JPS6253368A - Flame-retardant abs resin composition - Google Patents

Abstract

PURPOSE:To provide a flame-retardant ABS resin composition having excellent heat-resistance and impact-resistance and containing an ABS graft copolymer, a p-methylstyrene-vinyl cyanide copolymer and a flame retardant. CONSTITUTION:The objective resin composition is composed of (A) an ABS graft copolymer produced by grafting an aromatic vinyl compound [containing <15(wt)% p-methylstyrene unit] and a vinyl cyanide compound (20-40% of the grafted side chain) in the presence of a rubber component, (B) a p- methylstyrene-vinyl cyanide copolymer containing 20-40% vinyl cyanide monomer and (C) <=35pts.(wt.) (based on 100pts. of A+B) of a flame retardant such as chlorinated paraffin. The content of p-methylstyrene unit in the composition is 15-68pts. per 100pts. of the monomer components constituting the composition (i.e. the sum of monomers in the components A and B excluding the rubber component).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention is a material for manufacturing housings for electrical appliances such as radios, television sets, and electric refrigerators, and housings for office equipment such as office computers, microcomputers, and word processors; Other types of products with excellent impact resistance and heat resistance, commonly used for manufacturing molded products.
Flame retardant ABS.

System 0 (relating to fat ML compositions).

U Prior Art 1 Conventionally, it has been known to add a flame retardant to an ABS-based graft copolymer to produce a flame-retardant ABSM resin. However, in this case, the excellent properties that the ABS-based graft copolymer has, namely heat resistance and impact resistance, are
There was a drawback that the addition of refueling agent lowered the temperature.

In addition, when paramethylstyrene is used instead of styrene as a monomer component in the ABS-based graphograft copolymer, the heat resistance is improved, and moreover, the use of a small amount of flame retardant makes the ABS-based resin flame-retardant. There were high hopes for its development, as it might be possible to manufacture it.

However, in reality, the impact resistance of ABS-based graph graft copolymers using para-methylstyrene instead of styrene is low, and therefore, flame-retardant ABS-based resins obtained by adding flame retardants to this copolymer also have low impact resistance. It had the disadvantage of having low impact resistance and being unsatisfactory from a practical standpoint.

``Problems to be Solved by the Invention J'' The present invention solves the problem by adding a flame retardant, which has not been widely used in the past, to produce flame-retardant ABS with excellent heat resistance and impact resistance, which could not be solved by conventional methods. based resin composition,
This is what we are trying to provide.

[Means for Solving the Problems 1] The key point 19 of the present invention is that in a flame-retardant ABS resin composition containing an ABSi graft copolymer, a paramethylstyrene/vinyl cyanide copolymer, and a flame retardant, ,
It is a product obtained by grafting an aromatic vinyl compound and a vinyl cyanide compound to the above-mentioned ABS-based graft polymer component, and the content of the vinyl cyanide monoelectric element forming the graft side chain portion is 20/b40. % by weight, and the ratio of para-methylstyrene monomer units to the monomer heptad units of the aromatic vinyl compound is less than 15% by weight, and the para-methylstyrene/vinyl cyanide copolymer contains vinyl cyanide i The content of forest mass units is 20 to 40% by weight, and A
Flame retardant characterized by containing 15 to 68 parts of paramethylstyrene lj-mer Ilt-position component when the monomer component constituting the BS resin composition is 100 parts by weight. ABS tri fat composition.

The present invention will be explained in detail below.

In the present invention, ABS-based graft copolymer refers to a graft copolymer obtained by graft copolymerizing a vinyl cyanide compound monomer and an aromatic vinyl compound monomer in the presence of a rubber component.

Here, the rubber component refers to a copolymer of butadiene and other copolymerizable monomers, which contain polybutadiene or butanoene in 50 or more stacks.

Monomers that can be copolymerized with butanoene include styrene, α
- aromatic vinyl compounds such as methylstyrene, vinyltoluene (including isomers and mixtures thereof), acrylic acid, methacrylic acid and their alkyl esters such as methyl, ethyl, propyl, n-butyl or i-butyl; Acrylic compounds, acrylonitrile,
Examples include vinyl cyanide compounds such as methacrylonitrile. In addition to the tsene rubber, the rubber components include polyimbrene, trichlorobrene, ethylene-propylene copolymer, and ethylene-propylene-genmo heptamer terpolymer.

ABS-based graft copolymer, one QL used to produce a graft copolymer with the rubber component listed in H.
'! Examples of the f: compound include aromatic vinyl compounds represented by styrene or a-methylstyrene, and vinyl cyanide compounds represented by acrylonitrile and methacrylonitrile. Less than 15% by weight of the aromatic vinyl compound monomer to be grafted to the rubber component, for example,
Other aromatic vinyl compounds such as vinyltoluene, including paramethylstyrene, herodenated styrene and mixtures thereof, acrylic Nl or methacrylic acid or their methyl, ethyl, propyl, ■-butyl or i
- It may be substituted with an acrylic compound such as an alkyl ester such as butyl.

ABS-based graphograft copolymer, vinyl cyanide
It is necessary that the lt-mer unit accounts for 20% or more by weight of the entire monomer grafted onto the rubber component, and is usually contained in a range of 2O-40% by weight.

In addition, when producing an ABS-based graphograft copolymer, if a monoelectric substance such as para-methylstyrene or vinyltoluene is used as a copolymerization monomer instead of styrene or α-methylstyrene, the copolymer It is necessary to set the ratio to 15% or less based on the total amount of styrene and α-methylstyrene in the resin composition, and if it exceeds 15%, the impact resistance of the target resin composition will be impaired. .

The AnSi graft copolymer is a rubbery polymer with 20 and 6
Copolymerized with 0 parts by weight! 1t (preferably 80 to 40 heavy electric parts).

ABS-based graph graft copolymers can be produced by commonly used copolymerization methods, such as emulsion polymerization, bulk polymerization, solution polymerization, or bulk-suspension polymerization. But the rubber component? When producing ABS-based graft comonolymer with high agricultural yield, special consideration must be given to its handling when using the bulk polymerization method or bulk-suspension polymerization method because the viscosity of the solution increases during the first stage of production. Therefore, it is better to use the emulsion polymerization method.

In the present invention, paramethylstyrene/vinyl cyanide copolymer refers to paramethylstyrene and 7-crylonitrile,
It refers to a copolymer with a vinyl cyanide compound such as methacrylonitrile, but it may also be a mixture of methylstyrene with a high para-methylstyrene fi, in which a part of para-methylstyrene is replaced with another methylstyrene. but,
The higher the content of the para-methylstyrene, the better the heat resistance of the ABS resin composition obtained.
It is desirable that the amount of Ii be at least %.

The para-methylstyrene/vinyl cyanide copolymer of the present invention includes para-methylstyrene and vinyl cyanides such as 7-acrylonitrile and methacrylonitrile. 11. In addition to copolymers consisting of mixtures with monomers, copolymers with other lit Fi) bodies that can be copolymerized with these two types of monomers are included. Examples of such other copolymerizable tF-mers include acrylic acid, methacrylic acid, and their ethyl,
Compounds such as alkyl esters such as propyl, n-butyl, and i-butyl are mentioned, and are preferably selected in consideration of not impairing the compatibility of the obtained copolymer with the above-mentioned ABS-based graph graft copolymer. The copolymer may be produced by any commonly used polymerization method, such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization.

In the flame-retardant ABS resin composition according to the present invention, A
BS-based tree-resistant resin composition VJ contains a lit polymer component of 10
1 when 0 weight i parts, paramethylstyrene monomer j
It is necessary to select the lj-position component in the range of 15 to 68 parts by weight. That is, vinyl monomer components such as vinyl cyanide compounds and aromatic vinyl compounds, excluding the ABS-based graph graft copolymer component, and paramethylstyrene.
When the total amount of monoserous components forming the vinyl cyanide copolymer is 100 parts by weight, paramethylstyrene'i
L+? It is necessary that the component at +1j position be in the range of 15"-68 parts by weight. Paramethylstyrene monomer 1
When the charge of the 11th-position component is less than the 15 overlapped part, the obtained A
The flame retardant properties of BS resin compositions are not sufficient, and in order to improve the flame retardance of ABS resin compositions, it is necessary to add a field retardant from Jubei Dori Taden. In addition, if the para-methylstyrene monomer unit component exceeds 80 parts by weight, the reactivity of para-methylstyrene is low, so if it is contained in a large amount, the ABS-based graph graft copolymer para-methylstyrene cyanide. Vinyl copolymers are also not preferred because they are not easy to produce and are economically disadvantageous.

As the flame retardant used as an essential component of the present invention, those normally used as ABS-based O (fat r!i flame retardants) can be used.Specifically, perchloropentanecyclodecane and its modified products, paraffin, hexabromobenzene, tetrabromobisphenol A and its modifying agent, trisnobromopropyl phos7ate, decapromonophenyl ether, hexabromocyclododecane, pentabromochlorocyclohexane, hexachlorocyclopentanoene, octabromnophenyl , chlorinated polyethylene, tricune norphosphate, triethyl phosphate, tris-β-chloroethyl phosphate,
Examples include trischloroethyl phosphate, trisdichloropropyl phosphate, antimony trioxide, tin oxide, aluminum hydroxide, magnesium hydroxide, etc., and one or more of these can be blended in combination.

These flame retardants are the sum of ABS-based graphograft copolymer and para-methylstyrene/vinyl cyanide copolymer @, 1
It is usually blended at a ratio of 35 parts by weight or less to 00 parts by weight. This blending amount can exhibit sufficient flame retardancy even if it is more than -00% less than that of ABS type resin (fat) that does not contain a paramethylstyrene component.

[Effects of the Invention 1 The present invention has the following particularly remarkable effects, so its industrial utility value is extremely large.

(1) Since the flame-retardant ABS resin composition according to the present invention contains a specific amount of para-methylstyrene component, it can be molded to exhibit excellent flame retardancy just by adding a smaller amount of flame retardant than before. You can get the goods.

(2) The flame-retardant ABS resin composition according to the present invention allows molded articles with excellent heat resistance and impact resistance to be obtained.

“Example 4 Next, the present invention will be explained in more detail with reference examples, working examples, and comparative examples.
51゜Reference example <Example of production of Al3S graft conjugate> Stirring ￥ C, without being limited to the following examples.
A 5-1 reaction vessel equipped with a heating and cooling device and a raw material charging device was filled with small particle frame rubber latex (S-F-Ren 10%).
Contains 5BR1 with an average particle size of 0.25μ and a solid content of 23.
9% by weight) 251 o6 and large particle size rubber latex (styrene) Oil'j@, % containing 513R, average particle size 0.65 μmn, solid content 28.6% by weight) 524
．． was charged and the temperature was raised to 80'C.

During the temperature rise, ethylene glycol nometa 9 was added at 60″C.
') Re-) (EGDM) written in 3.0s-reaction m+
, :: added. When the internal temperature reaches 80℃, azobisisobutyronitrile (^I[lN) '3
, 6° Styrene 504 Iacrylic and nitrile 216 g were started to be added (this time was defined as the start of polymerization, α), and the mixture was continuously charged into the reaction vessel over a period of 2 hours from the start of polymerization.

Further, from the start of the polymerization, 120 g of potassium persulfate 2.48 deionized water as a water-soluble polymerization initiator was continuously charged into the reaction vessel over a period of 2 hours from the start of the polymerization.

During the course of the polymerization, 30 minutes after the start of the polymerization, 10% potassium hydroxide (2)8 g and Turbirun (7.2 g) were added.

Furthermore, 6.8 g of higher fatty acid sodium and 71 g of deionized water were added 1 hour and 1 hour and 30 minutes after the start of polymerization, respectively.

After the completion of charging the peach/mer mixture solution described in I-, the reaction was continued for an additional 30 minutes, and then the temperature inside the reaction vessel was cooled to terminate the reaction.

Add an antioxidant to the above graft polymer latex,
It was added to a solution of magnesium sulfate heated to 90° C. or higher with stirring, and solidified. After that, wash with water and dry to obtain (1) fat powder.This is then combined with the ABS graph F and vehicle assembly.

<Production examples of A13S graft copolymers B to D>-
■-] In the production example for the ABS graft copolymer,
Instead of styrene used as a monomer for graft copolymerization, a mixture of styrene and para-methylstyrene with a ratio of styrene/para-methylstyrene = 90/10 was used, and the other conditions were exactly the same. , this is AI
It is referred to as ES copolymer B.

AB, resin powder obtained in the same manner using a pure 3 compound of styrene/paramethylstyrene = 80/20.
0(
The fat powder is made into an ABS graft copolymer.

Production example of styrene-acrylonitrile copolymer E〉 120 kg of deionized water was placed in a glass-lined jacketed reactor equipped with a swept-blade stirrer with an internal volume of 450 mm.
61.2 kg of styrene was mixed in a separate tank after removing the air in the water by heating and purging while stirring.
1 acrylonitrile) +7 To Le 39.6, add 480 g of turvilcin and 42 g of not-t-butyl peroxide, and! Raise the temperature from 110"C to 124°C in 40 minutes. Hold at 124°C for 40 minutes, and add 36g of acrylic acid and 2-ethylhexyl acrylate copolymer as a suspension stabilizer.
A solution of No. 1 dissolved in water and a solution of V2 G Og of sodium carbonate dissolved in No. 31 water were added. Then, raise the reactor internal temperature to 145°C over 3 hours. Meanwhile 1
While continuously adding 9.2 kg of styrene to the reactor,
The reaction continued. Thereafter, the temperature was maintained at 145° C. for 30 minutes, and unreacted monomers were removed by steam distillation over a period of 2 hours.

The resulting slurry liquid was washed with alkaline water, then dehydrated and dried to obtain a bead-like resin. This will be referred to as copolymer E.

Production of Copolymer F-LiH> J In the production example of binary styrene-acrylonitrile copolymer E, styrene and paramethylstyrene of styrene/paramethylstyrene = 70730 were used instead of styrene used in the copolymerization. Using a mixture of
The copolymerization reaction was carried out in exactly the same manner as in Example 1-. The obtained resin will be referred to as copolymer F.

In addition, a resin obtained in the same manner using a mixture of styrene/para-methylstyrene = GO/40 was used as copolymer G, and a resin was obtained in the same manner using the total amount of para-methylstyrene (without fat). It is referred to as copolymer 1-1.

To the ABS-based graft copolymer A obtained as follows:
D, and the charge content of each component in copolymer E −=, H,
The results are shown in Table 1 and Table 2.

151 Table 2 Examples and Comparative Examples The ABS-based graph graft copolymers and copolymers obtained in Reference Example 1 were weighed in the proportions shown in Table 3, and mixed in a small Banbury mixer. The mixture was kneaded to obtain a resin pellet having the rubber component content and paramethylstyrene content listed in the table.

For 100 parts by weight of this paste, 100% is a flame retardant consisting of 25 parts by weight of tetrabromobisphenol A and 26 parts by weight of anti-dioxide, and 90% is obtained by reducing this amount by 10%. They were blended as shown in Table 3 to obtain a flame-retardant ABS resin composition.

A test piece was made from the obtained composition by injection molding, and its physical properties were evaluated by the following method. The results are shown in Table 3.

Izotsu impact strength: According to JIS K7110 (k
g-011170m). The thickness of the test piece was measured with a notch of 3.2 mm.

Vicat needle temperature: JIS K7206 Niji C)
Compliant.

MFI (g/105t): JIS K72101m
Compliant. Measurements were made at a load of 5 kg and a temperature of 200°C.

Flame retardancy: U L -94f, qI constant
3 From Table 3, the following is clear.

(1) The compositions according to the present invention (Examples 1 to 3) exhibit excellent flame retardancy by adding a small amount of flame retardant, and also have excellent impact resistance and heat resistance.

(2) On the other hand, Comparative Examples 1 to 5, which do not meet the requirements stipulated in the claims of the present invention, can be satisfied by adding a small amount of flame retardant. ! It does not provide good flammability, and when added in large amounts, it has the disadvantage of poor heat resistance.

Claims (1)

[Claims] (1) Flame retardant A containing ABS-based graft copolymer, para-methylstyrene/vinyl cyanide copolymer and flame retardant
In the BS resin composition, the ABS graft polymer is a rubber component grafted with an aromatic vinyl compound and a vinyl cyanide compound, and the vinyl cyanide monomer unit constituting the graft side chain portion is Concentration is 20-4
0% by weight, and the ratio of paramethylstyrene monomer units to the aromatic vinyl compound monomer units is less than 15% by weight, and the paramethylstyrene/vinyl cyanide copolymer is composed of vinyl cyanide monomer units. The content of mer units is 20 to 4
0% by weight, and when the monomer component constituting the ABS resin composition is 100 parts by weight, the paramethylstyrene monomer unit component is contained in the range of 15 to 68 parts by weight. A flame-retardant ABS resin composition.