JPH0867801A - Flame-retardant thermoplastic resin composition and flame retardant - Google Patents

Abstract

(57) [Summary] [Structure] A compound having a structure in which a thermoplastic resin (A), for example, a styrene resin, and a part or all of the epoxy groups of a halogenated epoxy resin are blocked with a fluorinated aliphatic carboxylic acid ( B ₁ ) and / or a halogenated epoxy resin or a compound having a structure in which some or all of the epoxy groups of the halogenated epoxy resin are blocked, and some or all of the epoxy groups of the epoxy resin are fluorinated aliphatic carvone. A mixture (B ₂ ) obtained by melting and mixing a compound having a structure blocked with an acid, for example, a flame retardant (B ₂ ) formed by blocking the epoxy group of a brominated bisphenol type epoxy resin with perfluoroheptanoic acid and tribromophenol. ) And a flame-retardant thermoplastic resin composition containing the flame retardant. [Effect] The flame-retardant thermoplastic resin composition containing the flame retardant of the present invention is excellent in thermal stability during molding and has low adhesion to metal, so that a molded product having a good appearance can be obtained. In addition, the moldability can be shortened and the productivity can be improved.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant thermoplastic resin composition having excellent mold releasability of a molded article from a mold and thermal stability at the time of molding, and good releasability and thermal stability. It relates to a flame retardant added to a plastic resin.

[0002]

2. Description of the Related Art Conventionally, as flame-retardant thermoplastic resin compositions, for example, JP-A-53-74557 and JP-A-5-74557 are known.
No. 4,915,57, Japanese Patent Publication No. 60-264313 and Japanese Patent Laid-Open No. 62-15256 disclose flame retardant resin compositions containing a flame retardant composed of a halogenated epoxy resin. Japanese Patent Laid-Open No. 62-15256 discloses a technique in which a flame retardant aid such as antimony trioxide is further added and blended.

[0003]

However, in these conventional flame-retardant thermoplastic resin compositions, since the compounded flame retardant has high adhesiveness to the metal part of a molding machine or a mold, molding is difficult. Inducing the mold releasability of the product from the mold, and the flame retardant that adheres and stays in the metal part of the molding machine causes thermal decomposition, causing discoloration of the molded product and appearance defects such as burning dust. Had the problem of.

The problem to be solved by the present invention is that the adhesiveness to the metal part of the molding machine or the mold is low, the mold releasability from the mold is excellent, and the appearance failure is caused by the thermal decomposition of the flame retardant. To provide a flame-retardant thermoplastic resin composition having excellent thermal stability during molding, which does not easily adhere to metal parts of a molding machine or a mold, and does not easily decompose thermally. is there.

[0005]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to solve the above-mentioned problems, some or all of the epoxy groups of halogenated epoxy resin as a flame retardant are fluorinated aliphatic carboxylic acids. A compound having a blocked structure, and / or a halogenated epoxy resin or a compound having a blocked structure of a part or all of the epoxy groups of the halogenated epoxy resin, and a part or all of the epoxy groups of the epoxy resin A flame-retardant thermoplastic resin having excellent mold releasability from a mold and thermal stability at the time of molding by using a flame retardant composed of a mixture obtained by melt-mixing with a compound having a structure blocked with a fluorinated aliphatic carboxylic acid. It was found that a composition was obtained, and the present invention was completed.

That is, the present invention comprises a thermoplastic resin (A),
A compound (B ₁ ) having a structure in which some or all of the epoxy groups of the halogenated epoxy resin are blocked with a fluorinated aliphatic carboxylic acid and / or a halogenated epoxy resin or a part of the epoxy groups of the halogenated epoxy resin Or a compound having a structure in which all of the epoxy groups are blocked and a compound (B ₂ ) obtained by melt-mixing a compound having a structure in which some or all of the epoxy groups of the epoxy resin are blocked with a fluorinated aliphatic carboxylic acid. A flame-retardant thermoplastic resin composition containing a flame retardant (B), a compound having a structure in which a part or all of the epoxy groups of a halogenated epoxy resin are blocked with a fluorinated aliphatic carboxylic acid ( B
₁ ) a flame retardant, and a halogenated epoxy resin or a compound having a structure in which a part or all of the epoxy groups of the halogenated epoxy resin are blocked, and a part or all of the epoxy groups of the epoxy resin A flame retardant, which is a mixture (B ₂ ) obtained by melt-mixing a compound having a structure in which all are blocked with a fluorinated aliphatic carboxylic acid.

The thermoplastic resin (A) used in the present invention is not particularly limited, and examples thereof include polystyrene, polymethylstyrene, and rubber-modified polystyrene (HI).
PS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-acrylic rubber-
Styrene copolymer (AAS resin), acrylonitrile-
Styrene resin such as ethylene propylene rubber-styrene copolymer (AES resin), alloy of ABS resin and polycarbonate, alloy of ABS resin and polyester resin, alloy of ABS resin and polyamide resin, alloy of polystyrene and polyphenylene oxide, etc. Polymer alloy containing styrene resin as a component, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyhexamethylene terephthalate,
Polyester resins such as polyethylene naphthalene dicarboxylate, polybutylene naphthalene dicarboxylate and polyhexamethylene naphthalene dicarboxylate, olefin resins such as polyethylene, polypropylene and polybutene, polyamide resins such as nylon 6 and nylon 66, polyphenylene oxide, Polycarbonate, an alloy of polycarbonate and polyester resin,
Examples include alloys of polycarbonate and polyamide resin.

Above all, the compatibility with the flame retardant composition is excellent,
H from the point that the effect of improving metal adhesion and thermal stability becomes remarkable
Styrene resin represented by IPS, ABS resin, etc., P
Polyester resin represented by BT, ABS resin and P
C alloys, polymer alloys containing styrene resins represented by alloys of PBT and PC, and polymer alloys containing polyester resins are preferable.

The flame retardant (B) used in the present invention is a compound (B ₁ ) having a structure in which a part or all of the epoxy groups of the halogenated epoxy resin is blocked with a fluorinated aliphatic carboxylic acid, as described above. And / or a halogenated epoxy resin or a compound having a structure in which a part or all of the epoxy groups of the halogenated epoxy resin are blocked, and a part or all of the epoxy groups of the epoxy resin is blocked with a fluorinated aliphatic carboxylic acid It is a flame retardant composed of a mixture (B ₂ ) obtained by melt-mixing with a compound having the above structure, and among them, the compound (B ₁ ) is preferable.

The halogenated epoxy resin used herein is not particularly limited, and examples thereof include halogenated bisphenol type epoxy resin, halogenated phenol novolac type epoxy resin, halogenated cresol novolac type epoxy resin, halogenated resorcin type epoxy resin, Examples include halogenated hydroquinone type epoxy resin, halogenated bisphenol A novolac type epoxy resin, halogenated methylresorcinol type epoxy resin, halogenated resorcinol novolak type epoxy resin, etc., but heat resistance and compatibility with thermoplastic resin (A) A halogenated bisphenol type epoxy resin is preferred because of its excellent properties.

The halogenated bisphenol type epoxy resin is not particularly limited, but it is dibromobisphenol A type epoxy resin, tetrabromobisphenol A type epoxy resin, dichlorobisphenol A type epoxy resin, tetrachlorobisphenol A type epoxy resin. Resin, dibromobisphenol F type epoxy resin, tetrabromobisphenol F type epoxy resin, dichlorobisphenol F type epoxy resin, tetrachlorobisphenol F type epoxy resin, dibromobisphenol S type epoxy resin, tetrabromobisphenol S
Type epoxy resin, dichlorobisphenol S type epoxy resin, tetrachlorobisphenol S type epoxy resin and the like.

Among these halogenated bisphenol type epoxy resins, brominated bisphenol A type epoxy resins having an average degree of polymerization of 0 to 50 are preferable. The fluorinated aliphatic carboxylic acid used in the present invention is an essential component that reduces the adhesiveness to the metal of the flame retardant of the present invention and imparts the effect of improving the releasability.

As the fluorinated aliphatic carboxylic acid,
Although not particularly limited, a fluorinated aliphatic carboxylic acid having 3 or more carbon atoms is preferable from the viewpoint of being excellent in the effect of reducing metal adhesion, and for example, perfluoropropionic acid,
Perfluorobutanoic acid, perfluoropentanoic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid , Perfluorotetradecanoic acid, perfluoropentadecanoic acid, perfluorohexadecanoic acid, perfluoroheptadecanoic acid,
Perfluorooctadecanoic acid, perfluorononadecanoic acid, perfluoroicosanoic acid, perfluorohenicosanoic acid, perfluorodocosanoic acid, perfluorotriacontanoic acid, perfluorotetracontanoic acid, and their fluorinated aliphatics Examples thereof include compounds in which some of the fluorine atoms of carboxylic acid are replaced with hydrogen atoms. Among these fluorinated aliphatic carboxylic acids, especially those having 3 to 2 carbon atoms
Perfluoroaliphatic carboxylic acids having 0 carbon atoms are preferable, and perfluoroaliphatic carboxylic acids having 3 to 12 carbon atoms are more preferable.

The compound (B ₁ ) having a structure in which a part or all of the epoxy groups of the halogenated epoxy resin used in the present invention is blocked with a fluorinated aliphatic carboxylic acid is one of the epoxy groups of the halogenated epoxy resin. Not only those having a structure in which a part or all is blocked with only a fluorinated aliphatic carboxylic acid, for example, a part or all of the epoxy groups are reactive with other epoxy groups together with the fluorinated aliphatic carboxylic acid. It may have a structure blocked with a compound having

The compound having reactivity with the epoxy group is not particularly limited as long as it is a compound having reactivity with an epoxy group other than the fluorinated aliphatic carboxylic acid, and examples thereof include a carboxyl group and an acid anhydride. Examples include compounds having functional groups such as groups, alcoholic hydroxyl groups, phenolic hydroxyl groups, phosphonium groups, amino groups, imino groups, acid amide groups, acid imide groups, thiol groups, and isocyanate groups, among which halogens as flame retardants. From the viewpoint of increasing the content, halogenated ones are preferable, and halogenated phenols are particularly preferable. Specific examples of the halogenated phenol include dibromophenol, dibromocresol,
Examples thereof include tribromophenol, pentabromophenol, dichlorophenol, dichlorocresol, trichlorophenol, pentachlorophenol, and the like, of which tribromophenol is most preferable.

The compound (B ₁ ) can be produced by various methods and is not limited by the production method. As the production method, a halogenated epoxy resin and a halogenated bisphenol type epoxy resin are used. A specific example of the manufacturing method of the thing is shown below.

That is, a halogenated bisphenol type epoxy resin, for example, a condensation product of halogenated bisphenol and epichlorohydrin, or a product obtained by further adding a halogenated bisphenol to this condensation product to obtain a high molecular weight product, is obtained. A halogenated bisphenol type epoxy resin, a fluorinated aliphatic carboxylic acid, and optionally a compound having reactivity with an epoxy group other than this, preferably a halogenated phenol in the presence or absence of a catalyst. A method of reacting by heating to 100 to 230 ° C., a condensate of a halogenated bisphenol and an epihalohydrin, a halogenated bisphenol and a fluorinated aliphatic carboxylic acid, and optionally a compound having reactivity with an epoxy group other than this. , Preferably with a halogenated phenol, of the catalyst Standing or below 100 in the absence
Examples include a method of reacting by heating to ~ 230 ° C. Among them, fluorination of epoxy group is advantageous in that a flame retardant having excellent releasability effect on metal, thermal stability during molding and heat distortion temperature is easy to produce. A method of blocking with an aliphatic carboxylic acid and a halogenated phenol is preferable, and a method having a significantly outstanding advantage in the production method that the production process is shortened is preferable.

Examples of the catalyst used here include alkali metal hydroxides such as sodium hydroxide, tertiary amines such as dimethylbenzylamine, imidazoles such as 2-ethyl-4methylimidazole, and tetramethylammonium chloride. Examples thereof include quaternary ammonium salts, phosphonium salts such as ethyltriphenylphosphonium iodide, and phosphines such as triphenylphosphine. The reaction solvent is not particularly necessary and may not be used.

The mixture (B ₂ ) used in the present invention comprises a halogenated epoxy resin or a compound having a structure in which a part or all of the epoxy groups of the halogenated epoxy resin are blocked, and an epoxy group of the epoxy resin. It is a mixture obtained by melt-mixing a part or all of a compound having a structure blocked with a fluorinated aliphatic carboxylic acid.

As the halogenated epoxy resin and the fluorinated aliphatic carboxylic acid used here, the above compounds (B
_The same as those used in ₁ ) are mentioned, and the same ones are preferably used.

In the compound having a structure in which a part or all of the epoxy groups of the halogenated epoxy resin are blocked, the sealing agent for blocking the epoxy groups of the halogenated epoxy resin is reactive with the epoxy group. It is not particularly limited as long as it is a compound having, but examples thereof include a fluorinated aliphatic carboxylic acid used in the above compound (B ₁ ) and a compound having reactivity with an epoxy group other than this, and usually halogen. Phenol, especially tribromophenol, is particularly preferably used.

Further, the epoxy resin is not particularly limited, and examples thereof include bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, resorcin type epoxy resin, hydroquinone type epoxy resin, bisphenol A novolac type epoxy resin, Methylresorcin type epoxy resin, resorcin novolac type epoxy resin and the like can be mentioned, but bisphenol type epoxy resin is preferable from the viewpoint of excellent heat resistance and compatibility with the thermoplastic resin (A).

The bisphenol type epoxy resin is not particularly limited, but bisphenol A
Type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and the like. Among them, bisphenol A type epoxy resin having an average degree of polymerization of 0 to 50 is preferable.

The mixture (B ₂ ) can be produced by, for example, a halogenated epoxy resin or a compound having a structure in which a part or all of the epoxy groups of the halogenated epoxy resin are blocked, and a part of the epoxy groups of the epoxy resin. To a compound having a structure in which all of them are blocked with a fluorinated aliphatic carboxylic acid, a method of heating and melting at a temperature at which all of them melt, for example, 120 ° C. to 230 ° C., and the like, and the like. Any of various heatable mixers can be used. Usually, 15 minutes ~ in a container with stirring blades
It is produced by a method of heating and stirring for about 3 hours, but a Banbury mixer, an extruder or the like may be used if necessary.

The halogenated epoxy resin, the raw material thereof and the halogenated phenol used in the present invention are as follows:
It is particularly preferable to use bromine as the halogen because a flame retardant having excellent flame retardancy can be obtained.

The content of the fluorinated aliphatic carboxylic acid contained in the flame retardant (B) comprising the compound (B ₁ ) and / or the mixture (B ₂ ) used in the present invention is not particularly limited, The range in which the content in the flame retardant (B) is 0.1 to 10% by weight is preferable from the viewpoint of excellent releasability to metal, thermal stability at the time of molding, and heat distortion temperature. The range of 0.5 to 5% by weight is particularly preferable. The amount of the fluorinated aliphatic carboxylic acid used may be in the range of more than 10% by weight, but in this case, improvement of the effect cannot be expected.

Flame retardant (B) for thermoplastic resin (A)
The compounding amount is not particularly limited, but is usually 1 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A), and among them, the flame retardant effect is high and the physical properties such as impact resistance are deteriorated. The amount is preferably 5 to 30 parts by weight.

The flame-retardant thermoplastic resin composition of the present invention comprises
Further, it is preferable to add a flame retardant aid (C) in order to enhance the flame retardant effect. Examples of the flame retardant aid (C) include antimony compounds such as antimony trioxide, antimony tetraoxide and antimony pentoxide, tin compounds such as tin oxide and tin hydroxide, molybdenum oxides such as molybdenum oxide and ammonium molybdate. Examples thereof include compounds, zirconium compounds such as zirconium oxide and zirconium hydroxide, and boron compounds such as zinc borate and barium metaborate.

The blending amount of these flame retardant aids (C) is usually 0.2 to 25 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). Among them, physical properties such as flame retardancy and impact resistance. The flame-retardant thermoplastic resin composition of the present invention, which is preferably 1 to 15 parts by weight in terms of a small decrease, has, for example, a thermoplastic resin (A), a flame retardant (B), and optionally a flame retardant auxiliary ( C) and other additive components are mixed in a predetermined amount and premixed with a mixer such as a Henschel mixer or a tumbler mixer, and then an extruder,
It can be easily produced by melt-mixing with a kneader, hot roll, Banbury mixer or the like.

The flame-retardant thermoplastic resin composition of the present invention contains other flame-retardant agents, for example, other flame-retardants within a range that does not significantly impair the thermal stability during molding and the releasability from the mold during injection molding. Bromine-based flame retardants, chlorine-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, inorganic flame retardants, etc. may be added, and if necessary, ultraviolet absorbers, light stabilizers, release agents, lubricants. , Colorants, plasticizers,
A filler, a foaming agent, an impact resistance improver, a compatibilizer, a coupling agent, a heat stabilizer, an antioxidant, a reinforcing material such as glass fiber, carbon fiber and aramid fiber can be added.

The flame retardant (B) of the present invention can be used not only as the thermoplastic resin (A) but also as a flame retardant for thermosetting resins such as epoxy resin, phenol resin and polyurethane resin. .

[0032]

EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples, but the scope of the present invention is not limited to these examples.

All parts and% in the examples are based on weight, and various physical properties are measured or tested by the following methods.

(1) Measurement of softening point (ring-and-ball type) It was measured according to JIS K-7234. (2) Measurement of epoxy group content The epoxy equivalent (g / eq) measured according to JIS K-7236 was measured, and the reciprocal thereof was determined. Unit is eq
/ G. (3) Measurement of heat distortion temperature According to ASTM D-648, a load of 18.6 kg /
It was measured in cm ² . The unit of measurement is ° C.

(4) Measurement of Izod impact strength (notched) According to ASTM D-256, notched thickness 1 /
It measured using the 4-inch test piece. The unit of measurement is k
It is g · cm / cm. (5) Flammability test (UL-94) Subject 9 of Underwriters Laboratories
Based on method No. 4, length 5 inches x width 1/2 inches x
The test was carried out using five 1/8 inch thick test pieces.

(6) Limit Injection Molding Test (Thermal Stability) A 5 ounce injection molding machine equipped with a mold of a disk-shaped molded product (outer diameter 100 mm × thickness 3 mm) was placed in a well-dried flame-retardant thermoplastic resin. Injection of resin composition pellets from the hopper is repeated, and the appearance of the obtained molded product is visually and visually observed with a magnifying glass (× 10) to ensure continuous discoloration and contamination. The thermal stability was evaluated by determining the limit number of times (the greater the number of limit injection molding, the better the thermal stability).

The discoloration referred to in this test means the case where the surface of the molded product is entirely colored in brown. In addition, the term “contamination of foreign matter” means that a foreign matter of 1.0 mm ² or more is present on one surface of the molded product.
The case where there are more than one is shown. The stability was evaluated according to the following ranks.

Judgment limit number of injection moldings ○: 200 times or more, practically no problem Δ: 100 to less than 200 times, practically difficult ×: less than 100 times, practically impossible to mass-produce The molding conditions are as follows. .

Cylinder temperature: ABS, HIPS,
Or, in the case of ABS / PC polymer alloy, 250 ° C PBT, or in the case of PBT / PC polymer alloy, 2
70 ° C. Injection pressure: 1400 to 500 kgf / cm ² Mold temperature: 60 to 80 ° C. Injection time / cooling time: 10 seconds / 20 seconds

(7) Mold releasability test (metal adhesion) Box-shaped molded product (size: width 200 mm × depth 100 m)
(m × height 50 mm × thickness 2.35 mm) A 10 ounce injection molding machine equipped with a die is charged with well-dried pellets of the flame-retardant thermoplastic resin composition from a hopper to perform injection molding. After cooling the molded product in the mold, the mold was opened, and the maximum resistance pressure when the ejector plate of the molding machine advanced to push out the ejector plate was measured by the pressure sensor. The metal adhesion of the flame-retardant thermoplastic resin composition was evaluated from the resistance pressure (unit: kg / cm ² ) at this time.

A pressure sensor (NSP-2C type manufactured by Technoplus Co., Ltd.) is attached between a plate for driving the ejecting rod and a hydraulic cylinder for moving the plate,
The pressure exerted on the stick was detected.

When the metal adhesion is low, the resistance pressure value becomes small and the obtained molded product does not deform. Therefore, the metal adhesion was evaluated according to the following ranks. Judgment Resistance pressure value Appearance of molded product ◎: 25 kgf / cm ² or less No deformation or whitening ◯: 26 to 35 kgf / cm ² Almost no deformation or whitening △: 36 to 45 kgf / cm ² Partial deformation and whitening Difficult to put into practical use ×: 46 to 65 kgf / cm ² Deformation or whitening is not possible for practical use XX: 66 kgf / cm ² or more There is significant deformation or whitening Injection molding conditions are as follows.

Cylinder temperature: ABS or HIP
In the case of S, 220-230 ° C ABS / PC polymer alloy, 240 ° C PBT 250-260 ° C PBT / PC polymer alloy, 250 ° C Injection pressure: 1400-500 kgf / cm ² Mold temperature : 60-80 ° C Injection time / cooling time: 10 seconds / 20 seconds

Next, the flame retardant used in the present invention and the flame retardant to be compared were produced by Examples 1 to 9 and Comparative Examples 1 to 3.

Example 1 EPICLON 152 [halogenated epoxy resin (condensation product of tetrabromobisphenol A and epichlorohydrin) manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 3
60 g / eq, average degree of polymerization 0.1, bromine content 48%]
720.0 g and tetrabromobisphenol A (hereinafter,
TBA (abbreviated as TBA) 150.0 g, 2,4,6-tribromophenol (abbreviated as TBP hereinafter) 438.0 g, and perfluoroheptanoic acid (carboxyl group equivalent 346 g / e)
q) 13.0 g was put in a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, the contents were heated and melted, and a 10% aqueous solution of sodium hydroxide was added at 100 ° C. After adding 1.3g, 150-180
The reaction was performed at 12 ° C for 12 hours. After the reaction, the reaction product was poured into a stainless steel pan, cooled, and then pulverized to obtain a pale yellow flame retardant powder. This flame retardant has a fluorinated aliphatic carboxylic acid content of 1.0% and an epoxy group content of 0.03 × 10 ⁻³ e
It had q / g, a softening point of 115 ° C., a bromine content of 56%, and an average degree of polymerization of 1. Hereinafter, this is referred to as flame retardant A.

Example 2 438.0 g of TBP and 13.0 of perfluoroheptanoic acid
Example 1 except that TBP 414.0 g and perfluoroheptanoic acid 40.0 g were used instead of g.
Flame retardant powder was obtained in the same manner as in. This flame retardant has a fluorinated aliphatic carboxylic acid content of 3.0%, an epoxy group content of 0.04 × 10 ⁻³ eq / g, a softening point of 109 ° C., a bromine content of 55%, and an average degree of polymerization of 1. Met. Hereinafter, this is referred to as flame retardant B.

Example 3 438.0 g of TBP and 13.0 of perfluoroheptanoic acid
Instead of g, TBP 418.0 g and perfluorooctanoic acid (carboxyl group equivalent 414 g / eq) 40.0 g
Flame retardant powder was obtained in the same manner as in Example 1 except that the above was used. This flame retardant has a fluorinated aliphatic carboxylic acid content of 3.0% and an epoxy group content of 0.03 × 10 5.
^-3 eq / g, softening point 110 ° C, bromine content 55%, average degree of polymerization 1 Hereinafter, this is referred to as flame retardant C.

Example 4 438.0 g of TBP and 13.0 of perfluoroheptanoic acid
Flame retardant powder was obtained in the same manner as in Example 1 except that TBP 424.0 g and perfluorononanoic acid (carboxyl group equivalent 502 g / eq) 40.0 g were used instead of g. This flame retardant has a fluorinated aliphatic carboxylic acid content of 3.0% and an epoxy group content of 0.04 × 10 ^−3.
It had an eq / g, a softening point of 110 ° C., a bromine content of 55%, and an average degree of polymerization of 1. Hereinafter, this is referred to as flame retardant D.

Example 5 438.0 g of TBP and 13.0 of perfluoroheptanoic acid
Instead of g, TBP 388.0 g and perfluorobutanoic acid (carboxyl group equivalent 214 g / eq) 39.0 g were used, and after pre-reaction at 110 to 120 ° C. for 6 hours, 150
Example 1 except that the reaction was carried out at ˜180 ° C.
Flame retardant powder was obtained in the same manner as in. This flame retardant has a fluorinated aliphatic carboxylic acid content of 3.0%, an epoxy group content of 0.04 × 10 ⁻³ eq / g, a softening point of 107 ° C., a bromine content of 55%, and an average degree of polymerization of 1. Met. Hereinafter, this is referred to as flame retardant E.

Example 6 The use of TBP was omitted, and 150.0 g of TBA, 13.0 g of perfluoroheptanoic acid and 10% of sodium hydroxide were used.
Instead of 1.3 g of the aqueous solution, 223.2 g of TBA, 40.0 g of perfluoroheptanoic acid and 10 parts of sodium hydroxide were used.
% Flame retardant powder was obtained in the same manner as in Example 1 except that 0.3 g of an aqueous solution was used. This flame retardant has a fluorinated aliphatic carboxylic acid content of 3.0%, an epoxy group content of 1.10 × 10 ⁻³ eq / g, a softening point of 109 ° C., a bromine content of 49%, and an average degree of polymerization of 1.6. It was the one. Less than,
This is called a flame retardant F.

Example 7 Omitting the use of TBP, TBA 490.0 instead of TBA 150.0 g and perfluoroheptanoic acid 13.0 g.
g and 37.4 g of perfluoroheptanoic acid,
A flame retardant powder was obtained in the same manner as in Example 1 except that the reaction was carried out at 0 to 230 ° C. for 12 hours. This flame retardant has a fluorinated aliphatic carboxylic acid content of 3.0%, an epoxy group content of 0.07 × 10 ⁻³ eq / g, and a softening point of 184.
It had a bromine content of 50% and an average degree of polymerization of 20. Hereinafter, this is referred to as flame retardant G.

Comparative Example 1 The use of perfluoroheptanoic acid was omitted and TBP43 was used.
A flame retardant powder was obtained in the same manner as in Example 1 except that TBP450.0 was used instead of 8.0 g.
This flame retardant has an epoxy group content of 0.05 × 10 ⁻³ eq.
/ G, softening point of 116 ° C., bromine content of 57%, and average degree of polymerization of 1. Hereinafter, this is referred to as flame retardant A '.

COMPARATIVE EXAMPLE 2 The use of TBP and perfluoroheptanoic acid was omitted and TB
A 150.0 g and 10% aqueous solution of sodium hydroxide 1.
223.2 g of TBA and sodium hydroxide instead of 3 g
Except that 0.3 g of 10% aqueous solution of
In the same manner as in Example 1, a flame retardant powder was obtained. This difficulty
The flame retardant has an epoxy group content of 1.22 × 10 ^-3eq / g,
Softening point 116 ° C, bromine content 50%, average degree of polymerization 1.6
It was the one. Hereinafter, this is referred to as flame retardant F '.

Comparative Example 3 The use of TBP and perfluoroheptanoic acid was omitted and TB
A 150.0 g and 10% aqueous solution of sodium hydroxide 1.
Instead of 3 g, use TBA 490.0 g and sodium hydroxide 10% aqueous solution 0.3 g, and 150-230 degreeC.
Flame retardant powder was obtained in the same manner as in Example 1 except that the reaction was performed for 12 hours. This flame retardant has an epoxy group content of 0.45 × 10 ⁻³ eq / g, a softening point of 162 ° C.,
The bromine content was 52% and the average degree of polymerization was 6. Hereinafter, this is referred to as a flame retardant G '.

Hereinafter, Examples 1 to 7 and Comparative Examples 1 to 3 will be described.
The raw material composition and property values of the flame retardant produced in 1. are shown in Tables 1 and 2.

[0056]

[Table 1]

[0057]

[Table 2]

Example 8 EPICLON 850 [epoxy resin (condensation product of bisphenol A and epichlorohydrin) manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 188 g / eq, average degree of polymerization 0.1] 376.0 g and perfluoropentane 504.0 g of acid (carboxyl group equivalent 264 g / eq) was placed in a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, the contents were heated and melted, and water was added at 100 ° C. 10% aqueous solution of sodium oxide 1.4
After adding g, the mixture was preliminarily reacted at 120 to 140 ° C. for 6 hours,
The reaction was carried out at 150 to 180 ° C. for 12 hours to obtain a pale yellow reaction product. This reaction product has a fluorinated aliphatic carboxylic acid content of 57.3% and an epoxy group content of 0.08 × 1.
It was 0 ^-3 eq / g. Hereinafter, this is referred to as compound h.

Next, 52.0 g of this compound h was added to the flame retardant A'1320 g in a molten state obtained by reacting at 150 to 180 ° C. for 12 hours in the same manner as in Comparative Example 1, and melt-mixed at the same temperature for 1 hour. After that, it was poured into a stainless steel pan, cooled, and then pulverized to obtain a pale yellow mixture powder. This mixture has a fluorinated aliphatic carboxylic acid content of 3.0%,
It had a softening point of 106 ° C. and a bromine content of 54%. Hereinafter, this is referred to as the flame retardant H.

Example 9 EPICLON 1055 [Dainippon Ink and Chemicals, Inc.]
Made with epoxy resin (condensation product of bisphenol A and epichlorohydrin), epoxy equivalent 460 g / eq, average degree of polymerization 2.3] 460.0 g and perfluoroheptanoic acid (carboxyl group equivalent 314 g / eq) 340.0 g, A light yellow reaction product was obtained in the same manner as in Example 8 except that the reaction was carried out at 150 to 180 ° C. for 12 hours. This reaction product has a fluorinated aliphatic carboxylic acid content of 42.5% and an epoxy group content of 0.07 × 10.
^-3 eq / g. Hereinafter, this is referred to as compound i.

Next, 92.0 g of this compound i was added to the flame retardant G'1320 g in a molten state obtained by reacting at 150 to 230 ° C. for 12 hours in the same manner as in Comparative Example 3, and melt-mixed at the same temperature for 1 hour. After that, it was poured into a stainless steel pan, cooled, and then pulverized to obtain a pale yellow mixture powder. This mixture has a fluorinated aliphatic carboxylic acid content of 3.0%,
It had a softening point of 180 ° C. and a bromine content of 48%. Hereinafter, this is referred to as flame retardant I.

The raw material composition and property values of the flame retardants produced in Examples 8 and 9 are shown in Table 3 below.

[0063]

[Table 3]

Examples 10 to 27 and Comparative Examples 4 to 13 Flame retardant resin compositions prepared by premixing the components shown in Tables 3 to 7 below with a tumbler mixer and pelletizing with a 30 mmφ twin-screw extruder. Got Then, a test piece is prepared by a 1 ounce injection molding machine, and a heat deformation temperature test, an Izod impact test and a flammability test are conducted, and further, a limit injection molding test is conducted by a 5 ounce injection molding machine and a gold is conducted by a 10 ounce injection molding machine. A mold releasability test was conducted. The test results are shown in Tables 4 to 8.

The cylinder set temperature of the twin-screw extruder is
In the case of HIPS, ABS resin, and ABS / PC polymer alloys, the temperature was 210 to 230 ° C, and in the case of PBT and PBT / PC polymer alloys, the temperature was 230 to 250 ° C.

In the table, ABS resin is "Sebian V-300" manufactured by Daicel Chemical Industries, Ltd., and HIPS is rubber modified styrene resin "GH-" manufactured by Dainippon Ink and Chemicals, Inc.
9650 ", PC resin is Mitsubishi Gas Chemical Co., Ltd. polycarbonate resin" Iupilon S-2000 ", PBT
Resin is "Barox 310" manufactured by Nippon GE Plastics Co., Ltd., and antimony trioxide is "P" manufactured by Nippon Seiko Co., Ltd.
ATOX-C ".

[0067]

[Table 4]

[0068]

[Table 5]

[0069]

[Table 6]

[0070]

[Table 7]

[0071]

[Table 8]

[0072]

The flame-retardant thermoplastic resin composition of the present invention comprises
Excellent heat stability during molding and low adhesion to metal, so molded products with good appearance can be obtained, and molding time can be shortened due to easy release, improving productivity in molding. it can.

Further, since the flame retardant of the present invention has low adhesion to the metal part of the molding machine or the mold and does not easily cause thermal decomposition, when it is used in combination with a thermoplastic resin composition. Further, good heat stability and mold releasability can be imparted to the resin composition.

Claims (20)

[Claims] 1. A compound (B ₁ ) having a structure in which a thermoplastic resin (A) and a part or all of the epoxy groups of a halogenated epoxy resin are blocked with a fluorinated aliphatic carboxylic acid.
And / or a halogenated epoxy resin or a compound having a structure in which a part or all of the epoxy groups of the halogenated epoxy resin are blocked, and a part or all of the epoxy groups of the epoxy resin is blocked with a fluorinated aliphatic carboxylic acid A mixture (B
A flame-retardant thermoplastic resin composition comprising a flame retardant (B) consisting of ₂ ). 2. The composition according to claim 1, wherein the flame retardant (B) is the compound (B ₁ ). 3. The compound (B ₁ ) which is obtained by reacting a halogenated bisphenol type epoxy resin with a fluorinated aliphatic carboxylic acid by heating, a halogenated bisphenol type epoxy resin being fluorinated aliphatic carboxylic acid and a halogenated phenol. And those obtained by heating a halogenated bisphenol and epihalohydrin to a condensate of halogenated bisphenol and epihalohydrin, and halogenated bisphenol and epihalohydrin condensate. The composition according to claim 2, which is one or more compounds selected from the group consisting of a compound obtained by reacting bisphenol, a fluorinated aliphatic carboxylic acid, and a halogenated phenol with heating. 4. A compound (B ₁ ) obtained by heating a condensation reaction product of a halogenated bisphenol and epihalohydrin with a halogenated bisphenol and a fluorinated aliphatic carboxylic acid, and / or a halogenated bisphenol and epihalohydrin. The composition according to claim 2, which is obtained by reacting the condensate of (1) with a halogenated bisphenol, a fluorinated aliphatic carboxylic acid and a halogenated phenol by heating. 5. The content of the fluorinated aliphatic carboxylic acid in the flame retardant (B) is 0.1 to 10% by weight.
The composition according to any one of 4 above. 6. The composition according to claim 5, wherein the fluorinated aliphatic carboxylic acid is a perfluoroaliphatic carboxylic acid. 7. The fluorinated aliphatic carboxylic acid is a fluorinated aliphatic carboxylic acid having 3 to 20 carbon atoms.
Or the composition according to 6. 8. The composition according to claim 1, wherein the halogen is bromine. 9. The composition according to claim 1, wherein the thermoplastic resin (A) is a styrene resin or a polymer alloy containing a styrene resin as a main component. 10. The composition according to claim 1, wherein the thermoplastic resin (A) is a polyester resin or a polymer alloy containing a polyester resin as a main component. 11. The composition according to claim 1, further comprising a flame retardant aid (C). 12. A flame retardant, which comprises a compound (B ₁ ) having a structure in which a part or all of the epoxy groups of a halogenated epoxy resin are blocked with a fluorinated aliphatic carboxylic acid. 13. The compound (B ₁ ) is a compound having a structure in which a part or all of the epoxy groups of the halogenated epoxy resin are blocked with a fluorinated aliphatic carboxylic acid and a halogenated phenol. Flame retardant. 14. The compound (B ₁ ) is obtained by heating a halogenated bisphenol type epoxy resin with a fluorinated aliphatic carboxylic acid, or a halogenated bisphenol type epoxy resin with a fluorinated aliphatic carboxylic acid and a halogenated phenol. And those obtained by heating a halogenated bisphenol and epihalohydrin to a condensate of halogenated bisphenol and epihalohydrin, and halogenated bisphenol and epihalohydrin condensate. The flame retardant according to claim 12, which is one or more compounds selected from the group consisting of a reaction of bisphenol, a fluorinated aliphatic carboxylic acid and a halogenated phenol by heating. 15. A compound (B ₁ ) obtained by heating a halogenated bisphenol and a fluorinated aliphatic carboxylic acid to a condensate of a halogenated bisphenol and epihalohydrin, and / or a halogenated bisphenol and epihalohydrin. The flame retardant according to claim 12, which is obtained by heating a condensate with a halogenated bisphenol, a fluorinated aliphatic carboxylic acid, and a halogenated phenol. 16. A halogenated epoxy resin or a compound having a structure in which a part or all of the epoxy groups of the halogenated epoxy resin are blocked, and a part or all of the epoxy groups of the epoxy resin is a fluorinated aliphatic carboxylic acid. A flame retardant, which is a mixture (B ₂ ) obtained by melt-mixing with a compound having a structure blocked by. 17. The flame retardant agent according to claim 12, wherein the content of the fluorinated aliphatic carboxylic acid is 0.1 to 10% by weight. 18. The flame retardant according to claim 17, wherein the fluorinated aliphatic carboxylic acid is a perfluoroaliphatic carboxylic acid. 19. The flame retardant according to claim 17, wherein the fluorinated aliphatic carboxylic acid is a fluorinated aliphatic carboxylic acid having 3 to 20 carbon atoms. 20. The method according to claim 12, wherein the halogen is bromine.
The flame retardant agent according to any one of 19.