JP2583340B2 - Flame retardant resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a flame-retardant resin composition mainly composed of polycarbonate having a wide range of applications such as building materials, electric component materials, decorative materials and the like.

Conventional technology and its problems In general, polycarbonate resin is known to have excellent mechanical properties, heat resistance and transparency, and has a self-extinguishing property to the resin itself due to its structure, and is relatively difficult to burn,
Since it is insufficient for applications requiring particularly severe flame retardancy, such as building materials and electric component materials, means for further increasing flame retardancy is required.

Conventionally, as a means for making a polycarbonate resin flame-retardant, for example, a method in which an alkali metal salt or an alkaline earth metal salt of aromatic sulfonic acid is blended as a flame retardant (Japanese Patent Publication No.
No. 43100), a method in which a specific branched polyphosphate is used in combination with decabromodiphenyl ether, etc. (Japanese Patent Publication No. 2-1185), and a flame-retardant polycarbonate is produced using tetrahalobisphenol A as a raw material and using an activated pyridine catalyst. (JP-A-64-65127) and a method of blending a brominated epoxy compound as a flame retardant (JP-B-60-17224).

However, in these proposed means, although the flame retardancy is improved, the transparency of the polycarbonate resin is reduced, and the inherent properties of the polycarbonate resin are easily impaired, such as causing the molded article to be colored or mixed into bubbles due to thermal decomposition during molding. In particular, in the case of an extruded product, there is a problem that the physical properties in the extrusion direction (longitudinal direction) and the direction perpendicular thereto (width direction) are greatly different by any of the means.

The present invention has been made in view of the above circumstances, and has as its object to provide a resin composition mainly composed of polycarbonate, which has excellent inherent properties and high flame retardancy.

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, by blending a specific compound as a flame retardant in a specific amount with respect to polycarbonate, the polycarbonate resin inherently excellent The present inventors have found that high flame retardancy can be imparted without impairing the mechanical properties, heat resistance, transparency, and the like, and have accomplished the present invention.

That is, the flame-retardant resin composition according to the present invention has the following general formula per 100 parts by weight of the polycarbonate resin: (However, A ₁ in the formula is X is a halogen atom, R is a lower alkyl group, i and j are in the range of 0 to 5 and (i + j) <
An integer of 5, A ₂ is a hydrogen atom, A ₁ or a glycidyl group,
B is an alkylene group having 1 to 4 carbon atoms, an alkylidene group or a —SO ₂ — group, l and m are integers in the range of 0 to 4 and all l and m are not 0, and the average degree of polymerization n is 0 to
5) The composition contains 1 to 15 parts by weight of a flame retardant represented by the following formula:

DETAILED DESCRIPTION OF THE INVENTION AND EFFECT OF THE INVENTION The polycarbonate resin used in the present invention includes various types, and two or more of them may be used in combination. For example, 2.2'-bis (4-hydroxyphenyl) may be used. ) 4.4 'such as propane (hereinafter referred to as bisphenol A), 2.2'-bis (4-hydroxyphenyl) methane (hereinafter referred to as bisphenol F)
-Dihydroxydiphenylalkane, 4,4'-dihydroxydiphenylsulfone (hereinafter referred to as bisphenol S), synthesized by transesterification or phosgene method using one or more bisphenol components such as 4,4'-dihydroxydiphenylether. Are preferred. Among them, 2.2 ′ using bisphenol A or the like is preferable.
-Bis (4-hydroxyphenyl) alkane-based polycarbonate is particularly preferred. The average molecular weight of such a polycarbonate resin is preferably 10,000 to 50,000, and more preferably about 20,000 to 40,000.

The compound of the general formula (I) used as a flame retardant in the present invention may be a halogenated bisphenol / diglycidyl ether and a halogenated phenol, or a compound obtained by further adding a halogenated bisphenol thereto.
80-250 ° C., preferably 100-180 ° C. in the presence of a basic catalyst
It can be obtained by heating and reacting at a temperature of ° C.

Here, as the above-mentioned halogenated bisphenol,
Halogenated bisphenol A, such as tetrabromobisphenol A, halogenated bisphenol F, halogenated bisphenol S, and the like can be used alone or in combination of two or more. Further, as the halogenated bisphenol / diglycidyl ether, a monomer or oligomer obtained by the addition polymerization reaction of the above-mentioned halogenated bisphenol and epihalohydrin can be used. As the halogenated phenols, halogenated phenols such as tribromophenol, dibromophenol and trichlorophenol, and halogenated alkylphenols such as dibromocresol can be used. As the basic catalyst,
Examples thereof include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal halides such as lithium chloride, tertiary amines such as tributylamine, and quaternary ammonium salts such as tetramethylammonium chloride.

In the above reaction, bisphenol A.
A non-halogenated component such as diglycidyl ether can be used in combination as long as flame retardancy is not affected.

The flame retardant thus synthesized needs to have n in the above general formula, that is, the average degree of polymerization of 5 or less. That is, if the average degree of polymerization n is larger than 5, the compatibility of the flame retardant with the polycarbonate resin becomes poor, and the transparency and mechanical properties of the resin composition are reduced. In addition,
The average degree of polymerization can be arbitrarily set by appropriately adjusting various conditions in the above-described synthesis reaction, and can be basically adjusted arbitrarily by changing the ratio of halogenated bisphenol diglycidyl ether to halogenated bisphenol.

The compounding amount of such a flame retardant is polycarbonate resin
1 to 15 parts by weight, particularly preferably 3 to 1 part by weight, per 100 parts by weight
When the amount is less than 1 part by weight, sufficient flame retardancy cannot be obtained. On the contrary, when the amount exceeds 15 parts by weight, no further improvement in flame retardancy is observed, and the physical properties of the resin composition, etc. Will have an adverse effect.

Incidentally, in a structure having a reactive epoxy group at both ends (especially an oligomer type having a low molecular weight), such as a compound in which both A ₁ and A ₂ in the general formula (I) each comprise a glycidyl group, the resin composition There is a problem that the composition is liable to be burned at the time of molding and the composition is gelled at a high temperature to deteriorate the flowability.

Incidentally, the flame-retardant resin composition of the present invention, together with the above-mentioned polycarbonate resin and flame retardant, optionally contains various additives such as a heat stabilizer, a weathering agent, a coloring agent, a matting agent, and an antistatic agent. Can be blended. These additives may be contained in advance in the polycarbonate resin.

In order to produce the flame-retardant resin composition according to the present invention, a mixture consisting of a polycarbonate resin powder or pellets, a flame retardant and, if necessary, the above-mentioned additive is kneaded by a conventional method. May be melt-mixed using a mixer or a Banbury mixer.

The flame-retardant resin composition thus obtained is thermoplastic, and can be formed into sheets, films, tubes, bottles, etc. by using various molding means such as injection molding, extrusion molding, blow molding, and compression molding. Can be formed into any shape. And, since this composition has good flame retardancy as well as excellent mechanical properties, heat resistance and transparency inherent to polycarbonate resin, it can be used for building materials, electric parts, interior goods, vehicle parts, automobile parts, miscellaneous goods, etc. For a wide range of applications.

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Synthesis Examples and Examples, but the present invention is not limited to these Synthesis Examples and Examples unless departing from the gist thereof.

Synthesis Example 1 Brominated bisphenol A type epoxy resin (trade name: SR-BS, manufactured by Sakamoto Pharmaceutical Co., Ltd., epoxy equivalent: 334, hereinafter abbreviated as BS) 3
34 g of IL and 331 g of tribromophenol (hereinafter abbreviated as TBP) equipped with a thermometer, nitrogen inlet pipe, exhaust pipe, and stirrer
-Transfer to a separable four-necked flask and add tributylamine
After adding 0.4 g, the mixture was reacted at 120 to 130 ° C. for 5 hours under a nitrogen stream. Thereafter, further 334 g of BS, 129 g of tetrabromobisphenol A (hereinafter abbreviated as TBA) and 134 g of TBP were added, and 100
Dissolve at ℃, tetramethyl ammonium chloride 0.
6 g was added and reacted at 140 ° C. for 6 hours, then at 160 ° C. for 2 hours. After completion of the reaction, the product was cooled and pulverized to an acid value of 0.2.
(MgKOH / g), epoxy equivalent 9340 (g / equivalent), softening point 112
C., a pale yellow powder having a bromine content of 58.3% was obtained. According to GPC analysis, n = 0 in the general formula (I) was obtained.
And the compound of n = 1 accounts for 80% or more, and the average degree of polymerization = 0.
It was five. Hereinafter, this is referred to as flame retardant A.

Synthesis Example 2 Brominated bisphenol A type epoxy resin (trade name: SR-TBA400 manufactured by Sakamoto Yakuhin, epoxy equivalent: 395, hereinafter TBA400
790 g and TBP347 g were placed in the same flask as in Synthesis Example 1, and after adding 0.8 g of tributylamine, the mixture was reacted at 120 to 130 ° C. for 7 hours under a nitrogen stream, and further reacted at 160 ° C. for 2 hours. Was. After completion of the reaction, a powder having an acid value of 0.1 (mgKOH / g), an epoxy equivalent of 1240 (g / equivalent), a softening point of 92 ° C, and a bromine content of 55.8% was obtained in the same manner as in Synthesis Example 1. According to GPC analysis, the compound of general formula (I) wherein n = 0 occupies 70% or more, and the average degree of polymerization was 0.2%.
Met. Hereinafter, this is referred to as flame retardant B.

Synthesis Example 3 790 g of BA400 (epoxy equivalent: 395), 343 g of TBA, and 222 g of TBP were placed in a flask similar to that of Synthesis Example 1 and capable of stirring a high-viscosity liquid, and 0.8 g of tributylamine was added. The reaction was carried out at a temperature of 160 ° C. for 3 hours and further at 160-170 ° C. for 15 hours. After completion of the reaction, the acid value was determined in the same manner as in Synthesis Example 1.
A powder having 0.5 (mg KOH / g), an epoxy equivalent of 18000 (g / equivalent), a softening point of 155 ° C. and a bromine content of 54.9% was obtained. This was found by GPC analysis to have an average degree of polymerization of 4.5 in the general formula (I). Hereinafter, this is referred to as flame retardant C.

Next, for comparison, those having an average degree of polymerization of 5 or more {synthesis were carried out as follows.

Synthesis Example 4 Synthesis Example 3 using 790 g of TBA400 (epoxy equivalent: 395) and 400 g of TBA
After adding 0.8 g of tributylamine, the mixture was further heated at 120 to 130 ° C. for 3 hours under a nitrogen stream, and further 170 to 1
The reaction was performed at 80 ° C. for 7 hours. After completion of the reaction, a powder having an acid value of 0.3 (mgKOH / g), an epoxy equivalent of 2200 (g / equivalent), a softening point of 162 ° C, and a bromine content of 51.8% was obtained in the same manner as in Synthesis Example 1.
This is represented by the following formula: average degree of polymerization in formula (I) =
Was 5.2. Hereinafter, this is referred to as flame retardant D.

Synthesis Example 5 790 g of TBA400 (epoxy equivalent: 395), 456 g of TBA, and 65 g of TBP were placed in the same flask as in Synthesis Example 3, and 0.9 g of tetramethylammonium chloride was added.
The reaction was carried out at ~ 140 ° C for 5 hours and further at 170-180 ° C for 7 hours. After completion of the reaction, an acid value of 0.5 (mgK
OH / g), epoxy equivalent 7920 (g / equivalent), softening point 181 ° C,
A powder with a bromine content of 53.2% was obtained. This had an average degree of polymerization of 11.2 in the general formula (I). Less than,
This is called flame retardant E.

Examples 1 to 5 and Comparative Examples 1 to 8 100 parts by weight of a polycarbonate resin powder (average molecular weight 27000) using bisphenol A as a raw material and the indicated number of flame retardants shown in the following table were uniformly mixed, and this was mixed with a 40 mm diameter. It was supplied to a screw type extruder, extruded, and processed into a 3.0 mm thick sheet. The flame retardant F in the following table is tetrabromobisphenol A (trade name BA-59p manufactured by Great Lakes Chemical), the flame retardant G is perbromodiphenyl ether (DE-83R manufactured by Great Lakes Chemical),
The flame retardant H is a compound (Arimoto Pharmaceutical Co., Ltd., trade name SR-T1000) in which both A ₁ and A ₂ in the general formula (I) are glycidyl groups and the average degree of polymerization is 2.0.

Test pieces were cut out from the sheets obtained in the above Examples and Comparative Examples, and were subjected to each test of flame retardancy, transparency, and impact resistance. The flame retardancy was measured by a UL-94 vertical combustion test. The transparency was evaluated as ○ when the total light transmittance measured by the method described in JISK-7105 was 80% or more and the haze was 5% or less, and as X when the haze was out of the range. Further, the impact resistance is measured by an Izod impact test according to the method described in ASTM D-256. In the table, MD indicates a sheet extrusion direction, and TD indicates a direction perpendicular to the extrusion direction.

Effects of the Invention According to the present invention, as a polycarbonate resin composition having high flame retardancy, the original transparency and mechanical properties of the resin are sufficiently maintained, and particularly in the extrusion direction and the direction perpendicular to the extrusion direction in an extruded product. A material with little difference in physical properties can be provided.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Katsuyuki Tamura, No. 5, 17-7 Showa-cho, Hamadera, Sakai-shi, Osaka (72) Ryoichi Kubo 1069, Kamiishikawa, Kanuma-shi, Tochigi 1069 Kamiishikawa, Kanuma City, Tochigi Prefecture (72) Inventor Yasuhiro Kadota 501-11 Harigaya-cho, Utsunomiya City, Tochigi Prefecture (56) References JP-A-1-306436 (JP, A)

Claims (1)

(57) [Claims] (1) The following general formula: (However, A ₁ in the formula is X is a halogen atom, R is a lower alkyl group, i and j are in the range of 0 to 5 and (i + j) <
An integer of 5, A ₂ is a hydrogen atom, A ₁ or a glycidyl group,
B is an alkylene group having 1 to 4 carbon atoms, an alkylidene group or a —SO ₂ — group, l and m are integers in the range of 0 to 4 and all l and m are not 0, and the average degree of polymerization n is 0 to
5. A flame-retardant resin composition comprising 1 to 15 parts by weight of a flame retardant represented by the following formula: