JPH0468047A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To prepare a resin compsn. excellent in flame retardancy, resistance to light and heat, and moldability by adding a flame retardant contg. a specific halogen compd. as an essential component to a mixture of two specific arom. vinyl compd./vinyl cyanate compd. copolymers. CONSTITUTION:70-30wt.% monomer mixture of an arom. vinyl compd. with 10-30wt.% vinyl cyanide compd. is polymerized in the presence of 30-70wt.% rubberlike polymer to give a graft copolymer having a graft ratio of 30-130wt.% and an intrinsic viscosity of methyl ethyl ketone soluble of 0.3-0.7dl/g; 10-70wt.% the graft copolymer is mixed with 90-30wt.% arom. vinyl compd./vinyl cyanide compd. copolymer having an intrinsic viscosity of 0.4-0.8dl/g and contg. 18-38wt.% vinyl cyanide compd.; and 100pts.wt. the resulting mixture is compound with 1-30pts.wt. halogen compd. of the formula, 0-20pts.wt. halogenated bisphenol compd., 0-10pts.wt. halogenated polyolefin, and 0-15pts.wt. antimony compd. to give a flame-retardant resin compsn.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a graft copolymer obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer, and a specific aromatic The main components are a resin composition consisting of a vinyl compound-vinyl cyanide compound copolymer and a specific flame retardant, and have excellent light resistance, heat resistance, practical moldability, impact resistance, and flame retardancy. The present invention relates to a flame retardant resin composition.

[Conventional technology]

Because ABS resin has excellent mechanical properties, electrical insulation, moldability, and molded appearance, it is widely used in various industrial products such as automobile parts, electrical equipment parts, and construction materials. has been done.

However, since ABS resin is easily flammable, in recent years,
Depending on its use, it is subject to various laws and regulations regarding flammability from the standpoint of safety, and for this reason flame-retardant ABS resins have been developed and commercially available.

As described above, flame-retardant ABS resin has come to be widely used as a molding material for various industrial products, and in addition to being flame-retardant, some parts are also required to have heat resistance to the extent that they do not deform even at relatively high temperatures. Moreover, when used as exterior materials for these devices, fading due to direct sunlight from windows or light from indoor fluorescent lights has recently become a particular problem, and it is essential that materials have excellent light resistance. It is a condition.

Furthermore, when these materials are used as exterior materials, most of them are large parts, and excellent practical moldability and impact resistance are required.

For this reason, flame-retardant ABS resins are required to have multifunctional properties, including not only flame retardancy but also excellent light resistance, heat resistance, practical moldability, and impact resistance.

Conventionally, in order to provide the above performance, it has been common practice to select the type of flame retardant, but a multifunctional flame retardant ABS resin that also has the above performance has not been obtained.

For example, attempts have been made to make ABS resin flame retardant by adding halogenated diphenyl ether to it, but the use of such flame retardants improves flame retardancy and heat resistance, but on the other hand, it reduces light resistance. A new problem arises, such as an extreme drop in energy consumption.

In addition, when ABSi (JIW) is blended with halogenated bisphenol type polycarbonate oligomer as a flame retardant, heat resistance and light resistance improve, but fluidity decreases and impact resistance due to poor dispersibility of the compounding agent increases. There were problems such as a decrease in properties, and it could not be used as an industrially practical material.

Furthermore, a composition in which ABS resin is blended with a halogenated bisphenol-type polycarbonate oligomer and a tetrahalogenated bisphenol compound in a specific ratio has been proposed (Japanese Patent Publication No. 60-54347); The purpose is to prevent pluming of bisphenol compounds and improve heat resistance, and ABS resin compositions containing only these ingredients have high light resistance and heat resistance, and are practical. This does not result in an ABS resin composition having moldability and impact resistance, and the material has not yet been satisfactory in fields that require such performance.

[Problem to be solved by the invention]

The present invention was made against the background of the above-mentioned prior art, and an object of the present invention is to provide a flame-retardant resin composition that is not only flame-retardant but also has excellent light resistance, heat resistance, practical moldability, and impact resistance. shall be.

[Means for Solving the Problems] The present invention provides the following components: (A) component 10 to 70% by weight and (B) component 90 to 30% by weight [However, (A) +
(B)=100% by weight), 1 to 30 parts by weight of component (C), and 0 parts by weight of component (D).
~20 parts by weight, 0 to 10 parts by weight of component (E) and (F)
The present invention provides a flame-retardant resin composition (hereinafter sometimes referred to as "first composition") characterized by containing 0 to 15 parts by weight of the component.

(A) 70 to 30% by weight of a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of 30 to 70% by weight of a rubbery polymer (however, a monomer mixture containing a rubbery polymer and a monomer mixture of 30 to 70% by weight) 100% by weight), the graft ratio is 30 to 130% by weight, and the intrinsic viscosity of the methyl ethyl ketone soluble portion [η] (methyl ethyl ketone, 30°C) is 0.
A graft copolymer having a content of 30 to 0.7 d1/g and a (co)polymerized cyanvinyl compound of 10 to 30% by weight.

(B) Intrinsic viscosity [η] obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound (methyl: L
L//7-) 7.30°c) 0.4-0.8a/g
, the (co)polymerized vinyl cyanide compound content is 1
8-38% by weight copolymer.

(C) - Noshiro (I) ・ ・ ・ ・ ・ ・ ・ ・ ・ (1) [In the formula, R' and R2 are the same or different, (where Y is a bromine atom or a chlorine atom, and j is 0 X is a bromine atom or chlorine atom, i is an integer of 1 to 4, m is an integer of 0 to 10), and has a softening point of 112 to 170°C 1 weight average molecule 500
~6,000, a halogen-containing compound having a bromine atom and/or chlorine atom content of 45 to 60% by weight.

(D) Halogenated bisphenol compound [However, (
C) excluding ingredients].

(E) Halogenated polyolefin.

(F) Antimony compound.

Further, the present invention provides the above-mentioned (A) component 10 to 50% by weight, (
B) component 10 to 80% by weight and the following (C,) component 10
~80% by weight [However, (A) + (B) + (G) −
100 parts by weight of the resin composition, 1 to 30 parts by weight of the component (C) and 0 to 1 part of the component (E)
A flame-retardant resin composition containing 0 parts by weight and 0 to 15 parts by weight of component (F) (hereinafter referred to as "second composition",
~2Mi compositions are sometimes collectively referred to as "flame-retardant resin compositions").

(G) Polycarbonate.

Hereinafter, first, (A) used in the first and second compositions of the present invention.
Component (G) will be explained, and then the first and second compositions will be explained in detail.

10 Lico-deficient component (A) is obtained by polymerizing 70 to 30% by weight of a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of 30 to 70% by weight of a rubbery polymer. Grafting rate: 30 to 130% by weight, intrinsic viscosity of methyl ethyl ketone soluble fraction [η] (methyl ethyl ketone, 30
℃) is 0. 3 to 0.7 d1/g and a (co)polymerized cyanvinyl compound content of 10 to 30% by weight.

Examples of the rubbery polymer used in component (A) include diene rubbery polymers such as polybutadiene, butadiene-styrene random copolymers, polyisoprene, styrene-butadiene block copolymers, etc. Hydrogenated substances, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, acrylic rubbers mainly composed of acrylic esters, isobutylene-isoprene copolymers, polyurethane rubbers, etc. can be used, among others. It is preferable to use diene-based rubbery polymers such as polybutadiene and butadiene-styrene copolymer from the viewpoint of easily obtaining the graft ratio specified in this application, and from the viewpoint of improving light resistance, ethylene- Use ethylene-α-olefin rubbery copolymers such as propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, and ethylene-butene copolymer, or hydrogenated product of diene-based rubbery polymer. It is preferable.

Examples of the aromatic vinyl compound constituting the monomer mixture grafted in the presence of the rubbery polymer include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, m-chlorostyrene, p- Examples include halogen-substituted styrene such as chlorostyrene, and styrene and α-methylstyrene are preferred.

Further, examples of the vinyl cyanide compound constituting the monomer mixture include acrylonitrile, methacrylaterile, and the like.

Note that the ratio (weight ratio) of the aromatic vinyl compound and the vinyl cyanide compound in the monomer mixture is usually 50 to 901.
It is about 50 to 10.

In addition to the above-mentioned monomers, other copolymerizable monomers can be used in combination in the monomer mixture, if necessary. Other monomers include acrylic ester,
Examples include methacrylic esters, such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Other monomers include acrylic acid, methacrylic acid, non-conjugated divinyl compounds represented by divinylbenzene, and one type of polyvalent (meth)acrylate compounds such as trimethylolpropane trimethacrylate and trimethylolpropane triacrylate. Alternatively, two or more types can be used as appropriate within a range that does not affect the polymerization process or the physical properties of the composition of the present invention. The amount of these other monomers used is about 50% by weight or less in the monomer mixture.

The graft copolymer (A) is a rubbery polymer 30 to 7.
70-30% by weight, preferably 70-65% by weight of said monomer mixture in the presence of 0% by weight, preferably 30-65% by weight.
Obtained by polymerizing 35% by weight, with a graft ratio of 30 to 130
% by weight, preferably 35 to 120% by weight, intrinsic viscosity of methyl ethyl ketone soluble content is 0.3 to 0.1 a/g, preferably 0.35 to 0.6 d/g, vinyl cyanide compound content is 10 to 1. 30% by weight, preferably 12-28% by weight.

Here, if the amount of the rubber-like polymer constituting component (A) is less than 30% by weight, a composition having excellent impact resistance, heat resistance, and practical moldability cannot be obtained; If it exceeds, the dispersibility into components (B) and (G) will deteriorate, and impact resistance and flame retardancy will decrease.

Furthermore, if the grafting rate of the graft copolymer (A) is less than 30% by weight, the impact resistance will decrease, while if it exceeds 120% by weight, the surface gloss of the molded product will tend to decrease and the heat resistance will decrease. Yes, it's not good.

Furthermore, if the intrinsic viscosity of the methyl ethyl ketone soluble portion of the (A) graft copolymer is less than 0.3 dl/g, the impact resistance will decrease, while if it exceeds 0.7 dl/g, the fluidity will deteriorate and molding will be difficult. becomes.

Furthermore, if the vinyl cyanide compound content in the graft copolymer (A) is less than 10% by weight, the impact resistance will decrease,
On the other hand, if it exceeds 30% by weight, thermal stability during molding will decrease.

The flame-retardant resin composition of the present invention has a specific ( B) By using the copolymer together,
The dispersibility and compatibility of the halogen-containing compound (C), which is a flame retardant, is further improved, and as a result, the performance of the halogen-containing compound is fully exhibited, and it has excellent light resistance and flame retardancy, and -
It becomes possible to prevent performance deterioration such as heat resistance, impact resistance, and practical moldability, which are generally considered to be deteriorated by the addition of flame retardants. Component (A) and/or (B) outside the above range
) component, the object of the present invention cannot be achieved.

(A) As a method for producing the graft copolymer, the monomer mixture may be polymerized in the presence of the rubbery polymer by known emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or the like.

At this time, the intrinsic viscosity of the methyl ethyl ketone soluble component can be adjusted by appropriately selecting the type and amount of the molecular weight regulator during polymerization. In addition, regarding the graft rate,
It is possible to adjust the molecular weight by appropriately selecting the type and amount of the molecular weight regulator, as well as the time for adding the monomer component (monomer mixture) to the polymerization system.

Component (B) is obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound, and has an intrinsic viscosity [η] (methyl ethyl ketone, 30°C) of 0.4 to 0.8 a/g, preferably is 0.4 to 0.75 a/g, and the content of (co)polymerized vinyl cyanide compound is 18 to 38% by weight, preferably 20 to 35% by weight.

The types and amounts of the aromatic vinyl compound, vinyl cyanide compound, and other copolymerizable monomers used as necessary for component (B) are the same as for component (A). .

Furthermore, the reasoning for the numerical ranges of the intrinsic viscosity and cyanvinyl compound content in component (B) is the same as that described in component (A).

Furthermore, the method for producing component (B) and the method for adjusting the intrinsic viscosity are almost the same as those shown for component (A).

” Danri ingredient (C) Ingredient is - Noshiro (I) is a halogen-containing compound which is 47-58% by weight.

As component (C), preferably the general formula (1)% formula% (
1) [In the formula, R1 and R2 are the same or different and are a group selected from (here, Y is a bromine atom or a chlorine atom, and j is an integer of 0 to 5), and X is a bromine atom or chlorine atom, i is an integer of 1 to 4, m is 0 to 10], and has a softening point of 112 to 170°C, preferably 112
~150°C 1 weight average molecular weight 500 to 6,000, preferably 1.200 to 4,000, bromine atom and/or chlorine atom content 45 to 60% by weight, preferably also X
and Y is a bromine atom.

For a general explanation of the halogen-containing compound (C) represented by -Noshiro (1), see, for example, JP-A-61-241.
This method is described in detail in, for example, Japanese Patent No. 322.

Component (C) used in the present invention has been specifically selected from known halogen-containing compounds for its softening point, weight average molecular weight, bromine atom and/or chlorine atom content, and has excellent heat resistance and practical moldability. , a flame-retardant resin composition with excellent impact resistance can be obtained.

If the softening point of component (C) is less than 112°C, the desired heat resistance cannot be obtained, while if it exceeds 170°C, the impact strength will decrease.

Furthermore, if the weight average molecular weight of component (C) is less than 500,
Thermal stability during molding is poor, and if it exceeds 6,000, the dispersibility into the resin component will be poor and the impact strength will decrease.

Furthermore, if the bromine atom and/or chlorine atom content of component (C) is less than 45% by weight, it is necessary to increase the amount added in order to obtain the desired flame retardancy, which inevitably reduces impact strength. On the other hand, if it exceeds 60% by weight, the thermal stability and light resistance during molding will decrease.

The ΣL component (D) is a halogenated bisphenol compound [excluding component (C)], such as tetrabromobisphenol A, tetrabromobisphenol S, etc., and preferably tetrabromobisphenol A.
It is.

Using component (D), without sacrificing flame retardancy,
Practical moldability and impact resistance can be further improved.

The component (E) is a halogenated polyolefin, such as chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, and chlorinated ethylene propylene copolymer. Among these are chlorinated polyethylene,
Chlorinated polyolefins such as chlorinated polypropylene, especially chlorinated polyethylene are preferred. The halogen content in these halogenated polyolefins is preferably 20 to 50% by weight, particularly 25 to 45% by weight.

By using component (E), flame retardance, light resistance, and impact resistance can be improved.

The component (F) is an antimony compound, and examples thereof include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, and antimony phosphate. Preferably, antimony trioxide and sodium antimonate are used. be.

When component (F) is used, much better flame retardancy can be obtained.

1S]" As the polycarbonate of the opening (G) component, for example, aromatic polycarbonate, aliphatic polycarbonate, aliphatic polycarbonate, etc.
Examples include aromatic polycarbonate. (
G) Polycarbonate is 2,2-bis(4-
It is a (co)polymer consisting of bisphenols such as oxyphenyl)alkane, bis(4-oxyphenyl)ether, bis(4-oxyphenyl)sulfide or sulfoxide, and can be substituted with halogen depending on the purpose. It may also be a (co)polymer using bisphenols. (C) The type of polycarbonate and its manufacturing method are detailed in "Polycarbonate Resin" published by Nikkan Kogyo Shimbun (September 30, 1962).

This component (G) can improve the heat resistance and impact resistance of the resulting composition.

Next, the first and second compositions of the present invention will be explained.

Eaves] Yuuki first composition is (A) component/(B) component -10 to 70/
90-30% by weight, preferably 20-60/80-40
(C
) component 1 to 30 parts by weight, preferably 3 to 25 parts by weight, (
D) component 0 to 20 parts by weight, preferably 0 to 15 parts by weight,
Particularly preferably 0. 5-15 parts by weight, component (E) 0-
10 parts by weight, preferably 0 to 8 parts by weight, particularly preferably 0.5 to 8 parts by weight, 0 to 15 parts by weight of component (F), preferably 0 to 10 parts by weight, particularly preferably 0.5 to 10 parts by weight A flame retardant resin composition containing

Regarding the component (D) and the component (E), preferably at least one component selected from the component (D) and the component (E) may be used in an amount of 0.5 to 10 parts by weight.

Here, component (A) (graft copolymer) and (B
) In the resin composition consisting of component (copolymer), component (A) is less than 10% by weight [that is, component (B) is 90% by weight
], the impact resistance and flame retardancy will decrease,
On the other hand, component (A) exceeds 70% by weight [i.e., (B
) component is less than 30% by weight], this is not preferable because the modulus, hardness, and flame retardance of the resulting flame-retardant resin composition decrease. When components (A) to (B) are within the above composition range, the dispersibility and compatibility of component (C) will be good.

Furthermore, if the amount of component (C) (halogen-containing compound) is less than 1 part by weight based on 100 parts by weight of the resin composition consisting of components (A) and (B), flame retardancy and heat resistance will decrease; On the other hand, if it exceeds 30 parts by weight, practical moldability and impact resistance will deteriorate, which is not preferable.

Furthermore, if component (D) (halogenated bisphenol compound) exceeds 20 parts by weight based on 100 parts by weight of the resin composition consisting of components (A) and (B), light resistance and heat resistance will decrease. So I don't like it.

Furthermore, component (E) (halogenated polyolefin)
Resin composition 100 consisting of component (A) and component (B)
If the amount exceeds 10 parts by weight, thermal stability and heat resistance will deteriorate, which is not preferable.

Furthermore, component (F) (antimony compound) is (-A)
If the amount exceeds 15 parts by weight based on 100 parts by weight of the resin composition consisting of component (B) and component (B), impact resistance decreases, which is not preferable.

The second composition is composed of (A) component/(B) component/(G) component.
A resin consisting of 10-50/10-80/10-80% by weight, preferably 10-40/10-70/20-70% by weight [however, (A) + (B) + (c) 100% by weight] 1 to 30 parts of component (C) per 100 parts by weight of the composition
Parts by weight, preferably 3 to 25 parts by weight, component (E) 0 to 1
0 parts by weight, preferably 0 to 8 parts by weight, particularly preferably 0
．． 5 to 8 parts by weight, 0 to 15 parts by weight of component (F), preferably 0 to 10 parts by weight, particularly preferably 0. It is a flame retardant resin composition containing 5 to 10 parts by weight.

Regarding the component (D) and the component (E), preferably at least one component selected from the component (D) and the component (E) may be used in an amount of 0.5 to 10 parts by weight.

Here, in the resin composition consisting of component (A) (graft copolymer), component (B) (copolymer) and component (G) (polycarbonate), if component (A) is less than 10% by weight, , impact resistance and flame retardancy decreased, while 50% by weight
Exceeding this is not preferable because the modulus, hardness and flame retardancy decrease.

In a resin composition consisting of components (A), (B) and (G), if component (B) is less than 10% by weight, the modulus, hardness and flame retardancy will decrease, while if it exceeds 80% by weight, the This is not preferred because impact resistance and flame retardancy are reduced.

In a resin composition consisting of components (A), (B) and (G), if component (G) is less than 10% by weight, heat resistance and impact resistance will decrease, while if it exceeds 80% by weight, practical molding will occur. This is not preferable because it reduces performance.

In addition, regarding the usage ratios of component (C) (halogen-containing compound), component (E) (halogenated polyolefin), and component (F) (antimony compound) in 2) II composition, and the reason thereof, please refer to the above-mentioned section. The contents are the same as those described for 1 composition.

A stabilizer, a lubricant, and the like can be added to the flame-retardant resin composition (first and second silk compositions) of the present invention described above. That is, when a small amount of phosphites, epoxy compounds, organic tin compounds, stearic acid, etc. are added as stabilizers, the thermal stability during molding is further improved. Addition of a small amount of hydrogenated castor oil, low molecular weight polyethylene, silicone oil, etc. as a lubricant improves moldability.

Also, the present invention! 1. The flammable resin composition contains fibrous substances such as glass fiber, potassium titanate fiber, ceramic fiber, metal filler, talc, calcium carbonate, titanium oxide, barium sulfate, etc. to improve heat resistance and rigidity. Fillers such as calcium oxide, aluminum oxide, mica, glass peas, glass flakes, etc. can also be added.

Among these fillers, the heat-resistant fiber and rigidity of the fibrous substance improve as the amount added increases, but the moldability decreases. The amount added to obtain practical moldability is determined according to the first aspect of the present invention.
2 to 70 parts by weight, preferably 5 to 60 parts by weight, based on 100 parts by weight of component (A) in the composition, and 100 parts by weight in total of components (A) and (G) in the second composition. It is.

The flame-retardant resin composition of the present invention also contains ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and succinate compounds, antioxidants such as hindered phenol compounds, dispersants, blowing agents, and colorants. Flame retardants other than those used in the present invention can also be added as additives.

Flame-retardant resin composition of the present invention (1st to 2nd & Il compositions) 10
By adding preferably 0.05 to 5 parts by weight, more preferably 0.1 to 2 parts by weight of a phosphite compound to 0 parts by weight, the molded product will have little discoloration when subjected to high temperature retention molding, and A flame-retardant resin composition with excellent heat resistance and less generation of silver can be obtained.

Examples of the phosphite compounds include triphenyl phosphite, tris(nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris(2,4-di-t - Phosphite esters with aromatic groups or aliphatic groups such as butylphenyl) phosphite; Phosphate ester, tetraphenyl dipropylene glycol diphosphite, distearyl pentaerythritol diphosphite, ditridecyl pentaerythritol diphosphite, dinonylphenyl pentaerythritol diphosphite, tetra(tridecyl)-4,4'-isopropylene Diphosphites such as lydendiphenyl diphosphite and bis(2,4 diphosphite)
-butylphenyl) pentaerythritol diphosphite and the like. Preferred phosphite compounds are distearyl pentaerythritol diphosphite and bis(2,4-di-E-butylphenyl) pentaerythritol diphosphite.

The flame-retardant resin compositions (first and second compositions) of the present invention can be produced without any changes from known methods for producing resin compositions, except for blending the above-mentioned ingredients.

That is, it can be produced by mixing the above-mentioned components and other necessary additives using a commonly used Henschel type mixer, tumbler, etc., and melt-mixing using a heated roll, extruder, Banbury mixer, etc. It is also possible to mix by a so-called masterbatch method, in which a masterbatch is prepared in advance in which the above-mentioned -part components are blended at a high concentration, and this is blended with the unblended components.

In the present invention, it is defined as a resin composition consisting of components (A) and (B) in the first Mi composition, or a resin composition consisting of components (A), (B) and (G) in the second composition. However, it goes without saying that these components may be mixed simultaneously to form a resin composition, or each of these components may be separately mixed with other components to prepare the resin composition.

The flame-retardant resin composition of the present invention can be further processed by extrusion molding.
Molded products are made by injection molding, compression molding, etc. In addition to mechanical properties, these molded products also have flame retardancy,
It has excellent heat resistance, light resistance, practical moldability, and impact resistance, and has a good surface appearance, making it extremely useful as mechanical parts, electrical parts, and automobile parts.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. Note that parts and percentages in the examples are each based on weight.

In addition, the methods for measuring the graft ratio and intrinsic viscosity and the evaluation of the physical properties of the obtained composition are as follows.

■Measurement of graft ratio A certain amount of graft copolymer ffi (X) was put into acetone and shaken for 2 hours in a shaker to elute the ungrafted (co)polymer component in the graft copolymer into acetone. let Next, the solution (eluate) is centrifuged at 2.30 rpm for 30 minutes using a centrifuge to obtain insoluble matter. Next, the insoluble matter was removed using a vacuum dryer at 120%
It was dried at ℃ for 1 hour to obtain an insoluble content (Y), which was calculated using the following formula.

Graft rate (%) = ■Dissolve the intrinsic viscosity (graft) copolymer in methyl ethyl ketone,
It was measured using a Uherode viscometer under a temperature condition of 30''C.

■Flammability test (flammability) 1 for UL94! Based on

Test piece; 1/8"XI/2" x 5" and 1/16"x
l/2" × 5" ■Impact test (impact resistance) In order to evaluate practical impact resistance, a saucer (30mmφ)
1 with a conical tip on a 2.4 mm thick plate placed on top
A 50cm striking rod with a diameter of 2.7mm and a load of 10.56kg
The falling weight impact strength was measured by dropping it from a height of .

■Practical moldability (fluidity) In order to evaluate practical processability, we used a spiral mold (thickness 2mm x 20mu+, gage) 2Xb and a 5oz injection molding machine at a molding temperature of 220°C and an injection pressure of 840 kg/c.
The flow length (cm) when molded under +fI conditions was determined.

■Heat resistance Compliant with ASTM D648.

Test piece: 1/2″ x 1/2″ x 5″ Load: 18.6 kg/cJ Light resistance test 100 using a xenon weather-o-meter
Color difference after time (black panel temperature 63℃ 1 no rain) (
ΔE) was calculated using the following formula.

8E-' (t, o -t,) f + (ao-a)!
+ bo -b) La, ao, bo; Brightness, redness, yellowness of the test piece before the 1-light test L, a, b; Brightness, redness, yellowness of the test piece after the light fastness test The 1-light test is , ΔE is smaller, the better it is determined.

Reference Example (Preparation of Each Component) Boots of the Ox 11 In the presence of polybutadiene latex, polymerization was carried out by emulsion polymerization using styrene, acrylonitrile, and polymerization chemicals to obtain the graft copolymer shown in Table 1. Ta.

The copolymers shown in Table 2 were obtained by bulk polymerization using styrene, acrylonitrile, and polymerization chemicals manufactured by Akira Kyori.

Enter the name of Table 1 and Table 2. 11 C-1; The following compound obtained by heating tetrabromobisphenol A diglycidyl ether (epoxy equivalent: 372) and tetrabromobisphenol A.

Compound.

Softening point: 118°C Weight average molecular weight: Approx. 1,700 Bromine content: 50% C-2: Tetrabromobisphenol A diglycidyl ether (epoxy equivalent: 372), tetrabromobisphenol A, and tribromobisphenol are heated The following softening point obtained by the reaction: 140°C Weight average molecular weight: Approximately 3,000 Bromine content: 5p% C-3; As a halogen-containing compound outside the scope of the present invention,
The halogenated bisphenol type polycarbonate oligomer shown below was used.

11 grilled crabs (D) As a component, tetrabromobisphenol A
(TBA) was used.

” As the component (E) manufactured by Danri Bobunko Dara, G235 (chlorine content 35%) manufactured by Daiso E-Ko was used.

1 ← Elf commandment jヅυran made Antimony trioxide was used as component (F).

-Taflon FN2, manufactured by Idemitsu Petrochemical ■, is used as the mouth sealant (G) component
200 (weight average molecular weight 23,000) was used.

Examples 1 to 12, Comparative Examples 1 to 5 The formulations shown in Table 3 were mixed using a Henschel mixer, and then mixed using a 50 mmφ extruder.
Pellets were prepared by melt-kneading at 00 to 230°C.

Using this pellet, various physical properties were evaluated. The results are also shown in Table 3.

As is clear from Table 3, Examples 1 to 12 are flame-retardant resin compositions of the present invention, and the objects of the present invention were obtained.

In Examples 11 and 12, the phosphite compound shown in Table 3 was added to the composition of Example 1, and after staying in the cylinder of an injection molding machine at 260°C for 10 minutes,
These are the results of evaluating the molded test piece. Compared to the composition of Example 1 molded under the same conditions, there was less discoloration and generation of silver, and the heat resistance was further improved.

On the other hand, Comparative Example 1 uses only component (A) without using component (B) as a resin composition, and the composition of component (A) is different from components (A) to (B) of Example 1. Although it is similar to the resin composition of Example 1 and has the same component (C), the dispersibility and compatibility of component (C) with the resin composition are insufficient, so the flame retardancy is lower than that of Example 1. poor in properties, impact resistance, practical moldability (fluidity), heat resistance, and light resistance.

Comparative Example 2 is a composition using a halogenated bisphenol type polycarbonate oligomer in place of component (C) of the present invention, and as compared to Example 1, good practical moldability was not obtained.

In Comparative Example 3, the ratio of component (A) exceeds the range of the present invention,
This is an example in which the component (B) is below the range, and the results are similar to those in Comparative Example 1.

Comparative Example 4 is an example in which the component (G) (polycarbonate) was used, but the component (A) was outside the scope of the present invention, and the dispersibility and compatibility of the resin composition were still insufficient. , inferior in flame retardancy, impact resistance, fluidity, heat resistance, and light resistance compared to Example 7.

Comparative Example 5 is an example outside the scope of the present invention in which component (B) is not used in Example 9, and the flame retardance and impact resistance are inferior.

(The following is a blank space) [Effects of the Invention] The present invention provides a method for improving the resin composition of the flame retardant by blending a specific flame retardant into a resin composition containing a specific graft copolymer and a specific copolymer. The dispersibility and compatibility in materials are greatly improved, the disadvantage of deterioration of physical properties that conventionally occurs due to the addition of flame retardants can be eliminated, and the performance of flame retardants can be fully exhibited. As a result, the flame-retardant resin composition of the present invention has extremely excellent light resistance, heat resistance, practical moldability, and flame retardancy.

Patent applicant: Japan Synthetic Rubber Co., Ltd. Agent: Patent Attorney Takashi Shirai

Claims (2)

[Claims] (1) 10 to 70% by weight of component (A) and 90 to 30% by weight of component (B) shown below [however, (A) + (B)
= 100% by weight], 1 to 30 parts by weight of component (C) and 0 to 20 parts by weight of component (D).
Parts by weight, 0 to 10 parts by weight of component (E) and 0 parts of component (F)
A flame-retardant resin composition characterized by containing ~15 parts by weight. (A) 70 to 30% by weight of a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of 30 to 70% by weight of a rubbery polymer (where rubbery polymer + monomer mixture = 100% by weight), the graft ratio is 30 to 130% by weight, and the intrinsic viscosity [η] of the methyl ethyl ketone soluble portion is 0 (methyl ethyl ketone, 30°C).
．． 30 to 0.7 dl/g and a (co)polymerized cyanvinyl compound content of 10 to 30% by weight. (B) Intrinsic viscosity [η] (methyl ethyl ketone, 30°C) 0.4 to 0.8 dl/g, (co)polymerized vinyl cyanide obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound A copolymer having a compound content of 18 to 38% by weight. (C) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・・・・・・・・・・(I) [In the formula, R^1 and R ^2 are the same or different, -
H, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, Y is a bromine atom or a chlorine atom, and j is 0 to 5.
X is a bromine atom or chlorine atom; A halogen-containing compound having an average molecular weight of 500 to 6,000 and a bromine atom and/or chlorine atom content of 45 to 60% by weight. (D) Halogenated bisphenol compound [However, (
C) excluding ingredients]. (E) Halogenated polyolefin. (F) Antimony compound. (2) 10 to 50% by weight of component (A) according to claim 1;
(B) component 10 to 80% by weight and the following (G) component 10
~80% by weight [However, (A) + (B) + (G) = 10
0% by weight] for 100 parts by weight of the resin composition,
The flame-retardant resin composition according to claim 1, comprising 1 to 30 parts by weight of component (C), 0 to 10 parts by weight of component (E), and 0 to 15 parts by weight of component (F). (G) Polycarbonate.