JP4359512B2 - Non-halogen flame retardant resin composition - Google Patents

Description

  The present invention relates to a non-halogen flame retardant resin composition that is excellent in safety to the environment because it has a soft and smooth feel and does not generate halogen gas during combustion, despite exhibiting high flame retardancy. .

  Since thermoplastic resins are flammable, various flame retarding techniques have been proposed for applications that require flame retardancy. Conventionally, a flame retardant formulation in which a halogen-based flame retardant such as a bromine compound having excellent flame retardancy and antimony oxide is blended in a resin has been widely used. Halogen flame retardant exhibits an excellent flame retardant effect due to radical trapping action and generation of non-flammable gas. However, since a halogen-based flame retardant generates a large amount of toxic gas at the time of a fire, recently, the emergence of a flame-retardant resin composition having a halogen-free formulation has been strongly desired.

  Various techniques using inorganic flame retardants such as magnesium hydroxide have recently been proposed for flame retardant formulations of polyolefin resins used as insulators and sheets for electric wires and cables. Inorganic flame retardants have the advantages of low toxicity, low smoke generation and low corrosiveness, and they exhibit flame retardant action by releasing crystal water during combustion, but the flame retardant is not strong, Even when 100 parts by mass of 100 parts by mass of low density polyethylene is blended, the oxygen consumption index shows only a value around 25. When an inorganic flame retardant surface-treated with a polyolefin resin and silicone are added, the flame retardancy is improved, but the flame retardant effect is not yet sufficient.

  The following have been proposed so far. A surface-treated inorganic flame retardant is used (see Patent Documents 1 to 3 in the next section). An inorganic flame retardant and organopolysiloxane are blended in the resin (see Patent Documents 4 to 6 in the next section).

  At present, the composition for electric wire coating that achieves VW-1 (passed the UL 758VW-1 standard) is 200 parts by mass or more of an inorganic flame retardant with respect to 100 parts by mass of the thermoplastic resin. Although it is obtained by blending, this has a drawback that the hardness (measured by a test based on hardness A of ISO 868) is too hard as 90 or more, and the contacted object is easily damaged.

JP-A-2-28434: A surface-treated inorganic flame retardant is used. JP-A-5-17692: A surface-treated inorganic flame retardant is used. JP-A-4-323265: A surface-treated inorganic flame retardant is used. JP-A-2-55751: An inorganic flame retardant and organopolysiloxane are blended in a resin. Japanese Patent Laid-Open No. 5-32830: An inorganic flame retardant and organopolysiloxane are blended in a resin. JP 2000-109622 A: An inorganic flame retardant and an organopolysiloxane are blended in a resin. JP 2003-128939 A: In addition to a mixture of a thermoplastic resin, an inorganic flame retardant, a highly polymerized dimethylorganopolysiloxane and a vinyl group-containing oily organopolysiloxane, a higher difficulty is obtained when a precious metal catalyst is blended. Shows flammability.

  Accordingly, the subject of the present invention is a non-halogen flame retardant resin that has high flame retardancy, has softness and smooth touch, does not generate halogen gas during combustion, and is excellent in environmental safety. It is to provide a composition.

  In order to solve the above-mentioned problems, the inventors have made various resin compositions as prototypes and studied them. As a result, an inorganic flame retardant, a high degree of polymerization dimethylorganopolysiloxane, and a vinyl group-containing oily organo When polysiloxane was blended, it was confirmed that an improvement in flame retardance exceeding expectations was observed. Furthermore, in addition to a mixture of a thermoplastic resin, an inorganic flame retardant, a highly polymerized dimethylorganopolysiloxane, and a vinyl group-containing oily organopolysiloxane, when a platinum group element-containing catalyst is blended, higher flame retardancy is achieved. It was confirmed (see Patent Document 7 in the previous section). However, even in the above composition, in order to clear VW-1, 180 parts by mass or more of an inorganic flame retardant must be compounded with respect to 100 parts by mass of the resin. The hardness was as high as 90 or more, and it was not possible to satisfy both softness and flame retardancy.

As a result of further investigations, the inventors further studied (A) 40-300 parts by mass of an inorganic flame retardant with respect to 100 parts by mass of the thermoplastic resin, and (C) high polymerization not containing an unsaturated functional group. Non-halogen flame retardant resin composition comprising 0.1 to 50 parts by mass of organopolysiloxane, (D) 0.01 to 10 parts by mass of unsaturated polyfunctional organopolysiloxane, and (E) 0.01 to 5 parts by mass of organic peroxide, and necessary Accordingly, an electric wire using a non-halogen flame retardant resin composition to which (F) a platinum group element-containing catalyst has been added as a coating agent is soft with a hardness of A85 or less and has a smooth tactile sensation. The present invention was completed by finding that it has flame retardancy that passes the above.
That is, the present invention relates to (A) 100 parts by mass of a thermoplastic resin, (B) 40 to 300 parts by mass of an inorganic flame retardant, and (C) a highly polymerized organopolysiloxane not containing an unsaturated functional group of 0.1 to A non-halogen flame retardant resin composition comprising 50 parts by mass, (D) 0.01 to 10 parts by mass of an unsaturated functional group-containing organopolysiloxane, and (E) 0.01 to 5 parts by mass of an organic peroxide. A non-halogen flame retardant resin composition in which a platinum group element-containing catalyst of component F) is added in an amount of 1 ppm to 5,000 ppm as a platinum group element with respect to the total amount of components (C) and (D).

  According to the present invention, a non-halogen flame retardant resin composition that exhibits high flame retardancy, has both softness and smooth touch and does not generate halogen gas during combustion, and is excellent in environmental safety.

  As the thermoplastic resin (A) in the present invention, low density polyethylene, high density polyethylene, linear low density polyethylene, ultra low density polyethylene, ultra high molecular weight polyethylene, polypropylene, polystyrene, ABS resin, polyamide, polycarbonate, polyethylene terephthalate Saponified ethylene-vinyl acetate copolymer such as polybutylene terephthalate, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene -Methyl acrylate copolymer, ethylene-acrylic acid amide copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-maleic anhydride copolymer Body, ionomer thermoplastic elastomers, polypropylene elastomers, there may be mentioned a polystyrene-based elastomer, but is not limited thereto. However, polyolefin resins are particularly preferred. These may be used alone or in combination of two or more.

  Examples of the inorganic flame retardant (B) in the present invention include metal hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimonate, and zinc borate. , Zirconium compound, molybdenum compound, calcium carbonate, silica, talc, titanium oxide, wax stone, quartz, diatomaceous earth, sulfide ore, sulfide calcined ore, graphite, bentonite, kaolinite, activated carbon, carbon black, zinc oxide, iron oxide , Marble powder, Portland cement, boron nitride, natural / synthetic mica, glass beads, sericite, and the like, but the present invention is not limited thereto. In particular, as the inorganic flame retardant (B), metal hydroxides are excellent, and among them, magnesium hydroxide, aluminum hydroxide and calcium hydroxide are preferable.

  The compounding quantity of (B) inorganic flame retardant in this invention is 40-300 mass parts of (B) component with respect to 100 mass parts of (A) component, Preferably, it is 50-150 mass parts. When the component (B) is less than 40 parts by mass, the flame retardant effect is insufficient, and when it exceeds 300 parts by mass, the hardness increases.

  In the present invention, the inorganic flame retardant of the component (B) is surface-treated with a compound other than the inorganic flame retardant treated with an unsaturated functional group-containing silane compound and the silane compound, or has been surface-treated. It is preferable to consist of no inorganic flame retardant. Moreover, it is preferable that mass ratio of both consists of 0.5: 99.5-100: 0, especially 20: 80-95: 5. The treatment amount of the unsaturated functional group-containing silane compound on the surface of the inorganic flame retardant is preferably 0.001 to 5% by mass of the amount of the inorganic flame retardant, and particularly preferably 0.01 to 3% by mass.

  The inorganic flame retardant surface-treated with the unsaturated functional group-containing silane compound is composed of the unsaturated functional groups of the silane compound, the thermoplastic resin of the component (A), or ( Crosslinks with the unsaturated functional group-containing organopolysiloxane of component D) to increase the strength of the composition.

  Unsaturated functional group-containing silane compounds used for the surface treatment of inorganic flame retardants include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (methacryloxypropyl) trimethoxysilane, etc. Can be mentioned.

式１中、Ｒ¹は炭素数１〜６の非置換又は置換一価炭化水素基、水酸基から選ばれる同種または異種の置換基である。このオルガノポリシロキサンの性状はオイル状、生ゴム状いずれであってもよい。 The highly polymerized organopolysiloxane which does not contain an unsaturated functional group as the component (C) in the present invention has a structure represented by the following formula 1.

In Formula 1, R ¹ is the same or different substituent selected from an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms and a hydroxyl group. The organopolysiloxane may be in the form of oil or raw rubber.

  If the value of n, which is the number of repeating siloxane units in Formula 1, is less than 2,200, the flame retardancy is lowered and the workability may be deteriorated. On the other hand, if n exceeds 4,000, the composition becomes too viscous and stirring during production becomes difficult, so n is 2,200 to 4,000, preferably 2,500 to 3,500.

Above, cyclo The unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms as R ¹ in Formula 1, for example, a methyl group, an ethyl group, a propyl group, an alkyl group, a cyclohexyl group, such as butyl Unsubstituted monovalent hydrocarbon groups such as alkyl groups and phenyl groups, and trifluoropropyl groups and cyanoethyl groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. A group selected from substituted monovalent hydrocarbon groups such as From the standpoint of characteristics, it is preferable that at least 80% of R ¹ contained in the entire highly polymerized organopolysiloxane not containing the unsaturated functional group of component (C) is a methyl group.

  The blending amount of the (C) high-polymerization degree organopolysiloxane not containing an unsaturated functional group in the present invention is 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the thermoplastic resin (A). More preferably, it is 2-15 mass parts. When the blending amount is less than 0.1 parts by mass, sufficient flame retardancy is not exhibited, and when it exceeds 50 parts by mass, the mechanical strength such as tensile strength and elongation may decrease. (C) component in this invention may use 2 or more types together.

（式２中、Ｒ¹は上述と同様の意味を示し、Ｒ²は不飽和官能基、ａは０≦ａ≦３、ｂは０＜ｂ≦３、ａ＋ｂは１≦ａ＋ｂ≦３の実数である。） The (D) unsaturated functional group-containing organopolysiloxane in the present invention has a structure represented by the following formula 2, and the molecular structure may be any of linear, branched or cyclic. The viscosity may be in the range of several mPa · s to tens of thousands mPa · s.

(In formula 2, R ¹ has the same meaning as described above, R ² is an unsaturated functional group, a is 0 ≦ a ≦ 3, b is 0 <b ≦ 3, and a + b is a real number 1 ≦ a + b ≦ 3. is there.)

R ² is an unsaturated functional group, and examples thereof include an alkenyl group having 2 to 8 carbon atoms and a (meth) acryloyl-containing group. Specific examples include a vinyl group, an allyl group, a hexenyl group, an acryloylmethyl group, a 3- (meth) acryloylpropyl group, a vinyloxypropyl group, and the vinyl group is particularly preferable from the viewpoint of reactivity.

  The viscosity at 25 ° C. of the (D) unsaturated functional group-containing organopolysiloxane in the present invention is preferably less than 10,000 mPa · s, and particularly preferably 500 mPa · s or less. In addition, the amount of unsaturated functional groups in the (D) unsaturated functional group-containing organopolysiloxane is preferably 2 mol% or more based on the total amount of substituents. In the case of less than 2 mol%, the flame retardancy decreases because the crosslinked film is weak. The kind of the substituent bonded to silicon other than the unsaturated group is not particularly limited.

  In the present invention, the mass ratio of (C) high-polymerization degree organopolysiloxane not containing unsaturated functional groups and (D) unsaturated functional group-containing organopolysiloxanes is excellent in flame retardancy in the range of 6: 4 to 9: 1. ing. Although the mechanism of flame retardancy is not clear, it is estimated as follows. That is, (C) the high-polymerization degree organopolysiloxane containing no unsaturated functional group increases the dispersion of (B) the inorganic flame retardant, and the high-polymerization degree organopolysiloxane or silica produced by combustion at the time of combustion is inorganic. Filling the space between flame retardants to improve flame retardancy, (D) Unsaturated functional group-containing organopolysiloxanes migrate to the combustion surface quickly due to their low molecular weight, and crosslink on the combustion surface. Forms a fuel film.

The (D) unsaturated functional group-containing organopolysiloxane in the present invention is blended in an amount of 0.01 to 10 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the (A) thermoplastic resin. When the amount of the unsaturated functional group-containing organopolysiloxane is less than 0.01 parts by mass, the unsaturated functional group reacts to form a crosslinked film that is weak and a film having sufficient strength cannot be formed. On the other hand, if the blending amount exceeds 10 parts by mass, the oily state causes slipping and insufficient dispersion.
Moreover, (D) addition of unsaturated functional group-containing organopolysiloxane lowers the glass transition point (Tg) of the composition and softens the composition. (E) Moderate crosslinking of (A) thermoplastic resin, (B) inorganic flame retardant or (C) unsaturated functional group-containing organopolysiloxane with an organic peroxide forms a strong network flame retardant coating. Therefore, the flame retardancy is further improved. Due to the synergistic effect of these plural components, the composition of the present invention can exhibit high flame retardancy while having a hardness A of 85 or less.

Examples of the organic peroxide (E) in the present invention include dicumyl peroxide, t-butylperoxy-2-ethylhexanate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t- Hexylperoxybenzoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-hexyl) Peroxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, n-butyl-4,4- Bis (t-butylperoxy) valerate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy) diiso Propylbenzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, t-butyl hydroperoxide, 1,1, Examples include 3,3-tetramethylbutylperoxy-2-ethylhexanate, benzoyl peroxide, t-butylperoxyacetate, and the like, but are not limited thereto.
Among these, organic peroxides belonging to peroxyketals and dialkyl peroxides are suitable for crosslinking because many of the generated free radicals are high.

(E) The type of the organic peroxide is selected in consideration of the 10-hour half-life temperature according to the temperature during normal processing. The processing temperature varies depending on the type of resin, but in the case of polyolefin resin, generally 80 to 250 ° C. is preferable.
The blending amount of the organic peroxide as the component (E) in the present invention is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the (A) thermoplastic resin.

By adding the (F) platinum group element-containing catalyst in the present invention, the flame retardant effect is further enhanced. Examples of the (F) platinum group element-containing catalyst in the present invention include platinum catalysts (such as platinum black), palladium catalysts, rhodium catalysts, chloroplatinic acid, chloroplatinic acid-olefin complexes, chloroplatinic acid-alcohol coordination compounds, Examples include rhodium-olefin complexes. (F) The platinum group element of the platinum group element-containing catalyst is particularly preferably platinum, palladium, or rhodium. In addition, the platinum group element-containing catalyst (F) is preferably not in the form of a platinum group element alone but in a complex state of the platinum group element, and particularly preferably a complex modified with siloxane or alcohol. Specifically, chloroplatinic acid, alcohol solution of chloroplatinic acid, reaction product of chloroplatinic acid and alcohol, reaction product of chloroplatinic acid and olefin compound, reaction product of chloroplatinic acid and vinyl group-containing siloxane, etc. Is mentioned.
In the present invention, the platinum group element-containing catalyst (F) is preferably blended in an amount of 1 to 5,000 ppm as the platinum group element content with respect to the total amount of the components (C) and (D). Even if a platinum group element-containing catalyst is not blended, (C) high polymerization degree polyorganosiloxane containing no unsaturated functional group and (D) unsaturated functional group-containing organopolysiloxane compounded to increase the flame retardant effect However, the flame retardancy is further increased by the addition of the (F) platinum group element-containing catalyst. However, if the platinum group element content exceeds 5,000 ppm, coloring due to complex formation may be observed, and if it is less than 1 ppm, the flame retardant effect may not be improved.

  In the non-halogen flame retardant resin composition of the present invention, additives can be blended depending on the purpose within a range not impairing the characteristics. Examples of the additives include antioxidants, ultraviolet absorbers, stabilizers, light stabilizers, compatibilizers, other types of non-halogen flame retardants, lubricants, fillers, adhesion aids, and rust inhibitors.

  Antioxidants that can be used in the present invention include 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl). ) Propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4 , 4′-butylidenebis- (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetra Oxaspiro [5,5] undecane, 4,4-thiobis- (2-tert-butyl-5-methylphenol), 2,2-methylenebis- (6-tert-butyl-methylphenol), 4,4-methylenebis- (2,6-di-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, trisnonylphenyl phosphite , Tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol phosphite, bis (2,6-di-) t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, teto Kiss (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, penta Erythritol tetrakis (3-laurylthiopropionate), 2,5,7,8-tetramethyl-2 (4,8,12-trimethyldecyl) chroman-2-ol, 5,7-di-t-butyl- 3- (3,4-Dimethylphenyl) -3H-benzofuran-2-one, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-dipentylphenyl acrylate 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, tetrakis (methylene) -3- (dodecylthiopropi Sulfonate) methane, and the like.

  Stabilizers that can be used in the present invention include lithium stearate, magnesium stearate, calcium stearate, barium stearate, zinc stearate, calcium laurate, barium laurate, zinc laurate, calcium ricinoleate, barium ricinoleate, ricinol Various metal soap stabilizers such as zinc acid, various organic tin stabilizers such as laurate, malate and mercapto, various lead stabilizers such as lead stearate and tribasic lead sulfate, and epoxy such as epoxidized vegetable oil Compounds, phosphite compounds such as alkylallyl phosphites, trialkyl phosphites, β-diketone compounds such as dibenzoylmethane and dehydroacetic acid, polyols such as sorbitol, mannitol, pentaerythritol, hydrotalcites Mention may be made of zeolites.

  Examples of light stabilizers that can be used in the present invention include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, oxalic anilide-based UV absorbers, and hindered amine-based light stabilizers. Agents and the like.

Examples of the compatibilizer usable in the present invention include acrylic organopolysiloxane copolymers, partially crosslinked products of silica and organopolysiloxane, silicone powder, MQ resin, anhydrous maleated graft-modified polyolefin, carboxylated graft-modified polyolefin, polyolefin Examples thereof include graft-modified organopolysiloxane.
Examples of the adhesion assistant that can be used in the present invention include various alkoxysilanes.

  Examples of other non-halogen flame retardants that can be used in the present invention include zinc borate, zinc stannate, various phosphorus flame retardants, expansive graphite, melamine cyanurate, guanidine sulfamate, and photo titanium oxide. . Examples of the filler include silicic acid, calcium carbonate, titanium oxide, carbon black, kaolin clay, calcined clay, aluminum silicate, magnesium silicate, calcium silicate and the like.

The non-halogen flame retardant resin composition of the present invention is prepared by heating and mixing the components (A) to (F) described above directly in a twin screw extruder, single screw extruder, Banbury mixer, or pressure kneader. However, preferably, an intermediate composition is prepared in advance by heating and mixing predetermined amounts of the components (B) to (F) other than the component (A) using the above-described mixing apparatus, and thereafter (A) A predetermined amount of the components are mixed, or a predetermined amount of the components (A) and (C) to (F) other than the component (B) is heated and mixed using the mixing apparatus described above to prepare an intermediate composition. Then, it is better in terms of handleability and dispersibility to prepare this composition by mixing a predetermined amount of component (B).
The non-halogen flame retardant resin composition of the present invention is particularly excellent as a flame retardant tube or flame retardant sheet molding material.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited to a following example. In addition, the number of the raw material column of Table 1 shows a mass part.
Various raw materials shown in Table 1 are put into a lab plast mill R250 mixer (manufactured by Toyo Seiki Co., Ltd.), mixed at 140 ° C., 30 rpm, 10 minutes, extruded as pellets, 150 ° C., 1 minute, 1 mm thick A sheet for hardness test was produced by press molding. Moreover, the above-mentioned pellet was coated on a copper wire having a cross-sectional area of 2 mm ² with a thickness of 0.8 mm to produce a VW-1 test electric wire.

(Hardness test)
Using the hardness test sheet prepared above, the hardness A was measured by a method based on ISO868, and the results are shown in Table 1.
(Flame retardancy test)
Using the VW-1 test wire prepared above, in accordance with UL standard UL758VW-1 “Vertical Flame Retardancy Test”, its flame retardancy was evaluated to determine pass / fail, and the results are shown in Table 1. Described.

The sources and product names of the raw materials listed in Table 1 are shown below.
(1) EVA (ethylene vinyl acetate) EVAFLEX 40LX
Made by Mitsui DuPont Polychemical Co., Ltd., trade name,
(2) EEA (ethylene ethyl acrylate) PES220
Made by Nihon Unicar, product name,
(3) Fine Mug MO-E methacryloxysilane treated magnesium hydroxide
Product name (4) Fine Mug MO-T Saturated fatty acid-treated magnesium hydroxide manufactured by TMG
Product name (5) High polymerization degree dimethylpolysiloxane, manufactured by TMG Co., Ltd. Dissolved viscosity at 25 ° C. 30,000 mPa · s (viscosity when dissolved in 30% xylene), estimated viscosity: about 2.4 million mPa · s
Made by Shin-Etsu Chemical Co., Ltd., trade name,
(6) Methyl vinyl silicone oil 10 mol% of vinyl groups in all substituents, viscosity at 25 ° C 700 mPa · s Shin-Etsu Chemical Co., Ltd.
(7) KF-96 Dimethyl silicone oil Viscosity at 25 ° C: 1 million mPa · s Product name manufactured by Shin-Etsu Chemical Co., Ltd.
(8) Perhexa 3M peroxyketal type organic peroxide, manufactured by NOF Corporation, trade name,
(9) CAT-PL-1 platinum complex Platinum amount: 2% Shin-Etsu Chemical Co., Ltd., trade name.
[Summary of Examples]

From the results of the examples described in Table 1, when comparing the hardness and flame retardancy of the test samples of Examples 1 to 6 and Comparative Examples 1, 2, 4, and 6, (A) component in the composition of the present invention The combination effect of all the components (E) is clearly shown, and the hardness and flame retardancy of the test samples of Examples 1 to 6 and Comparative Examples 3, 5, 7, 8, 9, and 10 are shown. From the comparison, it was found that if some of the combination components were missing, the effect was insufficient, and the effect of the composition of the present invention was proved.

Claims (12)

  (A) To 100 parts by mass of thermoplastic resin, (B) 40 to 300 parts by mass of an inorganic flame retardant, (C) 0.1 to 50 parts by mass of a highly polymerized organopolysiloxane not containing an unsaturated functional group, (D A halogen-free flame retardant resin composition comprising 0.01) to 10 parts by mass of an unsaturated functional group-containing organopolysiloxane and (E) 0.01 to 5 parts by mass of an organic peroxide.   Further, the platinum group element-containing catalyst of component (F) is a catalyst in which 1 ppm to 5,000 ppm is added as a platinum group element component with respect to the total amount of components (C) and (D). The non-halogen flame retardant resin composition according to claim 1.   The inorganic flame retardant of component (B) is an inorganic flame retardant surface-treated with an unsaturated functional group-containing silane compound and an inorganic flame retardant surface-treated with a compound other than the silane compound or not surface-treated. The non-halogen flame retardant resin composition according to claim 1 or 2, wherein the mass ratio of the two is 0.5: 99.5 to 100: 0.   The non-halogen flame retardant resin composition according to claim 3, wherein the amount of the unsaturated functional group-containing silane compound treated on the surface of the inorganic flame retardant is 0.001 to 5 mass% of the amount of the inorganic flame retardant.   The non-halogen flame retardant resin composition according to any one of claims 1 to 4, wherein the inorganic flame retardant as the component (B) is a metal hydroxide. The non-halogen flame retardant resin composition according to any one of claims 1 to 5, wherein the high-polymerization degree organopolysiloxane (C) has a structure represented by the following formula 1.

(In Formula 1, R ¹ is the same or different substituent selected from an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms and a hydroxyl group, and n = 2,200 to 4,000.) The halogen-free flame retardant resin composition according to any one of claims 1 to 6, wherein (D) the unsaturated functional group-containing organopolysiloxane has a structure represented by the following formula 2.

(In Formula 2, R ¹ has the same meaning as described above, R ² is an unsaturated functional group, a is 0 ≦ a ≦ 3, b is 0 <b ≦ 3, and a + b is a real number 1 ≦ a + b ≦ 3. is there.)   The halogen-free flame retardant resin composition according to any one of claims 1 to 7, wherein the unsaturated functional group-containing organopolysiloxane (D) has a viscosity at 25 ° C of 10,000 mPa · s or less. .   The unsaturated functional group content of the unsaturated functional group-containing organopolysiloxane of component (D) is 2 mol% or more based on the total amount of substituents bonded to silicon atoms. 9. The non-halogen flame retardant resin composition according to any one of 8 above.   The non-halogen flame retardant resin composition according to any one of claims 1 to 9, wherein the organic peroxide of component (E) is a peroxyketal or a dialkyl peroxide.   The halogen-free flame retardant resin according to any one of claims 2 to 10, wherein the platinum group element of the platinum group element-containing catalyst of component (F) is selected from platinum, palladium and rhodium. Composition. The non-halogen flame retardant resin composition according to any one of claims 1 to 11, wherein the thermoplastic resin is a polyolefin resin.