JP5136801B2 - Flame retardant thermoplastic resin composition and method for producing the same - Google Patents

Description

  The present invention relates to a flame retardant thermoplastic resin composition having no problem in terms of safety and environment, yet having excellent flame retardancy and mechanical properties (tensile strength, elongation), and a method for producing the same.

In recent years, the replacement of products using conventional flame retardants has been promoted due to increasing interest in safety and the environment.
That is, halogen-based flame retardants such as bromine and chlorine have high flame retardancy and can be formulated in a small amount, so that they have excellent mechanical strength and the like of the composition. Therefore, people in the building have difficulty breathing, and in the worst case, there is a problem that leads to death. Phosphate ester flame retardants are likely to elute from the resin surface, and there are concerns about toxicity and mutagenicity when they flow into nature. In addition, red phosphorus flame retardants have high flame retardant properties due to their high phosphorus concentration, but incomplete combustion generates highly toxic phosphine gas, and there is a risk that red phosphorus itself may ignite due to friction and impact. Have. That is, there is a recognition that such conventional halogen-based, phosphoric ester-based, and red phosphorus-based flame retardants are generally difficult to use because of their effects on safety and the environment.

Considering safety for the environment and life, flame retardants are limited to metal hydroxides, silicone flame retardants, non-halogen flame retardants (inorganic phosphorus flame retardants) containing phosphorus and nitrogen.
However, if the metal hydroxide is not blended in a large amount with respect to the resin (100 to 250 parts by mass with respect to 100 parts by mass of the resin), a sufficient flame retardant effect cannot be obtained. It becomes a fragile composition. Silicone flame retardants are weak in flame retardancy and are not suitable for other than polycarbonate resins having flame retardancy of UL-24 V-2 or higher. Non-halogen flame retardant containing phosphorus and nitrogen such as ammonium polyphosphate is not as much as metal hydroxide, but requires a certain amount of blending (60 to 70 parts by mass with respect to 100 parts by mass of resin). The problem is a decrease in mechanical strength such as tensile strength and elongation, and deterioration of the resin by phosphoric acid eluted in the presence of water.
For this reason, it is preferable to exhibit a flame-retardant effect with a small compounding amount of ammonium polyphosphate by using a flame retardant aid having a synergistic effect. As a typical flame retardant aid, for example, a polyhydric alcohol such as pentaerythritol is known, and by using this together, the amount of ammonium polyphosphate, which is a flame retardant, is reduced with respect to 100 parts by mass of the resin. Although it can be reduced to 25 parts by mass, it is still insufficient.
Also, various other flame retardant aids for ammonium polyphosphate have been proposed, but the amount of the flame retardant is still large and insufficient.

For example, Japanese Patent Laid-Open No. 05-039394 (Patent Document 1) describes (A) 0.5 to 25 parts by mass of an organosilicone compound, (B) ammonium polyphosphate or melamine-modified polyphosphorus, relative to 100 parts by mass of a polypropylene resin. A flame retardant polypropylene resin composition containing 18 parts by mass or more of ammonium acid and 8 parts by mass or more of (C) a polyhydric alcohol compound is disclosed. In this case, the flame retardant is the component (B) and the flame retardant aids are the components (A) and (C). As far as the examples are concerned, the amount of the component (B) with respect to 100 parts by mass of the polypropylene resin is 20 It is confirmed that the amount is more than mass parts.
In addition, the organic silicone compound in the document includes silicone oil, dimethylpolysiloxane, methylphenylpolysiloxane as a silicone resin, vinyltrimethoxysilane as a silane coupling agent, and a silicone surfactant, In these silicones, the flame retardant synergistic effect of ammonium polyphosphate and polyhydric alcohol is hardly recognized.

  JP-A-06-025465 (Patent Document 2) includes (a) one or more thermoplastic polymers or 90-50 parts by mass of rubber-like elastic polymer, and (b) cyanuric acid and piperazine. A self-extinguishing composition comprising 3 to 20 parts by weight of a reaction product and optionally 5 to 30 parts by weight of (c) one or more ammonium phosphates or amines or phosphate esters is disclosed. In this case, the flame retardant is the component (c) and the flame retardant aid is the component (b). In this example, the amount of the component (c) is 29.1 parts by mass with respect to 100 parts by mass of the component (a). It is confirmed that the content is as high as (20.15% by mass) or more.

  Furthermore, JP-A-07-097478 (Patent Document 3) describes (A) a polyhydric alcohol / boric acid metal complex in an amount of 1 to 30 parts by mass, (B) ammonium polyphosphate, or 100 parts by mass of a thermoplastic resin. A flame retardant thermoplastic resin composition containing 15 to 30 parts by mass of melamine-modified ammonium polyphosphate and (C) 3 to 30 parts by mass of melamine or a melamine derivative such as melamine cyanurate or melem is disclosed. In this case, the flame retardant becomes the component (B) and the flame retardant aid becomes the components (A) and (C). In this example as well, the amount of the component (B) with respect to 100 parts by mass of the thermoplastic resin is 20 masses. It is confirmed that there are many parts and more.

JP-A-09-0235407 (Patent Document 4) discloses (A) an ammonium polyphosphate compound as a thermoplastic resin in an amount of 1 to 30% by mass with respect to the composition and (B) a specific phosphate amine salt. Discloses a flame retardant thermoplastic resin composition containing 1 to 30% by mass of the composition. In this case, the flame retardant becomes the components (A) and (B). In this example, the amount of the components (A) and (B) with respect to 100 parts by mass of the thermoplastic resin is 33.9 parts by mass (25 parts by mass). %) Or more.
As described above, in any case, the amount of the flame retardant relative to the thermoplastic resin is large, there is no problem in terms of safety and environment, and yet the flame retardant thermoplastic resin has excellent flame retardancy and mechanical properties (tensile strength, elongation). The fact is that the composition does not exist.

Japanese Patent Laid-Open No. 05-039394 Japanese Patent Application Laid-Open No. 06-025465 Japanese Patent Application Laid-Open No. 07-097478 JP 09-235407 A

  The present invention has been made in view of the above circumstances, there is no problem in terms of safety and environment, yet flame retardant thermoplastic resin composition having excellent flame retardancy and mechanical properties (tensile strength, elongation) (however, An object of the present invention is to provide a method for producing the same and a polyurethane resin.

  As a result of intensive studies to achieve the above object, the present inventor has (A) a thermoplastic resin (excluding a polyurethane resin) as a main raw material, and (B) contains phosphorus and nitrogen as a flame retardant. A halogen-free flame retardant, (C) a polyhydric alcohol or derivative thereof as a flame retardant aid, and (D) a weight average molecular weight of 150 to 10,000, and the total amount of alkoxy groups or hydroxy groups is 10 to 85 in one molecule. A flame-retardant thermoplastic resin composition characterized by containing a silicon compound selected from organoalkoxysiloxane and organohydroxysiloxane in an amount of% by mass has no problems in terms of safety and environment, and yet has excellent flame retardancy And having mechanical properties (tensile strength, elongation), the present invention has been made.

That is, this invention provides the following flame-retardant thermoplastic resin composition and its manufacturing method.
Claim 1:
The following component (A) thermoplastic resin (excluding polyurethane resin): 100 parts by mass,
(B) Non-halogen flame retardant containing phosphorus and nitrogen: 5 to 25 parts by mass,
(C) Polyhydric alcohol or derivative thereof: 1 to 15 parts by mass,
(D) Organoalkoxysiloxane and organohydroxysiloxane represented by the following average composition formula (1), having a weight average molecular weight of 150 to 10,000 and a total amount of alkoxy groups or hydroxy groups of 10 to 85% by mass in one molecule. Silicon compounds selected from:
1-15 parts by mass
R ¹ _α Si (OX) _β O _{(4-α-β) / 2} (1)
(In the formula, R ¹ is an optionally substituted alkyl group or alkenyl group, and each R ¹ may be the same or different. X is an alkyl having 1 to 10 carbon atoms. It is a group or a hydrogen atom but always contains an alkyl group. Α is a real number of 0.0 to 3.0, β is 0.1 to 3.0, and α + β <4.0.
Containing a flame retardant thermoplastic resin composition.
Claim 2:
The flame retardant thermoplastic resin composition according to claim 1, wherein the halogen-free flame retardant containing phosphorus and nitrogen as components (B) is 5 to 18 parts by mass.
Claim 3:
The halogen-free flame retardant containing component (B) phosphorus and nitrogen is selected from guanidine phosphate, ammonium phosphate, melamine phosphate, ammonium polyphosphate, melamine surface-coated ammonium polyphosphate, and silicon compound surface-coated ammonium polyphosphate. The flame retardant thermoplastic resin composition according to claim 1, wherein the flame retardant thermoplastic resin composition is one type or two or more types.
Claim 4:
The flame-retardant thermoplastic resin composition according to any one of claims 1 to 3, wherein the polyhydric alcohol of component (C) or a derivative thereof is pentaerythritol or a pentaerythritol derivative.
Claim 5:
The polyhydric alcohol of component (C) or a derivative thereof is equal to or less than the non-halogen flame retardant containing phosphorus and nitrogen of component (B). The flame-retardant thermoplastic resin composition as described.
Claim 6:
It is a manufacturing method of the flame-retardant thermoplastic resin composition of any one of Claims 1-5, Comprising: In the component (A) heated and melted, at least component (B), (C) and (D) The flame-retardant thermoplastic resin composition according to any one of claims 1 to 5, wherein at least the components (B) and (D) must not be preliminarily mixed for 1 hour or more before mixing. Manufacturing method.

  According to the present invention, there can be provided a flame retardant thermoplastic resin composition having no problem in terms of safety and environment, yet having excellent flame retardancy and mechanical properties (tensile strength, elongation) and a method for producing the same. .

Hereinafter, the present invention will be described in more detail.
The flame-retardant thermoplastic resin composition of the present invention comprises (A) a thermoplastic resin (excluding a polyurethane resin), (B) a non-halogen flame retardant containing phosphorus and nitrogen, (C) a polyhydric alcohol or its A derivative and (D) a specific silicon compound are contained as essential components.

(A) As a thermoplastic resin of a thermoplastic resin component (A), a conventionally well-known thing except a polyurethane resin can be used.
Examples of such thermoplastic resins include polypropylene, polylactic acid, polyethylene, polycarbonate, ABS resin, styrene resin, polyethylene terephthalate, and polybutylene terephthalate. Among these, in particular, polypropylene and polylactic acid resin are easily flammable even though they are consumed in large quantities, and thus are useful as the component (A) of the flame retardant thermoplastic resin composition as in the present invention.

(B) Non-halogen flame retardant component containing phosphorus and nitrogen (B) Non-halogen flame retardant containing phosphorus and nitrogen includes guanidine phosphate, ammonium phosphate, melamine phosphate, ammonium polyphosphate, melamine surface coating Examples of the flame retardant include ammonium polyphosphate and silicon compound surface-coated ammonium polyphosphate, and one or more of these are used. From the viewpoint of flame retardancy, preferably, ammonium polyphosphate, melamine surface-coated ammonium polyphosphate, and silicon compound surface-coated ammonium polyphosphate are used, and more preferably silicon compound surface-coated ammonium polyphosphate is used.
A commercially available product can be used as ammonium polyphosphate.

  The blending amount of such halogen-free flame retardant containing phosphorus and nitrogen is preferably 5 to 25 parts by mass, more preferably 5 to 18 parts by mass, and most preferably 5 to 15 parts by mass with respect to 100 parts by mass of the thermoplastic resin. Part by mass. When the amount is less than 1 part by mass, a sufficient flame retardant effect cannot be obtained. When the amount exceeds 25 parts by mass, tensile strength and elongation may be reduced.

The halogen-free flame retardant containing phosphorus and nitrogen preferably has an average particle size of 1 to 25 μm, particularly 5 to 18 μm.
In addition, an average particle diameter can be calculated | required as a weight average value (or median diameter), for example using the particle size distribution measuring apparatus by a laser beam diffraction method.

Furthermore, such non-halogen flame retardants containing phosphorus and nitrogen can improve characteristics such as water repellency, dispersibility in resin, and decrease in elution of phosphoric acid by treating the surface with a silicon compound. it can.
Examples of the silicon compound used for the surface treatment include various silanes, silicone oils, silicone resins, and the like. However, since the coating property is good, the co-hydrolysis described in JP-A-2006-111844 is particularly preferable. A decomposition condensate is preferred.

(C) Polyhydric alcohol or its derivative component (C) The polyhydric alcohol or its derivative includes polyhydric alcohols such as pentaerythritol, sorbitol, dipentaerythritol, and derivatives thereof. The polyhydric alcohols or derivatives thereof may be used alone or in combination of two or more.
Examples of the polyhydric alcohol derivative include pentaerythritol monostearate, pentaerythritol distearate, ditrimethylsilylated pentaerythritol and the like. In the present invention, it is preferable to use pentaerythritol or a pentaerythritol derivative.

It is preferable that the compounding quantity of such a polyhydric alcohol or its derivative (s) is 1-15 mass parts with respect to 100 mass parts of thermoplastic resins. When the amount is less than 1 part by mass, the flame retardancy is not improved. When the amount exceeds 15 parts by mass, the flame retardancy and the tensile strength may be significantly reduced.
Furthermore, the compounding quantity of such polyhydric alcohol or its derivative (s) needs to be equal to or less than the non-halogen flame retardant containing phosphorus and nitrogen. It is because flame retardancy may fall when exceeding equal amount.

(D) The silicon compound of the silicon compound component (D) is represented by the following average composition formula (1), the weight average molecular weight is 150 to 10,000, and the total amount of alkoxy groups or hydroxy groups is 10 to 85 in one molecule. It is a silicon compound selected from organoalkoxysiloxanes and organohydroxysiloxanes in an amount of mass%.
R ¹ _α Si (OX) _β O _{(4-α-β) / 2} (1)
(In the formula, R ¹ is an optionally substituted alkyl group or alkenyl group, and each R ¹ may be the same or different. X is an alkyl having 1 to 10 carbon atoms. It is a group or a hydrogen atom but always contains an alkyl group. Α is a real number of 0.0 to 3.0, β is 0.1 to 3.0, and α + β <4.0.

  The silicon compound represented by the above average composition formula (1) preferably has a weight average molecular weight of 150 to 10,000, more preferably 200 to 6,000. When the weight average molecular weight is less than 150, sufficient flame retardancy is not exhibited, and when it exceeds 10,000, the tensile strength may decrease.

  In the average composition formula (1), the total amount of alkoxy groups or hydroxy groups represented by OX is preferably 10 to 85 mass%, more preferably 20 to 60 mass%. When the total amount of alkoxy groups or hydroxy groups is less than 10% by mass, the flame retardancy is lowered, and when it exceeds 85% by mass, the appearance of the composition may be deteriorated.

  It is preferable that the compounding quantity of such a silicon compound is 1-15 mass parts with respect to 100 mass parts of thermoplastic resins. When the compounding amount of the silicon compound is less than 1 part by mass, or when it exceeds 15 parts by mass, the flame retardancy may be insufficient.

Such a silicon compound can be obtained by the following two typical synthesis methods.
That is, one is a method in which chlorosilane is dropped into a mixed solution of water and alcohol to carry out a hydrolysis reaction, and after the reaction, the water tank is discarded and the dehydrochloric acid is neutralized, filtered and concentrated under reduced pressure. After adding an alkali catalyst or an acid catalyst to a mixture of an alkoxysilane or alkoxysiloxane oligomer and optionally a cyclic siloxane such as a tetramer or pentamer, an equilibration reaction is performed, and then a hydrolysis reaction is performed by dropping water. This is a method of carrying out a subsequent condensation reaction and neutralizing and concentrating the completed reaction product.

(E) Other components In addition to the above components (A) to (D), various additives are appropriately added to the flame retardant thermoplastic resin composition of the present invention in accordance with its purpose within a range that does not impair the properties. Can be blended.
Examples of 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 include 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate, Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-tert-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-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-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, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-di-phosphonite, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropio , Pentaerythritol 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 ( And methylene) -3- (dodecylthiopropionate) methane.

  Usable stabilizers include lithium stearate, magnesium stearate, calcium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc laurate, zinc ricinoleate, zinc stearate, etc. Various metal soap stabilizers; Laurate, malate and mercapto organotin stabilizers; Lead stabilizers such as lead stearate and tribasic lead sulfate; Epoxy compounds such as epoxidized vegetable oil, alkylallyl Examples thereof include phosphite compounds such as phosphites and trialkyl phosphites; β-diketone compounds such as dibenzoylmethane and dehydroacetic acid; hydrotalcites and zeolites.

  Usable light stabilizers include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, oxalic anilide-based UV absorbers, hindered amine-based light stabilizers, etc. Can be mentioned.

  Usable compatibilizers include acrylic organopolysiloxane copolymers, partially cross-linked products of silica and organopolysiloxane, silicone powder, anhydrous maleated graft modified polyolefin, carboxylated graft modified polyolefin, polyolefin graft modified organopolysiloxane, etc. Is mentioned.

  Examples of usable adhesion assistants include various alkoxysilanes.

  Examples of other non-halogen flame retardant that can be used include zinc borate, zinc stannate, and photo titanium oxide.

  Examples of usable fillers include silicic acid, calcium carbonate, titanium oxide, carbon black, kaolin clay, calcined clay, aluminum silicate, magnesium silicate, calcium silicate, barite, and the like.

Flame retardant thermoplastic resin composition, such as a method for producing a flame retardant thermoplastic resin composition, includes components (B), (C), (D) (and other components as necessary) in the heat-melted component (A). Although it can manufacture by mixing (E)), it is not preferable to mix at least components (B) and (D) in advance for 1 hour or more. This is because when a small amount of phosphoric acid remains on the surface of the component (B), the components (B) and (D) or the components (D) may react to form a resin or gel. Thus, when the component (D) forms a resin or gel, the flame retardancy is reduced, and V-0 in UL-94 may be rejected in UL-94.
Moreover, a well-known method is employable as a shaping | molding method of the obtained flame-retardant thermoplastic resin composition.

  EXAMPLES Hereinafter, although this invention is concretely demonstrated with a preparation example, an Example, and a comparative example, this invention is not limited to a following example. In the following examples, the average particle diameter is a value measured by a laser diffraction type particle size distribution analyzer (methanol solvent).

[Examples 1-7, Comparative Examples 1-6, and Reference Examples 1-3]
After blending various components described in the following Tables 1 to 4 and uniformly kneading with a Laboplast Mill R-60 mixer (manufactured by Toyo Seiki Co., Ltd.) at 180 ° C., 30 rpm, 3 minutes, 200 ° C. After press-molding uniformly under the conditions of polylactic acid resin, various test pieces having a thickness of 2 mm were prepared by press molding at 200 ° C. Using the test pieces thus obtained, flame retardancy UL-94, oxygen consumption index, tensile strength and elongation were evaluated. The obtained results are also shown in Tables 1 to 4.
The materials and evaluation methods used are shown below.

[Materials used]
(1) Polypropylene resin: PM854X Sun Allomer Co., Ltd. (2) Polylactic acid resin: Lacia H-100J Mitsui Chemicals, Inc. (3) Silicone surface-treated ammonium polyphosphate 1: Prepared according to the following procedure.
Preparation of silicone-based water repellent treatment agent 1 In a 500 ml four-necked flask equipped with a condenser, thermometer and dropping funnel, 85 g of methyltrimethoxysilane oligomer (0.37 mol in terms of dimer), 154 g of methanol and acetic acid 5. 1 g was added, and 6.8 g (0.37 mol) of water was added to the stirring place, and the mixture was stirred at 25 ° C. for 2 hours. There, 17.7 g (0.08 mol) of 3-aminopropyltriethoxysilane was added dropwise. Then, after heating to the reflux temperature of methanol and reacting for 1 hour, the methanol was distilled off with an ester adapter until the internal temperature reached 110 ° C., and the viscosity was 71 mm ² / s (25 ° C.) measured according to JIS K2283. 81 g of a pale yellow transparent solution was obtained (weight average molecular weight 1,100). The amount of residual methanol in this system was 5% by mass (silicone-based water repellent agent 1).
Preparation of surface-treated ammonium polyphosphate 1 To 100 parts by mass of ammonium polyphosphate (manufactured by Clariant: Peco Frame TC204P, average particle size 8 μm), 10 parts by mass of the above silicone-based water repellent agent 1 and 100 parts by mass of ethanol were added. After stirring these for 30 minutes, ethanol was distilled off under reduced pressure, and the mixture was pulverized with a pulverizer to obtain silicone surface-treated ammonium polyphosphate 1 having an average particle size of 10 μm.
(4) Pentaerythritol: Wako Pure Chemical Industries, Ltd. (5) Peco Frame TC204P: Surface untreated ammonium polyphosphate 2, Clariant Japan Co., Ltd., average particle size: 8 μm
(6) Alkoxysiloxane oligomer: The following compounds A to D were prepared according to the following procedure.
(Compound A)
After methyltrichlorosilane is stirred in methanol at 65 ° C. or lower and partially esterified, it is dropped into a mixed solution of methanol and water in a ratio of 3: 1 and hydrolyzed, and then the lower layer containing hydrochloric acid is discarded. The remaining organic layer (upper layer) is neutralized with sodium carbonate. After neutralization, the salt was removed by filtration, and synthesis was performed by concentration under reduced pressure at 100 ° C. or higher. The obtained compound was found to have the following average composition formula by Si ²⁹ -NMR. As for the amount of alkoxy groups, 1.0 g of a sample is collected in a 20 ml vial, 1N-KOH and IPA mixed solution is added, a rubber stopper is used, and the mixture is heated to 170 ° C. while pouring N 2. The alcohol content from the Teflon (registered trademark) tube connected to the vial was analyzed from the amount of methanol by GC analysis. The weight average molecular weight was calculated from toluene GPC.
Average composition formula (CH ₃ ) (OCH ₃ ) _1.5 SiO _0.75
Alkoxy group amount 46% by weight Weight average molecular weight 406
(Compound B)
It synthesize | combined by concentrate | evaporating under reduced pressure at 110 degreeC after stirring 70 degreeC and 5 hours with water and 1 mass part of sulfonic acid type | mold ion exchange resins (resin is divinibenzene crosslinked polystyrene) to 100 mass parts of compound A-100. The following average composition formula, alkoxy group amount, and weight average molecular weight were determined by the same analysis as for Compound A.
Average composition formula (CH ₃ ) _1.0 (OCH ₃ ) _1.2 SiO _0.9
Alkoxy group weight 28% by weight Weight average molecular weight 950
(Compound C)
Compound A-100 parts by mass and dimethyldimethoxysilane were synthesized in 110 parts by mass together with water, methanol and 1 part by mass of a sulfonic acid type ion exchange resin, followed by stirring at 70 ° C. for 5 hours and concentration under reduced pressure at 110 ° C. The following average composition formula, alkoxy group amount, and weight average molecular weight were determined by the same analysis as for Compound A.
Average composition formula (CH ₃ ) _1.69 (OCH ₃ ) _0.31 SiO ₁
Alkoxy group amount 12% by weight Weight average molecular weight 5,500
(Compound D)
After mixing 76 parts by weight of octamethyltetrasiloxane, 28.6 parts by weight of dimethyldimethoxysilane, and 95 parts by weight of dimethyltrimethoxysilane, after stirring at 70 ° C. for 5 hours with water, methanol and 1 part by weight of sulfonic acid type ion exchange resin And synthesized under reduced pressure at 110 ° C. The following average composition formula, alkoxy group amount, and weight average molecular weight were determined by the same analysis as for Compound A.
Average composition formula (CH ₃ ) _2.16 (OCH ₃ ) _0.17 SiO _0.835
Alkoxy group amount 7% by weight Weight average molecular weight 1,950
KF-96L-5CS: Shin-Etsu Chemical Co., Ltd.
Average composition formula (CH ₃ ) _2.18 SiO _0.91
Alkoxy group amount 0% by weight Weight average molecular weight 830

[Evaluation method]
(1) Flame retardancy UL-94: A test was conducted based on the UL-94 vertical combustion test.
(2) Average burning time: The UL-94 vertical burning test was measured 5 times, and an average value of 5 burning times (time until the fire was extinguished) was defined as an average burning time.
In addition, when all the test pieces were burned without extinguishing the fire, “burned” was set.
(3) Tensile strength, elongation: A 2 mm thick press-molded sheet was punched out into a No. 2 test piece with a dumbbell, and measured according to JIS-K7113.
(4) Weight average molecular weight: determined by GPC method (gel permeation chromatography). The analysis conditions are as follows.
(A) Solvent: Toluene (b) Column: TSKgel superH5000 + superH4000 + superH3000 + superH2000
(C) Detector: RI
(D) Flow rate: 0.6 ml / min (e) Column temperature: 40 ° C.

Claims (6)

The following component (A) thermoplastic resin (excluding polyurethane resin): 100 parts by mass,
(B) Non-halogen flame retardant containing phosphorus and nitrogen: 5 to 25 parts by mass,
(C) Polyhydric alcohol or derivative thereof: 1 to 15 parts by mass,
(D) Organoalkoxysiloxane and organohydroxysiloxane represented by the following average composition formula (1), having a weight average molecular weight of 150 to 10,000 and a total amount of alkoxy groups or hydroxy groups of 10 to 85% by mass in one molecule. Silicon compounds selected from:
1-15 parts by mass
R ¹ _α Si (OX) _β O _{(4-α-β) / 2} (1)
(In the formula, R ¹ is an optionally substituted alkyl group or alkenyl group, and each R ¹ may be the same or different. X is an alkyl having 1 to 10 carbon atoms. It is a group or a hydrogen atom but always contains an alkyl group. Α is a real number of 0.0 to 3.0, β is 0.1 to 3.0, and α + β <4.0.
Containing a flame retardant thermoplastic resin composition.   The flame retardant thermoplastic resin composition according to claim 1, wherein the halogen-free flame retardant containing phosphorus and nitrogen as components (B) is 5 to 18 parts by mass.   The halogen-free flame retardant containing component (B) phosphorus and nitrogen is selected from guanidine phosphate, ammonium phosphate, melamine phosphate, ammonium polyphosphate, melamine surface-coated ammonium polyphosphate, and silicon compound surface-coated ammonium polyphosphate. The flame retardant thermoplastic resin composition according to claim 1, wherein the flame retardant thermoplastic resin composition is one type or two or more types.   The flame-retardant thermoplastic resin composition according to any one of claims 1 to 3, wherein the polyhydric alcohol of component (C) or a derivative thereof is pentaerythritol or a pentaerythritol derivative.   The polyhydric alcohol of component (C) or a derivative thereof is equal to or less than the non-halogen flame retardant containing phosphorus and nitrogen of component (B). The flame-retardant thermoplastic resin composition as described.   It is a manufacturing method of the flame-retardant thermoplastic resin composition of any one of Claims 1-5, Comprising: In the component (A) heated and melted, at least component (B), (C) and (D) The flame-retardant thermoplastic resin composition according to any one of claims 1 to 5, wherein at least the components (B) and (D) must not be preliminarily mixed for 1 hour or more before mixing. Manufacturing method.