JP3871962B2 - Graft copolymer and impact-resistant and flame-retardant resin composition containing the same - Google Patents

Description

撹拌機、還流冷却器、チッ素吹込口、単量体追加口、温度計を備えた５口フラスコに、表２に示されるシードポリマーを、表２に示す量（固形分）を仕込んだ。その後、別途純水３００部、ＳＤＢＳ０．５部（固形分）、オクタメチルシクロテトラシロキサン９５部、メルカプトプロピルメチルジメトキシシラン５部の成分からなる混合物をホモミキサーで７０００ｒｐｍで５分間撹拌してポリオルガノシロキサン形成成分のエマルジョンを調製し、一括で添加した。
つぎに１０％ドデシルベンゼンスルホン酸水溶液１部（固形分）を添加したのち、系を撹拌しながら窒素気流下で８０℃まで昇温させた。８０℃到達後、８０℃で６時間撹拌を続けたのち、２５℃に冷却して２０時間放置した。その後、水酸化ナトリウムでｐＨを６．４にして重合を終了し、ポリオルガノシロキサン粒子を含むラテックスをえた。
つづいて撹拌機、還流冷却器、窒素吹込口、単量体追加口および温度計を備えた５口フラスコに、純水２４０部、および上記ポリオルガノシロキサン粒子７０部（固形分）を仕込み、系を撹拌しながら窒素気流下に４０℃まで昇温させた。４０℃到達後、ナトリウムホルムアルデヒドスルホキシレート（ＳＦＳ）０．２部、エチレンジアミン４酢酸２ナトリウム（ＥＤＴＡ）０．０１部、硫酸第一鉄０．００２５部を添加したのち、メタクリル酸アリル３部とクメンハイドロパーオキサイド０．０１部（固形分）の混合物を一括で追加し、４０℃で１時間撹拌を続けた。そののち、メタクリル酸メチル３０部とクメンハイドロパーオキサイド０．０６部（固形分）の混合物を１．５時間かけて滴下追加し、追加終了後１時間撹拌を続けることによってグラフト共重合体のラテックスをえた。平均粒子径を表２に示す。
【００５４】
つづいて、ラテックスを純水で希釈し、固形分濃度を１５％にしたのち、２５％塩化カルシウム水溶液４部（固形分）を添加して、凝固スラリーを得た。凝固スラリーを８５℃まで加熱したのち、５０℃まで冷却して脱水後、乾燥させてポリオルガノシロキサン系グラフト共重合体の粉体をえた。
【００５５】
つぎにポリカーボネート樹脂（出光石油化学株式会社製タフロンＦＮ１９００Ａ）および上記ポリオルガノシロキサン系グラフト共重合体の粉体を用いて表２に示す組成で配合した。なお滴下防止剤はポリテトラフルオロエチレン（ダイキン工業株式会社製ポリフロンＦＡ−５００）を示す。
【００５６】
えられた配合物を２軸押出機（日本製鋼株式会社製 ＴＥＸ４４ＳＳ）で２７０℃にて溶融混錬し、ペレットを製造した。えられたペレットをシリンダー温度２８０℃に設定した株式会社ファナック（ＦＡＮＵＣ）製のＦＡＳ１００Ｂ射出成形機で１／８インチのアイゾット試験片および１／１６インチ難燃性評価用試験片を作成した。えられた試験片を用いて前記評価方法に従って評価した。成型体の耐衝撃性と難燃性の結果を表２に示す。
（比較例１）
ポリカーボネート樹脂との配合においてポリオルガノシロキサン系グラフト共重合体を無添加にする以外は実施例１〜６と同様に配合・成型・評価を行いその結果を表２に示した。
（比較例２）
ポリオルガノシロキサン粒子を含むラテックスの重合時にシードポリマーを無添加にする以外は実施例１〜６と同様に合成・凝固・熱処理・脱水乾燥粉末化・配合・成型・評価を行いその結果を表２に示した。
（比較例３）
ポリカーボネート樹脂との配合においてポリオルガノシロキサン系グラフト共重合体を無添加にする以外は実施例７〜８と同様に配合・成型・評価を行いその結果を表２に示した。
（比較例４）
ポリオルガノシロキサン粒子を含むラテックスの重合時にシードポリマーを無添加にする以外は実施例７〜８と同様に合成・凝固・熱処理・脱水乾燥粉末化・配合・成型・評価を行いその結果を表２に示した。
【００５７】
【表２】

【００５８】
【発明の効果】
本発明により、熱可塑性樹脂に添加することにより、難燃性−耐衝撃性バランスの優れた熱可塑性樹脂組成物を与える難燃剤を得ることができ、また該難燃剤を熱可塑性樹脂に配合することにより難燃性−耐衝撃性に優れた難燃性樹脂組成物をうることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyorganosiloxane-containing graft copolymer and a resin composition containing the same and having excellent impact resistance and flame retardancy.
[0002]
[Prior art]
Polycarbonate resins are widely used as electric / electronic parts, OA equipment, household goods or building materials due to their excellent impact resistance, heat resistance, electrical characteristics, and the like. This resin has a high flame retardancy compared to polystyrene resins and the like, but when used in fields such as electrical and electronic parts and OA equipment that require high flame retardance, various flame retardants are used. Further flame retardant is performed by addition. Addition of organohalogen compounds and organophosphorus compounds has been widely used for flame retardancy, but many of these compounds have problems in terms of toxicity. In recent years, non-halogen / non-phosphorus flame retardants have been used. There is a growing demand for flame retardancy.
[0003]
As non-halogen / non-phosphorus flame retardants, use of polyorganosiloxane compounds has been proposed. For example, JP-A-54-36365 describes that a flame retardant resin can be obtained by kneading a silicone resin composed of monoorganopolysiloxane with a non-silicone polymer.
[0004]
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.
[0005]
Japanese Patent Laid-Open No. 8-113712 discloses a flame retardant resin composition in which a silicone resin prepared by mixing 100 parts by weight of a polyorganosiloxane and 10 to 150 parts by weight of a silica filler is dispersed in a thermoplastic resin. Is described.
[0006]
JP-A-10-139964 discloses a flame-retardant resin composition 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 described that
[0007]
However, the silicone resin described in the above publication has an insufficient effect of imparting flame retardancy, and if the amount is increased to compensate for this, there is a problem that the impact resistance of the resin composition is deteriorated.
[0008]
Japanese Patent Application Laid-Open No. 2000-17029 discloses that a composite rubber flame retardant obtained by graft polymerization of a vinyl monomer to a composite rubber composed of a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber is added to a thermoplastic resin. It is described that a flame retardant resin composition can be obtained.
[0009]
JP-A-2000-226420 discloses blending a thermoplastic resin with a polyorganosiloxane flame retardant obtained by grafting a vinyl monomer to a composite particle of a polyorganosiloxane having an aromatic group and a vinyl polymer. It is described that a flame retardant resin composition can be obtained.
[0010]
Japanese Patent Application Laid-Open No. 2000-264935 discloses a flame retardant resin by blending a thermoplastic resin with a polyorganosiloxane-containing graft copolymer obtained by graft-polymerizing a vinyl monomer to 0.2 μm or less polyorganosiloxane particles. It is described that a composition is obtained.
[0011]
Although any of the flame retardant resin compositions described in JP-A-2000-17029, JP-A-2000-226420, and JP-A-2000-264935 has satisfactory impact resistance, Since the property is insufficient, there is a problem that the flame retardancy / impact resistance balance is poor.
[0012]
As a technique for improving the impact resistance, a technique for dispersing a rubber component in a thermoplastic resin is widely known. For example, there is a method disclosed in Japanese Patent Publication No. 39-19035. Furthermore, various improvements have been made to the rubber component in order to improve the impact resistance. For example, a method of increasing the particle size of the rubber component (Japanese Patent Publication No. Sho 42-225419 or a method of lowering the Tg of the rubber component (JP-A-2-1763, However, it is difficult to meet the demands of the market that expects a significant improvement in impact resistance with these devices alone.
[0013]
[Problems to be solved by the invention]
It is an object of the present invention to provide a polyorganosiloxane-containing graft copolymer that can be used as a non-halogen / non-phosphorus flame retardant and has an excellent effect of improving flame retardancy and impact resistance, and using the graft copolymer, An object of the present invention is to provide a flame retardant resin composition having excellent flammability and impact resistance.
[0014]
[Means for Solving the Problems]
As a result of intensive studies on the above problems, the present inventors have found that the polyorganosiloxane in a latex state obtained by seed polymerization using a polymer that is hydrophilic and swells in the organosiloxane as a seed polymer. The The contained graft copolymer is excellent in flame retardancy and impact resistance improving effect, and the thermoplastic resin composition containing this polyorganosiloxane-containing graft copolymer exhibits excellent flame retardancy and impact resistance. And the present invention has been completed.
[0015]
That is, in the present invention, (A) in the presence of 30 to 95 parts by weight (solid content) of polyorganosiloxane in a latex state obtained by seed polymerization using a polymer that is hydrophilic and swells in 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 other copolymerizable monomers (b-2) 0 to Polymerize 0 to 10 parts by weight of a vinyl monomer composed of 50% by weight, and (C) 5 to 70 parts by weight of a vinyl monomer [100 parts in total of (A), (B) and (C) The polyorganosiloxane-containing graft copolymer obtained by polymerizing the polymer (Claim 1), the hydrophilicity of which is 20 times (weight) of water to the dried seed polymer and stirred for 1 hour at room temperature. Extraction rate of 10-100 The swellability of the organosiloxane was determined from the ratio of the latex particle size to the original particle size after adding 50% (weight) of the organosiloxane to the seed polymer latex and stirring at room temperature for 1 hour. The polyorganosiloxane-containing graft copolymer according to claim 1, wherein the swelling volume ratio is 3 to 50 times (claim 2), and the hydrophilicity is 20 times (weight) of water in the dry seed polymer. The mixture was stirred at room temperature for 1 hour, and then the extraction rate into water was 50 to 100% by weight, and the organosiloxane swelling property was 50 times (weight) of the seed polymer. The polyorgano according to claim 1, wherein the swelling volume ratio obtained from the ratio of the latex particle diameter after stirring for 1 hour to the original particle diameter is 3 to 15 times. Roxane-containing graft copolymer (Claim 3), vinyl monomer (C) is aromatic vinyl monomer, vinyl cyanide monomer, (meth) acrylic acid ester monomer and carboxyl group The at least one monomer selected from the group consisting of containing vinyl monomers Or Charged to 100 parts by weight of a polyorganosiloxane-containing graft copolymer according to claim 3 (Claim 4), a flame retardant comprising the polyorganosiloxane-containing graft copolymer according to Claim 1 (Claim 5), and a thermoplastic resin. Term 5 Impact resistance obtained by blending 0.1 to 30 parts by weight of the flame retardant described Flame retardant The present invention relates to a resin composition having excellent properties (claim 6).
[0016]
DETAILED DESCRIPTION OF THE INVENTION
The polyorganosiloxane-containing graft copolymer of the present invention is (A) a latex-like polyorganosiloxane 30 to 95 obtained by seed polymerization using a polymer that is hydrophilic and swells in the organosiloxane as a seed polymer. In the presence of parts (parts by weight, the same shall apply hereinafter) (B) 100 to 50% of polyfunctional monomer (b-1) containing two or more polymerizable unsaturated bonds in the molecule (% by weight, the same shall apply hereinafter) And other copolymerizable monomers (b-2) 0 to 10 parts of a vinyl monomer composed of 0 to 50%, and (C) 5 to 70 parts of a vinyl monomer [(A ), (B) and (C) in total 100 parts].
[0017]
The seed polymer used in the present invention can be obtained by ordinary emulsion polymerization, but the synthesis method is not particularly limited. The seed polymer is not limited to rubber components such as butyl acrylate rubber and butadiene rubber, and it may be a hard polymer such as butyl acrylate-styrene copolymer or styrene-acrylonitrile copolymer. In order to incorporate into the rubber, it is necessary to sufficiently swell the rubber monomer produced in the next step and to have strong hydrophilicity.
[0018]
In order to improve the swelling property of the seed polymer with respect to the organosiloxane, it is important to first select a seed polymer whose polarity is suitable for the organosiloxane, then use a chain transfer agent, a high polymerization temperature and a large initiator. It is effective to significantly reduce the molecular weight of the seed polymer by selection of use.
[0019]
The hydrophilicity of the seed polymer can be measured by the extraction rate into water after adding 20 times amount (weight) of water to the dried seed polymer and stirring at room temperature for 1 hour. The value should just be 1% or more. Preferably it is 10 to 100 weight%, More preferably, it is 50 to 100%.
[0020]
The swellability of the seed polymer into the organosiloxane is determined from the ratio of the latex particle size to the original particle size after adding 50 times (weight) of the organosiloxane to the seed polymer latex and stirring at room temperature for 1 hour. It can be measured by the swollen volume ratio. The value should just be 1.5 times or more. Preferably it is 3-50 times, More preferably, it is 3-15 times.
[0021]
Within these ranges, the effect of improving flame retardancy and impact resistance is remarkable.
(A) The average particle diameter of the polyorganosiloxane in the latex state is determined from a light scattering method or observation with an electron microscope, and is preferably 0.008 to 0.6 μm, more preferably 0.01 to 0.2 μm. It tends to be difficult to obtain particles having an average particle diameter of less than 0.008 μm, and when it exceeds 0.6 μm, flame retardancy and impact resistance tend to be deteriorated.
[0022]
The polyorganosiloxane may be used alone or may be a copolymer with diphenylsiloxane or the like.
[0023]
The polyorganosiloxane (A) includes, for example, (1) an organosiloxane, (2) a bifunctional silane compound, (3) an organosiloxane and a bifunctional silane compound, and (4) an organosiloxane and a vinyl polymerizable group-containing silane compound. (5) A bifunctional silane compound and a vinyl polymerizable group-containing silane compound or (6) an organosiloxane, a bifunctional silane compound, a vinyl polymerizable group containing silane compound, or the like, or a trifunctional or higher functional silane It can be obtained by adding a compound and polymerizing.
[0024]
The organosiloxane is a component constituting the main skeleton of the polyorganosiloxane chain. Specific examples of the organosiloxane include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane. (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8) 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, and octadecylmethyldimethoxysilane.
[0025]
The vinyl polymerizable group-containing silane compound is copolymerized with the organosiloxane, bifunctional silane compound, trifunctional or higher functional silane compound, etc., and introduces a vinyl polymerizable group into the side chain or terminal of the copolymer. This vinyl-based polymerizable group is a graft activity when chemically bonding to a vinyl-based (co) polymer formed from a vinyl-based monomer (B) or a vinyl-based monomer (C) described later. Acts as a point. Furthermore, it is a component that can be used as a crosslinking agent because it can form a cross-linking bond by radical reaction between graft active sites by a radical polymerization initiator.
[0026]
Specific examples of the vinyl polymerizable group-containing silane compound include, for example, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, and γ-methacryloyloxypropyldisilane. (Meth) acryloyloxy group-containing silane compounds such as ethoxymethylsilane, γ-acryloyloxypropyldimethoxymethylsilane, γ-acryloyloxypropyltrimethoxysilane, p-vinylphenyldimethoxymethylsilane, p-vinylphenyltrimethoxysilane, etc. Vinylphenyl group-containing silane compounds, vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and other vinyl group-containing silane compounds, DOO trimethoxysilane, mercapto group-containing silane compounds such as mercaptopropyl dimethoxymethyl silane and the like.
[0027]
Specific examples of the trifunctional or higher functional silane compound include tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, Examples thereof include tetrafunctional and trifunctional alkoxysilane compounds such as trifluoropropyltrimethoxysilane and octadecyltrimethoxysilane.
[0028]
The proportion of the organosiloxane, bifunctional silane compound, vinyl polymerizable group-containing silane compound, and trifunctional or higher functional silane compound used during polymerization is usually an organosiloxane and / or a bifunctional silane compound (organosiloxane and bifunctional). The ratio with the silane compound is usually 100/0 to 0/100, more preferably 100/0 to 70/30), 50 to 99.9%, further 60 to 99.5%, vinyl polymerizable group. The content of the silane compound is 0 to 40%, more preferably 0.5 to 30%, and the trifunctional or higher functional silane compound is preferably 0 to 50%, and more preferably 0 to 39%. The vinyl polymerizable group-containing silane compound and the trifunctional or higher functional silane compound do not simultaneously become 0%, and any of them is preferably used in an amount of 0.1% or more.
[0029]
When the use ratio of the organosiloxane and the bifunctional silane compound is too small, the resin composition obtained by blending tends to become brittle. When the amount is too large, the amount of the vinyl polymerizable group-containing silane compound and the trifunctional or higher functional silane compound is too small, and the effect of using these tends to be difficult to be exhibited. In addition, when the proportion of the vinyl polymerizable group-containing silane compound or the trifunctional or higher functional silane compound is too small, the effect of flame retardancy is reduced, and when the proportion is too large, The resin composition obtained by blending tends to be brittle.
[0030]
The polyorganosiloxane (A) is, for example, a polyorganosiloxane obtained by adding a trifunctional or higher functional silane compound such as the organosiloxane, bifunctional silane compound, vinyl polymerizable group-containing silane compound and the like. It is preferable to produce the component by emulsion polymerization.
[0031]
The vinyl monomer (B) is used to improve the flame retardancy effect and impact resistance improvement effect, and is a polyfunctional monomer containing two or more polymerizable unsaturated bonds in the molecule. Body (b-1) 100 to 50%, preferably 100 to 80%, and other copolymerizable monomer (b-2) 0 to 50%, preferably 0 to 20%. When the amount of the polyfunctional monomer (b-1) is too small, the amount of the copolymerizable monomer (b-2) is too large, The impact resistance improving effect tends to be low.
[0032]
Specific examples of the polyfunctional monomer (b-1) include allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, divinylbenzene and the like. These may be used alone or in combination of two or more.
[0033]
Specific examples of the copolymerizable monomer (b-2) include aromatic vinyl monomers such as styrene and α-methylstyrene, vinyl cyanide monomers such as acrylonitrile, methyl acrylate, And (meth) acrylic acid ester monomers such as ethyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. These may be used alone or in combination of two or more.
[0034]
The vinyl monomer (C) is a component used to obtain a polyorganosiloxane-containing graft copolymer. Furthermore, the graft copolymer is blended with a thermoplastic resin to provide flame retardancy and When improving impact resistance, it is also a component used to ensure the compatibility of the graft copolymer and the thermoplastic resin and to uniformly disperse the graft copolymer in the thermoplastic resin. Specific examples of the monomer include the same monomers as the other copolymerizable monomer (b-2) in the vinyl monomer (B).
[0035]
As a method for separating the polymer from the graft copolymer latex obtained by emulsion polymerization, for example, by adding a metal salt such as calcium chloride, magnesium chloride or magnesium sulfate to the latex, the latex is coagulated, separated, washed and dehydrated. And a method of drying. A spray drying method can also be used.
[0036]
The graft copolymer thus obtained is blended with various thermoplastic resins to give a flame retardant resin composition having excellent flame retardancy and impact resistance.
[0037]
As the thermoplastic resin, a polycarbonate resin containing 50% or more of polycarbonate is preferable in that good flame retardancy can be obtained. Preferable specific examples of the polycarbonate-based resin include polycarbonate, polycarbonate / polyethylene terephthalate mixed resin and polycarbonate / polybutylene terephthalate mixed resin such as polycarbonate / polyester 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 / acrylonitrile Lil - acrylic rubber - styrene copolymer (AAS resin) mixed resins. Further, the mixed resins may be further mixed and used.
[0038]
The amount of the polyorganosiloxane-containing graft copolymer added to the thermoplastic resin is 0.1 to 30 parts of the graft copolymer with respect to 100 parts of the thermoplastic resin from the viewpoint of flame retardancy and impact resistance. It is preferable to mix.
[0039]
The flame retardant powder composed of the polyorganosiloxane-containing graft copolymer separated from the latex and the thermoplastic resin are mixed with a Henschel mixer, ribbon blender, etc., and then melted with a roll, an extruder, a kneader, etc. It can be performed by kneading.
[0040]
At this time, usually used compounding agents, that is, antioxidants, anti-dripping agents, polymer processing aids, flame retardants, impact modifiers, plasticizers, lubricants, ultraviolet absorbers, pigments, glass fibers, fillers In addition, a polymer lubricant or the like can be blended.
[0041]
As a molding method of the flame retardant resin composition, a molding method used for molding a normal thermoplastic resin composition, that is, an injection molding method, an extrusion molding method, a blow molding method, a calendar molding method, or the like can be applied. it can.
[0042]
The use of the molded product obtained from the flame retardant resin composition of the present invention is not particularly limited. For example, desktop computers, notebook computers, tower computers, server computers, printers, copiers, FAX machines, Applications that require flame retardancy, such as housings and chassis parts of various OA / information / home appliances such as mobile phones, PHS, TVs, and VCRs, various building materials, and various automobiles.
[0043]
The obtained molded product is excellent in impact resistance and flame retardancy.
[0044]
【Example】
The present invention will be specifically described based on examples, but the present invention is not limited thereto.
[0045]
Measurements and tests in Examples and Comparative Examples were performed as follows.
[0046]
The average particle size of the seed polymer and the graft copolymer was measured using MICROTRAC UPA manufactured by Reed & Northrup Instruments.
[0047]
The impact resistance of the molded body was evaluated by an Izod test at −10 ° C. or 23 ° C. using a 1/8 inch bar with a notch in accordance with ASTM D-256.
[0048]
The flame retardancy of the molded body was evaluated by UL94 V test.
(Examples 1-6)
In a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer, 400 parts by weight of water and sodium dodecylbenzenesulfonate (SDBS) shown in Table 1 (solid content) ), The temperature is raised to 50 ° C., and after the liquid temperature reaches 50 ° C., nitrogen substitution is performed. Thereafter, 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 (solid content) of paramentane hydroperoxide was added and polymerized for 1 hour. Thereafter, 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. Post-polymerization was performed for 2 hours to obtain a seed latex (seed 1 to 4). The average particle diameter, hydrophilicity and swelling degree after synthesis were measured, and the results are shown in Table 1.
[0049]
A seed polymer shown in Table 2 in an amount (solid content) shown in Table 2 was charged into a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer. Thereafter, a mixture of 300 parts of pure water, 0.5 part of SDBS (solid content), 95 parts of octamethylcyclotetrasiloxane, and 5 parts of dimethylmethylsilylpropyl methacrylate was stirred with a homomixer at 7000 rpm for 5 minutes to form polyorgano. An emulsion of siloxane forming components was prepared and added in one go.
Next, after adding 1 part (solid content) of 10% aqueous solution of dodecylbenzenesulfonic acid, the temperature was raised to 80 ° C. under a nitrogen stream while stirring the system. After reaching 80 ° C., stirring was continued at 80 ° C. for 6 hours, then cooled to 25 ° C. and allowed to stand for 20 hours. Thereafter, 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 and 70 parts (solid content) of the above polyorganosiloxane particles were charged into a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port and thermometer. The mixture 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 and A mixture of cumene hydroperoxide 0.06 part (solid content) was added dropwise over 1.5 hours, and after completion of the addition, stirring was continued for 1 hour to obtain a latex of a graft copolymer. The average particle size is shown in Table 2.
[0050]
Subsequently, the latex was diluted with pure water to a solid content concentration of 15%, and then 4 parts of a 25% calcium chloride aqueous solution (solid content) was added to obtain a coagulated slurry. coagulation The The rally was heated to 95 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane graft copolymer powder.
[0051]
Next, a polycarbonate resin (Teflon FN2200A manufactured by Idemitsu Petrochemical Co., Ltd.) and a powder of the above polyorganosiloxane graft copolymer were blended in the composition shown in Table 2. The dripping inhibitor is polytetrafluoroethylene (polyflon FA-500 manufactured by Daikin Industries, Ltd.), the stabilizer is a phosphorus antioxidant (Adeka Stub PEP36 manufactured by Asahi Denka Co., Ltd.) and a phenol stabilizer (Topanol CA manufactured by Ripre Corporation). ).
[0052]
The obtained blend was melt-kneaded at 270 ° C. with a twin-screw extruder (TEX44SS manufactured by Nippon Steel) to produce pellets. A 1/8 inch Izod test piece and a 1/16 inch flame retardant evaluation test piece were prepared using a FAS100B injection molding machine manufactured by FANUC Corporation in which the obtained pellet was set to a cylinder temperature of 280 ° C. The obtained test piece was used for evaluation according to the evaluation method. Table 2 shows the results of impact resistance and flame retardancy of the molded body.
(Examples 7 to 8)
In a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer, 400 parts by weight of water and the amount (solid content) shown in Table 1 were mixed with sodium dodecylbenzenesulfonate. After that, the temperature is raised to 50 ° C., and after the liquid temperature reaches 50 ° C., nitrogen substitution is performed. Thereafter, a mixed solution of 10 parts of butyl acrylate and 3 parts of t-dodecyl mercaptan is added. After 30 minutes, 0.01 part (solid content) of paramentane hydroperoxide was added and polymerized for 1 hour. Thereafter, a mixed solution of 90 parts of butyl acrylate and 27 parts of t-dodecyl mercaptan is continuously added over 3 hours. Post-polymerization was performed for 2 hours to obtain a seed latex (seed 1-2). The average particle diameter, hydrophilicity and swelling degree after synthesis were measured, and the results are shown in Table 1.
[0053]
[Table 1]

A seed polymer shown in Table 2 in an amount (solid content) shown in Table 2 was charged into a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer. Thereafter, a mixture of 300 parts of pure water, 0.5 part of SDBS (solid content), 95 parts of octamethylcyclotetrasiloxane, and 5 parts of mercaptopropylmethyldimethoxysilane was stirred with a homomixer at 7000 rpm for 5 minutes to form a polyorgano An emulsion of siloxane forming components was prepared and added in one go.
Next, after adding 1 part (solid content) of 10% aqueous solution of dodecylbenzenesulfonic acid, the temperature was raised to 80 ° C. under a nitrogen stream while stirring the system. After reaching 80 ° C., stirring was continued at 80 ° C. for 6 hours, then cooled to 25 ° C. and allowed to stand for 20 hours. Thereafter, 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 and 70 parts (solid content) of the above polyorganosiloxane particles were charged into a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port and thermometer. The mixture was heated to 40 ° C. under a nitrogen stream while stirring. After reaching 40 ° C, 0.2 parts of sodium formaldehyde sulfoxylate (SFS), 0.01 parts of ethylenediaminetetraacetic acid disodium (EDTA), and 0.0025 parts of ferrous sulfate were added. A mixture of cumene hydroperoxide 0.01 part (solid content) was added all at once, and stirring was continued at 40 ° C. for 1 hour. Thereafter, 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 the latex of the graft copolymer was continued by stirring for 1 hour after the addition was completed. I gave The average particle size is shown in Table 2.
[0054]
Subsequently, the latex was diluted with pure water to a solid content concentration of 15%, and then 4 parts of a 25% calcium chloride aqueous solution (solid content) was added to obtain a coagulated slurry. coagulation The The rally was heated to 85 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane-based graft copolymer powder.
[0055]
Next, the composition shown in Table 2 was blended using a polycarbonate resin (Taflon FN1900A manufactured by Idemitsu Petrochemical Co., Ltd.) and a powder of the polyorganosiloxane graft copolymer. The anti-dripping agent is polytetrafluoroethylene (Daikin Industries, Ltd., Polyflon FA-500).
[0056]
The obtained blend was melt-kneaded at 270 ° C. with a twin-screw extruder (TEX44SS manufactured by Nippon Steel) to produce pellets. A 1/8 inch Izod test piece and a 1/16 inch flame retardant evaluation test piece were prepared using a FAS100B injection molding machine manufactured by FANUC Corporation in which the obtained pellet was set to a cylinder temperature of 280 ° C. The obtained test piece was used for evaluation according to the evaluation method. Table 2 shows the results of impact resistance and flame retardancy of the molded body.
(Comparative Example 1)
The blending, molding and evaluation were carried out in the same manner as in Examples 1 to 6 except that the polyorganosiloxane graft copolymer was not added in blending with the polycarbonate resin, and the results are shown in Table 2.
(Comparative Example 2)
Table 2 shows the results of synthesis, coagulation, heat treatment, dehydrated dry powdering, blending, molding, and evaluation in the same manner as in Examples 1 to 6, except that no seed polymer was added during polymerization of latex containing polyorganosiloxane particles. It was shown to.
(Comparative Example 3)
The blending, molding and evaluation were carried out in the same manner as in Examples 7 to 8 except that the polyorganosiloxane graft copolymer was not added in blending with the polycarbonate resin, and the results are shown in Table 2.
(Comparative Example 4)
Table 2 shows the results of synthesis, coagulation, heat treatment, dehydrated dry powdering, blending, molding, and evaluation in the same manner as in Examples 7 to 8, except that no seed polymer was added during polymerization of latex containing polyorganosiloxane particles. It was shown to.
[0057]
[Table 2]

[0058]
【The invention's effect】
According to the present invention, a flame retardant that gives a thermoplastic resin composition having an excellent balance of flame retardancy and impact resistance can be obtained by adding to a thermoplastic resin, and the flame retardant is blended with the thermoplastic resin. Thus, a flame retardant resin composition excellent in flame retardancy and impact resistance can be obtained.

Claims (6)

  (B) In the presence of 30 to 95 parts by weight (solid content) of a polyorganosiloxane in a latex state obtained by seed polymerization using a polymer that is hydrophilic and swells in organosiloxane as a seed polymer (B) Intramolecular A vinyl comprising 100 to 50% by weight of a polyfunctional monomer (b-1) containing two or more polymerizable unsaturated bonds and 0 to 50% by weight of another copolymerizable monomer (b-2) Polymerize 0 to 10 parts by weight of the monomer and further polymerize 5 to 70 parts by weight of the (C) vinyl monomer [100 parts by weight in total of (A), (B) and (C)]. A polyorganosiloxane-containing graft copolymer.   The hydrophilicity is 10 to 100% by weight when extracted with water after adding 20 times (by weight) water to the dried seed polymer and stirring at room temperature for 1 hour. The swelling property of the organosiloxane is 50% of that of the seed polymer. It is characterized in that the swelling volume ratio obtained from the ratio of the latex particle diameter after stirring for 1 hour at room temperature after adding double amount (weight) of organosiloxane to the seed polymer latex and the original particle diameter is 3 to 50 times. The polyorganosiloxane-containing graft copolymer according to claim 1.   Hydrophilicity: 20 times the amount (by weight) of water was added to the dried seed polymer and stirred for 1 hour at room temperature, followed by extraction with water of 50 to 100% by weight. Swellability of organosiloxane was 50 times that of seed polymer The amount (weight) of the organosiloxane is added to the seed polymer latex and stirred at room temperature for 1 hour, and the swelling volume ratio obtained from the ratio of the latex particle diameter to the original particle diameter is 3 to 15 times. The polyorganosiloxane-containing graft copolymer according to claim 1. The vinyl monomer (C) is selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, (meth) acrylic acid ester monomers and carboxyl group-containing vinyl monomers. The polyorganosiloxane-containing graft copolymer according to claim 1, 2 or 3, which is at least one monomer.   A flame retardant comprising the polyorganosiloxane-containing graft copolymer according to claim 1. 5. The flame retardant 0.1 to 30 parts by weight impact-resistant resin composition having excellent flame retardant properties obtained by blending the described relative to 100 parts by weight of the thermoplastic resin.