JP2008074906A - Flame-retardant resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition that contains neither a halogen atom nor a phosphorus atom, develops an extremely high flameproofing effect. <P>SOLUTION: The flame-retardant resin composition comprises 100 pts. by wt. of an aromatic ring-containing resin (A), 0.1-20 pts. by wt. of an aromatic ring-containing silicone compound (B) represented by an average composition formula (1) R<SP>1</SP><SB>m</SB>R<SP>2</SP><SB>n</SB>Si(OH)<SB>p</SB>O<SB>(4-m-n-p)/2</SB>(1) (R<SP>1</SP>s are each a 1-4C monofunctional aliphatic hydrocarbon group; R<SP>2</SP>s are each a 6-24C monofunctional aromatic hydrocarbon group; when a plurality of R<SP>1</SP>s and a plurality of R<SP>2</SP>s exist, respectively, they may be the same or different; m, n and p are each a number satisfying 0≤m<2.9, 0<n≤2.9 and 0.01≤p≤0.1) containing a silanol group as an essential substituent group and 0.1-20 parts by wt. of a metal silicate compound (C) having pH ≥8.0, comprising ≥30 wt.% of SiO<SB>2</SB>unit and having an average particle diameter of 1 nm-100 μm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a flame retardant resin composition that does not contain a halogen atom or a phosphorus atom as a flame retardant and is highly flame retardant.

  Flame retardant resin compositions are used in various fields such as the electrical and electronic fields and the building materials field in order to ensure safety against fire. These resin compositions generally use halogen-based compounds such as chlorine and bromine as flame retardants. However, in recent years due to increasing interest in environmental issues mainly in Europe, halogens including phosphorus-based flame retardants have been used. Various attempts have been made to use flame retardants that do not contain them.

  However, when using a phosphoric acid ester compound, which is a phosphorus-based flame retardant, the amount is generally large, an odor is generated during extrusion / molding, and mechanical and thermal properties are poor. Since there is a problem such as reduction, reduction of the amount added is desired.

On the other hand, as a resin composition flame-retarded without using a halogen or a phosphorus compound, a technique of adding a silicone flame retardant has been reported. For example, it has a silicone compound (for example, see Patent Documents 1 and 2) having RSiO _1.5 units and R ₂ SiO _1.0 units as constituents, a phenyl group, an alkyl group, and an alkoxy group, and has a molecular weight of 10,000 or less. A certain silicone compound (for example, refer to Patent Document 3) is disclosed. However, these silicone compounds are effective for the polycarbonate resin alone, but have little effect on the alloy of the polycarbonate resin and other resins, and cannot be used for general-purpose synthetic resins.

Silicone compounds that use flame retardant properties that are also useful for alloying polycarbonate resins with other resins, silicone resins with a specific structure containing SiO ₂ units, and silicones with specific melting characteristics Although resin is disclosed (for example, refer to Patent Documents 4, 5, and 6), further reduction of the silicone resin used as a flame retardant is desired from the viewpoint of economy.
Japanese Patent Laid-Open No. 10-139964 JP-A-11-140294 JP-A-11-222559 Japanese Patent Laid-Open No. 2001-311081 JP 2001-316671 A JP-A-2001-323269

  An object of the present invention is to provide a flame retardant resin composition that is highly flame retardant without using a halogen-based or phosphorus-based flame retardant.

  As a result of studying to solve the above problems, the present inventors have found that by combining a specific inorganic compound, the addition of a small amount of a silicone compound has a synergistically excellent flame retardancy, and further studies have been made. As a result, when the silicone compound has a specific amount with a silanol group as a substituent, it was found that even if a small amount of the silicone compound is added, it has excellent flame retardancy, and the present invention has been completed.

That is, the present invention relates to an average composition formula (1) with respect to 100 parts by weight of the aromatic ring-containing resin (A).
^{_{R 1 m R 2 n Si (}} OH) p O (4-m-n-p) / 2 (1)
(In the formula, R ¹ represents a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ² represents a monovalent aromatic hydrocarbon group having 6 to 24 carbon atoms. R ¹ , R ^When there are a plurality of ^2's , they may be the same or different.m, n, p are 0 ≦ m <2.9, 0 <n ≦ 2.9, 0.01 ≦ p. 0.1-20 parts by weight of an aromatic ring-containing silicone compound (B) having a silanol group represented by the following formula as an essential substituent, and a pH of 8.0 or more, SiO 2 _The present invention relates to a flame retardant resin composition comprising ₂ to 20% by weight and containing 0.1 to 20 parts by weight of a metal silicate compound (C) having an average particle diameter of 1 nm to 100 μm.

  The flame retardant resin composition of the present invention exhibits extremely excellent flame retardancy without using a flame retardant containing chlorine, bromine, phosphorus, nitrogen, etc., and hardly impairs the inherent characteristics of the resin. In addition, it can be synthesized relatively easily using inexpensive raw materials. Such a flame retardant resin composition is very useful industrially.

  The present invention is described in detail below.

  The aromatic ring-containing resin as component (A) of the present invention is a synthetic resin having at least one aromatic ring in the molecule. Among aromatic ring-containing resins, aromatic polycarbonate resins, aromatic polyester resins, polyphenylene ether resins, aromatic vinyl resins, polyphenylene sulfide resins, N-aromatic substituted maleimide resins and aromatic polyimide resins. It is preferable to use at least one selected from the group consisting of Among the aromatic ring-containing resins, it is more preferable to use at least one selected from aromatic polycarbonate resins, polyphenylene ether resins, and aromatic vinyl resins, and an alloy of polyphenylene ether resins and aromatic vinyl resins. Is more preferable.

  These resins may be used alone or in combination of two or more. There are no particular limitations on the combination of resins in the case of alloying, and examples thereof include an alloy of an aromatic polycarbonate resin and an ABS resin, and a combination of a polyphenylene ether resin and polystyrene or high impact polystyrene (HIPS). As a preferable composition in the case of alloying, for example, aromatic polycarbonate resin / ABS resin = 40 to 100/60 to 0 (wt%), polyphenylene ether resin / polystyrene or high impact polystyrene = 30 to 100/70. ˜0 (% by weight).

The aromatic ring-containing silicone compound as the component (B) of the present invention has an average composition formula (1)
^{_{R 1 m R 2 n Si (}} OH) p O (4-m-n-p) / 2 (1)
(In the formula, R ¹ represents a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ² represents a monovalent aromatic hydrocarbon group having 6 to 24 carbon atoms. R ¹ , R ^When there are a plurality of ^2's , they may be the same or different.m, n, p are 0 ≦ m <2.9, 0 <n ≦ 2.9, 0.01 ≦ p. It is a silicone compound having a silanol group represented by ≦ 0.1 as an essential substituent.

  The aromatic ring-containing silicone compound (B) represented by the average composition formula (1) must have at least one aromatic ring in the molecule as an organic group bonded on a silicon atom, and the remaining organic groups Is an aliphatic hydrocarbon group or a silanol group.

The monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms of R ¹ is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl. And an alkyl group such as t-butyl group. Among these, a methyl group and an ethyl group are preferred because of their excellent flame retarding effect, and a methyl group is more preferred. In the aromatic ring-containing silicone compound (B), when there are a plurality of portions corresponding to R ¹ , they may all be the same or different groups may be mixed. Moreover, when the number of carbon atoms of the aliphatic hydrocarbon group is 5 or more, the flame retardancy of the aromatic ring-containing silicone compound itself is lowered, so the flame retarding effect is lowered.

The monovalent aromatic hydrocarbon group having 6 to 24 carbon atoms of R ² is not particularly limited, and examples thereof include substituents such as a phenyl group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a naphthyl group, and an anthracenyl group. And an aryl group which may have Among these, an aromatic hydrocarbon group having no substituent on the aromatic ring is preferable because of its excellent flame retarding effect, and a phenyl group is more preferable. In the aromatic ring-containing silicone compound (B), there are a plurality of portions corresponding to R ² , all of which may be the same or different groups may be mixed.

In the average composition formula (1), the total of the monovalent aliphatic hydrocarbon group R ¹ having 1 to 4 carbon atoms and the monovalent aromatic hydrocarbon group R ² having 6 to 24 carbon atoms on the silicon atom is combined. The molar ratio m + n between the hydrocarbon group and the number of Si atoms is preferably 1.1 ≦ m + n ≦ 1.7, more preferably 1.15 ≦ m + n ≦ 1.65, and still more preferably 1.18 ≦ m + n ≦ 1. 6. When the value of m + n is in the range of 1.1 to 1.7, affinity with the resin and flame retardancy are further improved.

Further, the molar ratio n / m of the monovalent aliphatic hydrocarbon group R ¹ having 1 to 4 carbon atoms and the monovalent aromatic hydrocarbon group R ² having 6 to 24 carbon atoms depends on the affinity with the resin. From the viewpoint of flame retardancy, 0.4 ≦ n / m ≦ 2.5 is preferable. Furthermore, it is preferable that 1.1 ≦ m + n ≦ 1.7 and 0.4 ≦ n / m ≦ 2.5 are satisfied.

  The silicone compound described in the present invention is characterized by containing a silanol group as a functional group. The silanol group promotes thermal decomposition of the resin at the time of combustion, and at the same time, the silanol group itself crosslinks to form char, whereby an incombustible layer can be formed instantaneously after ignition. In the average composition formula (1), p defining the silanol group content is preferably 0.01 ≦ p ≦ 0.1, and more preferably 0.02 ≦ p ≦ 0.08. When there is too much silanol group content, only decomposition | disassembly of resin will be accelerated | stimulated and a flame retardance will deteriorate. If the silanol content is too small, the effect of the present application is difficult to obtain. In addition, the ratio of each element, each hydrocarbon group, and silanol group can be calculated using NMR of hydrogen, carbon, and silicon.

The aromatic ring-containing silicone compound (B) is composed of an aromatic group-containing organosiloxane compound, and includes Q units (SiO ₂ ), T units (RSiO _1.5 ), D units (R ₂ SiO), and M units ( Among the four types of structural units of R ₃ SiO _0.5 ), they are configured in any combination so as to satisfy the above average composition formula (1). In the formula, R is not particularly limited, but represents an aromatic hydrocarbon group or an aliphatic hydrocarbon group.

Further, the aromatic ring-containing silicone compound (B) has a T unit and / or a Q unit in the skeleton, more specifically an R ³ SiO _3/2 unit (in the formula, from the viewpoint of heat resistance and flame retardancy). R ³ represents an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 24 carbon atoms, and when there are a plurality of such units, R ³ may be the same or different. And / or SiO ₂ units are preferably contained so that Si atoms derived from the units are 10% or more (that is, 10 mol% or more) of all Si atoms, more preferably 15% or more, and more preferably 20% or more. Is more preferable.

The alkyl group having 1 to 4 carbon atoms for R ^3, include the same ones exemplified for the monovalent aliphatic hydrocarbon group of carbon number 1 to 4 above R ^1. The aromatic hydrocarbon group having 6 to 24 carbon atoms include the same ones exemplified for the monovalent aromatic hydrocarbon group of carbon number 6 to 24 above R ^2.

Such an aromatic ring-containing silicone compound (B) can be easily synthesized by a known silicone synthesis method. That is, a monofunctional silicon compound represented by R ₃ SiX, a bifunctional silicon compound represented by R ₂ SiX ₂ , a trifunctional silicon compound represented by RSiX ₃ , silicon tetrahalide, tetraalkoxysilane, And at least one, preferably at least two silicon compounds selected as necessary from organic silicon compounds which are condensates thereof and inorganic silicon compounds such as water glass and metal silicate. Can be synthesized. In the formula, R represents an aromatic hydrocarbon group or an aliphatic hydrocarbon group. X represents a group that can be condensed to form a siloxane bond, such as a halogen atom, a hydroxyl group, or an alkoxy group.

  The reaction conditions vary depending on the substrate used and the composition and molecular weight of the target compound. The condensation reaction can be generally carried out by mixing a silicon compound with heating if necessary in the presence of water, an acid and / or an organic solvent as necessary. The use ratio of each silicon compound is appropriately determined in consideration of the content of each unit and the ratio of the aromatic hydrocarbon group to the aliphatic hydrocarbon group so that the obtained aromatic ring-containing silicone compound satisfies the above conditions m and n. You only have to set it.

Generally, when an aromatic ring-containing silicone compound is synthesized by the above condensation reaction, X may remain as a condensed residue on a Si atom as a terminal structure. When X remains, depending on the type, it is not preferable because when added to the resin, the thermal stability of the resin is lowered or the flame retardancy is poor. In order to prevent this, X can be blocked by reacting and treating a monofunctional silicon compound represented by excess R ₃ SiX after polymerization. On the other hand, by adjusting the amount of the monofunctional silicon compound represented by R ₃ SiX, the amount of X remaining can be adjusted. X can be easily derived into a silanol group by hydrolysis by a known method. By using such a method, adjustment of the amount of silanol groups in the target silicone compound can be easily achieved.

  Furthermore, although the number average molecular weight of the said aromatic ring containing silicone compound is not specifically limited, 1000-200000 are preferable, 1500-1500000 are more preferable, 2000-100000 are further more preferable. In general, the molecular weight and flame retardancy are discussed in the silicone compounds mentioned in the prior art, but in the present invention, regardless of the molecular weight, the heat resistance of the silicone is determined by an arbitrary ratio of siloxane bonds in the molecule. Therefore, within the range of the number average molecular weight, the molecular weight does not critically affect the flame retardancy. When the number average molecular weight is less than 1000, the heat resistance of the aromatic ring-containing silicone compound tends to be low, and the flame retardancy tends to be insufficient. Moreover, when the number average molecular weight is larger than 200000, the dispersibility in the resin and the processability tend to be lowered. The polystyrene-reduced number average molecular weight can be determined by gel permeation chromatography (GPC) using chloroform as a solvent.

  The addition amount of the aromatic ring-containing silicone compound (B) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the aromatic ring-containing resin (A). -15 parts by weight is preferable, and 0.5-10 parts by weight is more preferable. When the addition amount is less than 0.1 parts by weight, the flame retardancy may be insufficient. When the addition amount exceeds 20 parts by weight, there is no particular problem in terms of physical properties, but more economical is required.

(C) used as the component is not particularly restricted but includes metal silicate compounds SiO ₂ units account for at least 30 wt%, K, Na, Li, Ca, Mn, Fe, Ni, Mg, Fe, Al, Ti One or more metal elements selected from Zn, Zr, and Zn are contained. Specific examples of the substance include magnesium silicate, aluminum silicate, calcium silicate, talc, mica, wollastonite, kaolin, diatomaceous earth, and smectite. Of these, mica, talc, kaolin, and smectite are preferable because they are excellent in flame retardancy and mechanical strength of the resulting resin composition, and talc is particularly preferable. Talc is hydrous magnesium silicate (compositional formula: Mg ₃ Si ₄ O ₁₀ (OH) ₂ ).

  The metal silicate compound (C) is fine particles having an average particle diameter of 1 nm to 100 μm. When the average particle diameter exceeds 100 μm, the appearance of the obtained molded product is impaired, and the impact strength of the resin composition tends to decrease. The thickness is preferably 1 nm to 70 μm, more preferably 10 nm to 50 μm, and further preferably 0.5 to 30 μm. In addition, the average particle diameter as used in the field of this invention can be measured by the micro track laser diffraction method. In addition, the term “particle” used herein is not limited to a spherical object, but may be a needle shape or a plate shape.

  Although it does not specifically limit about the shape of a metal silicate compound (C), A powder form, a granular form, needle shape, plate shape etc. are mentioned as a typical thing. This inorganic compound may be a natural product or synthesized. In the case of a natural product, there are no particular limitations on the production area and the like, which can be selected as appropriate.

  The metal silicate compound (C) of the present invention has a pH of 8.0 or higher. The fact that the pH of the metal silicate compound is 8.0 or more means that it has an ion-binding property composed of a silicate anion and a metal cation. In the case where a silicone compound coexists, it also has a synergistic effect on flame retardancy by chemically interacting with the silicone compound at high temperature conditions due to its ionic bond. In addition, pH as used in the field of this invention can be measured with a digital pH meter based on JIS-K-5101 B method.

  Such a metal silicate compound (C) may be subjected to a surface treatment with various surface treatment agents such as a silane treatment agent in order to enhance the adhesion to the resin. Although it does not specifically limit as a surface treating agent, Although a conventionally well-known thing can be used, epoxy group containing silane coupling agents, such as an epoxy silane, and amino group containing silane coupling agents, such as amino silane, are resin. It is preferable because the physical properties are hardly lowered. In addition, polyoxyethylene silane or the like can be used. The surface treatment method is not particularly limited, and a normal treatment method can be used.

  These metal silicate compounds (C) may be used alone or in combination of two or more different in average particle diameter, type, surface treatment agent and the like.

  The usage-amount of the metal silicate compound (C) in the thermoplastic resin composition of this invention is 0.1-20 weight part with respect to 100 weight part of aromatic ring containing resin (A). If the amount is less than 0.1 parts by weight, the flame retardancy of the resulting resin composition is insufficient, and if it exceeds 20 parts by weight, the flame retardancy and impact resistance of the resulting molded product are reduced and melted. Kneading with the resin during kneading tends to be difficult. Preferably it is 0.3-15 weight part, More preferably, it is 0.5-10 weight part.

  In the flame-retardant resin composition of the present invention, a fluorine-based resin (D) can be further added. The fluorine-based resin (D) is a resin having a fluorine atom. Specific examples include fluorinated polyolefin resins such as polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene / hexafluoropropylene copolymers, and polyvinylidene fluoride resins. it can. Moreover, you may use the copolymer obtained by using together the monomer used for manufacture of this fluororesin, and the monomer which can be copolymerized, and superposing | polymerizing. The copolymerizable monomer is not particularly limited, and a known monomer can be used.

  Of the fluororesin (D), a fluorinated polyolefin resin is preferable, and a fluorinated polyolefin resin having an average particle size of 700 μm or less is more preferable. The average particle size here means the average particle size of secondary particles formed by agglomeration of primary particles of a fluorinated polyolefin resin.

  Furthermore, among the fluorinated polyolefin resins, a fluorinated polyolefin resin having a density / bulk density ratio (density / bulk density) of 6.0 or less is preferable. The density and bulk density here are measured by the method described in JIS-K6891.

  The fluororesin (D) may be used alone or in combination of two or more. When two or more types are used in combination, the combination is not particularly limited. For example, different types or the like are arbitrarily used.

  When using a fluorine-type resin (D), the usage-amount is 0.005-1 weight part with respect to 100 weight part of aromatic ring containing resin (A), More preferably, it is 0.01-0.75. Part by weight, more preferably 0.02 to 0.6 part by weight. If the amount used is less than 0.005, the effect of improving flame retardancy by the component (D) tends to be insufficient. Tend to decrease.

  In the flame-retardant resin composition of the present invention, in order to further improve the molding fluidity or to further improve the flame retardancy, the present invention is difficult within the range that does not impair the characteristics of the present invention (such as flame retardancy). Silicone other than the component (B) as a flame retardant can be added.

  Silicone other than the component (B) of the present invention refers to a polyorganosiloxane in a broad sense excluding the component (B) of the present invention. Specifically, (poly) disiloxane such as dimethylsiloxane and phenylmethylsiloxane. Organosiloxane compounds; (poly) organosilsesquioxane compounds such as methyl silsesquioxane and phenyl silsesquioxane; (poly) triorganosyl hemioxanes such as trimethylsilhemioxane and triphenylsylhemioxane Compounds; copolymers obtained by polymerizing these; polydimethylsiloxane, polyphenylmethylsiloxane and the like. In the case of polyorganosiloxane, modified silicones whose molecular ends are substituted with epoxy groups, hydroxyl groups, carboxyl groups, mercapto groups, amino groups, ether groups, etc. are also useful. There is no restriction | limiting in particular in the shape of silicone, Arbitrary things, such as oil shape, gum shape, varnish shape, powder shape, pellet shape, can be utilized.

  Furthermore, the flame-retardant resin composition of the present invention may be used as a reinforcing material by combining reinforcing fillers within a range that does not impair the characteristics of the present invention (such as flame retardancy). That is, by adding a reinforcing filler, it is possible to further improve heat resistance, mechanical strength, and the like. Such reinforcing filler is not particularly limited, and examples thereof include fibrous fillers such as glass fibers, carbon fibers, and potassium titanate fibers; glass beads, glass flakes, calcium carbonate, calcium sulfate, barium sulfate, and the like. .

  In addition, in order to make the flame retardant resin composition of the present invention higher performance, an antioxidant such as a phenolic antioxidant, a thioether antioxidant, a thermal stabilizer such as a phosphorus stabilizer, etc. Or it is preferable to use together 2 or more types. Furthermore, as required, stabilizers, lubricants, mold release agents, plasticizers, UV absorbers, light stabilizers, pigments, dyes, antistatic agents, conductivity-imparting agents, dispersants, compatibilizing agents Additives such as agents and antibacterial agents can be used alone or in combination of two or more.

  Although it does not specifically limit as a manufacturing method of the flame-retardant resin composition of this invention, Mixing said (A), (B), (C) component, and also (D) component and various additives as needed. For example, the flame-retardant resin composition can be produced by kneading using a kneader such as a twin-screw extruder, a single-screw extruder, a heated roll kneader, or a Banbury mixer.

  The molding method of the flame-retardant resin composition produced in the present invention is not particularly limited, and a molding method generally used for thermoplastic resins, for example, injection molding, blow molding, extrusion molding, vacuum Molding, press molding, calendar molding, etc. can be applied.

  The use of the flame retardant resin composition of the present invention is not particularly limited. For example, housings of information communication equipment such as personal computers, printers, fax machines, DVDs, mechanical parts (chassis etc.), and housings of home appliances such as TVs. And internal parts, automobile interior and exterior parts (instrumental panels, wheel caps, etc.), vending machine internal parts, water supply / drainage equipment, medical equipment, and the like.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these. In the following description, “part” means part by weight and “%” means weight% unless otherwise specified.

  Moreover, the number average molecular weight calculated | required the number average molecular weight of polystyrene conversion by the gel permeation chromatography (GPC) using chloroform as a solvent. Columns (both made by Shodex) are GPC KG (guard column), GPC K-804 (exclusion limit 400,000), K-802.5 (exclusion limit 20,000) connected in series in this order Was used.

(Production Example 1) Production dichlorodiphenyl silane of the silicone compound (B1) (187 g), dichlorodimethylsilane (30 g), Tama Chemical Industry Co., Ltd. M silicate _{51 (Si n O n-1} (OCH 3) averaged over _{2n + 2} N = 4) (115 g) was weighed into a 2 L flask, methyl isobutyl ketone (MIBK) (480 g) was added, and water (130 g) was added dropwise at 10 ° C. or lower. Thereafter, the reaction mixture was heated to 80 ° C. and reacted for 3 hours. Next, after returning to room temperature, chlorotrimethylsilane (80 g) and then water (18 g) were added dropwise, followed by reaction at 60 ° C. for 3 hours. The obtained reaction mixture was washed with water until neutrality, and the solvent was distilled off from the separated organic phase under reduced pressure to obtain the desired silicone compound (B1) (number average molecular weight 2700). From the NMR analysis, the constitutional ratio represented by the average composition formula (1) is m = 0.76, n = 0.60, p = 0.020, and therefore m + n = 1.36, n / m = 0. .79. From the NMR analysis, the proportion of SiO ₂ units in all Si atoms was calculated to be 40.8 mol%.

(Production Example 2): Production of silicone compound (B2) Averaged with dichlorodiphenylsilane (190 g), dichlorodimethylsilane (32 g), M silicate 51 (Si _n O _n-1 (OCH ₃ ) _{2n + 2} ) manufactured by Tama Chemical Industries, Ltd. N = 4) (116 g) was weighed into a 2 L flask, methyl isobutyl ketone (MIBK) (480 g) was added, and water (132 g) was added dropwise at 10 ° C. or lower. Thereafter, the reaction mixture was heated to 80 ° C. and reacted for 3 hours. Next, after returning to room temperature, chlorotrimethylsilane (50 g) and then water (17 g) were added dropwise, followed by reaction at 60 ° C. for 3 hours. The obtained reaction mixture was washed with water until neutrality, and the solvent was distilled off from the separated organic phase under reduced pressure to obtain the desired silicone compound (B2) (number average molecular weight 2670). From the NMR analysis, the constitutional ratio represented by the average composition formula (1) is m = 0.70, n = 0.60, p = 0.044, and therefore m + n = 1.30, n / m = 0. .86. From the NMR analysis, the proportion of SiO ₂ units in all Si atoms was calculated to be 41.8 mol%.

(Production Example 3): Production of Silicone Compound (B3) Dichlorodiphenylsilane (190 g), dichlorodimethylsilane (31 g), M silicate 51 (Si _n O _n-1 (OCH ₃ ) _{2n + 2} manufactured by Tama Chemical Industry Co., Ltd.) N = 4) (117 g) was weighed into a 2 L flask, methyl isobutyl ketone (MIBK) (480 g) was added, and water (132 g) was added dropwise at 10 ° C. or lower. Thereafter, the reaction mixture was heated to 80 ° C. and reacted for 3 hours. Next, after returning to room temperature, chlorotrimethylsilane (37 g) and then water (15 g) were added dropwise, followed by reaction at 60 ° C. for 3 hours. The obtained reaction mixture was washed with water until it became neutral, and the solvent was distilled off from the separated organic phase under reduced pressure to obtain the desired silicone compound (B3) (number average molecular weight 2740). From the NMR analysis, the constituent ratios represented by the average composition formula (1) are m = 0.62, n = 0.61, p = 0.073, and therefore m + n = 1.23, n / m = 0. .98. From the NMR analysis, the proportion of the SiO ₂ units in all Si atoms was calculated to be 43.2 mol%.
(Reference production example 1): Production of organosiloxane compound (B4) Dichlorodiphenylsilane (468 g), dichlorodimethylsilane (80 g), M silicate 51 (Si _n O _n-1 (OCH ₃ ) _{2n + 2} manufactured by Tama Chemical Industries) On average, n = 4) (291 g) was weighed into a 5 L flask, methyl isobutyl ketone (MIBK) (1200 g) was added, and water (336 g) was added dropwise at 10 ° C. or lower. Thereafter, the reaction mixture was heated to 80 ° C. and reacted for 3 hours. Next, after returning to room temperature, chlorotrimethylsilane (268 g) and then water (44 g) were added dropwise, followed by reaction at 60 ° C. for 3 hours. The obtained reaction mixture was washed with water until it became neutral, and the solvent was distilled off from the separated organic phase under reduced pressure to obtain the desired silicone compound (B4) (number average molecular weight 2700). From the NMR analysis, the composition ratio represented by the average composition formula (1) is m = 0.82, n = 0.60, p = 0, and therefore m + n = 1.42, n / m = 0.73. It was possible to calculate. From the NMR analysis, the proportion of the SiO ₂ units in all Si atoms was calculated to be 39.9 mol%.
(Reference Production Example 2): Production of Organosiloxane Compound (B5) Dichlorodiphenylsilane (468 g), dichlorodimethylsilane (80 g), M silicate 51 (Si _n O _n-1 (OCH ₃ ) _{2n + 2} manufactured by Tama Chemical Industries) On average, n = 4) (291 g) was weighed into a 5 L flask, methyl isobutyl ketone (MIBK) (1200 g) was added, and water (336 g) was added dropwise at 10 ° C. or lower. Thereafter, the reaction mixture was heated to 80 ° C. and reacted for 3 hours. The obtained reaction mixture was washed with water until neutrality, and the solvent was distilled off from the separated organic phase under reduced pressure to obtain the desired silicone compound (B5) (number average molecular weight 2920). From the NMR analysis, the composition ratio represented by the average composition formula (1) is m = 0.20, n = 0.60, p = 0.25, and therefore m + n = 0.80, n / m = 3. Was calculated as 0.0. From the NMR analysis, the proportion of SiO ₂ units in all Si atoms was calculated to be 49.9 mol%.

The raw materials used in Examples and Comparative Examples are summarized below.
PPE: poly (2,6-dimethyl-1,4-phenylene) ether resin having a logarithmic viscosity of 0.50 (Mitsubishi Engineering Plastics, PX100F)
PS: Polystyrene resin (manufactured by PS Japan, GPPS HF77)
HIPS: Butadiene / styrene copolymer (manufactured by PS Japan Co., Ltd., HIPS HT60)
PC: Bisphenol A type polycarbonate having a viscosity average molecular weight of 22,000 (made by Idemitsu Kosan Co., Ltd., Toughlon A2200)
ABS: Acrylonitrile-butadiene-styrene copolymer (manufactured by Nippon A & L Co., Ltd., ABS GA-501)
PTFE: Fluororesin (Tetrafluoroethylene (Daikin Industries, Polyflon FA-500))
(C1): Metal silicate compound (Talc (Nihon Talc Co., Ltd. SG-200, pH = 9.3, SiO ₂ unit content = 60 wt%, average particle size = 3.2 μm))
(Example 1)
Preparation of resin composition 80 parts by weight of polyphenylene ether resin (PPE), 20 parts by weight of polystyrene resin (PS), 3 parts by weight of silicone compound (B1) as a flame retardant for resin addition produced in Production Example 1 3 parts by weight of metal silicate compound (C1) having an average particle size of 3.2 μm, 0.5 parts by weight of fluororesin (PTFE), and ADK STAB HP-10 as a phosphorus stabilizer and a phenolic antioxidant, respectively. And AO-60 (both manufactured by Asahi Denka) 0.2 parts by weight of each were dry blended in advance, and then a twin-screw extruder with a vent (33 mmφ, L / D) set at a cylinder temperature of 300 ° C. and a screw rotation speed of 100 rpm = 28, manufactured by Nippon Steel Works, product name TEX30HSS) and melt-extruded to obtain a pellet-shaped resin composition.

(Examples 2-15, Comparative Examples 1-15)
Resin compositions were obtained in the same manner as in Example 1 using the blending components and amounts shown in Tables 1 and 2.

  Using the resin compositions obtained in the above Examples and Comparative Examples, test pieces were prepared as follows and flame retardancy was evaluated.

Preparation of test piece After the obtained pellet was dried at 120C for 5 hours, using a 35t injection molding machine, the cylinder temperature was 295C, the mold temperature was 80C, and the thickness was 1.6 mm bar (width). 12 mm and a length of 127 mm) were prepared and evaluated as follows. The results are shown in Table 1.

Evaluation method Using the test piece obtained above, the flame retardancy was evaluated by the V test according to the UL-94 standard, and the total burning time was calculated.
The evaluation results are shown in Tables 1 and 2.

表１に示す通り、実施例では、いずれも非常に良好な難燃性を示し、短時間に自己消火した。これに対して、比較例１〜５、９〜１３では、実施例で使用したシリコーン化合物及び金属ケイ酸塩化合物が無添加であったり、どちらか一方のみを添加しているため、難燃性が不十分であった。比較例７、１５では、シリコーン化合物が有するシラノール基量が多すぎるため、樹脂を分解してしまい、難燃性が大幅に悪化している。比較例６、８、１４では、比較的良好な難燃性が得られているが、シラノール基を全く有しないシリコーン化合物を用いているため、実施例と同等の難燃性を得るためには、シリコーン化合物の添加量を増やす必要がある。また、添加量が同じ場合は、実施例ほどの難燃性は得られていない。よって、上記結果から、本発明の組成物を形成することにより、極少量のシリコーン化合物にて難燃性に優れた樹脂組成物が得られることがわかる。

As shown in Table 1, all of the examples showed very good flame retardancy and self-extinguished in a short time. On the other hand, in Comparative Examples 1-5 and 9-13, the silicone compound and metal silicate compound used in the examples were not added or only one of them was added, so that the flame retardancy Was insufficient. In Comparative Examples 7 and 15, since the amount of silanol groups contained in the silicone compound is too large, the resin is decomposed and the flame retardancy is greatly deteriorated. In Comparative Examples 6, 8, and 14, relatively good flame retardancy was obtained, but since a silicone compound having no silanol group was used, in order to obtain flame retardance equivalent to that of the Examples It is necessary to increase the amount of silicone compound added. Moreover, when the addition amount is the same, the flame retardancy as in the examples is not obtained. Therefore, it can be seen from the above results that a resin composition excellent in flame retardancy can be obtained with a very small amount of silicone compound by forming the composition of the present invention.

Claims (7)

Average composition formula (1) with respect to 100 parts by weight of the aromatic ring-containing resin (A)
^{_{R 1 m R 2 n Si (}} OH) p O (4-m-n-p) / 2 (1)
(In the formula, R ¹ represents a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ² represents a monovalent aromatic hydrocarbon group having 6 to 24 carbon atoms. R ¹ , R ^When there are a plurality of ^2's , they may be the same or different.m, n, p are 0 ≦ m <2.9, 0 <n ≦ 2.9, 0.01 ≦ p. 0.1-20 parts by weight of an aromatic ring-containing silicone compound (B) having a silanol group represented by the following formula as an essential substituent, and a pH of 8.0 or more, SiO 2 A flame retardant resin composition comprising ₂ to 20% by weight of a metal silicate compound (C) having an average particle diameter of 1 nm to 100 μm and occupying 30% by weight or more.   Furthermore, the flame-retardant resin composition of Claim 1 which contains 0.005-1 weight part of fluororesins (D). The aromatic ring-containing silicone compound of component (B) is an R ³ SiO _3/2 unit (wherein R ³ represents an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 24 carbon atoms, and 2. When there are a plurality of units, R ³ may be the same or different, and / or is a silicone compound containing 10% or more of SiO ₂ units in Si atoms derived from the units. Or the flame-retardant resin composition of 2.   In the average composition formula (1), the aromatic ring-containing silicone compound of the component (B) is such that m and n are 1.1 ≦ m + n ≦ 1.7 and 0.4 ≦ n / m ≦ 2.5. The flame retardant resin composition according to any one of claims 1 to 3, which is a silicone compound having a number satisfying   The flame-retardant resin composition according to any one of claims 1 to 4, wherein the aromatic ring-containing silicone compound (B) has a number average molecular weight of 1,000 to 200,000.   The (C) component metal silicate compound contains one or more metal elements selected from K, Na, Li, Ca, Mg, Mn, Fe, Ni, Al, Ti, Zn, and Zr. The flame-retardant resin composition according to any one of claims 1 to 5, wherein   The aromatic ring-containing resin (A) is an aromatic polycarbonate resin, aromatic polyester resin, polyphenylene ether resin, aromatic vinyl resin, polyphenylene sulfide resin, N-aromatic substituted maleimide resin, and aromatic resin. It is at least 1 sort (s) selected from the group which consists of polyimide resin, The flame-retardant resin composition as described in any one of Claims 1-7.