JP6398458B2 - Polymer production method, polymer, and fluidity improver for aromatic polycarbonate resin - Google Patents
Polymer production method, polymer, and fluidity improver for aromatic polycarbonate resin Download PDFInfo
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Description
本発明は、ビニル単量体混合物を酢酸フェニルの存在下でラジカル重合する、重合体の製造方法、その製造方法で得られた重合体、及び、その重合体からなる芳香族ポリカーボネート系樹脂用流動性向上剤に関する。 The present invention relates to a method for producing a polymer by radical polymerization of a vinyl monomer mixture in the presence of phenyl acetate, a polymer obtained by the production method, and a flow for an aromatic polycarbonate resin comprising the polymer. It relates to a property improver.
芳香族ポリカーボネート樹脂（以下「ＰＣ樹脂」という。）は、その優れた耐熱性、機械的特性、電気特性、寸法安定性等により、自動車部材、ＯＡ（オフィスオートメーション）機器、情報・通信機器、電気・電子機器、家庭電化機器等の様々な分野において幅広く利用されている。しかしながら、通常、ＰＣ樹脂は非晶性であるため、成形加工温度が高く、溶融流動性に劣るという問題点を有している。
近年、これらの用途では成形体の大型化、薄肉化、形状複雑化が進み、ＰＣ樹脂に対しては、成形加工時の溶融流動性の向上が要求されており、ＰＣ樹脂の優れた機械的特性を損なうことなく、成形加工時の溶融流動性を向上させる方法が盛んに検討されている（例えば、特許文献１〜３）。
しかしながら、特許文献１〜３では、ＰＣ樹脂の機械特性は維持されるものの、それらを向上させるような効果は得られてはいなかった。
Aromatic polycarbonate resin (hereinafter referred to as “PC resin”) is an automotive component, OA (office automation) device, information / communication device, electric device, etc. due to its excellent heat resistance, mechanical properties, electrical properties, dimensional stability, etc. -Widely used in various fields such as electronic devices and home appliances. However, since the PC resin is usually amorphous, it has a problem that the molding temperature is high and the melt fluidity is poor.
In recent years, in these applications, moldings have become larger, thinner, and more complicated in shape, and PC resins have been required to have improved melt fluidity during molding. A method for improving the melt fluidity at the time of molding without damaging the properties has been actively studied (for example, Patent Documents 1 to 3).
However, in Patent Documents 1 to 3, although the mechanical properties of the PC resin are maintained, the effect of improving them has not been obtained.
本発明者らは鋭意検討した結果、特定のビニル単量体混合物を酢酸フェニルの存在下でラジカル重合して得られた重合体を、芳香族ポリカーボネート系樹脂用流動性向上剤とし用いることで、ＰＣ樹脂の機械特性を低下させることなく、耐衝撃性が向上することを見出した。 As a result of intensive studies, the present inventors have used a polymer obtained by radical polymerization of a specific vinyl monomer mixture in the presence of phenyl acetate as a flow improver for an aromatic polycarbonate resin. It has been found that the impact resistance is improved without deteriorating the mechanical properties of the PC resin.
即ち、本発明は以下の態様を有する。
［１］ 下記式（Ｉ）で示すビニル単量体（ａ１）０．５〜９９．５質量％と、他のビニル単量体（ａ２）０．５〜９９．５質量％からなるビニル単量体混合物を、酢酸フェニルの存在下でラジカル重合する、重合体の製造方法。
・・・（Ｉ）
（式（Ｉ）中、Ｒ１は水素原子又はメチル基であり、Ｒ２は置換基を有していてもよいフェニル基である）。
［２］ 他のビニル単量体（ａ２）が芳香族ビニル単量体である、［１］に記載の重合体の製造方法。
［３］ 酢酸フェニルの量が、ビニル単量体（ａ１）１００質量部に対して０．１〜５．０質量部である、［１］又は［２］に記載の重合体の製造方法。
［４］ ［１］〜［３］のいずれか１項に記載の製造方法で得られた重合体。
［５］ ［４］に記載の重合体からなる、芳香族ポリカーボネート系樹脂用流動性向上剤。
That is, this invention has the following aspects.
[1] A vinyl monomer comprising 0.5 to 99.5% by mass of a vinyl monomer (a1) represented by the following formula (I) and 0.5 to 99.5% by mass of another vinyl monomer (a2). A method for producing a polymer, wherein a polymer mixture is radically polymerized in the presence of phenyl acetate.
... (I)
(In formula (I), R 1 is a hydrogen atom or a methyl group, and R 2 is a phenyl group which may have a substituent).
[2] The method for producing a polymer according to [1], wherein the other vinyl monomer (a2) is an aromatic vinyl monomer.
[3] The method for producing a polymer according to [1] or [2], wherein the amount of phenyl acetate is 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the vinyl monomer (a1).
[4] A polymer obtained by the production method according to any one of [1] to [3].
[5] A fluidity improver for an aromatic polycarbonate resin comprising the polymer according to [4].
本発明の製造方法によれば、芳香族ポリカーボネート系樹脂用流動性向上剤に用いることで、ＰＣ樹脂の機械特性を低下させることなく、耐衝撃性を向上させることが可能な重合体を得ることができる。
本発明の重合体は、芳香族ポリカーボネート系樹脂用流動性向上剤に用いることで、ＰＣ樹脂の機械特性を低下させることなく、耐衝撃性を向上させることが可能である。
本発明の芳香族ポリカーボネート系樹脂用流動性向上剤は、ＰＣ樹脂の機械特性を低下させることなく、耐衝撃性を向上させることが可能である。
According to the production method of the present invention, by using it as a flow improver for an aromatic polycarbonate resin, a polymer capable of improving impact resistance without deteriorating the mechanical properties of the PC resin is obtained. Can do.
By using the polymer of the present invention as a fluidity improver for aromatic polycarbonate resins, it is possible to improve impact resistance without deteriorating the mechanical properties of the PC resin.
The fluidity improver for aromatic polycarbonate resins of the present invention can improve impact resistance without deteriorating the mechanical properties of the PC resin.
＜製造方法＞
本発明の重合体の製造方法は、特定のビニル単量体混合物を、酢酸フェニルの存在下でラジカル重合する方法である。
<Manufacturing method>
The method for producing a polymer of the present invention is a method in which a specific vinyl monomer mixture is radically polymerized in the presence of phenyl acetate.
［ビニル単量体混合物］
本発明で用いるビニル単量体混合物は、後述するビニル単量体（ａ１）とビニル単量体（ａ２）からなる。
ビニル単量体混合物中の、ビニル単量体（ａ１）とビニル単量体（ａ２）の比率は、（ａ１）０．５〜９９．５質量％、（ａ２）０．５〜９９．５質量％である。
得られる重合体の、芳香族ポリカーボネート系樹脂用流動性向上剤としての性能が向上することから、前記比率は、（ａ１）１．０〜５０．０質量％、（ａ２）５０．０〜９９．０質量％が好ましく、（ａ１）５．０〜３０．０質量％、（ａ２）７０．０〜９５．０質量％がより好ましい。
[Vinyl monomer mixture]
The vinyl monomer mixture used in the present invention comprises a vinyl monomer (a1) and a vinyl monomer (a2) described later.
The ratio of the vinyl monomer (a1) to the vinyl monomer (a2) in the vinyl monomer mixture is (a1) 0.5 to 99.5% by mass, (a2) 0.5 to 99.5. % By mass.
Since the performance of the obtained polymer as a fluidity improver for an aromatic polycarbonate resin is improved, the ratio is (a1) 1.0 to 50.0% by mass, (a2) 50.0 to 99. 0.0 mass% is preferable, (a1) 5.0-30.0 mass%, (a2) 70.0-95.0 mass% is more preferable.
［ビニル単量体（ａ１）］
本発明で用いるビニル単量体（ａ１）は、下記式（Ｉ）で示すビニル単量体である。
・・・（Ｉ）
（式（Ｉ）中、Ｒ１は水素原子又はメチル基であり、Ｒ２は置換基を有していてもよいフェニル基である）。
[Vinyl monomer (a1)]
The vinyl monomer (a1) used in the present invention is a vinyl monomer represented by the following formula (I).
... (I)
(In formula (I), R 1 is a hydrogen atom or a methyl group, and R 2 is a phenyl group which may have a substituent).
ビニル単量体（ａ１）としては、例えば、（メタ）アクリル酸フェニル、（メタ）アクリル酸４−ｔ−ブチルフェニル、（メタ）アクリル酸ブロモフェニル、（メタ）アクリル酸ジブロモフェニル、（メタ）アクリル酸２，４，６−トリブロモフェニル、（メタ）アクリル酸モノクロルフェニル、（メタ）アクリル酸ジクロルフェニル、（メタ）アクリル酸トリクロルフェニルが挙げられる。
これらの単量体は、１種を単独で用いてもよく２種以上を併用してもよい。
得られる重合体を、芳香族ポリカーボネート系樹脂用流動性向上剤として用いる場合、ＰＣ樹脂に対する相溶性が高く、成形体の耐表層剥離性が損なわれないことから、（メタ）アクリル酸フェニルが好ましい。
尚、本発明において、（メタ）アクリルは、アクリル又はメタクリルを意味する。
Examples of the vinyl monomer (a1) include phenyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, (meth) Examples include 2,4,6-tribromophenyl acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate, and trichlorophenyl (meth) acrylate.
These monomers may be used individually by 1 type, and may use 2 or more types together.
When the obtained polymer is used as a fluidity improver for an aromatic polycarbonate resin, phenyl (meth) acrylate is preferred because it is highly compatible with PC resin and does not impair the peel resistance of the molded product. .
In the present invention, (meth) acryl means acryl or methacryl.
［ビニル単量体（ａ２）］
本発明で用いるビニル単量体（ａ２）は、（ａ１）以外のビニル単量体である。
尚、ビニル単量体（ａ２）を、「他のビニル単量体（ａ２）」と称する場合もある。
[Vinyl monomer (a2)]
The vinyl monomer (a2) used in the present invention is a vinyl monomer other than (a1).
The vinyl monomer (a2) may be referred to as “other vinyl monomer (a2)”.
ビニル単量体（ａ２）としては、例えば、（メタ）アクリル誘導体（エステル、アミド、アルデヒド、ニトリル等）；芳香族ビニル単量体；ビニルエーテル類が挙げられる。
これらの単量体は、１種を単独で用いてもよく２種以上を併用してもよい。
得られる重合体を、芳香族ポリカーボネート系樹脂用流動性向上剤として用いる場合、芳香族ビニル単量体であることが好ましい。
Examples of the vinyl monomer (a2) include (meth) acryl derivatives (esters, amides, aldehydes, nitriles, etc.); aromatic vinyl monomers; vinyl ethers.
These monomers may be used individually by 1 type, and may use 2 or more types together.
When the obtained polymer is used as a fluidity improver for an aromatic polycarbonate resin, it is preferably an aromatic vinyl monomer.
芳香族ビニル単量体としては、例えば、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ｐ−ｔ−ブチルスチレン、ｐ−メトキシスチレン、ｏ−メトキシスチレン、２，４−ジメチルスチレン、クロロスチレン、ブロモスチレン、ビニルトルエン、ビニルナフタレン、ビニルアントラセンが挙げられる。
この中では、スチレン、α−メチルスチレン、ｐ−ｔ−ブチルスチレンが好ましい。
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene, chlorostyrene, Examples include bromostyrene, vinyl toluene, vinyl naphthalene, and vinyl anthracene.
Among these, styrene, α-methylstyrene, and pt-butylstyrene are preferable.
[酢酸フェニル]
本発明の重合体は、酢酸フェニルの存在下で前記ビニル単量体混合物をラジカル重合することで得られる。
得られる重合体を、芳香族ポリカーボネート系樹脂用流動性向上剤として用いる場合、酢酸フェニルの量は、耐衝撃性が向上することから、ビニル単量体（ａ１）１００質量部に対して０．１〜５．０質量部である。
[Phenyl acetate]
The polymer of the present invention can be obtained by radical polymerization of the vinyl monomer mixture in the presence of phenyl acetate.
When the obtained polymer is used as a fluidity improver for an aromatic polycarbonate resin, the amount of phenyl acetate is 0.1% relative to 100 parts by mass of the vinyl monomer (a1) because the impact resistance is improved. 1 to 5.0 parts by mass.
[ラジカル重合]
本発明の重合体の製造方法におけるラジカル重合の方法としては、例えば、乳化重合、懸濁重合、溶液重合、塊状重合が挙げられる。この中では、回収方法が容易である点で懸濁重合、乳化重合が好ましい。尚、乳化重合の場合は、重合体中の残存塩が芳香族ポリカーボネート系樹脂の熱分解を引き起こすおそれがあるため、乳化重合の際には、カルボン酸塩乳化剤等を用い、重合体を酸析凝固等により回収をする、又はリン酸エステル等のノニオンアニオン系乳化剤等を用い、酢酸カルシウム塩等を用いた塩析凝固により重合体を回収することが好ましい。
重合開始剤としては、例えば、有機過酸化物、過硫酸塩、有機過酸化物又は過硫酸塩還元剤との組合せからなるレドックス系開始剤、アゾ化合物等が挙げられる。
[Radical polymerization]
Examples of the radical polymerization method in the polymer production method of the present invention include emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization. Among these, suspension polymerization and emulsion polymerization are preferable because the recovery method is easy. In the case of emulsion polymerization, the residual salt in the polymer may cause thermal decomposition of the aromatic polycarbonate resin. Therefore, in the case of emulsion polymerization, a carboxylate emulsifier or the like is used to acidify the polymer. The polymer is preferably recovered by coagulation or the like, or the polymer is recovered by salting out coagulation using a calcium acetate salt or the like using a nonionic anionic emulsifier such as a phosphate ester.
Examples of the polymerization initiator include redox initiators composed of a combination of an organic peroxide, a persulfate, an organic peroxide, or a persulfate reducing agent, an azo compound, and the like.
＜重合体＞
本発明の重合体は、前述した製造方法によって得られる。ビニル単量体（ａ１）とビニル単量体（ａ２）を重合して得られることから、その組成は、ビニル単量体（ａ１）とビニル単量体（ａ２）の共重合体である。
<Polymer>
The polymer of this invention is obtained by the manufacturing method mentioned above. Since it is obtained by polymerizing the vinyl monomer (a1) and the vinyl monomer (a2), its composition is a copolymer of the vinyl monomer (a1) and the vinyl monomer (a2).
重合体の質量平均分子量は、５,０００〜２００,０００が好ましい。質量平均分子量が５，０００以上であれば、相対的に低分子量物が少なくなるため、芳香族ポリカーボネート系樹脂用流動性向上剤として用いる場合に、耐熱性、剛性等の種々の特性を低下させない。また、溶融成形時の発煙、ミスト、機械汚れ、フィッシュアイ、シルバー等の成形品の外観不良といった問題が発生する可能性も低くなる。
高温時の透明性が良好な成形品（ヘイズの温度依存性が小さい成形品）が必要な場合は、重合体の質量平均分子量は高い方がよい。従って、重合体の質量平均分子量は１０，０００以上が好ましく、１５，０００以上がより好ましく、２５，０００以上が更に好ましく、３５，０００以上が特に好ましい。
また、重合体の質量平均分子量が２００，０００以下であれば、芳香族ポリカーボネート系樹脂組成物の溶融粘度の上昇が抑制され、溶融流動性の向上効果が充分に発現する。
著しい溶融流動性の向上効果が必要な場合は、重合体の質量平均分子量は低い方がよい。従って、重合体の質量平均分子量は１７０，０００以下が好ましく、１５０，０００以下がより好ましく、１２０，０００以下が更に好ましく、１００，０００以下が特に好ましい。
The mass average molecular weight of the polymer is preferably 5,000 to 200,000. When the mass average molecular weight is 5,000 or more, relatively low molecular weight products are reduced, and therefore, when used as a fluidity improver for an aromatic polycarbonate resin, various properties such as heat resistance and rigidity are not deteriorated. . In addition, the possibility of occurrence of problems such as poor appearance of molded products such as smoke, mist, mechanical dirt, fish eye, and silver during melt molding is reduced.
When a molded article having good transparency at high temperature (molded article having a low haze temperature dependency) is required, the polymer should have a higher mass average molecular weight. Accordingly, the mass average molecular weight of the polymer is preferably 10,000 or more, more preferably 15,000 or more, further preferably 25,000 or more, and particularly preferably 35,000 or more.
Moreover, if the mass mean molecular weight of a polymer is 200,000 or less, the raise of the melt viscosity of an aromatic polycarbonate-type resin composition will be suppressed, and the improvement effect of melt fluidity will fully express.
If a significant effect of improving melt fluidity is required, the polymer should have a lower mass average molecular weight. Accordingly, the mass average molecular weight of the polymer is preferably 170,000 or less, more preferably 150,000 or less, still more preferably 120,000 or less, and particularly preferably 100,000 or less.
＜芳香族ポリカーボネート系樹脂用流動性向上剤＞
本発明の芳香族ポリカーボネート系樹脂用流動性向上剤は、前述した重合体からなる。
重合体は、１種を単独で用いてもよく２種以上を併用してもよい。
尚、芳香族ポリカーボネート系樹脂用流動性向上剤とは、芳香族ポリカーボネート系樹脂に配合し、芳香族ポリカーボネート系樹脂の成形加工時の流動性を向上させる添加剤のことを指す。
<Flowability improver for aromatic polycarbonate resin>
The fluidity improver for an aromatic polycarbonate resin of the present invention is composed of the polymer described above.
A polymer may be used individually by 1 type and may use 2 or more types together.
The fluidity improver for an aromatic polycarbonate resin refers to an additive that is blended in an aromatic polycarbonate resin and improves the fluidity during molding of the aromatic polycarbonate resin.
＜芳香族ポリカーボネート系樹脂との配合＞
前述の芳香族ポリカーボネート系樹脂用流動性向上剤は、芳香族ポリカーボネート系樹脂に配合して、芳香族ポリカーボネート系樹脂組成物として使用する。
芳香族ポリカーボネート系樹脂用流動性向上剤の配合量は、芳香族ポリカーボネート系樹脂の機械特性を低下させることなく有効な溶融流動性の向上効果を得るよう、適宜設定すればよいが、例えば、芳香族ポリカーボネート系樹脂１００質量部に対して、０．１〜３０質量部である。
前記配合量が０．１質量部以上であれば、流動性の向上効果が充分に発現し、３０質量部以下であれば、芳香族ポリカーボネート系樹脂の機械特性を低下させることがない。
<Combination with aromatic polycarbonate resin>
The above-described fluidity improver for an aromatic polycarbonate resin is blended with an aromatic polycarbonate resin and used as an aromatic polycarbonate resin composition.
The blending amount of the fluidity improver for the aromatic polycarbonate resin may be appropriately set so as to obtain an effective effect of improving the melt fluidity without deteriorating the mechanical properties of the aromatic polycarbonate resin. It is 0.1-30 mass parts with respect to 100 mass parts of group polycarbonate-type resin.
If the blending amount is 0.1 parts by mass or more, the effect of improving the fluidity is sufficiently exhibited, and if it is 30 parts by mass or less, the mechanical properties of the aromatic polycarbonate resin are not deteriorated.
芳香族ポリカーボネート系樹脂と配合する場合、必要に応じて、紫外線吸収剤、光安定剤、酸化防止剤、熱安定剤等の任意の安定剤を共に配合してもよい。
これらは、１種を単独で用いてもよく２種以上を併用してもよい。
When blended with an aromatic polycarbonate-based resin, an optional stabilizer such as an ultraviolet absorber, a light stabilizer, an antioxidant, or a heat stabilizer may be blended together as necessary.
These may be used alone or in combination of two or more.
芳香族ポリカーボネート系樹脂組成物は、例えば、芳香族ポリカーボネート系樹脂、流動性向上剤、任意の安定剤等を、タンブラー、Ｖ型ブレンダー、スーパーミキサー、ナウターミキサー、バンバリーミキサー、混練ロール、押出機等で混合することによって調製ことができる。
各種原材料の混合は、一段階で実施してもよく、二段階以上に分けて実施してもよい。
Aromatic polycarbonate resin compositions include, for example, aromatic polycarbonate resins, fluidity improvers, optional stabilizers, tumblers, V-type blenders, super mixers, nauter mixers, Banbury mixers, kneading rolls, extruders. Etc., and can be prepared by mixing.
The mixing of various raw materials may be carried out in one stage or in two or more stages.
＜成形体＞
芳香族ポリカーボネート系樹脂組成物を成形する方法としては、例えば、芳香族ポリカーボネート系樹脂組成物をそのまま、又は溶融押出機で一旦ペレット状にしてから、射出成形、押出成形、圧縮成形、ブロー成形、注型成形等の公知の方法が挙げられる。
本発明で得られる成形体は、樹脂組成物の溶融流動性（成形加工性）が著しく優れていることから、近年要望が高まっている、電気・電子・ＯＡ機器用、光学部品用、精密機械用、自動車用、保安・医療用、建材用、雑貨用の各種大型・薄肉射出成形品、耐薬品性が要求される射出成形品に好適である。
<Molded body>
As a method for molding the aromatic polycarbonate resin composition, for example, the aromatic polycarbonate resin composition as it is or after being once pelletized with a melt extruder, injection molding, extrusion molding, compression molding, blow molding, A known method such as cast molding may be used.
The molded product obtained by the present invention is remarkably excellent in the melt flowability (molding processability) of the resin composition, so that there has been a growing demand in recent years for electrical / electronic / OA equipment, optical parts, precision machinery. It is suitable for various large-sized, thin-walled injection-molded products for automobiles, automobiles, safety / medical use, building materials, general goods, and injection-molded products that require chemical resistance.
以下、実施例により本発明を更に詳細に説明する。
尚、以下の記載において、「部」は「質量部」を表す。
Hereinafter, the present invention will be described in more detail with reference to examples.
In the following description, “part” represents “part by mass”.
以下の例における重合率、平均分子量は以下のように測定した。
（１）重合率
以下の手順により、第２工程終了時の重合率を測定した。
（ｉ）アルミニウム皿の質量（ｘ）を０．１ｍｇの単位まで測定した。
（ｉｉ）アルミニウム皿に重合体（Ｘ）のラテックスを約１ｇ取り、重合体（Ｘ）のラテックスの入ったアルミニウム皿の質量（ｙ）を０．１ｍｇの単位まで測定した。
（ｉｉｉ）重合体（Ｘ）のラテックスの入ったアルミニウム皿を１８０℃の乾燥機に入れ、４５分間加熱した。
（ｉｖ）アルミニウム皿を乾燥機から取出し、デシケーター内で室温まで冷却し、その質量（ｚ）を０．１ｍｇの単位まで測定した。
（ｖ）以下の式に基づいて、重合体（Ｘ）のラテックスの固形分濃度（％）を算出した。
固形分濃度（％）＝｛（ｚ−ｘ）／（ｙ−ｘ）｝×１００
（ｖｉ）重合体（Ｘ）を製造する際に仕込む全単量体が重合した際の固形分濃度に対する（ｖ）により算出した固形分濃度の百分率（％）を、第２工程終了時の重合率とした。
The polymerization rate and average molecular weight in the following examples were measured as follows.
(1) Polymerization rate The polymerization rate at the end of the second step was measured by the following procedure.
(I) The mass (x) of the aluminum pan was measured to a unit of 0.1 mg.
(Ii) About 1 g of the latex of the polymer (X) was taken in an aluminum dish, and the mass (y) of the aluminum dish containing the latex of the polymer (X) was measured to a unit of 0.1 mg.
(Iii) The aluminum dish containing the latex of the polymer (X) was placed in a dryer at 180 ° C. and heated for 45 minutes.
(Iv) The aluminum dish was taken out from the dryer, cooled to room temperature in a desiccator, and its mass (z) was measured to a unit of 0.1 mg.
(V) Based on the following formula, the solid content concentration (%) of the latex of the polymer (X) was calculated.
Solid content concentration (%) = {(z−x) / (y−x)} × 100
(Vi) The percentage of the solid content concentration (%) calculated by (v) with respect to the solid content concentration when all the monomers charged when the polymer (X) is polymerized is polymerized at the end of the second step. Rate.
（２）質量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）
ゲル浸透クロマトグラフィーを用いて、下記装置及び測定条件にて、標準ポリスチレンによる検量線を用いて重合体（Ｘ）のＭｗ，Ｍｎを測定した。
カラム ：東ソー（株）製 ＴＳＫ−ＧＥＬ ＳＵＰＥＲ ＨＺＭ−Ｎ
測定温度 ：４０℃
溶離液 ：クロロホルム
溶離液流速：０．６ｍｌ／分
検出器 ：屈折率計（ＲＩ）
(2) Mass average molecular weight (Mw), number average molecular weight (Mn)
Using gel permeation chromatography, Mw and Mn of the polymer (X) were measured using a standard polystyrene calibration curve with the following equipment and measurement conditions.
Column: Tosoh Corporation TSK-GEL SUPER HZM-N
Measurement temperature: 40 ° C
Eluent: Chloroform Eluent flow rate: 0.6 ml / min Detector: Refractometer (RI)
＜実施例１＞
冷却管及び攪拌装置を備えたセパラブルフラスコに、アニオン系乳化剤（「フォスファノールＲＳ−６１０ＮＡ」、東邦化学工業（株）製） １．０部、脱イオン水 ２９５部を仕込み、窒素雰囲気下、水浴で６０℃に加熱した。
次いで、セパラブルフラスコ内に、硫酸第一鉄 ０．０００１部、エチレンジアミン四酢酸二ナトリウム塩 ０．０００３部、ロンガリット ０．３部を脱イオン水 ５部に溶かしたものを加え、その後、スチレン ８７．５部、メタクリル酸フェニル １２．５部、酢酸フェニル ０．０４部（メタクリル酸フェニル１００部に対して０．３部）、ｔ−ブチルヒドロパーオキサイド ０．２部、ｎ−オクチルメルカプタン ０．５部の混合物を２４０分かけて滴下した。
その後、８０℃で６０分間攪拌し、重合体のラテックスを得た（重合率は９９％）。
<Example 1>
A separable flask equipped with a condenser and a stirrer was charged with 1.0 part of an anionic emulsifier (“Phosphanol RS-610NA”, manufactured by Toho Chemical Industry Co., Ltd.) and 295 parts of deionized water under a nitrogen atmosphere. And heated to 60 ° C. in a water bath.
Next, in a separable flask, 0.0001 part of ferrous sulfate, 0.0003 part of ethylenediaminetetraacetic acid disodium salt and 0.3 part of Rongalite were dissolved in 5 parts of deionized water, and then styrene 87 .5 parts, phenyl methacrylate 12.5 parts, phenyl acetate 0.04 parts (0.3 parts with respect to phenyl methacrylate 100 parts), t-butyl hydroperoxide 0.2 parts, n-octyl mercaptan 5 parts of the mixture was added dropwise over 240 minutes.
Then, it stirred at 80 degreeC for 60 minute (s), and obtained the polymer latex (polymerization rate is 99%).
脱イオン水に酢酸カルシウム ５部を溶解した水溶液６２５部を、９１℃に加熱して攪拌した。この中に、得られた重合体のラテックスを徐々に滴下し、滴下終了後に９５℃に加熱し、５分間保持して重合体のラテックスを凝固させた。
得られた凝固物を固液分離し、洗浄した後、７５℃で２４時間乾燥して、重合体（Ｘ−１）を得た。
質量平均分子量（Ｍｗ）は４０，０００、数平均分子量（Ｍｎ）は２２，０００、分子量分布（Ｍｗ／Ｍｎ）は１．９であった。
625 parts of an aqueous solution prepared by dissolving 5 parts of calcium acetate in deionized water was heated to 91 ° C. and stirred. The resulting polymer latex was gradually added dropwise, heated to 95 ° C. after completion of the addition, and held for 5 minutes to coagulate the polymer latex.
The obtained solidified product was subjected to solid-liquid separation, washed, and then dried at 75 ° C. for 24 hours to obtain a polymer (X-1).
The weight average molecular weight (Mw) was 40,000, the number average molecular weight (Mn) was 22,000, and the molecular weight distribution (Mw / Mn) was 1.9.
＜実施例２＞
酢酸フェニルを０．０６部（メタクリル酸フェニル１００部に対して０．５部）用いたこと以外は、実施例１と同様にして重合体（Ｘ−２）を得た。
質量平均分子量（Ｍｗ）は３９，０００、数平均分子量（Ｍｎ）は２１，０００、分子量分布（Ｍｗ／Ｍｎ）は１．８であった。
<Example 2>
A polymer (X-2) was obtained in the same manner as in Example 1 except that 0.06 part of phenyl acetate (0.5 part with respect to 100 parts of phenyl methacrylate) was used.
The weight average molecular weight (Mw) was 39,000, the number average molecular weight (Mn) was 21,000, and the molecular weight distribution (Mw / Mn) was 1.8.
＜実施例３＞
酢酸フェニルを０．１３部（メタクリル酸フェニル１００部に対して１．０部）用いたこと以外は、実施例１と同様にして重合体（Ｘ−３）を得た。
質量平均分子量（Ｍｗ）は３９，０００、数平均分子量（Ｍｎ）は２１，０００、分子量分布（Ｍｗ／Ｍｎ）は１．８であった。
<Example 3>
A polymer (X-3) was obtained in the same manner as in Example 1 except that 0.13 part of phenyl acetate (1.0 part with respect to 100 parts of phenyl methacrylate) was used.
The weight average molecular weight (Mw) was 39,000, the number average molecular weight (Mn) was 21,000, and the molecular weight distribution (Mw / Mn) was 1.8.
＜実施例４＞
酢酸フェニルを０．３８部（メタクリル酸フェニル１００部に対して３．０部）用いたこと以外は、実施例１と同様にして重合体（Ｘ−４）を得た。
質量平均分子量（Ｍｗ）は４０，０００、数平均分子量（Ｍｎ）は２１，０００、分子量分布（Ｍｗ／Ｍｎ）は１．９であった。
<Example 4>
A polymer (X-4) was obtained in the same manner as in Example 1 except that 0.38 parts of phenyl acetate (3.0 parts with respect to 100 parts of phenyl methacrylate) was used.
The weight average molecular weight (Mw) was 40,000, the number average molecular weight (Mn) was 21,000, and the molecular weight distribution (Mw / Mn) was 1.9.
＜比較例１＞
酢酸フェニルを添加しなかったこと以外は、実施例１と同様にして重合体（Ｘ’−５）を得た。
質量平均分子量（Ｍｗ）は４０，０００、数平均分子量（Ｍｎ）は２０，０００、分子量分布（Ｍｗ／Ｍｎ）は２．０であった。
<Comparative Example 1>
A polymer (X′-5) was obtained in the same manner as in Example 1 except that phenyl acetate was not added.
The weight average molecular weight (Mw) was 40,000, the number average molecular weight (Mn) was 20,000, and the molecular weight distribution (Mw / Mn) was 2.0.
＜実施例５〜８、比較例２＞
ＰＣ樹脂として高耐熱型ＰＣ樹脂（アペック１８００：バイエル（株）製）を用い、流動性向上剤として重合体（Ｘ−１）〜（Ｘ’−５）を用い、ＰＣ樹脂／流動性向上剤＝８５部／１５部の比率で配合した。
更に、イルガノックスＨＰ２９２１（チバ・ジャパン（株）製）を０．１部添加し、２軸押出機（ＴＥＭ−３５、東芝機械（株）製）に供給し、２７０℃で溶融混練して芳香族ポリカーボネート系樹脂組成物を得た。
これらの芳香族ポリカーボネート系樹脂組成物を用いて、以下の評価を実施した。評価結果を表１に示す。
<Examples 5 to 8, Comparative Example 2>
PC resin / fluidity improver using high heat-resistant PC resin (Apec 1800: manufactured by Bayer Co., Ltd.) as polymer and polymers (X-1) to (X′-5) as fluidity improvers = 85 parts / 15 parts.
Furthermore, 0.1 part of Irganox HP2921 (manufactured by Ciba Japan Co., Ltd.) is added and supplied to a twin screw extruder (TEM-35, manufactured by Toshiba Machine Co., Ltd.), melted and kneaded at 270 ° C. A polycarbonate resin composition was obtained.
The following evaluation was implemented using these aromatic polycarbonate resin compositions. The evaluation results are shown in Table 1.
（１）溶融流動性
芳香族ポリカーボネート系樹脂組成物のスパイラルフロー長さ（ＳＰＬ）を、射出成形機（ＩＳ−１００、東芝機械（株）製）を用いて測定した。
尚、成形条件としては、成形温度を２８０℃、金型温度を８０℃及び射出圧力を５０ＭＰａとし、得られる成形体の肉厚を２ｍｍ及び幅を１５ｍｍとした。
(1) Melt fluidity The spiral flow length (SPL) of the aromatic polycarbonate resin composition was measured using an injection molding machine (IS-100, manufactured by Toshiba Machine Co., Ltd.).
As molding conditions, the molding temperature was 280 ° C., the mold temperature was 80 ° C., the injection pressure was 50 MPa, and the thickness of the resulting molded body was 2 mm and the width was 15 mm.
（２）曲げ試験
射出成形機（ＩＳ−１００、東芝機械（株）製）を用いて芳香族ポリカーボネート系樹脂組成物を成形し、長さ８０ｍｍ×幅１０ｍｍ×厚さ４ｍｍの成形体を得た。曲げ試験はＩＳＯ１７８に準拠して測定し、曲げ速度は２ｍｍ／分とした。
(2) Bending test An aromatic polycarbonate resin composition was molded using an injection molding machine (IS-100, manufactured by Toshiba Machine Co., Ltd.) to obtain a molded body of length 80 mm x width 10 mm x thickness 4 mm. . The bending test was measured according to ISO178, and the bending speed was 2 mm / min.
（３）シャルピー衝撃試験
射出成形機（ＩＳ−１００、東芝機械（株）製）を用いて芳香族ポリカーボネート系樹脂組成物を成形し、長さ８０ｍｍ×幅１０ｍｍ×厚さ４ｍｍの成形体を得た。シャルピー衝撃試験はＩＳＯ１７９−１に準拠し、ＩＳＯ２８１８に準拠したＴｙｐｅＡのノッチを刻んで測定した。
(3) Charpy impact test An aromatic polycarbonate resin composition is molded using an injection molding machine (IS-100, manufactured by Toshiba Machine Co., Ltd.) to obtain a molded body of length 80 mm x width 10 mm x thickness 4 mm. It was. The Charpy impact test was based on ISO179-1, and was measured with a Type A notch in conformity with ISO2818.
表１から明らかなように、酢酸フェニルの存在下でラジカル重合を実施して得られた重合体（Ｘ−１）〜（Ｘ−４）を用いた芳香族ポリカーボネート系樹脂組成物の成形体のシャルピー衝撃試験結果（実施例５〜８）は、酢酸フェニルを添加せずに重合して得た重合体（Ｘ’−５）を用いた場合（比較例２）と比較して高い値を示し、その他の機械特性に関しては、ほとんど影響がないことが確認された。
As is apparent from Table 1, the molded article of the aromatic polycarbonate resin composition using the polymers (X-1) to (X-4) obtained by carrying out radical polymerization in the presence of phenyl acetate. The Charpy impact test results (Examples 5 to 8) show higher values compared to the case where the polymer (X′-5) obtained by polymerization without adding phenyl acetate was used (Comparative Example 2). As for other mechanical properties, it was confirmed that there was almost no influence.
Claims (3)
酢酸フェニルの存在下でラジカル重合する、重合体の製造方法。
（式（Ｉ）中、Ｒ１は水素原子又はメチル基であり、Ｒ２は置換基を有していてもよいフェニル基である）。 Vinyl monomer mixture comprising 0.5 to 99.5% by mass of the vinyl monomer (a1) represented by the following formula (I) and 0.5 to 99.5% by mass of the other vinyl monomer (a2). The
A method for producing a polymer, wherein radical polymerization is performed in the presence of phenyl acetate.
(In formula (I), R 1 is a hydrogen atom or a methyl group, and R 2 is a phenyl group which may have a substituent).
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