JPH03111445A - Resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention is used as a molding material for various molded products that require impact resistance and flame retardancy, such as home appliances, OA equipment, and automobile parts. The present invention relates to a resin composition.

[Conventional technology]

Styrenic resins have excellent processability and various physical properties, so they are industrially produced and used in a wide variety of fields. Especially in the field of light electrical appliances (for example, the field of home appliances,
Demand for flame retardancy is increasing in the field of office automation equipment (OA equipment).

In order to impart flame retardancy to styrene-based resins, it has been proposed to blend halogen-based flame retardants and antimony compounds (JP-A-53-149244, JP-A-60-13834).
issue). However, these compositions are prone to dripping during combustion and have unstable flame retardancy, and when a large amount of flame retardant is added, impact resistance decreases.

In order to prevent this drop in impact resistance, it has been proposed to use high-cis polybutadiene rubber (Japanese Patent Publication No. 57-26
No. 695. JP-A-62-179552).

Furthermore, in order to improve the flame retardancy of styrene resins, it has been proposed to add a halogen-containing evokilogenated flame retardant to styrene resins (Japanese Patent Laid-Open No. 62-47
No. 37, JP 54-44298, JP 60-19
No. 2761). It has also been proposed to use TBA and a high molecular weight product of TBA together (Japanese Patent Laid-Open No. 54-6085
No. 4).

Recently, in order to obtain styrenic resin compositions with excellent flame retardancy and good heat resistance and impact resistance, antimony oxide has been added to styrene resins as a flame retardant aid. Compositions using a combination of a chlorinated bisphenol type epoxy polymer and bis(tribromophenoxy)ethane or tetrabromobisphenol A and a brominated bisphenol A type epoxy polymer have been proposed (JP-A Nos. 1-182342, 1-1). No. 182343).

Furthermore, some of the inventors of the present invention have found that it not only has excellent heat resistance, but also good impact resistance, and is promising as a material for parts of electronic devices, electrical devices, etc., and has excellent flame retardancy. As a resin composition, a copolymer of an fAl styrene compound and an imide compound of α,β-unsaturated dicarboxylic acid or a copolymer of these compounds reinforced with a rubber reinforcing material, (b) a copolymer of these compounds reinforced with a rubber reinforcing material, Thermoplastic resins such as impact-resistant resins obtained by kraft copolymerization of styrene and acrylonitrile or styrene and methyl methacrylate (not necessarily blended)
, (C1 antimony oxide), (D) a bromine-containing reaction product obtained by reacting a bromine-containing epoxy compound with 1.3.5-tribromophenol, and (E) a silicone oil. (Japanese Patent Application No. 158508/1983).

[Problem to be Solved by the Invention 1] Generally, when TBA or bis(tribromophenoxy)ethane is added individually to a thermoplastic resin, flame retardance is improved, but heat resistance is reduced. For this purpose, in the invention described in JP-A-60-192761, high molecular weight halogenated bisphenol A
By using carbonate oligomers and bis(tribromophenoxy)ethane together, we are trying to maintain a balance of heat resistance, impact resistance, etc., but styrenic resins that have sufficient impact resistance, heat resistance, weather resistance, etc. The composition could not be obtained. Also, JP-A-54-608
Even when the invention disclosed in Japanese Patent No. 54 was applied to styrene resins, it was not possible to obtain a composition exhibiting sufficient effects.

Furthermore, JP-A-1-182342 and JP-A No. 1-1
Even if the invention described in 82:143 is applied to impact-resistant polystyrene resin, it is difficult to fully satisfy flame retardancy, especially in terms of dripping.
A large amount of flame retardant must be incorporated, which reduces the mechanical properties.

In addition, some of the inventors of the present invention have already proposed and filed a patent application filed in 1983.
The invention described in Specification No. 15850 not only has excellent mechanical properties such as impact resistance and tensile strength (but also has good heat resistance and moldability (fluidity)). Moreover, the composition has improved flame retardancy, especially dripping.

From the above, the present invention has excellent mechanical strength such as impact resistance and tensile strength, good weather resistance, and excellent moldability. The object of the present invention is to obtain a composition with improved flammability, especially dripping.

[Means and effects for solving the problems 1 According to the present invention, these problems are solved by (A) "polybutadiene rubber and/or styrene-butadiene copolymer rubber" (
A graft polymer in which an aromatic monovinyl monomer is grafted onto (hereinafter referred to as "rubber component"), fBl polystyrene resin, fCl antimony oxide, (DJ bromine-containing epoxy compound and 1.3.5-)
- a bromine-containing reaction product with a molecular weight of 1,200 to 6.000 and a bromine content of 5.0 to 60% by weight obtained by reacting with ribromophenol; and fE) silicone oil. , the proportion of non-grafted and grafted rubber in the total amount of the graft polymer and polystyrene resin is 1 to 15 as the total amount thereof.
The ratio of other components to 100 parts by weight of the total amount of the graft polymer and polystyrene resin is 1.0 to IO parts by weight of antimony oxide, and 5.0 parts by weight of the bromine-containing reaction product. ~40 parts by weight, and a resin composition in which the silicone oil is 0.1 to 3.0 parts by weight. The present invention will be explained in detail below.

(Al Graft Polymer The kraft polymer used in the present invention is obtained by grafting an aromatic monovinyl monomer to the rubber component described later.

The rubber components are polybutadiene rubber (butadiene homopolymer rubber) and styrene-butadiene copolymer rubber. Among these rubber components, styrene-butadiene copolymer rubber is a copolymer rubber with styrene containing butadiene as the main component (60% by weight), and is a random copolymer rubber obtained by copolymerizing using a free radical polymerization catalyst. It may be a polymer rubber or a block copolymer rubber obtained by copolymerizing using an organolithium catalyst. Mooney viscosity of these rubber components (M L , 100°C
) is usually 20 to 150, particularly preferably 30 to 130.

In addition, aromatic monovinyl monomers include styrene, α
-Methylstyrene, p-methylstyrene, etc., among which styrene is preferably used. These aromatic monovinyl monomers may be used alone or in combination of two or more.

The grafting method may be any one of bulk polymerization, solution polymerization, emulsion polymerization, and aqueous suspension polymerization, and methods that combine these methods (for example, partial bulk polymerization followed by aqueous suspension polymerization). It may be carried out by a method of turbid polymerization).

In producing 100 parts by weight of kraft polymer, the proportion of rubber used is generally 3 to 30 parts by weight, preferably 3 to 25 parts by weight, and particularly preferably 4 to 20 parts by weight. If the proportion of rubber used is less than 3 parts by weight to produce 100 parts by weight of the graft polymer, the resulting composition will have poor impact resistance. Note that a relatively large amount of the above-mentioned rubber may be used to produce a kraft polymer containing a large amount of rubber, and the polystyrene resin described below may be mixed into this kraft polymer.

The molecular weight of the aromatic monovinyl monomer bonded to the rubber component as a graft chain is usually from 50,000 to 30,000, preferably from 70,000 to 250,000. Generally, when graft polymerizing a 7-mer onto rubber, it is rare that the monomer is completely bonded to the rubber. Therefore, in the resulting kraft product, in addition to the graft polymer, a polymer of a monomer that does not bond to rubber and a rubber to which no heptamer is grafted coexist.

In the present invention, a polymer of aromatic monovinyl monomer that does not bond to the rubber component may be used as the polystyrene resin. Furthermore, the rubber component to which the aromatic monovinyl monomer is not grafted may be used as it is without being separated.

The kraft polymers of the present invention (including those containing polystyrene resins and rubber components) are industrially manufactured and used in a wide variety of fields, and their manufacturing methods and properties are widely known. This is what is being done.

(b) Polystyrene resin The polystyrene resin used in the present invention is obtained by polymerizing the above-mentioned aromatic monovinyl monomer by any one of bulk polymerization, solution polymerization, emulsion polymerization, and aqueous suspension polymerization. It can also be obtained by combining these methods and polymerizing. One type of aromatic monovinyl monomer may be used, or two or more types may be used in combination.

The molecular weight of the polystyrene resin is generally from 50,000 to 300,000, particularly preferably from 70,000 to 250,000.

In the composition of the present invention, even when using a graft polymer containing a polymer of an aromatic monovinyl monomer that does not bind to the rubber component obtained by graft polymerization as described above, the graft polymer and the polystyrene resin Even when used in combination with the graft polymer and polystyrene resin, the proportion of non-grafted and grafted rubber in the total amount of the graft polymer and polystyrene resin is 1 to 1.
15% by weight, preferably from 2 to 15% by weight, particularly preferably from 3 to xzl% by weight. If the proportion of non-grafted and grafted rubber in the total amount of the graft polymer and polystyrene resin is less than 1% by weight, the resulting composition will have poor impact resistance. On the other hand, if it exceeds 15% by weight, there will be problems in terms of mechanical strength such as tensile strength.

fc) Antimony oxide Furthermore, the antimony oxide used in the present invention is widely used as a flame retardant aid for general bromine-containing compounds. Representative examples include antimony trioxide, antimony pentoxide, and these antimony oxides. As an example, the average particle size of the antimony oxide is 1 to 150 μm.

fD) Bromine-containing reaction product A typical example of the bromine-containing reaction product used in the present invention is the reaction of the bromine-containing epoxy compound represented by formula (1) with 1.3.5-) ribromophenol. It is obtained by
) is shown by the formula. As a result, the terminal epoxy group of the bromine-containing epoxy compound represented by formula (I) reacts, and the remaining epoxy group is at most 15% of the initial epoxy amount.

In formulas (1) and (II), it is preferable that each l is 1 to 4.

The bromine-containing epoxy compound represented by formula (I) is prepared by mixing 4,4°-dioxydiphenylpropane (bisphenol A) containing at least one bromine atom and epichlorohydrin in the same manner as general ether type epoxy resins. It can also be manufactured. It can also be produced by reacting bromine-free ether-type epoxy resin with bromine.

The molecular weight of the bromine-containing reaction product is l, 200-6.0
00 te, especially 1,400 to 5,000 (7) is preferable. In addition, the bromine-containing residue is 5.0 to 6o weight%.
Especially desirable is one with a 10 to 60% fake.

fE) Silicone oil Furthermore, the viscosity of the silicone oil used in the present invention is generally 10 to 100 at a temperature of 25°C.
, 0 OcP (centipoise), 50 to 50
, 000 cP is desirable, especially 50 to 20.
00 cP is suitable. If a silicone oil with a viscosity of less than 10 cP at a temperature of 25° C. is used, there is a risk of volatilization during crosstalk. On the other hand, io, oo
.

If a material exceeding cP is used, the compatibility will be poor.

As typical examples of the silicone oil, polydimethylsiloxane, polymethylphenylsiloxane, and polymethylhydrogensiloxane are mainly used. Furthermore, polydialkyl (the number of carbon atoms in the alkyl group is usually 1 to 1)
(8) Modified silicone oil obtained by modifying the alkyl group of siloxane with epoxy, alkyl, amino, carboxyl, or alcohol can also be used.

(F1 composition ratio In the composition of the present invention, the composition ratios of other composition components, that is, antimony oxide, bromine-containing reaction product, and silicone oil, based on 100 parts by weight of the above-mentioned graft polymer and polystyrene resin are as follows. It is as follows.

Regarding antimony oxide, it is 1.0 to IO parts by weight, preferably 1.5 to 10 parts by weight, particularly 2.0 to 8.0 parts by weight.
0 parts by weight is preferred. The composition ratio of antimony oxide is 1
．． If it is less than 0 parts by weight, the synergistic flame retardant effect of the bromine-containing reaction product cannot be fully exhibited. On the other hand, 10
If the amount exceeds parts by weight, the mechanical strength of the resulting composition will decrease.

In the case of a bromine-containing reaction product, the amount is preferably 5.0 to 40 parts by weight, particularly preferably 5.0 to 35 parts by weight. If the composition ratio of the bromine-containing reaction product is less than 540 parts by weight, a composition exhibiting sufficient flame retardancy cannot be obtained. On the other hand, if the weight exceeds 40 parts, there is a problem in the impact resistance of the resulting composition.

Furthermore, the amount of silicone oil is 0.1 to 3.0 parts by weight, particularly preferably 0.1 to 2.5 parts by weight. If the composition ratio of silicone oil is less than 0.1 part by weight, the resulting composition will not be able to sufficiently exhibit the dripping prevention effect, and therefore there will be a problem in terms of flame retardancy. On the other hand, if it exceeds 3.0 parts by weight, slipping occurs during production of the composition.

Further, the ratio of the bromine-containing reaction product to 1 part by weight of antimony oxide is preferably 2 to 7 parts by weight.

(Production of G1 composition, molding method, etc.) In order to produce the composition of the present invention, a graft polymer containing the above-mentioned polystyrene resin or a graft polymer and a polystyrene resin, antimony oxide, a bromine-containing reaction product, and silicone are used. Stabilizers against heat, oxygen and light, anti-dehydrochlorination agents, fillers, and colorants are widely used in the field of polymeric substances, although the purpose can be achieved by uniformly blending them with oil. Depending on the intended use of the composition, additives such as lubricants, plasticizers, and antistatic agents may be added to the extent that they do not essentially impair the properties of the composition of the present invention.

In producing the composition, all the composition components may be mixed at the same time, or some of the composition components may be mixed in advance,
The resulting mixture and the remaining composition components may be mixed.

Mixing methods include a tri-blending method using a mixer such as a Henschel mixer, which is commonly used in the field of synthetic resins, and a method of tri-blending using a mixer such as an oven roll, extrusion mixer, kneader, and Banbury mixer while melting. One method is to mix them. Among these mixing methods, two or more of these mixing methods may be used in combination to obtain a uniform composition (for example,
(pre-triblending and then melt-mixing the mixture). In particular, even when tri-blend is used in combination, or when one or more melt-kneading methods are used in combination, when producing a molded product using the later molding method, pellets are produced using a pelletizer and used. It is preferable.

Of the above mixing methods, both melt kneading and molding using the molding method described below must be carried out at a temperature at which the polymeric substance used is melted. but,
If carried out at a high temperature, the polymer substance may undergo thermal decomposition or deterioration, or the bromine-containing epoxy compound may decompose, so it is necessary to carry out the process at a temperature below 280°C.

The composition of the present invention may be molded into a desired shape by applying molding methods commonly practiced in the field of synthetic resins, such as injection molding, extrusion molding, compression molding, and blow molding. Alternatively, after forming the sheet into a sheet using an extrusion molding machine, this sheet may be formed into a desired shape by a secondary processing method such as a vacuum forming method or a pressure forming method.

[Examples and Comparative Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the Examples and Comparative Examples, the melt flow rate (hereinafter referred to as rMFRJ) was measured at a temperature of 200° C. and a load of 5 kg in accordance with JIS 721O.

In addition, the tensile yield strength is determined according to ASTM 0638.
Measurement was performed using a TM No. 1 dumbbell at a strain rate of 5 mm/min. Furthermore, Izotsu impact strength is ASTM D
256, with a notch at a temperature of 23°C. In addition, regarding flame retardancy, the thickness is 1.6 mm (
Evaluation was performed according to the υL-94 method using a 1/16 inch) test piece. Furthermore, regarding the weather resistance test, we used a sunshine weather meter to visually evaluate the state of discoloration after 400 hours at a temperature of 60°C. Table 2 shows "○" when there is almost no discoloration, and "○" when there is almost no discoloration, and "○" when the discoloration is brown. In addition, the gel fraction is determined by immersing 0.5 g of the sample in a mixed solvent of methyl ethyl ketone and methyl alcohol at a ratio of 10:1 for 18 hours at room temperature, followed by centrifugation.Then, insoluble matter was aggregated. The insoluble matter was dried under reduced pressure at a temperature of 60° C. for 14 hours, and the weight was measured.

In addition, the manufacturing method, type,
The physical properties are shown below.

[(A) Graft polymer and polystyrene resin]

As a kraft polymer, 24kg of styrene was added to a 24I2 autoclave and the Mooney viscosity (MLl, 4
Butadiene homopolymer rubber with a temperature of 40 (10 °C) 1
．． 5 kg was added and completely dissolved. Then 1.5 g of tertiary-dodecyl mercaptan and 7.4 g of n-dodecyl mercaptan were added and at a temperature of 120° C.
．． Polymerization was carried out with sufficient stirring for 5 hours. From this solution, a solution containing 8 kg of polymer was taken out and 0.5
The above solution was poured into a 20ff autoclave to which 8I2 of polyvinyl alcohol aqueous solution of % i was added, and 20g
benzoyl peroxide and 8, Og tertiary-
Butyl-peroxyacetate was added and polymerization was carried out at a temperature of 90'C with sufficient stirring for 4 hours, then the polymerization system was raised to 135°C and polymerization was carried out at this temperature with sufficient stirring for 1 hour. . After the polymerization system was allowed to cool to approximately room temperature, the bead-shaped polymer was collected in a furnace, thoroughly washed with water, and then dried under reduced pressure at a temperature of 60°C for 18 hours to form a polymer E referred to as rHIPS(a). I got 1. The gel fraction of this HIPS (a) is 14.5%
The average molecular weight of the polystyrene resin in the soluble content was approximately 230,000.

In addition, instead of the butadiene homopolymer rubber used in manufacturing HIPS (a), Mooney viscosity (ML,...
, 100°C) Ka39-thealphtacyene m autopolymer 1.
4 kg and 0.8 kg of styrene-butadiene copolymer rubber having a Mooney viscosity (ML, . The amount of tertiary-dodecyl mercaptan used was changed to 9.6 g, the amount of n-dodecyl mercaptan used was changed to 12.0 g, and the amount of tertiary-butyl peroxyacetate was changed to 24 g. The use of polyvinyl alcohol and benzoyl peroxide M was the same as in the production of HIPS (a)), and the polymerization and post-polymerization treatments (washing with water, drying, etc.) were carried out under the same conditions as in the production of HIPS (a). The obtained polymer [hereinafter referred to as rllIPs(b)]
The gel fraction was 15%. The average molecular weight of the soluble polystyrene resin was about 210,000.

Furthermore, instead of the butadiene homopolymer rubber used in producing HIPS (a), Mooney viscosity (M L 1
．． The same amount of butadiene homopolymer rubber with a temperature of 35 (100°C) was used, no tertiary-dodecyl mercaptan was used, instead 8.0 g of n-dodecyl mercaptan was used, and benzoyl peroxide was used. Except that the amount was changed to 22 g and the amount of tertiary-butyl-peroxyacetate was changed to 15 g [the amounts of styrene and polyvinyl alcohol used were the same as in the production of HIPS (a)], HIPS ( Polymerization and post-polymerization treatment were carried out under the same conditions as in the production of a). The gel fraction of the obtained polymer [hereinafter referred to as rHI PS (c) J] was 15.7%. The average molecular weight of the soluble polystyrene resin was approximately 190,000. Fifty parts by weight of the polymer thus obtained and 50 parts by weight of a styrene homopolymer having an MFR of 10 g, 710 minutes were kneaded to produce a resin composition [hereinafter referred to as rHI PS (C)J].

[(B) Antimony Oxide] Furthermore, antimony dioxide (hereinafter referred to as r5b20.J) was used as antimony oxide.

[(C) Bromine-containing substance 1 Also, among the bromine-containing substances, as a bromine-containing reaction product,
Both are bromine-containing reaction products in which R1 is a hydrogen atom and R2 is a methyl group in the above formula (I) (average molecular weight approximately 2.000, bromine content 56% by mass, hereinafter referred to as "F"
bromine (a)) and bromine-containing substances are 55% by weight
A bromine-containing reaction product (hereinafter referred to as "bromine (b)") having an average molecular weight of about 3.600 was used.

Also, for comparison, decabromodiphenyl ether (
Hereinafter referred to as "bromine (C)") was used.

[(D) Silicone Oil] Furthermore, as a silicone oil, polydimethyl silicone oil (hereinafter referred to as r Si (1) J) having a viscosity (measured at 25°C, the same applies hereinafter) of 5.000 cP is used.
, polymethylphenyl silicone oil (hereinafter referred to as r Si f21 J) having a viscosity of 1.0 cP, polymethylhydrodiene silicone oil (hereinafter referred to as r Si f31 J) having a viscosity of 1.000 cP,
Epoxy silicone oil with a viscosity of 1.000cP (hereinafter referred to as rsif4 J) and a viscosity of 600c
P amino silicone oil (r Si (5
1J) was used.

Examples 1 to 8, Comparative Examples 1 to 4 Table 1 shows "graft polymer, polystyrene resin" (
Table 1 shows each compositional component and the respective formulation M, in which the type and amount of bromine-containing material and silicone oil (hereinafter referred to as "resin content"), bromine-containing material, and silicone oil are shown.
ao3 (antimony oxide) and 0.2 parts by weight of dibutyl chin malate (manufactured by Sankyoki Gosei Co., Ltd., trade name 5)
tann [1S-18) (as a stabilizer) were each triblended for 2 minutes using a Henschel mixer. Each mixture obtained was heated to a cylinder temperature of 220
A pellet (composition) was produced while kneading using a twin-screw extruder (diameter: 30 mm) set at .degree.

Each of the obtained compositions was evaluated in terms of MFR1 tensile yield strength and Izot impact strength (notched), as well as flame retardancy and weather resistance tests. These results are shown in Table 2.

(Hereinafter, blank spaces) From the results of the above examples and comparative examples, it is clear that the resin composition obtained by the present invention has excellent flame retardancy and impact resistance.

〔Effect of the invention〕

That is, by combining a bromine-containing reaction product and silicone oil, a resin composition with well-balanced physical properties can be obtained. Also, flame retardancy, especially dripping, is improved.

The resin composition obtained by the present invention not only has excellent flame retardancy and impact resistance, but also has the following effects (
It is a composition that exhibits characteristics).

l) Good moldability (fluidity).

2) The molded product has good gloss.

3) Excellent weather resistance and little discoloration.

Since the resin composition obtained by the present invention has the excellent characteristics described above, it can be used in various fields as described below.

■) Television receivers 2) Housings for OA equipment such as facsimiles, word processors, microcomputers, printers, etc. 3) Housings for home appliances

Claims (1)

[Scope of Claims] (A) A graft polymer in which an aromatic monovinyl monomer is grafted onto a polybutadiene rubber and/or a styrene-butadiene copolymer rubber, (B) a polystyrene resin, (C) an antimony oxide, (D) Bromine having a molecular weight of 1,200 to 6,000 and a bromine content of 5.0 to 60% by weight, obtained by reacting a bromine-containing epoxy compound and 1,3,5-tribromophenol. The proportion of ungrafted and grafted polybutadiene and styrene-butadiene copolymer rubber in the total amount of the graft polymer and polystyrene resin is determined by their total amount. The proportion of other components is 1.0 to 10 parts by weight for antimony oxide and 1.0 to 10 parts by weight for the total amount of graft polymer and polystyrene resin, and bromine-containing reaction product. is 5.0 to 40 parts by weight, and silicone oil is 0.1 to 3.0 parts by weight.