JP5462584B2 - Flame retardant resin composition containing glass long fiber and molded product - Google Patents

Description

  The present invention relates to a glass long fiber-containing flame-retardant resin composition and a molded article.

  Halogen-based flame retardants have been mainly used for flame-retarding polyolefin resins. However, in recent years, non-halogenation technology has been strongly desired from the viewpoint of environment and safety. Currently, as a non-halogenation technology, various flame retardants such as inorganic hydrate flame retardants, nitrogen flame retardants, phosphorus flame retardants, and expanded graphite flame retardants have been proposed. Further improvements have been attempted with respect to the properties of polyolefin resins with added flame retardants.

For example, Patent Document 1 describes a flame retardant resin composition in which melamine pyrophosphate, piperazine pyrophosphate, and a phosphate ester compound are added to a polypropylene resin to improve processability during molding. Patent Document 2 describes a technique for improving flame retardancy by adding a small amount of a metal oxide to a polypropylene resin containing a nitrogen-containing phosphorus flame retardant.
On the other hand, a technique for improving properties other than flame retardancy by adding the above-mentioned various non-halogen flame retardants to a polyolefin resin and further adding glass fibers is also known.
Patent Document 3 discloses that a flame retardant reinforced polyolefin resin in which expanded graphite and long glass fiber are added to a polyolefin resin, is inexpensive, has high mechanical strength, rigidity and impact strength, is lightweight, and has little warping deformation of a molded product. A molding material is disclosed. In Patent Document 4, ammonium polyphosphate, nitrogen-containing organic compound, and long glass fiber are added to polyolefin resin, and there is little generation of black smoke, toxic gas, etc. during combustion, and insulation, impact resistance, rigidity, and appearance are improved. A glass long fiber-containing resin composition that can suppress the decrease in surface resistivity by reducing the bleed-out of the flame retardant is well disclosed. In Patent Document 5, ammonium polyphosphate, nitrogen-containing organic compound, titanium oxide, and long glass fiber are added to polyolefin resin, and there is little generation of black smoke, toxic gas, etc. during combustion, insulation, impact resistance, rigidity A long glass fiber-containing resin composition having a good appearance is disclosed. In Patent Document 6, a flame retardant containing an ammonium polyphosphate and a nitrogen compound is added to a polyolefin resin, and long glass fibers are added. The balance between rigidity and impact resistance is excellent, and flame retardancy, elongation characteristics, and dimensional stability are improved. A long glass fiber-containing resin composition is described which is good and provides a drip prevention effect during combustion. Patent Document 7 discloses resin pellets containing polyolefin resin, polyphenylene ether, SEBS (polystyrene-poly (ethylene / butylene) block-polystyrene), aluminum phosphinate, and long glass fibers. By arranging the glass long fiber filler in the glass long fiber filler reinforced resin pellet in a spiral shape in the pellet with the length direction of the pellet as the central axis direction, longitudinal cracks during pellet transportation and long fiber filler Detachment from the pellet is extremely suppressed, the appearance of the pellet is excellent, and the long fiber filler at the time of molding is also excellent in defibration, making it possible to mold a molded body with extremely high heat resistance and impact resistance It has become.

JP2004-238568 JP-A-2005-42060 JP-A-8-143715 JP-A-9-227726 JP 10-310666 A JP 10-338774 A JP-A-2005-239939

  However, the techniques described in Patent Documents 6 to 7 still do not have sufficient flame retardancy. In order to increase the flame retardancy, it is necessary to add a large amount of flame retardant, but with the increase of the flame retardant, the inherent properties of the polyolefin-based resin become weaker and there is a limit to the formulation. In the inventions described in Patent Documents 1 to 5, although various properties are added or improved, with respect to flame retardancy, in Patent Document 3, there is an example in which the oxygen index is slightly increased by the addition of long glass fibers. It was only shown and a sufficiently high oxygen index was not obtained. In addition, weather resistance is not studied in any literature.

  In view of such a situation, the present invention contains a long glass fiber in a resin composition in which a phosphate compound is added as a flame retardant to a polyolefin-based resin, has a high oxygen index, and includes a long glass fiber excellent in weather resistance. An object is to provide a flame retardant resin composition and a molded article comprising the composition.

As a result of diligent research to solve the above problems, the present inventors have found that a resin composition comprising a polyolefin resin, a phosphate, and a long glass fiber has a high oxygen index and excellent weather resistance, The present invention was completed based on the knowledge.
That is, the present invention provides the following (A), (B) and (C) Ri name contains long glass fiber-containing flame-retardant resin composition characterized by containing neither expanded graphite and ammonium polyphosphate It is a thing.
(A) 100 parts by mass of polyolefin resin (B) 10 parts by mass or more and 200 parts by mass or less of a phosphate composed of the following (a) component and (b) component: (a) component: represented by the following general formula (1) Melamine pyrophosphate 1 to 99 parts by mass (b) Component: Piperazine pyrophosphate 1 to 99 parts by mass represented by the following general formula (3) (C) Polyolefin having an average length of 2 to 50 mm 0.5 to 200 parts by mass of the long glass fiber in the resin-impregnated glass long fiber pellet


(In the formula, n represents 2 and X ₁ is melamine represented by the following formula (2). P represents 2 )


Wherein Z ₁ and Z ₂ are —NH ₂ . ]


(Wherein, r is shown the 2, _{Y 1} is a pin Peraji down, q is 1.)

In the present invention, the component (B) is preferably 10 parts by mass or more and 111 parts by mass or less, more preferably 10 parts by mass or more and 95 parts by mass or less, and more preferably 10 parts by mass or more and 82 parts by mass or less. It is particularly preferred.
In this invention, it is preferable that they are 0.3 mass part or more and 360 mass parts or less of (C) component with respect to 100 mass parts of said (B) component.
Moreover, in this invention, it is preferable that the polyolefin resin of the said component (A) is a polypropylene.

  Further, in the present invention, the glass long fibers are blended as polyolefin resin pellets including glass long fibers having glass fibers arranged in parallel and having a length equal to a pellet length of 2 mm to 50 mm in length. Preferably there is.

The molded article of the present invention is characterized by comprising the above-described long glass fiber-containing flame-retardant resin composition.
Furthermore, the molded article of the present invention can be suitably used as a cable enclosure.

  Since the resin composition of the present invention comprises, for example, melamine pyrophosphate as the general formula (1), piperazine pyrophosphate as the general formula (3), and glass long fiber as the general formula (1). A flame retardant resin composition having a higher oxygen index, excellent weather resistance, less black smoke and toxic gas during combustion, and excellent insulation, impact resistance, rigidity, and appearance can be obtained. Accordingly, the long glass fiber-containing flame-retardant resin composition of the present invention includes an electric wire coating material, an optical fiber, an enclosure such as an electric wire, an end face plate, a power tool housing, a home appliance / OA product housing, an automobile material, a vehicle material, It is extremely useful for marine materials, aircraft materials and building materials.

It is a graph showing the relationship between the addition amount of a component (C) in each addition amount of a component (B), and an oxygen index. It is a graph showing the oxygen index rise width by addition of the component (C) in each addition amount of a component (B). The perspective view of the structural member of the enclosure for cables which concerns on one Embodiment of this invention.

Hereinafter, the present invention will be specifically described.
The long glass fiber-containing flame-retardant resin composition of the present invention is characterized by comprising the following (A), (B) and (C).
(A) 100 parts by mass of a polyolefin resin (B) 10 parts by mass or more and 200 parts by mass or less of a phosphate composed of the following (a) component and (b) component: (a) component: represented by the general formula (1) Phosphate compound 1 part by mass or more and 99 parts by mass or less (b) Component: Phosphate compound represented by the general formula (3) 1 part by mass or more and 99 parts by mass or less (C) The average length is 2 mm or more and 50 mm or less. In the polyolefin resin-impregnated glass long fiber pellet of 0.5 to 200 parts by mass of the long glass fiber, and 100 parts by mass of the (B) component, 0.3 to 360 parts by mass of the component (C).

[Component (A)]
Examples of the polyolefin resin as the component (A) include polypropylene resins, polyethylene resins, polybutene resins, polypentene resins, and thermoplastic elastomers. Examples of the polypropylene resin include a propylene homopolymer and a copolymer containing propylene as a main component. Examples of these copolymers include propylene / α-olefin copolymers. Examples of α-olefins include ethylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-octene, and the like. Examples include butene and 1-pentene.
Examples of the polyethylene resin include ethylene homopolymers and copolymers having ethylene as a main component. Examples of the copolymer include an ethylene / α-olefin copolymer. Examples of the α-olefin include 1-hexene, 4-methyl-1-pentene, 1-octene, 1-butene, 1 -A pentene etc. are mentioned. Moreover, polyethylene-type resin which has a polar group, for example, ethylene vinyl acetate copolymer (EVA), ethylene ethyl acrylate copolymer (EEA), etc. are mentioned.
Among the above-mentioned resins, polypropylene resin is particularly preferable in terms of rigidity and impact resistance.
In order to impart impact resistance, a polyolefin thermoplastic elastomer (TPO) or a styrenic thermoplastic elastomer such as SBR [polystyrene-polybutadiene rubber], SBS [polystyrene-polybutadiene block-polystyrene], SEBS [polystyrene-poly (ethylene / butylene) block-polystyrene], SIR [polystyrene-polyisoprene rubber], SIS [polystyrene-polyisoprene block-polystyrene], SEEPS [polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene. ], SEP [polystyrene-poly (ethylene / propylene) block], SEPS [polystyrene-poly (ethylene / propylene) block-polystyrene] and the like may be added. Of these, hydrogenated butadiene block copolymers and blocks TPO, SEBS, and SEPS are particularly preferably used. Examples of commercially available products include Clayton series such as Dynalon 6200 manufactured by JSR, R-110MP manufactured by Prime Polymer, Clayton G1651 manufactured by Shell Chemical Co., and Septon Series such as Septon 2104 manufactured by Kuraray, Asahi Kasei Chemicals The Tuftec H series manufactured by the company is listed.
Furthermore, in order to increase strength and rigidity, a polypropylene resin modified with maleic anhydride or the like, a polyethylene resin, a polybutene resin, a polypentene resin, a thermoplastic elastomer, or the like can be used.

[(B) component]
The phosphate compound represented by the general formula (1) used as the component (a) in the component (B) is a salt of phosphoric acid and a triazine derivative.
Examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by Z ₁ and Z ₂ in the general formula (2) include methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, and tertiary butyl. , Isobutyl, amyl, isoamyl, tertiary amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, decyl, etc. Examples of the 10 straight-chain or branched alkoxy groups include groups derived from these alkyl groups.
Specific examples of the triazine derivative include melamine, acetoguanamine, benzoguanamine, acrylic guanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, and 2,4-diamino-6-hydroxy-1. , 3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino- 6-ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2 , 4-diamino-6-mercapto-1,3,5-triazine, 2-amino-4,6-dimercapto-1,3,5-triazine and the like.
Examples of the phosphate compound represented by the general formula (1) preferably used as the component (a) include a salt of phosphoric acid and melamine. Examples of salts of phosphoric acid and melamine that are preferably used include melamine orthophosphate, melamine pyrophosphate, melamine polyphosphate, and the like. Among these, melamine polyphosphate in which p is 1 and X ₁ is melamine And melamine pyrophosphate in which n in the above general formula (1) is 2, p is 2, and X ₁ is melamine is particularly preferable. The salt of phosphoric acid and melamine can be obtained by the following method. For example, in the case of melamine pyrophosphate, sodium pyrophosphate and melamine are reacted by adding hydrochloric acid at an arbitrary reaction ratio, and neutralized with sodium hydroxide to obtain melamine pyrophosphate.

Among the components (B), the phosphate compound represented by the general formula (3) used as the component (b) is a salt of phosphoric acid and diamine or piperazine.
Specific examples of the diamine represented by Y ₁ in the general formula (3) include N, N, N ′, N′-tetramethyldiaminomethane, ethylenediamine, N, N′-dimethylethylenediamine, and N, N. '-Diethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N, N', N'-tetramethylethylenediamine, N, N, N ', N'-diethylethylenediamine, tetramethylenediamine, 1,2-propanediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10- Diaminodecane, piperazine, trans-2,5-dimethylpiperazine, 1, Examples include 4-bis (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine, and all commercially available products may be used.

Examples of the phosphate compound represented by the general formula (3) preferably used as the component (b) include a salt of phosphoric acid and piperazine. Specific examples of the salt of phosphoric acid and piperazine include piperazine orthophosphate, piperazine pyrophosphate, and piperazine polyphosphate. Among these, piperazine polyphosphate in which q in the general formula (3) is 1 and Y ₁ is piperazine is preferable, and piperazine pyrophosphate in which r is 2, q is 1 and Y ₁ is piperazine is particularly preferable.
The salt of phosphoric acid and piperazine can be obtained by the following method. For example, in the case of piperazine pyrophosphate, piperazine and pyrophosphoric acid are reacted in water or an aqueous methanol solution to easily obtain a poorly water-soluble precipitate. However, in the case of piperazine polyphosphate, a salt obtained from polyphosphoric acid and piperazine made of a mixture of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid and other polyphosphoric acids may be used, and the constitution of the raw material polyphosphoric acid is not particularly limited.

The mass ratio of the component (a) and the component (b) is 1:99 to 99: 1, preferably 10:90 to 90:10, and more preferably 30:70 to 70:30. When it is out of the range of 1:99 to 99: 1, the flame retarding effect is hardly exhibited.
The phosphate compound (B) having an average particle size of 40 μm or less, more preferably 10 μm or less is suitable from the viewpoint of flame retardancy. When the average particle diameter of the phosphate compound is larger than 40 μm, the dispersibility with respect to the polyolefin resin is deteriorated, and not only high flame retardancy may not be obtained, but also the mechanical strength of the molding resin is reduced. May bring.
(B) As for the compounding quantity of the phosphate compound of a component, 10 mass parts or more and 200 mass parts or less are preferable with respect to 100 mass parts of polyolefin resin, More preferably, they are 20 mass parts or more and 180 mass parts or less. When the blending amount is less than 10 parts by mass, a sufficient flame retarding effect cannot be obtained, and when it exceeds 200 parts by mass, the properties as a resin are deteriorated.
Examples of commercially available products of component (B) include FP2100J and FP2200 of ADEKA Corporation having piperazine pyrophosphate / melamine pyrophosphate = 60/40 (weight ratio).

[Component (C)]
As the component (C), continuous glass fibers can be used for the long glass fibers used in the present invention. An example of a continuous glass fiber bundle that is usually manufactured and marketed for resin reinforcement is glass roving. Usually, the average fiber diameter is 4 to 30 μm, the filament focusing number is 400 to 10,000, and the tex count is 300 to 20,000 g / km, preferably the average fiber diameter is 9 to 23 μm, the focusing number is 1, 000 to 6,000. From the viewpoint of the reinforcing effect, the surface is preferably subjected to silane treatment for imparting interfacial adhesion to the resin.
The long glass fiber used in the present invention is used as a pellet obtained by impregnating the above long glass fiber with polyolefin. Specifically, a long glass fiber roving consisting of thousands of filaments is guided to an impregnation die, uniformly impregnated with a molten polyolefin resin between the filaments, and then cut to the required length (2 mm to 50 mm). And a pellet-shaped composition comprising a polyolefin resin and long glass fibers is obtained. That is, the long glass fibers are arranged in parallel, and the length of the long glass fibers is equal to the pellet length of 2 mm to 50 mm.

In the present invention, for example, a glass long fiber-containing flame retardant resin composition molded article is obtained by dry blending a glass long fiber pellet and a polyolefin / phosphate flame retardant resin composition pellet and directly molding the mixture. can get.
In the present application, the average length of the long glass fiber is not the length of the long glass fiber in the molded product composition, but the length of the glass fiber in the long glass fiber pellet that is a blended raw material before molding.
The measuring method of the glass fiber length in the molded product of the glass fiber-containing flame-retardant resin composition is disclosed in the example of Japanese Patent No. 3422198 as follows. The molded product (about 5 g) is steamed at 600 ° C. for 5 hours, the residue is stirred in water, one part is transferred to a glass petri dish and dried, and the fiber length is measured. In the present invention, the glass fiber length measuring method described in the above-mentioned Japanese Patent No. 3422198, or the polyolefin component is eluted and removed from the molded product with hot xylene, and the length of the glass fiber is measured from the remaining phosphate / glass fiber mixture. The method to do was adopted.
When the glass fiber length in the molded article of the present invention is measured by these methods, the average is 1 to 6 mm. Since the length of the long glass fiber before molding is 2 mm or more and 50 mm or less, it indicates that the long glass fiber is cut when the screw rotates during molding and when the molten resin composition flows in the mold. .

  On the other hand, a short glass fiber is a glass fiber (chopped strand) having a fiber length of 3 mm. It is a chopped strand glass fiber that is not fundamentally impregnated with polyolefin, and cannot be directly molded like the above-mentioned long glass fiber pellet, and requires a melt-kneading step with polyolefin and phosphate, and then molded. . In the case of using short glass fibers, the glass short fibers are severely cut in the melt-kneading process, so that the average fiber length of the glass fibers in the molded product was 3 mm before molding. 1 mm or less.

The glass fiber length in the glass long fiber pellet is 2 mm or more and 50 mm or less, preferably 5 mm or more and 30 mm or less, and particularly preferably 5 mm or more and 20 mm or less. If it is less than 2 mm, the oxygen index, which is one of the flame retardancy evaluations, does not improve. If it exceeds 50 mm, it is difficult to bite the screw from the lower part of the hopper during molding, which is not realistic.
The compounding amount of the long glass fiber is 0.5 to 200 parts by mass, preferably 0.7 to 150 parts by mass, and particularly preferably 1.0 to 100 parts by mass. If it is less than 0.5 parts by mass, the oxygen index, which is one of the flame retardancy evaluations, is not improved, and if it exceeds 200 parts by mass, the properties as a resin are deteriorated, which is not preferable.
Moreover, the compounding quantity of the glass long fiber with respect to 100 mass parts of (B) component is 0.3 to 360 mass parts, Preferably it is 0.4 to 350 mass parts, Most preferably, it is 0.5. It is not less than 340 parts by mass. If it is outside the range of 0.3 parts by mass or more and 360 parts by mass or less, the oxygen index, which is one of the flame retardancy evaluations, is not improved.

(C) The following goods can be illustrated as a commercial item of the glass long fiber pellet of a component. Hereinafter, the propylene homopolymer is abbreviated as homo PP and the ethylene-propylene block copolymer is abbreviated as block PP.
Homo PP / glass long fiber = 50/50 weight ratio Nippon Polypro Funkster LR25Z, block PP / glass long fiber = 50/50 weight ratio Nippon Polypro Funkster LR85Z, Homo PP / glass long fiber = 42 Funkster LR26Y manufactured by Nippon Polypro Co., Ltd. with a / 58 weight ratio.

In the present invention, in addition to the above components, conventionally known flame retardants, flame retardant aids, additives, processing aids and the like can be added as necessary within a range that does not impair the purpose of the present invention. .
Examples of the flame retardant include halogen flame retardant, phosphate ester flame retardant, ammonium polyphosphate, red phosphorus, magnesium hydroxide, aluminum hydroxide, and expanded graphite.

As the flame retardant aid, both inorganic flame retardant aids and organic flame retardant aids can be added.
Inorganic flame retardant aids include magnesium hydroxide, hydrotalcite, talc, magnesium bicarbonate, zinc oxide, titanium oxide, aluminum oxide, magnesium oxide, silicon oxide, zirconium oxide, vanadium oxide, molybdenum oxide and their surface treatment Among them, magnesium bicarbonate, zinc oxide, titanium oxide, magnesium oxide and silicon oxide are preferably used from the viewpoint of the effect as a flame retardant aid. Specifically, magnesium bicarbonate (manufactured by Kamishima Chemical Co., Ltd., decomposition start temperature 210 ° C., magnesium carbonate having an average particle size of 15 μm), one type of zinc oxide (manufactured by Mitsui Kinzoku Co., Ltd.), partially coated zinc oxide (Mitsui Metal Fine Industry Co., Ltd.), Nano Fine 50 (Ultrafine Zinc Oxide with an average particle size of 0.02 μm: Sakai Chemical Industry Co., Ltd.), Nanofine K (Ultrafine particles coated with a zinc silicate with an average particle size of 0.02 μm) Zinc oxide: manufactured by Sakai Chemical Industry Co., Ltd.), TIPAQUE R-680 (titanium oxide: manufactured by Ishihara Sangyo Co., Ltd.), Kyowa Mag 150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.), Toxeal NP (silicon oxide, Tokuyama) For example).

Examples of the organic flame retardant aid include melamine, melamine cyanurate, pentaerythritol, dipentaerythritol, tripentaerythritol, monopentaerythritol, tris (2-hydroxyethyl) isocyanurate, polytetrafluoroethylene, and the like.
Each flame retardant aid may be used alone or in combination. Addition of flame retardant aids can reduce the amount of flame retardant blended, or flame retardancy that cannot be obtained with a flame retardant alone can be obtained, so use in combination as appropriate depending on the type and application of the resin blended with the flame retardant It is preferable. The particle size, melting point, viscosity, etc. of the flame retardant aid are selected so as to be excellent in flame retardancy and powder characteristics.

Examples of the antioxidant include phenolic compounds, phosphorus compounds, and thioether compounds.
Examples of phenolic antioxidants include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4- Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4′-thiobis (6-tert-butyl-m-cresol) 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tert-butyl- m-cresol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 2,2′-ethylidenebis (4-secondarybutyl-6-tert-butylphenol), , 1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanate Nurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl)- 2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-ditert-butyl) -4-hydroxyphenyl) propionate, tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate methyl] methane, thiodiethylene glycol bis [(3 5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4 -Hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-{(3-t Tributyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, And reethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate]. You may use these in mixture of 2 or more types.

  Examples of phosphorus antioxidants include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phos. Phyto, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tertiary) Tributylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite Phyto, bis (2,4-dicumylphenyl) pentae Thritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)- 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 2,2′-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2′-methylenebis (4,6- Tert-butylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4,6 Di-tert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl ) Oxy] ethyl) amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol, and the like. You may use these in mixture of 2 or more types.

  Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetra (β-alkylmercaptopropionate esters). These may be used as a mixture of two or more.

As the weathering agent, an ultraviolet absorber, a hindered amine light stabilizer, or the like can be used.
Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzo Triazol, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-tert-octyl) Phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′-methylenebis (4- 2- (2′-hydroxyphenyl) benzotriazole such as trioctyl-6- (benzotriazolyl) phenol), 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole Phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3,5-ditertiarybutyl-4-hydroxybenzoate, 2,4-ditertiaryamylphenyl-3,5-ditertiary Benzoates such as butyl-4-hydroxybenzoate and hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyloxanilide Substituted oxanilides such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl Cyanoacrylates such as ru-3- (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-ditert-butylphenyl) -s- Triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2, And triaryltriazines such as 4-ditertiarybutylphenyl) -s-triazine. You may use these in mixture of 2 or more types.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, and 2,2,6. , 6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-tetramethyl-4-piperidyl) sebacate Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4 Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6, 6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) ) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl- 4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2, 6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4- Piperidylamino) hex 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6 , 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis ( N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (1,2,2,6 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] hindered amine compounds such as aminoundecanoic the like. You may use these in mixture of 2 or more types.

As the lubricant, fatty acid amide, fatty acid ester, fatty acid, fatty acid metal salt system and the like can be used.
Examples of aliphatic amide lubricants include stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, ethylene biserucic acid amide, and ethylene bis lauric acid amide. It is done. You may use these in mixture of 2 or more types.

  Aliphatic ester lubricants include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl erucate, methyl behenate, butyl laurate, butyl stearate, isopropyl myristate, palmitic acid Isopropyl, octyl palmitate, octyl palm fatty acid, octyl stearate, beef tallow fatty acid octyl ester, lauryl lauryl, stearyl stearate, behenyl behenate, cetyl myristate, 28-30 carbon linear and unbranched saturated Monocarboxylic acid (hereinafter abbreviated as montanic acid) and ethylene glycol ester, montanic acid and glycerol ester, montanic acid and butylene glycol ester, montanic acid and trimethylolethane ester Esters of montanic acid and trimethylolpropane, esters of montanic acid and pentaerythritol, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquilate, sorbitan trioleate, polyoxyethylene sorbitan mono Examples thereof include laurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan trioleate. You may use these in mixture of 2 or more types.

Among the fatty acid lubricants, as saturated fatty acids, specifically, lauric acid (dodecanoic acid), isodecanoic acid, tridecylic acid, myristic acid (tetradecanoic acid), pentadecylic acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid) , Stearic acid (octadecanoic acid), isostearic acid, tuberculostearic acid (nonadecanoic acid), 2-hydroxystearic acid, arachidic acid (icosanoic acid), behenic acid (docosanoic acid), lignoceric acid (tetradocosanoic acid), serotic acid ( Hexadocosanoic acid), montanic acid (octadocosanoic acid), melicic acid and the like, and in particular, lauric acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid, and montanic acid.
Among the fatty acid lubricants, as the unsaturated fatty acid, specifically, myristoleic acid (tetradecenoic acid), palmitoleic acid (hexadecenoic acid), oleic acid (cis-9-octadecenoic acid), elaidic acid (trans-9-octadecenoic acid) ), Ricinoleic acid (octadecadienoic acid), vaccenic acid (cis-11-octadecenoic acid), linoleic acid (octadecadienoic acid), linolenic acid (9,11,13-octadecatrienoic acid), elestearic acid ( 9,11,13-octadecatrienoic acid), gadoleic acid (icosanoic acid), erucic acid (docosanoic acid), nervonic acid (tetradocosanoic acid), and the like. You may use these in mixture of 2 or more types.

  Examples of the fatty acid metal salt lubricant include lithium salt, calcium salt, magnesium salt and aluminum salt of the fatty acid of the above fatty acid lubricant. You may use these in mixture of 2 or more types.

Examples of the antistatic agent include cationic, anionic, nonionic, amphoteric, and fatty acid partial esters such as glycerin fatty acid monoester.
Specifically, alkyltrimethylammonium salt, dialkyldimethylammonium salt, benzalkonium salt, N, N-bis (2-hydroxyethyl) -N- (3-dodecyloxy-2-hydroxypropyl) methylammonium mesosulfate , (3-laurylamidopropyl) trimethylammonium methylsulfate, stearoamidopropyldimethyl-2-hydroxyethylammonium nitrate, stearoamidopropyldimethyl-2-hydroxyethylammonium phosphate, cationic polymer, alkylsulfonate Alkyl benzene sulfonate, sodium alkyl diphenyl ether disulfonate, alkyl nitrate ester salt, alkyl phosphate ester salt, alkyl phosphate amine salt, monoglyceride stearate , Pentaerythritol fatty acid ester, sorbitan monopalmitate, sorbitan monostearate, diglycerin fatty acid ester, alkyldiethanolamine, alkyldiethanolamine fatty acid monoester, alkyldiethanolamide, polyoxyethylene dodecyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol Examples thereof include monolaurate, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyether block copolymer, cetyl betaine, and hydroxyethyl imidazoline sulfate. You may use these in mixture of 2 or more types.

As the nucleating agent, rubitols, phosphorus-based, rosins, petroleum resins and the like can be used.
Examples of sorbitols such as alkyl-substituted benzylidene sorbitol include 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di- (p-methylbenzylidene) sorbitol, and 1,3-o-methyl. Benzylidene 2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di- (p-ethylbenzylidene) sorbitol, 1,3,2,4-di- (2 ′, 4′-dimethylbenzylidene) sorbitol . Examples of phosphorus-based compounds include bis (4-t-butylphenyl) sodium phosphate, 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) sodium phosphate, and organic phosphate-based composite products. In addition, sodium benzoate, pt-butyl aluminum benzoate, sodium montanate, calcium montanate, aluminum oxide, kaolin clay, talc, rosins, petroleum resins and the like can be mentioned. You may use these in mixture of 2 or more types.

As the metal deactivator, triazines, phosphones, epoxies, triazoles, hydrazides, oxamides, and the like can be used.
Specifically, N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, bis (2-phenoxypropionylhydrazide) isophthalate, decanedicarboxylic acid disali Tyroylbidazide, bisbenzylidenehydrazide oxalate, N, N′-bis {2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyl] ethyl} oxamide, 3- (N -Salicyloyl) amino-1,2,4, -triazole, acid amide, melamine, tris [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5-t-butyl) phenyl- 5-methyl] phosphite. You may use these in mixture of 2 or more types.

As the filler, talc, calcium carbonate, barium sulfate, carbon fiber, mica, wollastonite, whisker and the like can be used.
As the process stabilizer and softener, liquid paraffin, mineral oil softener (process oil), and mineral oil softener for non-aromatic rubber (process oil) can be used.
In addition, a coloring agent, an antiblooming agent, a surface treatment agent, an antibacterial agent, an anti-fogging agent (silicone oil described in JP-A-2009-120717, a monoamide compound of a higher aliphatic carboxylic acid, and a monovalent compound with a higher aliphatic carboxylic acid ˜Eye inhibitor such as a monoester compound obtained by reacting with a trivalent alcohol compound) may be added.

Examples of the method for producing the composition of the present invention include the following two methods.
(Method 1)
A glass fiber roving consisting of thousands of filaments is guided to an impregnation die and uniformly impregnated with a melted polyolefin resin between the filaments, and then cut to a required length (2 to 50 mm) to obtain a polyolefin resin and a long fiber. The glass long fiber pellet which is a pellet-like composition consisting of is obtained.
On the other hand, the polyolefin resin of component (A) and the phosphate of component (B) are mixed and melt-kneaded by an extruder to obtain a pellet-like flame retardant master batch composition.
Finally, the two pellets obtained above and, if necessary, polyolefin resin pellets are added, and the mixed pellets are dry blended and mixed with a tumbler or the like to obtain a long fiber reinforced resin composition.

(Method 2)
Glass fiber roving consisting of thousands of filaments is introduced into an impregnation die and uniformly impregnated with a molten resin composition of component (A) polyolefin resin and component (B) phosphate previously melt-kneaded between the filaments Then, it is cut into a required length (2 to 50 mm) to obtain a pellet-like long fiber reinforced resin composition.

(Melt-kneading method used in Method 1 and Method 2)
A flame-retardant resin composition can be produced by melt-kneading the blend of components (A) and (B) of the present invention by any method. Examples thereof include a method of using a high-speed stirrer represented by a Henschel mixer, a single- or biaxial continuous kneader, a roll mixer, etc. alone or in combination. In particular, the kneading extruder described in Japanese Patent No. 3964314 is preferably used. The kneading and extruding machine includes a biaxial kneading portion having a screw having a biaxial portion L / D (length / diameter) of 12 or more and having a damming structure at the end of the biaxial portion; A kneading and extruding machine in which the screw diameter D (mm) and the length L _f (mm) of the raw material supply section are in a relationship of (L _f /D)/D=0.12 to 0.33 mm ⁻¹ (1) Since the dispersibility of the flame retardant is remarkably improved, a high degree of flame retardancy is exhibited with a small amount of flame retardant, and mechanical properties are remarkably improved. (2) Surging does not occur, and from the open vent There is an advantage that the flame retardant is not ejected, productivity is improved, and (3) the extrusion performance (discharge amount) of melt-kneading is improved.

  Examples of the method for obtaining the molded article of the present invention include known and publicly-known molding methods using the composition of the present invention (injection molding, sheet molding, extrusion molding, profile extrusion molding, hot press molding, etc.), For reasons such as the appearance of the molded product obtained, a method of injection molding the composition of the present invention using an injection molding machine and a method of profile extrusion molding using a melt extruder are preferred.

Suitable examples of molded products include: wire covering materials, optical fibers, electric wire enclosures and end plates, power tool housings, home appliance / OA product housings, automotive materials, vehicle materials, marine materials, aircraft materials, and the like. Examples include building materials.
Also suitable are cable enclosures or end plates that require falling ball impact strength in products, tightening strength with metal bands, high flame resistance, ph of combustion gas, smoke concentration, molding heat resistance and weather resistance. .
Furthermore, building materials that require high flame retardancy such as quasi-incombustibility and non-combustibility are particularly suitable.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not restrict | limited at all by these Examples. The substances used in the following examples and comparative examples are as follows.

Component (A) Polyolefin SA06A (Homo PP) Made by Nippon Polypro
H-700 (Homo PP) made by Prime Polymer
J-784HV (Block PP) Made by Prime Polymer
B-780 (Block PP) Prime Polymer Component (B) Phosphate Compound
FP2100J (piverazine pyrophosphate / melamine pyrophosphate = 60/40 weight ratio) ADEKA component (C) Glass long fiber (as glass long fiber pellet)
LR-25Z (Homo PP / Glass long fiber = 50/50 weight ratio) Nippon Polypro Pellet length 10mm
LR-85Z (block PP / glass long fiber = 50/50 weight ratio) Nippon Polypro Pellet length 10mm
LR-26Y (Homo PP / Glass long fiber = 42/58 weight ratio) Pellets length 10mm made by Nippon Polypro
Short glass fiber
3J254S [Fiber diameter 13 μm, fiber length 3 mm glass fiber (chopped strand)] Other resin EG8200 (metallocene polyethylene resin) manufactured by Nittobo Glass Fiber Co., Ltd. Dow Chemical
Umex 1010 (Homo PP with 5% maleic anhydride addition) Other flame retardants manufactured by Sanyo Chemical Industries
AP422 (uncoated ammonium polyphosphate) manufactured by Clariant
GREP-EG (expanded graphite) made by Suzuhiro Chemical Co., Ltd.
AP745 (uncoated ammonium polyphosphate / tris (2-hydroxyethyl) isocyanurate / metal oxide = composition ratio not disclosed) Other flame retardant aid zinc oxide manufactured by Clariant Co., Ltd. Toxeal NP (silicon oxide) manufactured by Sakai Chemical Industry Co., Ltd. Tokuyama additive
ADK STAB AO-60 (phenolic antioxidant) Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane Made by ADEKA
ADK STAB 2112 (phosphorus antioxidant) Tris (2,4-di-t-butylphenyl) phosphite Made by ADEKA
Recommont ET132 (dispersant / lubricant) Montanate ester with saturated aliphatic carbon number 30 Made by Clariant
ADK STAB LA502 (Weatherproofing agent) N-methyl hindered amine / stabilizer mixture ADEKA
Diana Process Oil PW90 (Process Stabilizer) Mineral Oil Softener for Non-Aromatic Rubber Filler made by Idemitsu Kosan Co., Ltd.
JA-24RL (Talc) Asada Flour Mills

[1] Production The component (A) polyolefin resin, the component (B) (a) component and the phosphate (b) component and other components are mixed, melt-kneaded by an extruder, and pelletized flame retardant A production method for obtaining a master batch (hereinafter, master batch may be abbreviated as MB) composition was used. Hereinafter, each process will be described in detail.
(1) Preliminary mixing The components were mixed in the composition shown in Table 1, and premixed with a Henschel mixer. 0.2 100 parts by weight of Adeka Stub 2112, 0.1 part by weight of Adeka Stub AO-60, 0.3 part by weight of Recommont ET132, 0.6 part by weight of Adeka Stub LA502 and Diana Process Oil PW90 with respect to 100 parts by weight of the total amount of each component 0.3 parts by mass was added.

(2) Melt kneading According to the production method described in Japanese Patent No. 3964314, melt kneading was performed.
The obtained preliminary mixture was kneaded with an HTM type biaxial continuous kneading extruder HTM38 [screw system = 38 mm, L / D = 28 (biaxial part)] manufactured by CTE. The HTM kneading and extruding machine has a biaxial kneading part and a uniaxial kneading part in an integral structure, the screw is of a non-meshing different direction type, and the screw structure of the screw is a double thread, and the biaxial kneading part The first kneading part and the second kneading part have a Mixing Groter, and there is an open vent between the first kneading part and the second kneading part. At the end of the biaxial kneading part, a damming structure and resin flow rate adjustment Orifice adjustment function. The discharge amount of the flame retardant resin composition was adjusted by the damming structure and the orifice adjusting function. The orifice opening was fully open. From the orifice adjusting function part to the die is a uniaxial kneading part, and has a vacuum vent between them.
The screw size of the kneading machine is as follows: screw diameter D = 38 mm, L _{1 of} the first kneading part (mixin grouter length mm) / D = 12, L _{2 of} the second kneading part (mminx grouter length mm) / D = 3. Further, the operation conditions such as the discharge amount, the cylinder set temperature, and the screw rotation speed were kneaded under the operation conditions of the discharge volume 50 to 80 kg / h, the cylinder set temperature 200 to 210 ° C., and the screw rotation speed 500 rpm.
Table 1 shows the composition of flame retardant MB.

[2] Molding The flame retardant MB pellets obtained by melt-kneading, the glass long fiber pellets and, if necessary, the resin pellets are weighed to a predetermined composition shown in each table, dry blended, and mixed sufficiently uniformly.
This was put into a hopper of an injection molding machine and injection molded at a cylinder temperature of 190 to 210 ° C. and a mold temperature of 50 ° C. to produce a test piece and an enclosure member 1. FIG. 3 shows the produced enclosure member 1. The enclosure member 1 has a semi-cylindrical shape, and has an inner diameter of 190 mm (height 95 mm) and a length of 670 mm. In use, two enclosure members 1 are arranged opposite to each other and used in a cylindrical shape.

[3] Evaluation The characteristics of the test piece and the enclosure member 1 were evaluated by the following evaluation method. The evaluation results are shown in each table.
(1) Flame retardancy evaluation (oxygen index) Measured according to JIS K-7201.
Testing machine: Toyo Seiki Seisakusho Co., Ltd. Candle method combustion testing machine D-2 type
Test piece: A test piece of 120 × 6 × 3.2 mm was prepared from the ASTM D790 bending test piece.
Test method: A test piece was placed in an atmosphere of various oxygen concentrations, an igniter was brought close to the upper end of the test piece, and the oxygen concentration when a combustion time of 180 seconds or less and a combustion distance of 50 mm or less were satisfied after ignition was determined.
(2) Weather resistance evaluation Tester: Dewcycle Sunshine Super Long Life Weather Meter Suga Test Instruments Co., Ltd. Test piece: 50 x 50 x 3 mm
Test method: Using a sunshine weather meter, ultraviolet rays were irradiated for 1000 hours under the condition of 63 ° C. (with rain), the color difference (unit: ΔE) of the test piece before and after irradiation was measured, and the presence or absence of cracks was observed.
(3) Color difference ΔE measurement test machine: ΔE was measured by SM color computer SM-3 manufactured by Suga Test Instruments Co., Ltd.
(4) Flexural strength / elastic modulus Measured according to ASTM D790.
(5) Izod impact strength (with or without notch)
Measured according to ASTM D256.
(6) Measurement of glass fiber length in molded product The polyolefin component was eluted and removed from the molded product with hot xylene, and the length of the glass fiber was measured from the remaining phosphate / glass fiber mixture.
(7) Combustion gas ph
In accordance with JIS K-7217, the combustion gas was trapped, and its pH was measured and evaluated according to the following criteria.
○ pH is 5.0 or more △ pH is 3.5 or more and less than 5.0 x pH is less than 3.5 (8) Smoke concentration Measure the maximum smoke concentration during combustion according to JIS C-60695-6-31 And the following criteria evaluated.
○ Smoke density is less than 300 × Smoke density is 300 or more (9) Evaluation with enclosure members
[1] Ball drop impact strength A 3 kg steel ball was dropped from a height of 1.5 m and evaluated according to the following criteria.
○ It was not destroyed.
× Destroyed.
[2] Tightening strength with metal band The tightening load was 300 kg with a metal band, and the following criteria were used for evaluation.
○ It was not destroyed.
× Destroyed.
[3] Molding heat resistance The enclosure member 1 was molded at 190 to 210 ° C and evaluated according to the following criteria.
○ Good appearance of molded product and no moldability problems.
Δ: Appearance defects such as silver or flow mark were recognized on the surface of the molded product.
× There is a foaming phenomenon of the material during molding, and molding is impossible.

[Examples 1 to 24, Comparative Examples 1 to 6]
To the flame retardant MB pellets obtained in Table 1, glass long fiber pellets and, if necessary, polypropylene pellets are dry blended with the composition shown in Tables 2 and 3, followed by injection molding to form a molded product composition. Obtained. Tables 2 and 3 also show the results of evaluation of flame retardancy (oxygen index), physical properties, and weather resistance.

  Comparison in which composition (A) homo PP / component (B) FP2100J = 100/10 parts by mass, with component (C) glass fiber added in an amount of 0 to 25 parts by mass, no glass fiber added Although the oxygen index is 21 in Example 1, the oxygen index is increased by 2 and increased to 23 by adding only 1 part by mass of the glass long fiber in Example 1. In Example 2, 5 parts by mass of long glass fiber has an oxygen index of 24, in Example 3, 10 parts by mass of long glass fiber has an oxygen index of 25, and in Example 4, 25 parts by mass of long glass fiber has an oxygen index of 25. The glass fiber increased with the amount of long fiber added, and the glass long fiber reached almost the maximum value at 5 or 10 parts by mass, and then maintained without lowering.

Component (A) Homo PP / Component (B) FP2100J is composed of 100/30, 100/50, 100/82, 100/111 and 100/180 parts by mass of component (C) long glass fiber. Similar results were also obtained in the system to which was added.
The results are summarized in FIG. Thus, the addition of only 1 part by mass of component (C) glass long fiber to the composition of component (A) homo-PP / component (B) FP2100J increases the oxygen index, and together with the amount of glass long fiber added. The oxygen index increased and then reached the maximum value, and was maintained without decreasing even in the region where the amount of long glass fiber added was large.
Moreover, in each addition amount of component (B) FP2100J, the bending strength, the flexural modulus, and the impact strength increased with the addition amount of the long glass fiber. Furthermore, the weather resistance did not decrease even when glass long fibers were added.
In the composition system in which the composition of component (A) homo PP / component (B) FP2100J is 100/10, 100/30, 100/50, 100/82, 100/111, 100/180 parts by mass, component (B ) FIG. 2 shows the relationship between the increase in oxygen index due to the addition of long glass fibers (the maximum value of oxygen index when glass long fibers are added—the oxygen index when glass long fibers are not added) at each addition amount (part by mass) of FP2100J. . Thus, as the amount of component (B) FP2100J added increases, the range of increase in the oxygen index due to the addition of long glass fibers increased. This is considered to be because the amount of carbonized layer generated increases as the amount of component (B) FP2100J added increases, and a stronger carbonized layer is obtained due to the reinforcing effect of the long glass fiber, resulting in a high oxygen index.

  In particular, Examples 23 and 24 of the present invention have an oxygen index of 74 and substantially retain practical properties. In general, the oxygen index of a resin having a very high oxygen index is 36 to 37 for the super engineering plastic polyimide, 45 to 49 for the vinyl chloride, and 60 for the vinylidene chloride, respectively. While the long glass fiber-containing flame retardant resin composition of Examples 23 and 24 of the present invention uses PP having a flammable oxygen index of 18 as compared to a resin whose oxygen index is considered to be very high, It can be seen that the oxygen index has been dramatically improved (oxygen index 74).

[Examples 25-30, Comparative Examples 7-12]
The molding compositions of Examples 25 to 30 were obtained in the same manner as described in Examples 1 to 24 using the compositions described in Table 4.
In Comparative Examples 8 to 12, a master batch was not used, the entire formulation (composition breakdown in Table 4) was melt-kneaded, and the produced pellets were injection molded to obtain molded product compositions. The evaluation results are shown in Table 4.

In Table 4, when Examples 28 and 29 are compared, even if the component (A) homo PP / component (B) FP2100J / component (C) glass long fiber component (A) is changed from homo PP to block PP, It can be seen that there is no change in oxygen index, physical properties and weather resistance. Further, the difference between Examples 28 and 30 is that a small amount of zinc oxide was added. As a result, in Example 30, the oxygen index was further improved.
Example 28 is a long glass fiber, Comparative Example 8 is a short glass fiber, and Comparative Example 7 is an example with no glass fiber added. In Comparative Example 8 and Comparative Example 7, since the oxygen index is almost the same, the short glass fiber added system has almost the same oxygen index as the non-added system, that is, the effect of improving the oxygen index by adding the short glass fiber. There is no. Moreover, the physical property and the weather resistance of the short glass fiber addition system (Comparative Example 8) were lower than those of the long glass fiber addition system (Example 28).
Comparative Example 9 is an example in which the long glass fiber was replaced with talc in Example 28. When comparing the talc-added system (Comparative Example 9) and the non-added system (Comparative Example 7), the oxygen index of the talc-added system was lower than that of the non-added system. In addition, the physical properties and weather resistance of the talc-added system were lower than those of the glass long fiber-added system.

  Patent Document 7 describes a technology in which a nitrogen-containing phosphorus-based flame retardant is added to a polypropylene resin and a metal oxide is added. By adding a specific metal oxide in a small amount to a nitrogen-containing phosphorus-based flame retardant, It is disclosed that the oxygen index of the resin is increased. As shown in Comparative Examples 10-12, when FP2100J is used as the nitrogen-containing phosphorus-based flame retardant and silicon oxide is used as the metal oxide, an effect of improving the oxygen index is recognized with 1 to 3 parts by mass of silicon oxide, but 10 masses. The oxygen index decreased when the amount was more than 1 part. Moreover, physical properties and weather resistance were lowered. On the other hand, as shown in Examples 25 to 28, the system in which the long glass fiber was added increased the oxygen index with the addition amount of the long glass fiber, and the oxygen index did not decrease even when a large amount was added. Also, there is no decrease in physical properties and weather resistance.

[Examples 31-32, Comparative Examples 14-18]
Examples 31 to 32 and Comparative Examples 14 to 18 were obtained in the same manner as described in Examples 1 to 24 using the compositions described in Table 5. The evaluation results are shown in Table 5.

Patent Document 3 describes a technique of blending expanded graphite and long glass fibers with a polyolefin resin. Using the same composition, Example 1 of the patent document was reproduced as Comparative Example 15, and Comparative Example 1 of the patent document was reproduced as Comparative Example 14. First, when Comparative Example 14 and Comparative Example 15 are compared, in Comparative Example 15 in which glass long fibers were added, in Comparative Example 15 in which glass long fibers were not added, although the weather resistance was lowered, various physical properties were improved. Recognize. However, the oxygen index is only 1.5, and the effect of adding glass long fibers is small. This result is the same as the result described in Patent Document 3.
As a flame retardant, a phosphate compound was used instead of expanded graphite, and the present invention was carried out at a composition ratio similar to that of Patent Document 3. As shown in Comparative Example 13 and Example 31, Good weather resistance was obtained.

Patent Document 6 describes a resin composition in which AP745 in which ammonium polyphosphate and a flame retardant aid are blended as a flame retardant and a glass long fiber are added to a polyolefin resin. Using the same composition ratio in the present invention, Comparative Example 1 of the patent document was reproduced in Comparative Example 17, and Example 2 was reproduced in Comparative Example 18.
As a result, similar to the result described in Patent Document 6, the oxygen index was 43 in Comparative Example 17 where no long glass fiber was added, whereas the oxygen index was 40 in Comparative Example 18 where glass long fiber was added. Declined. Generally, as the amount of flame retardant added increases, the oxygen index increases. However, in these comparative examples, the oxygen index slightly decreases with the addition of long glass fibers.
When the present invention was carried out at the same composition ratio as that of Patent Document 6, as shown in Comparative Example 16 and Example 32, the present invention has a significantly higher oxygen index than the technique described in Patent Document 6. Moreover, bending strength and bending elastic modulus are high, and weather resistance is also good.

[Examples 33 to 34, Comparative Examples 19 to 20]
Examples 33 to 34 and Comparative Examples 19 to 20 in Table 6 are respectively Example 33 in Example 31 in Table 5, Example 34 in Example 32 in Table 5, and Comparative Example 19 in Comparative Example 15 in Table 5. Comparative Example 20 has the same composition as Comparative Example 18 in Table 5. Table 6 shows the pH of the combustion gas of each composition, the maximum smoke concentration during combustion, and the evaluation results of the enclosure molded product.

Patent Document 3 describes a technique of blending expanded graphite and long glass fibers with a polyolefin resin. Example 1 of the patent document was reproduced in Comparative Example 19 using the same composition. Moreover, when a phosphate compound was used instead of expanded graphite as a flame retardant, Example 33 in which the present invention was carried out at a composition ratio similar to that of Patent Document 3 was compared with Comparative Example 19, and Comparative Example 19 was observed during combustion. While harmful and corrosive acidic gas was generated, Example 33 of the present invention did not generate acidic gas. Expanded graphite is considered to generate acidic gas because concentrated sulfuric acid and concentrated nitric acid are intercalated between graphite layers. Furthermore, in terms of moldability, Comparative Example 19 has a slightly poor appearance of the molded product, but Example 33 of the present invention has a good appearance. Further, as shown in Table 5, Example 31 (Example 33) has better flame retardancy, physical properties, and weather resistance than Comparative Example 15 (Comparative Example 19), and Example 33 of the present invention. Is suitable for enclosures.

Patent Document 6 describes a resin composition in which AP745 in which ammonium polyphosphate and a flame retardant aid are blended as a flame retardant and a glass long fiber are added to a polyolefin resin. Example 2 of the patent document was reproduced as Comparative Example 20 using the same composition ratio in the present invention. Moreover, when Example 34 which implemented this invention by the composition ratio similar to patent document 6 and the comparative example 20 were compared, neither generation | occurrence | production of an acidic gas and smoke concentration were not high, but the comparative example 20 was a shaping | molding. Enclosure could not be molded due to foaming. Since the flame retardant used in Patent Document 6 has low heat resistance, when a large molded product such as an enclosure is molded, the flame retardant is caused by shearing heat generation due to a large screw diameter of a large injection molding machine. It is easy to thermally decompose and foam, making it difficult to mold. On the other hand, since the phosphate of the flame retardant of the present invention has high heat resistance, it can be molded without problems even in a large molded product such as an enclosure.

  The long glass fiber-containing flame-retardant resin composition of the present invention includes a wire covering material, an optical fiber, a sleeve for a closure such as an electric wire, a power tool housing, a home appliance / OA product housing, an automobile material, a vehicle material, and a marine material. It can be suitably used for aircraft materials and building materials.

    1 ... Enclosure material

Claims (9)

Following (A), (B) and (C) Ri name contains long glass fiber-containing flame-retardant resin composition characterized by containing neither expanded graphite and ammonium polyphosphate.
(A) 100 parts by mass of polyolefin resin (B) 10 parts by mass or more and 200 parts by mass or less of a phosphate composed of the following (a) component and (b) component: (a) component: represented by the following general formula (1) Melamine pyrophosphate 1 to 99 parts by mass (b) Component: Piperazine pyrophosphate 1 to 99 parts by mass represented by the following general formula (3) (C) Polyolefin having an average length of 2 to 50 mm 0.5 to 200 parts by mass of the long glass fiber in the resin-impregnated glass long fiber pellet

(In the formula, n represents 2 and X ₁ is melamine represented by the following formula (2). P represents 2 )

Wherein Z ₁ and Z ₂ are —NH ₂ . ]

(Wherein, r is shown the 2, _{Y 1} is a pin Peraji down, q is 1.) The (B) component, the long glass fiber-containing flame-retardant resin composition according to claim 1, characterized in that at most 111 parts by mass or more 10 parts by weight. The (B) component, the long glass fiber-containing flame-retardant resin composition according to claim 1, characterized in that at most 95 parts by mass or more 10 parts by weight. The (B) component, the long glass fiber-containing flame-retardant resin composition according to claim 1, characterized in that at most 82 parts by mass or more 10 parts by weight. The glass length according to any one of claims 1 to 4 , wherein the amount of the component (C) is 0.3 parts by mass or more and 360 parts by mass or less with respect to 100 parts by mass of the component (B). A fiber-containing flame-retardant resin composition. The glass fiber-containing flame-retardant resin composition according to any one of claims 1 to 5 , wherein the polyolefin resin as the component (A) is polypropylene. The said glass long fiber is mix | blended as a polyolefin resin pellet in which glass fiber is arranged in parallel and contains the glass long fiber of the length equal to the pellet length of 2 mm or more and 50 mm or less in length. 6. The long glass fiber-containing flame-retardant resin composition according to any one of 6 above. A molded article comprising the long glass fiber-containing flame-retardant resin composition according to any one of claims 1 to 7 . The molded article according to claim 8 , wherein the molded article is a cable enclosure.