JPH05331351A - Flame-retarding resin composition - Google Patents

Abstract

PURPOSE:To obtain a flame-retarding resin composition which can give a molding not suffering delamination and having excellent permanent antistatic properties by mixing a specified antistatic thermoplastic resin composition with a halogen-containing flame retardant and antimony oxide. CONSTITUTION:The composition of excellent permanent antistatic properties comprises 100 pts.wt. antistatic thermoplastic resin composition comprising 10-50wt.% graft copolymer prepared by grafting 40-90 pts.wt. monomer mixture comprising 50-90wt.% aromatic vinyl monomer, 10-50wt.% vinyl cyanide monomer and 0-20wt.% copolymerizable vinyl monomer onto 10-60 pts.wt. diene rubbery polymer, 5-85wt.% copolymer prepared by copolymerizing 30-90wt.% aromatic vinyl monomer with 10-50wt.% vinyl cyanide monomer and 0-20wt.% copolymerizable vinyl monomer and 5-45wt.% composition prepared by mixing 100 pts.wt. thermoplastic polyurethane elastomer with 2.0-15 pts.wt. inorganic alkali metal salt, 3-25 pts.wt. halogen-containing flame retardant and 0.5-15 pts.wt. antimony oxide.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition which is excellent in permanent antistatic property and flame retardancy.

[0002]

2. Description of the Related Art Generally, a styrene resin represented by ABS resin is widely used in electric and electronic equipment parts, OA equipment and the like, and various characteristics such as impact resistance and moldability are required. On the other hand, styrene-based resins are subject to various legal restrictions in accordance with the expansion of such uses, and flame retardant materials are required to have high flame retardancy. In addition, in the field of OA equipment, which is growing rapidly in its applications, antistatic properties are required in addition to the above flame retardancy.

Since the styrene resin has a high electric resistivity value, dust adheres to the molded product, and in electronic equipment, it has a drawback that electrostatic damage due to charged electricity occurs. Therefore, as these antistatic methods,
Generally, a method of kneading an antistatic agent, carbon black and metal powder is known.

The method of kneading an antistatic agent into a thermoplastic resin is effective as a method of imparting an antistatic property, but if it is kneaded until the antistatic property is exerted, there is a drawback that a molding failure occurs. However, there are drawbacks that the antistatic performance is not obtained and the antistatic effect is not permanent. On the other hand, the method in which carbon black or metal powder is kneaded can provide sufficient antistatic property, but has a drawback that the appearance, molding processability, impact resistance and the like of the molded product are deteriorated.

Further, as a method for imparting a permanent antistatic property, a method of mixing a polyether ester amide elastomer with a thermoplastic resin is known, but due to poor compatibility, the strength of a molded article is lowered and the layered peeling is caused. Occurs. Therefore, in the above mixing method, it is necessary to add a compatibilizer.

[0006]

[Problems to be Solved by the Invention]
The object of the present invention is to have excellent antistatic properties, impact resistance, moldability and flame retardancy by improving the resin composition without impairing the properties of the styrene-based resin, and when forming a molded article. It is intended to provide a flame-retardant thermoplastic resin composition which is excellent in permanent antistatic property without delamination.

[0007]

Means for Solving the Problems As a result of intensive studies conducted by the present inventor for this purpose, a resin composition obtained from a vinyl-based graft copolymer having a specific composition ratio and a vinyl-based copolymer having a specific composition ratio, and It has been found that the thermoplastic resin composition for the above purpose can be obtained by blending a flame retardant into a resin composition composed of a thermoplastic polyurethane elastomer mixed with a specific metal salt.

That is, the present invention is as follows: (A) in the presence of 10 to 60 parts by weight of a diene rubber polymer, 50 to 90% by weight of an aromatic vinyl monomer, 10 to 50% by weight of a vinyl cyanide monomer and, if necessary, copolymerization with them. Possible vinyl monomers 0 to 20% by weight monomer mixture
Graft polymerization of 40 to 90 parts by weight of graft copolymer (component A) 10 to 50% by weight, (B) aromatic vinyl monomer 30 to 90% by weight, cyanide vinyl monomer 10 ~ 50% by weight
And vinyl monomers copolymerizable with these as required
Copolymer obtained by copolymerizing 0 to 20% by weight (component B) 5 to
85% by weight and (C) thermoplastic polyurethane elastomer
1. 100 parts by weight of an antistatic thermoplastic resin composition comprising 5 to 45% by weight of a composition (component C) obtained by blending 2.0 to 15 parts by weight of an inorganic alkali metal salt with 100 parts by weight. Halogen-based flame retardant 3 to 35 parts by weight and 3. A flame-retardant resin composition excellent in permanent antistatic property, characterized by comprising 0.5 to 15 parts by weight of antimony oxide.

The present invention will be described in detail below. The diene rubber polymer used in the A-component graft copolymer of the present invention is a homopolymer or copolymer of a conjugated diene monomer, or a conjugated diene monomer and another copolymerizable monomer. Is a copolymer of.

The conjugated diene monomer mentioned here includes butadiene, isoprene, dimethylbutadiene and chloroprene.

Other copolymerizable monomers include styrene,
Examples include aromatic vinyl monomers such as α-methylstyrene and vinyltoluene, vinyl cyanide monomers such as acrylonitrile, and (meth) acrylic acid ester monomers such as methyl methacrylate and butyl acrylate.

As the diene rubber polymer used in the present invention, a copolymer obtained by copolymerizing a polyfunctional vinyl monomer as a crosslinking monomer can also be used.

As the polyfunctional vinyl monomer that can be used,
Examples include divinylbenzene, ethylene glycol dimethacrylate, triallyl cyanurate, allyl acrylate and vinyl acrylate.

As a method for producing the graft copolymer of the component A, a known graft polymerization method can be used. In the presence of the diene rubber polymer latex, vinyl cyanide monomer and aromatic vinyl monomer are contained. It can be obtained by further adding a monomer copolymerizable with these monomers to the body or these monomers, and copolymerizing these.

Examples of the vinyl cyanide monomer used for producing the graft copolymer include acrylonitrile and methacrylonitrile.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, dimethylstyrene and chlorostyrene.

The above monomers may be used alone or in combination of two or more.

Examples of the monomer copolymerizable with the above-mentioned monomer components include acrylic acid ester, methacrylic acid ester, acrylic acid, methacrylic acid, acrylic acid amide and methacrylic acid amide.

The graft copolymerization is preferably emulsion polymerization, and as an emulsifier used for emulsion polymerization, a fatty acid soap such as sodium stearate or potassium oleate, or an organic material such as disproportionated potassium rosinate or sodium dodecylbenzenesulfonate is used. Examples thereof include sulfonic acid.

Examples of the method for adding the monomer mixture for graft polymerization include batch addition, partial addition, and continuous division addition of all graft polymerization monomers.

In order to effectively carry out the graft copolymerization,
Continuous divided addition is preferred. The polymerization temperature is preferably in the range of 40 to 90 ° C.

The polymerization initiator is preferably a redox system in which a polyfunctional radical initiator and a metal salt such as ferrous sulfate, a chelating agent such as pyrophosphoric acid or ethylenediaminetetraacetic acid disodium salt are used in combination.

The amount of the polymerization initiator used is 100
It may be 0.05 to 1.0 parts by weight with respect to parts by weight.

The diene rubber polymer contained in the graft copolymer of the component A is 10 to 60 parts by weight. When it is less than 10 parts by weight, impact strength is low, and when it exceeds 60 parts by weight, moldability and rigidity are low. It is not preferable because it decreases.

The aromatic vinyl monomer is 50 to 90% by weight of all monomers excluding the diene rubber polymer. Below 50% by weight, the moldability and size characteristic of the aromatic vinyl compound are obtained. Stability is compromised.

The vinyl cyanide monomer is 10 to 50% by weight of all monomers excluding the diene rubber polymer, and 10% by weight.
If it is less than 50% by weight, heat resistance is low, and if it exceeds 50% by weight, moldability is deteriorated.

Next, examples of the aromatic vinyl monomer used in the B component copolymer of the present invention include styrene and α.
-Methylstyrene, m-methylstyrene, p-methylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene, vinylnaphthalene and the like can be mentioned.

The vinyl cyanide monomer may, for example, be acrylonitrile or methacrylonitrile.

Further, as the monomer copolymerizable with these monomer components, acrylic acid ester monomers, methacrylic acid ester monomers, vinylcarboxylic acid monomers such as acrylic acid and methacrylic acid are used. In addition, acrylic acid amide, methacrylic acid amide and the like can be mentioned.

The amount of aromatic vinyl monomer in the monomers used for the component B copolymer is 30 to 90% by weight, and if it is less than 30% by weight, the moldability and size characteristic of the aromatic vinyl compound are obtained. Stability is compromised.

In the monomers used for the component B copolymer, the vinyl cyanide monomer is 10 to 50% by weight, and 10% by weight.
If it is less than 50% by weight, heat resistance is low, and if it exceeds 50% by weight, moldability is deteriorated, which is not preferable.

As the method for mixing the A-component graft copolymer and the B-component copolymer of the present invention, a known method may be applied to mix them in an emulsified state or a particle state, or both components in a molten state may be mixed. A thermoplastic resin composition can be easily obtained by blending and melt-kneading. Furthermore, there is no problem even if it is a method of mixing with the C component composition described later.

The thermoplastic polyurethane elastomer used in the C component composition of the present invention is obtained by a polyaddition reaction using a long-chain polyol, a short-chain glycol, a diisocyanate, etc. as a raw material, through a urethane bond in the molecule. It is united.

The long-chain polyol which is a raw material of the thermoplastic polyurethane elastomer includes poly (1,4-butylene adipate), poly (1,6-hexane adipate), polycaprolactone, polyethylene glycol and polypropylene glycol. .. Further, the short chain glycol includes ethylene glycol, 1,4-butanediol, 1,4-hexanediol and the like, and the diisocyanate includes tolylene diisocyanate and hexamethylene diisocyanate.

The thermoplastic polyurethane elastomer is one in which a long chain polyol and a diisocyanate form a soft segment and a short chain glycol and a diisocyanate form a hard segment.

Examples of the inorganic alkali metal salts used in the C component composition of the present invention include inorganic alkali metal salts formed from an alkali metal such as Na or K and thiocyanic acid, and particularly preferably sodium thiocyanate. And potassium thiocyanate. Further, two or more kinds of inorganic alkali metal salts can be used in combination.

In the C component composition of the present invention, the mixing ratio of the thermoplastic polyurethane elastomer and the inorganic alkali metal salt is 2.0 to 15 parts by weight with respect to 100 parts by weight of the thermoplastic polyurethane elastomer.

If the amount of the inorganic alkali metal salt is less than 2.0 parts by weight, the antistatic property is poor, and if it exceeds 15 parts by weight, the strength is lowered and it is not practical.

The inorganic alkali metal salt used in the C component composition of the present invention is mixed with a thermoplastic polyurethane elastomer and then mixed with a styrene resin comprising a A component graft copolymer and a B component copolymer. Although it exhibits antistatic properties, the inorganic alkali metal salt alone cannot provide sufficient antistatic properties even when blended with the styrene resin. In addition, a feature of the present invention is that without adding a compatibilizer to obtain an antistatic thermoplastic resin composition,
That is, the styrene resin and the thermoplastic polyurethane elastomer are sufficiently mixed.

The power failure preventive thermoplastic resin composition of the present invention has a range of 10 to 50% by weight of the A component graft copolymer, 5 to 85% by weight of the B component copolymer and 5 to 45% by weight of the C component composition. By having the above, the moldability, mechanical strength and antistatic property are excellent.

Next, examples of the halogen flame retardant used in the present invention include chlorine flame retardants and bromine flame retardants. Examples of the chlorine-based flame retardant include perchloropentacyclodecane, chlorinated paraffin and chlorinated polyethylene. As the bromine-based flame retardant, hexabromobiphenyl ether, tribromophenol, decabromobiphenyl ether, decabromodiphenyl oxide, tetrabromobisphenol A, hexabromocyclododecane and the like are used.

As the halogen-based flame retardant, tris (chloroester) phosphate, tris (dichloropropyl) phosphate, bis (2,3dibromopropyl) 2,3dichloropropylphosphate, bis (chloropropyl) monooctylphosphate, etc. The halogen-containing phosphoric acid ester of is also used.

These halogen-based flame retardants are added in an amount of 3 to 35 parts by weight based on 100 parts by weight of the antistatic thermoplastic resin composition. If the halogen-based flame retardant is less than 3 parts by weight, the flame retardant effect is small, and if it exceeds 35 parts by weight, the mechanical strength is reduced.

Antimony oxide is added to the mixture of the antistatic thermoplastic resin composition and the halogen-based flame retardant. Antimony oxide exhibits high flame retardancy in combination with a halogen-based flame retardant, and its addition amount is 0.5 to 15 per 100 parts by weight of the antistatic thermoplastic resin composition.
Parts by weight. If the amount of antimony oxide added is less than 0.5 parts by weight, the flame-retardant effect is small, and if it exceeds 15 parts by weight, the mechanical strength decreases. As antimony oxide, for example,
There are antimony trioxide, antimony pentoxide and sodium antimonate.

The flame-retardant resin composition of the present invention is a dry blend prepared by mixing an antistatic thermoplastic resin composition, a halogen-based flame retardant and antimony oxide with a known mixer (tumbler, Henschel mixer, etc.), or The dry blend can be obtained by melting, kneading and extruding with an extruder.

Furthermore, if necessary, stabilizers, plasticizers, lubricants, colorants and the like can be added to the flame-retardant resin composition of the present invention.

[0047]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited by these examples as long as the gist thereof is not exceeded. In the following, "%" and "parts" are based on weight unless otherwise specified.

Examples 1 to 7 Comparative Examples 1 to 3 Preparation of Component A Graft Copolymer Polybutadiene latex (solid content 30
%, Weight average particle diameter 0.35 μm) 333 parts were added, and then 234 parts of pure water, 0.005 parts of ferrous sulfate, 0.01 parts of ethylenediaminetetraacetic acid disodium and 0.3 parts of sodium aldehyde sulfoxylate were added, and the mixture was placed in a nitrogen atmosphere. The stirred contents were kept at 50 ° C., and a monomer mixture consisting of 25 parts of acrylonitrile, 75 parts of styrene, 0.6 parts of t-dodecyl mercaptan and 0.2 part of benzoyl peroxide was continuously added to the above latex over 5 hours. After the addition of the monomer mixture was completed, 0.1 part of benzoyl peroxide was added, and a further 70
Polymerization was completed by stirring at ℃ for 2 hours.

The obtained latex is octadecyl-3.
After adding 1.0 part of-(3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by Ciba-Geigy, trade name; Irganox 1076), an aqueous solution containing 8 parts of calcium chloride was added to 95 ° C. The emulsion was destroyed by stirring for 3 minutes to obtain a slurry. The slurry was dehydrated, washed with water and dried to obtain a graft copolymer (component A).

Preparation of Component B Copolymer 100 parts of pure water, 2.5 parts of 0.2% potassium persulfate aqueous solution, 0.07 parts of tribasic calcium phosphate and 30 parts of styrene were put in an autoclave.
Part, acrylonitrile 25 parts, t-dodecyl mercaptan
0.6 part and 0.1 part of benzoyl peroxide were added, and the contents were stirred under a nitrogen atmosphere, and the contents were kept at 100 ° C.
45 parts were continuously added over 2 hours at 100 ° C, 2 hours at 103 ° C and 3 hours at 107 ° C over a total of 7 hours.

After the completion of the addition, the temperature is raised to 117 ° C. and the mixture is stirred for 2 hours to complete the polymerization. After cooling, hydrochloric acid is added to the polymerization solution to neutralize, dehydrate and dry the beads of the copolymer (component B). Got

Production of C Component Composition To 100 parts of a thermoplastic polyurethane elastomer (Takelac T-890, trade name, manufactured by Takeda Pharmaceutical Co., Ltd.), sodium thiocyanate and potassium thiocyanate in proportions shown in Table 1 were added. 18 using a 40 mm extruder
The pellets of the composition (component C) were obtained by melting and kneading at 0 ° C.

The component A graft copolymer, the component B copolymer, the component C composition and the flame retardant (halogen flame retardant, antimony oxide) obtained by the above method were blended according to the formulation shown in Table 1 to a Henschel mixer. Then, the mixture was melted and kneaded at 220 ° C. using a 40 mm extruder to prepare pellets. The evaluation of Table 2 was performed using the obtained pellets.

[0054]

[Table 1]

[0055]

[Table 2]

The physical properties were measured by the following methods. (1) Izod impact strength Using an injection molding machine (IS-80CNV) manufactured by Toshiba Machine Co., Ltd., sample pellets were molded at 220 ° C to prepare test pieces. About this test piece, ASTM D-
The Izod impact strength was measured according to 256.

(2) Flexural modulus Using an injection molding machine (IS-80CNV) manufactured by Toshiba Machine Co., Ltd., the sample pellets were molded at 220 ° C to prepare test pieces. About this test piece, ASTM D-
The flexural modulus was measured according to 790.

(3) Melt Flow Rate (MFR) The melt flow rate was measured using sample pellets according to JIS K-6874.

(4) Surface resistivity Using an injection molding machine (IS-80CNV) manufactured by Toshiba Machine Co., Ltd., sample pellets were molded at 220 ° C. and 2 mmt × 100 m
A disk of mΦ was produced. Room temperature 23 ℃ using this disk,
After conditioning in an atmosphere of 50% humidity RH for 24 hours, the surface resistivity was measured using a super insulation resistance meter manufactured by Toa Denpa Kogyo KK. Also, after leaving it for 1 month, the disc was washed with a detergent and the surface specific resistance value was measured in the same manner as described above.

(5) Flame Retardancy Underriders Laboratories (U
L) standardized subject 94 (abbreviated name UL-9)
Based on 4) length 5 inches x width 1/2 inches, thickness 1/16
Inch test piece is used, and the flame resistance class is B
N, 94V-2, 94V-1, 94V-0 were divided and judged.

[0061]

INDUSTRIAL APPLICABILITY As described above, the flame-retardant resin composition of the present invention is excellent in mechanical strength and moldability and has both permanent antistatic property and flame retardancy. It has a feature that it can be widely used as a molding material in the field of OA equipment and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08K 5/02 KFW 7242-4J C08L 25/12 LDY 9166-4J LEE 9166-4J 75/04 NGG 8620 -4J

Claims (1)

[Claims] 1. (A) in the presence of 10 to 60 parts by weight of a diene rubber polymer, 50 to 90% by weight of an aromatic vinyl monomer, 10 to 50% by weight of a vinyl cyanide monomer and, if necessary, copolymerization with them. Graft copolymer (A component) obtained by graft-polymerizing 40-90 parts by weight of a monomer mixture consisting of 0-20% by weight of possible vinyl monomers, and (B) an aromatic compound. Vinyl monomer 30-90% by weight, vinyl cyanide monomer
A copolymer (B component) obtained by copolymerizing 10 to 50% by weight and, if necessary, 0 to 20% by weight of a vinyl monomer copolymerizable therewith, and (C) a thermoplastic resin. Composition (component C) obtained by mixing 2.0 to 15 parts by weight of inorganic alkali metal salts with 100 parts by weight of polyurethane elastomer
Antistatic thermoplastic resin composition comprising 5 to 45% by weight
100 parts by weight, 2. Halogen-based flame retardant 3 to 35 parts by weight and 3. A flame-retardant resin composition having excellent permanent antistatic properties, characterized by comprising 0.5 to 15 parts by weight of antimony oxide.