JPH1110643A - Continuous fiber-reinforced thermoplastic resin structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent impregnability and dispersibility of continuous fiber reinforcing material by non-contact or contact type melt pultrusion molding reinforcing composition containing specific filler and specific continuous fiber reinforcing material. SOLUTION: Reinforcing composition containing 0.01 to 60 wt.% of filler having new Mohs' hardness of 4.0 or less as functional filler and 10 to 80 wt.% of reinforcing material having a mean size of 3 to 21 μm as continuous fiber reinforcing material in thermoplastic resin is contact or non-contact type melt pultrusion molded. Thus, continuous fiber reinforced-thermoplastic resin structure in which the continuous fiber reinforcing material dispersed in a structure is uniformly wetted by thermoplastic resin composite containing the functional filler and the continuous fiber reinforcing material is aligned substantially in parallel in substantially the same length in a lengthwise direction of a continuous structure part is molded. As the thermoplastic resin, crystalline polyolefin resin is used, and as the functional filler, calcium carbonate is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composite containing a functional filler and having a melt flow rate (MFR) of 80 measured according to the following standards.
g / 10min or more of the composite, introduced into the melt-drawing type fiber-opening impregnation device, and while the thermoplastic fiber composite uniformly wet the continuous fiber reinforcement, the continuous fiber reinforced thermoplastic resin structure (Sometimes abbreviated as “structure of the present invention”).

Here, the above-mentioned standard is a standard defined in JIS K7210 corresponding to a kind of thermoplastic resin generally used, and is propylene-based or higher (consisting of a monomer having three or more carbon atoms). Is a measured value (g / 10 min) at a melt flow rate [MFR (230 ° C .; 21.2 N)] for the thermoplastic resin, and a melt index [MI (190 ° C .; 21.2 N) for an ethylene-based thermoplastic resin. N)] defines the melt fluidity of the material by the measured value (g / 10 min).

[0003] The continuous fiber reinforced thermoplastic resin structure of the present invention is a thermoplastic resin composite matrix in which continuous fiber reinforced materials are arranged in substantially the same length in the length direction and substantially parallel. The continuous fiber reinforced thermoplastic resin structure of the present invention has excellent moldability, and the obtained molded article has excellent mechanical properties. It is interpreted that the reason is that the continuous glass fiber and the functional filler are uniformly dispersed in the molded article.

[0004] As a means for realizing this, in addition to selecting and blending a functional filler having an appropriate new Mohs hardness, selecting a resin having a suitable melt flow rate (MFR) as its base resin, and adding continuous fiber. As a means for opening and impregnating the reinforcing material, a die of a drawing method may be selected. The present inventors have found that according to the method of the present invention, the resulting structure can be operated for a long period of time while maintaining a high level of production stability even at high speed take-off.

[0005]

2. Description of the Related Art Conventionally, a fiber-reinforced composite material (base resin) using a thermosetting resin as a matrix has been used as a main material for various molding materials and the like. However, the toughness of the molded product,
Fiber-reinforced composite materials using a thermoplastic resin as a matrix have begun to attract attention from the viewpoints of storability and cycleability, and have been actively developed in recent years. However, it is difficult to impregnate the reinforcing fibers because the thermoplastic resin generally has a high melt viscosity. Therefore, various measures for avoiding these difficulties have been developed.

[0006] The above measures include, for example, a mixed fiber method in which a fiberized thermoplastic resin is uniformly mixed with reinforcing fibers, a method in which a thermoplastic resin powder is dispersed between reinforcing fibers, and a continuous fiber reinforcing material. Is introduced into the opening and impregnating device, and the composite in which the molten thermoplastic polymer is directly impregnated between the opened fiber reinforcements is drawn to the downstream side through a shaping die and shaped. An open fiber impregnation method has been developed.

[0007] Among the above methods, the melt drawing method is generally used, in particular, because of the short molding time and the relatively simple molding process. As a method of this melt drawing (spreading impregnation), a resin is melted by an extruder and then supplied to an impregnation die, and as a means for impregnating the reinforcing fibers therein, means for providing various protrusions in the impregnation die Alternatively, a pin provided to cross the flow path of the molten resin may be used. In this type of spread impregnating apparatus, the continuous fiber bundle to be spread is squeezed while orbiting the protrusion under tension, thereby performing the fiber opening of the bundle and impregnation of the resin between the fibers of the spread material. Is the way.

However, the conventional melt drawing method has the following problems. In other words, various resins used as the base material are hindered by the high viscosity developed during melting, which causes problems such as poor impregnation of the molten resin into the spread fiber or difficulty in improving the production speed.

As a measure for solving the above-mentioned problem of impregnation failure, JP-A-63-37694 employs a thermoplastic resin having a melt viscosity lower than 100 Ns / m ² when the shear rate is zero. ing.

On the other hand, in the existing method called “integral pultrusion molding method”, a continuous fiber reinforcement and a functional filler are used in combination in a matrix by a melt drawing method. Uniform dispersion involves considerable difficulties compared to the case of a continuous fiber reinforcement alone (non-filler). This can be attributed to the fact that the viscosity of the resin becomes extremely high as a result of the thickening action of the resin caused by the addition of the functional filler to the resin.

Further, the frictional resistance between the resin, the continuous fiber reinforcing material, and the functional filler increases due to the thickening effect of the addition of the functional filler. As a result, the continuous fiber reinforcement is not significantly damaged (damaged) in the opening and impregnating device (die), and the continuous fiber reinforcement generates fluff. It leads to a line stop (operation interruption) due to thread breakage. Due to this, it has been found that there is still a difficulty in stably producing a continuous fiber reinforced thermoplastic resin structure by a method of consistently drawing and molding a thermoplastic resin containing a functional filler. .

[0012] In addition to the fact that the above-mentioned problems are piled up in the integrated pultrusion method of a thermoplastic resin containing a functional filler, it is difficult to solve the problems. Prior literatures have described attempts to use functional fillers in combination.
The following describes each of the prior art documents in detail: (R1) Japanese Patent Publication No. Sho 63-37694 and its decision (refer to Japanese Patent Application Publication No. Hei 2-17153). bundle is passed in contact under tension spreader surface, as a low melt viscosity thermoplastic polymer at a location of the nip formed by the reinforcing fiber bundle and spreader, exist of less than the melt viscosity 100 Ns / m ² There is provided a method of performing impregnation in such a manner.

Knowledge of (R1): According to this method, a one-way reinforced resin structure excellent in impregnation can be obtained. In the claims, examples and text of the ruling, the viscosity of the resin to which the filler was added was not specified, and it was purported that the thermoplastic resin containing the functional filler was subjected to consistent drawing. No reports were found. In addition, since it is difficult to perform consistent pultrusion of a thermoplastic resin containing a filler in the above-mentioned method, when a filler and a reinforcing fiber are used in combination, a continuous fiber The desired composition is realized by blending the pellets with pellets containing no filler and containing continuous fibers.

However, in this blending method, even if various modifications are made to the length and shape of the pellet, the problem of classification (generation) still remains, and it has been found that there is a problem of variation in the physical properties obtained therewith. did.

This publication discloses fiber reinforced pellets having a length of 2 to 100 mm, comprising a low molecular weight thermoplastic polymer and at least 30% by volume of reinforcing filaments arranged in parallel. And further comprising a blend with a thermoplastic polymer having a higher molecular weight than the polymer of the fiber reinforced pellets and which may be the same or different from the polymer of the reinforced pellets. .

(R3) JP-A-3-13305 This publication discloses mixing fiber-reinforced thermoplastic resin pellets with thermoplastic pellets having a lower melting or softening temperature than the resin pellets or a higher melting index than the resin pellets. Disclosed are thermoplastic pellet mixtures.

(R4) Japanese Patent Application Laid-Open No. 4-316807 This publication discloses a fiber reinforced resin core in which reinforcing fibers are substantially arranged in the longitudinal direction of a pellet and a fiber non-reinforced fiber made of the same resin as the resin constituting the core. A continuous fiber reinforced resin pellet composition having a two-layer structure composed of a resin sheath is disclosed.

Knowledge of (R2, R3 and R4) The method of R2 and R3 is a method of blending continuous fiber reinforced pellets and pellets with or without filler to adjust the content of continuous fiber to an arbitrary value. The method cannot solve the problem of classification even if the length and shape of the pellets are variously modified as described above. In addition, there is a problem of variation in physical properties.

R4 is said to be capable of being specialized by being capable of containing a filler in the resin sheath portion, and is also excellent in dispersibility. However, the claims and examples do not disclose any examples of addition in the form of fillers, and do not disclose any production methods.

According to this method, the variation in physical properties associated with classification can be solved to some extent as compared with the blending method, but it is not sufficient. In this coating method, macroscopically, the continuous reinforcing fibers and the functional filler seem to be uniformly dispersed, but microscopically, the continuous reinforcing fibers and the functional filler are uniformly dispersed. Not. With the microscopic uneven dispersion, uneven dispersion of the fiber reinforcing material and the functional filler occurs. Accordingly, there arises a problem of physical property variation.

[0021]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a continuous fiber reinforced thermoplastic resin structure having the above characteristics. A second object of the present invention is to enable consistent pultrusion of a thermoplastic resin containing a functional filler, which has been considered impossible in the past.

A third object of the present invention is to eliminate the various disadvantages often associated with the above-mentioned prior art, and to obtain a thermoplastic resin and a functional filler and a continuous fiber reinforcement in the obtained continuous fiber reinforced thermoplastic resin structure. It is an object of the present invention to provide an integrated pultruding technique for a thermoplastic resin containing a functional filler, which has excellent impregnating properties and dispersibility of a material, and can continue operation for a long period of time while maintaining a high level of production stability even at high-speed drawing.
In detail, the purpose of the present invention is the key point of the continuous pultrusion molding technology of the thermoplastic resin containing the functional filler, which is the technical content of the present invention described above, a functional filler with an appropriate new Mohs hardness, the melt flow rate of the resin and It is to provide a drawing method.

[0023]

DISCLOSURE OF THE INVENTION The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention: That is, the present invention provides a novel filler as a functional filler in a thermoplastic resin. Filler with Mohs hardness of 4.0 or less 0.01-60
% By weight, average diameter of 3 to 21 μm as continuous fiber reinforcement
The reinforcing composition containing 10 to 80% by weight of the reinforcing material was formed into a continuous fiber reinforced thermoplastic resin structure through a non-contact type or contact type melt drawing process, and dispersed in the structure. The continuous fiber reinforcement is uniformly wetted by the thermoplastic resin composite containing the functional filler, and the continuous fiber reinforcement is arranged in substantially the same length in the length direction of the continuous structure and substantially in parallel. Is a continuous fiber reinforced thermoplastic resin structure.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a thermoplastic resin composite containing a functional filler is preferably used as a MFR.
Using a composite of 80 g / 10 min or more, this is introduced into a melt drawing apparatus as a fiber impregnation means, and the continuous fiber reinforcement obtained by a process of uniformly wetting the continuous fiber reinforcement is substantially the same in the longitudinal direction. And a continuous fiber reinforced thermoplastic resin structure which is arranged in a substantially parallel manner with the length. The present inventors have found that these structures of the present invention are excellent in moldability, that the reinforcing glass fibers and functional fillers are uniformly dispersed in the molded article, and that they are also excellent in mechanical properties. Found.

The above-mentioned MFR is a value measured under test conditions based on JIS K7210 defined corresponding to each type of resin generally used. 21.2N (2.16kgf)
Is a measured value of the amount of resin extruded in 10 minutes when is applied, and is expressed as MFR (230 ° C .; 21.2 N). On the other hand,
The MFR measurement for 6,6-polyamide (6,6-nylon) was performed under the condition that the same extrusion pressure was applied for the same time at a temperature of 275 ° C. The measured value was [MFR (275 ° C .; 21.2N)]. Notation.

In the present invention, a functional filler having an appropriate new Mohs hardness and a base resin having an appropriate MFR (melt flow rate) are selected, and a melt drawing and forming method is selected as a means for opening and impregnating the fibers. This is a joining technique, which makes it possible to carry out the opening and impregnation of a thermoplastic resin containing a functional filler by a continuous drawing molding, which was considered to be impossible in the past.

The present inventors have found that the method of the present invention can be carried out without any trouble and the production stability is excellent. The present inventors have also surprisingly found that the use of the non-contact method disclosed in Japanese Patent Application No. 7-336177 among the melt pultrusion methods makes it difficult to use the method together with a continuous fiber reinforcement. It has been found that it is also possible to add functional fillers with a new Mohs hardness of more than 4.0.
(In the contact method disclosed in Japanese Patent Publication No. 63-37694, which belongs to the prior art, a thermoplastic resin composite containing a functional filler exceeding 80 g / 10 min MFR and exceeding 4.0 new Mohs hardness is used. However, as a result of the resistance of the resin causing breakage of the continuous fiber reinforcement, the expected pultruding is difficult).

The continuous fiber reinforced thermoplastic resin structure used in the present invention is mainly composed of the following specific thermoplastic resin, functional filler and continuous fiber reinforced material. Each component is now described below:

(1) 0.01-60% by weight of a filler having a new Mohs hardness of 4.0 or less as a functional filler in a thermoplastic resin, and a reinforcing material 10-80 having an average diameter of 3-21 μm as a continuous fiber reinforcing material. % By weight of the reinforcing composition containing the reinforced thermoplastic resin is formed into a continuous fiber reinforced thermoplastic resin structure through a contact or non-contact type melt drawing process, and the continuous fiber reinforced material dispersed in the structure is obtained. Continuous fiber reinforcement which is uniformly wetted by a thermoplastic resin composite containing a functional filler, and wherein the continuous fiber reinforcement is aligned in substantially the same length in the length direction of the continuous structure portion and substantially in parallel. Thermoplastic resin structure.

(2) When the thermoplastic resin composite containing a functional filler used as an auxiliary agent for uniformly wetting the continuous fiber reinforcing material has an MFR of 80 when measured according to the following standard:
The continuous fiber-reinforced thermoplastic resin structure according to the above item 1 having a g / 10 min or more: [where the MFR is measured under test conditions based on JIS K7210 corresponding to a commonly used resin. Value.]

(3) A thermoplastic resin having a new Mohs hardness of 8.0 or less as a functional filler in an amount of 0.01 to 60% by weight.
And 10 as an average diameter of 3 to 21 μm as a continuous fiber reinforcement.
８０80% by weight of a continuous fiber reinforcing material, and in a fiber impregnating device, the continuous fiber reinforcing material is inserted into a predetermined gap set between an upper fiber opening pin of the device and a lower fiber opening pin which is a pair thereof. The fiber is opened by passing the fiber without being in contact with the fiber-spreading pin, and the fiber-reinforced continuous fiber that has been spread is uniformly wetted by the thermoplastic resin composite containing the functional filler, and Item 3. The continuous fiber-reinforced thermoplastic resin structure according to the above item 1 or 2, wherein the fiber reinforcements are arranged in substantially the same length in the length direction of the continuous structure portion and substantially in parallel.

(4) MFR8 of a thermoplastic resin composite containing a functional filler used as an auxiliary agent for uniformly wetting the continuous fiber reinforcement was measured according to the following standards.
The continuous fiber reinforced thermoplastic resin structure according to the above item 3, wherein the MFR is 0 g / 10 min or more: [The above MFR is determined by a test apparatus and conditions specified in JIS K7210 in accordance with a generally used resin type. Measured value].

(5) A molded article obtained by using the structure according to any one of the above items 1 to 4 as a continuous fiber reinforced thermoplastic resin structure.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION

<Thermoplastic resin (A)> As the thermoplastic resin (A) forming the continuous fiber reinforced thermoplastic resin structure used in the present invention, an open fiber of a continuous fiber reinforced material (single fiber or convergence with low convergence degree) Any material may be used as long as it is a material molten resin to be impregnated between the material and the resin. Crystalline polyolefin resin, for example, polyethylene, crystalline polypropylene, etc., thermoplastic polyamide resin (nylon; NL), for example, 6-polyamide (6-nylon), 6,6-polyamide (6,6-nylon), 6,
10-polyamide (6,10-nylon), 6,12-polyamide (6,12
-Nylon), 11-polyamide (11-nylon), 12-polyamide (12-nylon), polyamide-MXD6 (nylon-M
XD6; a co-condensation polymer of m-xylylenediamine and adipic acid), an acrylic (co) polymer such as an acrylonitrile-styrene copolymer (AS), an acrylonitrile-styrene-butadiene copolymer (ABS), etc. Among the thermoplastic polyester resins, polyalkylene terephthalates such as polyethylene terephthalate (PET) or poly-1,4
-Butylene terephthalate (PBT) and the like, and polycarbonate (PC).

As an example of the above, 6-polyamide (6-NL)
It is also possible to form a resin composition from a plurality of different types of resins such as a resin composition of polypropylene and polypropylene (PP), and use this resin composition as a thermoplastic resin base material.

Among the above crystalline thermoplastic resins (A),
For ordinary applications, polyolefin (crystalline) resins are frequently used from the viewpoints of properties and price. As polyolefin resins, α-olefins having usually about 2 to 10 carbon atoms
(1-olefin) crystalline homopolymer or crystalline copolymer or composition of two or more crystalline homopolymers, composition of two or more crystalline copolymers or one or more crystalline This is a concept including a composition of a homopolymer and one or more crystalline copolymers.

Examples of the above-mentioned "α-olefin having about 2 to 10 carbon atoms" include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene, etc., and not limited to one type, but may be a combination of two or more types.

Crystalline polyolefin (“crystalline poly-α-
Among olefin resins), crystalline polypropylene resins are the most versatile in practical use. In addition, polyethylene resin is most suitable for low temperature use, and poly-4-methyl-1-pentene resin is suitable for use where high temperature use is desired.

Further, the polyolefin resin used in the present invention may be a modified product. For example, when polypropylene is used, it may be a dicarboxylic acid, preferably maleic acid or the like, which is a modifier for imparting hydrophilicity. It is often preferred to use a modified product of the acid anhydride, preferably maleic anhydride or the like.

In the present invention, when a modified resin is used as the thermoplastic resin (A), the modification rate of the modified resin used, for example, the grafting rate when modifying polypropylene with maleic anhydride is as follows. Usually, it is desirable to be 1 to 10%.

For applications requiring a higher heat resistance, for example, a melting point exceeding 200 ° C., various polyamide resins or thermoplastic polyester resins are suitable. Here, as the polyamide resin, ring-opening addition polymerization type nylon, for example,
General-purpose brands such as 6-nylon and 6,6-nylon can be mentioned. When higher heat resistance is desired, a semi-aromatic polyamide resin, a wholly aromatic polyamide resin, or the like is used. A typical example of the former is "nylon MXD6", that is, a co-condensation polymer of m-xylylenediamine and adipic acid, and a typical example of the latter is a co-condensation polymer of m-xylylenediamine and terephthalic acid. And other wholly aromatic polyamide resins. The latter is trade name "Kelimide"
It is commercially available as

As the polyester resin, a co-condensed polymer of an aliphatic diol and an aromatic dicarboxylic acid is practical. Among them, ethylene glycol (or “ethylene oxide; ethylene oxide”) and terephthalic acid ("Polyethylene terephthalate"; abbreviation "PET") is the most common. As a polyester having even higher heat resistance, a co-condensation polymer using 1,4-butanediol instead of ethylene glycol which is an aliphatic diol ("poly-1,4-butanediol terephthalate"; Abbreviations of “PBT”), and highly heat-resistant wholly aromatic polyesters (also called “polyarylate”), for example, those marketed under the trade name of “Kevlar” can be mentioned.

<Functional Filler (B)> Examples of the functional filler (B) forming the continuous fiber reinforced thermoplastic resin structure used in the present invention include the following: calcium carbonate, aluminum hydroxide, Magnesium hydroxide,
Talc, mica, barium sulfate, carbon black,
Kaolin, clay, molybdenum disulfide, antimony trioxide, basic magnesium sulfate, zinc sulfide, lithopone, whisker, titanium oxide, zinc oxide, iron oxide, wollastonite, glass fiber chopped strand, glass beads and glass flakes.

In order to achieve the effect of the present invention, even if the functional filler (B) other than the above examples has a new Mohs hardness of 8.0 or less, preferably 5 or less, the thermoplastic resin The functional filler is not particularly limited as long as it is a functional filler that can be usually added. The functional filler (B) may be a single type or a combination of two or more types. Further, the functional filler surface-treated with a coupling agent such as a silane-based, titanate-based, boron-based, aluminate-based or zircoaluminate-based surface-treating agent may be used.

<< New Mohs Hardness >> The new Mohs hardness of each of the inorganic compounds described above is shown. The new Mohs hardness is a numerical value of the hardness of a filler measured by a Mohs hardness meter. The hardness of talc is set to 1, and the hardness of diamond is set to a maximum of 15. This hardness is a measure proposed to compare and indicate the hardness of minerals. In other words, the scratches are made softer by scratching each other, which is a kind of scratching. Therefore, a conventional Mohs hardness meter is used for the measurement.

The new Mohs hardness of the functional filler (B) shown above is, for example, as follows (the number following the substance name is the new Mohs hardness value): calcium carbonate 3.0, aluminum hydroxide 3.0, hydroxide Magnesium 3.0, Talc 1.0, Mica 2.5-3.5, Barium sulfate 3.0, Carbon black 1.
0-2.0, kaolin clay 2.0, molybdenum disulfide 1.5, antimony trioxide 2.5, basic magnesium sulfate 2.5, zinc sulfide 3.5, lithopone 3.0-3.5, whisker 4.0, titanium oxide
(Anatase type) 5.5-6.0, titanium oxide (rutile) 7.0-7.
5, zinc oxide 5.0, iron oxide 5.5-6.5, wollastonite 4.
5, glass fiber chopped strand 7.0, glass beads
7.0, glass flake 7.0.

The amount of the functional filler is 0.01-6.
0% by weight, preferably 0.02 to 50% by weight. When the amount is less than 0.01% by weight, the effect of adding the functional filler is not improved, and when the amount exceeds 60% by weight, breakage of the fiber reinforcing material is observed, mechanical strength is reduced, and impact properties are reduced. Causes poor appearance and poor appearance. Actually, there is an appropriate compounding amount depending on the purpose of use of the functional filler, but if it is 0.01 to 60% by weight as defined in the claims of the present specification, the purpose of all the functional fillers is To achieve. Also, when the value falls below or exceeds the lower limit defined in the claims, when the reinforcing effect of the functional filler is insufficiently exhibited, or conversely, the fiber reinforcing material is broken. This causes a problem that the reinforcing effect of the fiber reinforced material is insufficient.

The functional fillers are classified according to their uses, for example, as follows: ◆ Colorant fillers include barium sulfate, carbon black, zinc sulfide, lithopone, titanium oxide (anatase type), and titanium oxide (rutile type). , Iron oxide, zinc oxide, etc. ◆ As reinforcing fillers, glass fiber chopped strands, glass beads, glass flakes, aramid fibers, carbon fibers, wollastonite, potassium titanate,
Zonotorite, basic magnesium sulfate, talc, mica, etc. ◆ As fillers for increasing the amount, calcium carbonate, talc,
Clay, silica and the like; ◆ The fillers for imparting special functions are subdivided into, for example, the following: Carbon black, graphite,
-Carbon fiber, tin oxide, zinc oxide, etc .;-Mica, graphite, potassium titanate, zonolite, carbon fiber, etc. as damping fillers;-Baum sulfate, etc. as sound insulating filler;-Sliding filler , Graphite, molybdenum sulfide, talc, etc.;-As light scattering and reflecting fillers, titanium oxide, glass beads, calcium carbonate, etc.;-As heat ray radiating fillers, magnesium oxide, hydrotalcite, basic magnesium sulfate, etc .; -Flame retardant fillers include antimony oxide, aluminum hydroxide, magnesium hydroxide, zinc carbonate, hydrotalcite, dawsonite, etc .;-Radiation protective fillers such as barium sulfate;-UV protective fillers include titanium oxide and oxidized. Zinc, iron oxide, etc .; as dehumidifying (water) fillers, calcium oxide, The presence or absence.

<Blending Amount (Content) of Functional Filler> One example of a suitable blending amount of the coloring agent functional filler is shown below.
<> The compounding amount of the colorant filler is 0.01 to 20% by weight, preferably 0.02 to 15% by weight. This compounding amount is 0.
When the content is less than 005% by weight, the coloring effect becomes insufficient,
If the content is more than 25% by weight, the molded article becomes unduly heavy and, in addition, the coloring effect cannot be improved by adding a large amount, which is uneconomical.

A thermoplastic resin composition used for uniformly wetting the surface of a continuous fiber reinforcing material by a melt pultrusion method, wherein the functional filler described above is incorporated into the thermoplastic resin described above. The appropriate melt flow index of the thermoplastic composite containing is a melt flow rate (MFR) measured under test conditions for each resin generally used based on JIS K7210, and is 80 g / 10 min or more, preferably 100 g or more. / 10min to 400g / 10min.

The appropriate melt flow index (MF) of the thermoplastic composite
When R) is 60 g / 10 min or less, the dispersion of the functional filler and the continuous fiber reinforcement in the thermoplastic composite becomes non-uniform because the appropriate melt flow index of the thermoplastic composite is too high. In addition, it becomes difficult to continue high-speed pick-up operation while maintaining a high level of production stability. The cause lies in the generation of fluff and breakage of yarn. If the proper melt flow index of the thermoplastic composite is abnormally high, the appropriate viscosity of the thermoplastic composite should not exceed 1000 g / 10 min to prevent the loss of various properties expected of the molten resin. You need to control.

Test conditions for each resin generally used based on JIS K7210 used in the present specification are shown below: For polyethylene resin, a test temperature of 190 ° C. and a test load of 21.2 N (2.16 kgf ), ・ For polypropylene resin, test temperature 230 ° C, test load 21.2N (2.16kgf) ・ For acrylic resin, test temperature 230 ° C, test load 2
1.2N (2.16kgf), ・ For polyamide resin, test temperature 230 ° C, test load 21.2N (2.16kgf) ・ For 6-nylon, test temperature 275 ° C, test load 21.2N
(2.16kgf), ・ ・ For 6,6-nylon, test temperature 280 ° C, test load 21.2N
(2.16kgf), ・ For polycarbonate, test temperature 280 ° C, test load 21.
It is 2N (2.16kgf).

<Means for Achieving the Appropriate Melt Flow Index> In order to achieve the above-mentioned appropriate melt flow index, for example, a molecular weight depressant may be added to the base thermoplastic resin. The molecular weight depressants that can be used are listed below for each resin:-As organic peroxides useful for polyolefin-based resins, for example, benzoyl peroxide (BPO), dicumyl peroxide (DCPO), 2,5-dimethyl ( t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, and the like.-As a molecular weight depressant useful for polyamide resins, for example, adipic acid.

<Continuous fiber reinforced material (long fiber reinforced material)> The continuous fiber reinforced material constituting the continuous fiber reinforced thermoplastic resin structure of the present invention usually has an average fiber length of 3 to 30 mm, preferably 5 to 25 mm. And a single fiber constituting the reinforcing material has an average diameter (average fiber diameter) of 3 to 21 μm, preferably 9 to
２１21 μm, and they are about 500-400
It is provided as a bundle of about 0 bundles.

When the average fiber diameter of a single fiber is 2.5 μm or less, fiber breakage is apt to occur during molding, and the impact strength of the obtained molded product is insufficient. On the other hand, if the average fiber diameter of the single fibers is 22 μm or more, the resulting molded article has poor appearance and the mechanical strength of the molded article is insufficient.

This continuous fiber bundle is usually called "roving". Furthermore, these rovings etc.
It can also be used in the form of two or more yarns. The compounding amount of the glass versatile fiber which is the most versatile as a continuous fiber reinforcing material is 10 to 80% by weight, preferably 20 to 80% by weight, based on the whole composition.
60% by weight. 5% by weight of glass continuous fiber
In the case where it is below, the effect of improving various physical properties such as tensile strength, bending strength, rigidity and heat resistance of the obtained molded product is too small. On the other hand, when the blending amount of the continuous glass fiber is 85% by weight or more, the obtained molded product has low moldability, and the molded product has poor appearance.

In the present invention, it is necessary that the continuous fiber reinforcing material is aligned substantially parallel to the major axis in the columnar body, and that the length is substantially the same as the length of the columnar body. This type of continuous fiber reinforced columnar body can be obtained by, for example, a method described below using a fiber reinforced material (fiber bundle) provided in a substantially endless form.

The continuous fiber reinforcement meeting the above conditions can be roughly classified into inorganic fibers and organic fibers. ◆ Examples of the inorganic fibers include glass (silicate glass; silicate glass) fibers, carbon fibers, (fused) quartz fibers, (natural) mineral fibers such as rock wool, and artificial fibers such as metal fibers. Among them, glass fiber is the most widespread fiber reinforcing material in view of both physical properties and price.
The disadvantages are that they are relatively heavy (unfavorable in specific strength), are easily broken, and are susceptible to alkalis. On the other hand, carbon fiber is the highest in lightness, especially in specific strength. There is hardly any comparable application in applications where weight and specific strength are more important than price.

These inorganic fiber reinforcing materials may be used alone or in combination of two or more thereof. Further, the surface of the inorganic fiber reinforcing material may be treated with a surface treatment agent such as a coupling agent (for example, at least one of a silane-based, titanate-based, boron-based, aluminate-based, and zircoaluminate). good.

Among the fiber reinforcing materials, the most useful glass fiber for ordinary use is selected as a general-purpose example, and the present invention will be described later. The material of the glass fiber selected as a representative continuous fiber reinforcing material constituting the continuous fiber reinforced modified propylene resin structure of the present invention is usually hard glass (potassium glass commonly known as "E glass") or the like. Examples thereof include silicate glass (silicate glass) and borosilicate glass (borosilicate glass) which is a heat-resistant glass. Examples of the organic fiber meeting the above conditions include, for example, a wholly aromatic polyamide (trade name: aramid) fiber having excellent mechanical and heat resistance, and a semi-aromatic polyamide fiber such as nylon MXD6, PET
(Polyethylene terephthalate) fiber, PBT (poly-1,4-
(Butylene terephthalate) fiber, wholly aromatic polyester
(Eg, trade name: Kepler) fiber and the like. These may be used alone or in combination of two or more thereof.

As a molding method similar to the melt drawing method for producing the continuous fiber reinforced thermoplastic resin structure of the present invention, there is a contact-type melting drawing method represented by JP-B-63-37694. Molding method, Japanese Patent Application No. Hei 7-33617
No. 7 non-contact type melt pultrusion molding method.

The contact-type melt drawing method is most suitable for the embodiment using a functional filler having a new Mohs 'hardness of 4 or less, and the non-contact type melt drawing method is a functional filler having a new Mohs' hardness of 8. It is most suitable for the mode using the thing of 0 or less.

However, even in the case of the contact-type melt pultrusion molding method, it is a thermoplastic resin composite containing a functional filler having a new Mohs' hardness of 4 or more, and has an appropriate melt flow index index of 80 g. If a material having a length of / 10 min or more is used, pultruding becomes difficult, contrary to expectations. The cause is hampered by slight resistance of the resin, and is required to cause breakage (breakage or the like) of the continuous fiber reinforcement. That is, a high-speed take-off operation while maintaining a high level of production stability cannot be continued for a long period of time. The cause is required for generation of fluff and yarn breakage.

On the other hand, even in the case of the non-contact type melt pultrusion molding method, the new filler has a new Mohs hardness of 8 as a functional filler.
When a thermoplastic resin composite containing the above-mentioned thermoplastic resin having an appropriate melt flow index of 80 g / 10 min or more is used, pultruding becomes difficult contrary to expectations. The cause is hampered by slight resistance of the resin, and is required to cause breakage (breakage or the like) of the continuous fiber reinforcement. That is, also in this case, the high-speed take-off operation while maintaining a high level of production stability cannot be continued for a long period of time. The cause is required for generation of fluff and yarn breakage.

Here, the contact-type melt drawing method is
Usually, the continuous glass fiber bundle is opened in a staggered circular contact with the surfaces of a plurality of opening means arranged in series from the upstream side to the downstream side in a melt drawing apparatus equipped with an opening impregnation function. This is a method for producing a resin structure reinforced with a continuous fiber reinforcement by impregnating a molten thermoplastic resin composite (containing a functional filler) between the opened continuous fiber reinforcements while spreading.

In addition to the above, the contact-type melt pultrusion method is not limited to the method described above.
No. 64326, Japanese Patent Publication No. 5-68327, Japanese Patent Application Laid-Open No. 4-278311, Japanese Patent Application Laid-Open No. 6-254857, Japanese Patent Application Laid-Open No. 6-91645,
JP-A-6-143440, each method shown in JP-A-63-132036 and JP-A-1-208118, that is, a method of opening the fiber bundle by contacting a pin or a convex portion, A fiber opening method in which the fiber bundle is tensioned and brought into contact with a roll, the fiber bundle is passed through an S-shaped die under tension, and the fiber bundle is brought into contact with the S-shaped portion, and the fiber bundle is moved up and down in a roll. Method of mechanically impregnating the resin between the fibers by pressing with
Any method of mechanically opening and impregnating the fiber bundle by pressing the fiber bundle from above and below with a combination of a convex roll and a concave roll may be used. Further, the contact-type melt drawing method is not limited to the method described above. The non-contact type melt drawing method (non-contact type fiber opening impregnation method) means that a continuous glass fiber bundle is usually set at a predetermined gap set between an upper fiber opening pin and a lower fiber opening pin which is a pair thereof. The fiber is opened by passing it without contacting any of the fiber opening pins, and continuous by fully impregnating the molten thermoplastic resin composite (containing functional filler) between the opened continuous fiber reinforcements. This is a method for producing a resin structure reinforced with a fiber reinforcing material.

In the composition of the present invention, various additives, antioxidants, light stabilizers, clarifying agents, nucleating agents, lubricants, antistatic agents, antifogging agents, which are usually added to the thermoplastic resin, An anti-blocking agent, a drip-free agent, a dispersant such as metal soap or a neutralizing agent can be used in combination within a range not to impair the object of the present invention.

[0068]

The continuous fiber-reinforced thermoplastic resin structure of the present invention is based on a resin having a high MFR and exhibits the following various effects by the MFR adjusted by adding a specific functional filler to the resin. The molded article has, in addition to the above effects, another excellent property: (1) excellent moldability (evaluated by "impregnating property") (2) long fiber reinforcement in the structure In the same direction, the fillers are arranged in parallel with the same length on average, and the functional fillers are also uniformly dispersed (evaluated by “dispersibility”). (3) Molded product obtained from the above structure Has excellent mechanical properties (evaluated by "bending strength").

[0069]

The present invention will be specifically described below with reference to Examples and Comparative Examples where useful. However, the invention is not limited thereby. [Test Method] (Test 1) Resin impregnating property The obtained continuous fiber-reinforced strand or rod, which is a unidirectional reinforced resin structure, is cut into a length of about 100 mm, and a section of 10 mm from one end is colored with a color indicator. After immersing for 30 minutes in a methyl red propanol solution (50 ml of a saturated solution of methyl red in propanol, the pH of which was adjusted with 1 ml of hydrochloric acid to improve the color development of methyl red), the liquid level of the color indicator was observed. did. Observation was made on ten samples, and the results were determined as follows.

Judgment condition Excellent No liquid level rise was observed in any of the samples. Good In one or two samples, the liquid level rises in a part of the cross section.

Slightly poor In 3 to 10 samples, a liquid level rise is seen in a part of the cross section. Defective A remarkable rise in liquid level over the entire cross section is observed in all ten samples. (Trial 2) Dispersibility of filler The strand or rod, which is the obtained unidirectional reinforced resin structure, is cut in a direction perpendicular to the single direction,
The cut surface was observed and evaluated with an electron microscope. [Evaluation method] (Review 1) Stable productivity (evaluated by the number of fluffs generated from the shaping nozzle): Excellent Not generated Good 1 to 5 times Slightly poor 5 to 10 times Bad 11 or more times Not possible Not possible.

(Review 2) Classification Fifty test pieces for bending test were manufactured by injection molding.
While performing the specific gravity measurement and bending test of 50 test pieces,
The variation in specific gravity and the variation in tensile strength were measured. The value obtained by subtracting the minimum value from the maximum value of the measured values was used as an index of the variation. This indicates that the classification increases as the index value increases.

(Evaluation 3) Bending strength Measured according to JIS K7203. (Evaluation 4) Measurement of specific gravity Measured according to JIS K7112.

<Continuous Glass Fiber Reinforced Thermoplastic Resin Rod Forming Method> Non-contact type melt drawing method: using a fiber impregnating and impregnating apparatus (1) shown in FIG. 1, glass fiber roving (2) [average single fiber Diameter 17μm; Tex count 2310g / km; Focusing number 4000
While the seven pieces were arranged horizontally and supplied from the slit-like fiber supply port (3) of the opening and impregnating apparatus (1), they were passed through the apparatus (1) and continuously taken from the downstream side.

On the other hand, an extruder (not shown) supplies a melt of the thermoplastic resin composite containing a functional filler into the device (1) and sufficiently impregnates the molten resin between the opened continuous fibers. I let it. As the opening means, two pairs of opening pins (4u1 and 4d1), (4u2 and 4d2), and (4u3 and 4d3) each pair of the upper opening pin (4u) and the lower opening pin
(4d) and the defined distance (H; clearance) (H41, H42
And H43) were both set to 1 mm.

The temperature in the opening and impregnating device (1) was adjusted to a predetermined value, and a resin structure reinforced in a single direction with glass continuous fibers was taken up in the form of a rod at a take-up speed of 30 m / min. Roving of glass fiber introduced into the opening and impregnating device (1)
(2) passed through a shaping nozzle (6; inner diameter 6 mm) provided at the outlet of the device (1) and was taken as a continuous glass fiber reinforced thermoplastic resin rod (7) shaped into a circular cross section. The property value of the obtained rod (7) was measured and the measurement result was evaluated.

Contact-type melt pultrusion molding method: As shown in FIG.
The same operation as in the non-contact method shown in FIG. 1 was carried out under the same conditions as in the non-contact method shown in FIG. An attempt was made to manufacture a reinforced thermoplastic resin rod (7), and its properties were measured and the measurement results were evaluated.

<Continuous Glass Fiber Reinforced Thermoplastic Resin Pellet Forming Method> ◆ Integral method: Non-contact type fiber opening impregnation apparatus (1) shown in FIG.
Roving of continuous glass fiber (2) [average single fiber diameter: 17 μm; tex count: 2310 g / km; number of bundles: 4000] One tube is installed horizontally and the upstream end wall (1 wL While passing through the slit-shaped fiber introduction port (3) formed in (1), the strand-like material impregnated and spread through this apparatus (1) was formed in the downstream end wall (1wR). It was continuously withdrawn from the downstream side via a shaping nozzle. On the other hand, an extruder (not shown) connected to a resin inlet (5) formed in the bottom of the device (1) by a pipe (not shown) has a filler-containing thermoplastic resin composite. While supplying the melt, the molten resin was sufficiently impregnated between the opened continuous fibers.

At this time, a pair of opening pins (4;
(Inclusive name) 3 pairs: (4u1 and 4d1), (4u2 and 4d2)
And (4u3 and 4d3), the defined distance (H; clearance) between each pair of the upper opening pin (4u) and the lower opening pin (4d), that is, each of H41, H42 and H43 is 1 m.
Set to m. The temperature in the opening and impregnating apparatus (1) was adjusted to a predetermined value, and a resin structure reinforced in a single direction with continuous glass fibers was taken out at a speed of 30 m / min in the form of a strand.

The roving (2) of the glass fiber introduced into the fiber impregnating and impregnating device (1) is opened in the device (1).
A shaping nozzle (outlet; 6; inner diameter 2.6 mm) perforated on the downstream end wall (1 wR) after the resin is impregnated between the obtained opened fibers
And formed into a circular cross section, and the shaped product was taken as a continuous glass fiber reinforced thermoplastic resin strand (7). After cooling, the obtained strand (7) was cut into an average length of 6 mm to obtain a pellet structure. ◆ Blending method: glass fiber roving (2) [average unit] through slit-type fiber introduction hole (3) drilled in the upstream end wall (1 wL) of the opening and impregnating device (1) shown in FIG. Fiber diameter
17μm; Tex number 2310g / km; Focusing number 4000 pieces]
One of them is set horizontally and spread while passing through this device (1), and the impregnated melted resin coming from the following resin inlet (5) is placed between the obtained spread products at the downstream end. It was continuously taken downstream via a shaping nozzle (6) drilled in the wall (1wR).

At the same time, an extruder (not shown) connected by a pipe to a resin inlet (5) formed in the bottom plate of the device (1).
Supplied a thermoplastic resin composite melt containing no filler.

At this time, three pairs of the upper and lower two opening pins mounted in the opening and impregnating device (1), that is, (4u1 and 4d
1), (4u2 and 4d2) and (4u3 and 4d3) each defined distance (H; clearance) H41, H42 between each pair of upper and lower opening pins (4u) and (4d). H4
3 were both set to 1 mm. The temperature in the opening and impregnating device (1) is adjusted to a predetermined value, and the resin structure reinforced in a unidirectional manner by continuous glass fibers is fed at a speed of about 3 in the form of a strand.
Withdrawn at 0 m / min.

The glass fiber roving (2) introduced into the opening and impregnating device (1) is a shaping nozzle (6; outlet; 1.9 mm inner diameter) formed in the downstream end wall (1 wL) of the device (1). ), And was shaped into a circular cross section. The shaped product was taken in the form of a continuous glass fiber reinforced thermoplastic resin strand (7). The obtained reinforced strand (7) was cooled and then cut into an average length of 6 mm to produce a reinforced pellet structure.

The reinforced pellet structure and the resin reinforced with 60% by weight (based on the composition) of the filler were uniformly blended in a tumbler mixer on a one-to-one basis (by weight) to obtain a molding composition. . ◆ Coating method: Using a fiber impregnating and impregnating device (1) shown in Fig. 1, roving of glass fiber (2) [average single fiber diameter: 17 µm; tex count: 2310 g / km; number of bundles: 4000] It is installed and introduced from a slit-like fiber inlet (3) drilled in the upstream end wall (1 wL) of the opening and impregnating device (1).
While passing through (1) to spread the fiber, the downstream end wall (1wR) is continuously impregnated with the molten resin supplied from the following molten resin inlet (5) between the obtained spread fibers. It was taken to the downstream side via the shaping nozzle (6) drilled in. An extruder (not shown) is connected to the molten resin inlet (5) via a pipe (not shown).

At the same time, an extruder connected by a conduit to a resin inlet (5) drilled in the bottom plate of the fiber impregnating and impregnating device (1).
(Not shown), a melt of the thermoplastic resin composite containing no filler was supplied. At this time, the upper stage of each pair of three pairs of opening pins, ie, (4u1 and 4d1), (4u2 and 4d2) and (4u3 and 4d3), mounted in the opening and impregnating device (1). The defined distance (H; clearance; H41, H42 and H43) between the opening pin (4u) and the lower opening pin (4d) was set to 1 mm.

The temperature in the opening and impregnating apparatus (1) is adjusted to a predetermined value, and the resin structure reinforced in a single direction by continuous glass fibers is fed at a speed of about 30 m / min in the form of a reinforced strand.
I took it over.

The glass fiber roving (2) introduced into the opening and impregnating device (1) is introduced from a slit-like fiber inlet (3) formed in the upstream end wall (1 wL) of the device (1). , This device
(1) The shaping nozzle (6; 1.9 m inner diameter) continuously drilled in the downstream end wall (1 wR) while passing and impregnating the fiber
After passing through m), it was shaped into a circular cross section and taken off. Taken is a continuous glass fiber reinforced thermoplastic resin strand
(7).

[0088]

Examples 1 to 9 and Comparative Examples 1 to 4 The drawing method in Examples 1 to 9 and Comparative Examples 1 to 4 and fillers used for uniformly wetting continuous glass continuous fibers The composition and MFR of the thermoplastic resin composite are shown in Table 1.

<Test pieces of Examples 1 to 4> A reinforced strand was obtained by a consistent method using the composites having the compositions shown in Table 1, and the obtained strand was chopped into a predetermined average length of 6 mm. Pellets were made. A test piece was prepared by an injection molding method using the reinforced pellet.

The compositions of the pellet structures of Examples 1 to 4 obtained above were as follows. In these pellet structures, component (A) was a maleic anhydride graft-modified polypropylene; component (B) was mica (new Mohs hardness of 3) and component (C) was glass continuous fiber. 65% by weight of component (A) and component (B)
110 g of composite MFR (230 ° C; 21.2N) with 35% by weight
/ 10 min contains 39% by weight of component (C). In Example 2, 110% / 10% MFR (230 ° C; 21.2N) of the composite with 75% by weight of component (A) and 25% by weight of (B)
n: 46% by weight of component (C). In Example 3, compound (A): 65% by weight, (B): 35% by weight, MFR of composite (230 ° C; 21.2N): 250 g / 10mi
n contains 39% by weight of the component (C). In Example 4, the compound (A) contains 65% by weight and (B) 35% by weight contains 110 g / 10mi of MFR (230 ° C .; 21.2N) of the composite.
n contains 39% by weight of the component (C).

Table 1 also shows the final composition of each test piece and the evaluation results. <Specimens of Comparative Examples 1 and 2> Reinforced strands were obtained using the composites having the compositions shown in Table 1, and were cut into predetermined average lengths of 6 mm to produce reinforced pellets. A test piece was prepared by an injection molding method using the reinforced pellet. ◇ In Comparative Example 1, 65% by weight of component (A) and component (B)
20 g / MFR (230 ° C; 21.2N) of the composite at 35% by weight
Component (C) was not contained in 10 minutes. In Comparative Example 2, the component (A) was blended at 65% by weight and (B) was blended at 35% by weight, and the composite MFR (230 ° C; 21.2N) was 60 g / 10min.
Contains 44% by weight of component (C).

<Test Pieces of Examples 5 to 8> Reinforced strands were obtained using the composites having the compositions shown in Table 1, and were cut into predetermined average lengths of 6 mm to produce reinforced pellets. did. A test piece was prepared by an injection molding method using the reinforced pellet.

The compositions of the obtained pellet structures of Examples 5 to 8 were as follows. In these pellet structures, component (A) is a maleic anhydride graft-modified polypropylene) and component (C) is a continuous glass fiber,
(B) was variously selected as follows: で は In Example 5, 65% by weight of component (A) and component (B)
35% by weight of talc (new Mohs hardness 1) containing 110 g / 10 min of MFR (230 ° C; 21.2N)
In Example 6, 65% by weight of component (A) was blended and calcium carbonate was used as component (B) (new Mohs hardness of 3.5; abbreviation "charcoal").
110 g of composite MFR (230 ° C; 21.2N) with 35% by weight
/ 10 min contains 39% by weight of component (C). ◇ In Example 7, 80% by weight of component (A) was blended, and 20% by weight of titanium oxide (new Mohs hardness 7) was blended as component (B). (230 ° C .; 21.2N) 110 g / 10 min contains 41% by weight of component (C). ８In Example 8, 65% by weight of component (A) was blended and wollastonite (new Mohs hardness of 4. 5) 35% by weight
The compound (M) (230 ° C .; 21.2N) 110 g / 10 min of the composite contains 39% by weight of the component (C).

Table 1 also shows the final composition of each test piece and the evaluation results. The compositions of the obtained pellet structures of Comparative Examples 5 to 8 were as follows. In these pellet structures, component (A) was a maleic anhydride graft-modified polypropylene; component (B) was mica (new Mohs hardness of 3) and component (C) was a glass continuous fiber. Each body was charged into an injection molding machine to form a specific gravity measurement test piece (length 60 mm × width 10 mm × thickness 3 mm) and a bending measurement test piece (length 100 mm × width 10 mm × thickness 4 mm),
After condition adjustment (23 ° C. × 48 h), specific gravity measurement and bending strength test were performed.

The obtained molding composition was charged into an injection molding machine, and a specific gravity measurement test piece (length 60 mm × width 10 mm × thickness 3 mm)
And bending test specimen (length 100mm x width 10mm x thickness 4m
m) was molded and adjusted in condition (23 ° C. × 48 h), and then subjected to specific gravity measurement and bending strength test.

[0096]

Examples 10 and 11 and Comparative Examples 5 to 8
, And 11 and Comparative Examples 5 to 8 are shown in Table 2. That is, in Examples 10 and 11, a functional filler-containing resin composite in which continuous fibers were uniformly wetted (wet) by an integrated method was produced.

In both Examples 10 and 11, the same maleic anhydride graft-modified polypropylene (A) as in Example 1 was blended at 40% by weight, and the continuous fiber reinforcement (C) was used.
In Example 10, 30% by weight of mica (new Mohs hardness 3) was blended as a functional filler (B) in Example 10 in addition to 30% by weight of glass continuous fiber.
30% by weight of talc (new Mohs hardness 1) was blended as (B) to prepare a continuous fiber-reinforced resin composite.

<Coated Reinforced Strand (7c)> In Comparative Examples 7 and 8, the obtained reinforced strand (7) is passed through a straight line of a normal crosshead die (not shown), and A molding resin (composition) reinforced with 80% by weight of a functional filler is supplied as a coating resin composition from an extruder (not shown) into a side pipe joining into a road, and the reinforced strand is formed. By forming a resin coating centered on (7), a coated reinforced strand (7c) having a predetermined glass content and filler content was obtained. After cooling, the coated reinforced strand (7c) was cut into an average length of 6 mm to produce coated reinforced pellet structures of both comparative examples.

The obtained reinforced structural body with pellets (pellet) was charged into an injection molding machine, and a specific gravity measurement test piece (length 60 mm × width 10 mm × thickness 3 mm) and a bending measurement test piece (length 100 mm ×
Form 10mm wide x 4mm thick) and adjust the condition (23 ° C x 48
After h), the specific gravity measurement and the bending strength test were performed.

The performance of the produced continuous glass fiber reinforced polypropylene composite in Example 10 was as follows: specific gravity dispersion width 0.003, bending strength dispersion width 5 MPa and average bending strength 2
In Example 11, the dispersion width of specific gravity was 0.003 and the dispersion width of bending strength was 5 MPa, but the average bending strength was 190 MPa.

In Comparative Examples 5 and 6, the same composite as in Examples 10 and 11 was produced by the blending method, and in Comparative Examples 7 and 8 by the coating method. 4
The modified thermoplastic resin (A) used in the comparative example was mixed with 40% by weight of the same maleic anhydride graft-modified polypropylene as in Example 1, and the functional filler (B) was 30% by weight.
Glass continuous fiber 3 as compounding and continuous fiber reinforcement (C)
However, in Comparative Examples 5 and 7, mica (new Mohs hardness 3) was used as the functional filler (B), and Comparative Example 6 was used.
In Examples 8 and 9, talc (new Mohs hardness 1) was blended.

4 Regarding the performance of the molded article in Comparative Example 5, the dispersion width of specific gravity is 0.051, the dispersion width of bending strength is 30 MPa and the average bending strength is 200 MPa in Comparative Example 5, and the dispersion width of specific gravity is 0.050 in Comparative Example 6. Bending strength dispersion width 30MPa and average bending strength 180MPa, Comparative Example 7: specific gravity dispersion width 0.045, bending strength dispersion width 20MPa and average bending strength 205MPa, Comparative Example 8: specific gravity dispersion width 0.0433, bending strength Was 20 MPa and the average bending strength was 180 MPa.

<Remarks of all experimental examples> [Remarks: Comparative Example 1] If a thermoplastic resin composite containing filler used for uniformly wetting continuous glass fibers was used, fluff and yarn breakage occurred frequently, and the fiber was pulled out. Could not be molded. The cause is required because the MFR of the complex was too low.

[Remarks: Comparative Example 2] In the case of using a thermoplastic resin composite containing a filler, which is used for uniformly wetting continuous glass fibers, pultruding was possible, but fluff and thread breakage were possible. In addition to the occurrence, the resulting composite was inferior in impregnation, dispersibility and bending strength. The cause is required because the MFR of the complex was too low.

[Remarks: Comparative Example 3] In the contact-type melt drawing method, when a functional filler having a new Mohs hardness of 7 or more is used, it is prevented from generating fluff and yarn breakage during the operation. , Could not be drawn.

[Remarks: Comparative Example 4] In the contact-type melt pultrusion molding method, when a functional filler having a new Mohs hardness of 4.5 was used, pultruding molding was possible, but fluffing during the operation In addition to the occurrence of thread breakage, the resulting composite was inferior in impregnation, dispersibility and bending strength.

[Remarks: Comparative Examples 5 to 8] In the blending method and the coating method, the specific gravity of the pellets and the strength of the molded product obtained therefrom are larger than those of the integrated method, due to the classification. In addition, the average strength of the molded product was slightly inferior.

[0108]

[Table 1]

[0109]

[Table 2]

[Brief description of the drawings]

FIG. 1 is a continuous fiber reinforced thermoplastic resin structure rod (long body) of the present invention by a non-contact type melt drawing method.
1 is an embodiment of an opening and impregnating apparatus for producing a fiber.

FIG. 2 is another embodiment of the fiber impregnation apparatus for producing the continuous fiber reinforced thermoplastic resin structure rod of the present invention by a contact type melt drawing method.

[Explanation of symbols]

DESCRIPTION OF REFERENCE NUMERALS 1 Non-contact type melt-drawing and impregnating apparatus itself 2 Continuous fiber bundle (long fiber roving) 3 Introducing port of continuous fiber bundle drilled in upstream end wall of apparatus 4 Fixed round bar type fiber opening Pin (inclusive name) 5 Inlet for molten resin composition containing functional filler perforated on bottom plate of apparatus 6 Shaping nozzle perforated on downstream end wall of apparatus 7 Continuous fiber reinforced resin strand impregnated with open fiber 1wL Upstream end wall of opening and impregnating tank 1wR Downstream end wall of opening and impregnating tank 4u Upper opening pin (collectively) 4d Lower opening pin (collectively) H Defined distance

Continued on the front page (51) Int.Cl. ⁶ Identification code FI B29K 105: 12 105: 16

Claims (5)

[Claims] 1. In a thermoplastic resin, 0.01 to 60% by weight of a filler having a new Mohs hardness of 4.0 or less as a functional filler and 10 to 80% by weight of a reinforcing material having an average diameter of 3 to 21 μm as a continuous fiber reinforcing material. % Is formed into a continuous fiber-reinforced thermoplastic resin structure through a contact or non-contact type melt drawing process, and the continuous fiber reinforcement dispersed in the structure functions. Continuous fiber reinforced heat which is uniformly wetted by a thermoplastic resin composite containing a conductive filler, and wherein the continuous fiber reinforcement is aligned in substantially the same length in the length direction of the continuous structure portion and substantially in parallel. Plastic resin structure. 2. The thermoplastic resin composite containing a functional filler used as an auxiliary agent for uniformly wetting the continuous fiber reinforcement has an MFR of 80 g when measured according to the following standard.
The continuous fiber-reinforced thermoplastic resin structure according to claim 1, wherein the MFR is / 10 min or more: [where the above MFR is measured under test conditions based on JIS K7210 corresponding to a generally used thermoplastic resin. Value.] 3. A thermoplastic resin having a new Mohs hardness of 8.0 or less as a functional filler in a thermoplastic resin 0.01 to 60% by weight.
And 10 as an average diameter of 3 to 21 μm as a continuous fiber reinforcement.
８０80% by weight of a continuous fiber reinforcing material, and in a fiber impregnating device, the continuous fiber reinforcing material is inserted into a predetermined gap set between an upper fiber opening pin of the device and a lower fiber opening pin which is a pair thereof. The fiber is opened by passing the fiber without being in contact with the fiber-spreading pin, and the fiber-reinforced continuous fiber that has been spread is uniformly wetted by the thermoplastic resin composite containing the functional filler, and A continuous fiber reinforced thermoplastic resin structure in which fiber reinforcements are arranged in substantially the same length in the length direction of the continuous structure portion and substantially in parallel. 4. A thermoplastic resin composite containing a functional filler which is used as an auxiliary agent for uniformly wetting a continuous fiber reinforcement, and has a MFR80 measured according to the following standard:
The continuous fiber reinforced thermoplastic resin structure according to claim 3, which is not less than g / 10min: [where the MFR is measured under test conditions based on JIS K7210 corresponding to a generally used thermoplastic resin. Value. ] 5. A molded article obtained by using the structure according to claim 1 as a continuous fiber reinforced thermoplastic resin structure.