JP5234914B2 - Dry mixture and production method thereof - Google Patents

Description

  The present invention relates to a composition comprising a long fiber reinforced thermoplastic resin pellet, a flame retardant pellet, and a lubricant, and even if a flame retardant is added, a decrease in the concentration of long fibers in the composition can be greatly suppressed. The present invention relates to a composition capable of forming a molded article that can achieve both high mechanical strength and flame retardancy at a high level, a method for producing the same, a method for producing the molded article, and a molded article thereof.

  It is known that a resin composition (fiber reinforced thermoplastic resin composition) with mechanical strength can be obtained by adding fibers to the thermoplastic resin. Since the fiber-reinforced thermoplastic resin composition has excellent mechanical strength, it is used as a material (or molding material) for various products that require high strength. Fiber reinforced thermoplastic resin compositions have been used widely in applications such as automobile parts, machine parts, and sporting goods, taking advantage of their excellent mechanical strength. Applications for applications that require flammability are beginning to be considered.

  For example, in Japanese Patent No. 3399234 (Patent Document 1), the long-fiber reinforcing material is formed of 90 to 20% by weight of a polyolefin crystalline resin as a base resin and 10 to 80% by weight of a long-fiber reinforcing material. 0.0015-0.15% by weight of calcium stearate externally added to a long fiber reinforced polyolefin crystalline resin column having an average length of 3 to 50 mm and substantially parallel to each other. Disclosed compositions are disclosed. In this document, the composition is prepared by charging a mixture of the long fiber reinforced polyolefin crystalline resin columnar externally added (post-added) with calcium stearate into a tumbler mixer and uniformly shaking and mixing the composition. It is also described that the was manufactured. This document also describes that the composition can be used for high-strength products (for example, automobile parts such as bumpers for automobiles, side moldings, and household appliance parts).

  JP-A-5-9380 (Patent Document 2) discloses that (A) a polyamide resin, (B) a fibrous reinforcing material having a length of 3 mm or more, 5 to 80% by weight (in the composition), and (C) carbon. A long fiber reinforced polyamide resin composition comprising 0.01 to 3% by weight (in the composition) of a metal salt of a fatty acid of 22 to 32 is disclosed. This document also describes that the long fiber reinforced polyamide resin composition is in the form of pellets having a length of 3 to 50 mm. Further, this document describes that the long fiber reinforced polyamide resin composition can form various molded articles by injection molding. However, the compositions of Patent Documents 1 and 2 use long fiber reinforcing materials and have excellent mechanical strength, but are inferior in flame retardancy, and therefore are used in applications where flame retardancy is required (or It is not suitable for molded products.

  JP 2006-181776 A (Patent Document 3) discloses (A) a long fiber reinforced thermoplastic resin pellet containing reinforcing fibers having substantially the same length as the pellet, and (B) a weight average fiber length of 0. A short fiber reinforced thermoplastic resin pellet containing reinforcing fibers of 1 to 0.5 mm and a fiber reinforced flame retardant resin mixture for molding containing (C) a flame retardant is disclosed. This document also states that it is preferable to add an additive (filler) to the molding fiber-reinforced flame retardant resin mixture for the purpose of obtaining good molding characteristics and a good product appearance at the time of injection molding. Has been.

  Although the said fiber reinforced flame retardant resin mixture for shaping | molding uses a fiber reinforced thermoplastic resin pellet (A) (B) and a flame retardant (C), it improves mechanical strength and provides flame retardance. Both are easy to separate and inferior in miscibility (or dispersibility) between them, so it is difficult to obtain a molded product having excellent mechanical strength and flame retardancy. Further, since the molding fiber reinforced flame retardant resin mixture is an irregularly shaped pellet containing fibers, it is inferior in bite to the injection molding machine (or its screw), and in the molding fiber reinforced flame retardant resin mixture, It is impossible to form a molded product that can stably achieve both high mechanical strength and flame retardancy at a high level.

  Further, JP-A-2006-193551 (Patent Document 4) discloses (A) 50-100 parts by weight of a polyamide resin and (B) 0-50 parts by weight of an elastic polymer having a glass transition temperature of -20 ° C or lower. (E) a long fiber reinforced resin composition pellet (a) containing 30 to 250 parts by weight of a long fibrous reinforcing material having an average fiber length of 3.0 mm or more, and (A) polyamide (C) 10 to 100 parts by weight of a brominated flame retardant with respect to 100 parts by weight in total of 50 to 100 parts by weight of resin and (B) 0 to 50 parts by weight of an elastic polymer having a glass transition temperature of -20 ° C or lower. (D) A flame retardant resin composition pellet (b) containing 5 to 50 parts by weight of at least one selected from an antimony compound and zinc borate, and a ratio of pellet (a) / pellet (b) is 1 to 12 (Weight ratio) range Blend of mixed polyamide resin composition is disclosed to be. In this document, it is described that a known additive may be added to the pellet (a) or (b) and kneaded in the blend.

The blend of Patent Document 4 also uses the long fiber reinforced resin composition pellet (a) and the flame retardant resin composition pellet (b) to improve mechanical strength and impart flame retardancy. However, the ratio of the (C) brominated flame retardant contained in the flame retardant resin composition pellet (b) is small. Therefore, in order to impart sufficient flame retardancy to the blend, it is necessary to add a large amount of the flame retardant resin composition pellet (b), but the amount of the flame retardant resin composition pellet (b) to be added As the amount increases, the content (or concentration) of the long fibrous reinforcement decreases. Furthermore, in the blend, the long fiber reinforced resin composition pellets (a) and the flame retardant resin composition pellets (b) are easily separated and inferior in miscibility (or dispersibility) between them, and the long fiber reinforced Since the resin composition pellet (a) is an irregularly shaped pellet containing fibers, the resin composition pellet (a) does not mesh well with the injection molding machine (or its screw), and the blended product has stable mechanical strength and flame retardancy. Therefore, it is impossible to form a molded product that can be compatible at a high level.
Japanese Patent No. 3399234 (Claim 1, paragraphs [0027] and [0037]) JP-A-5-9380 (Claims 1 and 3) JP 2006-181776 A (Claim 1, paragraph [0028]) JP 2006-193551 A (Claim 1, paragraph [0046])

  Accordingly, an object of the present invention is to provide a composition capable of forming a molded article capable of achieving both high mechanical strength and flame retardancy at a high level, a method for producing the composition, a method for producing the molded article, and a molded article thereof. is there.

  Another object of the present invention is to reduce the voids between pellets even in irregular shaped pellets containing fibers, a high bulk density composition, a method for producing the same, and a method for producing the molded article and the molding thereof. Is to provide goods.

  Still another object of the present invention is to provide a composition that is excellent in pellet mixing and homogeneity and that can maintain the homogeneity over a long period of time, a method for producing the same, a method for producing the molded article, and a molded article thereof. There is.

  Another object of the present invention is to provide a composition excellent in biting property with respect to a melt molding machine (or a screw thereof) such as an injection molding machine, and a method for producing the same, even for irregularly shaped pellets containing fibers, and the molded article. It is in providing the manufacturing method of this and its molded article.

  Still another object of the present invention is to provide a method for increasing the bulk density of a composition in order to effectively reduce transportation costs, storage space, and the like.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventor used specific long fiber reinforced thermoplastic resin pellets and flame retardant pellets, and further mixed the lubricant in a specific ratio, and the long fiber reinforced thermoplastic resin. Even if the resin pellets are irregularly shaped (for example, columnar) pellets, a composition (uniform blend) that can form a molded article that is excellent in mixing with the flame retardant pellets and has both high mechanical strength and flame retardancy. The present invention was completed.

  That is, the composition of the present invention is a composition (or dry mixture) obtained by dry-mixing at least (A) long fiber-reinforced thermoplastic resin pellets, (B) flame retardant pellets, and (C) a lubricant, The (A) long fiber reinforced thermoplastic resin pellets are columnar pellets composed of (A1) thermoplastic resin and (A2) long fibers, and the content of the (C) lubricant is relative to the whole composition. 0.005 to 0.15% by weight.

  The (A) long fiber reinforced thermoplastic resin pellet may be a pellet in which the (A2) long fiber is contained in substantially the same length as the pellet and substantially parallel to the length direction. The composition may further include (D) a thermoplastic resin pellet, and the ratio of the (A) long fiber reinforced thermoplastic resin pellet to the (D) thermoplastic resin pellet is the former / The latter (weight ratio) may be about 99/1 to 40/60. The (B) flame retardant pellet is composed of a masterbatch composed of (B1) a flame retardant and (B2) a thermoplastic resin, and the content of (B1) flame retardant is (B) the entire flame retardant pellet. It may be about 70 to 99% by weight.

Moreover, content of the said (B1) flame retardant is about 1 to 40 weight% with respect to the said whole composition, and content of the said (A2) long fiber is 30-70 with respect to the said whole composition. It may be about wt%. Wherein (C) lubricants, saturated _{C 12-30} fatty acids, saturated _{C 12-30} fatty acid metal salt, may be at least one member selected from the group consisting of saturated _{C 12-30} fatty acid ester and saturated _{C 12-30} fatty acid amide.

  In the composition, (A) the long fiber reinforced thermoplastic resin pellet may have an average diameter of about 0.5 to 5 mm and an average length of about 3 to 20 mm. The (C) lubricant may be a granular material having an average particle size of 5 to 500 μm.

In the present invention, (A1) the thermoplastic resin is a polyamide-based resin, (C) the lubricant is an alkaline earth metal salt of a saturated C _16-22 fatty acid, and the composition (C) The content is 0.01 to 0.1% by weight, (B1) the flame retardant content is 5 to 30% by weight, and (A2) the long fiber content is 35 to 65% by weight. Also included are compositions that are:

  Moreover, this invention also includes the method of manufacturing the said composition by dry-mixing at least (A) a long fiber reinforced thermoplastic resin pellet, (B) a flame retardant pellet, and (C) a lubricant. In the manufacturing method, (D) thermoplastic resin pellets may be further dry mixed. In the present invention, a method of increasing the bulk density of the mixture by adding (C) a lubricant to a mixture containing at least columnar long fiber reinforced thermoplastic resin pellets (A) and (B) flame retardant pellets. Is also included.

  Furthermore, this invention also includes the method of manufacturing the molded article by melt-molding the said composition. In the above method, the melt molding may be injection molding. Furthermore, the present invention includes a molded product obtained by the above method.

  The composition of the present invention comprises a specific (A) long fiber reinforced thermoplastic resin pellet, a specific (B) flame retardant pellet and a specific (C) lubricant, and contains the lubricant in a specific ratio. In addition, it is possible to form a molded product that can achieve both mechanical strength and flame retardancy at a high level. In the composition, because the (C) lubricant is included in a specific ratio, the long fiber reinforced thermoplastic resin pellets have irregular shapes (for example, columnar shapes), but there are voids between the pellets. Is reduced and the bulk density is increased. Therefore, transportation costs, storage space, etc. can be reduced. Moreover, since the mixing property of the said long fiber reinforced thermoplastic resin pellet and a flame retardant pellet is improved and both are mixed uniformly, the said composition is homogeneous and can maintain homogeneity over a long period of time. Therefore, a molded product obtained by molding the composition can stably exhibit excellent mechanical strength and flame retardancy. In addition, although the said composition contains the pellet of the unusual shape (for example, columnar shape) containing a fiber, it is excellent in the bite property with respect to melt molding machines (or its screw), such as an injection molding machine, and is high kneading | mixing. Show the effect. Further, since it is easily plasticized, it is suitable for molding, and even when subjected to molding, it has excellent mechanical strength and has uniform flame retardance throughout the entire molded product. Therefore, it is useful for various molded products (for example, molded products that require flame retardancy).

[Composition]
The composition (dry mixture) of the present invention comprises at least (A) long fiber reinforced thermoplastic resin pellets, (B) flame retardant pellets, and (C) a lubricant.

((A) Long fiber reinforced thermoplastic resin pellets)
(A) The long fiber reinforced thermoplastic resin pellet is composed of (A1) a thermoplastic resin and (A2) long fibers.

((A1) thermoplastic resin)
(A1) As the thermoplastic resin, a conventional thermoplastic resin can be used. For example, an olefin resin (for example, α-C _2-20 chain olefin resin such as polyethylene resin, polypropylene resin, and methylpentene resin). Cyclic olefin resins, etc.), polystyrene resins [eg polystyrene (GPPS), high impact polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-acrylonitrile-butadiene copolymer (ABS resin) Styrene-methyl methacrylate-butadiene copolymer (MBS resin, etc.)], vinyl chloride resin (for example, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, etc.), vinyl acetate resin [for example, ethylene-acetic acid Vinyl copolymer (EVA resin), etc.], polyvinyl alcohol type Radical polymerization resins such as fats [for example, ethylene-vinyl alcohol copolymer (EVOH resin), etc.], acrylic resins [for example, polymethyl methacrylate (PMMA), etc.]; polyester resins [for example, polyalkylene arylates ( Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene-2,6-naphthalate (PEN), etc.)], polycarbonate resin, polyamide resin, thermoplastic polyimide resin, polyphenylene sulfide (PPS) resin Polycondensation resins such as polyether ether ketone (PEEK) resins; (modified) polyphenylene ether (PPE) resins, polyacetal resins; thermoplastic elastomers (for example, polyolefin elastomers, polystyrenes) Elastomers, polyester elastomers and polyamide-based elastomer) and the like. These thermoplastic resins may be used alone or in combination of two or more. Among the thermoplastic resins, olefin resins, polystyrene resins, polyester resins, polycarbonate resins, polyamide resins, polyphenylene sulfide (PPS) resins, and the like are preferable from the viewpoint of moldability and the like. From the viewpoints of heat resistance, chemical resistance, mechanical properties, and the like, polypropylene resins, polystyrene resins, polycarbonate resins, polyamide resins, and the like are more preferable. In the present invention, in particular, polypropylene resins and polyamide resins are preferably used.

Specifically, the polypropylene resin may be a homopolymer of propylene or a copolymer of propylene and another copolymerizable monomer. Other copolymerizable monomers include, for example, olefinic monomers (for example, α-C _2-20 chain such as ethylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, etc. Olefins, cyclic olefins, etc.), vinyl ester monomers (eg, vinyl acetate, vinyl propionate, etc.), (meth) acrylic monomers [eg, (meth) acrylic acid, alkyl (meth) acrylate, (meth) ) Vinyl cyanide monomers such as acrylonitrile], diene monomers (for example, butadiene, etc.), unsaturated polycarboxylic acids or acid anhydrides (for example, maleic acid, itaconic acid, citraconic acid or acid anhydrides thereof) Products), imide monomers [for example, N such as maleimide, N-alkylmaleimide (for example, N—C _1-4 alkylmaleimide, etc.) -Substituted maleimide] and the like. These copolymerizable monomers can be used alone or in combination of two or more.

More specifically, as the polypropylene resin, in addition to polypropylene which is a homopolymer, examples of the copolymer include propylene-ethylene copolymer, propylene-butene-1 copolymer, and propylene-ethylene-butene-1. Examples thereof include propylene-α _2-20 chain olefin copolymers (such as random copolymers and block copolymers) having a propylene content of 80% by weight or more such as copolymers. Of these polypropylene resins, polypropylene and propylene-α _2-6 chain olefin copolymers are preferred, and more preferred polypropylene resins are polypropylene and propylene-ethylene copolymers. These polypropylene resins may be used alone or in combination of two or more.

  Examples of the polystyrene-based resin include homopolymers and copolymers formed with an aromatic vinyl monomer as a main constituent unit. Examples of the aromatic vinyl monomer for forming the polystyrene-based resin include styrene, alkyl-substituted styrene (for example, vinyl toluene, vinyl xylene, p-ethyl styrene, butyl styrene, etc.), halogen-substituted styrene (for example, bromo Examples thereof include styrene and the like, and α-alkyl-substituted styrene (eg, α-methylstyrene and the like). These aromatic vinyl monomers can be used alone or in combination of two or more. Of these monomers, styrene, vinyl toluene, α-methylstyrene and the like are usually used.

  The aromatic vinyl monomer may be used in combination with a copolymerizable monomer in order to impart a soft component and improve rigidity, impact resistance and the like. Examples of the copolymerizable monomer include the copolymerizable monomers exemplified in the section of (A1) thermoplastic resin. These copolymerizable monomers can be used alone or in combination of two or more. The amount of the copolymerizable monomer used in all monomers can be selected from the range of usually 1 to 50 mol%, preferably 3 to 40 mol%, more preferably about 5 to 30 mol%.

  The polystyrene resin also includes a rubber-containing styrene resin. Rubber-containing styrenic resins are used to improve mechanical properties and buffering properties, and rubbery polymers are formed into particles in a matrix composed of the styrenic resin by copolymerization (such as graft polymerization). A dispersed polymer may be used. Usually, at least an aromatic vinyl monomer is polymerized by a conventional method (bulk polymerization, bulk suspension polymerization, solution polymerization, emulsion polymerization, etc.) in the presence of a rubbery polymer. It is a graft copolymer (rubber graft polystyrene polymer) obtained by doing.

Examples of the rubber-like polymer include diene rubber [polybutadiene (low cis type or high cis type polybutadiene), polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, butadiene-acrylonitrile copolymer, isobutylene. -Isoprene copolymer, styrene-isobutylene-butadiene copolymer rubber, etc.], ethylene-vinyl acetate copolymer, acrylic rubber (copolymer elastomer having polyacrylic acid C _2-8 alkyl ester as a main component), ethylene -Α-olefin copolymer [ethylene-propylene rubber (EPR), etc.], ethylene-α-olefin-polyene copolymer [ethylene-propylene-diene rubber (EPDM), etc.], urethane rubber, silicone rubber, butyl rubber, water Diene rubber (hydrogenated steel) Down - butadiene copolymer, and hydrogenated butadiene polymer) and the like. The copolymer may be a random or block copolymer, and the block copolymer includes a copolymer having an AB type, ABA type, tapered type, radial teleblock type structure, or the like. . These rubbery polymers can be used alone or in combination of two or more. A preferred rubbery polymer is a polymer of conjugated 1,3-diene or a derivative thereof, particularly a diene rubber [polybutadiene (butadiene rubber), isoprene rubber, styrene-butadiene copolymer, etc.].

  In the rubber-containing styrenic resin, the content of the rubber-like polymer can be selected from the range of about 2 to 50% by weight, for example, 3 to 15% by weight, preferably 4 to 15% by weight, and more preferably 5 to 15% by weight. % May be sufficient.

  Specific examples of the polystyrene resin include polystyrene (GPPS), styrene-acrylonitrile copolymer (AS resin), styrene-methyl methacrylate copolymer, acrylonitrile-styrene-methyl methacrylate copolymer, and styrene-anhydrous. Non-rubber-containing styrene resin such as maleic acid copolymer (SMA resin) (styrene resin not containing rubber component or non-rubber reinforced styrene resin), impact-resistant polystyrene (HIPS), styrene-acrylonitrile-butadiene Copolymer (ABS resin), α-methylstyrene-modified ABS resin, imide-modified ABS resin, styrene-methyl methacrylate-butadiene copolymer (MBS resin), rubber component X (acrylic rubber, chlorinated polyethylene, ethylene-propylene Rubber (EPDM), ethylene Acrylonitrile A and styrene S acid vinyl copolymer, and the like) is rubber-modified styrenic resin such as AXS resin graft-polymerized. These polystyrene resins can be used alone or in combination of two or more. Among these polystyrene resins, rubber-containing styrene resins (such as rubber components) such as impact-resistant polystyrene (HIPS) and styrene-acrylonitrile-butadiene copolymer (ABS resin) from the viewpoint of impact resistance and compatibility. A copolymer in which at least an aromatic vinyl monomer is grafted is preferred.

The polycarbonate-based resin is usually a resin obtained by a reaction between a dihydroxy compound and a carbonate such as phosgene or diphenyl carbonate. The dihydroxy compound may be an alicyclic compound or the like, but is preferably an aromatic compound (particularly a bisphenol compound). Examples of the bisphenol compound include bis (hydroxyaryl) C _1-6 alkane; bis (hydroxyaryl) C _4-10 cycloalkane; 4,4′-dihydroxydiphenyl ether; 4,4′-dihydroxydiphenyl sulfone; '-Dihydroxydiphenyl sulfide; 4,4'-dihydroxydiphenyl ketone and the like. Preferred polycarbonate-based resins include bisphenol A type polycarbonate.

  In addition, as the polyamide-based resin, polyamide obtained by polycondensation using diamine and dicarboxylic acid as polymerization components; polyamide obtained by polycondensation using aminocarboxylic acid, and optionally diamine and / or dicarboxylic acid; lactam And polyamides obtained by the ring-opening polymerization. The polyamide may be a copolyamide.

Examples of the diamine include aliphatic diamines (eg, C _3-10 alkylene diamines such as trimethylene diamine, tetramethylene diamine, hexamethylene diamine, 2,2,4-trimethylhexamethylene diamine, octamethylene diamine, etc.); Examples include alicyclic diamines (for example, bis (4-amino-3-methylcyclohexyl) methane); aromatic diamines (for example, phenylenediamine, metaxylylenediamine, and the like). These diamines may be used alone or in combination of two or more.

  Examples of the dicarboxylic acid include aliphatic dicarboxylic acids (for example, alkane dicarboxylic acids having about 4 to 20 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, octadecanedioic acid, etc.) An alicyclic dicarboxylic acid (for example, cyclohexane-1,4-dicarboxylic acid); an aromatic dicarboxylic acid (for example, phthalic acid, isophthalic acid, terephthalic acid) or an acid anhydride thereof (for example, phthalic anhydride) Etc. are included. These dicarboxylic acids may be used alone or in combination of two or more.

  Examples of the aminocarboxylic acid include aminocarboxylic acids having about 4 to 20 carbon atoms such as aminoheptanoic acid, aminononanoic acid, aminoundecanoic acid, and aminododecanoic acid. These aminocarboxylic acids may be used alone or in combination of two or more.

  Examples of the lactam include lactams having about 4 to 20 carbon atoms such as butyrolactam, pivalolactam, caprolactam, capryllactam, enantolactam, undecanolactam, and dodecanolactam. These lactams may be used alone or in combination of two or more.

  Typical polyamide resins include aliphatic polyamides such as polyamide 46, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11 and polyamide 12; terephthalic acid and / or isophthalic acid and hexamethylenediamine. Aromatic polyamides such as polyamides, polyamides obtained from adipic acid and metaxylylenediamine (MXD-6), polyamides obtained from terephthalic acid, adipic acid and hexamethylenediamine; at least two of these polyamides differ And a copolyamide (for example, polyamide 6/11, polyamide 6/12, etc.) formed by the polyamide component. These polyamides may be used alone or in combination of two or more. Of these polyamide resins, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11, polyamide 12 and the like are preferably used.

((A2) long fiber)
(A2) The long fibers (or reinforcing fibers) may be fibers composed of conventional fibers and having a specific length (or fiber length). The average fiber length of the (A2) long fiber is 3 mm or more (for example, about 3 to 20 mm), preferably 5 mm from the viewpoint of sufficiently exerting mechanical strength in the (A) long fiber reinforced thermoplastic resin pellet. It may be more (for example, about 5 to 18 mm), more preferably 7 mm or more (for example, about 7 to 15 mm). The average diameter of the (A2) long fiber may be, for example, 3 to 50 μm, preferably 5 to 40 μm, and more preferably about 7 to 30 μm.

  The fiber constituting the (A2) long fiber can be appropriately selected according to the use and the like. For example, the fiber may be a natural fiber such as a cellulose fiber or a protein fiber, but the natural fiber is usually a short fiber. The (A2) long fibers are preferably chemical fibers (or artificial fibers). Examples of the chemical fibers include inorganic fibers (for example, glass fibers; carbon fibers such as PAN-based carbon fibers, pitch-based carbon fibers, and carbon nanofibers); gold / silver threads, steel fibers, aluminum fibers, lead fibers, stainless fibers, and the like. Metal fiber; Alumina fiber; Silicon carbide fiber; Boron fiber; Tyranno fiber; Ceramic fiber; Rock fiber; Basalt fiber, etc.); Organic fiber [For example, regenerated fiber such as regenerated cellulose fiber (eg, rayon), regenerated protein fiber, etc. Semi-synthetic fibers such as cellulose acetate fibers; synthetic fibers (for example, polyamide fibers such as nylon and aramid, polyester fibers, acrylic fibers, polyolefin fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyurethane fibers, polyacetal fibers, fluorine fibers , Polypheny Nsurufido fibers, heterocyclic ring-containing fibers (e.g., polyimide fibers etc.), etc.), etc.]. These (A2) long fibers may be used alone or in combination of two or more. Among these (A2) long fibers, from the viewpoint of efficiently improving various properties (for example, mechanical properties) of the (A1) thermoplastic resin, the (A2) long fibers are glass fibers, carbon fibers, Inorganic fibers such as metal fibers, semi-synthetic fibers such as cellulose acetate fibers; polyamide fibers such as aramid (fully aromatic polyamide resins), polyester fibers, acrylic fibers, polyvinyl chloride fibers, polyphenylene sulfide fibers, and other organic fibers In particular, glass fiber, carbon fiber and the like are particularly preferable from the viewpoint of high strength and low cost. In addition, when conductive fibers such as metal fibers and carbon fibers are used as the (A2) long fibers, conductivity can be imparted to the composition.

  The ratio of (A1) thermoplastic resin to (A2) long fibers is the former / the latter (weight ratio) = 20/80 to 70/30, preferably 25/75 to 65/35, more preferably 30/70 to It may be about 60/40. Moreover, although said (A2) long fiber is based also on a kind, (A) 30-80 weight% with respect to the whole long fiber reinforced thermoplastic resin pellet, Preferably it is 32-78 weight%, More preferably, it is 35-75. It may be contained in a proportion of about 37% by weight, particularly about 37 to 72% by weight (for example, 40 to 70% by weight). If the (A2) long fiber content is too large, it will be difficult to prepare (A) long fiber reinforced thermoplastic resin pellets, which will be described later. On the other hand, if the (A2) long fiber content is too small, sufficient machine Strength cannot be obtained.

  Such (A1) long fiber reinforced thermoplastic resin pellets composed of (A1) thermoplastic resin and (A2) long fibers are irregularly shaped, for example, columnar (columnar, prismatic, etc.), rod, plate It may be a long shape such as a shape, a strip shape (or a tape shape); a pellet having various shapes such as an oval shape, a flat shape, and an indefinite shape. Especially, since the said (A2) long fiber can be utilized effectively, (A) long fiber reinforced thermoplastic resin pellets are columnar (column shape, prismatic shape, etc.), strip | belt shape (or tape shape) etc., for example. Is preferred. In particular, the (A) long fiber reinforced thermoplastic resin pellet may be columnar (columnar, prismatic, etc.).

  In the columnar long fiber reinforced thermoplastic resin pellet (A), the (A2) long fiber may be coated with the (A1) thermoplastic resin and contained substantially parallel to the length direction of the pellet. In addition, although the (A2) long fiber contained in the (A) long fiber reinforced thermoplastic resin pellet may be a small number (for example, about 1 to 50), it is usually 50 or more (for example, 100). ˜50000), preferably 500 to 30000, and more preferably about 1000 to 25000. When a plurality of (A2) long fibers are arranged, the fibers may be arranged in parallel in the (A) long fiber reinforced thermoplastic resin pellet.

  In such (A) long fiber reinforced thermoplastic resin pellets, for example, as will be described later, a plurality of filament yarns obtained by opening a roving (fiber bundle) while taking it into a melted state (A1) heat Examples include pellets obtained by appropriately cutting strand pellets obtained by continuously impregnating a plastic resin. In such (A) long fiber reinforced thermoplastic resin pellets, (A2) long fibers are usually contained in (A) long fiber reinforced thermoplastic resin pellets in substantially the same length as the pellets.

  The average length (pellet length) of the (A) long fiber reinforced thermoplastic resin pellet is, for example, 3 to 20 mm, preferably 5 to 18 mm, from the viewpoint of suppressing separation (or peeling) between the pellets in the composition. Preferably, it may be about 7 to 15 mm. The average diameter of the (A) long fiber reinforced thermoplastic resin pellet may be, for example, about 0.5 to 5 mm, preferably about 0.6 to 4.5 mm, and more preferably about 0.8 to 4 mm. . In addition, when (A) the long fiber reinforced thermoplastic resin pellet is a non-cylindrical columnar shape (for example, a prismatic shape or the like), the average length of the bottom side is defined as the average diameter.

  Such (A) long fiber reinforced thermoplastic resin pellets can be produced by utilizing (or applying) conventional methods. For example, see JP-A-2006-167882, JP-A-6-107944, and the like. Can be manufactured. For example, (A) long fiber reinforced thermoplastic resin pellets are obtained by impregnating (A2) a filament fiber obtained by melting and spinning a raw material of long fibers with (A1) a thermoplastic resin in a molten state and pelletizing it. However, in the case of producing a (A) long fiber reinforced thermoplastic resin pellet containing a plurality of (A2) long fibers, the filament yarn is twisted. It is preferable to use a roving (fiber bundle) which is bundled and combined without any problem. That is, a plurality of filament yarns obtained by opening the roving while taking the roving are continuously impregnated with the molten (A1) thermoplastic resin, pelletized into strands, and cut into a desired pellet length. Manufacturing is effective because the number of manufacturing steps can be reduced. Such (A) long fiber reinforced thermoplastic resin pellets can be obtained, for example, from Daicel Chemical Industries, Ltd. under the trade name “Plastoron”.

((B) Flame retardant pellet)
(B) The flame retardant pellet may be a pellet composed of (B1) a flame retardant alone, but from the viewpoint of miscibility with the (A) long fiber reinforced thermoplastic resin pellet, moldability, etc. , (B1) a flame retardant and (B2) a masterbatch composed of a thermoplastic resin are often used.

((B1) Flame retardant)
As the flame retardant, a conventional flame retardant can be used. For example, a halogen flame retardant; a phosphorus flame retardant; an organic flame retardant {for example, a halogen-free organic acid metal salt flame retardant [diphenylsulfone-disulfonic acid Metal salts, organic carboxylic acids such as metal salts of diphenylsulfonesulfonic acid, or alkali metal (Na, K, etc.) salts, alkaline earth metal salts of organic sulfonic acids, etc.]; inorganic flame retardants (for example, silicone flame retardants) , Phosphazene flame retardants, metal oxides, metal hydroxides (aluminum hydroxide, magnesium hydroxide, etc.), nitrogen-containing flame retardants such as triazine flame retardants, etc.]. These flame retardants can be used alone or in combination of two or more. Of these flame retardants, halogen flame retardants and phosphorus flame retardants are preferably used because of their high flame retardancy.

  Examples of the halogen-based flame retardant include halogen-containing styrene resins [halogenated polystyrene (halides obtained by halogenating styrene resins such as brominated polystyrene and chlorinated polystyrene, halogenated styrene monomers alone or in combination). Polymers)), halogen-containing polycarbonate resins (brominated polycarbonates, halogenated polycarbonates such as chlorinated polycarbonate), halogen-containing (or halogenated) thermoplastic resins such as halogen-containing acrylic resins; halogen-containing epoxy compounds [ Halogen-containing phenoxy such as bromine-containing epoxy resins (such as brominated epoxy resins), halogen-containing epoxy resins such as chlorinated epoxy resins (such as halogenated epoxy resins); Bromine-containing phenoxy resins (such as brominated phenoxy resins) Fat (halogenated phenoxy resin, etc.), halogen-containing triazine compounds (eg, bromine-containing triazine compounds such as tris (tribromophenoxy) triazine), halogen-containing isocyanuric acid compounds [eg, tris (2,3-dibromopropyl) ) Bromine-containing isocyanuric acid compounds such as isocyanurates], halogenated aromatic imide compounds [for example, brominated aromatic imide compounds such as ethylene bisbrominated phthalimide (for example, bisimide compounds), etc.], halogenated alicyclics Hydrocarbons (bridged cyclic saturated or unsaturated halogenated alicyclic hydrocarbons, such as halogenated polycycloalkadienes such as dodecachloropentacyclooctadeca-7,15-diene) and the like. Halogen flame retardants can be used alone or in combination of two or more.

  The phosphorus-based flame retardant may be an inorganic phosphorus-based flame retardant (red phosphorus-based flame retardant, such as red phosphorus), or may be an organic phosphorus-based flame retardant from the viewpoint of versatility. Examples of the organic phosphorus flame retardant include phosphate esters; phosphate amine salts composed of diamine and / or triazine derivatives and (poly or pyro) phosphoric acid. These organophosphorous flame retardants may be used alone or in combination of two or more.

  Representative phosphate esters include aromatic phosphate esters {eg (a) tri (aryl) phosphates and tri (alkyl-substituted aryl) phosphates [eg triphenyl phosphate, cresyl diphenyl phosphate, tris (tolyl) ) Phosphates, etc.], (b) arylene bis (aryl) phosphates and arylene bis (alkyl substituted aryl) phosphates [eg resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), resorcinol bis (dixylenyl phosphate), etc.] (C) bisphenol bis (aryl) phosphate and bisphenol bis (alkyl-substituted aryl) phosphate [eg 4,4′-biphenol bis (diphenyl phosphate) ), 4,4′-biphenol bis (dixylenyl phosphate), bis (diphenyl phosphate) of bisphenols (such as bisphenol A), bis (dixylenyl phosphate) of bisphenols (such as bisphenol A), etc.] It is done. The phosphate esters may include halogen-containing phosphate esters. The halogen-containing phosphate esters include halides of the phosphate esters, and examples thereof include tris (4-bromophenyl) phosphate and tris (2,4-dibromophenyl) phosphate. Moreover, as a phosphoric acid amine salt comprised by a diamine and / or a triazine derivative and (poly or pyro) phosphoric acid, it combines diamine and / or a triazine derivative and (poly or pyro) phosphoric acid which are normally used suitably. Can be configured. For example, in the phosphoric acid amine salts, the diamine is a piperazine (for example, piperazine, 1,4-bis (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine, etc.) and the like. Also included are phosphate amine salts (for example, melamine phosphate, melamine phosphate, etc.) that are formula amines and whose triazine derivatives are melamines (eg, melamine, condensed melamine, melam, melem, etc.). Phosphorus flame retardants can be used alone or in combination of two or more.

  Of these (B1) flame retardants, halogen-based flame retardants are preferable from the viewpoint of flame retardancy, and in particular, from the viewpoint of easily forming a masterbatch with a thermoplastic resin (B2) described later, ) A thermoplastic resin is preferred.

  Moreover, you may use (B1) a flame retardant in combination with a conventional flame retardant adjuvant as needed. For example, a flame retardant aid suitable for combination with a halogenated flame retardant is an antimony-containing compound. Examples of the antimony-containing compound include antimony oxides such as antimony trioxide and antimony pentoxide; and metal antimonate salts such as sodium antimonate. These antimony-containing compounds may be used alone or in combination of two or more. A preferred flame retardant aid is antimony oxide (particularly antimony trioxide). The ratio of the flame retardant aid is, for example, 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.07 to 1 part by weight (1 part by weight of the flame retardant (B1). In particular, it may be about 0.1 to 0.5 parts by weight.

((B2) thermoplastic resin)
(B) The thermoplastic resin constituting the flame retardant pellet (B2) may also be a conventional thermoplastic resin, for example, the thermoplastic resin exemplified in the section of (A1) thermoplastic resin. It can select suitably according to the kind of flame retardant. Specifically, as (B2) the thermoplastic resin, it is preferable to select a thermoplastic resin having a high affinity with (B1) a flame retardant. For example, the (B1) flame retardant contains a halogen (or halogenated). When it is a thermoplastic resin, (B2) the thermoplastic resin is the same type of thermoplastic resin as the halogen-containing thermoplastic resin (for example, a thermoplastic resin obtained by dehalogenating the halogen-containing thermoplastic resin). Is preferred.

  More specifically, as an example, when (B1) the flame retardant is a halogen-containing styrene resin (for example, brominated polystyrene), (B2) the thermoplastic resin is, for example, the same as the halogen-containing styrene resin. It is preferable to use a thermoplastic resin of a system (for example, a polystyrene resin), and a polystyrene resin is particularly preferably used. (B2) The thermoplastic resins may be used alone or in combination of two or more.

  Examples of the polystyrene resin include the polystyrene resin (or rubber-containing styrene resin) exemplified in the section of (A1) thermoplastic resin. These polystyrene resins can be used alone or in combination of two or more. Among the polystyrene resins, rubber-containing styrene resins such as styrene or alkyl-substituted styrene homopolymers (for example, polystyrene), impact-resistant polystyrene (HIPS), styrene-acrylonitrile-butadiene copolymer (ABS resin), etc. In particular, polystyrene and high impact polystyrene (HIPS) are preferably used.

  The polystyrene resin may contain a soft component such as a soft resin (for example, an olefin resin or an olefin wax) in order to improve impact resistance, fluidity, and the like.

Examples of the olefin resin (or olefin wax) include homopolymers or copolymers of olefin monomers. The olefin monomer may be a chain olefin monomer or a cyclic olefin monomer, but is usually a chain olefin monomer (for example, ethylene, propylene, 1-butene, Α-C _2-20 chain olefins such as isobutene, 1-pentene, 4-methyl-1-pentene, especially α-C _2-4 chain olefins) are used. These olefinic monomers can be used alone or in combination of two or more.

More specifically, examples of the olefinic monomer homopolymer or copolymer include α-C _2-20 chain olefins such as polyethylene (polyethylene such as high-density polyethylene and low-density polyethylene) and polypropylene (particularly, α-C _2-20 chain olefins (particularly α-C _2-4 chain olefins) such as (α-C _2-4 chain olefins) homopolymers and ethylene-propylene copolymers can be exemplified. .

  The olefin resin (or olefin wax) may also be a copolymer with another copolymerizable monomer. Examples of the copolymerizable monomer include the copolymerizable monomer exemplified in the section of (A1) thermoplastic resin. These copolymerizable monomers can be used alone or in combination of two or more. The amount of the copolymerizable monomer used in all monomers can be selected from the range of usually 1 to 50 mol%, preferably 3 to 40 mol%, more preferably about 5 to 30 mol%.

The said olefin resin can be used individually or in combination of 2 or more types. Among these olefin resins, α-C _2-4 chain olefin homopolymers or copolymers (or waxes thereof) such as polyethylene (polyethylene such as high-density polyethylene and low-density polyethylene), polypropylene, and ethylene-propylene copolymer. Etc.) are preferred.

  As described above, the (B2) thermoplastic resin can be appropriately selected according to the type of the (B1) flame retardant, and the combination of the (B1) flame retardant and the (B2) thermoplastic resin is a halogen-containing styrene resin. The combination is not limited to styrene resin, and other combinations may be used. The (B2) thermoplastic resin and the (A1) thermoplastic resin may be the same from the viewpoint of miscibility, or may be different from the viewpoint of imparting various characteristics.

  The ratio (content ratio) of (B1) flame retardant and (B2) thermoplastic resin is the former / the latter (weight ratio) = 99.9 / 0.1-60 / 40, preferably 99.7 / 0.3. ~ 65/35, more preferably about 99.5 / 0.5 to 70/30. Further, the (B1) flame retardant depends on the type, but (B) 65 to 99.5% by weight, preferably 70 to 99% by weight, more preferably 75 to 97% by weight, based on the whole flame retardant pellet. In particular, it may be contained in a proportion of about 78 to 96% by weight (for example, 80 to 95% by weight). Since the ratio (or concentration) of the (B1) flame retardant is high as described above, the flame retardancy can be effectively imparted even if the amount of the (B) flame retardant pellet added is small.

  The shape of the (B) flame retardant pellet composed of the (B1) flame retardant and the (B2) thermoplastic resin is not particularly limited, and is spherical (or true spherical), irregular (columnar (cylindrical) , A prismatic shape, a rod shape, a plate shape, a belt shape, an elliptical sphere shape, a flat shape, an indefinite shape, etc.). In addition, the shape of the flame retardant pellet (B) may be the same shape as the shape of the (A) long fiber reinforced thermoplastic resin pellet (that is, a column shape (columnar shape, prismatic shape, etc.), a belt shape, etc.) It may have a different shape (for example, spherical shape, elliptical spherical shape, etc.). When the (B) flame retardant pellet is columnar (columnar, prismatic, etc.), the average length (pellet length) of the (B) flame retardant pellet is, for example, 0.5 to 20 mm, preferably 1 to It may be 18 mm, more preferably about 1.5 to 15 mm. Moreover, the average diameter of the flame retardant pellet (B) may be, for example, about 0.5 to 10 mm, preferably about 1 to 8 mm, and more preferably about 2 to 5 mm. In addition, when (B) a flame retardant pellet is a non-columnar columnar shape (for example, prismatic shape etc.), let the average length of the edge | side of a bottom face be the said average diameter.

  Such (B) flame retardant pellets can be produced using (or applying) conventional methods. For example, (B) a flame retardant pellet is obtained by using (B1) a flame retardant and (B2) a thermoplastic resin by using a conventional melt kneader (eg, roll, kneader, single screw extruder, twin screw extruder, etc.). It may be prepared by melt-kneading, extruding into various shapes (for example, plate shape, strand shape, etc.) and cutting into a desired shape. In addition, (B) flame retardant pellets are melted as described above after (B1) flame retardant and (B2) thermoplastic resin are previously mixed using a conventional mixer (eg, tumbler, mixer, etc.). It may be prepared by kneading.

((C) Lubricant)
(C) Lubricants include conventional lubricants such as lipids, waxes, silicone resins and the like.

Examples of lipids include higher fatty acids (for example, saturated C _8-35 fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid (preferably saturated C _{12- 30} fatty acids, more preferably saturated C _16-22 fatty acids), unsaturated C _10-35 fatty acids such as _palmitooleic acid, oleic acid, erucic acid, etc.) or derivatives thereof (eg higher fatty acid salts (eg lauric acid) _C8-35 fatty acid metal salts such as barium, zinc laurate, calcium stearate, magnesium stearate and zinc stearate); higher fatty acid esters [for example, higher fatty acids such as cetyl alcohol, stearyl alcohol, oleyl alcohol and the like and monovalent Esters with alcohol; Sucrose fatty acid ester (For example, ester of sucrose such as sucrose mono to hexastearate and the higher fatty acid), glycerin fatty acid ester (for example, ester of glycerin such as glycerin mono to tristearate and the higher fatty acid), An ester of pentaerythritol and the higher fatty acid, an ester of diglycerin and the higher fatty acid, an ester of the higher fatty acid and a polyhydric alcohol such as an ester of polyglycerol and the higher fatty acid, etc.]; a higher fatty acid amide (for example, _C8-35 fatty acid amide such as stearic acid amide, alkylene bis fatty acid amide such as methylene bis stearic acid amide, ethylene bis stearic acid amide, etc.). These lipids can be used alone or in combination of two or more.

Examples of the wax include aliphatic hydrocarbon wax (poly C _2-4 olefin wax such as polyethylene wax, ethylene copolymer wax, polypropylene wax, paraffin wax, microcrystalline wax, etc.), plant or animal. And waxes such as carnauba wax, beeswax, shellac wax, and montan wax. These waxes can be used alone or in combination of two or more.

  Examples of silicone resins include alkylpolysiloxanes such as dimethylpolysiloxane, diethylpolysiloxane, and trifluoropropylpolysiloxane; arylpolysiloxanes such as diphenylpolysiloxane; alkylarylpolysiloxanes such as methylphenylpolysiloxane, and the like. . The silicone resin may be a chain polysiloxane or a cyclic polysiloxane. These silicone resins can be used alone or in combination of two or more.

These lubricants can be used alone or in combination of two or more. Among these lubricants, a solid (or solid) lubricant is preferable at normal temperature (for example, about 5 to 35 ° C.). As the lubricant, for example, lipids, in particular, lauric acid, palmitic acid, stearic acid, saturated _{C 12-30} fatty acid metal salts such as saturated _{C 12-30} fatty acids, calcium and magnesium stearate, such as behenic acid, glycerol mono To glycerin mono to _trisaturated C _12-30 fatty acid ester such as tristearic acid ester, alkylene _bissaturated C _12-30 fatty acid amide such as ethylene _bisstearic acid amide, etc. are preferable, especially saturated C such as palmitic acid and stearic acid. _16-22 a fatty acid, such as saturated _{C 16-22} fatty acid alkaline earth metal salts such as calcium and magnesium stearate are preferably used.

  The shape of the (C) lubricant is not particularly limited, and may be, for example, powder, granule (or granule), strand, rod, plate, tubular, block, etc. It is preferable that it is a powder form and a granular form from the point which can mix both by adhering to the said (A) long fiber reinforced thermoplastic resin pellet and (B) flame retardant pellet. When the (C) lubricant is a granular material, the average particle diameter may be, for example, 0.5 to 1000 μm, preferably 1 to 800 μm, more preferably about 5 to 500 μm.

  The composition further comprises (D) a thermoplastic resin pellet as necessary in order to adjust the ratio of (A2) long fibers in the composition to obtain desired mechanical strength, moldability, and the like. You may go out.

  (D) The thermoplastic resin (or corresponding thermoplastic resin) constituting the thermoplastic resin pellet may also be a conventional thermoplastic resin. For example, the thermoplastic resin exemplified in the section of (A1) thermoplastic resin It may be. The corresponding thermoplastic resin is preferably an olefin resin, a polystyrene resin, a polyester resin, a polycarbonate resin, a polyamide resin, a polyphenylene sulfide (PPS) resin, or the like from the viewpoint of moldability and the like. From the viewpoints of heat resistance, chemical resistance, mechanical properties, etc., polypropylene resins, polystyrene resins, polycarbonate resins, polyamide resins and the like are more preferable. The corresponding thermoplastic resin and (A1) thermoplastic resin may be different, but are preferably the same from the viewpoint of miscibility (or affinity).

  The shape of the (D) thermoplastic resin pellet is not particularly limited, and may be the shape exemplified in the section of (B) the flame retardant pellet. The shape of the thermoplastic resin pellet (D) is the same as the shape of the (A) long fiber reinforced thermoplastic resin pellet and (B) the flame retardant pellet (that is, columnar (columnar, prismatic, etc.), belt-shaped. Etc.) or different shapes (for example, spherical, elliptical spherical, etc.). In addition, you may select suitably the shape of the said (D) thermoplastic resin pellet according to the kind of the said corresponding thermoplastic resin. For example, when the (D) thermoplastic resin pellet is columnar (columnar, prismatic, etc.), the average length (pellet length) of the (D) thermoplastic resin pellet is, for example, 0.5 to 20 mm, Preferably it may be about 1 to 18 mm, more preferably about 1.5 to 15 mm. The average diameter of the thermoplastic resin pellets (D) may be, for example, about 0.5 to 10 mm, preferably 1 to 8 mm, and more preferably about 2 to 5 mm. In addition, when the thermoplastic resin pellet (D) is a non-cylindrical columnar shape (for example, a prismatic shape or the like), the average length of the bottom side is defined as the average diameter.

  In addition, (D) thermoplastic resin pellets can also be manufactured using (or applying) conventional methods, for example, using (or applying) the same (or similar) methods as (B) flame retardant pellets. It may be manufactured.

(Ratio of each component in the composition)
(A) The long fiber reinforced thermoplastic resin pellet is 100 to 1500 parts by weight, preferably 200 to 1400 parts by weight, more preferably 250 to 1300 parts by weight, and particularly 300 to 100 parts by weight of (B) the flame retardant pellets. It may be about 1200 parts by weight. When the composition contains (D) thermoplastic resin pellets, the ratio of (A) long fiber reinforced thermoplastic resin pellets to (D) thermoplastic resin pellets is the former / the latter (weight ratio) = 99 / It may be 1 to 40/60, preferably 95/5 to 50/50, more preferably about 90/10 to 60/40. When the ratio (content ratio) of (A) long fiber reinforced thermoplastic resin pellets to (B) flame retardant pellets (or (D) thermoplastic resin pellets) is larger than the above range, the moldability of the composition decreases. On the other hand, if it is smaller than the above range, the mechanical strength of the molded product obtained by molding the composition is lowered.

  (A) The content of the long fiber reinforced thermoplastic resin pellets may be 50 to 95% by weight, preferably 60 to 90% by weight, and more preferably about 70 to 85% by weight with respect to the entire composition. The content of (A2) long fibers contained in the (A) long fiber reinforced thermoplastic resin pellets is 25 to 75% by weight, preferably 30 to 70% by weight, more preferably 35 to 35% by weight based on the entire composition. It may be about 65% by weight, particularly about 40 to 60% by weight.

  (B) The content of the flame retardant pellets is 5 to 40% by weight, preferably 7 to 35% by weight, more preferably 10 to 30% by weight, particularly about 12 to 25% by weight, based on the entire composition. Also good. The content of the flame retardant (B1) contained in the flame retardant pellets (B) is 1 to 40% by weight, preferably 3 to 35% by weight, more preferably 5 to 30% by weight, based on the entire composition. In particular, it may be about 7 to 25% by weight.

  The feature of the present invention is that the use of a small amount of (C) lubricant improves the mixing property of the long fiber reinforced thermoplastic resin pellets and the flame retardant pellets and improves the homogeneity, moldability, etc. of the composition. is there. (C) Lubricant is (A) long fiber reinforced thermoplastic resin pellets, (B) flame retardant pellets and (D) thermoplastic resin pellets ((D) thermoplastic when not including (D) thermoplastic resin pellets. 0.005 to 0.15 parts by weight, preferably 0.007 to 0.12 parts by weight, and more preferably 0.01 to 0.1 parts by weight per 100 parts by weight of the resin pellets) Part, especially about 0.015 to 0.08 part by weight. The content of (C) lubricant is 0.005 to 0.15% by weight, preferably 0.007 to 0.12% by weight, more preferably 0.01 to 0.1% by weight, based on the entire composition. %, Particularly about 0.015 to 0.08% by weight.

  In addition, (A) long fiber reinforced thermoplastic resin pellet, (B) flame retardant pellet, (C) lubricant and (D) thermoplastic resin pellet ((D) heat when not including (D) thermoplastic resin pellet The total content of the plastic resin pellets is 0 part by weight) is 85 to 100% by weight, preferably 90 to 100% by weight, more preferably 95 to 99.9% by weight (for example, based on the total composition) 96 to 99.8% by weight).

  Such (A) long fiber reinforced thermoplastic resin pellets, (B) flame retardant pellets, (C) lubricants, and optionally (D) thermoplastic resin pellets, have mechanical strength and It is possible to form a molded product that can achieve both flame retardancy and a high level. More specifically, in the present invention, since (B) flame retardant pellets containing (B1) flame retardant at a high concentration are used as (B) flame retardant pellets, the flame retardant is effectively flame retardant even if the addition amount is small. And (A) high miscibility with the long fiber reinforced thermoplastic resin pellets. Furthermore, since the addition amount of the flame retardant pellet (B) is small, it is possible to suppress a decrease in the content ratio (or concentration) of (A2) long fibers (including fibers from which (A2) long fibers have been cut). In the object, the mechanical strength can be sufficiently exhibited. For example, in the composition of the present invention, for example, even if (B1) the flame retardant is contained at a high ratio of about 1 to 40% by weight (particularly 5 to 30% by weight) with respect to the whole composition, (A2 ) Decrease in the ratio (or concentration) of long fibers (including fibers from which (A2) long fibers are cut) can be suppressed, and high concentration (for example, 25 to 75% by weight (particularly, 40 to About 60% by weight).

In addition, because the composition contains the lubricant (C) at a specific ratio, the long fiber reinforced thermoplastic resin pellets are irregularly shaped (particularly columnar), but the long fiber reinforced Thermoplastic pellets and flame retardant pellets are easily mixed and homogenized. In addition, since the composition contains the lubricant (C) at a specific ratio, voids between pellets are reduced (or reduced), bulk density is increased, and transportation costs, storage space, etc. are effectively reduced. it can. Specifically, the bulk density of the composition of the present invention comprised of (A) long fiber reinforced thermoplastic resin pellets, (B) flame retardant pellets and (C) lubricant is (A) long fiber reinforced thermoplastic resin. 5-20%, preferably 6-18%, more preferably compared to the bulk density of the pellet and the mixture of (B) flame retardant pellets (or (C) the lubricant-free composition corresponding to the composition) May be about 7-15% larger. In addition, the said bulk density measures the weight (g) of a composition of fixed volume (mL), and a following formula Bulk density (g / mL) = Weight of composition (g) / Volume of composition (mL)
Is calculated using Furthermore, as described above, the composition is homogenized and the voids between the pellets are reduced (or reduced), and thus the pellets are excellent in form stability without separation (or separation). Therefore, the composition can maintain homogeneity over a long period of time and is excellent in storage stability.

  Furthermore, since the composition is excellent in biting ability with a melt molding machine (or a screw thereof) such as an injection molding machine, although it contains irregular shaped pellets containing fibers, as described later, Suitable for molding. Such a composition is useful for various molded articles (for example, molded articles that require flame retardancy) because excellent mechanical strength and flame retardancy are stably obtained even when subjected to molding. is there.

  In addition, the composition may contain conventional additives such as plasticizers, softeners, colorants, dispersants, mold release agents, stabilizers (hindered phenol antioxidants, phosphorus oxides) as necessary. Antioxidants such as antioxidants, sulfur-based antioxidants, UV absorbers, heat stabilizers, etc., antistatic agents, antiblocking agents, crystal nucleus growth agents, fillers (particulate fillers such as silica and talc) ) And the like. These additives may be used alone or in combination of two or more. The ratio of the additive can be appropriately selected depending on the type, and for example, 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, and more preferably 0.05 to 100 parts by weight of the composition. About 3 parts by weight may be used. The additive may be contained in (A) long fiber reinforced thermoplastic resin pellets, (B) flame retardant pellets, (C) lubricants and / or (D) thermoplastic resin pellets. It may be included independently.

[Method for Preparing Composition]
The composition consists of (A) long fiber reinforced thermoplastic resin pellets, (B) flame retardant pellets and (C) lubricant, and (D) thermoplastic resin pellets (hereinafter collectively referred to as “materials”) as necessary. May be prepared by dry blending (or dry blending). When the above materials are dry mixed (or dry blended), (A) long fiber reinforced thermoplastic resin pellets and (B) flame retardant pellets are uniformly mixed, and voids (or voids) between the pellets are reduced (or A reduced blend is obtained. In the present invention, since the mixing property of (A) long fiber reinforced thermoplastic resin pellets and (B) flame retardant pellets is improved, a mechanical operation (for example, melting) that deforms or eliminates the shape of the pellets A uniform blend having an increased bulk density can be obtained without going through kneading. Therefore, even if it uses for various shaping | molding, the excessive crushing of (A2) long fiber can be prevented.

  Specifically, the composition is often prepared by mixing (dry mixing) using a conventional mixer (for example, a conventional tumbler, mixer, etc.). The composition may be prepared by mixing the materials at once, or may be prepared by mixing the materials stepwise (or individually) in order to efficiently mix the materials.

  In addition, the method of preparing the composition containing the additive includes the (A) long fiber reinforced thermoplastic resin pellet, (B) flame retardant pellet, (C) lubricant, and (D) in the manufacturing process of each material. It may be a method of dry-mixing (or dry blending) a material containing an additive in at least one selected from thermoplastic resin pellets, and the material and the additive independent of the material are dry-type A method of mixing (or dry blending) may be used.

[Molding]
The composition can form various molded articles using a conventional molding method. Examples of the molding method include compression molding (or transfer molding), injection molding, extrusion molding, hollow molding (blow molding), and melt molding (or primary molding) such as calendar molding. Among these, the composition (or a molded product thereof) is used by utilizing the point that the composition is well entangled with the screw and is easily plasticized with a high kneading effect (in this specification, “excellent in biting property”). In order to further improve the uniformity (or homogeneity), it is preferable to use a molding method through melt-kneading, for example, injection molding, extrusion molding, calendar molding, or the like. In particular, it is preferable to use injection molding because it is excellent in productivity and quality stability (or dimensional accuracy) and can be easily molded even in a complicated shape. The injection molding machine that can be used is not particularly limited, and a conventional injection molding machine, for example, a pre-plunger plunger type injection molding machine in which the plasticizing process and the injection process are separate processes, the plasticizing process and the injection process are 1 A screw in-line injection molding machine that is a process can be used.

  Specifically, when the composition is injection molded using a screw in-line type injection molding machine, the supplied composition is heated and melted, and the screw is rotated and moved forward and backward to move the composition. The resulting resin composition may be injected into a mold, cooled and cured to form various molded articles.

  The heating temperature may be about 240 to 320 ° C, preferably about 260 to 310 ° C, and more preferably about 280 to 300 ° C. The cooling temperature (or mold temperature) may be 70 to 150 ° C, preferably 80 to 135 ° C, and more preferably about 90 to 120 ° C.

  In the present invention, in addition to using the composition having high uniformity (or homogeneity) as a molding material, the composition is excellent in biting property with respect to a melt molding machine (or a screw thereof) such as an injection molding machine. Since it exhibits a kneading effect and is easily plasticized, a resin composition with further improved uniformity can be obtained in the plasticizing step. Therefore, in a molded product obtained by molding the composition (or resin composition), (A2) the fibers from which the long fibers have been cut and (B1) the flame retardant are homogeneously dispersed. The mechanical strength and flame retardancy are evenly exhibited.

  In the present invention, as described above, (A) long fiber reinforced thermoplastic resin pellets containing (A2) long fibers having an average fiber length of 3 mm or more (particularly about 7 to 20 mm) are used, and dry mixing ( Since the composition is prepared by dry blending, the (A2) long fibers are not excessively cut even when subjected to molding (for example, injection molding), and the resulting molded product has relatively large fibers. Long fibers remain. Depending on the production conditions and molding conditions of the composition, the resulting molded article has, for example, an average fiber length of 0.5 to 5 mm, preferably 0.7 to 4 mm, more preferably 1 to 3 mm (for example, , 1.2 to 2 mm) may be included.

  As described above, the composition of the present invention is useful as a molded product (in particular, an injection-molded product), and particularly useful for various industrial products (or parts thereof) that require mechanical strength and flame retardancy. is there. For example, the composition of the present invention includes, for example, household appliances such as a washing machine, a washing / drying machine, and a dishwasher or parts thereof (for example, exterior members); electric / electronic parts (for example, personal computers, mobile phones, digital) It is useful as an office automation (OA) device such as a camera, or a casing or housing of an electric / electronic device such as a breaker.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, each evaluation method and symbol in an Example, a comparative example, and a reference example are as follows.

[Evaluation method]
(Tensile strength)
The tensile strength was measured according to ISO 527-1. Note that the measurement was performed on a completely dry sample.

(Charpy impact strength)
The Charpy impact strength was measured according to ISO 179 / 1eA (edgewise). Note that the measurement was performed on a completely dry sample.

(Load deflection temperature)
The deflection temperature under load was measured under the condition of 1.80 MPa in accordance with ISO75 / A.

(Flame retardance)
Flame retardancy was evaluated based on the UL94V standard. Thirty strip test pieces (thickness 1.6 mm) were prepared, and the flame retardancy was evaluated on five randomly selected test pieces. Burning duration (X seconds) after 10 seconds of indirect flame (first flame contact) using a burner at the lower end of the test piece, then burner again when the flame due to the first flame disappears Was used to measure the flammable combustion duration (Y seconds) after 10 seconds of indirect flame (second flame contact), and flame retardancy was determined based on the UL94V standard. In addition, in order to observe a flame-retardant variation, the said determination was similarly performed about another five test pieces selected at random.

(Average fiber length)
About 5 g of a sample was cut out from the molded product (ISO multi-purpose test piece) and incinerated at 650 ° C. to take out fibers contained in the molded product. The weight average fiber length was calculated from the lengths of 500 fibers randomly selected from the extracted fibers.

[Explanation of abbreviations]
(A) Long fiber reinforced thermoplastic resin pellets Long fiber reinforced thermoplastic resin pellets 1: “Plastron PA66-GF60-01” [60% by weight glass fiber reinforced polyamide 66 resin (pellet length 11 mm, Pellet diameter 2.5 mm)]
Long fiber reinforced thermoplastic resin pellet 2: “Plastoron PP-GF40-02” manufactured by Daicel Polymer Co., Ltd. [40% by weight glass fiber reinforced polypropylene resin (pellet length 11 mm, pellet diameter 2.9 mm)]
(B) Flame retardant pellet: “Hiromaster PC-80G” (manufactured by Suzuhiro Chemical, brominated polystyrene / antimony trioxide 90% masterbatch) and thermoplastic resin (mixture of polystyrene and polyethylene wax) are mixed, and Pellets prepared by melt kneading (columnar: pellet length 3 mm, pellet diameter 4.2 mm, (B1) flame retardant concentration 90 wt%, (B2) thermoplastic resin concentration 10 wt%)
(C) Lubricant Lubricant 1: Calcium stearate [manufactured by Sakai Chemical Industry Co., Ltd., “SC-100”]
Lubricant 2: Magnesium stearate [manufactured by Sakai Chemical Industry Co., Ltd., “SM-1000”]
(D) Thermoplastic resin pellets: polyamide 66 (manufactured by Ube Industries, “UBE nylon 2020U”), cylindrical (pellet length 2 mm, pellet diameter 2.7 mm)
Colorant: Black masterbatch for polyamide 66 (manufactured by Sumika Color Co., Ltd., “Black PAM-8A1649”)
Chopped strand glass fiber: “CSX 3J 451S” manufactured by Nittobo.

(Examples 1-4 and Comparative Examples 1-3)
(A) Long fiber reinforced thermoplastic resin pellets, (B) flame retardant pellets, (C) lubricant and (D) thermoplastic resin pellets are dry-mixed (or dry blended) in the proportions shown in Table 1 to obtain a composition. Prepared. The obtained composition was injection-molded under conditions of a molding temperature of 290 ° C. and a mold temperature of 100 ° C. using an injection molding machine (manufactured by Nippon Steel, “J150EII” cylinder diameter φ50 mm). About the obtained injection molded product, tensile strength, Charpy impact strength, deflection temperature under load, flame retardancy, and average fiber length of the molded product were evaluated.
In Comparative Example 3, (B) flame retardant pellets, (D) thermoplastic resin pellets and chopped strand glass fibers were used in the ratio shown in Table 1, using a twin-screw extruder (manufactured by Nippon Steel, “TEX30α”). The mixture was melt-kneaded and pelletized in advance (extrusion temperature 260 ° C.), and the resulting pellet (pellet length 3 mm, pellet diameter 3.5 mm) was injection-molded in the same manner as in the examples. About the obtained injection molded product, tensile strength, Charpy impact strength, deflection temperature under load, flame retardancy, and average fiber length of the molded product were evaluated.

  The results are shown in Table 1. In the table, “long fiber concentration” indicates the content of long fibers with respect to the entire composition, and X and Y in the “flame retardant” section, X and Y are respectively described in the section of the evaluation method. As shown, the flaming combustion duration after the first and second flame contact is shown.

  As can be seen from Table 1, the compositions of the examples are composed of specific (A) long fiber reinforced thermoplastic resin pellets, specific (B) flame retardant pellets and specific (C) lubricants. ) Since the lubricant is contained in a specific ratio, a molded product having excellent mechanical strength and flame retardancy can be formed. In Comparative Example 2, since the content of the (C) lubricant was high, the material did not bite into the injection molding machine, and slipped and could not be molded.

(Example 5, Reference Example 1 and Comparative Examples 4 to 5)
(A) Long fiber reinforced thermoplastic resin pellets, (B) flame retardant pellets, (C) lubricant and (D) thermoplastic resin pellets are dry-mixed (or dry blended) in the proportions shown in Table 2 to obtain a composition. Prepared. The obtained composition was filled into a 100 mL graduated cylinder, and the weight (Wg) and volume (VmL) of the filled composition were measured.
Bulk density (g / mL) = W (g) / V (mL)
The bulk density was calculated based on the formula represented by: The results are shown in Table 2.

  As is apparent from Table 2, in Example 5 containing (C) a lubricant, the bulk density was increased by about 9% compared to Comparative Example 4. In Reference Example 1, the bulk density was increased by about 9% compared to Comparative Example 5, indicating the usefulness of (C) the lubricant.

Claims (12)

A composition obtained by dry-mixing at least (A) a long fiber reinforced thermoplastic resin pellet, (B) a flame retardant pellet, and (C) a lubricant,
The (A) long fiber reinforced thermoplastic resin pellets are columnar pellets composed of (A1) thermoplastic resin and (A2) long fibers,
The (B) flame retardant pellet is composed of a master batch composed of (B1) a halogen-based flame retardant and (B2) a thermoplastic resin, and (B1) the content of the flame retardant is (B) a flame retardant. 70 to 99% by weight based on the whole pellet,
Wherein (C) lubricant _is a _{C 8-35} fatty acid _{magnesium, C 8-35} fatty acid _{calcium, C 8-35} fatty acid barium and _{C 8-35,} at least one member selected from the group consisting of fatty acid zinc salts, the (C ) A composition having a lubricant content of 0.005 to 0.15% by weight based on the whole composition.   The composition according to claim 1, wherein (A) the long fiber reinforced thermoplastic resin pellet is a pellet in which (A2) the long fiber is contained in substantially the same length as the pellet and substantially parallel to the length direction.   Further, (D) thermoplastic resin pellets are included, and the ratio of (A) long fiber reinforced thermoplastic resin pellets to (D) thermoplastic resin pellets is the former / the latter (weight ratio) = 99/1 to 40/60. The composition according to claim 1 or 2. (B1) The content of the halogen-based flame retardant is 1 to 40% by weight with respect to the entire composition, and (A2) the content of long fibers is 30 to 70% by weight with respect to the entire composition. Item 2. The composition according to Item 1 . (A) The long fiber reinforced thermoplastic resin pellet has an average diameter of 0.5 to 5 mm and an average length of 3 to 20 mm, and (C) the lubricant is a granular material having an average particle diameter of 5 to 500 μm. 5. The composition according to any one of 4 . (A1) The thermoplastic resin is a polyamide-based resin, and (C) the lubricant is saturated C _16-22 fatty acid magnesium and / or saturated C _16-22 fatty acid calcium . The content is 0.01 to 0.1% by weight, (B1) the flame retardant content is 5 to 30% by weight, and (A2) the long fiber content is 35 to 65% by weight. The composition according to any one of claims 1 to 5 . Process for producing at least (A) a long fiber-reinforced thermoplastic resin pellets, a flame retardant pellets (B), the composition according to any one of claims 1 to 6 were dry mixed and (C) a lubricant. Furthermore, (D) The method of Claim 7 which dry-mixes the thermoplastic resin pellet. A method of increasing the bulk density of the mixture by adding (C) a lubricant to a mixture containing at least columnar long fiber reinforced thermoplastic resin pellets (A) and (B) flame retardant pellets ,
The (A) long fiber reinforced thermoplastic resin pellets are columnar pellets composed of (A1) thermoplastic resin and (A2) long fibers,
The (B) flame retardant pellet is composed of a master batch composed of (B1) a halogen-based flame retardant and (B2) a thermoplastic resin, and (B1) the content of the flame retardant is (B) a flame retardant. 70 to 99% by weight based on the whole pellet,
Wherein (C) lubricant _is a _{C 8-35} fatty acid _{magnesium, C 8-35} fatty acid _{calcium, C 8-35} fatty acid barium and _{C 8-35,} at least one member selected from the group consisting of fatty acid zinc salts, the (C ) A method in which the content of the lubricant is 0.005 to 0.15% by weight based on the entire composition . Method for producing a molded article by melting a composition according to any one of claims 1-6. The method of claim 10 , wherein the melt molding is injection molding. A molded article obtained by the method according to claim 10 or 11 .