JPH0411652A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. excellent in transparency, mechanical properties, heat resistance, and flame retardance by compounding a polycarbonate resin with a specified amt. of a specific flame retardant. CONSTITUTION:100 pts.wt. polycarbonate resin is compounded with 1-15 pts.wt. flame retardant of formula I {wherein A1 is a group of formula II [wherein X is halogen; R is lower alkyl; i and j are each an integer of 0-5 provided that (i+j)<5]; A2 is H, A1, or glycidyl; B is 1-4C alkylene, alkylidene, or -SO2-; land m are each an integer of 0-4 provided that all of l and m are not simultaneously 0; and n is 0-5}.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to a flame-retardant resin composition mainly composed of polycarbonate, which has a wide range of uses such as building materials, electrical component materials, and decorative materials.

Conventional technology and its problems In general, polycarbonate resin is known to have excellent mechanical properties, heat resistance, and transparency, and is also structurally self-extinguishing, making it relatively flammable. Since it is insufficient for applications that require particularly severe flame retardancy, such as materials for electronic parts and electrical parts, a means to further improve flame retardance is required.

Conventionally, as a means to make polycarbonate resin flame retardant, for example, a method of blending an alkali metal salt or an alkaline earth metal salt of aromatic sulfonic acid as a flame retardant (Japanese Patent Publication No. 1983-
43100), a method of using a specific branched polyphosphate in combination with decabromodiphenyl ether, etc. (
Japanese Patent Publication No. 2-1185), a method for producing flame-retardant polycarbonate using an activated pyridine catalyst using tetrahalobisphenol A as a raw material (Japanese Patent Publication No. 64-6512)
7), a method of blending a brominated epoxy compound as a flame retardant (Japanese Patent Publication No. 60-17224), etc. have been proposed.

However, while these proposed methods improve flame retardancy, they tend to impair the original properties of polycarbonate resin, such as decreasing transparency and causing thermal decomposition during molding, resulting in discoloration and air bubbles in the molded product. Especially in the case of extrusion-molded products, there is a problem in that no matter which method is used, there is a large difference in physical properties between the extrusion direction (longitudinal direction) and the direction perpendicular thereto (width direction).

In view of the above-mentioned circumstances, it is an object of the present invention to provide a resin composition that is mainly composed of polycarbonate and has both its inherent excellent properties and high flame retardancy.

Means for Solving the Problems In order to achieve the above object, the inventors have made intensive studies and found that by blending a specific amount of a specific compound as a flame retardant into polycarbonate, the inherent superiority of polycarbonate resin can be improved. The present inventors have discovered that high flame retardance can be imparted without impairing the mechanical properties, heat resistance, transparency, etc., and have thus come up with the present invention.

[Margin below]

That is, the flame-retardant resin composition according to the present invention is prepared based on 100 parts by weight of polycarbonate resin as shown below: The groups i and j range from O to 5 and (i+D <
5, A2 is a hydrogen atom, Al or a glycidyl group, B is an alkylene group having 1 to 4 carbon atoms, an alkylidene group or a -802- group, Ω and m are in the range of O to 4, and all Ω and m is an integer that does not become 0, and the average degree of polymerization n is θ to 5).

Detailed structure and operation of the invention The polycarbonate resin used in this invention includes various types, and two or more of them may be used in combination, but for example, 2,2゛-bis(4-hydroxyphenyl ) propane (hereinafter referred to as bisphenol A), 4,4°- such as 2,2゛-bis(4-hydroxyphenyl)methane (hereinafter referred to as bisphenol F)
Synthesized by transesterification or phosgene method using one or more bisphenol components such as dihydroxydiphenylalkane, 4,4'-dihydroxydiphenylsulfone (hereinafter referred to as bisphenol S), and 4,4°-dihydroxydiphenyl ether. Among these, 2.2°-polycarbonate using bisphenol A, etc.
Bis(4-hydroxyphenyl)alkane polycarbonates are particularly preferred. Moreover, the average molecular weight of such polycarbonate resin is 10,000 to 50,000,
Preferably it is about 20,000 to 40,000.

The above general formula (I) used as a flame retardant in this invention
The compound is prepared by heating a halogenated bisphenol diglycidyl ether and a halogenated phenol, or a mixture thereof with a halogenated bisphenol, in the presence of a basic catalyst at a temperature of 80 to 250°C, preferably 100 to 250°C.
It is obtained by carrying out a heating reaction at 180°C.

Here, as the above-mentioned halogenated bisphenol, halogenated bisphenol A such as tetrabromobisphenol A, halogenated bisphenol F, halogenated bisphenol S, etc. can be used alone or in combination of two or more kinds.

Furthermore, as the halogenated bisphenol diglycidyl ether, monomers or oligomers obtained by the addition polymerization reaction of the above-mentioned halogenated bisphenol and epihalohydrin can be used. As the halogenated phenols, in addition to halogenated phenols such as tribromophenol, dibromophenol, and trichlorophenol, halogenated alkylphenols such as dibromocresol can also be used. Basic catalysts include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide;
Examples include alkali metal halides such as lithium chloride, tertiary amines such as tributylamine, and quaternary ammonium salts such as tetramethylammonium chloride.

In the above reaction, a non-halogenated component such as bisphenol A diglycidyl ether can be used in combination with the halogenated bisphenol diglycidyl ether within a range that does not affect flame retardancy.

In the flame retardant thus synthesized, it is necessary that n in the general formula, that is, the average degree of polymerization, be 5 or less. That is, when the average degree of polymerization n becomes larger than 5, the compatibility of the flame retardant with the polycarbonate resin deteriorates, leading to a decrease in the transparency and mechanical properties of the resin composition. Note that this average degree of polymerization can be arbitrarily set by appropriately adjusting various conditions in the synthesis reaction described above, and basically can be arbitrarily adjusted by changing the ratio of halogenated bisphenol diglycidyl ether and halogenated bisphenol. can.

The blending amount of such flame retardant is 1% of polycarbonate resin.
1 to 15 parts by weight, particularly preferably 3 parts by weight per 00 parts by weight
-10 parts by weight, if it is less than 1 part by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 15 parts by weight, no further improvement in flame retardance is observed, and the physical properties of the resin composition are deteriorated. etc. will have a negative impact.

By the way, in a structure (especially an oligomer type with a low molecular weight) having a reactive epoxy group at both ends, such as a compound in which A1 and A2 in the general formula (1) are both glycidyl groups, when molding the resin composition, Can easily cause heat burns,
The problem is that the composition gels at high temperatures, resulting in poor flowability.

In addition, the flame-retardant resin composition of the present invention may contain various additives such as a heat stabilizer, a weathering agent, a coloring agent, a matting agent, an antistatic agent, etc., as necessary, in addition to the above-mentioned polycarbonate resin and flame retardant. Can be mixed.

These additives may be included in the polycarbonate resin in advance.

In order to produce the flame-retardant resin composition according to the present invention, a mixture consisting of polycarbonate resin powder or pellets, a flame retardant, and the additives blended as necessary is kneader-screw extruded. They may be melted and mixed using a machine, a Banbury mixer, or the like.

The flame-retardant resin composition thus obtained is thermoplastic and can be shaped into sheets, films, tubes, bottles, etc. by using various molding methods such as injection molding, extrusion molding, blow molding, and compression molding. It can be molded into any shape. This composition has excellent mechanical properties, heat resistance, and transparency inherent to polycarbonate resin, as well as good flame retardancy, so it can be used in construction materials, electrical parts, interior goods, vehicle parts, automobile parts, miscellaneous goods, etc. It can be suitably used in a wide range of applications.

EXAMPLES Hereinafter, the present invention will be specifically explained based on synthesis examples and examples, but the present invention is not limited to these synthesis examples and examples unless it departs from the gist thereof.

Synthesis Example 1 334 g of brominated bisphenol A epoxy resin (trade name 5R-BS, manufactured by Itamoto Pharmaceutical Co., Ltd., epoxy equivalent: 334, hereinafter abbreviated as BS) and tribromophenol (hereinafter abbreviated as TBP) 3315F were heated using a thermometer and nitrogen was introduced. pipe, exhaust pipe,
The mixture was placed in an IL-separable four-bottle flask equipped with a stirring device, and 0.4 g of tributylamine was added thereto, followed by reaction at 120 to 130° C. for 5 hours under a nitrogen stream. after that,
Furthermore, add B53349, 129 g of tetrabromobisphenol A (hereinafter abbreviated as TBA), and 134 g of TBP.
0.6 g of tetramethylammonium chloride was added and heated at 140° C. for 6 hours, followed by 160° C.
The reaction was carried out at ℃ for 2 hours. After the reaction, the product is cooled and pulverized to give an acid value of 0.2 (RIKOH/g), an epoxy equivalent of 9340 (g/equivalent), a softening point of 112°C, and a bromine content of 5.
A pale yellow powder of 8.3% was obtained. According to GPC analysis, this product has compounds with n=o and n=1 in the general formula (I) accounting for 80% or more, and an average degree of polymerization Fi=0. 5
Met. Hereinafter, this material will be referred to as flame retardant A.

Synthesis Example 2 Brominated bisphenol A type epoxy resin (trade name 5R-TBA400 manufactured by Itamoto Yakuhin Co., Ltd., epoxy equivalent: 395, hereinafter abbreviated as TBA400) 7909 and 347 g of TBP were placed in the same flask as in Synthesis Example 1, and tributylamine 0
．． After adding 8 g, the reaction was carried out at 120 to 130°C for 7 hours under a nitrogen stream, and then further reacted at 160°C for 2 hours. After the reaction is completed, the acid value is 0.1 in the same manner as in Synthesis Example 1.
(IRgKOH/g), epoxy equivalent 1240 (g
/equivalent), a softening point of 92° C., and a bromine content of 55.8%. This product was determined by GPC analysis to have the general formula (
The compound with n=0 in I) accounted for 70% or more, and the average degree of polymerization n=0.2. Below, we will refer to this as flame retardant B.
That's what it means.

Synthesis example 3 BA400 (epoxy equivalent: 395) 790g, TBA
343 g of TBP and 222 g of TBP were placed in a flask similar to Synthesis Example 1 and capable of stirring high viscosity liquids, and after adding 0.8 g of tributylamine, 120 to 13 g of TBP was added under a nitrogen stream.
The reaction was carried out at 0°C for 3 hours and then at 160-170°C for 15 hours.

After the reaction is completed, the acid value is 0°5 (I
ft! JKOH/g), epoxy equivalent weight 18000 (g
/equivalent), a softening point of 155° C., and a bromine content of 54.9%. According to GPC analysis, this product had an average degree of polymerization n=4.5 in the general formula (I). below,
This material is called flame retardant C.

Next, for comparison, a compound with an average degree of polymerization of 5-5 or more was synthesized as follows.

Synthesis example 4 TBA400 (epoxy equivalent: 395) 7909, TB
A4009 was placed in the same flask as in Synthesis Example 3, and 0.8 g of tributylamine was added thereto.
The reaction was carried out at ~130°C for 3 hours and further at 170-180°C for 7 hours. After the reaction is completed, the acid value is 0 in the same manner as in Synthesis Example 1.
．． 3 (lRgKOH/9), epoxy equivalent 2200 (
9/equivalent), a softening point of 162°C, and a bromine content of 51°/8%. This product had an average degree of polymerization n=5.2 in the general formula (I).

Hereinafter, this substance will be referred to as a flame retardant.

Synthesis example 5 TBA400 (epoxy equivalent: 395) 7909, TB
A4569 and TBP659 were placed in the same flask as in Synthesis Example 3, and 0.9 g of tetramethylammonium chloride was added.
After adding, the mixture was reacted at 130 to 140°C for 5 hours and further at 170 to 180°C for 7 hours under a nitrogen stream. After the reaction is completed, the acid value is reduced to 0. 5 (ayKO
A powder with an epoxy equivalent of 7920 (9/equivalent), a softening point of 181° C., and a bromine content of 53.2% was obtained. This product has an average degree of polymerization n=11.
It was 2. Hereinafter, this material will be referred to as flame retardant E.

Examples 1-5. Comparative Examples 1 to 8 100 parts by weight of polycarbonate resin powder (average molecular weight 27,000) made from bisphenol A as a raw material and the indicated number of parts of the flame retardant shown in the table below were mixed uniformly, and 40 mg of this was mixed.
3. Supply to a + diameter screw extruder for extrusion molding;
It was processed into a sheet with a thickness of 0 m. The flame retardant F in the table below is tetrabromobisphenol A (GreatLak
(Product name BA-59p manufactured by es Chemica1)
, flame retardant G is perbromodiphenyl ether (Gre
In the flame retardant H (trade name DE-83R) manufactured by Lakes Chemica 1, A1 and A2 in the general formula (I) are both glycidyl groups, and the average degree of polymerization is 5-2.
゜0 compound (trade name 5R- manufactured by Sakamoto Pharmaceutical Co., Ltd.)
T100O).

Test pieces were cut out from the sheets obtained in the above Examples and Comparative Examples, and subjected to flame retardancy, transparency, and impact resistance tests. The flame retardancy was determined by the UL-94 vertical combustion test. Transparency is defined as 01 if the total light transmittance measured by the method shown in JISK-7105 is 80% or more and haze is 5% or less;
It was evaluated as Furthermore, the impact resistance is ASTM D-25.
In the table, MD indicates the extrusion direction of the sheet, and Tff indicates the direction perpendicular to the extrusion direction.

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Table 1 Effects of the Invention According to the present invention, as a polycarbonate resin composition having high flame retardancy, it sufficiently maintains the original transparency and mechanical properties of the resin, and in particular, It is possible to provide a product with almost no difference in physical properties in the orthogonal direction.

that's all

Claims (1)

[Claims] For 100 parts by weight of polycarbonate resin, the following general formula; It is a group represented by ▼, where 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)<
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 in the range of 0 to 4, and all l and m is an integer that does not become 0, and the average degree of polymerization n is 0 to 5.) A flame retardant resin composition containing 1 to 15 parts by weight of a flame retardant.