JPS6239653A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having extremely excellent thermal stability in molding and having high impact resistance and flame-retardance, by adding an organic tin compound and a cyanurate derivative to a mixture of a styrene resin and a vinyl chloride resin. CONSTITUTION:The objective composition can be produced by compounding (A) 100pts.(wt.) of a flame-retardant resin composed of (i) 0-85wt% styrene resin wherein the intrinsic viscosity of the methyl ethyl ketone-soluble component is 0.25-0.70 in dimetylformamide and (ii) 100-15wt% vinyl chloride resin having a polymerization degree of 400-1,500 with (B) 0.5-8pts. of an organic tin compound and (C) 0.05-6pts. of the cyanurate derivative of formula I [two or more of R1-R3 are group of formula II (R4 and R7 are H or 1-8C alkyl; R5 and R6 are tert-butyl or methyl), the substituent group other than the group of formula II is H or 1-8C alkyl]. The amounts of the components A and B (x and y pts.) are selected to satisfy the formula 0.01<=y/(x+y)<=0.5.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a flame-retardant resin composition that has extremely excellent thermal stability, and more specifically, has extremely excellent thermal stability during molding processing, The present invention also relates to a flame retardant resin composition having good impact resistance and flame retardancy.

ABS flame-retardant resins are increasingly being used in various fields because of their good heat deformation resistance, impact resistance, workability during molding, and gloss of the resulting molded products.

(Conventional technology and problems) Among ABS-based flame-retardant resins, ABS-based flame-retardant resins made by blending vinyl chloride resins are particularly characterized by excellent weather resistance, impact resistance, and flame retardancy. Recently, OA
This feature has been recognized in the equipment field, and demand is increasing. However, since a vinyl chloride resin is used, the processability is poor, and there is a problem in that, especially during long processing and molding, defects such as discoloration and black spots occur in the molded product due to decomposition of the resin.

Conventionally, to solve these problems, stabilizers such as organic tin compounds, epoxy compounds, and metallic soaps have been added, but in order to suppress decomposition, it is necessary to add large amounts of these stabilizers. As a result, additives bleed out, heat deformation resistance decreases, impact strength decreases, etc., which are disadvantageous.

(Means and Effects for Solving the Problems) As a result of intensive study on a method for suppressing the decomposition of resin without adding a large amount of stabilizer, the present inventors discovered that a special cyanurate derivative was added to the organotin compound together with an organotin compound. It has been found that the thermal stability of the resin can be significantly improved by using the compound in a specific ratio.

That is, in the present invention, a styrene resin whose intrinsic viscosity of the methyl ethyl ketone soluble portion is in the range of 0.25 to 0.70 in the dimethyl formamide g solution and a polymerization degree of 4 is used.
For 100 parts by weight of a flame retardant resin consisting of 100 to 15% by weight of a vinyl chloride resin of 0.0 to 1500%, 0.5 to 8 parts by weight of an organic tin compound and a cyanurate derivative represented by the structural formula (1) shown below. 0.05 to 6 parts by weight, and 0.0 parts by weight of the organotin compound and cyanurate derivative [1]
It was revealed that a flame retardant resin composition having a property of 1≦ could be obtained. Here, y represents the weight of the cyanurate derivative, and X represents the weight of the organotin compound.

The present invention will be explained in detail below.

The styrene resin referred to as the component (A) in the present invention has a reduced viscosity of the methyl ethyl ketone soluble portion in dimethyl formamide solution M of 0.25 to 0.70,
It is preferably 0 to 85% by weight, more preferably 35 to 75% by weight in the Gυ component. Styrenic resins include ABC resin, As, m resin, MABS resin, MBS, FB resin, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, acrylonitrile-methyl methacrylate-butadiene-styrene-α-methyl It includes all common styrene resins that can be mixed with vinyl chloride resins, such as styrene copolymers, AAS resins, AES resins, styrene-maleic anhydride copolymers, and styrene-maleimide copolymers. If the reduced viscosity of the soluble part in dimethylformamide solution is less than 0.25, the impact strength will decrease and
．． When it exceeds 7, fluidity decreases and molding specific heat stability deteriorates. Also, in component (5), styrene resin is 85% by weight.
If it exceeds this, the impact strength will decrease significantly and the flame retardancy will also decrease. On the other hand, the vinyl chloride resin in the carrier component includes a homopolymer and/or copolymer in which at least 80% by weight is vinyl chloride, and post-chlorinated polyvinyl chloride. The copolymer contains 20 monovinylidene compounds such as ethylene, vinyl acetate, methyl methacrylate, butyl acrylate, etc.
The content may be less than % by weight. The amount of the vinyl chloride compound in component (3) is preferably 15 to 100% by weight, more preferably 25 to 65% by weight, for the same reason as described for the styrene resin. The degree of polymerization is 400 to 150
0, and more preferably 400 to 700. Degree of polymerization is 4
When it is less than 00, impact strength decreases, and when it exceeds 1500, thermal stability is significantly decreased.

The organic tin compound referred to as component (B) is (7X)
The amount is 0.5 to 8 parts by weight, more preferably 2 to 6 parts by weight, based on 100 parts by weight of the component. If the amount is less than 0.5 parts by weight, the thermal stability will be significantly reduced, and if it exceeds 8 parts by weight, the impact strength will be significantly reduced.

Examples of organic tin compounds include alkylmalates such as dibutyltin maleate polymer, dibutyltinmalate, dioctyltinmalate polymer, dioctyltinmalate, and dibutyltinlaurate; alkyltinmerates such as alkyllaurates and dibutyltin bisalkyl mercaptoacetate; Contains all organotin compounds commonly used to improve the thermal stability of vinyl chloride resins, such as kabutides.

The cyanurate derivatives that are blended into the FA component together with the above organotin compounds to exhibit high thermal stability are the following compounds. That is, it is a cyanurate derivative having a hindered phenol as a substituent, and is a compound represented by the following structural formula [ID]. Here, cyanurate derivative (I)
At least two or more of the substituents RI+ R2+ R3 are hindered phenols having the structural formula (ID), and it is further preferable that all of RI+ R21R8 are hindered phenols (It). R1+ R2+ R3
When the number of hindered phenols (It) is one or less, the effect of improving thermal stability is small.

The substituent other than the hindered phenol [''] is preferably H or an alkyl group having 1 to 8 carbon atoms.

Structural formula (1) Structural formula [1] Hindered phenol (In the substituents in ID, RlHR6 is t
-butyl group or methyl group, R4°R7 is preferably Hl or an alkyl group having 1 to 8 carbon atoms.

Cyanurate derivative CI in component (B) of the present invention
] is, for example, a compound represented by the following structural formula (ST). (In the formula, ÷ of r represents a tertiary-butyl group).

H Sodium (IV) [■] (VI) Also, the cyanurate derivative in the component (B) of the present invention (
1) is (0.05 to 6 parts by weight per 100 parts by weight of the seaweed component).When the weight of compound (1) is less than 005 weight, there is little substantial effect of improving thermal stability, and when it exceeds 6 parts by weight, There is a significant decrease in impact strength.

It is preferable to mix the organotin compound and cyanide in the component (B) of the present invention in proportions (the tin compound is X parts by weight and the cyanurate derivative is 7 parts by weight). In other words, the thermal stability is significantly lowered, which is not preferable.

As described above, the present invention provides a flame retardant resin (A) consisting of a mixture of a styrene resin and a vinyl chloride resin, an organotin compound and a cyanurate derivative having a specific ratio and a special structure ( This is a flame-retardant composition characterized by containing 1) as an essential component. The composition of the present invention may contain not only well-known additives such as antioxidants, heat stabilizers, and lubricants, but also UV absorbers, antistatic agents, flame retardants, and flame retardant aids, if necessary. They can also be used together.

In particular, phenolic antioxidants and phosphite stabilizers used in styrene resins, lead stabilizers and epoxy stabilizers blended with vinyl chloride resins, and various fatty acid esters, metal soaps, waxes, etc. A lubricant or the like can be used to make the composition of the present invention more practical as a molding resin. In addition, the composition of the present invention exhibits good flame retardancy due to the effective action of the vinyl chloride resin.
Depending on the degree of flame retardancy required, a small amount of a flame retardant aid such as a halogen flame retardant or an antimony compound may be added.

(Example) The present invention will be illustrated below with specific examples.

Examples 1 to 8 Comparative Examples 1 to 12 As shown in Table 1, ABS resins a, b, and c with different intrinsic viscosities were used as the styrene resins, and polyvinyl chloride d and e with different degrees of polymerization were used as the vinyl chloride resins. , f were used, and the resin component was set to 0. Moreover, an organic tin compound g having a different structure as a tin compound.

h, i, Cyanurate compound J was used as a stabilizer (B).

A mixture of a predetermined amount of resin component (5), stabilizer (B), and lubricant was blended using a mixer, and pelletized using a 40r11/lT'I extruder. A test piece was molded from this pellet using a 5-ounce injection molding machine. After sampling a test piece for each example, the physical properties were evaluated.

Thermal stability was determined by stopping molding with the resin held in the cylinder at 200°C in the molding machine mentioned above, allowing the resin to dwell for 30 minutes and thermally decompose, and then molding the test piece again. The degree of discoloration was used as an index.

Thermal stability was evaluated on a 5-point scale, with the highest score being 5 and the lowest score being 1.

The impact strength was evaluated by Izot impact strength using a 1/4 inch test piece.

Flame retardancy was tested based on UL standards.

The results in Table 1 show that the composition of the present invention has good thermal stability, impact strength,
It can be seen that it is excellent in terms of flame retardancy.

Styrene resin: ABS resin a (η, l=0.2
1b = 0.89 Styrenic resin: ABS [, fat C [η,) = 0.74
Vinyl chloride-based fat: polyvinyl chloride dP=350e
″ = 64O f ″ = 1700 Lubricant: Ethylene bisstearylamide (manufactured by NOF ■)
15 parts organotin compound: ')jfJIy7. <Todo (Kyodo Pharmaceutical Co., Ltd.) g Dioctino μzu Cerate (manufactured by Nitto Kasat) h Divul l Pun Md'lid (Kyodo Pharmaceutical ■
)i Examples 9-11 Comparative Examples 13-15 ABS resin b1 Polyvinyl chloride e1 Tin compound g1 Cyanurate derivative J+ J e+ "+ Antioxidant n
, o were blended with lubricants in the proportions shown in Table 2 in the same manner as in the previous example, and the physical properties were evaluated.

As can be seen from Table 2, the shea slate derivative specified by the present invention is superior to the conventional antioxidants n and o.

Cyanurate derivative antioxidant: BEIT (manufactured by Ketomi Pharmaceutical) nB B M (
(manufactured by Sumitomo Chemical) 0 Table 1 *Addition of 4 parts by weight of 5b2o3 Table 2

Claims (1)

[Scope of Claims] [A] 0 to 85% by weight of a styrene resin whose methyl ethyl ketone soluble portion has an intrinsic viscosity of 0.25 to 0.70 in a dimethyl formamide solution and a degree of polymerization of 400 to 15
For 100 parts by weight of a flame retardant resin consisting of 100 to 15% by weight of vinyl chloride resin, [B] 0.5 to 8 parts by weight of an organotin compound and the following structural formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, at least two of R_1, R_2, R_3 are ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (However, R_4, R_7 is hydrogen or C_1_～_8
(R_5, R_6 are tert-butyl groups or methyl groups), substituents other than (II) are hydrogen or C_1_ to_8 alkyl groups] 0.05 to 6 weight of the cyanurate derivative represented by and the tin compound and the cyanurate derivative [I] in a ratio of 0.01≦y/(x+y)≦0.5 (the tin compound is x parts by weight and the cyanurate derivative is y parts by weight). A flame-retardant resin composition with excellent thermal stability.