JPH0826228B2 - Flame-retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial field of application" The present invention relates to thermoplastic polyester resins such as polyethylene terephthalate and polybutylene terephthalate, thermoplastic polyamide resins such as nylon 6 and nylon 66, acrylonitrile / butadiene / styrene copolymers. A flame-retardant resin composition comprising a thermoplastic resin such as a united resin (ABS resin) and a polycarbonate resin, and a specific flame retardant and antimony trioxide as essential components.

"Conventional technology" Polyethylene terephthalate (hereinafter abbreviated as PET)
In addition, terephthalic acid-based polyester resins such as polybutylene terephthalate (hereinafter abbreviated as PBT) exhibit excellent physical properties, molding processability, and mechanical properties, and are widely used in engineering parts, electrical parts, and other fields as engineering plastics in recent years. It has been used. These thermoplastic resins are used by themselves, but glass fibers, inorganic reinforcing fillers, and flame retardants are blended to enhance various properties and are applied. In the fields of textiles, building materials, electric and electronic parts, the demand for safety against fire has increased more and more in recent years, and the flame retardancy of such resin compositions is urgently required, and various regulations regarding flame retardancy represented by US UL standards. Have been strengthened or required.

Terephthalic acid-based polyester resins such as PET and PBT, polyamide resins such as nylon 6 and nylon 66, and thermoplastic resins such as ABS resins are themselves flammable, and their flame retardance according to UL standards is UL94HB, UL94HB, UL94V, respectively. -2, U
L94V-2, UL94HB and it is necessary to use various flame retardants to achieve UL94V-0. Conventionally, a technique of adding various halogenated organic compounds to these resins to impart flame retardancy has been proposed. For example, heat typified by hexabromobenzene, decabromobiphenyl ether, and tetrabromobisphenol A. Aromatic halogen compounds, which have relatively high stability, and inorganic compounds such as antimony trioxide are also used as flame retardant aids. Regarding the method of using a halogenated bisphenol A type epoxy resin as a flame retardant, the epoxy group at one end of the resin is reacted with a halogenated phenol to form a one-end blocked epoxy having one epoxy group in the molecule. Resin
53-18068, JP-A-62-15256, JP-A-56-32538
No.) and a method using a high molecular halogenated bisphenol A type epoxy resin having a high degree of polymerization (JP-A-58-118849,
Nos. 60-171713, 61-293257, and USP4605708) are known.

“Problems to be Solved by the Invention” Hexabromobenzene, decabromobiphenyl ether, and tetrabromobisphenol A, which have been used as flame retardants in the past, are molding temperatures of thermoplastic polyester resin, polyamide resin, ABS resin, etc. At temperatures above ℃, it easily evaporates and decomposes, and bleeds out in the molded product, which impairs the external appearance and causes a serious problem that the flame retardancy decreases due to escape from the molded product for a long period of time. Further, since these are low molecular weight compounds, it is unavoidable that the material is softened and the physical properties of the original material are extremely deteriorated. In order to solve these problems, halogenated bisphenol A type epoxy resins are known, and low molecular weight type to high molecular weight type epoxy resins are widely used. However, since the molding processing temperature of PET and PBT of these epoxy resins is generally high at 230 to 270 ° C, the halogenated epoxy resin added is three-dimensionally crosslinked to increase the melt viscosity in the cylinder of the molding machine. It causes gelation and is often problematic because of strand breakage and inclusion as foreign matter in the molded product. Further, many low molecular weight substances are present in these halogenated epoxy resins, and at the time of melt-kneading, wrapping and non-uniformity occur near the screw, and generation of bleeding substances cannot be completely prevented. However, it is also thermally unstable and is a cause of lowering the original properties of the polyester resin.

Also, in order to reduce low molecular weight compounds in halogenated epoxy resin, a method of reacting low molecular weight halogenated epoxy resin with halogenated phenol and further using high molecular weight halogenated epoxy resin or halogenated phenoloxy resin is proposed. Has been done. However, even these high molecular weight halogenated epoxy resins have not reached a satisfactory molecular weight, and in order to further increase the degree of polymerization, a large amount of catalyst is used or high temperature heat treatment is performed in an extruder with a single screw vent to increase the molecular weight. There is. In addition, a method such as transferring to a tray or the like and performing heat treatment while impurities are present is performed. Accordingly, the reaction of intramolecular branching proceeds to deteriorate the melting characteristics or discolor, thereby causing various problems. Further, it is unavoidable that the elongation and impact strength of the resin composition decrease. Therefore, a high-molecular halogenated polyhydroxypolyether resin which is substantially linear, has a low molecular weight, is low in thermal stability, and has substantially no epoxy group is required.

"Means for Solving Problems" The present invention relates to a flame-retardant composition containing the following [A], [B] and [C], and particularly to the effect of the [B] component And [A] 100 parts by weight of thermoplastic resin such as thermoplastic polyester resin, thermoplastic polyamide resin, acrylonitrile / budadiene / styrene copolymer resin, polycarbonate resin [B] halogenated bisphenols and halogenated bisphenols The reduced viscosity obtained by a substantially equimolar reaction with a diglycidyl ether or a mixture of a halogenated bisphenol and a halogenated bisphenol diglycidyl ether and a mixture of bisphenol diglycidyl ether is 0.2 or more. , Halogen content is 2
0 to 62% by weight, phenolic acid value 1 mgKOH / g or less, epoxy value 2 mgKOH / g or less, content of low molecular weight compound having an average molecular weight of 1800 or less is 0.5% by weight or less, and molecular weight of 20,000 or more is substantially epoxy. A flame-retardant composition comprising 3 to 40 parts by weight of a linear halogen-containing polyhydroxypolyether resin containing no group [C] 2 to 10 parts by weight of antimony trioxide. The thermoplastic polyester resin, thermoplastic polyamide resin, acrylonitrile / butadiene / styrene copolymer resin, and polycarbonate resin of the component (A) used in the present invention are generally commercially available engineering plastics, typically polyethylene terephthalate. , Polybutylene terephthalate resin such as polybutylene terephthalate, polyamide resin of nylon 6, nylon 66, ABS resin, polyolefin, polystyrene, AS resin, MBS resin, ASA resin, acrylic resin, vinyl acetate resin, ethylene-vinyl acetate copolymer Polymers, polyacetals, other polymers such as modified PPO resins, elastomers such as acrylic rubber and grafters, or various organic polymers such as rubber components may be used alone or as a mixture. The above-mentioned halogenated polyhydroxypolyether resin is used as a flame retardant component of the composition of the present invention, and is a halogen of high purity and low in low molecular weight compounds obtained by the production method shown below. Must be a modified polyhydroxypolyether resin. The low molecular weight compound can be measured by the following method. HLC-802 manufactured by Toyo Soda Co., Ltd. by dissolving 0.25 g of sample in 10 ml of tetrahydrofuran.
A, 1 ml of a sample was injected by a GPC device under the conditions of a flow rate of 1.1 ml / min, a column temperature of 38 ° C. and a pressure of 57 Kg / cm ² for measurement. The data obtained is a chromatoprocessor manufactured by Toyo Soda Co., Ltd.
Treated with CP-8000 and shown as area percentage. This production method is filed by the applicant as Japanese Patent Application No. 62-24231, and a substantially equimolar reaction of a halogenated bisphenol and a halogenated bisphenol diglycidyl ether,
Or in a substantially equimolar reaction of a halogenated bisphenol with a mixture of a halogenated bisphenol, a halogenated bisphenol, a diglycidyl ether and a bisphenol diglycidyl ether, the raw materials and the product are dissolved in the presence of a catalyst. 100% using a non-reactive high boiling solvent
After the reaction is carried out at a temperature of ℃ to 220 ℃ until the reduced viscosity becomes 0.20 or more, a low boiling point solvent in which the reaction product is hardly soluble is added to the reaction mixture to separate and purify the reaction product.
The product obtained by this process has a phenolic acid value of 1 mgK.
It is a halogenated polyhydroxypolyether resin having a OH / g or less and an epoxy value of 2 mgKOH / g or less, which has not been obtained in the prior art and which does not substantially contain an epoxy group, and which has a high purity and a high molecular weight. Examples of halogenated bisphenols used in this production method are represented by the general formula (In the formula, Xi and Xi ′ may be the same or different and are a halogen atom, that is, a chlorine atom, a bromine atom, an iodine atom or a fluorine atom, and R ₂ is -CH ₂ -, - SO ₂ - a group, i and i is an integer of 1 to 4. ) Typically, 2,2-bis {4-hydroxy-2,3,
5,6 tetrabromophenyl) propane, 2,2 bis (4-hydroxy-2,3,5,6 tetrabromophenyl) methane, 2,2
Examples thereof include bis (4-hydroxy-2,3,5,6 tetrabromophenyl) sulfide. Examples of diglycidyl ethers of halogenated bisphenols include diglycidyl ethers prepared by a known method from halogenated bisphenols represented by the general formula [I] and epichlorohydrin, and diglycidyl ethers and halogenated bisphenols. It is a diglycidyl ether polymerized by a known method with phenols. Typically, it is brominated bisphenol A diglycidyl ether (for example, YDB-400 manufactured by Tohto Kasei Co., Ltd.), and other bifunctional epoxy resins such as bisphenol A diglycidyl ether, diphenyl sulfone diglycidyl ether, and tetrabromodiphthel. You may use together the enyl sulfone diglycidyl ether in 0-66 weight part range.
The reaction solvent used in the present production method is a non-reactive high-boiling point aliphatic cyclic ketone, high-boiling point aromatic hydrocarbon, or ethylene glycol lower alkyl ether ester used alone or as a mixture of the above solvents, The concentration of the reaction product is 25 to 80 parts by weight. It is necessary to select the composition of the mixed solvent within a range that can be dissolved in the reaction product. Examples of the high boiling aliphatic cyclic ketones include cyclohexanone and methylcyclohexanone. As the high boiling aromatic hydrocarbon, tri or tetramethylbenzene,
Examples of alkyl (C = 2 to 4) toluene, branched alkylbenzene (C = 3 to 36), diethylbenzene and ethylene glycol lower alkyl ether esters include ethylene glycol monoethyl ether acetate and ethylene glycol monobutyl ether. Preferably, those having a boiling point in the range of 100 to 220 ° C are effective. The catalyst used in this reaction is an organic compound or a salt thereof, and a known catalyst which is usually used in a reaction between a phenolic OH and an epoxy group can be used. For example, there are phosphine compounds such as tertiary amine, quaternary ammonium salt, and triphenylphosphine, and salts thereof. Typical examples are tetramethylammonium chloride, triphenylphosphine, triphenylphosphonium bromide, butoxyl-2-hydroxypropyltrifene. Examples thereof include enylphosphonium bromide. In order to obtain a high-purity and high-molecular weight halogenated polyhydroxypolyether resin in the present production method, diglycidyl ether is more preferably in the range of 0.96 to 1.05 mol with respect to 1 mol of halogenated bisphenols in the above solvent. Reacts in a substantially equimolar range in the range of 0.985 to 1.015, and the reaction temperature is 110 ° C to 220 ° C near the boiling point of the reaction solvent, and the reaction is continued until the reduced viscosity becomes 0.20 or more. The reduced viscosity should be controlled within the range of 0.20 to 0.4, and preferably within the range of 0.25 to 0.35. Substantially, the reaction time requires 5 hours or more. When the reduced viscosity reaches 0.2 or more, the reaction is terminated, but the reaction product at this point still contains 1 to 5% of unreacted low molecular weight compound. The most characteristic point of this production method is as follows. The reaction solution after completion of the reaction is a viscous transparent liquid, which is diluted with the reaction solvent while stirring to lower the temperature to adjust the concentration of non-volatile components to the range of 20 to 60% by weight. Next, the reaction liquid is cooled while cooling the amount of aromatic hydrocarbons, ketones, alcohols, and aliphatic hydrocarbons, which are poorly soluble low boiling point solvents in the reaction product, to the range of 20 to 200% by weight of the total solvent amount. When added to, the polymer reaction product alone is selectively separated by precipitation. When the addition of all the components is completed, the unreacted low-molecular compound and most of the catalyst used in the reaction are selectively dissolved in the reaction solvent, and this precipitate is washed with the same solvent or alcohols added after the reaction. After that, it is dried under a vacuum in a drying chamber at a temperature of 60 to 100 ° C. The white product obtained contains halogen in the range of 20-62% by weight,
Moreover, the amount of low molecular compounds and impurity ions is extremely small.
Also, phenolic acid value 1mgKOH / g or less, epoxy value 2mgKOH / g
The following are halogenated polyhydroxy polyethers having substantially no epoxy group and having excellent linear and thermal stability. Aromatic hydrocarbons, ketones, alcohols, and aliphatic hydrocarbons that are low boiling point solvents for precipitating products are typically benzene, toluene, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, normal hexane, etc. Is mentioned. The component (B) in the present invention has a very low low molecular weight content and contains substantially no epoxy group. Therefore, the flame-retardant composition according to the present invention bleeds out and generates foreign matter (gelation).
It does not have the drawbacks described above, has good thermal stability, and retains a flame-retardant effect for a long period of time, which is a remarkable effect in the present invention.
By adding antimony trioxide as the component [C], the flame retardant effect is further enhanced. As the component [C], in addition to antimony trioxide, antimony tetraoxide or antimony pentaoxide, sodium pyroantimonate, tin dioxide, zinc metaborate, aluminum hydroxide, zirconium oxide, molybdenum oxide or the like may be used in combination. Although the flame-retardant resin composition according to the present invention is the most basic composition, glass fiber, carbon fiber, calcium carbonate, potassium titanate fiber, calcium silicate, magnesium silicate as a reinforcing filler are further added to this composition. Calcium sulfate, barium sulfate, iron oxide, mica, asbestos, glass peas or glass powder, and pigments, antioxidants, ultraviolet absorbers, plasticizers,
Additives such as lubricants may be appropriately added and are included in the present invention. In the present invention, the thermoplastic resin of component [A], the flame retardant of component [B] and the flame retardant aid of component [C] are 3 to 40 parts by weight of component [B] per 100 parts by weight of component [A], Preferably, 5 to 30 parts by weight and the component [C] are used in 2 to 10 parts by weight, preferably 4 to 9 parts by weight. [A] Component 10
If the amount of the component (B) is less than 3 parts by weight with respect to 0 parts by weight, the flame retardant effect is lowered, and if it exceeds 40 parts by weight, the impact resistance is lowered.
If the amount of the component [C] is less than 2 parts by weight relative to 100 parts by weight of the component [A], the flame retardant effect is lowered, and if it exceeds 10 parts by weight, the impact resistance tends to be lowered. As a method often used for the flame-retardant composition according to the present invention, there is a method of containing glass fiber, but in this case, a fiber having a fiber length of 0.4 to 6 mm, which is preferably a commercially available product that has been subjected to various treatments it can. The glass fiber content is preferably 5 to 60 parts by weight based on the component (A). If it is less than 5 parts by weight, the reinforcing effect of the glass fiber is not sufficient, and if it exceeds 60 parts by weight, the fluidity is lowered and the molding process tends to be difficult. The component [B] is a thermoplastic resin itself and has excellent mechanical properties.

"Action" The flame-retardant composition in the present invention is particularly due to the action of the flame-retardant [B] component obtained by the above-mentioned production method, and it is possible to obtain the properties of the flame-retardant resin composition which have not been achieved conventionally. it can. That is, the flame retardant [B] component is a high-purity and high-molecular weight halogenated polyhydroxypolyether resin which has never been seen before, and the low molecular weight compound contained in this resin is very small at 0.1 to 0.3% by weight. It is a linear polyether resin containing no epoxy group, and has very few impurities. This is a thermoplastic resin itself, and can be injection-molded by the same method as other engineering plastics. The properties of this molded product are excellent in mechanical strength, very small water absorption rate, excellent performance, and flame retardant. Also, it is easily mixed with other engineering plastics and is easy to mold. Therefore, due to the escape of the flame retardant due to thermal decomposition, which has been a problem in the past, the extreme deterioration of the physical properties of the material, the softening phenomenon when heated, the occurrence of bleeding in the cylinder of the molding machine, and the three-dimensional crosslinking of the epoxy resin. The inclusion of foreign matter due to gelation, strand breakage in the extrusion process, poor appearance, etc. could be solved by using the flame retardant [B]. Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

"Examples and Comparative Examples" Synthesis Example 1 Production Example of Flame Retardant [B] Tetrapromobisphenol A-epichlorohydrin type epoxy resin having an epoxy equivalent of 401.3 g / eq (YDB-400 manufactured by Tohto Kasei Co., Ltd., Br = 48.9% by weight). ) 178.1 g, tetrabromobisphenol A 121.9 g, and a mixed solvent of cyclohexanone and solvent naphtha (mixing weight ratio 1/1) 53 g as a solvent were charged in a separable flask of 1, and stirred and heated while purging with nitrogen. When the internal temperature reached 110 ° C, 250 ppm of catalyst butoxyl 2-hydroxypropyltriphenylphosphonium bromide was added. The temperature is gradually raised and the reaction is carried out at 160 ° C ± 5 ° C. The viscosity gradually increases, so after 3 hours, 47 g of mixed solvent and 250 ppm of catalyst phosphonium salt.
Was added. After another 2 hours, 62 g of a mixed solvent was added. Further, the mixture was reacted for 7 hours under stirring. The reduced viscosity of the product at this time was 0.30 cst. Thereafter, the temperature was lowered to about 100 ° C. while adjusting the nonvolatile content to 40% by weight with a mixed solvent, 338 g of methanol was added, and crystallization was performed with stirring. The crystals were filtered and washed with methanol at 40 ° C. to 50 ° C. with stirring for 30 minutes, and then overdried. 293.4 g of the product were obtained. This product is a white fine-grained solid with a bromine content of 52.9 wt.
%, Low molecular content 0.29vl%, epoxy value 0.89mgKOH / g,
Phenolic acid value 0.45mgKOH / g, Na ⁺ 1ppm or less, Cl ^- 1ppm
Hereinafter, Br ^- 1 ppm or less, Atsuta in P content 0. The following characteristics were obtained by injection molding of this product alone. Tensile strength 880Kg f / cm ² , bending strength 1470Kg f / cm ² , Rockwell hardness R-126, water absorption rate 0.05%, heat distortion temperature 111 ° C (measurement method conforms to JIS K 6911.) Synthesis Comparative Example 1 Epoxy equivalent 401.3 g / eq of YDB-400, 754 g, tetrabromobisphenol A 446 g, and catalyst 10% aqueous solution of tetramethylammonium chloride 0.6 g were charged into a stainless steel separable flask, and after nitrogen substitution, 150
After reacting for 3 hours at 180 ° C., it was further reacted for 2 hours at 180 ° C. After the obtained resin was pulverized and 1 g of the above catalyst was added to and mixed with 1000 g, the screw was rotated at 200 ° C. for 2 minutes at 200 ° C. with a twin-screw extruder to carry out a further reaction by adjusting the rotation speed of the screw. The resin thus obtained was pulverized into a yellow powder. Table 1 shows the analysis results of the obtained resin.

Synthetic Comparative Example 2 YDB-400 having epoxy equivalent of 401.3 g / eq, 561.8 g, tetrabromobisphenol A 214.6 g, and tribromophenol.
After 201.9 g was charged into a 2 stainless steel separable flask and purged with nitrogen, it was heated and melted, and 0.56 g of tributylamine was added to 140 ° C. and reacted at 160 ° C. to 230 ° C. for 10 hours. The resin thus obtained was pulverized into a yellow powder. Table 1 shows the analysis results of the obtained resin.

The resin synthesized by the production method shown in Table 1 as shown in Table 1 has a remarkably low content of low-molecular compounds analyzed by GPC analysis (measurement method described in this section), a small amount of impurity ions, and a number average. A high molecular weight, substantially linear polyhydroxypolyether was obtained. The resin obtained in the above synthesis example is used as a component [B], and the component [A] is a polybutylene terephthalate resin (Mitsubishi Kasei Co., Ltd., trade name Novador 5008) or a polyethylene terephthalate resin (Toyobo Co., Ltd.).
Product name RE-500), nylon 6 (Ube Industries, Ltd. product name U)
BE Nylon 1013B), ABS resin (Ube Saikon Co., Ltd. trade name Psycholac AM-1001), polycarbonate (Idemitsu Petrochemical Co., Ltd. trade name A-2200), flame retardant aid antimony trioxide as component [C] The ingredients were blended in the proportions shown in 2 and mixed for 5 minutes with a Henschel mixer, and then pelletized with a twin screw extruder at a cylinder temperature of 220 to 300 ° C. Then, injection molding is performed at a molding temperature of 220 to 320 ° C to form a sheet, and a test piece is prepared. The tensile strength of each flame-retardant composition is 300 ° C.
The thermal stability characteristics, flame retardancy test, and appearance of molded products were evaluated by a 30-minute heating loss method. Examples I to
As shown in Table 2 for V and Comparative Examples I-1 to V-4, remarkable properties of the flame-retardant resin composition of the present invention were obtained.

[Advantages of the Invention] The present invention uses a linear halogen-containing polyhydroxypolyether resin having specific physical properties and substantially no epoxy group as a flame retardant, so that the thermoplastic resin such as thermoplastic polyester itself The flame-retardant composition of the present invention can be flame-retarded without deteriorating its properties and can provide a flame-retardant composition far superior to conventional flame-retardants.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 62-4737 (JP, A) JP 59-149954 (JP, A) JP 59-206460 (JP, A) JP 61- 261346 (JP, A) JP 58-118849 (JP, A) JP 58-21442 (JP, A) JP 58-101145 (JP, A)

Claims (1)

[Claims] 1. A flame-retardant resin composition containing the following (A), (B) and (C). (A) Thermoplastic polyester resin, thermoplastic polyamide resin, acrylonitrile / budadiene / styrene copolymer resin, polycarbonate resin, etc. 100 parts by weight of thermoplastic resin (B) Halogenated bisphenols and halogenated bisphenols diglycidyl Obtained by a substantially equimolar reaction with an ether or a substantially equimolar reaction with a mixture of a halogenated bisphenol and a halogenated bisphenol diglycidyl ether and a bisphenol diglycidyl ether, and a reduced viscosity of 0.2 or more, a halogen Content is 20 ~ 6
2% by weight, phenolic acid value 1 mgKOH / g or less, epoxy value 2
mgKOH / g or less, average molecular weight of 1800 or less Low molecular weight compound content of 0.5% by weight or less, and molecular weight of 20,000 or more linear epoxy-containing linear polyhydroxypolyether resin 3-40 weight Parts (C) 2-10 parts by weight of antimony trioxide