JP2001055395A - Sodium-2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate compound, its production and polyolefin polymer composition containing the compound - Google Patents
Sodium-2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate compound, its production and polyolefin polymer composition containing the compoundInfo
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- JP2001055395A JP2001055395A JP23084899A JP23084899A JP2001055395A JP 2001055395 A JP2001055395 A JP 2001055395A JP 23084899 A JP23084899 A JP 23084899A JP 23084899 A JP23084899 A JP 23084899A JP 2001055395 A JP2001055395 A JP 2001055395A
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- compound
- butylphenyl
- methylenebis
- phosphate
- sodium
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規な結晶構造を
有するホスフェート化合物に関し、詳しくは、Ｘ線回折
測定による回折角（２θ）において５．００゜〜６．０
０゜及び１３．００゜〜１４．００゜の範囲に回折ピー
クを有するナトリウム−２，２’−メチレンビス（４，
６−ジ第三ブチルフェニル）ホスフェート化合物に関す
る。[0001] The present invention relates to a phosphate compound having a novel crystal structure, and more specifically, to a diffraction angle (2θ) by X-ray diffraction measurement of 5.00 ° to 6.0 °.
Sodium-2,2'-methylenebis (4,0) having diffraction peaks in the range of 0 ° and 13.00 ° to 14.00 °.
6-di-tert-butylphenyl) phosphate compound.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】ナトリ
ウム−２，２’−メチレンビス（４，６−ジ第三ブチル
フェニル）ホスフェートは、ポリオレフィン、ポリエス
テル、ポリアミド等結晶性高分子化合物の結晶剤、ポリ
カーボネート系高分子化合物の難燃剤等の高分子化合物
の機能性付与剤、抗菌剤、防臭剤及び各種工業薬品の中
間体として有用な化合物である。2. Description of the Related Art Sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate is a crystallization agent for crystalline polymer compounds such as polyolefins, polyesters and polyamides. It is a compound useful as a function-imparting agent for polymer compounds such as polycarbonate-based flame retardants, antibacterial agents, deodorants, and intermediates for various industrial chemicals.
【０００３】該化合物は、結晶性の固体であり、その製
造方法は、特公平５−６０４７２号に２，２’−メチレ
ンビス（４，６−ジ第三ブチルフェニル）ホスフェート
と水酸化ナトリウムをごく少量の水、有機溶剤類を用い
て反応させて得られた結晶性固体を粉砕する方法が記載
されている。この方法では、製造時の操作性、収率、純
度について改善できるものの、得られる粉体は嵩比重が
小さく、粉砕工程時に発生する微細粒子を含むので、使
用時の浮遊粉塵、輸送性（輸送が容易かどうか）、計量
性（計量しやすいかどうか）等の操作性に問題があっ
た。The compound is a crystalline solid, and its production method is described in Japanese Examined Patent Publication No. Hei. 5-60472, in which 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate and sodium hydroxide are used. A method of pulverizing a crystalline solid obtained by reacting with a small amount of water and an organic solvent is described. According to this method, although the operability, yield and purity during production can be improved, the resulting powder has a low bulk specific gravity and contains fine particles generated during the pulverization process, so that the suspended powder during use, transportability (transportation) Easiness) and operability such as weighability (whether weighing is easy).
【０００４】[0004]
【課題を解決するための手段】本発明者等は、上記課題
を解決するため検討を重ねた結果、新規な結晶構造を有
するナトリウム−２，２’−メチレンビス（４，６−ジ
第三ブチルフェニル）ホスフェート化合物が、使用時の
操作性が良好であるとの知見を得て、本発明に到達し
た。The inventors of the present invention have conducted various studies to solve the above-mentioned problems, and as a result, have found that sodium-2,2'-methylenebis (4,6-di-tert-butyl) having a novel crystal structure. The inventors have found that the phenyl) phosphate compound has good operability at the time of use, and have reached the present invention.
【０００５】即ち本発明の第１によれば、Ｘ線回折測定
による回折角（２θ）において５．００゜〜６．００゜
及び１３．００゜〜１４．００゜の範囲に回折ピークを
有する下記一般式（Ｉ）で表されるナトリウム−２，
２’−メチレンビス（４，６−ジ第三ブチルフェニル）
ホスフェート化合物が提供される。また本発明の第２に
よれば、一般式（Ｉ）において０＜ｎ≦５である本発明
の第１のホスフェート化合物の結晶水を除くことを特徴
とするｎ＝０である本発明の第１のナトリウム−２，
２’−メチレンビス（４，６−ジ第三ブチルフェニル）
ホスフェート無水物の製造方法が提供される。更に本発
明の第３によれば、本発明の第１のナトリウム−２，
２’−メチレンビス（４，６−ジ第三ブチルフェニル）
ホスフェート化合物を含有させてなるポリオレフィン系
高分子組成物が提供される。That is, according to the first aspect of the present invention, diffraction peaks are found in the range of 5.00 ° to 6.00 ° and 13.00 ° to 14.00 ° in diffraction angle (2θ) by X-ray diffraction measurement. Sodium-2 represented by the following general formula (I),
2'-methylenebis (4,6-di-tert-butylphenyl)
A phosphate compound is provided. According to a second aspect of the present invention, there is provided the first aspect of the present invention wherein n = 0, wherein water of crystallization of the first phosphate compound of the present invention in which 0 <n ≦ 5 in the general formula (I) is excluded. 1 of sodium-2,
2'-methylenebis (4,6-di-tert-butylphenyl)
A method for producing a phosphate anhydride is provided. Further according to a third aspect of the present invention, the first sodium-2,2,2,3,4,5-6,5-6,5-6,5-6,5-6,5-6,5-6,5-6,5-6,7,10,10,10,10,10,10,10,10,10,12,13,14,14,15,14,15,15,15,15,14,15,14,15,14,13,14,13,14,13,14 for the first invention.
2'-methylenebis (4,6-di-tert-butylphenyl)
A polyolefin polymer composition containing a phosphate compound is provided.
【０００６】[0006]
【化２】 Embedded image
【０００７】[0007]
【発明の実施の形態】以下、上記要旨をもってなる本発
明について詳述する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention having the above gist will be described below in detail.
【０００８】本発明に係る新規な結晶構造を有する上記
一般式（Ｉ）で表されるナトリウム−２，２’−メチレ
ンビス（４，６−ジ第三ブチルフェニル）ホスフェート
化合物は次の特徴を有する。[0008] The sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate compound represented by the above general formula (I) having a novel crystal structure according to the present invention has the following characteristics. .
【０００９】（１）Ｘ線回折測定による回折角（２θ）
において、５．００゜〜６．００゜及び１３．００゜〜
１４．００゜の範囲に回折ピークを有し、操作性に優れ
た粉体を与える。粉体の操作性の目安となるものに、嵩
比重、安息角、微細粒子があり、嵩比重が小さい場合及
び／又は微細粒子が存在すると粉体が飛散しやすいので
浮遊粉塵による作業安全性、計量性が問題になり、安息
角が大きいと粉体の流動性が無く、輸送性、計量性が問
題になる。本発明の新規な結晶構造を有するナトリウム
−２，２’−メチレンビス（４，６−ジ第三ブチルフェ
ニル）ホスフェート化合物（以下、「新規結晶ホスフェ
ート」と記載する。）は、後記実施例に記載の通り、従
来のナトリウム−２，２’−メチレンビス（４，６−ジ
第三ブチルフェニル）ホスフェート（以下、「既存品」
と記載する。）と比較してＸ線回折測定による回折角
（２θ）において５．００゜〜６．００゜及び１３．０
０゜〜１４．００゜の範囲に回折ピークを有するので区
別でき、かつ良好な操作性を示す。(1) Diffraction angle (2θ) by X-ray diffraction measurement
5.00 to 6.00 and 13.00 to
It has a diffraction peak in the range of 14.00 ° and gives powder having excellent operability. As a measure of the operability of the powder, there are bulk specific gravity, angle of repose, and fine particles. If the angle of repose is large, there is no fluidity of the powder, and if the angle of repose is large, the transportability and the weighability become problems. The sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate compound having a novel crystal structure of the present invention (hereinafter referred to as "new crystalline phosphate") is described in Examples described later. As described above, conventional sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate (hereinafter referred to as "existing product")
It is described. ) To 5.00 ° to 6.00 ° and 13.0 in diffraction angle (2θ) by X-ray diffraction measurement.
Since it has a diffraction peak in the range of 0 ° to 14.00 °, it can be distinguished and shows good operability.
【００１０】（２）工業薬品中間体及び機能性付与剤と
しての機能は、既存品と同等である。本発明の新規結晶
ホスフェートは、化学的機能に関わる構造は既存品と同
一であるので、工業薬品中間体及び機能性付与剤として
はその水和度に依らず、既存品と同等の機能を発現する
ものである。例えば、ポリオレフィン系高分子等の結晶
性高分子化合物の結晶剤、ポリカーボネート系高分子化
合物の難燃剤等の高分子化合物の機能性付与剤等として
は、既存品と全く同様の用途に使用することができる。(2) The functions as an industrial chemical intermediate and a function-imparting agent are the same as existing products. The novel crystalline phosphate of the present invention has the same structure related to the chemical function as the existing product, so it exhibits the same function as the existing product regardless of the degree of hydration as an intermediate for industrial chemicals and a function-imparting agent. Is what you do. For example, as a crystallizing agent for a crystalline polymer compound such as a polyolefin-based polymer, or as a function-imparting agent for a polymer compound such as a flame retardant of a polycarbonate-based polymer compound, it should be used for the same purpose as an existing product. Can be.
【００１１】本発明の新規結晶ホスフェートにおいて、
ｎが０より大きく５以下である水和物（以下、「水和
物」と記載する。）の製造方法については、特に制限を
受けないが、例えば、原料の環状酸性リン酸エステルに
水酸化ナトリウム水溶液を滴下して水和物を析出させる
方法や、既存の方法で得られたナトリウム−２，２’−
メチレンビス（４，６−ジ第三ブチルフェニル）ホスフ
ェート（既存品）を水−メタノール溶媒に溶解させた
後、この溶液から晶析させることにより得られる。In the novel crystalline phosphate of the present invention,
The method for producing a hydrate in which n is greater than 0 and 5 or less (hereinafter, referred to as “hydrate”) is not particularly limited. A method of precipitating a hydrate by dropping an aqueous solution of sodium or a method of preparing sodium-2,2'- obtained by an existing method.
It is obtained by dissolving methylenebis (4,6-di-tert-butylphenyl) phosphate (existing product) in a water-methanol solvent and then crystallization from this solution.
【００１２】水和物であることは、ＩＲ測定において３
７００ｃｍ-1〜３６００ｃｍ-1の範囲に現れる結晶水由
来の鋭い吸収により確認でき、その水和度は、固体用昇
温脱離方式のカールフィッシャー水分計による水分測定
及び結晶水を除いた（脱水した）際の重量変化で確認で
きる。[0012] The fact that the substance is a hydrate means that it is 3 in IR measurement.
700 cm -1 can be confirmed by a sharp absorption of crystal water from appearing in the range of ～3600Cm -1, the degree of hydration is to remove water measurement and crystal water by Karl Fischer moisture meter for solids Atsushi Nobori method (dehydrated ) Can be confirmed by the change in weight.
【００１３】本発明の水和物は、後記実施例に示した通
り、ＩＲ測定において３６５０ｃｍ -1近辺に鋭い吸収を
示し、その水和度は温度等の製造条件により異なる。ま
た該化合物は、Ｘ線回折測定による回折角（２θ）にお
いて５．００゜〜６．００゜及び１３．００゜〜１４．
００゜に特徴的な回折ピークを有する。[0013] The hydrate of the present invention can be prepared by using
3650 cm in IR measurement -1Sharp absorption in the vicinity
The degree of hydration varies depending on the production conditions such as temperature. Ma
The compound has a diffraction angle (2θ) determined by X-ray diffraction measurement.
5.00 to 6.00 and 13.00 to 14.
It has a characteristic diffraction peak at 00 °.
【００１４】上記水和物は、水和物の状態で高分子化合
物の機能性付与剤として使用することができ、その効果
は、既存品と全く同一であり、粉砕工程が必要である既
存品と比較すると、晶析によって得られるので、均一な
粒子が得られること、粒径の制御が可能であること、粉
砕工程時に発生する微細粒子起因の浮遊粉塵が無いこと
の諸点で優れる。The above hydrate can be used in the form of a hydrate as a function-imparting agent for a polymer compound, and its effect is exactly the same as that of an existing product, and an existing product requiring a pulverizing step is required. Compared with the method of (1), it is excellent in various points that uniform particles can be obtained, the particle size can be controlled, and there is no floating dust caused by fine particles generated in the pulverizing step.
【００１５】本発明の新規結晶ホスフェートにおいて、
ｎ＝０である無水物（以下、「無水物」と記載する。）
は、上記水和物の結晶水を除くことによって得られる。
また、該ホスフェート無水物は後記実施例に示した通
り、Ｘ線回折測定による回折角（２θ）において５．０
０゜〜６．００゜及び１３．００゜〜１４．００゜に特
徴的な回折ピークを有する点で従来品とは異なる結晶で
あり、この新規結晶は嵩比重、安息角等の操作性に関わ
る性状が良好である。In the novel crystalline phosphate of the present invention,
An anhydride in which n = 0 (hereinafter referred to as “anhydride”)
Is obtained by removing the water of crystallization of the above hydrate.
Further, as shown in Examples described later, the phosphate anhydride has a diffraction angle (2θ) of 5.0 by X-ray diffraction measurement.
This crystal is different from the conventional crystal in that it has characteristic diffraction peaks at 0 ° to 6.00 ° and 13.00 ° to 14.00 °, and this new crystal has poor operability such as bulk specific gravity and angle of repose. The properties involved are good.
【００１６】本発明のナトリウム−２，２’−メチレン
ビス（４，６−ジ第三ブチルフェニル）ホスフェート無
水物の製造方法とは、前述の水和物を原料にその結晶水
を除いて上記無水物を得る方法のことであり、水和物の
結晶水が除かれる際に結晶粒子が破砕され、より細かく
均一で操作性の良好な粒子が得られることが特徴であ
る。この様子は下記の図１の電子顕微鏡写真で観察でき
る。結晶水を除く方法については特に制限を受けない
が、例えば、水和物を有機溶媒中或いは無溶媒で加熱す
る方法が挙げられる。The method for producing anhydrous sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate of the present invention is characterized in that the above-mentioned hydrate is used as a raw material and the water of crystallization is removed therefrom. This is a method of obtaining a product, which is characterized in that crystal particles are crushed when water of crystallization of the hydrate is removed, and finer, uniform particles with good operability are obtained. This can be observed in the electron micrograph of FIG. 1 below. The method for removing water of crystallization is not particularly limited, and examples thereof include a method of heating a hydrate in an organic solvent or without a solvent.
【００１７】図１は、大きく晶析させた２．５水和物
（後記製造例２と同様の配合で晶析を静置で行ったも
の）を１００℃で減圧下（５０Ｔｏｒｒ）で３０分加熱
乾燥した結晶の電子顕微鏡写真（２００倍）を示す。結
晶水が除かれるときに破砕される様子が観察できる。FIG. 1 shows that a heavily crystallized 2.5 hydrate (which was crystallized and allowed to stand still with the same composition as in Production Example 2 described below) at 100 ° C. under reduced pressure (50 Torr) for 30 minutes. The electron microscope photograph (200 times) of the heat-dried crystal is shown. It can be observed that crushing occurs when the water of crystallization is removed.
【００１８】上記方法で得られた無水物について、ＩＲ
測定、水分測定による分析により、結晶水を含まないこ
とが確認できる。また、Ｘ線回折測定においても結晶水
を持たないナトリウム−２，２’−メチレンビス（４，
６−ジ第三ブチルフェニル）ホスフェートに特徴的な回
折角（２θ）６．５゜近辺の大きなピークを確認でき
る。With respect to the anhydride obtained by the above method, IR
By measurement and analysis by moisture measurement, it can be confirmed that water of crystallization is not contained. Also, in the X-ray diffraction measurement, sodium-2,2'-methylenebis (4,4
A large peak near 6.5 ° diffraction angle (2θ) characteristic of 6-di-tert-butylphenyl) phosphate can be confirmed.
【００１９】本発明の新規結晶ホスフェートは、その用
途について特に制限を受けないが、結晶性高分子化合物
の結晶剤として有用であり、従来品と同様、ポリエチレ
ン、ポリプロピレン等のポリオレフィン系高分子化合物
の結晶剤として、優れた透明性、強度を与え、かつ使用
時の操作性に優れるので特に有用である。The novel crystalline phosphate of the present invention is not particularly limited in its use, but is useful as a crystallizing agent for a crystalline polymer compound. It is particularly useful as a crystallization agent because it imparts excellent transparency and strength and has excellent operability during use.
【００２０】[0020]
【実施例】以下、本発明を製造例、評価例によって具体
的に説明するが、本発明は以下の実施例によりなんら制
限されるものではない。EXAMPLES The present invention will be specifically described below with reference to production examples and evaluation examples, but the present invention is not limited to the following examples.
【００２１】（製造例１：ナトリウム−２，２’−メチ
レンビス（４，６−ジ第三ブチルフェニル）ホスフェー
ト１水和物の製造）２，２−メチレンビス（４，６−ジ
−第三ブチルフェニル）ホスフェート４８．６ｇ（０．
１ｍｏｌ）のキシレン溶液１４５．８ｇに室温で５０％
水酸化ナトリウム水溶液８．０ｇを滴下し、滴下終了後
５０℃で２時間反応させた。メタノール９７．２ｇを加
えた後、３５℃で水９７．２ｇを滴下して晶析させ、濾
取した結晶を７０℃の減圧下（７６Ｔｏｒｒ）で乾燥
し、結晶Ａ４４．２ｇ（収率８４％）を得た。(Production Example 1: Production of sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate monohydrate) 2,2-methylenebis (4,6-di-tert-butyl) 48.6 g of phenyl) phosphate (0.
1 mol) in 145.8 g of xylene solution at room temperature
8.0 g of an aqueous sodium hydroxide solution was added dropwise, and the mixture was reacted at 50 ° C. for 2 hours after completion of the addition. After addition of 97.2 g of methanol, 97.2 g of water was added dropwise at 35 ° C. to cause crystallization, and the crystal collected by filtration was dried under reduced pressure (76 Torr) at 70 ° C. to obtain 44.2 g of crystal A (yield 84%). ) Got.
【００２２】（製造例２：ナトリウム−２，２’−メチ
レンビス（４，６−ジ第三ブチルフェニル）ホスフェー
ト２．５水和物の製造）２，２−メチレンビス（４，６
−ジ−第三ブチルフェニル）ホスフェート４８．６ｇ
（０．１ｍｏｌ）のキシレン溶液１４５．８ｇに室温で
５０％水酸化ナトリウム水溶液８．０ｇを滴下し、滴下
終了後室温で６時間反応させた。メタノール９７．２ｇ
を加えた後、２０℃で水９７．２ｇを滴下して晶析さ
せ、濾取した結晶を５０℃の減圧下（７６Ｔｏｒｒ）で
乾燥し、結晶Ｂ４３．７ｇ（収率７９％）を得た。(Production Example 2: Production of sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate hemihydrate) 2,2-methylenebis (4,6
-Di-tert-butylphenyl) phosphate 48.6 g
8.0 g of a 50% aqueous sodium hydroxide solution was added dropwise to 145.8 g of a xylene solution (0.1 mol) at room temperature, and the mixture was reacted at room temperature for 6 hours after completion of the addition. 97.2 g of methanol
Was added, and 97.2 g of water was added dropwise at 20 ° C. for crystallization. The crystals collected by filtration were dried at 50 ° C. under reduced pressure (76 Torr) to obtain 43.7 g of crystal B (yield 79%). .
【００２３】（製造例３：水和物からのナトリウム−
２，２’−メチレンビス（４，６−ジ第三ブチルフェニ
ル）ホスフェート無水物の製造）結晶Ａ及びＢをそれぞ
れ減圧乾燥機（１０Ｔｏｒｒ）で１２０℃で乾燥し、結
晶水を除き結晶Ａ’を４２．７ｇ、結晶Ｂ’を４０．２
ｇ得た。(Production Example 3: Sodium from hydrate)
Preparation of 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate anhydride) Crystals A and B were each dried at 120 ° C. in a reduced pressure drier (10 Torr) to remove water of crystallization. 42.7 g, 40.2 g of crystal B ′
g was obtained.
【００２４】（比較製造例：ナトリウム−２，２’−メ
チレンビス（４，６−ジ第三ブチルフェニル）ホスフェ
ートの製造）２，２−メチレンビス（４，６−ジ−第三
ブチルフェニル）ホスフェート１０００ｇ（２．０６ｍ
ｏｌ）、水酸化ナトリウム８２．４ｇ（２．０６ｍｏ
ｌ）、水３６０ｇ、メタノール２００ｇをニーダーに仕
込み、室温で１時間混練し、１００℃の減圧下（７６Ｔ
ｏｒｒ）で１時間乾燥した後、粉砕して結晶Ｃ１０２８
ｇ（収率９８．２％）を得た。(Comparative Production Example: Production of sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate) 1,000 g of 2,2-methylenebis (4,6-di-tert-butylphenyl) phosphate (2.06m
ol), 82.4 g of sodium hydroxide (2.06 mol
l), water (360 g) and methanol (200 g) were charged into a kneader, and kneaded at room temperature for 1 hour.
orr) for 1 hour, and then pulverized to give crystal C1028.
g (98.2% yield).
【００２５】上記、製造例（実施例に相当する）及び比
較製造例により得られた結晶について、ＩＲ、Ｘ線回折
（Ｃｕ−Ｋα、粉末法、常温で測定）、水分測定（固体
用昇温脱離装置付カールフィッシャー、重量法、試料温
度；１５０℃、キャリアガス；窒素、２１０ｍｌ／ｍｉ
ｎ）、平均粒径（水分散液のレーザー回折式粒度分布
計：shimadzu LASER DEFFRACTION PARTICLE SIZE ANALY
ZER SALD-100使用）の分析を行った。結果を表１に示
す。IR, X-ray diffraction (Cu-Kα, powder method, measured at room temperature), and moisture measurement (temperature rise for solids) of the crystals obtained by the above-mentioned Production Examples (corresponding to Examples) and Comparative Production Examples Karl Fischer with desorption device, gravimetric method, sample temperature; 150 ° C, carrier gas; nitrogen, 210 ml / mi
n), Average particle size (Laser diffraction particle size distribution analyzer of aqueous dispersion: shimadzu LASER DEFFRACTION PARTICLE SIZE ANALY
(Using ZER SALD-100). Table 1 shows the results.
【００２６】[0026]
【表１】 [Table 1]
【００２７】（評価例１）結晶粒子の評価 顕微鏡により結晶粒を観察した。図２、図３及び図４は
下記結晶の顕微鏡写真（６００倍）である。 図２：結晶Ａ（図２−１），結晶Ａ’（図２−２） 図３：結晶Ｂ（図３−１），結晶Ｂ’（図３−２） 図４：結晶Ｃ(Evaluation Example 1) Evaluation of Crystal Particles Crystal grains were observed with a microscope. 2, 3 and 4 are micrographs (magnification: 600) of the following crystals. Fig. 2: Crystal A (Fig. 2-1), crystal A '(Fig. 2-2) Fig. 3: Crystal B (Fig. 3-1), crystal B' (Fig. 3-2) Fig. 4: Crystal C
【００２８】（評価例２）嵩比重、安息角の評価 結晶水を持たないナトリウム−２，２’−メチレンビス
（４，６−ジ第三ブチルフェニル）ホスフェート（結晶
Ａ’、Ｂ’、Ｃ）について嵩比重、安息角を評価した。
結果を表２に示す。(Evaluation Example 2) Evaluation of Bulk Specific Gravity and Angle of Repose Sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate without water of crystallization (crystals A ', B', C) Was evaluated for bulk specific gravity and angle of repose.
Table 2 shows the results.
【００２９】[0029]
【表２】 [Table 2]
【００３０】上記分析結果及び評価結果より、以下の事
項が確認できる。 （１）結晶Ａ、Ｂ、Ａ’、Ｂ’は、Ｘ線回折測定による
回折角（２θ）において５．００゜〜６．００゜及び１
３．００゜〜１４．００゜の範囲に回折ピークを有し、
それぞれ既存品である結晶Ｃとは異なった結晶構造であ
る。 （２）結晶Ａ及び結晶Ｂから結晶水を除いて得られる結
晶Ａ’及び結晶Ｂ’の結晶構造は同一である。 （３）結晶Ａ、Ｂは、それぞれ結晶水を有し、その水和
度は結晶Ａが１、結晶Ｂは２．５である。 （４）結晶Ａ、Ｂ、Ａ’、Ｂ’は、均質な粒子であり、
浮遊粉塵の原因となる微細粉末を実質上含まない。 （５）結晶Ａ’及びＢ’は、結晶Ｃに比べ嵩比重が大き
く、安息角が小さいので浮遊粉塵、輸送性、計量性等使
用時の操作性に優れる。The following items can be confirmed from the above analysis results and evaluation results. (1) The crystals A, B, A ′, and B ′ have a diffraction angle (2θ) of 5.00 ° to 6.00 ° and 1 in X-ray diffraction measurement.
Having a diffraction peak in the range of 3.00 ° to 14.00 °,
Each has a different crystal structure from the existing crystal C. (2) The crystal structures of crystals A ′ and B ′ obtained by removing crystal water from crystals A and B are the same. (3) Crystals A and B each have water of crystallization, and the degree of hydration is 1 for crystal A and 2.5 for crystal B. (4) The crystals A, B, A ′, B ′ are homogeneous particles,
Substantially free of fine powder that causes airborne dust. (5) Crystals A ′ and B ′ have a higher bulk specific gravity and a smaller angle of repose than Crystal C, so that they are excellent in operability during use, such as suspended dust, transportability, and weighability.
【００３１】（評価例３）結晶剤としての評価 下記配合の高分子組成物をミキサーで５分間混合した
後、２５０℃、２５ｒｐｍの条件で押出加工でペレット
を成形し、得られたペレットを２５０℃で射出成形して
得た厚さ１ｍｍ試験片のヘイズ値（ＪＩＳ Ｋ７１０
５）及び曲げ弾性率（ＡＳＴＭ Ｄ−７４７−６３）を
評価した。結果を表３に示す。 （配合） 高分子化合物：ポリプロピレン；出光石油化学（株）製
Ｈ７００（１００重量部） 安定剤： ステアリン酸カルシウム（０．１０重量部） トリ−２，４−第三ブチルホスファイト（０．１重量
部） テトラキス[メチレン−３−（３，５−ジ第三ブチル−
４−ヒドロキシフェニル）プロピオネート]メタン
（０．１重量部） 結晶剤：表３記載（０．１重量部）(Evaluation Example 3) Evaluation as Crystallizing Agent A polymer composition having the following composition was mixed with a mixer for 5 minutes, and pellets were formed by extrusion at 250 ° C. and 25 rpm. Haze value of a 1 mm thick test piece obtained by injection molding at ℃ (JIS K710
5) and flexural modulus (ASTM D-747-63) were evaluated. Table 3 shows the results. (Blend) Polymer compound: polypropylene; H700 (100 parts by weight) manufactured by Idemitsu Petrochemical Co., Ltd. Stabilizer: calcium stearate (0.10 parts by weight) tri-2,4-tert-butyl phosphite (0.1 parts by weight) Part) tetrakis [methylene-3- (3,5-di-tert-butyl-
4-Hydroxyphenyl) propionate] methane (0.1 part by weight) Crystallizing agent: described in Table 3 (0.1 part by weight)
【００３２】[0032]
【表３】 [Table 3]
【００３３】上記結果より、本発明の新規な結晶構造を
有するナトリウム−２，２’−メチレンビス（４，６−
ジ第三ブチルフェニル）ホスフェート化合物は既存のナ
トリウム−２，２’−メチレンビス（４，６−ジ第三ブ
チルフェニル）ホスフェートと同等の添加効果を示すこ
とを確認した。From the above results, it was found that sodium-2,2'-methylenebis (4,6-
It was confirmed that the di-tert-butylphenyl) phosphate compound exhibited an addition effect equivalent to that of the existing sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate.
【００３４】[0034]
【発明の効果】本発明は、新規な結晶構造を有し、使用
時の操作性の改善されたナトリウム−２，２’−メチレ
ンビス（４，６−ジ第三ブチルフェニル）ホスフェート
化合物を与える。The present invention provides a sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate compound having a novel crystal structure and improved operability during use.
【図面の簡単な説明】[Brief description of the drawings]
【図１】本発明の新規結晶ホスフェートの水和物から無
水物を製造する際に、結晶粒子が破砕され、より細かく
均一で操作性の良好な粒子が得られる様子を示す電子顕
微鏡写真である。FIG. 1 is an electron micrograph showing that crystal grains are crushed when producing an anhydride from a hydrate of a novel crystalline phosphate of the present invention, whereby finer, uniform, and operable particles are obtained. .
【図２】本発明の新規結晶ホスフェート（水和物：結晶
Ａ及びその無水物：結晶Ａ’）の電子顕微鏡写真であ
る。FIG. 2 is an electron micrograph of a novel crystalline phosphate (hydrate: crystal A and its anhydride: crystal A ′) of the present invention.
【図３】本発明の新規結晶ホスフェート（水和物：結晶
Ｂ及びその無水物：結晶Ｂ’）の電子顕微鏡写真であ
る。FIG. 3 is an electron micrograph of a novel crystalline phosphate (hydrate: crystal B and its anhydride: crystal B ′) of the present invention.
【図４】比較製造例により得られた結晶Ｃの電子顕微鏡
写真である。FIG. 4 is an electron micrograph of a crystal C obtained by a comparative production example.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4H028 AA35 AA42 BA06 4H050 AA01 AA02 AA03 AB03 AB48 AB80 AC90 4J002 BB001 BB121 EW046 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H028 AA35 AA42 BA06 4H050 AA01 AA02 AA03 AB03 AB48 AB80 AC90 4J002 BB001 BB121 EW046
Claims (3)
いて５．００゜〜６．００゜及び１３．００゜〜１４．
００゜の範囲に回折ピークを有する下記一般式（Ｉ）で
表されるナトリウム−２，２’−メチレンビス（４，６
−ジ第三ブチルフェニル）ホスフェート化合物。 【化１】 1. A diffraction angle (2θ) by X-ray diffraction measurement of 5.00 ° to 6.00 ° and 13.00 ° to 14.
Sodium-2,2'-methylenebis (4,6) represented by the following general formula (I) having a diffraction peak in the range of 00 °
-Di-tert-butylphenyl) phosphate compound. Embedded image
請求項１記載のホスフェート化合物の結晶水を除くこと
を特徴とするｎ＝０である請求項１記載のナトリウム−
２，２’−メチレンビス（４，６−ジ第三ブチルフェニ
ル）ホスフェート無水物の製造方法。2. The sodium compound according to claim 1, wherein n = 0 in the general formula (I), wherein 0 <n ≦ 5, wherein water of crystallization of the phosphate compound is excluded.
A method for producing 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate anhydride.
メチレンビス（４，６−ジ第三ブチルフェニル）ホスフ
ェート化合物を含有させてなるポリオレフィン系高分子
組成物。3. The sodium-2,2′- according to claim 1,
A polyolefin-based polymer composition containing a methylene bis (4,6-di-tert-butylphenyl) phosphate compound.
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|---|---|---|---|
| JP23084899A JP2001055395A (en) | 1999-08-17 | 1999-08-17 | Sodium-2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate compound, its production and polyolefin polymer composition containing the compound |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23084899A JP2001055395A (en) | 1999-08-17 | 1999-08-17 | Sodium-2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate compound, its production and polyolefin polymer composition containing the compound |
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|---|---|
| JP2001055395A true JP2001055395A (en) | 2001-02-27 |
Family
ID=16914249
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