JP2005036135A5 - - Google Patents

Description

That is, the flame-retardant resin composition according to the present invention is 1 to 30 parts by weight of a phosphorus-based flame retardant (B) and 100% by weight of the rubber-reinforced styrene resin (A) and the following general formula (1). A resin composition comprising 0.1 to 20 parts by weight of the modified phenolic resin (C) represented, wherein the rubber-reinforced styrene resin (A) is added to the rubbery polymer as a single aromatic vinyl monomer. A graft polymer or copolymer (A-1) obtained by graft polymerization of a monomer or monomer mixture containing a monomer and a monomer or monomer mixture containing an aromatic vinyl monomer A vinyl polymer or copolymer (A-2) obtained as described above, wherein the vinyl polymer or copolymer (A-2) is a maleimide group-modified vinyl copolymer or glycidyl group-modified vinyl. Table in containing system copolymer, and the following general formula (1) Modified phenolic resin (C) consists of those wherein the following condition is satisfied to.
(A) Solution viscosity at 25 ° C. of a 50 wt% 1,4-dioxane solution is 30 to 100 mm ² / s
(B) The amount of residual carbide at 600 ° C. is 30% or more by TGA measurement when the temperature is raised at 40 ° C./min in an air atmosphere.

[Example 1-7, Comparative Examples 1-11]
Vented with (A) rubber-reinforced styrene resin, (B) phosphorus flame retardant, (C) modified phenolic resin, and other necessary additives prepared in the reference example at the mixing ratio shown in the table. A pellet-shaped polymer was produced by performing melt kneading and extrusion at 220 to 270 ° C. using a 30 mmφ twin-screw extruder (Ikegai Iron Works, PCM-30). Next, each test piece was molded with an injection pressure (lower limit pressure + 1 MPa) using an injection molding machine (manufactured by Sumitomo Heavy Industries, Promat 40/25), and the physical properties were measured under the following conditions.

Example 1 or Rawakaru so on, epoxy-modified vinyl copolymer portion of the ABS resin, and by the maleimide-modified vinyl copolymer, not only it is possible to shorten the combustion time, It can be seen that the impact resistance is greatly improved and the heat resistance is also improved.

On the other hand, from the measurement results of Examples 1 to 4 , the modified phenolic resins <C-1> and <C- of the present invention together with the phosphorus flame retardant <B-1> or <B-2> with respect to the ABS resin. By adding 2>, flame retardancy is improved, and a resin composition having excellent impact resistance, heat resistance, and color tone is obtained.

From the comparison of Example 1 and Example 5 , with respect to the ABS resin, the flame retardant resin composition comprising the modified phenolic resin <C-1> together with the phosphorus flame retardant <B-1>, and the silicone resin ( It can be seen that the addition of D-1) not only shortens the combustion time but also improves the impact resistance. Furthermore, from comparison with Example 7, it can be seen that when silicone oil (D-2) is added, the reduction in combustion time is small, but the impact resistance is greatly improved.

Furthermore, from the comparison between Example 1 and Example 7 , the anti-oxidation further to the flame retardant resin composition comprising the phosphorus-based flame retardant <B-1> and the modified phenolic resin <C-1> with respect to the ABS resin. It can be seen that the combustion time is greatly shortened by adding the agent.

As a result of comparison between Example 1 and Comparative Example 4, when the modified phenolic resin <C-3> having a solution viscosity outside the scope of the present invention was used, not only the combustion time was greatly extended, but also the impact resistance. It can be seen that the property also decreases.

Furthermore, by comparison between Example 1 and Comparative Examples 5 to 7, modified phenolic resins <C-4> to <C-6 having a solution viscosity outside the range of the present invention and a residual amount of 600 ° C. of 30% or less. When> is used, it can be seen that not only the test piece is dripped during combustion but the flame retardancy is significantly reduced, and the heat resistance is remarkably lowered.

Further, according to the comparison between Example 1 and Comparative Example 8, the residual amount at 600 ° C. is 30% or more, but when the modified phenolic resin <C-7> whose solution viscosity is outside the scope of the present invention is used, It can be seen that not only the test piece dripping during combustion cannot be suppressed, but also the heat resistance is lowered.

According to the comparison between Example 1 and Comparative Example 9, when a large amount of the modified phenolic resin <C-1> is added, not only the test piece is dripped, but the flame retardancy is lowered, and the mechanical properties are remarkably lowered. I understand that.

According to the comparison between Example 1 and Comparative Example 10, the flame retardancy is not obtained when no phosphorus flame retardant is added, and the flame retardancy is added when a large amount of phosphorus flame retardant is added as in Comparative Example 11. However, the mechanical properties are remarkably deteriorated and the material becomes impractical.

Claims (5)

1 to 30 parts by weight of a phosphorus-based flame retardant (B) and 0.1 parts of a modified phenolic resin (C) represented by the following general formula (1) with respect to 100 parts by weight of the rubber-reinforced styrene resin (A) A resin composition comprising ˜20 parts by weight, wherein the rubber-reinforced styrene resin (A) grafts a monomer or a monomer mixture containing an aromatic vinyl monomer on a rubber polymer. A vinyl polymer or copolymer obtained by polymerizing a graft polymer or copolymer (A-1) obtained by polymerization and a monomer or monomer mixture containing an aromatic vinyl monomer ( A-2), wherein the vinyl polymer or copolymer (A-2) contains a maleimide group-modified vinyl copolymer or a glycidyl group-modified vinyl copolymer, and has the following general formula: The modified phenolic resin (C) represented by (1) is The flame retardant resin composition characterized by satisfying the matter.
(A) Solution viscosity at 25 ° C. of a 50 wt% 1,4-dioxane solution is 30 to 100 mm ² / s
(B) The amount of residual carbide at 600 ° C. is 30% or more by TGA measurement when the temperature is raised at 40 ° C./min in an air atmosphere.

(In the above formula, R ¹ represents an organic residue having 1 to 10 carbon atoms. R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) The flame retardant resin composition according to claim 1, wherein the modified phenolic resin (C) is a modified phenolic resin represented by the following general formula (2).

(In the above formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) The flame retardant resin composition according to claim 1 or 2, wherein the phosphorus-based flame retardant (B) is represented by the following general formula (3).

(In the above formula, R ^{4 to} R ¹¹ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are the same or different phenyl groups or Y represents a phenyl group substituted with a halogen-free organic residue, Y represents a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, and Ph represents a phenyl group. In addition, n is an integer of 0 or more and may be a mixture of different n. K and m are each an integer of 0 to 2, and k + m is an integer of 0 to 2. The flame-retardant resin composition according to any one of claims 1 to 3, further comprising 0.01 to 10 parts by weight of a silicone compound (D) with respect to 100 parts by weight of the rubber-reinforced styrene resin (A). object. The molded article which consists of a flame-retardant resin composition in any one of Claims 1-4.