JPS5835222B2 - Nannenseinos Gretajiyusoshibutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition having excellent fluidity, heat resistance, impact resistance and flame retardancy.

Sunalene resins such as ABS resin and MBS resin have many characteristics such as excellent impact resistance, heat resistance, ease of processing during molding, and good gloss of molded products, and are used in large quantities as general-purpose thermoplastic resins. It is used.

However, these impact-resistant snalene resins, like polyolefins such as polyethylene and polypropylene, are easily flammable, so their uses may be limited.

Particularly in recent years, synthetic resins used for building materials, furniture, vehicles, and electrical products are required to have flame-retardant properties, and impact-resistant materials such as ABS resin and MBS resin are also required to be flame-retardant. Increasingly, it is necessary to carry out chemical treatment.

As a flame retardant treatment method for impact-resistant snalene resins such as ABS resins, there is a method of kneading an appropriate amount of an aliphatic, alicyclic or aromatic halogen compound and an annamon compound into the resin to be flame retardant. It is widely known and put into practical use.

In this case, as the halogen of the halogen compound, bromine or chlorine has an excellent flame retardant effect, and a compound with a high halogen content is preferably used.

The blending amount of these compounds may be varied depending on the required degree of flame retardancy, but it should be determined that they exhibit non-flammability and self-extinguishing properties according to standard flame retardant standards or judgment methods, such as UL-94 method. (In the case of ABS resin, for 100 parts by weight of this resin, 15 to 50 parts by weight of the above-mentioned halogen-containing organic compound, 10 to 30 parts by weight of annamon trioxide)
It is necessary to mix parts by weight.

However, as the amount of these additives increases, the impact resistance, which is a characteristic of this type of resin, decreases significantly, and the thermal stability of the halogenated organic compound is poor.

It often discolors during molding, adversely affecting the resin material, or deteriorating the heat deformation resistance of the resin material.

In order to improve this drawback, methods described in Japanese Patent Publication No. 43 28616, Japanese Patent Application Laid-Open No. 48-11341, etc. have been proposed.

The method described in Japanese Patent Publication No. 43-28616 is an ABS
This method improves the flammability of ABS resin by blending post-chlorinated polyvinyl chloride and an annamon compound with the resin.

When using this method, the heat deformation resistance of the resin material is rarely deteriorated, but there is a drawback that fluidity and impact resistance are unavoidably lowered.

On the other hand, the method described in JP-A-48-11341 is
Regarding a flame retardant material with improved impact resistance and fluidity (molding method) by blending polyvinyl chloride and chlorinated polyethylene with ABS resin. However, even with this method, the resin composition has a decrease in heat deformation resistance. I can't deny it.

In view of this situation, the present inventors have determined that fluidity, impact resistance,
The present invention was arrived at as a result of extensive research into impact-resistant resin compositions that do not deteriorate in heat deformation resistance and have improved flame retardancy.

The purpose of the present invention is to improve the impact resistance and heat deformation resistance of ordinary AB
While maintaining S resin level, UL standard 94VO to 94V-
To provide a sunalene resin composition that has flame retardancy that passes 1 and has extremely excellent fluidity (molding processability).
There it is.

Therefore, the above object of the present invention is to (4) provide a rubbery polymer with:
Monovinyl aromatic monomer, unsaturated nitrile monomer, α,
A polymer of the above monomer mixture is blended into a kraft copolymer or a graft copolymer obtained by polymerizing a monomer mixture of two or more β-monoolefinic unsaturated carboxylic acids and derivatives thereof. Polymer 50-70 obtained by
Weight % (based on the final resin composition.

same as below. ) (B) chlorinated polyvinyl chloride having a viscosity average degree of polymerization of 400 to 800 and chlorinated to a chlorine content of 65% or more, 225 to 45% by weight; and (C) degree of chlorination of 25 to 455 to 45% by weight. This can be easily achieved by using a resin composition with excellent fluidity, impact resistance and flame retardancy, which is composed of 5 to 25% by weight of polyenalene.

In the following, the present invention will be described in detail. In addition to natural rubber, the rubbery polymers used in the present invention include polybutadiene, butadiene-snarene copolymer, butadiene-acrylonitrile copolymer, polyisoprene, polychloroprene,
Various synthetic rubbers include enalene-propylene-diene monomer rubber, ethylene-vinyl acetate copolymer, epichlorohydrin rubber, and acrylic rubber.

A typical example of the monovinyl aromatic monomer in the present invention is sunalene, and other examples include α-memethysnarene, chlorsnarene, dichlorsnarene, and the like.

A typical example of the vesicular monomer is acrylonitrile, and other examples include methacrylonitrile and ethacrylonitrile.

Examples of α,β-monoolefinically unsaturated carboxylic acids and their derivatives include (meth)acrylic acid esters, maleic acid, fumaric acid, or itaconic acid hepano- or diesters, crotonic acid esters, (meth)acrylic acid, and crotonic acid. Examples include acids, maleic acid, itaconic acid, etc.

The graft copolymer in the composition of the present invention includes the rubbery polymer (monovinyl aromatic monomer, unsaturated nitrile monomer, α,β-monoolefinic unsaturated carboxylic acid and derivatives thereof). It is obtained by graft polymerization of a mixture of two or more monomers.

Two or more types of monomers may mean two or more types of monomers included in the same category, such as monovinyl aromatic monomers, but one type of monovinyl aromatic monomers and two or more types of vesicles may be used. ) IJ
It is more preferable to use a combination of monomers included in other categories, such as one type of monomer.

This graft copolymer has a rubbery polymer content of 5 to 5.
30% by weight is preferred.

Further, the first component in the composition of the present invention is a mixture of the graft copolymer with a polymer obtained by polymerizing only the monomer mixture (without the presence of a rubbery polymer).
Craft blend type) may also be used.

In this case as well, it is preferable that the content of the graft copolymer (the rubbery polymer derived therefrom) be in the range of 5 to 30% by weight.

The above-mentioned graft copolymer may be produced by any method, and examples thereof include emulsion polymerization method, solution polymerization method, bulk polymerization method, bulk-suspension polymerization method, and emulsion-suspension polymerization method. legal method, emulsion-bulk polymerization method, etc.

The resin composition according to the present invention contains chlorinated polyvinyl chloride as a second component.

Chlorinated polyvinyl chloride here refers to a homopolymer of vinyl chloride with a viscosity average degree of polymerization in the range of 400 to 800 according to JIS, a dominant amount of vinyl chloride and a minor amount of other copolymerizable monomers. means a chlorinated copolymer with

It is inappropriate to use a polyvinyl chloride having a viscosity average degree of polymerization of 400 or less as the base material of this component because the impact resistance of the resin composition finally obtained will be significantly reduced.

In addition, when using a material with a viscosity average degree of polymerization of 800 or more,
This is not preferable because the fluidity of the resin composition finally obtained decreases, and therefore the temperature during molding must be increased, which accelerates the thermal decomposition reaction.

The chlorine content after chlorinating polyvinyl chloride may be 65% or more by weight.

If the chlorine content is less than 65% by weight, the thermal stability of the final resin composition will be poor, which is not preferable.

In addition, chlorinated polyvinyl chloride has a chlorine content of 72% by weight.
If it exceeds 5, the mechanical strength of the final resin composition will decrease, which is not preferable.

The proportion of this chlorinated polyvinyl chloride in the resin composition finally obtained is 25 to 45% by weight.

If the proportion of chlorinated polyvinyl chloride is greater than the above range, the impact resistance of the final resin composition will decrease, which is undesirable, and if it is less than the above range, the final resin composition will have a lower impact resistance. This is not preferred because the flame retardance of the material is not improved.

The resin composition of the present invention contains chlorinated polyethylene having a degree of chlorination of 25 to 45 by weight as a third component.

If the degree of chlorination is less than 25 weight, the effect of improving impact resistance due to the rubber elasticity of chlorinated polyethylene will not be exhibited, and if the degree of chlorination is more than 4570, the chemical and physical properties of the chlorinated polyethylene will change to polychloride. It becomes close to that of vinyl, and the combined effect of chlorinated polyethylene is lost.

The chlorinated polyethylene used in the present invention is preferably made from high-density polyethylene with a melt index of 15 or less.

The proportion of this chlorinated polyethylene in the final resin composition is 5 to 25% by weight.

If the proportion of chlorinated polyethylene is less than the above range, it is undesirable as it will reduce the impact resistance of the final resin composition, and if it is more than the above range, the tensile strength of the final resin composition will decrease. This is not preferred because strength and heat deformation resistance decrease.

In the present invention, it is essential that the above three components are blended, but in addition to these, colorants, stabilizers, plasticizers, fillers, foaming agents, ultraviolet absorbers, and other car invention compositions may be added depending on the purpose. Of course, additives may be added in types and amounts that do not impede the properties of the product.

To mix the above-mentioned components, they are mixed in advance using a conventional mixer, such as a tumbler, kneader, Henschel mixer, etc., and then melt-kneaded on a Banbury mixer 1 heated roll or kneaded using an extruder. , the desired object can be obtained.

The composition of the present invention has excellent impact resistance, heat deformation resistance, and flame retardancy, and has extremely excellent flowability (molding processability).

Therefore, since it can be molded at a low temperature during molding, burning and thermal decomposition reactions are unlikely to occur during molding, and its industrial utility value is extremely high.

Next, the present invention will be explained by examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

In addition, in the following examples, evaluation of mechanical properties, flame retardancy, and thermal stability test were conducted according to the following method.

Tensile strength: JISK-6871 Izot impact strength: JISK-6871 Heat distortion temperature
:JISK-6871 Fluidity: Melt indexer
Evaluation of flame retardancy: UL standard 94 method.

Test piece thickness 1/8" (3.2 mm).

The UL94 method was developed by Underwriters Laboratories, Inc. in the United States.
sInc,) standards, during a vertical combustion test, the burning drippings do not ignite dry surgical cotton, and the time it takes to emit a flame and burn is less than 10 seconds (within 5 seconds on average, and the flame is emitted). (It takes less than 30 seconds to become red hot and burn without burning) is said to pass 94V-O.

Burning drops will not ignite dry surgical cotton burns with a flame Time less than 30 seconds (average 25 seconds) Red within and without emitting flames. It takes less than 60 seconds to heat and burn. ) is considered to have passed 94V-1. say.

Thermal stability test: The test piece was kept in a gear oven maintained at 210°C for 1 hour, and the degree of discoloration of the taken out test piece was evaluated and displayed on a scale of 1 to 5.

h is the best, 5 is the worst, 2-4 is in between, and there are few The potatoes have little discoloration.

Examples 1 to 6 Composition raw materials were blended in the proportions shown in Table 1, each composition was kneaded for several minutes in a Banbury mixer, and further heated at 150°C.
The mixture was thoroughly kneaded with heated rolls held at a temperature of 100 mL to form a sheet, which was then ground to obtain a resin composition.

Using each of the obtained compositions, test pieces were prepared using an injection molding machine, and their mechanical properties were measured according to the measurement method described above.

The results are shown in Table 1. Comparative Examples 1 to 6 Composition raw materials were blended in the proportions shown in Table 1, kneaded in the same manner as in the examples, and used to create test pieces using an injection molding machine to measure mechanical properties. .

The results are shown in Table 1. The following is clear from Table 1.

The composition according to the present invention has excellent flame retardancy that satisfactorily passes UL-standard V-0 or V-1, and also exhibits particularly excellent fluidity.

It also has high impact resistance, tensile strength, heat deformation resistance, etc., and excellent thermal stability.

However, the composition consisting of two components of ABS resin and chlorinated polyvinyl chloride (Comparative Example 2) is UL-compliant in terms of flame retardancy.
Even if it is possible to pass the 94 standard, the impact resistance will be significantly reduced, and even if the resin composition consists of three components (
Comparative Example 3 and Comparative Example 6) If the degree of polymerization of polyvinyl chloride, which is the basis of chlorinated polyvinyl chloride, is high, the fluidity of the resin composition will be extremely deteriorated.

In addition, the degree of polymerization of polyvinyl chloride serving as the base of chlorinated polyvinyl chloride is within the range (400 to SOO) in the present invention.
Even if the chlorine content is within the range of the present invention (65
% or more) (Comparative Example 4), the thermal stability of the resin composition finally obtained is deteriorated.

Claims (1)

[Scope of Claims] 1(A) A rubbery polymer containing a monovinyl aromatic monomer, a vesicle monomer, an α,β-monoolefinically unsaturated carboxylic acid and its derivatives. A graft copolymer obtained by polymerizing a monomer mixture consisting of more than one species, or a polymer obtained by blending a polymer of the above monomer mixture with this graft copolymer, 50 to 70% by weight (final (B) 25 to 45% by weight of chlorinated polyvinyl chloride obtained by chlorinating polyvinyl chloride with a viscosity average degree of polymerization of 400 to 800 to a chlorine content of 65% or more, and (5-25% by weight of chlorinated polyethylene with a degree of chlorination of 0 and 25-45% by weight)
A resin composition with excellent fluidity, impact resistance, and flame retardancy.