JP2016108531A - Reinforced thermoplastic resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply provide a filler reinforced thermoplastic resin composition which achieves a technology for finding a new substance that can function as a sizing agent, enhancing adhesion to various thermoplastic resins including a filler, engineering plastic and super engineering plastic by using the sizing agent, and effectively kneading the filler in a thermoplastic resin by melting and mixing the filler with a twin-screw extruder or the like, and is more excellent in functionality.SOLUTION: There are provided a thermoplastic resin composition where a thermoplastic resin is used as a matrix resin, the resin is filled with a filler, and a mechanical strength is enhanced, in which the filler is dispersed in the thermoplastic resin in a state where a fluorene compound is selectively adhered to the surface of the filler; and a method for producing the same.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a filler-reinforced thermoplastic resin composition and a method for producing the same.

  Thermosetting resins such as unsaturated polyesters and epoxy resins are often used as matrix resins for composite materials in which fibers such as glass fibers are added as reinforcing materials to the resin, but thermoplastic resins are also used. In general, thermoplastic resins are advantageous in terms of impact resistance, moldability (workability), cost, etc. compared to thermosetting resins, and are suitable for mass production. Therefore, various proposals using a thermoplastic resin as a matrix resin have been made.

  For example, in Patent Document 1, a thermoplastic resin is used as a matrix resin, and by combining a reinforcing fiber such as a carbon fiber and a thermoplastic heat-resistant organic fiber under a certain condition, a projection is particularly produced. It discloses that it becomes a fiber-reinforced plastic that exhibits excellent mechanical properties even with respect to its shape. The reason why such an effect is obtained is that the thermoplastic resin exists in a fiber shape and is reinforced between other reinforcing fibers such as carbon fibers. Is said to penetrate into the gaps between the heat-resistant organic fibers. Patent Document 2 discloses that carbon fibers are generally poor in wettability (impregnation property) with respect to thermoplastic resins. A laminate in which carbon fibers are sandwiched between thermoplastic resin films is heated and pressurized. In addition, it is disclosed that, by irradiating an electron beam under specific conditions, the adhesion between the thermoplastic resin and the carbon fiber is improved, and a molded article having excellent mechanical strength can be obtained. In Cited Document 3, since conventional methods using various sizing agents, which are performed to improve the interfacial adhesion between the carbon fiber and the thermoplastic resin, are not sufficient, the carbon fiber and the thermoplastic resin are used. It is said that the interfacial adhesion between the carbon fiber and the thermoplastic resin is enhanced by using a specific sizing agent in which a specific epoxy compound and a specific tertiary amine compound are blended in the resulting composition.

JP 2014-062146 A JP 2010-058286 A JP2013-231178A

  However, in the invention described in the cited document 1, it is necessary to make the structure of the reinforcing material unique, and in the invention described in the cited document 2, the reinforcing material is sandwiched between the thermoplastic resin films and the heating is performed. Both of these technologies are complicated, requiring pressurization and electron beam irradiation, and these technologies are in a direction that impairs the advantages of thermoplastic resins in terms of formability (workability) and cost. It can be said that there is. In addition, the invention described in the cited document 3 requires a step of attaching the sizing agent to the carbon fiber in order to obtain the carbon fiber previously coated with the sizing agent. In these respects, the invention described in the cited document 3 also has practical problems and has to be improved.

  In view of the above-described circumstances, the present inventors have used a composite material that uses a thermoplastic resin as a matrix resin, and does not use a reinforcing material such as carbon fiber and a thermoplastic resin without performing complicated operations and treatments. It has come to the recognition that it would be extremely useful if a technology that can be simply and reinforced thermoplastic resin composition excellent in functionality by being kneaded with a screw extruder or the like is developed. In addition, the present inventors do not need a step of preparing carbon fibers in which a sizing agent is sufficiently applied before kneading with a thermoplastic resin, which is performed by the technique described in the above cited reference 3. In order to make it possible, when a thermoplastic resin is kneaded with a reinforcing material with a twin screw extruder or the like, a simple configuration that can effectively incorporate a reinforcing material such as carbon fiber into the thermoplastic resin. Recognizing the importance of finding new sizing agents.

  Further, the present inventors can use a thermoplastic resin that can be used for a reinforced thermoplastic resin composition, which is a composite material using a thermoplastic resin as a matrix resin, from general-purpose ones to engineering plastics (hereinafter referred to as engineering plastics). And super engineering plastics (hereinafter referred to as super engineering plastics), etc., which have extremely high functionality, in particular, a thermoplastic resin having excellent heat resistance is used as a matrix resin, and further a reinforcing material (filler) in the resin. ), It is possible to effectively knead into the above-described thermoplastic resin having excellent heat resistance, the mechanical strength and heat resistance are further improved, and the reinforced thermoplastic resin composition having superior functionality. Has been recognized as being extremely effective in practical use.

  Therefore, an object of the present invention is to find a new substance that can function as a sizing agent, and by using this sizing agent, various thermoplastics including fillers and engineering plastics and super engineering plastics having excellent characteristics such as heat resistance described above. Filler-reinforced thermoplastic resin with improved functionality that achieves a technology that enables the filler to be effectively kneaded into the thermoplastic resin by improving the adhesion with the resin and melt-kneading with a twin-screw extruder etc. It is simply to provide a composition. In addition, the object of the present invention is to achieve the above-described excellent effect even when a thermoplastic resin such as polyphenylene sulfide having excellent heat resistance is used as a matrix resin, among those classified as engineering plastics or super engineering plastics. It is simply providing a filler-reinforced thermoplastic resin composition that realizes heat resistance and high mechanical strength.

  The above object is achieved by the present invention described below. That is, the present invention is a thermoplastic resin composition obtained by using a thermoplastic resin as a matrix resin and adding a filler in the resin to enhance mechanical strength, wherein the filler is contained in the thermoplastic resin, Provided is a reinforced thermoplastic resin composition characterized in that the fluorene compound is dispersed in a state where the fluorene compound is selectively attached to the filler surface.

  The following are mentioned as a preferable form of the said reinforced thermoplastic resin composition of this invention. The thermoplastic resin has an aromatic ring or an amide bond in its structure; the thermoplastic resin is at least one selected from the group consisting of polyphenylene sulfide, polyamide resin, polycarbonate resin, and polyester resin The melting point of the fluorene compound is lower than the melting point of the thermoplastic resin; the melting point of the fluorene compound is from room temperature to 273 ° C .; the filler is a carbon-based filler; It is contained in a range of 0.1 to 20 parts in 100 parts of the reinforced thermoplastic resin composition on a mass basis; the use ratio of the fluorene compound to the filler is 1 on a mass basis. The filler: fluorene compound is 1: 0.01 to 1;

  As another embodiment, the present invention provides a method for producing a reinforced thermoplastic resin composition according to any one of the above, and includes a step of melt-kneading a thermoplastic resin, a fluorene compound, and a filler. A method for producing a reinforced thermoplastic resin composition is provided.

  As another embodiment, the present invention provides a method for producing a reinforced thermoplastic resin composition according to any one of the above, wherein a thermoplastic resin and a fluorene compound are introduced into a twin screw extruder, and further from a side feeder. Provided is a method for producing a reinforced thermoplastic resin composition, which comprises a step of charging fillers and melt-kneading them.

  According to the present invention, by using a specific sizing agent, among those classified as engineering plastics or super engineering plastics, particularly when a thermoplastic resin having excellent heat resistance such as polyphenylene sulfide is used as a matrix resin, the filler is used. When kneaded into a thermoplastic resin, the adhesion between the filler and the thermoplastic resin can be improved. As a result, it is possible to provide a reinforced thermoplastic resin composition having excellent heat resistance and mechanical strength. Become. Since such a reinforced thermoplastic resin composition provided by the present invention is excellent in handleability such as processability, its practical value is extremely high.

It is a figure of the SEM image (2000 times) of Example 2. FIG. It is a figure of the SEM image (10000 time) of Example 2. FIG. It is a figure of the SEM image (2000 times) of the comparative example 2. It is a figure of the SEM image (10000 time) of the comparative example 2.

  Next, the present invention will be described in detail with reference to preferred embodiments for carrying out the invention. As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a fluorene compound is useful as a new substance that can function as a filler sizing agent, and have reached the present invention. In particular, when a fluorene compound is used in combination with a thermoplastic resin, these are melt kneaded with a twin screw extruder, and when a filler such as carbon fiber is present at that time, the fluorene compound selectively adheres to the filler, As a result, it was found that the adhesion between the filler and the thermoplastic resin was remarkably improved, and that the composite material having excellent functionality was obtained by adding the filler to the thermoplastic resin. In particular, for example, for thermoplastic resins having a high processing temperature such as polyphenylene sulfide, there is nothing that can effectively act as a sizing agent from the viewpoint of its heat resistance, whereas it could not be a good composite material, It has been found that by using a fluorene compound, the adhesion between the filler and the thermoplastic resin having a high processing temperature can be improved, and as a result, a composite material having both excellent heat resistance and mechanical strength can be obtained.

  The reinforced thermoplastic resin composition of the present invention is a thermoplastic resin composition in which a thermoplastic resin is used as a matrix resin and a filler is added to the resin to enhance mechanical strength, and the thermoplastic resin is contained in the thermoplastic resin. The filler is dispersed in a state in which a fluorene compound is selectively attached to the filler surface. Hereinafter, each configuration will be described.

<Composition>
The reinforced thermoplastic resin composition of the present invention comprises a thermoplastic resin, a filler as a reinforcing material, and a fluorene compound as essential components. First, these compositions will be described. The use ratio (content) of the fluorene compound constituting the composition of the present invention is 0.1 to 20 parts, more preferably 0.1 parts in 100 parts of the thermoplastic resin composition on a mass basis. Part to 15 parts, and more preferably 1.7 parts to 10 parts. If the proportion of the fluorene compound used exceeds 20 parts out of 100 parts of the thermoplastic resin composition, the original physical properties of the thermoplastic resin constituting the composition of the present invention may be impaired. On the other hand, if the amount is too small, the effects of the present invention may not be sufficiently obtained, which is not preferable.

  Moreover, the use ratio (content) of the filler which comprises the reinforced thermoplastic resin composition of this invention is 2 parts-60 parts in 100 parts of this reinforced thermoplastic resin composition by mass reference | standard, More preferably It is preferable to be included within the range of 5 to 30 parts. Of the 100 parts of the reinforced thermoplastic resin composition, the proportion of filler used is preferably 60 parts, because the amount of filler is excessive and the resin may not be contained in a good state. Absent. On the other hand, if the proportion of filler used is less than 2 parts, the mechanical strength of the thermoplastic resin, which is achieved by adding a filler to form a composite, may not be sufficiently enhanced, such being undesirable. Furthermore, the use ratio (mass ratio) of the fluorene compound and the filler constituting the thermoplastic resin composition of the present invention is such that the filler is 1, and the filler: fluorene compound is about 1: 0.01-1. It is more preferable that the ratio be about 1: 0.1 to 0.8.

<Fluorene compound>
As described above, in the reinforced thermoplastic resin composition of the present invention, when the thermoplastic resin is used as a matrix resin, by using a fluorene compound, the filler contained in the thermoplastic resin is dispersed with good adhesion. Has achieved. The fluorene compound characterizing the present invention has the following structure. In the present invention, the following compounds can be used.

Examples of the fluorene compound that can be used in the present invention include 9,9-bis (4-hydroxyphenyl) fluorene (other names: bisphenolfluorene, abbreviated as BPF), and 9,9-bis (4-hydroxy-3-methyl). 9,9-bis (C 1-4 alkylhydroxyphenyl) fluorene such as phenyl) fluorene (also referred to as biscresol fluorene, abbreviated as BCF), 9,9-bis (3-hydroxy-2-methylphenyl) fluorene Kind;
For example, 9,9-bis (4-hydroxy-2,6-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-) Bisphenol fluorenes such as 9,9-bis (dihydroxy 1-4 alkylhydroxyphenyl) fluorene such as 3,5-di-t-butylphenyl) fluorene;
For example, 9,9-bis (3,4-dihydroxyphenyl) fluorene (other name: biscatecholfluorene, abbreviated as BCAF), 9,9-bis (2,4-dihydroxyphenyl) fluorene, 9,9-bis (2 9,9-bis (dihydroxyphenyl) fluorenes such as, 5-dihydroxyphenyl) fluorene,
For example, 9,9-bis (carbon number 1) such as 9,9-bis (3,4-dihydroxy-5-methylphenyl) fluorene and 9,9-bis (3,4-dihydroxy-6-methylphenyl) fluorene. -4 alkyl-dihydroxyphenyl) fluorene For example, 9,9-bis (dicarbon number 1-4 alkyl-dihydroxyphenyl) such as 9,9-bis (2,4-dihydroxy-3,6-dimethylphenyl) fluorene ) 9,9-bis (dihydroxyphenyl) fluorenes such as fluorene,
For example, 9,9-bis (2,4,6-trihydroxyphenyl) fluorene, 9,9-bis (2,3,5-trihydroxyphenyl) fluorene, 9,9-bis (2,4,5- Trihydroxyphenyl) fluorene, 9,9-bis (3,4,5-trihydroxyphenyl) fluorene, 9,9-bis (2,3,4-trihydroxyphenyl) fluorene, 9,9-bis (2, 9,9-bis (trihydroxyphenyl) fluorenes such as 9,9-bis (trihydroxyphenyl) fluorene such as 3,6-trihydroxyphenyl) fluorene,
For example, 9,9-bis such as 9,9-bis (4-glycidyloxyphenyl) fluorene (abbreviated as BPFG) and 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene (abbreviated as BCFG) (Monoglycidyloxyphenyl) fluorenes;
For example, 9,9-bis (diglycidyloxyphenyl) fluorenes such as 9,9-bis [3,4-di (glycidyloxy) phenyl] fluorene (other name: biscatecholfluorenetetraglycidyl ether);
For example, 9,9-bis (triglycidyloxyphenyl) fluorenes such as 9,9-bis [3,4,5-tri (glycidyloxy) phenyl] fluorene,
For example, 9,9-bis (4-glycidyloxyethoxyphenyl) fluorene (other name: bisphenoxyethanol fluorenediglycidyl ether, abbreviated as BPEFG), 9,9-bis (4-glycidyloxyethoxy-3-methylphenyl) fluorene ( 9,9-bis (glycidyloxyalkoxyphenyl) fluorenes such as 9,9-bis (monoglycidyloxyalkoxyphenyl) fluorene such as BCEFG);
For example, 9,9-bis (4-aminophenyl) fluorene (other name: bisaniline fluorene), 9,9-bis (4-amino-3-methylphenyl) fluorene, 9,9-bis (3-amino-2) 9,9-bis (amino-alkyl having 1-4 carbon atoms) fluorenes such as -methylphenyl) fluorene,
9,9-bis (4-amino-3,5-dimethylphenyl) fluorene, 9,9-bis (4-amino-3,5-di-t-butylphenyl) fluorene, 9,9-bis (4- And 9,9-bis (amino-dialkyl having 1-4 carbon atoms) fluorenes such as amino-2,6-dimethylphenyl) fluorene.

  In addition, commercially available fluorene compounds include those listed below, and any of them can be suitably used in the present invention. Specifically, for example, Ogsol MF-11 (trade name, melting point: 162 ° C., compound name: BPEF (bisphenoxyethanol fluorene)), Ogsol MF-12 (trade name, melting point: 221 ° C.) manufactured by Osaka Gas Chemical Co., Ltd. , Compound name: BPF (bisphenol fluorene)), Ogsol MF-31 (trade name, melting point: 66 ° C.), Ogsol MF-32 (trade name, melting point: liquid at room temperature (25 ° C.)), Ogsol MF-35 (product) Name, melting point: 273 ° C.).

  Depending on the thermoplastic resin used for the matrix resin, for example, when a resin having a high processing temperature such as polyphenylene sulfide is used for the matrix, from the viewpoint of molding temperature, among the above-mentioned commercially available products, the melting point is It is preferable to use higher ogsol MF-11, ogsol MF-12 or ogsol MF-35.

In terms of compound names, among those listed above, for example, 9,9-bis (4-glycidyloxyphenyl) fluorene (BPFG), 9,9-bis (4-glycidyloxy-3-methylphenyl) 9,9-bis (monoglycidyloxyphenyl) fluorenes such as fluorene (BCFG),
9,9-bis (diglycidyloxyphenyl) fluorenes such as 9,9-bis [3,4-di (glycidyloxy) phenyl] fluorene (biscatecholfluorene tetraglycidyl ether),
9,9-bis (triglycidyloxyphenyl) fluorenes such as 9,9-bis [3,4,5-tri (glycidyloxy) phenyl] fluorene,
For example, 9,9-bis (4-glycidyloxyethoxyphenyl) fluorene (other name: bisphenoxyethanol fluorenediglycidyl ether (BPEFG)), 9,9-bis (4-glycidyloxyethoxy-3-methylphenyl) fluorene (BCEFG) 9,9-bis (glycidyloxyalkoxyphenyl) fluorenes such as 9,9-bis (monoglycidyloxyalkoxyphenyl) fluorenes are preferred from the relationship with the thermoplastic resin of the matrix resin.

  As described above, the fluorene compound used in the present invention is preferably one having an appropriate melting point in consideration of the melting point of the thermoplastic resin used in the matrix. According to the study by the present inventors, it is preferable to use a fluorene compound used in the present invention having a melting point lower than that of the thermoplastic resin used for the matrix. For this reason, it can be said that the fluorene compound used in the present invention can be used as long as its melting point is not lower than room temperature (about 25 ° C.), and the fluorene compound used in the present invention is combined with the melting point of the matrix resin. What is necessary is just to select suitably. In order to obtain a reinforced thermoplastic resin composition having excellent heat resistance by using the fluorene compound used in the present invention, for example, the melting point is from room temperature to 273 ° C, and further from 120 ° C to 273 ° C. It is more preferable to use a fluorene compound. As will be described later, for example, a thermoplastic resin having a high processing temperature, such as polyphenylene sulfide, could not effectively act as a sizing agent from the viewpoint of its heat resistance, and could not be a good composite material. On the other hand, by using a fluorene compound having a high melting point, the adhesion between the filler and the thermoplastic resin having a high processing temperature can be improved.

<Filler>
As the filler constituting the reinforced thermoplastic resin composition of the present invention, any filler conventionally used as a reinforcing material for reinforcing the mechanical strength and the like of the matrix resin can be used. In that case, it may be appropriately selected and used according to the required performance to be strengthened, but specifically, the following can be used. For example, carbon fillers such as carbon black, graphite, carbon nanotubes, carbon fibers, carbon hollow spheres, and silicon carbide; oxides such as silica, diatomaceous earth, barium ferrite, beryllium oxide, pumice, and pumice balun; Hydroxides such as aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate; carbonates such as calcium carbonate, magnesium carbonate, dolomite, and dawsonite; sulfates or sulfites such as calcium sulfate, barium sulfate, ammonium sulfate, and calcium sulfite; Silicates such as talc, clay, mica, glass fiber, glass balloon, glass beads, calcium silicate, wollastonite, montmorillonite, bentonite; molybdenum sulfide, boron fiber, zinc borate, barium metaborate, potassium borate Cium, sodium borate, magnesium oxysulfate, basic magnesium sulfate fiber, potassium titanate fiber, aluminum borate fiber, calcium silicate fiber, calcium carbonate fiber, various metal fibers, aromatic polyamide fiber, cellulose fiber, nylon fiber , Various synthetic fibers such as polyester fiber and polypropylene fiber, and thermosetting resin powder. Among these, carbon-based fillers, particularly carbon fibers, are preferable in terms of easy availability and cost, and, as will be described later, by placing them in a thermoplastic resin having a high processing temperature such as polyphenylene sulfide, In addition, a composite material with improved mechanical strength can be easily obtained. As the carbon fiber used at this time, it is preferable to use a short fiber or the like, although it depends on the required performance.

<Thermoplastic resin>
The thermoplastic resin constituting the present invention may be appropriately selected according to the required performance such as use, heat resistance and mechanical strength, and is not particularly limited, but is not limited to general-purpose resins, engineering plastics, and spar engineering as listed below. Plastic or the like can be used. These can be used alone or in combination of two or more. Specifically, for example, polycarbonate resin (PC); polyphenylene ether resin such as polyphenylene ether (PPE) or polyphenylene ether / styrene resin; acrylonitrile-butadiene-styrene resin (ABS), acrylonitrile / ethylene / propylene / diene / Styrene resins such as styrene resin (AES), acrylonitrile-styrene-acrylate resin (ASA), acrylonitrile-styrene resin (AS resin), high impact polystyrene (HIPS), polystyrene (PS); olefins such as polyethylene and polypropylene Resin; Thermoplastic polyester resin such as polybutylene terephthalate, polyethylene terephthalate, polyarylate; Polyamide 6 (PA6, Nylon 6), Polyamide 6 (PA66, nylon 66), polyamide-based resin such as polyamide 46 (PA46, nylon 46), polyamide 12 (PA12, nylon 12); polyacetal (POM), vinyl chloride resin (PVC), polysulfone (PSF), polyether Examples include sulfone (PES), polyphenylene sulfide (PPS), ethylene-vinyl alcohol copolymer resin (EVOH), and ethylene-vinyl acetate copolymer.

  Among these, it is preferable to use those classified into engineering plastics and super engineering plastics in terms of heat resistance and mechanical strength. Specifically, for example, heat selected from polyphenylene sulfide (PPS), polycarbonate resin (PC), polyester resin such as polybutylene terephthalate, polyamide resin such as polyamide 6 (PA6, nylon 6), and the like. A plastic resin is mentioned. Among these, polyphenylene sulfide (PPS) having the following chemical structure exhibits high rigidity and strength, is excellent in flame retardancy and dimensional stability, and has high heat resistance that can be used continuously at 200 ° C. or higher. It is excellent, and it is particularly useful because it has better mechanical strength and heat resistance when it is reinforced with a filler such as the carbon fiber mentioned above to form a composite material. As mentioned above, thermoplastic resins with high processing temperatures such as polyphenylene sulfide are not effective as a sizing agent from the viewpoint of their heat resistance, and cannot be made into a good composite material by a simple method. In contrast, in the present invention, as described below, this problem is solved by using a fluorene compound. Even when an engineering plastic or super engineering plastic having excellent characteristics is used as a matrix resin, the machine is used. Achieves improved mechanical strength and heat resistance.

  Surprisingly, the present inventors have used the above-mentioned fluorene compound in combination with polyphenylene sulfide, and by adding a filler such as carbon fiber as a reinforcing material in them, surprisingly, the electron micrographs of FIGS. As shown in the figure, the fluorene compound selectively adheres to the surface of the fibrous filler, and as a result, the filler is buried in the polyphenylene sulfide and becomes a tightly adhered state, improving the mechanical strength and heat resistance. As a result, the present invention has been found. The surprising effect of the combined use of the fluorene compound is apparent from a comparison with the electron micrographs of FIGS. 3 and 4 in the same configuration except that the fluorene compound is not used in combination.

  The inventors of the present invention, for example, the reason why the fluorene compound can be selectively attached to the surface of the fibrous filler when melt-kneaded, is due to the unique structure of the fluorene compound. I believe. That is, if it explains in the form which put the filler in the resin system which used the fluorene compound together with polyphenylene sulfide (PPS) which is a suitable combination in the present invention, as described below, from the structural characteristics of these components. As a result of the affinity of the fluorene compound with PPS and filler, it plays a role of bridging, and as a result, it is inferred that the adhesion between PPS and filler is improved. That is, since a π-π interaction occurs between the aromatic ring of the fluorene compound and the aromatic ring of the PPS, the bonding force works, and the fluorene compound and the filler are considered to be on the hydroxyl group and filler surface of the fluorene compound. Since the force of the hydrogen bond is generated between the hydroxyl group to be formed, the bonding force works, and as a result, the fluorene compound selectively adheres to the surface of the filler. As a result, the electron micrographs in FIGS. As shown, it is considered that the filler was brought into a tightly adhered state through the fluorene compound in the PPS. Therefore, it is preferable that the thermoplastic resin constituting the present invention has an aromatic ring in the structure. Examples of such materials include polycarbonate, polyphenylene ether, polybutylene terephthalate, polyarylate, polysulfone, and polyethersulfone in addition to the above polyphenylene sulfide.

  Further, according to the study by the present inventors, it is preferable that the fluorene compound used has a lower melting point than the thermoplastic resin that is the matrix resin. For example, while the melting point of polyphenylene sulfide is around 278 ° C., the melting point of the fluorene compound is lower than this, and this is considered to be one of the factors that the fluorene compound can selectively adhere to the filler. .

<Manufacturing method / use>
The method for producing a reinforced thermoplastic resin composition of the present invention includes a step of melt-kneading the above-described thermoplastic resin such as polyphenylene sulfide, the fluorene compound as mentioned above, and a filler such as carbon fiber. Features. Specifically, for example, for the production of pellets such as thermoplastic resin and fluorene compound are fed into the twin screw extruder from the upstream feeder, filler is further fed from the side feeder, and these are melted and kneaded. It can be easily obtained by using a widely used conventional method. What is necessary is just to determine the conditions for melt-kneading suitably according to melting | fusing point of the thermoplastic resin to be used and a fluorene compound. According to the study by the present inventors, for example, when polyphenylene sulfide is used as the thermoplastic resin, it is preferable to melt knead at a temperature of about 290 ° C. that is equal to or higher than the melting point and close to the melting point.

  The reinforced thermoplastic resin composition of the present invention is preferably pelletized according to a conventional method after melt-kneading with a twin-screw extruder. Since the pellet obtained in this way is a thermoplastic resin composition, it can be freely molded by heating, and the filler in the thermoplastic resin is fixed in the resin with good adhesiveness. Therefore, mechanical strength, heat resistance, etc. are improved and it can be applied to various uses. Specifically, the reinforced thermoplastic resin composition of the present invention is a combination of a fluorene compound, so that when the filler is added to the thermoplastic resin to form a composite, the filler is in good contact with the thermoplastic resin. As a result, the mechanical strength and heat resistance of the lightweight and easy-to-handle thermoplastic resin are effectively enhanced. For this reason, the reinforced thermoplastic resin composition of this invention can be used suitably as a forming member and components, such as a motor vehicle, sports goods, an aircraft, for example, and the practical value is very high.

  Next, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to this. In the following text, “part” is based on mass unless otherwise specified.

Example 1
As the thermoplastic resin, 93.3 parts of TORELINA M2588 (trade name, manufactured by Toray Industries, Inc., melting point 278 ° C.) which is polyphenylene sulfide, and Ogusol MF-35 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., melting point 273 ° C.) which is a fluorene compound ) 1.7 parts is introduced by a feeder upstream of a twin screw extruder (manufactured by Nippon Steel Co., Ltd., trade name: tex30α), and further carbon filler (manufactured by Toho Tenax, trade name: Tenax HT-C432-6MM). ) 5 parts were charged from the side feeder. And it melt-kneaded at 290 degreeC with the said twin-screw extruder, and obtained the strand-shaped (string shape extruded from die | dye) thermoplastic resin composition. Then, the thermoplastic resin composition was rapidly cooled in a water tank, cut with a pelletizer, and pelletized to obtain a pellet-like reinforced thermoplastic resin composition of this example.

(Examples 2 and 3)
The pellet-shaped reinforced thermoplastic resin compositions of Examples 2 and 3 were obtained in the same manner as in Example 1 except that the amounts of polyphenylene sulfide, fluorene compound and carbon filler were changed to the formulations shown in Table 1. It was.

(Comparative Example 1)
95 parts of Torelina M2588 (trade name, manufactured by Toray Industries, Inc.), which is the same polyphenylene sulfide as used in the examples, was introduced by a feeder upstream of the same twin-screw extruder as used in the examples, and further used in the examples. 5 parts of the same carbon filler was charged from the side feeder. And it carried out similarly to the Example, it melt-kneaded at 290 degreeC, and obtained the strand-shaped thermoplastic resin composition. Then, the thermoplastic resin composition was rapidly cooled in a water tank, cut with a pelletizer, and pelletized to obtain a pellet-like reinforced thermoplastic resin composition of this comparative example.

(Comparative Examples 2 and 3)
Except that the amounts of polyphenylene sulfide and carbon filler were changed to the formulations shown in Table 1, pellet-like reinforced thermoplastic resin compositions of Comparative Examples 2 and 3 were obtained in the same manner as Comparative Example 1, respectively.

[Evaluation]
(Tensile test)
Using the pellets of the reinforced thermoplastic resin compositions obtained in Examples and Comparative Examples obtained above, injection molding was performed at a resin temperature of 320 ° C. and a mold temperature of 150 ° C. to obtain a measurement sample. And the tension test was implemented according to the standard of ASTM D-638, using the sample for measurement obtained in this way for each. Specifically, Young's modulus, maximum stress, and breaking strain were measured. The results are summarized in Table 1. Table 1 also shows the composition of each reinforced thermoplastic resin composition. As a result, as shown in Table 1, when the amount of filler was compared in the same example in the comparative example not using the fluorene compound and the example using the fluorene compound, the Young's modulus was about 1.3 times, It was confirmed that the maximum stress was improved by about 1.02 to 1.2 times and the breaking strain was improved by about 1.2 to 1.5 times.

(SEM image)
Using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, trade name: S-4800), the fracture surfaces of the dumbbell pieces of Example 2 and Comparative Example 2 after the tensile test were observed. 1 and 2 are electron micrographs showing the observation results of the sample of Example 2. FIG. 3 and 4 are electron micrographs showing the observation results of the sample of Comparative Example 2 in which no fluorene compound was added. As is clear from the comparison of these SEM images, in the case of Example 2 using the fluorene compound of FIGS. 1 and 2, unlike the case of FIGS. 3 and 4 of Comparative Example 2, deposits are clearly seen on the filler surface. Furthermore, as shown in FIG. 1, the sample of Example 2 is in a state in which the filler is firmly fixed in the resin, and the sample of Example 2 is compared. It was confirmed that the adhesion between the filler and the resin was improved as compared with the case of the sample of Example 2.

  ADVANTAGE OF THE INVENTION According to this invention, the filler reinforced thermoplastic resin composition which puts a filler in a thermoplastic resin, can be combined with a simple means, and is excellent in mechanical strength compared with the conventional one is provided. More specifically, the reinforced thermoplastic resin composition of the present invention uses a fluorene compound when kneading the filler into the thermoplastic resin, thereby improving the adhesion between the filler and the thermoplastic resin. Excellent strength. Furthermore, according to the technology of the present invention, even when a thermoplastic resin having excellent heat resistance is used as the matrix resin, the adhesiveness between the filler and the thermoplastic resin can be improved. It is possible to provide a filler-reinforced thermoplastic resin composition with improved strength and heat resistance. The filler reinforced thermoplastic resin composition excellent in mechanical strength and heat resistance provided by the present invention is expected to be used in various fields, and further, since the matrix resin is a thermoplastic resin, its processing It has excellent properties and moldability, is suitable for mass production, has extremely high practical value, and is expected to be widely used.

Claims (10)

  A thermoplastic resin composition obtained by using a thermoplastic resin as a matrix resin and reinforcing the mechanical strength by adding a filler in the resin, wherein the filler is contained in the surface of the filler and a fluorene compound on the filler surface. A reinforced thermoplastic resin composition characterized by being dispersed in a state where is selectively attached.   The reinforced thermoplastic resin composition according to claim 1, wherein the thermoplastic resin has an aromatic ring or an amide bond in its structure.   The reinforced thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin is at least one selected from the group consisting of polyphenylene sulfide, polyamide resin, polycarbonate resin, and polyester resin.   The reinforced thermoplastic resin composition according to any one of claims 1 to 3, wherein a melting point of the fluorene compound is lower than a melting point of the thermoplastic resin.   The reinforced thermoplastic resin composition according to any one of claims 1 to 4, wherein the fluorene compound has a melting point of from room temperature to 273 ° C.   The reinforced thermoplastic resin composition according to claim 1, wherein the filler is a carbon-based filler.   The reinforced heat according to any one of claims 1 to 6, wherein the fluorene compound is contained in a range of 0.1 to 20 parts in 100 parts of the reinforced thermoplastic resin composition on a mass basis. Plastic resin composition.   The reinforcing ratio according to any one of claims 1 to 7, wherein a use ratio of the fluorene compound and the filler is 1 to 0.01 to 1 in a filler: fluorene compound in which the filler is 1 on a mass basis. Thermoplastic resin composition. A method for producing a reinforced thermoplastic resin composition according to any one of claims 1 to 8,
A method for producing a reinforced thermoplastic resin composition, comprising a step of melt-kneading a thermoplastic resin, a fluorene compound, and a filler. A method for producing a reinforced thermoplastic resin composition according to any one of claims 1 to 8,
A method for producing a reinforced thermoplastic resin composition, comprising a step of introducing a thermoplastic resin and a fluorene compound into a twin-screw extruder, further adding a filler from a side feeder, and melt-kneading them.