JP2003327635A - Graft copolymer and impact resistant and flame retardant resin composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a flame retardance-impact resistance modifier for a thermoplastic resin. <P>SOLUTION: The modifier is a graft copolymer containing a polyorganosiloxane, wherein the graft copolymer is obtained by polymerizing (B) 0-10 pts.wt. vinyl monomers consisting of 100-50 wt.% of (b-1) a multifunctional monomer containing two or more polymerizable unsaturated bonds in the molecule and 0-50 wt.% of (b-2) other polymerizable monomers, and further by polymerizing (C) 5-70 pts.wt. of a vinyl monomer [wherein the total of (A), (B) and (C) amounts to 100 pts.wt.] in the presence of 30-95 pts.wt. (in terms of solid) of a polyorganosiloxane in a latex state obtained by seed polymerizing a polymer that has hydrophillic property and is capable of swelling in an organosiloxane, using as the seed polymer. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyorganosiloxane-containing graft copolymer and a resin composition containing the same, which is excellent in impact resistance and flame retardancy.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used as electric / electronic parts, OA equipment, household products or building materials because of their excellent impact resistance, heat resistance and electrical characteristics. This resin has higher flame retardancy than polystyrene resins, but when used in the fields of electrical / electronic parts, OA equipment, etc., where high flame retardancy is required, it can be used as a flame retardant of various types. Flame retardation is further achieved by addition. Conventionally, addition of organic halogen-based compounds and organic phosphorus-based compounds has been widely used for flame retardation, but many of these compounds have problems in terms of toxicity. The demand for flame retardancy is increasing.

The use of polyorganosiloxane compounds has been proposed as a non-halogen / non-phosphorus flame retardant. For example, JP-A-54-36365 describes that a flame-retardant resin can be obtained by kneading a silicone resin composed of a monoorganopolysiloxane with a non-silicone polymer.

Japanese Patent Publication No. 3-48947 discloses that a mixture of a silicone resin and a Group IIA metal salt imparts flame retardancy to a thermoplastic resin.

JP-A-8-113712 discloses that 100 parts by weight of polyorganosiloxane and 10 to 10 parts of silica filler are used.
A method for obtaining a flame-retardant resin composition by dispersing a silicone resin prepared by mixing with 150 parts by weight in a thermoplastic resin is described.

JP-A-10-139964 discloses a flame-retardant resin composition obtained by adding a silicone resin soluble in a solvent having a weight average molecular weight of 10,000 to 270,000 to a non-silicone resin containing an aromatic ring. It is stated that you can get things.

However, the silicone resin described in the above publication is insufficient in imparting flame retardancy, and there is a problem that the impact resistance of the resin composition is deteriorated if the amount is increased to compensate for it.

JP-A-2000-17029 discloses a composite rubber-based flame retardant obtained by graft-polymerizing a vinyl-based monomer onto a composite rubber composed of a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber as a thermoplastic resin. It is described that a flame-retardant resin composition can be obtained by blending.

Japanese Patent Laid-Open No. 2000-226420 discloses that
A flame-retardant resin composition can be obtained by blending a thermoplastic resin with a polyorganosiloxane-based flame retardant obtained by grafting a vinyl-based monomer onto composite particles of a polyorganosiloxane having an aromatic group and a vinyl-based polymer. Is described.

Japanese Patent Laid-Open No. 2000-264935 discloses that
It is described that a flame-retardant resin composition can be obtained by blending a thermoplastic resin with a polyorganosiloxane-containing graft copolymer obtained by graft-polymerizing vinyl-based monomers onto polyorganosiloxane particles of 0.2 μm or less. There is.

The above-mentioned JP-A-2000-17029, JP-A-2000-226420 and JP-A-2000-26.
Any of the flame-retardant resin compositions described in Japanese Patent No. 4935,
Although the impact resistance is at a satisfactory level, it has a problem of poor balance between flame resistance and impact resistance due to insufficient flame resistance.

As a technique for improving impact resistance, a technique of dispersing a rubber component in a thermoplastic resin is widely known. For example, there is a method shown in Japanese Examined Patent Publication No. 39-19035. Further, various improvements have been made to the rubber component in order to improve impact resistance. For example, a method of increasing the particle size of the rubber component (Japanese Patent Publication No. 42-225419 and a method of lowering the Tg of the rubber component (Japanese Patent Laid-Open No. 2-1763, JP-A-8-10009
5) is proposed. However, it is difficult to meet the demands of the market, which is expected to greatly improve the impact resistance, only with these measures.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyorganosiloxane-containing graft copolymer which can be used as a non-halogen / non-phosphorus flame retardant and is excellent in flame retardancy / impact resistance improving effect. The purpose of the present invention is to provide a flame-retardant resin composition excellent in flame retardancy and impact resistance by using a graft copolymer.

[0014]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a polymer having hydrophilicity and swelling into an organosiloxane is used as a seed polymer.
The graft copolymer containing a polyorganosiloxane in a latex state obtained by seed polymerization used as a composition is excellent in flame retardancy and impact resistance-improving effect, and this polyorganosiloxane-containing graft copolymer was blended. The inventors have found that the thermoplastic resin composition exhibits excellent flame retardancy and impact resistance, and have completed the present invention.

That is, according to the present invention, 30 to 95 parts by weight (solid content) of (A) a polyorganosiloxane in a latex state obtained by seed polymerization using a polymer having hydrophilicity and swelling as an organosiloxane as a seed polymer. In the presence of (B) a polyfunctional monomer (b-1) 100 to 50 containing two or more polymerizable unsaturated bonds in the molecule
% By weight and other copolymerizable monomer (b-2) 0
Polymerization of 0 to 10 parts by weight of a vinyl-based monomer consisting of ˜50% by weight, and further 5 to 70 parts by weight of (C) vinyl-based monomer [(A), (B) and (C) combined 100 parts by weight) Department]
The polyorganosiloxane-containing graft copolymer obtained by polymerizing the above (claim 1), hydrophilicity, to the water after adding 20 times (weight) amount of water to the dry seed polymer and stirring at room temperature for 1 hour The extraction rate is 10 to 100% by weight, and the swelling property of organosiloxane is 50 times as much as the seed polymer (by weight). The organosiloxane is added to the seed polymer latex, and the latex particle size and the original particle after stirring at room temperature for 1 hour The swelling volume ratio determined from the diameter ratio is 3 to 50 times, and the polyorganosiloxane-containing graft copolymer according to claim 1 (claim 2) is 20 times more hydrophilic than the dry seed polymer. After adding an amount (weight) of water and stirring at room temperature for 1 hour, the extraction rate into water is 50 to 100% by weight,
The swelling property of the organosiloxane is 50 times that of the seed polymer.
A swelling volume ratio of 3 to 15 was obtained by adding a double amount (weight) of organosiloxane to the seed polymer latex and stirring the mixture at room temperature for 1 hour, and then calculating the ratio of the latex particle size and the original particle size.
The polyorganosiloxane-containing graft copolymer according to claim 1 (claim 3), wherein the vinyl monomer (C) is an aromatic vinyl monomer and a vinyl cyanide monomer. A monomer, at least one monomer selected from the group consisting of (meth) acrylic acid ester monomers and carboxyl group-containing vinyl monomers.
Alternatively, with respect to the polyorganosiloxane-containing graft copolymer according to claim 4 (claim 4), the flame retardant comprising the polyorganosiloxane-containing graft copolymer according to claim 1 (claim 5) and 100 parts by weight of the thermoplastic resin. Claim 6
The present invention relates to a resin composition (Claim 6) which is excellent in impact resistance and impact resistance and which comprises 0.1 to 30 parts by weight of the flame retardant described above.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The polyorganosiloxane-containing graft copolymer of the present invention comprises (A) a polymer which is hydrophilic and swells into an organosiloxane as a seed polymer.
In the presence of 30 to 95 parts (parts by weight, the same applies hereinafter) of a polyorganosiloxane in a latex state obtained by seed polymerization used as (2), a polymerizable unsaturated bond in the molecule (B) is 2
100 to 50% of polyfunctional monomer (b-1) containing one or more
(Wt%, the same shall apply hereinafter) and 0 to 50% of other copolymerizable monomer (b-2) vinyl monomer 0 to 1
It is obtained by polymerizing 0 part, and further polymerizing 5 to 70 parts of (C) vinyl-based monomer [100 parts in total of (A), (B) and (C)].

The seed polymer used in the present invention can be obtained by ordinary emulsion polymerization, but the synthetic method is not particularly limited. The seed polymer is not limited to rubber components such as butyl acrylate rubber and butadiene rubber, and butyl acrylate-styrene copolymers and styrene-hard polymers such as acrylonitrile copolymers may be used, but water particles In order to be taken in, it is necessary that the monomer of the rubber produced in the next step is sufficiently swollen and has a strong hydrophilicity.

As a method of improving the swelling property of the seed polymer with respect to the organosiloxane, it is important to use a seed polymer whose polarity is suitable for the organosiloxane, and then to use a chain transfer agent, a high polymerization temperature, or the like. It is effective to make the molecular weight of the seed polymer extremely low by, for example, selecting a large amount of initiator.

The hydrophilicity of the seed polymer can be measured by the extraction ratio to water after adding 20 times (weight) amount of water to the dry seed polymer and stirring the mixture at room temperature for 1 hour. The value may be 1% or more. It is preferably 10 to 100% by weight, more preferably 50 to 100%.

The swelling property of the seed polymer to the organosiloxane is determined by adding 50 times (by weight) the amount of the organosiloxane to the seed polymer latex and stirring the mixture at room temperature for 1 hour. It can be measured by the swelling volume ratio obtained from the ratio. The value should be 1.5 times or more. It is preferably 3 to 50 times, more preferably 3 to 15 times.

Within these ranges, the effects of improving flame retardancy and impact resistance are remarkable. The average particle diameter of the (A) latex polyorganosiloxane is determined by light scattering method or electron microscope observation, and is preferably 0.008 to 0.6 μm, but 0.01 to
More preferably, it is 0.2 μm. The average particle size is 0.
It tends to be difficult to obtain a particle size of less than 008 μm,
If it exceeds 0.6 μm, the flame retardancy and impact resistance tend to deteriorate.

The above polyorganosiloxane may be used alone, or may be a copolymer with diphenylsiloxane or the like.

Examples of the polyorganosiloxane (A) include (1) organosiloxane, (2) bifunctional silane compound, (3) organosiloxane and bifunctional silane compound, (4) organosiloxane and vinyl-based polymerizable group. A silane compound containing, (5) a bifunctional silane compound and a vinyl-based polymerizable group-containing silane compound or (6) an organosiloxane, a bifunctional silane compound, a vinyl-based polymerizable group-containing silane compound, or the like, or a trifunctional compound. It can be obtained by adding the above silane compound and polymerizing.

The organosiloxane is a component constituting the main skeleton of the polyorganosiloxane chain. Specific examples of the organosiloxane include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and decamethyl. Cyclopentasiloxane (D5), Dodecamethylcyclohexasiloxane (D
6), tetradecamethylcycloheptasiloxane (D
7), hexadecamethylcyclooctasiloxane (D
8) and the like. Specific examples of the bifunctional silane compound include diethoxydimethylsilane, dimethoxydimethylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and heptadecafluorodecyl. Examples thereof include methyldimethoxysilane, trifluoropropylmethyldimethoxysilane, octadecylmethyldimethoxysilane and the like.

The vinyl-based polymerizable group-containing silane compound is an organosiloxane, a bifunctional silane compound, or a trifunctional silane compound.
It is a component for copolymerizing with a functional silane compound or the like to introduce a vinyl-based polymerizable group into the side chain or terminal of the copolymer. The vinyl-based polymerizable group is a vinyl-based monomer (B ) Or a vinyl-based (co) polymer formed from the vinyl-based monomer (C), which acts as a grafting active point. Furthermore, it is a component that can be used as a cross-linking agent by radically reacting between graft active points with a radical polymerization initiator to form a cross-linking bond.

Specific examples of the vinyl-based polymerizable group-containing silane compound include, for example, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane and γ-methacryloyl. Oxypropyldiethoxymethylsilane, γ-acryloyloxypropyldimethoxymethylsilane, γ-
(Meth) acryloyloxy group-containing silane compound such as acryloyloxypropyltrimethoxysilane, p-
Vinylphenyl group-containing silane compounds such as vinylphenyldimethoxymethylsilane and p-vinylphenyltrimethoxysilane, vinyl group-containing silane compounds such as vinylmethyldimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane, mercaptopropyltrimethoxysilane, Examples thereof include mercapto group-containing silane compounds such as mercaptopropyldimethoxymethylsilane.

Specific examples of the trifunctional or higher functional silane compound include tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane and heptadecafluorodecyltri. Examples thereof include tetrafunctional and trifunctional alkoxysilane compounds such as methoxysilane, trifluoropropyltrimethoxysilane and octadecyltrimethoxysilane.

The ratio of the organosiloxane, the bifunctional silane compound, the vinyl-based polymerizable group-containing silane compound, and the trifunctional or higher functional silane compound used during the polymerization is usually an organosiloxane and / or a bifunctional silane compound (organosiloxane). The ratio of the difunctional silane compound to the bifunctional silane compound is usually 100/0 to 0/100, further 1
00/0 to 70/30) 50 to 99.9%, and further 6
0-99.5%, vinyl-based polymerizable group-containing silane compound 0
-40%, more preferably 0.5-30%, trifunctional or higher functional silane compound 0-50%, and further preferably 0-39%. Incidentally, vinyl-based polymerizable group-containing silane compounds, 3
Functional silane compounds do not become 0% at the same time, and it is preferable to use 0.1% or more of any of them.

If the use ratio of the organosiloxane and the bifunctional silane compound is too small, the resin composition obtained by blending tends to be brittle. On the other hand, when the amount is too large, the amounts of the vinyl-based polymerizable group-containing silane compound and the trifunctional or higher functional silane compound are too small, and the effect of using them tends to be difficult to be exhibited. Further, when the ratio of the vinyl-based polymerizable group-containing silane compound or the trifunctional or higher functional silane compound is too small, the flame retardancy-producing effect is low, and when the ratio is too large, The resin composition obtained by blending tends to be brittle.

The polyorganosiloxane (A) is obtained by adding a trifunctional or higher functional silane compound, if necessary, such as the organosiloxane, a bifunctional silane compound, or a vinyl-based polymerizable group-containing silane compound. It is preferably produced by emulsion polymerization of the polyorganosiloxane-forming component.

The vinyl-based monomer (B) is used for improving the flame retarding effect and the impact resistance improving effect, and is a polyfunctional compound containing two or more polymerizable unsaturated bonds in the molecule. Monomer (b-1) 100 to 50%, preferably 1
00-80%, and other copolymerizable monomers (b
-2) 0 to 50%, preferably 0 to 20%. When the amount of the polyfunctional monomer (b-1) is too small or when the amount of the copolymerizable monomer (b-2) is too large, both of the finally obtained graft copolymers are obtained. The impact resistance improving effect tends to be low.

Specific examples of the polyfunctional monomer (b-1) include allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
Examples include divinylbenzene. These may be used alone or in combination of two or more.

Specific examples of the copolymerizable monomer (b-2) include aromatic vinyl monomers such as styrene and α-methylstyrene, vinyl cyanide monomers such as acrylonitrile, and acryl. Examples thereof include (meth) acrylic acid ester-based monomers such as methyl acidate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. These may be used alone 2
You may use together 1 or more types.

The vinyl-based monomer (C) is a component used to obtain a polyorganosiloxane-containing graft copolymer, and it is difficult to blend the graft copolymer with a thermoplastic resin. It is also a component used to ensure compatibility of the graft copolymer with the thermoplastic resin and to evenly disperse the graft copolymer in the thermoplastic resin when improving the flammability and impact resistance. . Specific monomers include the same as the other copolymerizable monomer (b-2) in the vinyl-based monomer (B).

As a method for separating the polymer from the graft copolymer latex obtained by emulsion polymerization, the latex is coagulated, separated and washed with water by adding a metal salt such as calcium chloride, magnesium chloride or magnesium sulfate to the latex. , Dehydration, and drying. Also, a spray drying method can be used.

The graft copolymer thus obtained is blended with various thermoplastic resins to give a flame-retardant resin composition excellent in flame retardancy and impact resistance.

As the thermoplastic resin, a polycarbonate resin containing 50% or more of polycarbonate is preferable in that good flame retardancy can be obtained. Specific preferred examples of the polycarbonate-based resin include polycarbonate, polycarbonate / polyester mixed resin such as polycarbonate / polyethylene terephthalate mixed resin and polycarbonate / polybutylene terephthalate mixed resin, polycarbonate / acrylonitrile-styrene copolymer mixed resin, polycarbonate / butadiene-styrene. Copolymer (HIPS resin) mixed resin, polycarbonate / acrylonitrile-butadiene rubber-styrene copolymer (ABS resin) mixed resin, polycarbonate / acrylonitrile-butadiene rubber-α-methylstyrene copolymer mixed resin, polycarbonate / styrene-butadiene Rubber-acrylonitrile-N-phenylmaleimide copolymer mixed resin, polycarbonate / acryloni Lil - acrylic rubber - styrene copolymer (AAS
Resin) A mixed resin or the like can be used. Further, the mixed resins may be further mixed and used.

The amount of the polyorganosiloxane-containing graft copolymer added to the thermoplastic resin is 100 parts of the thermoplastic resin in terms of flame retardancy and impact resistance.
It is preferable to add 0.1 to 30 parts of the graft copolymer.

The flame retardant powder composed of the polyorganosiloxane-containing graft copolymer separated from the latex is mixed with the thermoplastic resin by mixing with a Henschel mixer, a ribbon blender or the like, and then with a roll, an extruder,
It can be performed by melt-kneading with a kneader or the like.

At this time, the compounding agents usually used, that is, antioxidant, anti-dripping agent, polymer processing aid, flame retardant,
Impact resistance improver, plasticizer, lubricant, UV absorber, pigment,
Glass fibers, fillers, polymeric lubricants and the like can be added.

As the molding method of the flame-retardant resin composition, a molding method used for molding a usual thermoplastic resin composition, that is, an injection molding method, an extrusion molding method, a blow molding method, a calender molding method or the like is applied. can do.

The use of the molded article obtained from the flame-retardant resin composition of the present invention is not particularly limited, but for example,
Desktop computer, notebook computer, tower computer, server computer, printer, copier, fax machine, mobile phone, PH
Applications include flame-retardant properties such as housings and chassis parts of various OA / information / home electric appliances such as S, TV, and video decks, various building material members, and various automobile members.

The obtained molded product has excellent impact resistance and flame retardancy.

[0044]

EXAMPLES The present invention will be specifically described based on examples, but the present invention is not limited to these.

Measurements and tests in Examples and Comparative Examples were carried out as follows.

The average particle size of the seed polymer and the graft copolymer was measured using MICROTRAC UPA manufactured by Reed & Northlap Instruments.

The impact resistance of the molded article is ASTM D-25.
According to 6, use a 1/8 inch bar with a notch -1
It was evaluated by an Izod test at 0 ° C or 23 ° C.

The flame retardancy of the molded product was evaluated by the UL94 V test. (Examples 1 to 6) Stirrer, reflux condenser, nitrogen blowing port,
Add water to a 5-neck flask equipped with a monomer addition port and thermometer.
0 parts by weight and sodium dodecylbenzene sulfonate (S
After mixing DBS) in an amount (solid content) shown in Table 1, 50
After the temperature is raised to 0 ° C and the liquid temperature reaches 50 ° C, nitrogen replacement is performed. Then, a mixed solution of 10 parts by weight of butyl acrylate and 3 parts by weight of t-dodecyl mercaptan is added. After 30 minutes, 0.01 part by weight of paramenthane hydroperoxide (solid content) was added and polymerized for 1 hour. Then, a mixed solution of 90 parts by weight of butyl acrylate and 27 parts by weight of t-dodecyl mercaptan is continuously added over 3 hours. After 2 hours of polymerization, seed latex (seed 1 to 4) was obtained. The average particle size, hydrophilicity and swelling degree after synthesis were measured, and the results are shown in Table 1.

A seed polymer shown in Table 2 and an amount (solid content) shown in Table 2 were placed in a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen blowing port, a monomer addition port, and a thermometer. I prepared it. Then, separately 300 parts of pure water, 0.5 part of SDBS (solid content), octamethylcyclotetrasiloxane 95
Part, 5 parts of dimethylmethylsilylpropyl methacrylate, 7,000 rpm with a homomixer
The mixture was stirred for 5 minutes to prepare an emulsion of the polyorganosiloxane-forming component, which was added all at once. Next, 1 part (solid content) of a 10% dodecylbenzenesulfonic acid aqueous solution was added, and then the system was heated to 80 ° C. under a nitrogen stream while stirring. After reaching 80 ° C., stirring was continued at 80 ° C. for 6 hours, then cooled to 25 ° C. and left for 20 hours. Then, the pH was adjusted to 6.4 with sodium hydroxide to complete the polymerization, and a latex containing polyorganosiloxane particles was obtained. Subsequently, 240 parts of pure water was added to a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen blowing port, a monomer addition port and a thermometer.
And 70 parts (solid content) of the above polyorganosiloxane particles were charged, and the system was heated to 40 ° C. under a nitrogen stream while stirring. After reaching 40 ° C, 0.2 part of sodium formaldehyde sulfoxylate (SFS), 0.01 part of ethylenediaminetetraacetic acid disodium (EDTA), and 0.0025 part of ferrous sulfate were added, and then 30 parts of methyl methacrylate was added. Cumene hydroperoxide 0.06
Part (solid content) of the mixture was added dropwise over 1.5 hours,
After the addition was completed, stirring was continued for 1 hour to obtain a latex of the graft copolymer. The average particle size is shown in Table 2.

Subsequently, the latex was diluted with pure water to a solid content concentration of 15%, and then 4 parts (solid content) of a 25% calcium chloride aqueous solution was added to obtain a coagulated slurry.
Coagulation The coagulated slurry was heated to 95 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane-based graft copolymer powder.

Next, a polycarbonate resin (Taflon FN2200A manufactured by Idemitsu Petrochemical Co., Ltd.) and the powder of the polyorganosiloxane-based graft copolymer were blended in the composition shown in Table 2. The anti-dripping agent is polytetrafluoroethylene (Polyflon FA-500 manufactured by Daikin Industries, Ltd.), the stabilizer is a phosphorus-based antioxidant (Adeka Stab PEP36 manufactured by Asahi Denka Co., Ltd.) and a phenol-based stabilizer (Topanol CA manufactured by Ripre Co., Ltd.). ) Shows the mixture.

The obtained blend was melt-kneaded at 270 ° C. with a twin-screw extruder (TEX44SS manufactured by Nippon Steel Co., Ltd.) to produce pellets. The obtained pellets were set at a cylinder temperature of 280 ° C.
A FAS100B injection molding machine manufactured by UC) was used to prepare 1/8 inch Izod test pieces and 1/16 inch flame retardancy evaluation test pieces. The obtained test pieces were used for evaluation according to the evaluation method described above. The results of impact resistance and flame retardancy of the molded product are shown in Table 2. (Examples 7 to 8) Stirrer, reflux condenser, nitrogen blowing port,
Add water to a 5-neck flask equipped with a monomer addition port and thermometer.
After mixing 0 parts by weight and sodium dodecylbenzenesulfonate in the amounts (solid content) shown in Table 1, the temperature was raised to 50 ° C.,
After the liquid temperature reaches 50 ° C., nitrogen replacement is performed. Then, a mixed solution of 10 parts of butyl acrylate and 3 parts of t-dodecyl mercaptan is added. After 30 minutes, 0.01 part of paramenthane hydroperoxide (solid content) was added and polymerized for 1 hour. Then, a mixed solution of 90 parts of butyl acrylate and 27 parts of t-dodecyl mercaptan is continuously added over 3 hours.
After 2 hours of polymerization, seed latex (seed 1-2)
Got The average particle size, hydrophilicity and swelling degree after synthesis were measured, and the results are shown in Table 1.

[0053]

[Table 1] The seed polymer shown in Table 2 and the amount (solid content) shown in Table 2 were charged into a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen blowing port, a monomer addition port, and a thermometer. Then, 300 parts of pure water, 0.5 part of SDBS (solid content),
A mixture of 95 parts of octamethylcyclotetrasiloxane and 5 parts of mercaptopropylmethyldimethoxysilane was stirred with a homomixer at 7,000 rpm for 5 minutes to prepare an emulsion of polyorganosiloxane-forming components, which were added all at once. Next, 1 part (solid content) of a 10% dodecylbenzenesulfonic acid aqueous solution was added, and then the system was heated to 80 ° C. under a nitrogen stream while stirring. 80
After reaching ℃, the mixture was continuously stirred at 80 ℃ for 6 hours, cooled to 25 ℃ and left for 20 hours. Then, the pH was adjusted to 6.4 with sodium hydroxide to complete the polymerization, and a latex containing polyorganosiloxane particles was obtained. Next, stirrer,
A 5-necked flask equipped with a reflux condenser, a nitrogen blowing port, a monomer addition port and a thermometer was charged with 240 parts of pure water and 70 parts (solid content) of the above polyorganosiloxane particles, and nitrogen was added while stirring the system. The temperature was raised to 40 ° C under an air stream. Four
After reaching 0 ° C., 0.2 part of sodium formaldehyde sulfoxylate (SFS), 0.01 part of ethylenediaminetetraacetic acid disodium (EDTA), 0.001 of ferrous sulfate.
After adding 25 parts, a mixture of 3 parts allyl methacrylate and 0.01 part cumene hydroperoxide (solid content) was added all at once, and stirring was continued at 40 ° C. for 1 hour. After that, a mixture of 30 parts of methyl methacrylate and 0.06 part of cumene hydroperoxide (solid content) was added dropwise over 1.5 hours, and after the addition was completed, stirring was continued for 1 hour to obtain a latex of the graft copolymer. I got it. The average particle size is shown in Table 2.

Subsequently, the latex was diluted with pure water to make the solid content concentration 15%, and then 4 parts of 25% calcium chloride aqueous solution (solid content) was added to obtain a coagulated slurry.
Coagulation The coagulated slurry was heated to 85 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane-based graft copolymer powder.

Next, a polycarbonate resin (Taflon FN1900A manufactured by Idemitsu Petrochemical Co., Ltd.) and the powder of the polyorganosiloxane-based graft copolymer were blended in the composition shown in Table 2. The anti-dripping agent is polytetrafluoroethylene (Polyflon FA-500 manufactured by Daikin Industries, Ltd.).

The obtained blend was melt-kneaded at 270 ° C. with a twin-screw extruder (TEX44SS manufactured by Nippon Steel Co., Ltd.) to produce pellets. The obtained pellets were set at a cylinder temperature of 280 ° C.
A FAS100B injection molding machine manufactured by UC) was used to prepare 1/8 inch Izod test pieces and 1/16 inch flame retardancy evaluation test pieces. The obtained test pieces were used for evaluation according to the evaluation method described above. The results of impact resistance and flame retardancy of the molded product are shown in Table 2. Comparative Example 1 Compounding, molding and evaluation were carried out in the same manner as in Examples 1 to 6 except that the polyorganosiloxane-based graft copolymer was not added in the compounding with the polycarbonate resin, and the results are shown in Table 2. (Comparative Example 2) Synthesis, coagulation, heat treatment, dehydration and dry powdering, blending, molding, and evaluation were performed in the same manner as in Examples 1 to 6 except that the seed polymer was not added during the polymerization of the latex containing polyorganosiloxane particles. The results are shown in Table 2. (Comparative Example 3) Compounding, molding and evaluation were carried out in the same manner as in Examples 7 to 8 except that the polyorganosiloxane-based graft copolymer was not added in the compounding with the polycarbonate resin, and the results are shown in Table 2. (Comparative Example 4) Synthesis, coagulation, heat treatment, dehydration / drying powdering, blending, molding, and evaluation were performed in the same manner as in Examples 7 to 8 except that the seed polymer was not added during the polymerization of the latex containing polyorganosiloxane particles. The results are shown in Table 2.

[0057]

[Table 2]

[0058]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a flame retardant which gives a thermoplastic resin composition having an excellent flame retardancy-impact resistance balance when added to a thermoplastic resin, and the flame retardant By blending with a plastic resin, a flame-retardant resin composition having excellent flame retardancy-impact resistance can be obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Nobuo Miyatake             1-8 Miyamae-cho, Takasago-cho, Takasago-shi, Hyogo             Takasago Industry Co., Ltd. (72) Inventor Akira Takagi             5-1-1 Torikai Nishi, Settsu City, Osaka Prefecture Kanebuchi Chemical             Industry Co., Ltd.Osaka factory F-term (reference) 4H028 AA49 BA06                 4J002 BN121 BN151 BN212 BN222                       CG001 GL00 GQ00                 4J026 AA45 AA68 AB44 AC35 BA05                       BA07 BA27 BA28 BA31 BB02                       DA04 DB04 GA01

Claims (6)

[Claims] 1. In the presence of 30 to 95 parts by weight (solid content) of (A) a polyorganosiloxane in a latex state obtained by seed polymerization using a polymer having hydrophilicity and swelling as an organosiloxane as a seed polymer. (B) 100 to 50% by weight of a polyfunctional monomer (b-1) containing two or more polymerizable unsaturated bonds in the molecule and another copolymerizable monomer (b-2) 0 to 50 Polymerize 0 to 10 parts by weight of a vinyl-based monomer composed of 10% by weight, and
A polyorganosiloxane-containing graft copolymer obtained by polymerizing 5 to 70 parts by weight of a vinyl-based monomer [100 parts by weight in total of (A), (B) and (C)]. 2. The hydrophilicity is such that after adding 20 times (weight) amount of water to the dry seed polymer and stirring at room temperature for 1 hour, the extraction ratio into water is 10 to 100% by weight, and the swelling property of the organosiloxane is The swelling volume ratio calculated from the ratio of the latex particle size and the original particle size after adding 50 times (by weight) the amount of organosiloxane to the seed polymer latex to the seed polymer latex at room temperature for 1 hour was 3 to 50 times. The polyorganosiloxane-containing graft copolymer according to claim 1, which is present. 3. The hydrophilicity is such that 20 times by weight (weight) of water is added to the dry seed polymer and the mixture is stirred at room temperature for 1 hour, and then the extraction ratio into water is 50 to 100% by weight, and the swelling property of the organosiloxane is The swelling volume ratio calculated from the ratio of the latex particle size to the original particle size after adding 50 times (by weight) the amount of organosiloxane to the seed polymer latex to the seed polymer latex and stirring at room temperature for 1 hour is 3 to 15 times. The polyorganosiloxane-containing graft copolymer according to claim 1, wherein 4. The vinyl-based monomer (C) is selected from aromatic vinyl-based monomers, vinyl cyanide-based monomers, (meth) acrylic acid ester-based monomers and carboxyl group-containing vinyl-based monomers. The polyorganosiloxane-containing graft copolymer according to claim 1, which is at least one monomer selected from the group consisting of: 5. A flame retardant comprising the polyorganosiloxane-containing graft copolymer according to claim 1. 6. A resin composition excellent in impact resistance and impact resistance, which is obtained by mixing 0.1 to 30 parts by weight of the flame retardant according to claim 6 with 100 parts by weight of a thermoplastic resin.