KR910009862B1 - Combustion retardant styrene resin composition which is excellent ultravioleta stability - Google Patents

Abstract

The resin compsn. comprises (A) 100 wt. pts. of styrenic resin comprising more than 15 wt. pts. of the graft copolymer (A-1), less than 85 wt. pts. of the polymer (A-2) and less than 85 wt. pts. of the styrene-butadiene block copolymer (A-3); (B) 1-20 wt. pts. of antimon trioxide; and (C) 5-40 wt. pts. of the diglycidyl ether polymer (I) of the tetrabromo bisphenol A. The graft copolymer (A-1) is prepd. by polymerizing one or more monomer solected from aromatic monoalkenyl monomer, vinylcyanide monomer or (meth)acrylic acid alkyl ester monomer, in presence of the dienic rubbric component of alkyl acrylate rubbric component. The polymer (A-2) is prepd. polymerizing one or more monomer selected from the said monomers.

Description

Flame retardant styrene resin composition with excellent UV stability

The present invention relates to a flame retardant styrene resin composition having excellent ultraviolet stability. Recently, according to the trend of advanced electronic and electronic devices, not only internal parts but also external materials are advanced, and various functions such as flame retardancy, electromagnetic shielding, and weather resistance, which are not required in the past, are required.

In order to meet these demands, many studies have been conducted on styrene resins, which are mainly used as exterior materials for electrical and electronic devices, and in particular, many studies have been conducted and commercialized. In general, flame retardant styrene resins are produced by adding flame retardance by adding at least one component selected from halogen-containing organic compounds and antimony-containing inorganic compounds to the styrene resin.

The halogen-containing organic compounds are mainly bromine or chlorine compounds, and especially bromine compounds have excellent flame retardant effects when used in styrene resins, but exhibit various disadvantages such as impact strength reduction and UV stability deterioration. Furthermore, in recent years, exterior materials used for computers and office automation devices are often not painted or coated. Therefore, resins containing butadiene rubber in the styrene resins of the exterior materials due to ultraviolet rays have excellent impact strength but poor UV stability. It has a disadvantage of discoloration easily, and when the flame retardant is added, the discoloration becomes more severe, even if the product is used indoors, the color change is noticeable. Accordingly, the present inventors have made efforts to solve these shortcomings. As a result, the inventors have invented a flame retardant styrene resin having excellent ultraviolet stability without damaging the physical properties of the styrene resin itself and completed the present invention.

The composition of the present invention is bulk, suspended or suspended in the presence of a diene rubber component or an alkyl acrylate rubber component of one or more monomers selected from aromatic mono alkenyl monomers, vinyl cyan monomers and alkyl ester monomers of acrylic acid or methacrylic acid. At least 15 parts by weight of the graft copolymer (A-1) obtained by emulsion polymerization, one or more monomers selected from among aromatic monoalkenyl monomers, vinylcyanate monomers and alkyl ester monomers of acrylic acid or methacrylic acid Or (B) antimony trioxide based on 100 parts by weight of (A) styrene-based resin consisting of 85 parts by weight or less of polymer (A-2) obtained by emulsion polymerization and 85 parts by weight or less of styrene-butadiene block copolymer (A-3). -20 parts by weight (C) Diglycidyl ether of tetrabromo bisphenol-A consisting of 5-40 parts by weight of tetrabromo bisphenol A A resin composition according to claim.

Each composition used in the present invention will be described below.

The graft copolymer of component (A-1) is prepared by bulk, suspension, emulsion polymerization, or a mixed polymerization method thereof. Among these, emulsion polymerization is described as follows.

First, a rubber component is polymerized to prepare a rubber component polymer latex, and then an aromatic monoalkenyl monomer, a vinyl cyanide monomer and an acrylic acid or methacrylic acid alkyl ester are used with respect to 3-70% by weight, preferably 5-60% by weight of the rubber component polymer. 30-97% by weight, preferably 40-95% by weight of one or more monomers selected from the monomers is added to emulsion polymerization in the presence of a small amount of emulsifier to prepare a graft copolymer (A-1). Rubber components used in the graft copolymers include butadiene rubbers, isoprene rubbers, butadiene and styrene copolymers, alkyl acrylate rubbers, and the like, and the particle diameter thereof is 0.1-15 micrometers (μ), preferably 0.2-. 5μ. The monomer components are styrene, α-methylstyrene, p-methylstyrene, acrylonitrile, methacrylic acid methyl ester, methacrylic acid ethyl ester, and the like. The composition ratio of each component is used to determine the content of the remaining monomers injected into the rubber component latex. By adjusting, arbitrary adjustment is possible.

The polymer of the component (A-2) is prepared by bulk, suspension, emulsion polymerization or a mixed polymerization method thereof in the same manner as the component (A-1), and the monomers used for preparing the copolymer are the same as those of the above (A-1). Do.

The copolymer of component (A-3) is a styrenebutadiene block copolymer having a butadiene content of 50-90% by weight.

The three components (A-1), (A-2) and (A-3) are basic resins of the resin composition of the present invention, and the component (A-1) is 15-100 parts by weight, preferably 40-100 parts by weight. The component (A-2) and the component (A-3) are each used in an amount of 0-85 parts by weight, preferably 0-60 parts by weight, so that the sum of the three components is 100 parts by weight.

Component (B) of the present invention is a commercially available material, the amount of which is used in 100 parts by weight of the mixed resin (A) of the three components (A-1), (A-2) and (A-3). 1-20 parts by weight, preferably 2-15 parts by weight, is used. When the component (B) of the present invention is used in the above range or less, a synergistic effect with the flame retardant is less, and sufficient flame retardant effect is not obtained. When the component (B) is used in the above range, the impact strength of the resin is lowered to balance water growth.

The polymer of component (C) of the present invention is a bulk or solution polymer of epichlorohydrin and tetrabromo bisphenol-A, having an epoxy equivalent of 320-900, preferably represented by general formula (I) in the range of 320-600. It is a substance.

In the general formula, n is an integer of 0 or more.

Its use amount is 5-40 weight part with respect to 100 weight part of mixed resins (A) of the three components of (A-1), (A-2), and (A-3), Preferably it is 10-35 weight part. When the component (C) of the present invention is used below the above range, it is difficult to expect a flame retardant effect, and when using above the above range, the impact strength is severely lowered, which is not preferable. In addition, even when used in an amount within the above range, when the epoxy equivalent is larger than the above range, the impact strength of the resin is severely lowered, so that the physical properties cannot be balanced. In addition to the above components, heat stabilizers, antioxidants, plasticizers, ultraviolet stabilizers, lubricants and the like can be further added to the appropriate amount of other additives to further improve the physical properties and processability of the composition of the present invention.

Hereinafter, the composition of the present invention will be described in detail in the following examples.

The parts used here are all parts by weight.

[Production Example 1]

In a closed reactor, 100 g of butadiene, 100 g of ion-exchanged water, 0.2 g of sodium lauryl sulfate, and 0.1 g of t-dodecyl mercaptan were added and polymerized for 30 hours to obtain polybutadiene latex. 80 g of polybutadiene latex, 150 g of ion-exchanged water, 45 g of styrene, 15 g of acrylonitrile, 0.3 g of sodium lauryl sulfate, and 0.1 g of t-dodecyl mercaptan were added to a new closed reactor, and the temperature of the reactor reached 70 ° C. 0.1 g of potassium persulfate was added to polymerize for 3 hours, and the obtained polymer was dried to a dry powder through a post-treatment process.

The final graft copolymer obtained here is referred to as ABS.

[Production Example 2]

8 g of polybutadiene rubber, 92 g of styrene, 0.05 g of benzoyl peroxide, and 0.21 g of t-dodecyl mercaptan were added to a closed reactor for 1 hour at 90 ° C., followed by reaction with 300 g of ion-exchanged water, 0.05 g of dicumyl peroxide, 1.0 g of polyvinyl alcohol was polymerized in a new reactor at 140 ° C. for 2 hours to obtain a copolymer.

The copolymer obtained here is called HIPS.

[Manufacture example 3]

75 g of styrene, 25 g of acrylonitrile, and 0.3 g of t-dodecyl mercaptan were added to a closed reactor, and then subjected to bulk polymerization at 180 ° C. for 1 hour to obtain a copolymer.

The copolymer obtained here is called SAN.

Example 1

65 g of ABS prepared in Preparation Example 1, 35 g of SAN prepared in Preparation Example 3, 5 g of antimony trioxide, and a flame retardant (C) component, 30 g of a polymer having an epoxy equivalent of 450, 1.0 g of calcium stearate, and 1.0 g of diphenylisooctylphosphate. The resulting resin mixture was uniformly mixed with a Henschel mixer and then extruded into pellets to extrude. After injection molding the pellets obtained as described above to produce a flame retardant test specimen (11 cm × 1.25 cm × 0.3 cm), impact strength test specimen (6 cm × 1.25 cm × 0.3 cm) and UV stability test specimen (6 cm × 3 cm) Each specimen was tested with the prepared specimens. The flame retardant test was determined by testing according to the UL-94 V-0, V-1 and V-2 determination test method regulations, the impact strength was tested by the Izod notch impact strength test method of ASTM D-256. UV stability test was carried out for 300 hours in an Atlas Fade-O-meter according to the method of ASTM D4459 to measure the discoloration (Hunter E) by the Hunter method. The test results are shown in Table 1.

Example 2

HIPS 90g prepared in Preparation Example 2, 10g of Tuprene-A (Asahi Chemical Co., Ltd.) as a component (A-3), 4g of antimony trioxide, 20g of (C) component having an epoxy equivalent of 540 and stearic acid 1.0 g of calcium and 1.0 g of diphenylisooctyl phosphate were mixed and tested in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1

Component (C) in Example 1 was replaced with a polymer having the same general formula but having an epoxy equivalent of 1100, and tested in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2

Component (C) in Example 2 was replaced with a polymer having the same general formula but an epoxy equivalent of 1900, and tested in the same manner as in Example 2, and the results are shown in Table 1.

Comparative Example 3

In the same manner as in Example 1 using 20 g of DE-83R (Decabromo diphenyloxide; Great Lakes, USA) instead of the component (C) which is a flame retardant in Example 1, the results are shown in Table 1.

TABLE 1

As shown in the above table, it can be seen that the composition of the present invention using a flame retardant having a low epoxy equivalent weight is superior in discoloration and impact strength than the comparative composition.

Claims (2)

Graft copolymer obtained by polymerizing one or more monomers selected from aromatic monoalkenyl monomers, vinyl cyan monomers and acrylic acid or methacrylic acid alkyl ester monomers in the presence of a diene rubber component or an alkyl acrylate rubber component (A- 1) 15 parts by weight or more, 85 parts by weight or less of polymer (A-2) obtained by polymerizing one or more monomers selected from an aromatic monoalkenyl monomer, a vinyl cyan monomer and an acrylic acid or methacrylic acid alkyl ester monomer -Diglyci of (B) 1-20 parts by weight of antimony trioxide and (C) tetrabromo bisphenol A based on 100 parts by weight of (A) styrene resin consisting of 85 parts by weight or less of butadiene block copolymer (A-3) A resin composition, characterized by consisting of 5-40 parts by weight of a dill ether polymer. The resin composition according to claim 1, wherein the component (C) is represented by the following general formula, and the epoxy equivalent has a value of 320 to 900.

In the general formula, n is an integer of 0 or more.