JP2007009026A5

JP2007009026A5 -

Info

Publication number: JP2007009026A5
Application number: JP2005190345A
Authority: JP
Filing date: 2005-06-29
Publication date: 2008-08-07
Anticipated expiration: 2025-06-29

Description

本発明の要旨は、平均粒子径が２０μｍ以上であり、１０μｍ以下の粒子の占める割合が３０質量％未満である樹脂用改質剤であって、４０ｗの超音波を５分間照射した後に、１０μｍ以下の粒子の占める割合が３０質量％以上となり、その１次粒子の平均粒子径が３００ｎｍ以上、６００ｎｍ未満の範囲内にある樹脂用改質剤にある。
また、本発明の要旨は、前記樹脂用改質剤１〜４０質量％と、熱可塑性樹脂もしくは硬化性樹脂９９〜６０質量％（両者の合計量が１００質量％）からなる樹脂組成物にある。
更に本発明の要旨は、前記樹脂組成物を成形してなる成形品にある。
The gist of the present invention is a resin modifier having an average particle diameter of 20 μm or more and a proportion of particles of 10 μm or less of less than 30% by mass, and after irradiation with 40 w ultrasonic waves for 5 minutes, 10 μm The proportion of the following particles occupies 30% by mass or more, and the average particle size of the primary particles is in the range of 300 nm or more and less than 600 nm .
The gist of the present invention resides in a resin composition comprising 1 to 40% by mass of the resin modifier and 99 to 60% by mass of a thermoplastic resin or a curable resin (the total amount of both is 100% by mass). .
Furthermore, the gist of the present invention resides in a molded product formed by molding the resin composition.

本発明の樹脂用改質剤に用いるグラフト共重合体は、噴霧乾燥により回収されるが、この時熱可塑性樹脂や硬化性樹脂中での分散性を向上させるために、最終的に得られた乳化重合ラテックス粒子、すなわち１次粒子の平均粒子径が、３００ｎｍ以上、６００ｎｍ未満の範囲内にあることが必要である。さらに好ましくは４００ｎｍ以上、６００ｎｍ未満であり、より好ましくは５００ｎｍ以上、６００ｎｍ未満である。平均粒子径が３００ｎｍより小さい場合には、得られた粉体状樹脂用改質剤の１次粒子が融着し、良好な分散性を示すことが出来ない。また同様に粉体分散性制御の点から、ラテックス粒子の粒子径分布は、出来るだけ狭いほうが、さらに１５０ｎｍ以下の粒子は存在しても特に不都合は無いが、出来るだけ少ないほうがより好ましい。逆に７００ｎｍ以上の場合、重合時の安定性が低下し、凝集物が増加するため、生産安定性、および重合体の回収率が著しく低下するため好ましくない。
なお、グラフト共重合体ラテックスには、必要に応じてあらかじめ適当な酸化防止剤や添加剤を加えることが出来る。
The graft copolymer used for the resin modifier of the present invention is recovered by spray drying, and at this time, it was finally obtained in order to improve the dispersibility in the thermoplastic resin and the curable resin. It is necessary that the average particle size of the emulsion polymerization latex particles, that is, the primary particles is in the range of 300 nm or more and less than 600 nm . More preferably, it is 400 nm or more and less than 600 nm , More preferably, it is 500 nm or more and less than 600 nm . When the average particle size is smaller than 300 nm, the primary particles of the obtained modifier for powdery resin are fused, and good dispersibility cannot be exhibited. Similarly, from the viewpoint of controlling powder dispersibility, the particle size distribution of latex particles is preferably as narrow as possible, and even if particles of 150 nm or less are present, there is no particular inconvenience, but it is more preferable that the particle size distribution is as small as possible. On the other hand, when the thickness is 700 nm or more, stability during polymerization is decreased and aggregates are increased, so that production stability and a polymer recovery rate are significantly decreased.
An appropriate antioxidant or additive can be added to the graft copolymer latex in advance as needed.

参考例、実施例１、比較例１〜３
硬化性樹脂１００質量部に対して、得られた樹脂用改質剤を１０質量部配合し、シート状成形試験片を得た。その試験片を用いて、アイゾット衝撃強度、及び樹脂用改質剤の分散性を評価した。結果を表２に示した。
なお、実施例における硬化性樹脂組成物には以下のものを使用した。
ビスフェノールＡ型エポキシ樹脂（旭電化（株）製アデカレジンＥＰ−４１００Ｅ）１００部、テトラヒドロメチル無水フタル酸（旭電化（株）製アデカハードナーＥＨ−３３２６）８５部、および樹脂用改質剤１０部を６０℃にて攪拌機を用いて１５０ｒｐｍにて９０分間攪拌した後、Ｎ−ベンジル−２−メチルイミダゾール１部を加え更に攪拌混合し、得られた組成物を金型に充填し８０℃で２時間、１２０℃で６時間加熱して試験片を作成した。
また、評価方法は以下の方法を用いた。
（１）衝撃強度：シート状試験片を成形し切断後、ＡＳＴＭＤ２５６に基づき評価した。（厚み：１／４インチ、単位：Ｊ／ｍ）
（２）分散性：シート状試片を用い、試験片を液体窒素を用い凍結破断させ破断面をＳＥＭ観察することにより、樹脂用改質剤の分散状態（凝集状態）を用いて下記の基準で評価した。
○：１０μｍ以上の粒子は観察されない。
△：５０μｍ以上の粒子は観察されないが、１０μｍ以上の粒子は観察される。
×：５０μｍ以上の粒子が観察される。
Reference Example, Example 1 , Comparative Examples 1-3
10 parts by mass of the obtained resin modifier was blended with 100 parts by mass of the curable resin to obtain a sheet-shaped molded test piece. The Izod impact strength and the dispersibility of the resin modifier were evaluated using the test piece. The results are shown in Table 2.
In addition, the following were used for the curable resin composition in an Example.
100 parts of bisphenol A type epoxy resin (Adeka Resin EP-4100E manufactured by Asahi Denka Co., Ltd.), 85 parts of tetrahydromethylphthalic anhydride (Adeka Hardener EH-3326 manufactured by Asahi Denka Co., Ltd.), and 10 parts of a modifier for resin After stirring for 90 minutes at 150 rpm using a stirrer at 60 ° C., 1 part of N-benzyl-2-methylimidazole was added and further stirred and mixed, and the resulting composition was filled in a mold and stirred at 80 ° C. for 2 hours. A test piece was prepared by heating at 120 ° C. for 6 hours.
Moreover, the following method was used for the evaluation method.
(1) Impact strength: After a sheet-like test piece was molded and cut, it was evaluated based on ASTM D256. (Thickness: 1/4 inch, unit: J / m)
(2) Dispersibility: Using a sheet-like specimen, the specimen is freeze-fractured using liquid nitrogen and the fracture surface is observed by SEM, and the following criteria are used using the dispersion state (aggregation state) of the modifier for resin. It was evaluated with.
○: Particles of 10 μm or more are not observed.
Δ: Particles of 50 μm or more are not observed, but particles of 10 μm or more are observed.
X: Particles of 50 μm or more are observed.

Claims

A resin modifier having an average particle diameter of 20 μm or more and a proportion of particles of 10 μm or less of less than 30% by mass, and a proportion of particles of 10 μm or less after 40 minutes of ultrasonic irradiation for 5 minutes Is a modifier for resin having an average particle diameter of primary particles in the range of 300 nm or more and less than 600 nm .

A resin composition comprising 1 to 40% by mass of the resin modifier according to claim 1 and 99 to 60% by mass of a thermoplastic resin or a curable resin (the total amount of both is 100% by mass).

A molded product formed by molding the resin composition according to claim 2.