JPH08165437A - Flame-retardant thermoplastic resin composition, flame retardant and production of flame retardant - Google Patents

Abstract

PURPOSE: To obtain a flame-retardant thermoplastic resin composition containing a thermoplastic resin, a compound having a specific structure, a specific mixture, having excellent mold release property and light resistance and useful as a flame retardant. CONSTITUTION: This composition contains (A) a thermoplastic resin, (B) a compound obtained by blocking (i) a part or all of an epoxy group of a halogenated epoxy resin (a halogenated bisphenol type epoxy resin, etc., having 0-10 average degree of polymerization) with (ii) a functional group-containing hindered amine- based compound (e.g. 4-hydroxyl-2,2,6,6-tetramethylpiperidine) and/or (C) a mixture obtained by melting and mixing the component (i) with the component (ii) (e.g. at 130 to 250 deg.C for about 10-120min by a blender such as Brabender).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant thermoplastic resin composition having excellent mold releasability and light resistance, a flame retardant which imparts excellent releasability and light resistance to a thermoplastic resin, and a flame retardant thereof. It relates to a manufacturing method.

[0002]

2. Description of the Related Art Conventional flame retardants for thermoplastic resins include compounds containing a halogen element in the molecule, such as decabromodiphenyl oxide, tetrabromobisphenol A, halogenated epoxy resin, halogenated polycarbonate oligomer and the like. However, in recent years, halogenated epoxy resins have been increasingly used in view of their heat resistance and light resistance.

[0003]

However, since the halogenated epoxy resin has an epoxy group remaining at its terminal, the epoxy group is ring-opened during heating (melt kneading of resin, molding), and a molding machine is used. Reacts to the screw and mold. As a result, molten resin adheres to the metal surface, causing problems such as mold release defects and foreign matter contamination. Then, in order to avoid such a problem, it has been proposed to block the terminal epoxy group with tribromophenol or the like, but in that case, the light resistance, which is an advantage when using a halogenated epoxy resin, decreases. There is a drawback that.

On the other hand, as a means for improving such light resistance, for example, the addition of an ultraviolet stabilizer can be considered.
When the halogenated epoxy resin and the UV stabilizer are simply melt-mixed with the thermoplastic resin, some improvement in light resistance is observed, but it is not yet satisfactory,
Also, it is not sufficient from the viewpoint of physical property balance.

[0005]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, in order to impart light resistance to halogenated epoxy resins used as flame retardants, And / or the halogenated epoxy resin in which a part or all of the epoxy groups of the epoxidized epoxy resin are blocked with a functional group-containing hindered amine compound (hereinafter, simply referred to as a hindered amine compound) It was found that a resin composition excellent in mold releasability, light resistance, and physical property balance can be obtained by using a mixture in which and a hindered amine compound are melt-mixed in advance, and arrived at the present invention.

That is, the present invention is based on the thermoplastic resin (A).
And a compound (B) having a structure in which some or all of the epoxy groups of the halogenated epoxy resin are blocked with a hindered amine-based compound and / or a mixture (C) obtained by melting and mixing the halogenated epoxy resin and the hindered amine-based compound. A flame-retardant thermoplastic resin composition, a flame retardant comprising a compound having a structure in which some or all of the epoxy groups of a halogenated epoxy resin are blocked with a hindered amine compound, and a halogen. Of a flame retardant obtained by heating a epoxidized epoxy resin with a hindered amine compound, a condensation reaction of a halogenated bisphenol and epichlorohydrin, and a heat treatment of a hindered amine compound or a halogenated bisphenol and a hindered amine compound. Providing a method for producing a combustion agent A.

The flame-retardant thermoplastic resin composition of the present invention will be described in detail below.

Examples of the thermoplastic resin used in the present invention include polystyrene, acrylonitrile-styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin and other styrene resins, and polyethylene, polypropylene and other polyolefin resins. Examples thereof include resins, polyester resins such as polybutylene terephthalate and polyethylene terephthalate, polycarbonate resins, polyamide resins, polyphenylene ether resins and the like.

In particular, the above-mentioned styrene resin is a polymer mainly composed of an aromatic vinyl compound, which is a homopolymer of an aromatic vinyl compound, a copolymer of an aromatic vinyl compound and another vinyl compound, A graft copolymer obtained by polymerizing an aromatic vinyl compound alone or an aromatic vinyl compound and another vinyl compound in the presence of a rubbery polymer, and a mixture thereof. Aromatic vinyl compounds include styrene and α-methylstyrene, and other vinyl compounds include acrylonitrile, methacrylonitrile and other vinyl cyanide compounds, methyl (meth) acrylate,
Examples thereof include (meth) acrylic acid ester compounds such as ethyl (meth) acrylate, maleimide compounds such as maleimide and N-phenylmaleimide, and the like. As the rubber-like polymer, polybutadiene, diene rubber such as styrene-butadiene copolymer, ethylene-propylene copolymer, ethylene-propylene rubber such as ethylene-propylene-non-conjugated diene copolymer, acrylic rubber Examples thereof include rubber.

Examples of the halogenated epoxy resin used in the present invention include halogenated bisphenol type epoxy resin, halogenated phenol novolac type epoxy resin, halogenated cresol novolac type epoxy resin, halogenated resorcin type epoxy resin and halogen. Hydroquinone type epoxy resin, halogenated bisphenol A novolac type epoxy resin, halogenated methylresorcinol type epoxy resin, halogenated resorcinol novolak type epoxy resin, etc., but the average degree of polymerization is 0 to
It is preferable to use 10 halogenated bisphenol type epoxy resins.

Examples of the halogenated bisphenol constituting the halogenated bisphenol type epoxy resin include dibromobisphenol A, tetrabromobisphenol A, dichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, tetrabromobisphenol F, dichlorobisphenol. F,
Examples thereof include tetrachlorobisphenol F, dibromobisphenol S, tetrabromobisphenol S, dichlorobisphenol S, tetrachlorobisphenol S, and the like.

As a method for producing a halogenated epoxy resin, for example, when a halogenated bisphenol type epoxy resin is taken as an example, it is usually obtained by subjecting a halogenated bisphenol and epichlorohydrin to a condensation reaction. It is also possible to increase the molecular weight by carrying out an addition reaction.

Further, the halogenated epoxy resin is
A part of the epoxy group may be blocked with, for example, a halogenated phenolic compound or the like within a range that does not impair the effects of the present invention. Examples of the halogenated phenol compound include dibromophenol, dibromocresol, tribromophenol, pentabromophenol, dichlorophenol, dichlorocresol, trichlorophenol, pentachlorophenol and the like.

The hindered amine compound used for blocking a part or all of the epoxy groups of the halogenated epoxy resin in the present invention is a functional group having a hindered piperidine skeleton and having reactivity with an epoxy group. It is a compound having a group. Here, as the functional group having reactivity with the epoxy group, for example, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an aldehyde group and the like can be mentioned. Further, specific compounds thereof include, for example, 4-
Hydroxyl-2,2,6,6-tetramethylpiperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-carboxyl-2,2,6,6-tetramethylpiperidine, 1,8- Examples thereof include bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine.

As a method for producing the compound (B) in which a part or all of the epoxy groups of the halogenated epoxy resin is blocked with a hindered amine compound, the halogenated epoxy resin is heated to react with the hindered amine compound. It can be obtained by a method of heating a halogenated epoxy resin with a halogenated bisphenol compound and a hindered amine compound.

In the case of producing a halogenated bisphenol type epoxy resin, more specifically, a halogenated bisphenol and epichlorohydrin are subjected to a condensation reaction,
Further, it can be obtained by heating a hindered amine compound or a halogenated bisphenol and a hindered amine compound. In addition, a catalyst may be used if necessary in these heating reactions, and the heating reaction can usually be carried out at a temperature of 130 to 250 ° C.

Examples of the catalyst include alkali metal hydroxides such as sodium hydroxide, tertiary amines such as dimethylbenzylamine, imidazoles such as 2-ethyl-4methylimidazole, and fourth amines such as tetramethylammonium chloride. A quaternary ammonium salt, a phosphonium salt such as ethyltriphenylphosphonium iodide, and a phosphine such as triphenylphosphine can be used. In addition, these reactions may be carried out in a solvent such as benzene, toluene and methyl ethyl ketone.

When the hindered amine compound is heated and reacted, a blocking agent such as halogenated phenol may be used together with the hindered amine compound, if necessary.

The amount of the hindered amine compound used is not particularly limited, but the functionalization ratio of the hindered amine compound residue to the residual epoxy groups of the halogenated epoxy resin is 10 mol% or more, preferably 3%.
It is preferably used in an amount of 0 mol% or more, more preferably 50 to 100 mol%.

The mixture (C) used in the flame-retardant thermoplastic resin composition of the present invention is a mixture in which a halogenated epoxy resin and a hindered amine compound are melt-mixed. As the halogenated epoxy resin and the hindered amine compound used in the mixture (C), the same halogenated epoxy resin and hindered amine compound used in the compound (B) can be used.

The mixture (C) can be produced by melt mixing at a temperature at which both the halogenated epoxy resin and the hindered amine compound are melted, for example, 130 to 250 ° C. A known heatable mixer can be used for the melt mixing. Examples of such a mixer include a Brabender and an extruder. Usually, it can be produced by mixing with a Brabender for about 10 to 120 minutes.

The amounts of the halogenated epoxy resin and the hindered amine compound used in obtaining the mixture (C) are not particularly limited, but the functionalization of the hindered amine compound residue with respect to the residual epoxy groups of the halogenated epoxy resin is performed. 10 mol% or more, preferably 30 mol%
It is preferably used in the above range.

The amount of the flame retardant ((B) and / or (C)) used in the present invention is not particularly limited, but in the range of 1 to 25 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). It is preferably used, and particularly preferably 5 to 25 parts by weight.

The flame retardant in the present invention can be applied not only to thermoplastic resins but also to thermosetting resins.

In the flame-retardant thermoplastic resin composition of the present invention, other organic or inorganic flame retardants are added within a range that does not impair the effect of the present invention, and further, in order to enhance the flame retardant effect, for example, trioxide. It is also possible to use flame-retardant aids such as antimony, antimony tetroxide, antimony pentoxide.

Further, the resin composition of the present invention contains other additives such as an antioxidant [2,6-di-t-butyl-4].
-Methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2,2-methylenebis- (4-ethyl-6-t-methylphenol),
4,4'-thiobis- (6-t-butyl-3-methylphenol), dilaurylthiodipropionate, tris (di-nonylphenyl) phosphite and the like are exemplified. ], An ultraviolet absorber [pt-butylphenyl salicylate, 2,2'-dihydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole and the like are exemplified. . ], Lubricants [paraffin wax, stearic acid, hydrogenated oil, stearamide, methylenebis stearamide,
Examples thereof include ethylene bis stearamide, n-butyl stearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride and the like. ], A colorant [eg titanium oxide, carbon black], a filler [eg calcium carbonate, clay,
Examples thereof include silica, glass fiber, glass sphere, carbon fiber and the like. ] Etc. can be added as needed.

The resin composition in the present invention has the above (A)
The components, (B) and / or (C) components and, if necessary, other additives are pre-mixed by a known mixer such as a Henschel mixer or a tumbler, and then an extruder, a kneader,
It can be produced by melt mixing with a roll, Banbury mixer or the like.

[Examples] In order to more specifically describe the present invention, examples and comparative examples will be described below. However, the present invention is not limited to these. The parts and% shown in the examples are based on weight unless otherwise specified. The evaluation of various tests is based on the following methods.

(1) Releasability: 1 kg of pellets obtained by granulation was sandwiched between two aluminum plates cut into a size of 50 × 50 × 0.5 mm and set to 240 ° C. 100Kgf / using a compression molding machine
Press at a pressure of cm ² for 10 minutes. After the completion, it was cooled to room temperature and observed whether or not it adhered to the aluminum plate. ○: Adhesion to aluminum plate ×: No adhesion to aluminum plate

(2) Impact resistance: A 3.5 ounce injection molding machine was used to prepare a test piece at a cylinder set temperature of 220 ° C., and the notched Izod impact strength (30 ° C.) was measured according to ASTM D-256. It was measured. Unit: kg / cm / c
m ²

(3) Light resistance: Using an 1 ounce injection molding machine, a flat plate (3 × 90 ×
55 mm) and made by Atlas Xenon WOOM
After conducting a light resistance test for 300 hours under the conditions of an irradiation intensity of 0.35 w / m ² , a black panel temperature of 63 ° C. and no rain, the degree of discoloration was measured using a color difference meter CR-300 manufactured by Minolta. (ΔE) was measured.

(4) Flame retardance: 6 ounce injection molding machine, 12.7 × 127 at a cylinder temperature setting of 220 ° C.
A test piece of 1.5 mm was molded, and the flame retardancy was measured based on the vertical combustion test method of UL-94.

(5) Mold Contamination: Using an 1 ounce injection molding machine, at a cylinder set temperature of 220 ° C., a flat plate (3 × 90 ×)
After making 100 shots of 55 mm), the mold surface was observed to confirm the presence or absence of contamination. ○: No pollution ×: Contamination

Component (A) A-1: ABS resin (Clarastic GA-701 manufactured by Sumitomo Dow Co., Ltd.)

Component (B) B-1: Brominated bisphenol A type epoxy resin (Prasam EP-16 manufactured by Dainippon Ink and Chemicals, Inc.)
(Molecular weight 1600, bromine content 50%) 300 g and 4-
100 g of hydroxyl-2,2,6,6-tetramethylpiperidine and 100 g of hydroxyl-2,2,6,6-tetramethylpiperidine were placed in a 1-liter four-necked flask equipped with a thermometer and a stirrer, and the inside was replaced with nitrogen gas. After adding 1.0 g of a 10% aqueous solution of sodium hydroxide at 140 ° C, 140 to 160
The reaction was performed at 8 ° C. for 8 hours. Next, the reaction product was flown out to a stainless steel pad, cooled and then pulverized to obtain a powdery flame retardant B-1. The functionalization rate of the hindered amine compound of this flame retardant B-1 was 95 mol%. Regarding the functionalization rate, GPC (HP manufactured by Hewlett-Packard Co.
1090, column: SEC-G15 (polystyrene gel), detector: RI, solvent: tetrahydrofuran).

B-2: Brominated bisphenol A type epoxy resin (Prasam EP-16 manufactured by Dainippon Ink and Chemicals, Inc.) (molecular weight 1600, bromine content 50%) 3
00 g and 200 g of 1,8-bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine
A flame retardant B-2 in powder form was obtained in the same manner as B-1 except that was used. The functionalization rate of this hindered amine compound of flame retardant B-2 was 60 mol%.

B-1: brominated bisphenol A type epoxy resin (Prasam EP-16, manufactured by Dainippon Ink and Chemicals, Inc.) (molecular weight 1600, bromine content 50%) b-2: terminal with tribromophenol Blocked brominated bisphenol A type epoxy resin (Prasam EC-20 manufactured by Dainippon Ink and Chemicals, Inc.) (molecular weight 20
00, bromine content 56%)

Component (C) C-1: Brominated bisphenol A type epoxy resin (Prasam EP-16 manufactured by Dainippon Ink and Chemicals, Inc.)
(Molecular weight 1600, bromine content 50%) 1000g and 4
-Hydroxyl-2,2,6,6-tetramethylpiperidine (400 g) was melt-mixed with a Brabender at 150 ° C for 30 minutes, and then the reaction product was flown out to a stainless pad.
After cooling, it was pulverized to obtain a powdery flame retardant C-1. The functionalization rate of this hindered amine compound of flame retardant C-1 was 38 mol%.

UV stabilizer: Hindered amine UV stabilizer (Tinuvin 770 manufactured by Ciba-Geigy)

Examples 1 to 5 and Comparative Examples 1 to 5 The components shown in Table 1 were premixed with a Henschel mixer, then granulated using a twin-screw extruder and pelletized. Then, based on each test method described above obtained pellets,
Each test was conducted. Table 1 shows the test results.

[0041]

[Table 1]

[0042]

As described above, the flame-retardant thermoplastic resin composition of the present invention has excellent releasability and light resistance, and the flame retardant of the present invention is It is possible to impart excellent releasability and light resistance.

Claims (5)

[Claims] 1. A compound (B) 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 functional group-containing hindered amine compound having reactivity with an epoxy group. And / or a flame-retardant thermoplastic resin composition comprising a mixture (C) obtained by melt-mixing a halogenated epoxy resin and a functional group-containing hindered amine compound having reactivity with an epoxy group. 2. The flame-retardant thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is a styrene resin. 3. A flame retardant, which comprises a compound having a structure in which a part or all of the epoxy groups of a halogenated epoxy resin are blocked with a functional group-containing hindered amine compound having reactivity with an epoxy group. 4. A method for producing a flame retardant, which comprises reacting a halogenated epoxy resin with a functional group-containing hindered amine compound having reactivity with an epoxy group by heating. 5. A flame retardant characterized by subjecting a halogenated bisphenol and epichlorohydrin to a condensation reaction, and further reacting the functional group-containing hindered amine compound having reactivity with an epoxy group or the halogenated bisphenol with the hindered amine compound by heating. Manufacturing method.