JP3464712B2 - Flame retardant resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition. More specifically, the present invention relates to a flame-retardant resin composition in which a phosphorus compound, a silicon-containing compound and a phenolic polymer are blended with a thermoplastic resin. [0002] Hitherto, flame retardation of thermoplastic resins has been achieved mainly by using halogen-based flame retardants, phosphorus-based flame retardants, antimony trioxide or the like alone or in combination. It is known that flame retardancy is synergistically improved when a flame retardant and a phosphorus flame retardant are combined. However, when a halogen-based flame retardant or antimony trioxide is used, there is a problem that a highly toxic gas such as hydrogen halide or antimony halide is generated during combustion. [0003] In recent years, many home appliances using flame-retardant resins have become widespread in ordinary households. However, flame-retardant resins with high flame retardancy and high safety that do not generate toxic gases and the like are required. Has been used as a halogen-free flame retardant,
For example, silicone oil or silicone resin has attracted attention. This is due to the fact that silicone oil and silicone resin are not only flame retardant themselves but also do not generate toxic gas during combustion. [0004] Examples of using the properties of silicone include:
For example, the surface of metal hydroxide is surface-treated with a silane coupling agent to increase the heat resistance of the flame retardant, or halogen-free is achieved by using a crosslinkable silicone oil and a silicone resin called MQ resin. In addition to those reported, some have been reported in combination with phosphorus-based flame retardants. However, these flame retardants also have a poor effect on styrene-based resins having a low melt viscosity, and have a drawback in that, in particular, they cannot prevent dripping during burning. Incidentally, the silicon-containing compound used in the present invention,
As a flame retardant for a thermoplastic resin, it is known together with a compound containing phosphorus or nitrogen. However, there is no known example in which a silicon-containing compound and a phenolic polymer are simultaneously used. When a chlorine- or bromine-containing compound is used to make a thermoplastic resin flame-retardant, the effect of the flame-retardation is relatively large, but toxic or harmful substances are eliminated at the time of fire or incineration. This causes problems such as making rescue or fire fighting difficult, or causing environmental pollution. Therefore, development of a flame-retardant resin containing no chlorine or bromine-containing compound at all or containing a small amount of chlorine or bromine-containing compound is desired. Further, when an inorganic substance such as antimony trioxide is used as the flame retardant component, there is a problem that the mechanical properties of the flame retardant resin are reduced. As a means for solving these problems, a technique disclosed in Japanese Patent Application Laid-Open No. 6-49302 is known.
However, this technique requires a small amount of a halogen-based flame retardant, and the addition of other flame-retardant components in order to reduce the amount of the halogen-based flame retardant. Have to be forced. Further, in the technique disclosed in JP-A-5-302013, a halogen-based flame retardant is not used, but it is necessary to incorporate a phosphorus compound and a char forming component in an amount of about 30% by weight based on the thermoplastic resin. There is a problem that the original performance is impaired. SUMMARY OF THE INVENTION The present invention is to solve these conventional problems, and an object of the present invention is to use a flame retardant which does not substantially contain chlorine or bromine, and to provide an excellent flame retardant. An object of the present invention is to provide a resin composition having flame retardancy. Means for Solving the Problems The present inventors have found that a particularly excellent flame-retardant effect can be obtained by combining a thermoplastic resin with a phosphorus compound, a silicon-containing compound and a phenolic polymer. It has been found that the present invention has been reached. That is, the present invention provides (A) a thermoplastic resin,
It is a flame-retardant resin composition comprising (B) a phosphorus compound, (C) a silicon-containing compound and (D) a phenolic polymer as essential components. In addition, the present invention relates to the above (A) component 1
1 to 30 parts by weight of the component (B) per 100 parts by weight,
It is a flame-retardant resin composition obtained by mixing the component (C) in a proportion of 0.05 to 10 parts by weight based on the silicon content and the component (D) in a proportion of 1 to 30 parts by weight. Hereinafter, the present invention will be described in detail. The thermoplastic resin used in the present invention can be appropriately selected from known ones . Polycarbonate resin, polystyrene resin, ABS resin, polyester resin (P
BT, including the PET), (modified) polyethylene, (modified) polypropylene, (modified) ethylene-propylene copolymer resins, polyamides resin, polyacetal, polymethyl methacrylate, and the like, these resins 2 It is also possible to use combinations of more than one species. The phosphorus compound (B) used in the present invention is not particularly limited as long as it has a phosphorus atom, but is preferably represented by the following general formula (I): (Wherein R1, R2, R3 and R4 independently of one another
Represents a hydrogen atom or an organic group, wherein R1 = R2 = R3 = R
Except when 4 = H. X represents a divalent or higher valent organic group;
Is 0 or 1, q is an integer of 1 or more, and r is an integer of 0 or more. ). In the above formula, examples of the organic group include:
Examples thereof include an alkyl group which may or may not be substituted, a cycloalkyl group, and an aryl group. When substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, and the like. Further, a group obtained by combining these substituents (for example, an arylalkoxyalkyl group or the like), or these substituents A group (for example, an arylsulfonylaryl group) combined by bonding with an oxygen atom, a sulfur atom, a nitrogen atom, or the like may be used as a substituent. The divalent or higher valent organic group means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above-described organic group. For example, alkylene groups, (substituted) phenylene groups, polynuclear phenols such as those derived from bisphenols, and the relative positions of two or more free valences are arbitrary.
Particularly preferred are hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxydiphenyl, p, p'-dihydroxydiphenylsulfone, dihydroxynaphthalene and the like. As an example of these phosphorus compounds, phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, and tricresyl phosphate. , Trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (o-phenylphenyl) phosphate, tris (p-phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xyenyl diphenyl phosphate, diphenyl (2- Ethylhexyl) phosphate, di (isopropylphenyl) phenylphosphate, o-phenylphenyldicresylphosphate Eto, dibutyl phosphate,
Monobutyl phosphate, di-2-ethylhexyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate and These condensates are exemplified. Examples of the phosphite include trimethyl phosphite, triethyl phosphite, tributyl phosphite, tri (2-ethylhexyl) phosphite, tributoxyethyl phosphite, trioleyl phosphite, triphenyl phosphite and tricresyl phosphite. Phyte, trixylenyl phosphite, tris (isopropylphenyl) phosphite, trisnonylphenyl phosphite, tris (o-phenylphenyl) phosphite, tris (p-phenylphenyl) phosphite, trinaphthyl phosphite, cresyl diphenyl Phosphite, xylenyl diphenyl phosphite, diphenyl (2-ethylhexyl) phosphite, di (isopropylphenyl) phenyl phosphite, o-phenylphenyl dichloride Phosphite, dibutyl phosphite, monobutyl phosphite, di-2-ethylhexyl phosphite, monoisodecyl phosphites and condensates thereof and the like. Examples of the phosphorus compounds other than the above include triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate and the like. One of these phosphorus compounds may be used alone, or two or more of them may be used in combination. The mixing amount of these phosphorus compounds is 100 parts by weight of the component (A),
A range of 1 to 30 parts by weight is preferred. If the amount is less than 1 part by weight, a sufficient flame-retardant effect cannot be obtained, and if the amount is more than 30 parts by weight, the heat resistance of the obtained composition is significantly reduced,
In some cases, adverse effects such as an increase in volatile components during molding may occur. The silicon-containing compound used in the present invention may be separate from the thermoplastic resin of the present invention, or may be contained as a structural unit. The silicon-containing compound may be either an organic silicon-containing compound or an inorganic silicon-containing compound. As long as the compound contains silicon, a compound having a wide range of molecular weight, for example, several hundreds to several millions can be used. When compounded separately with the thermoplastic resin, the form may be any of oil, varnish, gum, resin and the like. The thermoplastic resin having a silicon-containing structure is not particularly limited, but includes a silicone rubber-based graft polymer, a silicone-modified polycarbonate-based resin, polyarylene silicon, a copolymer of a methacryloxy-modified silicone and a vinyl-based resin. And a copolymer of an amino-modified silicone and a maleic anhydride reactant. The amounts of these silicon-containing compounds are as follows:
(A) 0.05 parts by weight of silicon per 100 parts by weight of component
A range of from 10 to 10 parts by weight is preferred. If the amount is less than 0.05 part by weight, a sufficient flame-retardant effect cannot be obtained, and if the amount is more than 10 parts by weight, the effect is not remarkably increased, and the mechanical properties of the thermoplastic resin are lowered. Causes the adverse effects of The phenolic polymer used in the present invention and
Is a phenol resin. The phenolic resin is not particularly limited, but is obtained by reacting a phenol with an aldehyde and / or a ketone in a known manner under an acidic or alkaline catalyst. Phenols include phenol,
Cresol, xylenol, ethylphenol, propylphenol, butylphenol, amylphenol,
Nonylphenol, phenylphenol, phenoxyphenol, hydroquinone, resorcinol, catechol, dihydroxydiphenyl, bis (hydroxyphenyl) pentane, dihydroxydiphenylmethane, bis (hydroxyphenyl) butane, dihydroxydiphenylsulfone, dihydroxydiphenylketone, bis (hydroxyphenyl) propane, etc. And mixtures thereof. Examples of the aldehyde include formaldehyde, paraformaldehyde, acetaldehyde, glyoxal and the like. Examples of ketones include acetone and the like. In the present invention, either a resol type or a novolak type phenol resin can be used, but a novolak type phenol resin is preferably used. A novolak-type phenol resin obtained by replacing a part or all of the aldehyde and / or ketone with a diol compound and reacting with a phenol can also be used. Preferred diol compounds include p-xylene-α, α'-diol and the like. The amount of the phenolic polymer comprising the phenolic resin is from 1 to 30 per 100 parts by weight of the component (A).
A range of parts by weight is preferred. If the amount is less than 1 part by weight, a sufficient anti-drip effect cannot be obtained, and if the amount is more than 30 parts by weight, adverse effects such as a remarkable decrease in the impact resistance of the obtained composition are caused. There are no particular restrictions on the method of mixing the resin and the flame retardant, and any means capable of making them uniform can be employed. For example, mixing, kneading, and the like by various mixing machines such as an extruder, a Henschel mixer, a Banbury mixer, a kneader, and a heating roll can be appropriately adopted. In the present invention, if necessary, various fillers, additives, and the like can be blended in amounts in which the effect is exhibited as long as the flame retardancy is not impaired. Examples thereof include fluororesins, glass fibers, asbestos, carbon fibers, aromatic polyamide fibers, potassium titanate whisker fibers, metal fibers, ceramic fibers, fibrous fillers such as boron whisker fibers, mica, silica, talc, clay, Fillers such as calcium carbonate, glass beads, glass balloons, glass flakes, release agents, lubricants, plasticizers, ultraviolet absorbers, light stabilizers, antioxidants, heat stabilizers, antiaging agents,
Additives such as dyeing (face) preparations are included. Furthermore, an impact strength improver for improving the properties of the polymer blend,
Compatibilizing components and the like can also be blended. The present invention will be described in more detail with reference to the following examples. Examples 1 to 4 and Comparative Examples 1 to 4 According to the formulation shown in Table 1, after mixing with a Henschel mixer, a 30φ twin screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.)
And melt-kneaded and extruded at 220 to 280 ° C., and pelletized by a pelletizer. From the pellets obtained in this way, using an injection molding machine to produce a test piece,
The flammability was evaluated. The results are shown in Table 1. In the UL combustion test, a combustion test piece of 127 mm × 12.7 mm × 1.6 mm was prepared from the obtained pellets by injection molding, and a subject 94 (UL-94) manufactured by Underwriters Laboratory, USA, was manufactured. It was measured according to the combustion test. [Table 1] The raw materials in Table 1 are as follows. Thermoplastic resin (1): AS resin AS-W manufactured by Denki Kagaku Kogyo Co., Ltd. Thermoplastic resin (2): Modified maleimide resin MS-L2A manufactured by Denki Kagaku Kogyo Co., Ltd. Thermoplastic resin (3): ABS resin GR manufactured by Denki Kagaku Kogyo -G
T-14 Thermoplastic resin (4): Silicone / acrylic rubber-based graft copolymer Metablen S-2001 manufactured by Mitsubishi Rayon Co., Ltd. Phosphorus compound: Triphenyl phosphate silicon-containing compound manufactured by Daihachi Chemical Industry Co., Ltd .: Toray Dow Resin powder refill R-910 manufactured by Sharp Corporation Phenolic polymer (1): Novolac phenolic resin MEH7800 manufactured by Meiwa Kasei Co., Ltd. Weight average molecular weight 1
000, the average structural formula is represented by the following formula (III). Embedded image Examples 1 and 2 are examples in which a silicon component is blended as a silicon-containing graft polymer, and Examples 3 and 4 are examples in which a silicon resin is blended separately from a thermoplastic resin. In any of the blending methods, remarkable improvement in flame retardancy is observed as compared with the comparative examples . As described above, a phosphorus compound is added to a thermoplastic resin.
By blending the silicon-containing compound and the phenolic polymer, the flame retardancy of the thermoplastic resin can be greatly improved. Furthermore silicon-containing compound may be contained as a structural unit of the thermoplastic resin, in the case of that has excellent flame retardancy with a small amount of a flame retardant amount is obtained.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-100785 (JP, A) JP-A-8-41312 (JP, A) JP-A-7-173401 (JP, A) JP-A-7-173 90148 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (1)

(57) [Claims] [Claim 1] The following (A), (B), (C) and (D)
In the flame-retardant resin composition that requires each component of,
Component (A) (however, epoxy group, hydroxyl group, carboxy
At least one member selected from the group consisting of
Having an active group and having an N-substituted maleimide unit
(But) 1 to 30 parts by weight of component (B) and silicon content of component (C) 0.05 per 100 parts by weight.
A flame-retardant resin composition obtained by mixing 10 to 10 parts by weight and the component (D) in a proportion of 1 to 30 parts by weight. (A) polycarbonate resin, polystyrene resin,
ABS resin, polyester resin (PBT, PE
T), (modified) polyethylene, (modified) polypropylene, (modified) ethylene-propylene copolymer resin, polyamide-based resin, polyacetal and at least one thermoplastic resin selected from polymethyl methacrylate (B) phosphorus compound (C) ) Silicon-containing compound (D) Phenolic polymer comprising phenolic resin