JP2001151974A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition which is excellent in flame-retardancy, flowability, rigidity, impact resistance and thermal resistance. SOLUTION: The flame-retardant resin composition, containing 100 pts.wt. of (A) a rubber-modified styrenic resin consisting essentially of (a-1) a graft copolymer formed by (co)polymerizing a monomer mixture having the essential component of an aromatic monomer in the presence of a rubbery polymer and (a-2) a (co)polymer having the essential component of an aromatic vinyl monomer and 1-20 pts.wt. of (B) a phosphorus compound, is characterized in that the graft polymer (a-1) has an weight-average molecular weight of the methyl ethyl ketone soluble matter of 70,000 to 150,000 and the (co)polymer (a-2) has an weight-average molecular weight of 100,000 to 200,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant resin composition. More specifically, the present invention relates to a flame-retardant resin composition containing a rubber-modified styrene resin excellent in flame retardancy, fluidity and rigidity as an essential component without using a bromine-based flame retardant.

[0002]

2. Description of the Related Art Conventionally, rubber-modified styrene resins such as acrylonitrile-butadiene-styrene copolymer (hereinafter abbreviated as ABS resin) have been used in a wide variety of applications due to their excellent balance of physical properties and good moldability. I have. However, in some applications, it is necessary to have flame retardancy. For example, it is used as an electric / electronic device part, an OA device, a household product, or a building material. As a method for imparting flame retardancy to a rubber-modified styrenic resin, a bromine-based flame retardant is generally added, but a part of the bromine-based flame retardant is decomposed at the time of kneading and molding, and free bromine gas or bromine is added. Compounds are formed and corrode the surfaces of cylinders, screws and dies of kneading machines and injection molding machines, and in the field of electric and electronic equipment parts, corrode metal parts and cause poor contact and poor conduction. Furthermore, brominated dibenzodioxins and dibenzofurans, which are said to be toxic, have been pointed out in bromine-based flame retardants, which are extremely small at the time of molding and burning. In addition, when incinerating a resin product containing such a brominated flame retardant, there is a sufficient risk of contaminating the natural environment.

[0003] As a method for eliminating such a drawback, a phosphorus compound such as red phosphorus or ammonium polyphosphate is used in place of the brominated flame retardant, and if necessary, a metal oxide, a phenol resin or a polyhydroxy compound is further converted to styrene. (Japanese Patent Laid-Open No. 4-10614)
0, JP-A-5-140412, JP-A-7-140
No. 53879). However, these resin compositions have a problem that any one of mechanical properties, water resistance, and coloring property is impaired.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has no risk of generating harmful substances during molding and combustion.
An object of the present invention is to provide a dripping flame-retardant resin composition containing a rubber-modified styrenic resin excellent in fluidity, rigidity and coloring property as an essential component.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, a resin composition containing a rubber-modified styrene resin and a phosphorus compound as essential components has been identified. Combination of a (co) polymer having a weight-average molecular weight of 0.5% and a graft copolymer having a specific weight-average molecular weight of a methyl ethyl ketone-soluble component provides excellent drip-resistant flame retardancy, excellent fluidity and rigidity The inventors have found that a resin composition can be obtained, and have reached the present invention. That is,
The present invention relates to (A) a graft copolymer (a-1) obtained by (co) polymerizing a monomer mixture containing an aromatic vinyl monomer as an essential component in the presence of a rubbery polymer and an aromatic copolymer. It is difficult to contain (B) 1 to 20 parts by mass of a phosphorus compound per 100 parts by mass of a rubber-modified styrenic resin comprising a (co) polymer (a-2) containing a vinyl monomer as an essential component. In the flame-retardant resin composition, the weight average molecular weight of the methyl ethyl ketone-soluble portion of the graft copolymer (a-1) is from 70,000 to
150,000, wherein the weight average molecular weight of the (co) polymer (a-2) is from 100,000 to 200,000.

Hereinafter, the present invention will be described in more detail.
The rubber-modified styrene resin as the component (A) is (a-1)
A rubber-modified styrenic resin composed of a graft copolymer and (a-2) (co) polymer having an aromatic vinyl monomer as an essential component. First, (a-1) the graft copolymer will be described. (A-1) The graft copolymer is an aromatic vinyl monomer and, if necessary, in the presence of a rubbery polymer,
It can be obtained by subjecting a monomer mixture to which a vinyl monomer copolymerizable therewith is added to known bulk polymerization, bulk suspension polymerization, emulsion polymerization and solution polymerization. The mass ratio of the aromatic vinyl monomer to the copolymerizable vinyl monomer in the matrix containing the aromatic vinyl monomer as an essential component is 50 to 1
00 / 50-0, preferably 60-100 / 40-
0, particularly preferably 70-100 / 30-0.
When the proportion of the aromatic vinyl monomer is less than 50% by mass, at least one property of moldability, heat resistance and elastic modulus is impaired.

(A-1) Styrene, an aromatic vinyl monomer which is an essential component used in the graft copolymer,
α-methylstyrene, vinyltoluene, t-butylstyrene, halostyrene, sodium styrenesulfonate,
Indene, acenaphthylene and the like, preferably,
Styrene and α-methylstyrene.

The copolymerizable vinyl monomers that can be used as required include vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, fumaronitrile, α-chloroacrylonitrile, methyl acrylate and ethyl acryl. Acrylate monomers such as acid esters and butyl acrylate esters; methacrylate monomers such as methyl methacrylate ester, ethyl methacrylate ester and cyclohexyl methacrylate ester; and unsaturated carboxylic acids such as acrylic acid and methacrylic acid Monomers, unsaturated carboxylic acid ester monomers such as monomethyl itaconate and monomethyl fumarate, unsaturated carboxylic acid amide monomers such as acrylamide and methacrylamide, maleimide, N-methylmaleimide, N-ethyl Maleimide, N Unsaturated dicarboxylic acid imide monomers such as propylmaleimide, N-hexylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (alkyl-substituted phenyl) maleimide, maleic acid, Itaconic acid, unsaturated dicarboxylic anhydrides such as citraconic acid and aconitic acid and glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether,
Allyl glycidyl ether, glycidyl cinnamate, methallyl glycidyl ether, N- {4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl} acrylamide, N- {4- (2,3-epoxypropoxy)- Vinyl monomers containing an epoxy group such as 3,5-dimethylbenzyl methacrylamide and the like,
Preferably, acrylonitrile, methyl methacrylate,
Acrylic acid, methacrylic acid, N-phenylmaleimide,
Vinyl monomers such as maleimide, maleic anhydride and glycidyl methacrylate. Of course, two or more of these vinyl monomers may be used in combination.

(A-1) The rubbery polymer used for the graft copolymer must have a glass transition temperature (Tg) of 10 ° C. or less, and if it exceeds 10 ° C., the impact resistance is reduced. I do. Examples of rubbery polymers include polybutadiene,
Diene rubbers such as butadiene-styrene copolymer, butadiene-styrene block copolymer, butadiene-acrylonitrile copolymer, polyisoprene, isoprene-styrene copolymer, chloroprene rubber, and (partial) hydrogenation of the diene rubber Rubber, isobutylene-isoprene copolymer, acrylic rubber, ethylene-propylene (diene component) copolymer, and the like. Particularly preferred is a diene rubber.

The amount of the rubbery polymer in the graft copolymer is 2 to 70% by mass, preferably 3 to 65% by mass, and particularly preferably 4 to 60% by mass. If the content of the rubbery polymer is less than 2% by mass, the impact resistance is reduced, while
If it exceeds 70% by mass, at least one property of heat resistance, flame retardancy and fluidity tends to be impaired.

The rubber volume average particle diameter in the rubber-modified styrene resin is 0.1 to 5.0 μm, preferably 0.2 to 5.0 μm.
3.0 μm, particularly preferably 0.3 to 2.0 μm
m. When the volume average particle diameter is within the above range, the impact resistance becomes particularly good. Note that the rubber volume average particle diameter is TEM
(Transmission electron microscope) It can be measured by observation or light scattering after dispersion in a solvent.

In the present invention, the weight average molecular weight of the (a-1) graft copolymer soluble in methyl ethyl ketone is 70.
000-150,000, preferably 75,000-1400
00, particularly preferably 80,000 to 120,000. Methyl ethyl ketone soluble matter has a weight average molecular weight of 70
If it is less than 000, the impact strength of the flame-retardant resin composition decreases, while if it exceeds 150,000, the drawback of insufficient drip-resistant flame retardancy becomes significant. In other words, the weight average molecular weight of the methyl ethyl ketone soluble component is 70,000 to 150,000.
Is the specific molecular weight (a-
2) The present inventors have found that a flame-retardant resin composition excellent in impact strength, rigidity, fluidity, dripping flame retardancy can be obtained when used in combination with a (co) polymer. In addition,
The weight average molecular weight can be measured by a GPC method using tetrahydrofuran as an eluent as described later and converted by a calibration curve using standard polystyrene.

Next, the (a-2) (co) polymer will be described. (A-2) The (co) polymer is prepared by subjecting a monomer mixture containing an aromatic vinyl monomer and, if necessary, a vinyl monomer copolymerizable therewith to a known bulk polymerization and bulk suspension. It is obtained by polymerization, emulsion polymerization and solution polymerization. The mass ratio of the aromatic vinyl monomer to the copolymerizable vinyl monomer is 30-100 / 70-0, preferably 40-1.
00 / 60-0, particularly preferably 50-100 / 50
０0. 30% by mass of vinyl aromatic monomer
If it is less than 1, at least one property of moldability, heat resistance and impact resistance is impaired.

The aromatic vinyl monomer and the copolymerizable vinyl monomer include the aromatic vinyl monomer, vinyl cyanide monomer and acrylate ester exemplified in the (a-1) graft copolymer. Monomer, methacrylate monomer,
It may be an unsaturated carboxylic acid amide monomer, an unsaturated dicarboxylic acid imide monomer, or a vinyl monomer containing an epoxy group, and any of these monomers can be used alone or in combination of two or more. (A-2) Specific examples of the (co) polymer include polystyrene, α-methylstyrene / acrylonitrile copolymer, styrene / acrylonitrile copolymer,
Styrene / acrylonitrile / methyl methacrylate copolymer, styrene / N-phenylmaleimide copolymer, styrene / N-phenylmaleimide / acrylonitrile copolymer and the like.

(A-2) The weight average molecular weight of the (co) polymer is 100,000 to 200,000, preferably 11,000.
0 to 180,000, particularly preferably 120,000 to 17
0000. If it is less than 100,000, the impact strength tends to decrease, and if it exceeds 200,000, the fluidity decreases and the drip-resistant flame retardancy decreases. The weight average molecular weight can be controlled by the type and amount of the polymerization initiator, the polymerization temperature, the type and amount of the chain transfer agent, and the like. Although the weight average molecular weight of the (a-2) (co) polymer in the present invention is larger than the acetone-soluble component of the resin component disclosed in JP-A-10-279775, the (a-1) graft copolymer The present inventors have found that, by optimizing the molecular weight with coalescence, a flame-retardant resin composition having excellent physical properties such as impact strength and rigidity can be obtained while maintaining drip-resistant flame retardancy. It is.

(A-1) Graft copolymer and (a-2)
The weight ratio of the (co) polymer is from 5 to 70:95 to 30, preferably from 10 to 60:90 to 40, and particularly preferably from 15 to 5
0: 85 to 50. When the ratio of the (a-1) graft copolymer is less than 5 in mass ratio, the impact strength decreases, and conversely,
If it exceeds 70, there will be a drawback in that the fluidity and drip-ability flame retardancy are reduced.

The phosphorus compound (B) used in the present invention is not particularly limited as long as it has a phosphorus atom. Phosphoric acid ester, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, phenylphosphonic acid Examples thereof include diethyl, phosphazene compounds, melamine phosphate, melamine polyphosphate, ammonium polyphosphate, and resin coatings of ammonium polyphosphate. Preferably, an organic phosphorus compound represented by the general formula (1) is used.

[0018]

Embedded image (Wherein, R1, R2 and R3 independently represent a hydrogen atom or an organic group, except when R1 = R2 = R3 = H. X represents a divalent or higher valent organic group, and Y represents an oxygen atom Or a sulfur atom, Z represents an alkoxy group or a mercapto group, n is 0 or 1, p is 0 or 1, q
Is an integer of 1 to 30, and r represents an integer of 0 or more. However, it is not limited to these. )

In the above formula, examples of the organic group include an alkyl group which may or may not be substituted, a cycloalkyl group and an aryl group. When substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, and the like. In addition, a group obtained by combining these substituents (for example, an arylalkoxyalkyl group) or these substituents is used. A group (for example, an arylsulfonylaryl group) combined by bonding with an oxygen atom, a sulfur atom, a nitrogen atom, or the like may be used as a substituent. Further, the divalent or higher valent organic group means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above-mentioned organic group, for example, an alkylene group, and preferably (substituted or substituted) ) Phenylene groups, polynuclear phenols such as those derived from bisphenols, and the relative positions of two or more free valences are arbitrary. Particularly preferred are hydroquinone, resorcinol, bis (4-hydroxyphenyl) methane,
2,2-bis (4-hydroxyphenyl) propane [bisphenol A], dihydroxydiphenyl, p, p '
-Dihydroxydiphenylsulfone, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone and the like.

Illustrative examples of these phosphorus compounds include phosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate and tricresyl phosphate. , Trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (o-phenylphenyl) phosphate, tris (p-phenylphenyl) phosphate, trinaphthylphosphate, cresyldiphenylphosphate, xyenyldiphenylphosphate, diphenyl (2- Ethylhexyl) phosphate, di (isopropylphenyl) phenylphosphate, o-phenylphenyldicresylphosphate Eto, dibutyl phosphate,
Monobutyl phosphate, di-2-ethylhexyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, etc. And condensates thereof such as resorcinol bis (diphenyl phosphate), resorcinol bis (dicresyl phosphate), resorcinol bis (dicylenyl phosphate), hydroquinone bis (diphenyl phosphate), hydroquinone bis (dicresyl phosphate), and hydroquinone bis (dicylide) (Silenyl phosphate), biphenol bis (dixylenyl phosphate), bisphenol Bis (diphenyl phosphate), bisphosphate and polyphosphate oligomers such as bisphenol A bis (dicresyl phosphate), and the like.

In addition, triphenyl phosphate, tricresyl phosphate, and their condensed phosphates may be used.
A hydroxyl group-containing aromatic phosphate containing one or more phenolic hydroxyl groups can also be used as the phosphorus compound. Examples of the hydroxyl group-containing aromatic phosphate include diphenyl resorcinol phosphate, phenyl diresorcinol phosphate, dicresyl resorcinol phosphate, and the like.

In the present invention, phosphoric acid esters are preferably used as the organic phosphorus compound, and among them, particularly preferred are triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, cresyl diphenyl phosphate, and xylide. Monophosphates such as nildiphenyl phosphate and di (isopropylphenyl) phenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl phosphate) And the like. These phosphorus compounds may be used alone or in combination of two or more.

The component (C) used in the present invention includes:
Natural wax, synthetic wax, fatty acid, fatty acid salt, fatty acid ester, fatty acid amide, fluororesin having a melting point of 200 ° C. or less, kinematic viscosity at 25 ° C. of 1 × 10 ⁻³ m ² /
s or less. These components (C) can improve fluidity and impact strength without impairing flame retardancy.

Examples of the natural wax and the synthetic wax include liquid paraffin, natural paraffin, micro wax, polyolefin wax, synthetic paraffin, terpene resin, terpene phenol resin, and partial oxides thereof.

Examples of fatty acids include caproic acid, hexadecanoic acid, palmitic acid, stearic acid, hydroxystearic acid, behenic acid, lauric acid, oleic acid, phenylstearic acid, 12-hydroxystearic acid, ferronic acid, ricinoleic acid, lysine Veridic acid, tallow acid, 9-oxy-12-octadecenoic acid, rosin acid, disproportionated rosin acid and montanic acid.

The fatty acid salts include calcium, magnesium, zinc, tin, aluminum,
Barium, nickel, iron, copper, lithium, sodium,
And salts such as potassium.

Examples of the fatty acid ester include the above-mentioned fatty acid monoglyceride, diglyceride, triglyceride, polyglycerin, pentaerythritol, sorbitol,
Examples include (partial) esters with propylene glycol, polyoxyethylene, and higher alcohols. In addition, as a higher alcohol, stearyl alcohol, coconut alcohol, merisil alcohol, cetyl alcohol and the like can be mentioned.

Examples of the fatty acid amide include the above fatty acid monoamide, ethylenebisamide, methylenebisamide, oleylamide, erucamide, palmitoamide and the like.

Examples of the fluororesin having a melting point of 200 ° C. or lower include copolymers of tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride and the like having a number average molecular weight of 50,000 to 400,000.
When the melting point exceeds 200 ° C., there is a tendency that the dripping flame retardancy is impaired.

The kinematic viscosity at a temperature of 25 ° C. is 1 × 10 ⁻³ m ² /
Examples of the silicone oil which are not more than s include polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, polymethylhydrogensiloxane, or amino group, mercapto group, epoxy group at the terminal or in the molecular chain of these polyorganosiloxanes. , A carboxyl group, a vinyl group, a hydroxyl group, an amide group, an ester group and the like. Particularly preferred are polymethylphenylsiloxane and polydimethylsiloxane having a molar ratio of phenyl to methyl of 0 to 30: 100 to 70. These polyorganosiloxanes have a kinematic viscosity at a temperature of 25 ° C. of 1 × 10 ^−5.
１1 × 10 ⁻³ m ² / s, preferably 2 × 10 ^{−5 to} 7 × 1
0 ⁻⁴ m ² / s, particularly preferably 3 × 10 ^{−5 to} 5 × 10 ⁻⁴
m ² / s. Kinematic viscosity at a temperature of 25 ° C. is 1 × 10 ⁻⁵ m ²
If it is less than / s, the flame retardancy and the decrease in mold contamination due to volatilization of the polyorganosiloxane appear, and the kinematic viscosity is 1 × 10 ^−3.
If it exceeds m ² / s, the dripping flame retardancy is reduced.

In the present invention, the proportions of the components (B) and (C) are each 1 part by mass per 100 parts by mass of the component (A).
To 20 parts by mass, 0 to 10 parts by mass, preferably 2 to 18 parts by mass
Parts by mass, 0.01 to 8 parts by mass, particularly preferably 3 to 1 part by mass.
5 parts by mass, 0.03 to 7 parts by mass. (B) Component is 1
If the amount is less than 20 parts by mass, the flame retardancy is insufficient. If the amount is more than 20 parts by mass, physical properties tend to be reduced in any of heat resistance, impact strength and the like. If the component (C) exceeds 10 parts by mass, any of heat resistance, impact strength, and flame retardancy tends to decrease.

As required for the resin composition of the present invention, red phosphorus, melamine borate, ammonium borate, metaboric acid, boric acid, borax, boric anhydride, zinc borate, zinc metaborate, barium metaborate, magnesium borate, cadmium borate. , Lead borate, boron compounds such as barium orthoborate, zinc compounds such as zinc borate, zinc stannate, zinc oxide, zinc sulfide, zinc carboxylate, tin compounds such as zinc stannate, zinc hydroxy stannate, tin oxide, silane -Based coupling agents, titanium-based coupling agents, aluminum-based coupling agents, triazine skeleton-containing compounds, fluorine-based elastomers, hydroxystyrene-based resins, phenolic resins, thermally expandable graphite, silica, metal compounds other than boron, zinc, and tin , Aramid fibers, polyacrylonitrile fibers, processing aids, and the like.

Specific examples of the triazine skeleton-containing compound include melamine, melamine cyanurate, melem, melon, melamine oxalate, melamine sulfate, melamine phthalate, succinoguanamine, adipoguanamine, methylglutaloganamine, melamine resin, BT resin And the like. Melamine cyanurate and melamine sulfate are particularly preferred from the viewpoint of low volatility and improvement in flame retardancy.

The silica may be crystalline silicon dioxide or amorphous silicon dioxide. Further, the shape may be either a crushed shape or a spherical shape, but preferably, the average particle size is 10
μm or less, particularly preferably 1 μm or less. These silicas are more preferably treated with various coupling agents in order to improve the dispersibility in the resin composition.

As a metal compound other than boron, zinc and tin,
Iron, titanium, manganese, magnesium, zirconium,
Hydroxide, oxide, nitrate, sulfonate and carboxylate of metals such as molybdenum, cobalt, bismuth, chromium, antimony, nickel, copper, tungsten and aluminum, aluminum hydroxide treated with oxalate anion, and nickel compound treated Of magnesium hydroxide, ferrocene and the like.

In the present invention, if necessary, a thermoplastic resin other than the component (A) may be contained as long as physical properties such as flame retardancy and impact resistance are not impaired. Typical examples thereof include polyesters such as polycarbonate, polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, 6-nylon, 6,6-nylon, and aromatic nylon of meta-xylylenediamine / adipic acid. Such as polyamide resin, polyarylate, (modified) polyethylene, (modified) polypropylene, (modified) ethylene-propylene copolymer resin, polymethylpentene, polyphenylene ether, polyphenylene sulfide, polyacetal, polyetheresteramide, polyetherimide, poly Ether ether ketone, polymethyl methacrylate and the like can be mentioned. These resins can be used in combination of two or more kinds, and if necessary, a block polymer or a compatibilizer having a functional group can be blended.

The flame-retardant resin composition of the present invention can be obtained without using a compound containing bromine or chlorine as a flame-retardant component.
Although it exhibits an excellent flame retardant effect, a commonly used flame retardant additive such as a chlorine- or bromine-containing compound which is commonly used can be used.

The method of mixing the resin and the flame retardant is not particularly limited, and any means can be employed as long as they can be uniformly mixed. For example, mixing by various mixing machines such as a single screw extruder, a twin screw extruder, a Henschel mixer, a Banbury mixer, a kneader, a heating roll,
Kneading and the like can be appropriately adopted. In kneading, each component may be kneaded at once, or after kneading any components, the remaining components may be added and kneaded. A preferred kneading method is a method using an extruder, and a twin-screw extruder is particularly preferred as the extruder.

At this time, if necessary, various fillers, additives and the like can be blended in such an amount that the effect is exhibited as long as the flame retardancy is not impaired. Examples include fibrous fillers such as glass fiber, asbestos, carbon fiber, potassium titanate whisker fiber, metal fiber, ceramic fiber, boron whisker fiber, mica, talc, clay, calcium carbonate, glass beads, glass balloon, glass. Fillers such as flakes, release agents, plasticizers, dispersants, ultraviolet absorbers,
Additives such as light stabilizers, antioxidants, heat stabilizers, antioxidants, dyeing (face) agents, and the like. Further, an impact strength improver for improving the properties of the resin composition, a compatibilizing component, and the like can be added.

[0040]

The following examples are provided to further illustrate the present invention but are not intended to limit the invention in any way. Unless otherwise specified, all parts and ratios described in this specification are based on mass.

The resins, phosphorus compounds, flame-retardant auxiliaries and the like used in Examples and Comparative Examples are shown below. (A-1) Graft copolymer 80 parts of polybutadiene latex (volume average particle diameter 31
0 μm, solid content concentration 50%), water 150 parts, ethylenediaminetetraacetic acid disodium salt 0.1 part, ferric sulfate 0.1 part.
001 parts, 0.3 parts of sodium formaldehyde sulfoxylate, and after heating to 55 ° C., a mixture consisting of 14 parts of acrylonitrile, 46 parts of styrene, 0.2 parts of cumene hydroperoxide and 0.1 part of t-dodecyl mercaptan was added. It was added continuously in 3 hours and polymerized at 60 ° C. for 2 hours. The obtained latex is precipitated with an aqueous acid solution, washed with water, filtered and dried, and the powder obtained is abbreviated as A11.

Further, 80 parts of polybutadiene latex (volume average particle diameter 310 μm, solid content concentration 50%) were mixed with 150 parts of water and disodium ethylenediaminetetraacetate 0.1%.
1 part, ferric sulfate 0.001 part, sodium formaldehyde sulfoxylate 0.3 part, and after heating to 55 ° C., acrylonitrile 14 parts, styrene 46 parts, cumene hydroperoxide 0.2 part were added to t, respectively. A mixture consisting of 0.2 parts, 0.4 parts, 0.8 parts and 1.2 parts of dodecyl mercaptan was added continuously over 3 hours each and polymerized at 60 ° C. for 2 hours. The obtained latex is precipitated with an aqueous acid solution, washed with water, filtered and dried, and the powders obtained are abbreviated as A12, A13, A14 and A15, respectively.

After 1 part of each graft copolymer was dispersed in 30 parts of methyl ethyl ketone in an emulsion state,
After centrifugation at 0 G for 30 minutes to collect soluble components, the weight average molecular weight was measured by GPC. The weight-average molecular weight of the methyl ethyl ketone-soluble component is A11, A12, A13, A1
4, A15 163000, 142000, 11 respectively
7000, 83000, 67000. Note that G
The PC was measured using SYSTEM-21 (RI) (manufactured by Tosoh Corporation) and converted by a calibration curve using standard polystyrene with tetrahydrofuran as an eluent.

(A-2) (Co) polymer An aqueous solution of a dispersing agent previously mixed with 100 parts of water, 4 parts of magnesium hydroxide and 0.002 part of sodium lauryl sulfate is added to
After 25 parts of acrylonitrile, 75 parts of styrene, 0.32 parts of lauroyl peroxide and 0.1 part of t-dodecylmercaptan were charged and suspended, polymerization was carried out at 70 ° C. for 10 hours. The obtained particles are washed with water and dried, and the obtained copolymer is abbreviated as A21.

100 parts of water, magnesium hydroxide 4
Acrylonitrile, 25 parts of styrene and 75 parts of styrene,
Parts, lauroyl peroxide 0.32 parts, t-
Dodecyl mercaptan 0.2 part, 0.3 part, 0.5 part,
After charging a mixture consisting of 0.6 parts and suspending each,
Polymerization was performed at 70 ° C. for 10 hours. The obtained particles were washed with water and dried, and the obtained copolymers were A22, A23 and A2, respectively.
4, A25. In addition, these copolymer A2
1, A22, A23, A24, and A25 have a weight average molecular weight of 211,000, 182000, and 14900, respectively.
0, 114,000 and 98,000.

Acrylonitrile 20 parts, styrene 80
Parts and t-dodecyl mercaptan except for 0.3 part, a copolymer A26 having a weight average molecular weight of 127000 was obtained in the same manner as A21. MS-NB manufactured by Denki Kagaku Co., Ltd. as a styrene-maleic anhydride-N-phenylmaleimide copolymer
(Weight average molecular weight 131,000)
Abbreviated.

(B) Phosphorus compound Triphenyl phosphate, resorcinol bis (dixylenyl phosphate) and resorcinol (diphenyl phosphate) manufactured by Daihachi Chemical Industry Co., Ltd. are used, and are abbreviated as BTPP, BPX and BCR, respectively.

(C) Component Wax S (manufactured by Clariant Japan) as a fatty acid
And hereinafter abbreviated as CWS. Zinc stearate (Zn-St, manufactured by Nitto Kasei Kogyo Co., Ltd.) is used as the fatty acid salt, and is hereinafter abbreviated as CSZn. As the fatty acid amide, kaowax EB-P (ethylene bis (stearyl amide, manufactured by Kao Corporation) is used, and is abbreviated as CEBP hereinafter. As a synthetic wax, wax PED521 (polyethylene oxide, manufactured by Clariant Japan) is used. The fluorocarbon resin having a softening point of 200 ° C. or lower is Hostamont VPFN901.
(Softening point 125 ° C., manufactured by Clariant Japan Co., Ltd.), hereinafter abbreviated as CFR. KF96 as silicone
-100 (dimethyl silicone, kinematic viscosity of 10 at 25 ° C)
^-4 m ² / s, manufactured by Shin-Etsu Chemical Co., Ltd.). (D) Other thermoplastic resin Iupilon S3000FN manufactured by Mitsubishi Engineering Co., Ltd. was used as a polycarbonate resin.
Abbreviated. Parapet GC-1000 manufactured by Kuraray Co., Ltd. was used as polymethyl methacrylate resin.
Abbreviated.

Examples 1 to 18 and Comparative Examples 1 to 5 Mixing and stirring by a Henschel mixer with the blending of parts by mass shown in Tables 1 and 2, and a twin screw extruder (ZSK-L / D = 35)
Using 25), the mixture was melt-kneaded and extruded at a barrel set temperature of 230 ° C. at a fixed feed rate of 15 kg / hr, and pelletized by a pelletizer. After sufficiently drying the pellet thus obtained, a test piece was prepared by injection molding, and evaluated and measured by the following methods. (1) Izod impact strength: Measured using a notched test piece at a temperature of 23 ° C. and a thickness of ４ inch in accordance with ASTM D256. (2) Heat deformation temperature: Measured under a load of 1.82 MPa in accordance with ASTM D648. (3) Melt flow rate (MFR): ASTM D1
In accordance with H.238, the measurement was performed under the conditions of a load of 49 N and a temperature of 200 ° C. (4) Flexural modulus: Measured according to ASTM-D790. (5) Flame retardancy: 1.5 mm according to UL-94 test method
The evaluation was performed using a test piece having a thickness, and the judgment was also in accordance with UL-94. The results are shown in Tables 1 and 2.

[0050]

[Table 1]

[0051]

[Table 2]

From the comparison between Examples 1 to 7 and Comparative Examples 1 to 5, the weight average molecular weight of the methyl ethyl ketone soluble portion of the graft copolymer was 70,000 to 150,000, and the weight average molecular weight of the copolymer was 100,000 to 200,000. Only in the case of, the flame retardancy of V-2 and the Izod impact strength were 10
A resin composition having 0 J / m or more and a flexural modulus of 2700 MPa or more is obtained.

From the comparison between Example 8 and Example 9, (C)
The addition of the component additives improves the fluidity and impact strength without impairing the flame retardancy.

Examples 10 to 12 are examples in which a styrene-maleic anhydride-N-phenylmaleimide copolymer is used as the component (B), and a polymethyl methacrylate resin and a polycarbonate resin are used in combination as other thermoplastic resins, respectively. However, in Example 10, the heat resistance was improved, and in Example 11,
Is the light transmittance of a 2 mm thick plate (ASTM D-
Transparent V- having a value of 59% (measured according to 1003).
In Example 12, the impact strength and the heat resistance were improved by alloying with an engineering plastic.

All the samples of Examples 1 to 18 and Comparative Examples 1 to 5 have the same hue as the ABS resin containing no flame retardant.
It is a resin composition which has no problem in appearance and colorability.

[0056]

The resin composition of the present invention is a flame-retardant resin composition comprising a rubber-modified styrene resin as an essential component and having excellent flame retardancy, fluidity, rigidity, impact resistance and heat resistance. It can be suitably used for applications such as electronic and electrical products and OA equipment, and as various component materials.

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Claims (2)

[Claims] 1. A graft copolymer (a-1) obtained by (co) polymerizing a monomer mixture containing an aromatic vinyl monomer as an essential component in the presence of a rubbery polymer (A). (B) per 100 parts by mass of the rubber-modified styrene resin composed of the (co) polymer (a-2) containing an aromatic vinyl monomer as an essential component,
A flame-retardant resin composition containing 1 to 20 parts by mass of a phosphorus compound, wherein the graft copolymer (a-1)
Has a weight-average molecular weight of 700 soluble in methyl ethyl ketone.
A flame-retardant resin composition, wherein the weight-average molecular weight of the (co) polymer (a-2) is from 100,000 to 200,000. 2. The components (A) and (B) according to claim 1, further comprising, as component (C), a fatty acid, a fatty acid salt, a fatty acid ester, a fatty acid amide, a natural wax, a synthetic wax, and a melting point of 200. ° C. or less is fluororesin, and one or more additive components kinematic viscosity is chosen from silicone oil is less than 1 × 10 ^-3 m ² / s at a temperature 25 ° C. 0.
A flame-retardant resin composition containing from 0.01 to 10 parts by mass.