filing date: 1998-03-25
Publication date: 1998-10-08
Also published as: DE19882262T1; AU6517298A; TW418226B

Abstract

A long fiber-reinforced thermoplastic resin covered composite body comprising a core portion which is a thermoplastic resin composite body reinforced in a longitudinal direction by reinforcing fibers and a covering portion made of a thermoplastic resin and covering the peripheral surface of the core portion, wherein the content of the reinforcing fibers is at least 10 weight %, the mean diameter or the mean thickness of the core portion is 3 mm or more and the mean thickness of the covering portion is 0.3 to 1.5 mm. Particularly when this composite body has a reinforcing fiber content of l0 to 80 weight %, a mean diameter of the section when the composite body is cut perpendicularly to the longitudinal direction is 3 mm or more and a mean deviation of the diameter is 0.10 or less, the shape accuracy of the composite body is excellent, and the composite body can be used alone as a product. Such a composite body can be obtained by passing the resin through at least two shaping/cooling slits within a specific temperature range. Further, the covered composite body can be easily obtained by using a production apparatus including a box-shaped molten resin bath whose top is open, and which is equipped with one or a plurality of inlet nozzles arranged horizontally on a side surface thereof and with one or a plurality of outlet nozzles on the opposed surface aligned with the inlet nozzles.

Description

Specification

Long Fiber Reinforced Thermoplastic Composite Technical Field

The present invention relates to a thermoplastic resin composite reinforced with continuous reinforcing fibers (hereinafter, referred to as a composite), using the composite as a core material, and forming a peripheral surface of the composite using a thermoplastic resin. The present invention relates to a long-fiber-reinforced thermoplastic resin-coated composite covered with a covered portion (hereinafter, referred to as a coated composite) and a method for producing the same. Background art

Various types of industrial rods use FRP rods. However, this FRP rod has problems such as difficulty in bending and difficult processing. Therefore, rods that are easy to be added (and easy to bend) are required:

As a molded product with improved workability of FRP rods, for example, Japanese Patent Publication No. 1-38668 discloses “Material for forming coated FRP products”: The FRP core material part, a thermoplastic resin covering the core material part, and an intermediate layer straddling both of them, are obtained by shaping before the core material part is hardened. In addition to the limited shaping time, it has the drawback that reshaping is not possible, and the resulting molded article is difficult to bend.

As an improvement over such a drawback of FRP, for example, Japanese Patent Publication No. 63-36964 discloses “Fiber Reinforced Structure and Method for Producing the Same”. Is a thermoformable composite made of a thermoplastic resin reinforced with modified reinforcing fibers: However, if the resulting composite has a fixed diameter, the content of reinforcing fibers in it is As it increases, it is necessary to bend and break the composite Although the stress (bending resistance) increases, it has the disadvantage that the composite becomes difficult to bend.

Based on the above facts, if the diameter or thickness of the obtained composite is the same, if the content of the reinforcing fiber contained therein is reduced, it becomes easier to bend, and the composite is bent. It is easy to process, but it is not possible to obtain one with sufficient bending fracture resistance: Conversely, it is obtained by increasing the content of reinforcing fibers in the composite and improving the bending fracture resistance. The composite becomes difficult to bend, and the post-workability, such as bending, deteriorates .: Therefore, a molded article having an effective balance of the opposing properties of bendability and bending fracture resistance is desired:

In addition, the composite material that constitutes the core material of the coated composite material is generally difficult to become a product by itself.-Because the composite material is difficult to mold, it is a high-quality composite material with good shape accuracy. Therefore, it was difficult to produce a stable product: Therefore, in order to make it a practical product, the obtained composite was cut into berets, and injection molding was performed. At present, it was not possible to make full use of the inherent properties of continuous reinforcing fibers: In such a situation, it was used in a continuous, long shape and within a practical range. A composite having the shape accuracy as possible was desired.

Japanese Patent Publication No. Sho 63-376694 discloses such a composite and a method for producing the same, but has such a shape accuracy that it can be used within a practical range. At present, no complex was obtained:

In addition, in order to continuously coat a conventionally continuous composite, the composite is passed through the center of the crosshead die, and the extruder is used to push the mature plastic resin into the crosshead die, and the surroundings of the composite are extruded. It was very common to form a resin film on the surface and coat it, however, this method was poor in productivity and difficult to manufacture: Disclosure of the invention

An object of the present invention is to provide a coated composite which is easy to bend and has excellent resistance to bending fracture, a composite whose shape accuracy is remarkably improved, a method for producing the same, and a large number of composites which can be simultaneously coated. An object of the present invention is to provide a method for producing a coated composite which is easy to maintain and a production apparatus having a simple structure suitable for the production method:

The coated composite according to one aspect of the present invention is a coated composite comprising a core material, which is a composite reinforced in the longitudinal direction with reinforcing fibers, and a thermoplastic resin coating that covers the peripheral surface of the core material. The core material has a reinforcing fiber content of at least 10% by weight, the core material has an average diameter or average thickness of 3 mm or more, and the coating has an average thickness of 0.3 mir. ! ~ 1.5 mm, it is a coated composite.

A composite according to one aspect of the present invention is a composite reinforced in the longitudinal direction with reinforcing fibers, wherein the content of the reinforcing fiber is 10 to 80% by weight, and the composite is formed in the longitudinal direction. A composite with an average cross-sectional diameter of at least 3 mm when cut at right angles and an average deviation of its diameter of less than 0.10:

In addition, in the method for producing a composite according to one embodiment of the present invention, the reinforcing fiber is introduced into the fiber-opening impregnation tank, and is impregnated with the molten mature resin. The reinforcing fiber impregnated with the thermoplastic resin obtained by pulling it out of the chair is cooled so that the surface temperature is within the crystallization temperature range of the thermoplastic resin, and at least within the temperature range. This is a method for producing a composite having a reinforcing fiber content of 10 to 80% by weight and an average diameter of 3 mm or more through two or more shaped cooling slits:

One aspect of the present invention is a method for producing a coated composite, comprising: a molten resin tank for coating a composite reinforced in a longitudinal direction with reinforcing fibers; an inlet nozzle into which the composite is introduced; and a molten resin tank. The outlet nozzle from which the coated composite coated with the molten resin filled in is sent out is on a straight line, and the resin pressure in the molten resin tank is about the same as the liquid head pressure of the molten resin. Without forced pressurization, the thickness of the coating is regulated by the size of the outlet nozzle. The method of making the overlying composite is:

Further, in the coated composite manufacturing apparatus according to one aspect of the present invention, one or more inlet nozzles are located horizontally on the side surface of a box-shaped molten resin tank having an open upper part, It is a coated composite manufacturing device with one or more outlet nozzles on its opposite face and in line with the inlet nozzle: Brief description of the drawings

FIG. 1 is a cross-sectional view of the coated composite cut at right angles to the longitudinal direction, in which FIG. 1A is a schematic perspective view of the coated composite of the present invention, and FIG. IB is a core material. FIG. 4 is a schematic enlarged cross-sectional view showing a unit area and a verification area set in a cross section of a part (composite).

FIG. 2 is an explanatory view of a manufacturing apparatus for obtaining the composite described in the example. FIG. 3 is an external view of a manufacturing apparatus of the coated composite of the present invention.

FIG. 4 is an explanatory cross-sectional view of a coated composite manufacturing apparatus according to the present invention.

The composite of the present invention, the coated composite and the method for producing them will be specifically described.First, the coated composite of the present invention will be described with reference to FIG. 1-.

In FIG. 1A, (1) is the coated composite of the present invention, (11) is its coating, (1 2) is its core, and (1 2 ί ′) is reinforcing material penetrating the core. In FIG. 1B, (Tzl), (Tz2) and (Tz3) represent three unit areas randomly set in the core section (1 2), respectively. (Dzll) and (Dzl2) are two test areas randomly provided in (Tzl), and (Dz21) and (Dz22) are two test areas randomly provided in (Tz2) and ( (Dz31) and (Dz32) represent the two test areas randomly set in (Tz3): Here, the plurality of unit areas are congruent with each other, but have the same unit area (for example, (

T zl)) a plurality of test regions in, for example, test areas (Dzll) and test area (Dzl2) has size similar shapes are different, if usually the former is a 0. 1 mm ² the latter 1 mm ² : Of course, vice versa:

The content C11 of the reinforcing fiber penetrating through this test area (for example, (Dzll)) (the area occupied by the reinforcing fiber Z and the area of the Z test range) is measured by cross-sectional photography, and this procedure is carried out by another test. The content C12 of the reinforcing fiber is repeatedly obtained for the region (for example, (Dzl2)), and applied to the test region (for example, (Dz21)) in another unit region (for example, (Tz2)). To obtain the reinforcing fiber content C22 by applying it to another test area (for example, (Dz22)) to obtain the arithmetic mean value (arithmetic mean X c) and then calculate the deviation δ from each content C and the arithmetic mean Mc:

Then, the standard deviation σ is calculated using the respective deviations δ to obtain the degree of dispersion in the cross section of the reinforcing fiber:

The coated composite of the present invention is excellent in bending fracture resistance because the core is composed of the reinforcing fiber having a high content, and the coating existing on the peripheral surface of the core is relatively soft. Since it is composed of a thermoplastic resin with a large elongation, it is excellent in bendability and cracking resistance: Such bending resistance and bending resistance are contradictory characteristics. In order to maintain a good balance, the following configuration is particularly desirable:

In other words, two kinds of similar and different sizes are placed in a randomly set unit area (無) in the core material cross section that appears when the coated composite is cut along a plane perpendicular to the long axis. The test areas (Dzl, Dz2) are defined, and the content (C1, C2) of the reinforcing fiber penetrating each test area is determined. This is performed for three unit areas (Tzl, Τζ2, and Τζ3). The calculated six content rates (C1 and C12, C21, C22, C31 and C32) are all Mc ± 3 o [Mc: arithmetic mean, σ: standard deviation], preferably Mc ± 2 Desired to be in the range of a,- Here, the effective balance between bendability and bending fracture resistance referred to in the present invention is a value measured by a bending fracture stress test described below, which is a test for examining bending fracture resistance. The value of the coated composite is 1.2 times or more the value of the composite (core material), and the value measured by the 1% radius stress test described below, which is a test for examining the bendability. However, the value of the coated composite is 1.2 times or less the value of the composite (core part).

In the coated composite of the present invention, the content of the reinforcing fiber in the core portion is at least 10% by weight, the average diameter or the average thickness of the core portion is 3 mm or more, and the average thickness of the coated portion. 0.3 mn! Is ~ 1.5 mm:

If the reinforcing fiber content of the core material is considerably less than 10% by weight and the average diameter or average thickness of the core material is significantly less than 3 mm, the bending resistance of the obtained coated composite is reduced. Extremely destructive and impractical. Also, the cladding does not perform as expected:

In addition, when the average thickness of the coated portion is considerably less than 0.3 mm, even if the core portion is coated with a thermoplastic resin, the bending resistance of the coated composite is improved only to a small extent. When the average thickness of the portion is considerably larger than 1.5 mm, the obtained coated composite has improved bending fracture resistance, but is hardly bent.

The shape of the core material constituting the coating composite of the present invention, that is, the cross-sectional shape of the core material when the coating composite is cut at a right angle to the longitudinal direction is not particularly limited: a circle, a triangle, a square, or a hexagon. Any polygon (including not only regular polygons but also inequilateral polygons) can be used.

The thermoplastic resin constituting the core part (12) used in the present invention includes a polyolefin resin, a polyamide resin, a polyester resin, a polycarbonate resin, and an acrylic resin. Resin, polysulfone resin, polyethylene resin, polyurethane resin Examples of the resin include a resin, a polyether resin, and a polyacetal resin. In the present invention, the term “resin” is not limited to a crystalline polymer, but is generally used in the polymer processing industry for polymer materials. The concept encompasses resinous materials that are traded as such and are subjected to molding or processing:

These thermoplastic resins may be a single resin or a composition in which two or more thermoplastic resins are combined. It is difficult to obtain various properties (properties) with a single thermoplastic resin, but it can be solved by combining two or more thermoplastic resins. :

As a specific example of such a composition, there may be mentioned a composition of a polyphenylene ether resin and a polystyrene resin: The polyphenylene ether resin has a melting point and a decomposition point. The moldability is poor due to the close proximity, but good moldability can be maintained by combining with the low-melting resin, polystyrene resin:

As another example, the lack of compatibility (affinity) between two types of thermoplastics results in a means of solving weaknesses that do not allow for successful thermal bonding (fusion). An improvement in which a third thermoplastic resin having compatibility with both thermoplastic resins is blended into both or at least one of them so that the thermoplastic resin can be fused, or the third thermoplastic resin is formed into a layer. And intervene between them:

As the thermoplastic resin, polyolefin resin is excellent: The core portion is provided with excellent flexural fracture resistance by the reinforcing fiber contained therein, but this performance is effectively used. This is because Bolbropyrene resin is generally dominant:

Among the propylene resins, the one with the highest rigidity is crystalline poly (vinylene) obtained by homopolymerization of propylene: However, in applications mainly used in a low-temperature environment, the propylene single weight is used. It is preferable to use a (crystalline) polypropylene copolymer composed of at least one kind of α-olefin such as ethylene instead of coalescing. As the reinforcing fibers constituting the core part (12) used in the present invention, single fibers having an average diameter of 3 to 21 zra, preferably 9 to 21 / zm, are preferably 500 to 500. A bundle of about 4.00 bundles (hereinafter sometimes referred to as roving) is desirable. If the average diameter of the reinforcing fibers is 1 μm or less, it is difficult to form a composite. The fibers are easily broken, and the impact strength of the molded article tends to be insufficient. If the average diameter of the continuous fibers is 25 μm or more, the appearance of the composite becomes poor and the mechanical strength tends to deteriorate.

The average length of the fiber reinforcement is preferably substantially equal to the average length of the composite: obtained by reinforcing fibers reinforcing a continuous body such as a composite. The tensile strength in the longitudinal direction of the composite and the flexural fracture resistance of the composite are improved:

Examples of the above reinforcing fibers include inorganic fibers and organic fibers. Examples of the inorganic fibers include artificial fibers such as glass fiber, carbon fiber and metal fiber. Of these, glass fibers are preferably used because of their excellent physical properties and economy: Hard glass is preferred as the glass fiber, and in particular, in addition to E-glass, which is alkali-free glass, Borosilicate glass (porosilicate glass) is preferably used.

The inorganic fibers may be, for example, a silane-based cutting agent, a titanium-based cutting agent, a boron-based cutting agent, an aluminum-based cutting agent, and a zirco-aluminum-based cutting agent. The inorganic fiber may be used after being subjected to a surface treatment with at least one of surface treatment agents: When the inorganic fiber is subjected to a surface treatment, it has an affinity for a hydrophobic mature plastic resin such as polystyrene or pyrene. Strength is enhanced and the thermoplastic resin is more likely to be impregnated between the reinforcing fiber spreads:

Examples of the organic fibers include polyolefin fibers, such as polyethylene fibers, polystyrene fibers and poly-4-methyl-tribenten fibers, and polyamide fibers such as 6-polyamide (6- Nylon), 7-polyamide, U-polyamide, 12-polyamide, 6,6-polyamide, 6,7-polyamide, 6,10- Polyamide, 6, 12-Polyamide, Semi-aromatic Polyamide Thermoplastic fiber such as nylon fiber MXD 6 (co-condensate of m-xylylene diamine and adipic acid), wholly aromatic polyamide fiber [aramid fiber (trade name: Kepler)], etc. Polyester fibers, for example, PET (polyethylene terephthalate) fibers, PBT (poly-1,4-butylene terephthalate) fibers, and wholly aromatic polyester fibers, etc .: Preferred because of its high melting point and excellent mechanical strength: The above-mentioned inorganic fibers and organic fibers may be used alone or in combination of two or more. Include two or more combinations in inorganic fibers or two or more combinations in organic fibers.

Cover part (1 1)>

The coating part constituting the coating composite of the present invention is preferably one whose inner wall surface is firmly adhered to the outer wall surface of the core part, or one which is slidably contacted. : Therefore, the thermoplastic resin used for the core part and the mature resin used for the coating part are those which show mutual adhesion, affinity or compatibility, etc., but do not show Combinations of materials are desirable: In addition, it is important that the composite does not adversely affect the flexural failure resistance of the composite

More specifically, polyolefin resin is preferred for both the thermoplastic resin used for the covering part and the mature plastic resin used for the core part.- The covering part impairs the bending fracture resistance of the core part. In order to avoid this, it is preferable to use a polypropylene copolymer of propylene and ethylene or other α-olefin as the propylene resin.

In particular, the propylene copolymer occupies at least 80 mol%, preferably 85 to 97 mol%, more preferably 90 to 95 mol%, of the propylene unit in the polypropylene copolymer. In addition, it is preferable that the remaining amount is usually 20 mol% or less, preferably 15 to 3 mol%, more preferably 1 () to 5 mol%, in other α-olefin units. _ Ethylene is preferred as a comonomer to form this α-olefin unit: The role of the coating, in addition to the above, also includes the role of protecting the core against contamination, moisturizing and other undesirable effects: ± this role, but also polyolefin. Fat is useful.

Next, the composite of the present invention will be described: The composite of the present invention also corresponds to the core part of the coated composite of the present invention. That is, it can be used even without the covering portion.

The thermoplastic resin and the reinforcing fibers that constitute the composite of the present invention are as described above in the <core part (

1 2)> It is possible to use the same as the above, but in the composite of the present invention, the reinforcing fiber is contained in the range of 10 to 80% by weight:

When the content of the reinforcing fiber is less than 10% by weight, the amount of the ripened resin becomes too large, control of the shape becomes difficult, and it becomes difficult to obtain a product having a smooth surface and a high commercial value. If the content of the fibers for use exceeds 80% by weight, the impregnated fibers are liable to generate fluff at the exit of the die and become unstable in shape, so that not only the external appearance is deteriorated, but also stable continuous production cannot be performed.

The composite of the present invention has an average cross-sectional diameter of 3 mm or more when cut at a right angle to the longitudinal direction.

If the average diameter of the cross section is less than 3 mm, the shape accuracy does not improve even if the impregnated fiber is shaped, and only products with low commercial value can be obtained.

The composite of the present invention has an average deviation of the cross-sectional diameter when cut at a right angle to the longitudinal direction in a range of 0.10 or less-when the average deviation exceeds 0.10, the composite obtained is obtained. The body has poor shape accuracy: preferably less than 0.05, particularly preferably less than 0.02:

Since the composite of the present invention has excellent shape accuracy, it is useful for columns for tunnel houses, side guides for automobiles, handrails on boules, and the like.

Further, the method for producing a composite of the present invention comprises the steps of: 3807 PT / JP98 / 01316

11

This is a method in which at least two or more shaped cooling slits are passed within the temperature range while controlling the surface temperature to be within the crystallization temperature range of the thermoplastic resin. If the impregnated fiber is passed through the shaped cooling slit at a temperature where the surface temperature of the impregnated fiber is significantly below the crystallization temperature range of the thermoplastic resin, the composite will enter the shaped cooling slit before entering. However, since the surface of the impregnated fiber is solidified, the shaping of the impregnated fiber becomes difficult, and finally the production becomes impossible:

On the other hand, when the impregnated fiber is passed through the shaped cooling slit at a temperature that greatly exceeds the crystallization temperature range of the thermoplastic resin, the impregnated fiber in the shaped cooling slit is At the inlet (opening impregnation tank side entrance), a pool of molten thermoplastic resin will form, making shape control difficult and eventually impossible to manufacture:

The crystallization temperature range referred to here is the extrapolated crystallization onset temperature (T ic) obtained by differential scanning calorimetry (DSC) of a thermoplastic resin based on JISK-7121-1987. ) And the extrapolated crystallization end temperature (T ec), and in the case of helium at the horizon, about 90 C to 130-C is a guideline.

In the production method of the present invention, a plurality of shaped cooling slits are used, and the diameter of the shaped cooling slit closest to the spread impregnation tank is farthest from the spread impregnation tank. It is desirable that the diameter of the slit is larger than the diameter of the shaped cooling slit.-The diameter of the slit should be determined in consideration of the degree of shrinkage of the thermoplastic resin used. The method and apparatus for producing the coated composite of the present invention will be described with reference to FIGS. 3 and 4:

The molten resin tank (36) used in the present invention has a box shape with an open top, and one or more inlet nozzles (31) are located horizontally on the side surface. It has one or more exit nozzles (32) on its opposite surface.

The molten resin (35) is stored in the molten resin tank (36). 807

12

The resin (35) is supplied from the existing extruder: the molten resin (35) is marginally separated from the extrusion pressure from the extruder and is almost free of pressure. The molten resin is stored in the molten resin tank (36): The molten resin is basically the same as the ripened resin described in the above <Coating part (11)>.

The molten resin tank (36) is heated by a heater (not shown), so that the internal molten resin (35) can be maintained at the set temperature.

The upper part is open to prevent the resin pressure from being applied to the molten resin tank (36). If the structure is capable of releasing the pressure, the lid may be attached. Peni

When the composite (3) passes through between the inlet nozzle (31) and the outlet nozzle (32) of the molten resin tank (36), the composite (3) is formed by the molten resin (35). Coated around it:

The positional relationship between the inlet nozzle (31) located on the side surface of the molten resin tank (36) and the outlet nozzle (32) located on the opposite surface of the molten resin tank (36) is such that the composite is broken by both nozzles. It is desirable to connect them with one straight line so that the music does not stick

The center of the inlet nozzle (31) and the center of the outlet nozzle (32) are positioned so that they are aligned in a straight line in the axial direction of both nozzles. The thickness of the part can be made uniform and uneven thickness can be reduced:

In addition, if the complex (33) is not placed without completely removing the moisture attached to the surface, the molten resin (35) that has been ripened and melted to about 27O0C in the molten resin tank (36) can be obtained. ) Is present, which causes the attached water to boil and roughen the surface of the coated composite (34):

Since the present invention is an improvement on a conventional coating device such as a cross head die, it is possible to replace the composite (33) with a metal wire such as a copper wire, an iron wire, or an aluminum wire. Toka Glass fiber, carbon fiber (carbon fiber), polyester fiber, and polyamide fiber ( Nylon), organic fibers such as polyurethane fiber, etc. Polyester resin—, Polyamide (Nylon) resin, Polyurethane resin, Polypropylene resin, Polyethylene The composite (33) may be covered with a monofilament such as resin or polyvinyl chloride resin. The time required for the complex (33) to pass through the molten resin tank (36) is also important. If the length is too short, the coating will be insufficient, and if the length is too long, the composite (33) will melt and the shape will not be maintained: the temperature (resin viscosity) of the molten resin (35), the coating thickness and the line Depending on the speed, such defects can be adjusted.

The inlet nozzle (31) located on the side of the molten resin tank (36) facilitates the passage of the complex, and the molten resin (35) in the molten resin tank (36) is filled with the inlet nozzle (3). It must be slightly larger than the cross section of the complex so that it does not seep out of 1): For example, if the complex has a substantially circular cross section, the It is good to make it about 0.2 mm larger

When the composite (33) coated in the molten resin tank (36) passes through the outlet nozzle (32), the molten resin (3 To squeeze 5), the coating thickness coated on the composite (33) can be adjusted by considering the size of the exit nozzle (32): For example, the composite (33) is In the case of a substantially circular shape, the thickness of the coating is generally obtained by subtracting the radius of the composite (33) from the radius of the exit nozzle (32) and considering the shrinkage of the molten resin (35). Can be inferred

Since the molten resin (35) adheres to the periphery of the composite (33) and is consumed, it is necessary to supply the molten resin (35) to the molten resin tank (36). It may be replenished, but as a precaution, a method that does not apply resin pressure must be adopted- W / 3807

14

The invention's effect "

The coated composite of the present invention has significantly improved flexural fracture resistance of the core, while preserving the flexibility of the coated composite at the same level as that of the core. Almost no fluff is generated, the surface appearance is extremely smooth, and post-processing such as bending is easy.

The composite of the present invention is very close to a perfect circle, has very good shape accuracy, and is practical and of high commercial value.

Further, the method for producing a composite of the present invention can stably produce the composite of the present invention with a shape very close to a perfect circle and with extremely excellent shape accuracy:

According to the method for producing a coated composite of the present invention, a plurality of composites can be simultaneously coated in one molten resin tank, and the thickness of the coated portion can be controlled relatively easily. Variations in volume can also be reduced:

In addition, the apparatus for producing a coated composite of the present invention can carry out the method for producing a coated composite with an apparatus having an extremely simple structure.

Hereinafter, the coating composite of the present invention will be specifically described based on examples and sometimes with reference to useful comparative examples. However, the present invention is not limited to these examples. Not subject to any restrictions :.

Each of the composites (core part) obtained in Reference Examples 1 to 5 and the bending fracture stress and the 1% flexural stress of each of the coated composites obtained in Examples 1 to 7 and Comparative Examples 1 to 2 were measured according to JIS K7203- Measured according to 1982: At this time, the test speed was 1.5 mmZ min, and the distance between supports was 100 ± 0.5 mm (fixed):

The larger the value of the flexural fracture stress, the better the flexural fracture resistance. In addition, the 1% flexural stress has a smaller value, indicating that it is more bendable. The diameter of each composite and the coated composite was measured according to JIS K69U-1979.

[Reference Example 1]

Maleic anhydride-modified poly (propylene) [MFR (230 ^: C; 21.18N) 1, with four orifices of glass fiber, the bundle of reinforcing fibers shown below, adjusted to a temperature of 270 [0 0 g / 10 min], and the impregnation was continuously carried out while supplying the melt to the opening impregnation tank. A glass fiber orifice is introduced into the open fiber impregnation tank from the reinforcing fiber introduction port of the tank: Also, a thermoplastic resin is introduced into the tank from the molten resin inlet port formed in the bottom plate of the tank. This thermoplastic resin is usually melt-kneaded in an extruder and then charged into the tank via a pipe or directly.

All of the reinforcing fibers introduced into the above-mentioned opening and impregnating tank have an average single fiber diameter of 17 μπ! And are used as a mouthpiece having a fiber count of 115 g / km. :

In the tank, a pair of two open fiber fins, one pair above and below, are formed between the left side wall and the right side wall forming the left and right long sides with the flow path of the thermoplastic resin and the reinforcing fiber therebetween. The vertical spacing (H) between the two opened fibers constituting each pair is set within the range expressed by the following relational expression with respect to the average diameter (D) of the reinforcing fibers. Has been:

1 0 D≤ H≤ 5 0 0 D _:

Here, the vertical interval (H) is defined to include the case where the line passing through the center axis of the upper and lower opening bins is inclined with respect to the vertical line. If the line connecting the center of the opening fiber and the center of the lower opening pin is not on the vertical line, one of the opening bins is slid parallel to the flow direction of the reinforcing fiber, The vertical interval (H) is the interval when the center of is on the vertical line:

Fiber reinforcement inlet located upstream of the fiber impregnation tank (perforated on the upstream end wall or upstream end 3807

16

The reinforcing fibers are introduced from the top plate, and are passed through the gap between the first opening bin pair at the upstream end in a non-contact manner, and then opened, and then the second opening adjacent to the downstream side is opened. The fiber was opened by passing through the pin gap of the bin pair in a non-contact manner, and finally opened by passing through the pin gap of the third spreading bin pair located downstream of the bin in a non-contact manner. The molten thermoplastic resin is impregnated between the reinforcing fibers of the spread.

The composite obtained from the reinforcing fiber and the thermoplastic resin that has passed through the third opening pin is shaped through a shaping nozzle (inside diameter 5.7 O ram) formed in the downstream end wall of the opening and impregnating tank. Cooling after shaping results in a composite (average diameter 5.63 mm) containing longitudinally aligned reinforcing fibers. The content of the reinforcing fiber in this composite was 18.2% by weight.The results of measuring its properties are shown in Table 1.

[Reference Examples 2 to 5]

In Reference Examples 2 to 5, a composite serving as a core material was obtained basically in the same manner as in Reference Example 1. However, the number of roving fibers for reinforcing fibers used in the production and the installation of an opening and impregnating apparatus were used. The shape nozzle diameter and the content of reinforcing fibers in the obtained composite are different from those in Reference Example 1, respectively. The measurement results of the properties are shown in Table 1:

\ mm π-Nozzle composite Composite fiber content of reinforcing fiber penetrating the cross section of the core of the composite Curved 1% Reinforced fiber in a bottle zl Τζ2 Tz: i Average Standard Deflection deflection Diameter average Diameter fiber content C11 C12 C21 C22 C31 C32 value Deviation Stress Stress Stress number (.mm (wt%) (%) (%) (%) (%) (%) (%) (Mc) (σ) (Ν ) (Ν)

1 4 5.7 5.63 18.2 β.4 6.8 7.8 9.9 6.2 8.4 7.6 1.15 5 23 Reference 2 2 3.4 3.2 1 2 6. 3 1 3. 6]. 9 8. 1 7.5 1 0. 8 1 5. 2 11.7 3.1 3 1 3

8 4. 5 4. 3 2 48. 2 20. 4 1 8. 8 29. 1 2 Η Η 26. 3 2 7. 7 24.8 3.8 1 () 2 1 5 Example 4 8 5. 7 5. 6 8 3 2.11.6.8 18.1.11.1 1.2.5 15.9.1.4 14.8 2.3 1 8 6 3 2

5 20 6.0 5.84 59.2 3 1.2 30.1 3 5.8 3 2.93 3 5.1 3 7.0 0 33.6 2.5 28 7 63

[Example 1] ^_

While introducing the composite obtained in Reference Example 1 into a crosshead die (adjusted to 240 ^: C), polypropylene (MFR (230; 21.18N) 5 g Omin) was placed in a circular die (diameter: (6.9 mm) in the form of coating on the surface of the composite while supplying it to the composite surface to obtain a coated composite (average diameter 6.73 mm) having a coating (average thickness 0.55 mm). The results of measurements of the properties of the coated composite are shown in Table 2:

In addition, the content C11 of the reinforcing fiber penetrating the test area (D zll: 0.1 mm ') in the unit area (T zl) set in the core section of the obtained coated composite and the test In addition to obtaining the content C12 of the reinforcing fiber penetrating the region (Dζ12: 1 ram ² ), the test region was also determined for the other two unit regions ((T z2) and (T z3)). ((D z21) and (D z22)) and the test area ((D z31) and (D z32)) are set, and the content of four reinforcing fibers penetrating each (C 21 and C 22 and C31 and C32), and the difference between the content of these six reinforcing fibers (C11 and C12, C21 and C22 and C31 and C32) and the arithmetic mean Mc c—C mn; m and n are each an integer of 1 to 3 and 6 deviations δ ran (m and η are the same as above); δ 11 and δ 12, δ 21 and δ 22 and δ 31 And δ32) and standard deviation using δηηη Table 1 shows the arithmetic mean value Mc and standard deviation σ for which σ was calculated, and the property value measurement results of the complex.

[Examples 2 to 7 and Comparative Examples 1 and 2]

The coated composite was obtained basically in the same manner as in Example 1. However, the method of producing the composite, the diameter of the circular die, and the diameter of the coated composite were changed according to each experimental example and comparative example. As a result, the results are different from those in Example 1. The content of the reinforcing fiber in the cross-section of the core material of the obtained coated composite, such as the conditions in each experimental example and the comparative examples, C mn, and their arithmetic mean values Tables 1 and 2 show the deviation δ _mn of the difference (M c-C ran) between Mc, \ c and the content C mn of each reinforcing fiber, the standard deviation calculated therefrom, and the property values of the composite. Show. Table 2

\ Experiment Circular dies of composites Reinforcement of composites on H-head

'

Production method's inner diameter ': average it!): WJ- river fiber content 1, force stress number,, (, mm (mm) (mm) (wt%) (N) (Ν)

1 Reference example 1 6. 9 6. 7 3 0.5 5 1 8.2 2 1 2 3 Actual 2 Reference example 2 4. 5 4. 2 9 0.5 5 4 2 6. 3 5 7 4

3 Reference example 3 5. 7 5.5 6 0.β 2 4 8.2 1 69 1 β application 4 Reference example 4 7.2 β. 9 2 0.6 .5 3 2. 1 2 8 2 3 5

5 Reference Example 5 6. 6 6. 5 0 0.3; ¾ 5 9.2 3 6 7 6 7 Example 6 Reference Example 5 7. 2 6. 9 ti 0.5. 6 5 9.2 4 0 8 β 7

7 Reference Example 5 8.5 5 8.5 4 1 0 5 9. 2 5 9 5 7 4 Ratio 1 Reference Example 5 K. 3 H. 2 B 0.2 1 5 9. 2; 3 9 6 4 Compare 2 Reference example 5 9. 5 9. 4 (i 1.8 1 5 9. 26 1 β 8 1 example

Hereinafter, the composite of the present invention and the method for producing the same will be described in detail with reference to Examples and, where necessary, with reference to useful Comparative Examples. Is a method of evaluating a complex without any restrictions by these examples>

* Diameter: The diameter of the obtained composite was measured in accordance with JIS K 6911-1979. That is, the diameter of the cross section of the composite when cut at a right angle to the longitudinal direction was measured on the same plane. Four points were measured at intervals of ° (Dll, D12, D13, D14)-This operation was also determined for other sections set for the same complex (D21, D22, D23, D24), and the arithmetic mean ( The MD obtained by measuring the average deviation (roundness MD) from the average diameter Dm) is derived from the following equation.The smaller the MD value, the closer to a perfect circle and the higher the shape accuracy. Do:

8

D = ∑: Dm-Di: I 8

i = l

[Example 8]

In Example 8, a composite was formed by using an apparatus as shown in FIG. 2-that is, 20 gussets (21) of glass fibers as reinforcing fibers were used to form a thermoplastic resin. Opening in which maleic anhydride-modified polyfluorophenyl FR (230-C; 21.18N) 100 g / lOmin] is filled with a melt adjusted to a temperature of 270 ° C Impregnation tank (2

2) and continuously impregnated at a take-off speed of lOOcniZmin

As the roving (21), an average single fiber diameter of 17μ and a tex number of 1150gZkm was used-and the roving (21) was provided in the opening impregnation tank (22). Opened with fine fiber (23) and impregnated with the melted modified polybrohillene · Next, roving impregnated with the melted modified polybrohillen ( 2 1) passes through a die (24) with an inner diameter of 6.0 mm provided at the outlet of the opening and impregnating tank (22), and then an air cooling tank ( After passing through 25), the surface temperature is adjusted to 125 ^: C. ―

In addition, the impregnated rovings (21) are made of a 10 mm wide steel, controlled at a temperature of 30 ^: C, and have an inner diameter of 6 lmm, spaced at 40 mni intervals. A composite having an average diameter of 5.85 mm was obtained by sequentially passing through the shaped cooling slit (26) and the second shaped cooling slit (27) with an inner diameter of 5.9 ram. .:

The obtained composite had extremely small variation in shape-and the glass fiber content was 59% by weight. Table 3 shows the evaluation results of the obtained composites based on the following measurement tests:

[Example 9]

Example 9 is substantially the same as Example 8, but differs in that the number of orifices (21) is different and that three shaped cooling slits are provided. :.

That is, in the same manner as in Example 8, 10 glass fiber rovings (21) were filled with a melt of maleic anhydride-modified polypropylene at a temperature of 270 ^: C. It was fed to the impregnation tank (22) and continuously impregnated at a take-off speed of lOOcm / min: and the roving (21) impregnated with the molten modified polypropylene was sent to the open fiber impregnation tank (22). After passing through a 6.0 _mm inner diameter die (24) provided at the outlet of 22), the air passes through an air cooling tank (25) and the surface temperature is adjusted to 125C:

In addition, the impregnated rovings (21) are made of steel with a width of 1 Omra, controlled at a temperature of 30 C, arranged at intervals of 40 mm and 20 mm and having an inner diameter of 6.1 mm. 1 shaped cooling slit (26), 2nd shaped cooling slit (27) with an inner diameter of 5.9, and 3rd shaped cooling slit (28) with an inner diameter of 5.8 ) To give a composite with an average diameter of 5.75 mm:

The composite obtained had very little variation in shape: the glass fiber content was 37% by weight. /. Table 3 shows the evaluation results of the obtained composite based on the following measurement tests. [Example 10]-This example 10 is substantially the same as example 8, except that the number of mouths per bing (2 1) is different, and four shaped cooling slits are provided. In other words, in the same manner as in Example 8, four glass fiber orifices (21) were used, and maleic anhydride-modified polypropylene copolymer having a temperature of 270 ^: C was used. The fiber was fed to a fiber impregnation tank (22), which was filled with the molten material, and was continuously impregnated at a take-off speed of lOOcra / min:

The orifice (21) impregnated with the molten modified polypropylene is passed through a die (24) with an inner diameter of 6.0 mm provided at the outlet of the fiber impregnation tank (22). Passing through the air cooling tank (25), the surface temperature is adjusted to 125C:

Furthermore, one impregnating port bing (21) is made of steel 10 mm in width, controlled at a temperature of 30 ^: C, and has inner diameters arranged at intervals of 10 mm, 20 mm and 20 mm. 6 · lmm first shaped cooling slit (26), inner diameter 5.9mm second shaped cooling slit (27), inner diameter 5.8mm third shaped cooling slit (28) and a fourth shaped cooling slit (29) having an inner diameter of 5.7 mra, a composite having an average diameter of 5.65 mm was obtained.

The obtained composite had extremely small variation in shape. The glass fiber content was 18% by weight. The evaluation result of the obtained composite based on the following measurement test was obtained. Table 3 shows:

[Example 11]

Example 11 is substantially the same as Example 8, except that the number of the orifices (21), the dies (24) and the diameter of the first shaped cooling slit (26) are smaller. The diameter of the second shaped cooling slit (27) is different:

That is, in the same manner as in Example 8, 10 orifices (21) of orifices of glass fiber were filled with a melt of maleic anhydride-modified orifice at a temperature of 270 ° C. Was fed to the open impregnation tank (22), and was continuously impregnated at a take-off speed of lOOcm / min: The orifice (21) impregnated with the molten modified polypropylene passes through a die (24) having an inner diameter of 3.5 provided at the outlet of the fiber impregnation tank (22). After passing through the air cooling bath (25), the surface temperature is adjusted to 125 ^: C:

In addition, the impregnating port one bing (21) is made of steel with a width of 10 mm, is controlled at a temperature of 30 ^: C, and has an inner diameter of 3.6 mm, which is arranged at intervals of 20 mm. A composite having an average diameter of 3.46 mm was obtained by sequentially passing through the first shaped cooling slit (26) and the second shaped cooling slit (27) having an inner diameter of 3.5 mm. Was:

The obtained composite had a very small variation in shape: the glass fiber content was 73% by weight: The evaluation results of the obtained composite based on the following measurement test were shown. 3 Show:

[Comparative Example 3]

In the same manner as in Example 8, the opening impregnation in which 20 (2 1) glass fiber orifices are filled with a melt of maleic anhydride-modified polypropylene at a temperature of 2700 ^: C. It was fed to the tank (2 2) and was continuously impregnated at a take-off speed of lOOcDiZrain:

The roving (21) impregnated with the molten modified polypropylene is passed through a 6. Omrn die (24) having an inner diameter of 6. Omrn provided at the outlet of the fiber impregnation tank (22). After passing through the air cooling tank (25), the surface temperature is adjusted to 125C-.

Then, the impregnating port bing (2 1) was used without using a shaped cooling slit to obtain a composite having an average diameter of 5.87 mm:

However, the composites obtained in this way had a large variation in shape: the glass fiber content was 59% by weight: Table 3 shows the evaluation results based on:

[Comparative Example 4]

In the same manner as in Example 8, opening and impregnating 10 glass fiber orifices (21) with a melt of maleic anhydride-modified poly (vinylene) at a temperature of 270 ^: C. Tank (2 2), and continuously impregnated at a take-off speed of lOOcmZrain / "This: And the roving (2 1) impregnated with the molten modified polypropylene is sent to the open fiber impregnation tank (2 After passing through the dice (24) of 3.5 inner diameter provided at the exit of 2), it passes through the air cooling tank (25), and the surface temperature is adjusted to 125 ^: C:

Then, the impregnated rovings (2 1) can be made to have an average diameter without using a shaped cooling slit.

3.44mm composite was obtained:

However, the composite thus obtained had a large variation in shape. The glass fiber content was 73% by weight: The following measurement test of the obtained composite Table 3 shows the evaluation results based on the following:

[Comparative Example 5]

In the same manner as in Example 8, 20 glass fiber orifices (21) are filled with a melt of maleic anhydride-modified polypropylene having a temperature of 270 ^: C. It was fed into the impregnation tank (2 2) and continuously impregnated at a take-off speed of lOOcmZmin:

The orifice (21) impregnated with the molten modified polypropylene passes through a die (24) with an inner diameter of 6. Omm provided at the outlet of the fiber impregnation tank (22). After passing through the air cooling bath (25), the surface temperature is adjusted to 14 OC:

In addition, the impregnating port one bing (2 1) is made of 1 Omm wide steel, controlled at a temperature of 30 C, and has a 6.2 mm inner diameter first shaping cooling slit. (26), a molten pool of propylene resin was formed at the slit inlet, the line stopped, and no composite was obtained. The evaluation results are shown in Table 3.

[Comparative Example 6]

In the same manner as in Example 8, an opening impregnation tank in which 20 glass fiber orifices (21) are filled with a melt of maleic anhydride-modified polypropylene at a temperature of 270 ^: C. (22) and continuously impregnated at a take-off speed of lOOcmZmin:

Then, the roving (21) impregnated with the molten modified polypropylene is opened. 6. After passing through the Omra dice (24 :;) at the outlet of the fiber impregnation tank (22), it passes through the air cooling tank (25), and the surface temperature is adjusted to 60 ^: C. RU:

In addition, the impregnating port one bing (21) is made of a 10mm-wide steel, controlled at a temperature of 30C, and has a 6.2mm inner diameter first shaped cooling slit (21). After passing through 26), the solidified polypropylene resin at the slit entrance caught the entrance and could not be shaped, the line stopped, and no composite was obtained .: Evaluation results Table 3 shows:

Hereinafter, the method and apparatus for producing a coated composite of the present invention will be specifically described based on examples and referring to a useful comparative example as the case may be. However, the present invention is not limited in any way by these examples: 7

26

[Example 12]-

This Example 12 formed a coated composite using an apparatus as shown in FIGS. 3 and 4.

Three glass fiber orifices filled with molten maleic anhydride modified polypropylene [MFR (230R; 21.18N) 100g / 10min] adjusted to a temperature of 270: C The fiber was fed into an open fiber impregnation tank and was continuously impregnated at a take-off speed of 15 _m / min: As a single bing, an average single fiber diameter of 17 μm and a tex number of 2300 g / kni was used:

The melted reforming port The three rovings impregnated with pyrene pass through an inside die with an internal diameter of 2 and Omni, which is provided at the outlet of the fiber opening impregnation tank, and then pass through an air-cooled tank, where the surface temperature rises. Is adjusted below 1 25 ^: C:

In addition, the three rovings are made of steel with an inner diameter of 2.2mni and 2.0mm, respectively, and a width of Omm, controlled at a temperature of 30 ^: C, and arranged at intervals of 40mni. By sequentially passing through each of the shaped cooling slits, three composites (33) were obtained.

Next, a molten resin tank (36) was set up on that line, and three of the obtained composites (33) were passed through a 2.2mm φ inlet nozzle (31), respectively, and heated and melted at 270C. The melted resin (35) [Vitrocene 352 (MI 30g / 10min)] was attached to the periphery of the composite (33), and a 3.5mra φ outlet nozzle (32) was attached at 15m / After passing through at a speed of min, the mixture was passed through a cooling bath to obtain a coated composite (34) of 3 の φ.

The molten resin tank (36) has a size of 200mmW x 80mm LX lOOmmH, and has 2.2mm φ inlet nozzles (31) on the opposing sides and 3 3.5mm φ outlet nozzles (32) It has three holes and the upper part is opened to prevent resin pressure .: A heater is attached around the molten resin tank (36) so that the resin temperature can be secured. Natsu is—

In addition, the resin supply to the molten resin tank (36) is based on the fact that the liquid level of the molten resin (35) The molten resin (35) was dropped from the open upper part so that it would not be lower than lOmra above (33).

The obtained coated composite (34) was cut to a fixed size, weighed, and the adhesion amount of the molten resin (35) was determined. As a result, the variation in the coating amount among the three composites (33) was excellent within 5%:

[Example 13]

The composite (33) of Example 12 was replaced with a linear product made of a pyrene resin (33) having a diameter of 4 mm and passed through an inlet nozzle (31) having a diameter of 4.2πιηη, and each of the composites (33) was 270 °. While adhering the molten resin (35) [Petrocene 35 2 (Μ. 30 g / 10min)], which was heated and melted, to the periphery of the linear object (33), the outlet nozzle of 5.5πιπιφ (32) ) At a speed of 15 m / min, and then passed through a cooling bath to obtain a coated linear object (34) of Omra φ-The obtained coated linear object (34) was reduced to a fixed size. After cutting, the weight was measured, and the adhesion amount of the molten resin (35) was determined. As a result, the variation in the coating amount among the three linear objects (33) was excellent within 5%.

Claims

The scope of the claims _

1. A long-fiber-reinforced thermoplastic resin-coated composite consisting of a core material, which is a thermoplastic resin composite reinforced in the longitudinal direction with reinforcing fibers, and a thermoplastic resin coating that covers the peripheral surface of the core material. The core material has a reinforcing fiber content of at least 10% by weight, the core material has an average diameter or average thickness of 3 mm or more, and the coating has an average thickness of 0.3 mm to 1 mm. .5 mm long fiber reinforced thermoplastic coated composite:

2. Define two similar and different test areas (Dzl, Dz2) in a unit area (Tz) randomly set in the cross section of the core material, and penetrate each test area. The content (Cl, C2) of the reinforcing fibers to be obtained is calculated for the three unit regions (Tzl, Tz2, and Tz3), and the obtained content (C11, C12, C12) is determined. C21, C22, C31 and C32) are all within the range of Mc ± 3a [Mc: arithmetic mean value, σ: standard deviation]. The long fiber reinforced thermoplastic resin-coated composite according to claim 1, wherein:

3. One area (Dzl) of the test area defined in the unit area (Tz) is 0.1 mm

^3. The long fiber reinforced thermoplastic resin-coated composite according to claim 1 or ² , wherein the other area (Dz2) is 1πιπτ ′.

4. When the thermoplastic resin in the coating part is 80 mol% or more of propylene unit, ethylene,

1 - butene, 4-methyl - Bok pentene, 1-Okuten the least one and selected from Bok decene alpha - Orefi emission unit 2 () mol ^_0/0 below the crystalline polybutenyl port arsenide les emissions formed by The long fiber reinforced thermoplastic resin-coated composite according to any one of claims 1 to 3, which is a resin.

5. The long fiber reinforced thermoplastic resin-coated composite according to any one of claims 1 to 4, wherein the outer wall surface of the core portion and the inner wall surface of the coating portion are substantially slidably in contact with each other.

6. In the long fiber reinforced thermoplastic resin composite reinforced in the longitudinal direction with the reinforcing fiber, the content of the reinforcing fiber was 10 to 80% by weight, and the composite was cut at right angles to the longitudinal direction. The long fiber-reinforced matured plastic composite having an average cross-sectional diameter of 3 mm or more and an average deviation of the diameter of 0.10 or less:

7. The content of reinforcing fibers in the core is 1 () to 80% by weight. /. The long fiber reinforced thermoplastic according to claim 1, wherein an average diameter of a cross section when the core material is cut at a right angle to a longitudinal direction is 3 mm or more and an average deviation of the diameter is 0.10 or less.榭 Resin-coated composite:

8. Introduce the reinforcing fiber into the open fiber impregnation tank, impregnate it with the molten thermoplastic resin, and then pull it out of the die at the outlet of the open fiber impregnation tank. While cooling the fibers for use so that the surface temperature is within the crystallization temperature range of the thermoplastic resin, the fibers are passed through at least two or more shaped cooling slits within the temperature range. A method for producing a long fiber-reinforced thermoplastic resin composite having a fiber content of 10 to 80% by weight and an average diameter of 3 mm or more.

9. When shaping and cooling by passing through the plurality of shaping cooling slits, the diameter of the shaping cooling slit closest to the opening and impregnating tank is farthest from the opening and impregnating tank. 9. The method for producing a long-fiber-reinforced thermoplastic resin composite according to claim 8, wherein the diameter is larger than the diameter of the shaped cooling slit.

10. Melting to cover thermoplastic resin composite reinforced in the longitudinal direction with reinforcing fibers In the resin tank, an inlet nozzle into which the composite is introduced and an outlet nozzle through which the coated composite coated with the molten resin and the molten resin filled in the tank are sent out are linear. The resin pressure in the tank is about the same as the liquid level head pressure of the molten resin, no forcible pressure is applied, and the thickness of the coating is regulated by the size of the outlet nozzle. How to make the body.

11. The method for producing a long-fiber thermoplastic resin-coated composite according to claim 10, wherein at least two or more composites are simultaneously coated in 1 1.1 molten resin tanks.

1 2. One or more inlet nozzles are located on the side of a box-shaped molten resin tank with an open top, and one or more outlet nozzles are located on the opposite surface. Equipment for manufacturing long-fiber thermoplastic resin-coated composites located on one straight line with the inlet nozzle.