JPH07286066A - Nucleator composition and polyolefin resin composition - Google Patents

Nucleator composition and polyolefin resin composition

Info

Publication number
JPH07286066A
JPH07286066A JP10605094A JP10605094A JPH07286066A JP H07286066 A JPH07286066 A JP H07286066A JP 10605094 A JP10605094 A JP 10605094A JP 10605094 A JP10605094 A JP 10605094A JP H07286066 A JPH07286066 A JP H07286066A
Authority
JP
Japan
Prior art keywords
nucleating agent
component
group
polyolefin resin
resin composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP10605094A
Other languages
Japanese (ja)
Inventor
Toshiaki Kobayashi
稔明 小林
Shizumi Sakai
鎮美 酒井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
New Japan Chemical Co Ltd
Original Assignee
New Japan Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by New Japan Chemical Co Ltd filed Critical New Japan Chemical Co Ltd
Priority to JP10605094A priority Critical patent/JPH07286066A/en
Publication of JPH07286066A publication Critical patent/JPH07286066A/en
Pending legal-status Critical Current

Links

Abstract

PURPOSE:To obtain an odorless nucleator compsn. which exhibits highly active clarifying and nucleating characteristics at a low content when compounded into a polyolefin resin by incorporating specific compds. into the compsn. CONSTITUTION:A nucleator compsn. contains a diacetal compd. (A) of formula I [wherein, when X<1> is 3,4-dimethlbenzylidene, then X<2> is a group of formula II (wherein R<1> is 1-3C alkyl, Cl, or methyloxymethyl) or 5,6,7,8-tetrahydro-2- naphthyl; and when X<2> is 3,4-dimethylbenzylidene, then X<1> is a group of formula II or 5,6,7,8-tetrahydro-2-naphthyl] and bis(O-3,4-dimethylbenzylidene)sorbitol (B) pref. in a wt. ratio (A/B) of (4:1)-(1:9).

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、核剤組成物及び当該核
剤組成物を含有してなるポリオレフィン系樹脂組成物に
関する。
FIELD OF THE INVENTION The present invention relates to a nucleating agent composition and a polyolefin resin composition containing the nucleating agent composition.

【0002】[0002]

【従来の技術】芳香族アルデヒドとソルビトールとを酸
触媒の存在下、アセタール縮合させて調製されるジベン
ジリデンソルビトール化合物(以下「DBS化合物」と
略称する。)は、ポリオレフィン系樹脂組成物用の核剤
として賞用されているものであって、本発明者らは、こ
れまでにもより優れた特性を有する核剤を提供すべく鋭
意検討の下、種々のDBS化合物を提案してきたところ
である。
BACKGROUND OF THE INVENTION A dibenzylidene sorbitol compound (hereinafter abbreviated as "DBS compound") prepared by acetal condensation of an aromatic aldehyde and sorbitol in the presence of an acid catalyst is a core for a polyolefin resin composition. It has been widely used as an agent, and the present inventors have been proposing various DBS compounds by earnestly studying to provide a nucleating agent having more excellent properties.

【0003】しかしながら、核剤に対する要望は多岐に
亘っているため、広範囲の用途に適用するためには、
尚、改善の余地が認められる。
However, since there are various demands for a nucleating agent, in order to apply it to a wide range of applications,
There is room for improvement.

【0004】具体的には、1,3:2,4−ビス(O−ベンジ
リデン)ソルビトール(以下「DBS」と略称する。)
を用いると、得られるポリオレフィン系樹脂成形物から
得られる成形物の光学的特性、特にその透明性が大幅に
改善され得るが、より高い透明性を必要とする分野に対
しては充分その要望を満足するものではない。
Specifically, 1,3: 2,4-bis (O-benzylidene) sorbitol (hereinafter abbreviated as "DBS").
When using, the optical properties of the molded product obtained from the obtained polyolefin resin molded product, especially its transparency can be significantly improved, but there is a sufficient demand for fields requiring higher transparency. I'm not satisfied.

【0005】かかる問題点を解消するものとして、我々
はベンズアルデヒドの代りにメチル置換ベンズアルデヒ
ドを出発物質として使用して調製される1,3:2,4−ビス
(O−メチルベンジリデン)ソルビトール(以下「Me
−DBS」と略称する。)を提案した(特開昭53−1
17044号、特開昭54−28348号)。
In order to solve such a problem, we have prepared 1,3: 2,4-bis (O-methylbenzylidene) sorbitol (hereinafter referred to as “the benzaldehyde”, which is prepared by using a methyl-substituted benzaldehyde as a starting material instead of benzaldehyde. Me
-DBS ". ) Was proposed (JP-A-53-1).
17044, JP-A-54-28348).

【0006】このものを適用することにより、格段に優
れた透明性を有する樹脂組成物を得ることができるが、
メチル置換ベンズアルデヒドは、香料としても用いられ
る化合物であって香気が極めて良好なため、樹脂組成物
を加熱して成形加工するに際し、臭気を発生し易いとい
う欠点が認められる。
[0006] By applying this, it is possible to obtain a resin composition having a remarkably excellent transparency,
Methyl-substituted benzaldehyde is a compound that is also used as a fragrance and has an extremely good odor. Therefore, it is recognized that an odor is easily generated when the resin composition is heated and molded.

【0007】1,3:2,4−ビス(O−ポリアルキルベンジ
リデン)ソルビトール(特開昭56−45934号)
や、各芳香環に夫々異なる種類や数の置換基を有する、
いわゆる非対称型のDBS化合物(特開昭59−129
51号)は、Me−DBSを使用した場合と同様に、優
れた透明性を有する成形体の製造に適したポリオレフィ
ン系樹脂組成物を与えるとともに、Me−DBSの欠点
である加熱成形時における臭気の発生が大幅に抑制され
たものである。
1,3: 2,4-bis (O-polyalkylbenzylidene) sorbitol (JP-A-56-45934)
Or having a different type and number of substituents on each aromatic ring,
A so-called asymmetric DBS compound (JP-A-59-129)
No. 51) provides a polyolefin resin composition suitable for the production of a molded product having excellent transparency, as well as the case of using Me-DBS, and has a drawback of Me-DBS, which is an odor during heat molding. The occurrence of is greatly suppressed.

【0008】一方、DBS化合物は、従来の核剤である
金属塩やシリカ等の「分散型」とは異なり、その融点又
はそれ以上の温度で融解し、樹脂中に均一に溶解するこ
とがポイントとなる「溶解型」の核剤であるため、ポリ
オレフィン系樹脂の成形加工時においては核剤を高速度
で融解混合することが、効率の良い成形加工のために大
切である。
On the other hand, unlike the conventional "dispersion type" of nucleating agents such as metal salts and silica, the DBS compound is melted at a temperature equal to or higher than its melting point and uniformly dissolved in the resin. Since it is a "dissolution type" nucleating agent, it is important to melt-mix the nucleating agent at a high speed at the time of molding the polyolefin resin for efficient molding.

【0009】従って、使用する核剤の融点が高いと、そ
のような核剤を含有する樹脂組成物の成形を高温での過
酷な条件下に行わねばならない不利がある。核剤の融点
以下の温度で成形をするには、事前に核剤とポリオレフ
ィン系樹脂とを当該核剤の融点以上の高温度に加熱溶融
し、高濃度マスターバッチを調製するという余分の工程
が必要である。よって、使用する核剤の融点が低い程、
これを含有するポリオレフィン系樹脂組成物の成形時の
加工性は優れているといえる。
Therefore, if the nucleating agent used has a high melting point, there is the disadvantage that the molding of a resin composition containing such a nucleating agent must be carried out under severe conditions at high temperatures. In order to mold at a temperature below the melting point of the nucleating agent, an extra step of preparing a high-concentration masterbatch by heating and melting the nucleating agent and the polyolefin resin at a high temperature above the melting point of the nucleating agent in advance. is necessary. Therefore, the lower the melting point of the nucleating agent used,
It can be said that the workability of the polyolefin resin composition containing this during molding is excellent.

【0010】又、これらのDBS化合物は、一般に融点
近傍で昇華性を有している。このため、成形時の金型汚
れや成形機種の汚れの原因となり加工性の悪化を招いて
いる。
Further, these DBS compounds generally have sublimability near the melting point. For this reason, it causes stains on the mold during molding and stains on the molding model, resulting in deterioration of workability.

【0011】しかしながら、本発明者らの研究によれ
ば、用いる核剤の融点が高い程、これを含有するポリオ
レフィン系樹脂組成物は、加工性の問題はあるが、透明
性その他の性質において優れた成形体を与える傾向があ
る。従って、核剤の低融点に基づく加工性を向上させ、
同時に成形体の透明性その他の特性をも向上させること
は、二律背反の困難な問題である。
However, according to the research conducted by the present inventors, the higher the melting point of the nucleating agent used, the more the polyolefin resin composition containing the nucleating agent has the problem of workability, but the excellent transparency and other properties. Tend to give molded bodies. Therefore, the workability based on the low melting point of the nucleating agent is improved,
At the same time, improving the transparency and other properties of the molded product is a trade-off difficult problem.

【0012】例えば、前記1,3:2,4−ビス(O−ポリア
ルキルベンゼン)ソルビトールやMe−DBS化合物を
核剤として含有するポリオレフィン系樹脂組成物は、透
明性その他の特性において優れた性質を有する成形体を
与えるものの、含有する前記核剤の融点が260℃程度
以上と高いため、通常、高温条件下で成形しなければな
らない。従って、260℃程度以下の加熱加工条件しか
採用できない一般成形加工分野においてDBS化合物の
優れた核剤効果を得るためには、適用する核剤の融点以
上の温度で高濃度マスターバッチを調製する工程を余分
に必要とする等、一定の困難性を伴っていた。又、成形
時に核剤の昇華性に基づく成形性不良の問題は解消され
ていなかった。
For example, a polyolefin resin composition containing the 1,3: 2,4-bis (O-polyalkylbenzene) sorbitol or Me-DBS compound as a nucleating agent has excellent properties in transparency and other properties. Although it gives a molded product having the above, the melting point of the nucleating agent contained therein is as high as about 260 ° C. or more, and therefore the molded product usually has to be molded under high temperature conditions. Therefore, in order to obtain the excellent nucleating agent effect of the DBS compound in the general molding processing field where only heat processing conditions of about 260 ° C. or less can be adopted, a step of preparing a high-concentration masterbatch at a temperature equal to or higher than the melting point of the applied nucleating agent. It was accompanied by certain difficulties such as requiring extra. Further, the problem of poor moldability due to the sublimability of the nucleating agent during molding has not been solved.

【0013】本発明者らは、先に、かかる問題点を解消
した新規有用なジアセタール組成物及び当該組成物を核
剤として配合してなるポリオレフィン系樹脂組成物を提
案した(特開平2−206627号)。これは、ジメチ
ル基或いはトリメチル基を置換基とする芳香環と置換基
を有しない芳香環とを有する特定の構造の非対称型ジア
セタールを主成分とする核剤組成物が、これまでに知ら
れていた同種の化合物に比してその融点が格段に低く、
しかも昇華性が小さく、当該核剤組成物を含有する樹脂
組成物は加工性が大幅に改善されるのみならず、透明性
その他の各種性質において優れた成形体を与えるもので
あるとの知見に基づいてなされたものである。
The present inventors have previously proposed a novel and useful diacetal composition which solves the above problems and a polyolefin resin composition prepared by blending the composition as a nucleating agent (JP-A-2-206627). issue). This is because a nucleating agent composition mainly containing an asymmetric diacetal having a specific structure having an aromatic ring having a dimethyl group or a trimethyl group as a substituent and an aromatic ring having no substituent has been known so far. Its melting point is much lower than that of similar compounds,
Moreover, it was found that the sublimability is small, and that the resin composition containing the nucleating agent composition not only greatly improves the processability but also gives a molded article excellent in transparency and various other properties. It was made based on.

【0014】ちなみに、上記ジメチル体としては、2,4
−、2,5−、3,4−及び3,5−ジ置換体が挙げられ、トリ
メチル体としては、2,4,6−及び3,4,5−トリ置換体が挙
げられる。
By the way, as the dimethyl compound, 2,4
-, 2,5-, 3,4- and 3,5-di-substituted products are mentioned, and the trimethyl form includes 2,4,6- and 3,4,5-tri-substituted products.

【0015】[0015]

【発明が解決しようとする課題】本発明は、より少ない
配合量でポリオレフィン系樹脂に対する優れた透明化効
果を有し、且つ250℃以下の低融点で、臭気の発生及
び核剤組成物の未分散に起因するフィッシュアイが発生
しない新規有用な核剤組成物並びに当該核剤組成物を配
合してなるポリオレフィン系樹脂組成物を提供すること
を目的とする。
DISCLOSURE OF THE INVENTION The present invention has an excellent transparency-improving effect on a polyolefin resin with a smaller blending amount, has a low melting point of 250 ° C. or lower, and produces odor and does not have a nucleating agent composition. It is an object of the present invention to provide a novel and useful nucleating agent composition which does not generate fish eyes due to dispersion, and a polyolefin resin composition containing the nucleating agent composition.

【0016】[0016]

【課題を解決するための手段】本発明者らは、ポリオレ
フィン系樹脂の核剤としての各種の対称型、非対称型の
DBS化合物の置換基の位置、置換基の種類、置換基の
数及びそれらの組み合わせと、それらの核剤特性につい
て深く検討した結果、従来の核剤の組み合わせによる予
測を越えて、特定の構造を有する非対称型DBS系化合
物と特定の構造を有する対称型DBS系化合物との混合
系のみが、他の単独系及び混合系と比較して特に際だっ
た所定の効果、即ち、低融点で、とりわけ少量の添加で
高活性な透明化核剤特性を示し、無臭性、低飛散性等の
効果をポリオレフィン系樹脂に対して奏することを見い
だし、かかる知見に基づいて本発明を完成するに至っ
た。
DISCLOSURE OF THE INVENTION The present inventors have found that the positions of the substituents, the types of the substituents, the number of the substituents, and the like of various symmetric and asymmetric DBS compounds as nucleating agents for polyolefin resins. Of the asymmetric DBS-based compound having a specific structure and a symmetric DBS-based compound having a specific structure, beyond the expectations of conventional combinations of nucleating agents. Only the mixed system exhibits a particularly remarkable predetermined effect as compared with other single systems and mixed systems, that is, a low melting point, a highly active clearing nucleating agent property even in a small amount of addition, odorlessness and low It was found that the effects such as the scattering property are exerted on the polyolefin resin, and the present invention has been completed based on such knowledge.

【0017】即ち、本発明に係る核剤組成物は、下記の
非対称型DBS系化合物(A成分)、対称型DBS系化
合物(B成分)及び要すれば更にC成分とを含有するこ
とを特徴とする。を含有することを特徴とする。
That is, the nucleating agent composition according to the present invention is characterized by containing the following asymmetric DBS compound (component A), symmetric DBS compound (component B) and, if necessary, component C. And It is characterized by containing.

【0018】[0018]

【化4】 [式中、X1が3,4−ジメチルベンジリデン基を表すと
き、X2は一般式(2)で表される基又は5,6,7,8−テト
ラヒドロ−2−ナフチル基を表す。X2が3,4−ジメチル
ベンジリデン基を表すとき、X1は一般式(2)で表さ
れる基又は5,6,7,8−テトラヒドロ−2−ナフチル基を表
す。]
[Chemical 4] [In the formula, when X 1 represents a 3,4-dimethylbenzylidene group, X 2 represents a group represented by the general formula (2) or a 5,6,7,8-tetrahydro-2-naphthyl group. When X 2 represents a 3,4-dimethylbenzylidene group, X 1 represents a group represented by the general formula (2) or a 5,6,7,8-tetrahydro-2-naphthyl group. ]

【0019】[0019]

【化5】 [式中、R1は炭素数1〜3のアルキル基、クロル基又
はメチルオキシメチル基を表す。]
[Chemical 5] [In the formula, R 1 represents an alkyl group having 1 to 3 carbon atoms, a chloro group or a methyloxymethyl group. ]

【0020】[0020]

【化6】 [式中、X3は前記一般式(2)で表される基又は5,6,
7,8−テトラヒドロ−2−ナフチル基を表す。]
[Chemical 6] [In the formula, X 3 is a group represented by the general formula (2) or 5, 6,
It represents a 7,8-tetrahydro-2-naphthyl group. ]

【0021】本発明によれば、次の如き優れた利点が達
成される (1)本発明の樹脂組成物は、成形時に臭気の発生が実
質上ないものである。 (2)結晶化温度の向上により成形サイクル時間が短縮
される。 (3)上記本発明の核剤組成物の融点が低いため、低温
での成形が可能であり、しかも、核剤の不完全な融解に
基づくフィッシュアイの成形が防止される。 (4)本発明樹脂組成物は、ひけを生成することなく、
且つ顔料を分散させた場合にも体積収縮を伴うことな
く、成形できる。 (5)延伸フィルムが、向上した寸法安定性をもって製
造できる。 (6)本発明樹脂組成物から得られる成形物は、透明性
が大幅に向上している。 (7)該成形物は、更に光沢も向上している。 (8)該成形物は、弾性率、耐衝撃性、熱変形温度等の
力学的及び熱的性質においても優れている。 (9)成形時の金型汚れが殆ど認められないため、連続
成形が容易となる。 (10)特定の第三級脂肪族アミン、例えば、ジステア
リルメチルアミンやステアリルジエタノールアミンを当
該核剤に事前に均一配合しておくと、樹脂組成物の透明
性がより一層向上する。
According to the present invention, the following excellent advantages are achieved. (1) The resin composition of the present invention has substantially no odor during molding. (2) The molding cycle time is shortened by improving the crystallization temperature. (3) Since the nucleating agent composition of the present invention has a low melting point, it can be molded at a low temperature, and furthermore, fisheye formation due to incomplete melting of the nucleating agent is prevented. (4) The resin composition of the present invention does not generate sink marks,
Moreover, even when the pigment is dispersed, molding can be performed without causing volume shrinkage. (5) Stretched films can be produced with improved dimensional stability. (6) The molded product obtained from the resin composition of the present invention has significantly improved transparency. (7) The molded product also has improved gloss. (8) The molded product is also excellent in mechanical and thermal properties such as elastic modulus, impact resistance, and heat distortion temperature. (9) Since almost no mold stain is observed during molding, continuous molding is facilitated. (10) When a specific tertiary aliphatic amine, such as distearylmethylamine or stearyldiethanolamine, is uniformly mixed in advance with the nucleating agent, the transparency of the resin composition is further improved.

【0022】本発明に係る特定の組成を有する核剤組成
物が、何故、かかる特段に優れた核剤効果を示すかにつ
いては、未だ充分に明かではない。
The reason why the nucleating agent composition having a specific composition according to the present invention exhibits such a particularly excellent nucleating agent effect is not yet sufficiently clear.

【0023】本発明に係る核剤組成物において、A成分
とB成分の配合比率(重量基準)は、所定の効果が得ら
れる限り、特に限定されるものではないが、A成分/B
成分=4/1〜1/9が推奨される。かかる範囲を外れ
た場合には、核剤効果が低下したり、高融点によるフィ
ッシュアイの発生をきたす傾向が認められ、好ましくな
い。
In the nucleating agent composition according to the present invention, the compounding ratio (weight basis) of the A component and the B component is not particularly limited as long as a predetermined effect can be obtained.
Ingredients = 4/1 to 1/9 are recommended. If it is out of this range, the effect of the nucleating agent is lowered, and fish eyes tend to be generated due to the high melting point, which is not preferable.

【0024】更に、A成分とB成分とC成分との総量に
対するC成分の配合比率(重量基準)は、所定の効果が
得られる限り、特に限定されるものではないが、C成分
/(A成分+B成分+C成分)が0.4以下であること
が推奨される。かかる範囲を外れた場合には、核剤効果
が低下する傾向が認められ、好ましくない。
Further, the mixing ratio (weight basis) of the C component to the total amount of the A component, the B component and the C component is not particularly limited as long as a predetermined effect can be obtained, but C component / (A It is recommended that component + B component + C component) be 0.4 or less. If the amount is out of this range, the effect of the nucleating agent tends to decrease, which is not preferable.

【0025】A成分、B成分及びC成分において、一般
式(2)に係るR1がメチルオキシメチル基である化合
物は新規に見いだされた化合物であり、一方、メチルオ
キシメチル基を除くR1を有する化合物は、いずれも公
知の化合物である。
In the components A, B and C, the compound of the general formula (2) in which R 1 is a methyloxymethyl group is a newly discovered compound, while R 1 excluding the methyloxymethyl group is The compounds having are all known compounds.

【0026】A成分、B成分及びC成分は、いずれも公
知方法に従い容易に製造できる。又、一般式(2)に係
るR1がメチルオキシメチル基である新規化合物も同様
の公知方法に準じて容易に製造できる。よって、本発明
に係る核剤組成物は、A成分とB成分、要すればC成分
とを夫々、所定の比率で混合することにより調製でき
る。
Each of the components A, B and C can be easily produced by a known method. Further, the novel compound represented by the general formula (2) in which R 1 is a methyloxymethyl group can be easily produced according to the same known method. Therefore, the nucleating agent composition according to the present invention can be prepared by mixing the component A and the component B, and if necessary, the component C, respectively, in a predetermined ratio.

【0027】又、ソルビトールに特定の置換ベンズアル
デヒド或いは5,6,7,8−テトラヒドロ−2−ナフチルアル
デヒドと3,4−ジメチルベンズアルデヒドとの適当な混
合物を反応させることによって、所定の比率でA成分及
びB成分を一挙に製造することもできる。この具体法の
一例を後記製造例に示す。
Further, by reacting sorbitol with a specific substituted benzaldehyde or an appropriate mixture of 5,6,7,8-tetrahydro-2-naphthylaldehyde and 3,4-dimethylbenzaldehyde, the component A is mixed in a predetermined ratio. The B component and the B component can also be manufactured all at once. An example of this specific method is shown in the production example described later.

【0028】本発明に係る核剤組成物は、以下で詳しく
述べるポリオレフィン系樹脂用の核剤としてのみなら
ず、液状物質の流動性消失効果をもたらすゲル化剤、粘
度調整剤、揺変剤、塗料・インキ・接着剤等のタレ防止
剤、水上や水中の油分を吸着する効果をもたらす油水分
離剤、凝集剤等として機能し、接着剤、塗料、樹脂の改
質、固形芳香剤、水処理剤、流出油の固化・回収、香
料、化粧料、土木・建材、潤滑油、防錆剤、農薬、医
薬、医療外製品、固形燃料、インキ、糊等、本発明に係
るジアセタールが従来用いられてきた分野において同様
に適用される。
The nucleating agent composition according to the present invention is not only used as a nucleating agent for a polyolefin resin, which will be described in detail below, but also a gelling agent, a viscosity modifier, a thixotropic agent, which brings about the effect of eliminating the fluidity of a liquid substance, It functions as an anti-sagging agent for paints, inks, adhesives, etc., an oil-water separating agent that has the effect of adsorbing oil on water and in water, a flocculant, etc., adhesives, paints, resin modification, solid fragrance, water treatment Agents, solidification / collection of spilled oil, fragrances, cosmetics, civil engineering / construction materials, lubricating oils, rust preventives, pesticides, pharmaceuticals, non-medical products, solid fuels, inks, glues, etc. The same applies in the fields that have been used.

【0029】本発明は、前記核剤組成物を含有してなる
有用なポリオレフィン系樹脂組成物をも提供するもので
もある。
The present invention also provides a useful polyolefin resin composition containing the nucleating agent composition.

【0030】本発明に係る核剤組成物のポリオレフィン
系樹脂に対する配合量は、所定の効果が得られる限り特
に限定されるものではなく、適宜選択することができる
が、通常、ポリオレフィン系樹脂100重量部当り0.
05〜3重量部程度、好ましくは0.07〜1重量部程
度配合される。これらの範囲内の配合により、充分に本
発明所定の効果を得ることができる。
The blending amount of the nucleating agent composition according to the present invention with respect to the polyolefin resin is not particularly limited as long as a predetermined effect can be obtained, and can be appropriately selected. 0 per department.
The amount is about 0.5 to 3 parts by weight, preferably about 0.07 to 1 part by weight. By blending within these ranges, the effects prescribed by the present invention can be sufficiently obtained.

【0031】核剤組成物の添加法としては一段添加法が
好ましいが、例えば、2〜15%程度の高濃度マスター
バッチの形態での添加による二段法を採用しても何ら差
し支えない。
As a method of adding the nucleating agent composition, a one-step addition method is preferable, but for example, a two-step method by addition in the form of a high-concentration masterbatch of about 2 to 15% may be adopted.

【0032】本発明に係る核剤が適用されるポリオレフ
ィン系樹脂としては、ポリエチレン系樹脂及びポリプロ
ピレン系樹脂が例示され、より具体的には、高密度ポリ
エチレン、中密度ポリエチレン、直鎖状ポリエチレン、
エチレン含量50重量%以上のエチレンコポリマー、プ
ロピレンホモポリマー、プロピレン含量50重量%以上
のプロピレンコポリマー、ブテンホモポリマー、ブテン
含量50重量%以上のブテンコポリマー、メチルペンテ
ンホモポリマー、メチルペンテン含量50重量%以上の
メチルペンテンコポリマー、ポリブタジエン等が例示さ
れる。
Examples of the polyolefin resin to which the nucleating agent according to the present invention is applied include polyethylene resins and polypropylene resins, and more specifically, high density polyethylene, medium density polyethylene, linear polyethylene,
Ethylene copolymer having an ethylene content of 50% by weight or more, propylene homopolymer, propylene copolymer having a propylene content of 50% by weight or more, butene homopolymer, butene copolymer having a butene content of 50% by weight or more, methylpentene homopolymer, methylpentene content of 50% by weight or more Examples thereof include methyl pentene copolymers and polybutadienes.

【0033】上記コポリマーは、ランダムコポリマーで
あってもよく、ブロックコポノマーであってもよい。こ
れらの樹脂の立体規則性は、アイソタクチックでもシン
ジオタクチックでもよい。
The above copolymer may be a random copolymer or a block coponomer. The stereoregularity of these resins may be isotactic or syndiotactic.

【0034】上記コポリマーを構成し得るコモノマーと
して、具体的にはエチレン、プロピレン、ブテン、ペン
テン、ヘキセン、ヘプテン、オクテン、ノネン、デセ
ン、ウンデセン、ドデセン等のα−オレフィン、1,4−
エンドメチレンシクロヘキセン等のビシクロ型モノマ
ー、(メタ)アクリル酸メチル、(メタ)アクリル酸エ
チル等の(メタ)アクリル酸エステル、酢酸ビニル等が
例示できる。
Specific examples of the comonomer capable of forming the above copolymer include α-olefins such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, and dodecene;
Examples thereof include bicyclo-type monomers such as endomethylenecyclohexene, methyl (meth) acrylate, (meth) acrylates such as ethyl (meth) acrylate, vinyl acetate and the like.

【0035】ポリオレフィン系樹脂の透明性を更に向上
せしめるために、例えば、公知のジアセタール類等の核
剤、テトラヒドロフタール酸やヘキサヒドロフタール酸
等のアルキルエステル類、フタール酸やトリメリット酸
のアルキルエステル類、アジピン酸やアゼライン酸のア
ルキルエステル類或いはトリカルバリル酸トリシクロペ
ンチルアミド、トリカルバリル酸トリシクロヘキシルア
ミド、トリカルバリル酸トリス(2−メチルシクロヘキ
シルアミド)等のトリカルバリル酸系アミド化合物を配
合することができる。
In order to further improve the transparency of the polyolefin resin, for example, known nucleating agents such as diacetals, alkyl esters such as tetrahydrophthalic acid and hexahydrophthalic acid, phthalic acid and trimellitic acid are used. Compounding with alkyl esters, alkyl esters of adipic acid or azelaic acid, or tricarballylic amide compounds such as tricarballylic tricyclopentylamide, tricarballylic tricyclohexylamide, tricarballylic tris (2-methylcyclohexylamide) be able to.

【0036】更に、本発明に係るポリオレフィン系樹脂
組成物には、使用目的やその用途に応じて適宜、従来公
知のポリオレフィン用改質剤を本発明の効果を損なわな
い範囲で添加することができる。
Further, a conventionally known modifier for polyolefin can be added to the polyolefin resin composition according to the present invention as appropriate depending on the purpose of use and its application within a range that does not impair the effects of the present invention. .

【0037】かかるポリオレフィン用改質剤としては、
例えば、ポリオレフィン等衛生協議会編「ポジティブリ
ストの添加剤要覧」(1990年10月)に記載されて
いる各種添加剤が挙げられ、より具体的には、安定剤
(金属化合物、エポキシ化合物、窒素化合物、燐化合
物、硫黄化合物等)、紫外線吸収剤(ベンゾフェノン系
化合物、ベンゾトリアゾール系化合物等)、酸化防止剤
(フェノール系化合物、亜リン酸エステル系化合物、イ
オウ系化合物等)、界面活性剤、滑剤(パラフィン、ワ
ックス等の脂肪族炭化水素、炭素数8〜22の高級脂肪
酸、炭素数8〜22の高級脂肪酸金属(Al、Ca、M
g、Zn)塩、炭素数8〜18の脂肪酸、炭素数8〜2
2の脂肪族アルコール、ポリグリコール、炭素数4〜2
2の高級脂肪酸と炭素数4〜18の脂肪族1価アルコー
ルとのエステル、炭素数8〜22の高級脂肪酸アマイ
ド、シリコーン油、ロジン誘導体等)、充填剤(タル
ク、ハイドロタルサイト、マイカ、ゼオライト、パーラ
イト、珪藻土、炭酸カルシウム、ガラス繊維等)、発泡
剤、発泡助剤、ポリマー添加剤の他、可塑剤、架橋剤、
架橋促進剤、帯電防止剤、防曇剤、ポリマーアロイ成分
(ブロックSBR或いはランダムSBR及びそれらの水
素化物等のゴム類やポリスチレン等)、難燃剤、分散
剤、有機・無機の顔料、染料、加工助剤等の各種添加剤
が例示される。
As such a modifier for polyolefin,
Examples thereof include various additives described in "Positive List of Additives" (October 1990) edited by the Council for Hygiene of Polyolefins, and more specifically, stabilizers (metal compounds, epoxy compounds, nitrogen). Compounds, phosphorus compounds, sulfur compounds, etc.), ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, etc.), antioxidants (phenolic compounds, phosphite compounds, sulfur compounds, etc.), surfactants, Lubricants (aliphatic hydrocarbons such as paraffin and wax, higher fatty acids having 8 to 22 carbon atoms, higher fatty acid metals having 8 to 22 carbon atoms (Al, Ca, M
g, Zn) salt, fatty acid having 8 to 18 carbon atoms, 8 to 2 carbon atoms
2 aliphatic alcohols, polyglycols, 4 to 2 carbon atoms
Esters of 2 higher fatty acids and aliphatic monohydric alcohols having 4 to 18 carbon atoms, higher fatty acid amides having 8 to 22 carbon atoms, silicone oil, rosin derivatives, etc., fillers (talc, hydrotalcite, mica, zeolite) , Perlite, diatomaceous earth, calcium carbonate, glass fiber, etc.), foaming agents, foaming aids, polymer additives, plasticizers, crosslinking agents,
Crosslinking accelerator, antistatic agent, antifogging agent, polymer alloy component (rubber such as block SBR or random SBR and hydrides thereof, polystyrene, etc.), flame retardant, dispersant, organic / inorganic pigment, dye, processing Various additives such as auxiliary agents are exemplified.

【0038】当該樹脂組成物を製造するに際しては、従
来公知のいずれの方法をも適用することができ、例え
ば、ポリオレフィン系樹脂に本発明に係る核剤組成物を
タンブラーやミキサーを用いてブレンドしてから最終成
形加工してもよく、予め当該樹脂に上記核剤組成物を配
合して、これをペレット化し、しかる後に最終成形加工
してもよい。予め当該核剤と有機アミンとをブレンドし
た後に、上記の方法で成形加工しても良い。
In producing the resin composition, any conventionally known method can be applied. For example, the nucleating agent composition of the present invention is blended with a polyolefin resin using a tumbler or a mixer. After that, final molding may be carried out. Alternatively, the nucleating agent composition may be blended with the resin in advance and pelletized, and then final molding may be carried out. The nucleating agent and the organic amine may be blended in advance and then molded by the above method.

【0039】又、本発明に係る樹脂組成物を成形するに
際しては、射出成形、押し出し成形、ブロー成形、圧空
成形、回転成形、フィルム成形等、従来公知の成形方法
のいずれをも採用できる。
Further, when molding the resin composition according to the present invention, any conventionally known molding method such as injection molding, extrusion molding, blow molding, pressure molding, rotational molding, film molding and the like can be adopted.

【0040】本発明に係るポリオレフィン系樹脂組成物
は、従来DBS類を核剤組成物として配合してなるポリ
オレフィン系樹脂組成物が用いられてきたと同様の各種
分野において適用され、より具体的には、熱や放射線等
により滅菌されるディスポーザブル注射器、輸液・輸血
セット、採血器具等の医療用器具類;放射線等により滅
菌される食品・植物等の包装物;衣料ケースや衣料保存
用コンテナ等の各種ケース類;食品を熱充填するための
カップ、レトルト食品の包装容器;電子レンジ用容器;
ジュース、茶等の飲料用、化粧品用、医薬品用、シャン
プー用等の缶、ビン等の容器;味噌、醤油等の調味料用
容器及びキャップ;水、米、パン、漬物等の食品用ケー
ス及び容器;冷蔵庫用ケース等の雑貨;文具;電気・機
械部品;自動車用部品等の素材として好適である。
The polyolefin resin composition according to the present invention is applied in various fields similar to those where a polyolefin resin composition prepared by blending DBSs as a nucleating agent composition has been used, more specifically. , Medical instruments such as disposable syringes, infusions / transfusion sets, blood collection devices that are sterilized by heat or radiation; packages of foods, plants, etc. that are sterilized by radiation; various kinds of clothing cases, containers for storing clothing, etc. Cases; cups for heat-filling food; packaging containers for retort foods; microwave oven containers;
Containers such as cans and bottles for beverages such as juice and tea, cosmetics, pharmaceuticals, shampoos; containers and caps for seasonings such as miso and soy sauce; cases for food such as water, rice, bread and pickles It is suitable as a material for containers; miscellaneous goods such as refrigerator cases; stationery; electrical / mechanical parts; automobile parts.

【0041】[0041]

【実施例】以下に実施例及び比較例を掲げ、本発明を詳
しく説明する。尚、下記の各例における評価は、次の方
法により行なった。
EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples. The evaluation in each of the following examples was performed by the following method.

【0042】核剤組成物の融点(Tm ) 示差走査熱量計を用い、室温から20℃/分で昇温した
ときの発熱ピーク温度で示す。
Melting point (Tm) of the nucleating agent composition is shown by an exothermic peak temperature when the temperature is raised from room temperature at 20 ° C./min using a differential scanning calorimeter.

【0043】 ポリオレフィン系樹脂組成物の透明性(Haze値) ヘーズメーターを用いて曇度(%)及び光沢を測定した
(JIS K 6714、JIS K 6717)。曇
度は小さい程その光学的特性は優れている。(尚、測定
の結果、実施例及び比較例において、DBS系化合物を
配合した樹脂組成物は、何れも良好な光沢を示した。)
Transparency (Haze value) of the polyolefin resin composition The haze (%) and gloss were measured using a haze meter (JIS K 6714, JIS K 6717). The smaller the haze, the better the optical properties. (In addition, as a result of the measurement, in the examples and the comparative examples, the resin compositions containing the DBS compound showed good gloss.)

【0044】フィッシュアイ発生の程度 射出成形して得たテストピース表面を目視にて観察し、
テストピース30個中において未分散核剤が認められる
テストピースの個数に基づいて、以下のとおり3段階に
評価した。 ○:フィッシュアイの発生が認められない ×:フィッシュアイの発生が認められる
Degree of Fish Eye Occurrence Visually observing the surface of the test piece obtained by injection molding,
Based on the number of test pieces in which the undispersed nucleating agent was observed in 30 test pieces, evaluation was performed in the following three grades. ◯: No fish eyes were found ×: Fish eyes were found

【0045】臭気の発生の程度 ペレット30gを200mlのガラスビン中に密封し、1
30℃の恒温槽に1時間放置した後、その臭気の有無に
よって判定する。 ○:臭気が認められない △:臭気が少し認められる ×:臭気が認められる
Degree of generation of odor 30 g of the pellet was sealed in a 200 ml glass bottle, and 1
After leaving it in a constant temperature bath at 30 ° C. for 1 hour, it is judged by the presence or absence of its odor. ◯: No odor is observed Δ: Some odor is observed ×: Odor is observed

【0046】製造例1 攪拌翼、デカンター付コンデンサー、温度計及び仕込み
口を備えた1.5リットル反応缶に粉末ソルビット1
8.2g(0.1モル)、3,4−ジメチルベンズアルデ
ヒド13.4g(0.1モル)、p−クロロベンズアル
デヒド14.3g(0.1モル)、シクロヘキサン20
0ml、メタノール50ml及びパラトルエンスルホン酸
2.0gを仕込み、昇温し、還流下に生成水及びメタノ
ールを系外に抜きだした。反応を1.5時間で停止し、
冷却、中和、水洗後、濾過、乾燥して目的物39.3g
を得た。得られた目的物の純度(ガスクロマトグラフィ
ーによる。以下同様)は99.8%、反応収率は92.
3%であった。又、当該目的物(本核剤1)の組成(ガ
スクロマトグラフィーによる。以下同様)は以下のとお
りであった。又、本核剤1の融点は、233〜234℃
であった。
Production Example 1 Powdered sorbit 1 was placed in a 1.5-liter reaction can equipped with a stirring blade, a condenser with a decanter, a thermometer and a charging port.
8.2 g (0.1 mol), 3,4-dimethylbenzaldehyde 13.4 g (0.1 mol), p-chlorobenzaldehyde 14.3 g (0.1 mol), cyclohexane 20
0 ml, 50 ml of methanol and 2.0 g of p-toluenesulfonic acid were charged, the temperature was raised, and the produced water and methanol were discharged out of the system under reflux. Stop the reaction in 1.5 hours,
After cooling, neutralizing, washing with water, filtering, drying, and 39.3 g of the desired product.
Got The purity of the obtained target product (by gas chromatography, the same applies hereinafter) is 99.8%, and the reaction yield is 92.
It was 3%. The composition of the target product (the present nucleating agent 1) (by gas chromatography; the same applies hereinafter) was as follows. Also, the melting point of this nucleating agent 1 is 233 to 234 ° C.
Met.

【0047】 A成分 1,3−O−3,4−ジメチルベンジリデン−2,4−O−p−クロロベンジリデンソル ビトールと1,3−O−p−クロロベンジリデン−2,4−O−3,4−ジメチルベンジ リデンソルビトールとの混合物 52% B成分 1,3:2,4−ビス(O−3,4−ジメチルベンジリデン)ソルビトール 23% C成分 1,3:2,4−ビス(O−p−クロロベンジリデン)ソルビトール 25%Component A 1,3-O-3,4-dimethylbenzylidene-2,4-Op-chlorobenzylidene sorbitol and 1,3-Op-chlorobenzylidene-2,4-O-3, Mixture with 4-dimethylbenzylidene sorbitol 52% B component 1,3: 2,4-bis (O-3,4-dimethylbenzylidene) sorbitol 23% C component 1,3: 2,4-bis (Op -Chlorobenzylidene) sorbitol 25%

【0048】製造例2 p−クロロベンズアルデヒド14.3g(0.1モル)
に代えて、p−メチルオキシメチルベンズアルデヒド1
5.5g(0.1モル)を用いる以外は製造例1と同様
にして目的物32.6g(収率75.8%)を得た。こ
の反応生成物(本核剤2)の組成は、以下のとおりであ
った。又、本核剤2の融点は、219〜220℃であっ
た。
Production Example 2 14.3 g (0.1 mol) of p-chlorobenzaldehyde
Instead of p-methyloxymethylbenzaldehyde 1
32.6 g (yield: 75.8%) of the desired product was obtained in the same manner as in Production Example 1 except that 5.5 g (0.1 mol) was used. The composition of this reaction product (the present nucleating agent 2) was as follows. The melting point of the present nucleating agent 2 was 219 to 220 ° C.

【0049】A成分 1,3−O−3,4−ジメチルベンジリデン−2,4−O−p−メ
チルオキシメチルベンジリデンソルビトールと1,3−O
−p−メチルオキシメチルベンジリデン−2,4− O−3,
4−ジメチルベンジリデンソルビトールとの混合物
51% B成分 1,3:2,4−ビス(O−3,4−ジメチルベンジリデン)ソル
ビトール 23%C成分 1,3:2,4−ビス(O−p−メチルオキシメチルベンジリデ
ン)ソルビトール26%
Component A 1,3-O-3,4-dimethylbenzylidene-2,4-Op-methyloxymethylbenzylidenesorbitol and 1,3-O
-P-methyloxymethylbenzylidene-2,4-O-3,
Mixture with 4-dimethylbenzylidene sorbitol
51% B component 1,3: 2,4-bis (O-3,4-dimethylbenzylidene) sorbitol 23% C component 1,3: 2,4-bis (Op-methyloxymethylbenzylidene) sorbitol 26%

【0050】製造例3 p−クロロベンズアルデヒド14.3g(0.1モル)
に代えて、p−エチルベンズアルデヒド13.6g
(0.1モル)を用いる以外は製造例1と同様にして反
応し、目的物33.4g(収率80.0%)を得た。こ
の反応生成物の組成は、以下のとおりであった。
Production Example 3 p-Chlorobenzaldehyde 14.3 g (0.1 mol)
Instead of, 13.6 g of p-ethylbenzaldehyde
The reaction was performed in the same manner as in Production Example 1 except that (0.1 mol) was used to obtain 33.4 g of the desired product (yield 80.0%). The composition of this reaction product was as follows:

【0051】 A成分 1,3−O−3,4−ジメチルベンジリデン−2,4−O−p−エチルベンジリデンソル ビトールと1,3−O−p−エチルベンジリデン−2,4−O−3,4−ジメチルベンジ リデンソルビトールとの混合物 52% B成分 1,3:2,4−ビス(O−3,4−ジメチルベンジリデン)ソルビール 23% C成分 1,3:2,4−ビス(O−p−エチルベンジリデン)ソルビトール 25%Component A 1,3-O-3,4-dimethylbenzylidene-2,4-Op-ethylbenzylidene sorbitol and 1,3-Op-ethylbenzylidene-2,4-O-3, Mixture with 4-dimethylbenzylidene sorbitol 52% B component 1,3: 2,4-bis (O-3,4-dimethylbenzylidene) sorb beer 23% C component 1,3: 2,4-bis (Op -Ethylbenzylidene) sorbitol 25%

【0052】これに1,3:2,4−ビス(O−p−エチルベン
ジリデン)ソルビトールと1,3:2,4−ビス(O−3,4−ジ
メチルベンジリデン)ソルビトールとを混合して、最終
的に下記の組成の核剤組成物(本核剤3)を調製した。
又、本核剤3の融点は、232〜234℃であった。
To this, 1,3: 2,4-bis (Op-ethylbenzylidene) sorbitol and 1,3: 2,4-bis (O-3,4-dimethylbenzylidene) sorbitol were mixed, Finally, a nucleating agent composition (present nucleating agent 3) having the following composition was prepared.
The melting point of the present nucleating agent 3 was 232 to 234 ° C.

【0053】 A成分 1,3−O−3,4−ジメチルベンジリデン−2,4−O−p−エチルベンジリデンソル ビトールと1,3−O−p−エチルベンジリデン−2,4−O−3,4−ジメチルベンジ リデンソルビトールとの混合物 30% B成分 1,3:2,4−ビス(O−3,4−ジメチルベンジリデン)ソルビール 40% C成分 1,3:2,4−ビス(O−p−エチルベンジリデン)ソルビトール 30%Component A 1,3-O-3,4-dimethylbenzylidene-2,4-Op-ethylbenzylidene sorbitol and 1,3-Op-ethylbenzylidene-2,4-O-3, Mixture with 4-dimethylbenzylidene sorbitol 30% B component 1,3: 2,4-bis (O-3,4-dimethylbenzylidene) sorber beer 40% C component 1,3: 2,4-bis (Op -Ethylbenzylidene) sorbitol 30%

【0054】製造例4 p−クロロベンズアルデヒド14.3g(0.1モル)
に代えて、5,6,7,8−テトラヒドロ−2−ナフチルアルデ
ヒド16.0g(0.1モル)用いた他は製造例1と同
様に反応して、目的物33.4g(収率75.9%)を
得た。この反応生成物(本核剤4)の組成は、以下のと
おりであった。又、本核剤4の融点は、222〜225
℃であった。
Production Example 4 14.3 g (0.1 mol) of p-chlorobenzaldehyde
Instead of using 5,6,7,8-tetrahydro-2-naphthylaldehyde 16.0 g (0.1 mol), the reaction was conducted in the same manner as in Production Example 1 to obtain 33.4 g of the desired product (yield 75 .9%) was obtained. The composition of this reaction product (the present nucleating agent 4) was as follows. The melting point of the present nucleating agent 4 is 222 to 225.
It was ℃.

【0055】 A成分 1,3−O−3,4−ジメチルベンジリデン−2,4−O−5,6,7,8−テトラヒドロ−2 − ナフチルソルビトールと1,3−O−5,6,7,8−テトラヒドロ−2−ナフチル−2 ,4 −O−3,4−ジメチルベンジリデンソルビトールとの混合物 52 %B成分 1,3:2,4−ビス(O−3,4−ジメチルベンジリデン)ソルビトール 23% C成分 1,3:2,4−ビス(O−5,6,7,8−テトラヒドロ−2−ナフチル)ソルビトール 25%Component A 1,3-O-3,4-dimethylbenzylidene-2,4-O-5,6,7,8-tetrahydro-2-naphthylsorbitol and 1,3-O-5,6,7 , 8-Tetrahydro-2-naphthyl-2,4-O-3,4-dimethylbenzylidene sorbitol mixture 52% B component 1,3: 2,4-bis (O-3,4-dimethylbenzylidene) sorbitol 23 % C component 1,3: 2,4-bis (O-5,6,7,8-tetrahydro-2-naphthyl) sorbitol 25%

【0056】実施例1 エチレン含有量2.0重量%のアイソタクチックランダ
ムポリプロピレン樹脂(以下「ポリプロピレンA」と略
記する。)に対し、本核剤1、テトラキス[メチレン−
3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニ
ル)プロピオネート]メタン(商品名、イルガノックス
1010、チバ・ガイギー社製)及びステアリン酸カル
シウムを下記の組成で加えて、5分間ヘンシェルミキサ
ーにより混合し、次いで、240℃でラボプラストミル
押出機により混練して押し出し、水冷法によりペレット
を得た。このペレットを230℃で射出成形して、厚み
1.0mmのシートを得て試料に供し、その特性を評価し
た。得られた結果を第1表に示す。
Example 1 With respect to an isotactic random polypropylene resin having an ethylene content of 2.0% by weight (hereinafter abbreviated as "polypropylene A"), the present nucleating agent 1, tetrakis [methylene-] was used.
3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (trade name, Irganox 1010, manufactured by Ciba Geigy) and calcium stearate are added in the following composition for 5 minutes by a Henschel mixer. And then kneaded at 240 ° C. with a Labo Plastomill extruder and extruded to obtain pellets by a water cooling method. The pellets were injection-molded at 230 ° C. to obtain a sheet having a thickness of 1.0 mm, which was used as a sample to evaluate its characteristics. The results obtained are shown in Table 1.

【0057】 ポリプロピレンA 100 重量部 本核剤1 0.2 重量部 イルガノックス1010 0.05重量部 ステアリン酸カルシウム 0.03重量部Polypropylene A 100 parts by weight Nucleating agent 1 0.2 parts by weight Irganox 1010 0.05 parts by weight Calcium stearate 0.03 parts by weight

【0058】実施例2〜4 本核剤1の代わりに本核剤2〜4を夫々配合して樹脂組
成物を得、このものの特性を実施例1に準じて評価し
た。得られた結果を第1表に示す。
Examples 2 to 4 The nucleating agents 2 to 4 were blended in place of the nucleating agent 1 to obtain resin compositions, and the characteristics of the resin compositions were evaluated according to Example 1. The results obtained are shown in Table 1.

【0059】比較例1 本核剤1の代わりにビス(p−クロロベンジリデン)ソ
ルビトール(融点251〜253℃、比較核剤1)を配
合して樹脂組成物を得、このものの特性を実施例1に準
じて評価した。得られた結果を第1表に示す。
Comparative Example 1 Bis (p-chlorobenzylidene) sorbitol (melting point 251 to 253 ° C., comparative nucleating agent 1) was blended in place of the present nucleating agent 1 to obtain a resin composition. It was evaluated according to. The results obtained are shown in Table 1.

【0060】比較例2 本核剤1の代わりにビス(p−メチルベンジリデン)ソ
ルビトール(融点255〜260℃、比較核剤2)を配
合して樹脂組成物を得、このものの特性を実施例1に準
じて評価した。得られた結果を第1表に示す。
Comparative Example 2 Bis (p-methylbenzylidene) sorbitol (melting point: 255 to 260 ° C., comparative nucleating agent 2) was blended in place of the present nucleating agent 1 to obtain a resin composition, and the characteristics of this resin composition were obtained in Example 1. It was evaluated according to. The results obtained are shown in Table 1.

【0061】比較例3 本核剤1の代わりに2,4−ジメチルベンジリデン−ベン
ジリデンソルビトール(融点234〜235℃、比較核
剤3)を配合して樹脂組成物を得、このものの特性を実
施例1に準じて評価した。得られた結果を第1表に示
す。
Comparative Example 3 2,4-dimethylbenzylidene-benzylidene sorbitol (melting point 234 to 235 ° C., comparative nucleating agent 3) was blended in place of the present nucleating agent 1 to obtain a resin composition, and the characteristics of this resin composition were evaluated. Evaluation was made according to 1. The results obtained are shown in Table 1.

【0062】比較例4 本核剤1を配合しない他は実施例1と同様にして樹脂組
成物を得、このものの特性を実施例1に準じて評価し
た。得られた結果を第1表に示す。
Comparative Example 4 A resin composition was obtained in the same manner as in Example 1 except that the present nucleating agent 1 was not added, and the characteristics of this resin composition were evaluated according to Example 1. The results obtained are shown in Table 1.

【0063】実施例5 対象樹脂を直鎖状低密度ポリエチレン100重量部に対
し、本核剤1を2重量部配合してなる樹脂組成物をヘン
シェルミキサーで5分間混合した後、240℃で押し出
し成形してマスターバッチペレット(以下「ペレット
A」という。)を作成した。同時に、上記と同じ直鎖状
低密度ポリエチレンのペレット(以下「ペレットB」と
いう。)を粉末から作成した。両者をペレットA/ペレ
ットB=1/9の割合で混合した後、200℃で押し出
し成形して1.0mm厚みのシートを作成し、その特性を
評価した。得られた結果を第2表に示す。
Example 5 A resin composition obtained by mixing 2 parts by weight of the present nucleating agent 1 with 100 parts by weight of a linear low-density polyethylene was mixed with a Henschel mixer for 5 minutes and then extruded at 240 ° C. It shape | molded and created the masterbatch pellet (henceforth "pellet A"). At the same time, the same linear low-density polyethylene pellet as described above (hereinafter referred to as "pellet B") was prepared from the powder. Both were mixed at a ratio of Pellet A / Pellet B = 1/9 and then extruded at 200 ° C. to form a 1.0 mm thick sheet, and its characteristics were evaluated. The results obtained are shown in Table 2.

【0064】実施例6〜8 所定の核剤組成物(本核剤2〜4)を夫々配合してなる
樹脂組成物の特性を実施例5に準じて評価した。得られ
た結果を第2表に示す。
Examples 6 to 8 The properties of resin compositions prepared by blending the prescribed nucleating agent compositions (the present nucleating agents 2 to 4) were evaluated in accordance with Example 5. The results obtained are shown in Table 2.

【0065】比較例5 本核剤1の代わりに比較核剤1を配合して樹脂組成物を
得、このものの特性を実施例5に準じて評価した。得ら
れた結果を第2表に示す。
Comparative Example 5 A resin composition was obtained by mixing Comparative Nucleating Agent 1 in place of the present Nucleating Agent 1, and the characteristics of this resin composition were evaluated according to Example 5. The results obtained are shown in Table 2.

【0066】比較例6 本核剤1の代わりに比較核剤2を配合して樹脂組成物を
得、このものの特性を実施例5に準じて評価した。得ら
れた結果を第2表に示す。
Comparative Example 6 A resin composition was obtained by mixing Comparative Nucleating Agent 2 in place of the present Nucleating Agent 1, and the characteristics of this resin composition were evaluated according to Example 5. The results obtained are shown in Table 2.

【0067】比較例7 本核剤1の代わりに比較核剤3を配合して樹脂組成物を
得、このものの特性を実施例5に準じて評価した。得ら
れた結果を第2表に示す。
Comparative Example 7 A resin composition was obtained by mixing Comparative Nucleating Agent 3 in place of the present Nucleating Agent 1, and the characteristics of this resin composition were evaluated according to Example 5. The results obtained are shown in Table 2.

【0068】比較例8 本核剤1を配合しない他は実施例5と同様にして樹脂組
成物を得、このものの特性を実施例5に準じて評価し
た。得られた結果を第2表に示す。
Comparative Example 8 A resin composition was obtained in the same manner as in Example 5 except that the nucleating agent 1 was not added, and the characteristics of this resin composition were evaluated according to Example 5. The results obtained are shown in Table 2.

【0069】[0069]

【発明の効果】本発明に係るポリオレフィン系樹脂組成
物は、最高度の透明性を有するばかりでなく、成形加工
時における熱分解による臭気の発生も認められない。し
かも、当該核剤組成物の融点は250℃以下と、従来の
優秀な性能を有するDBS類の融点と比較して著るしく
低いため、成形温度を低減することができる。
EFFECT OF THE INVENTION The polyolefin resin composition according to the present invention has not only the highest degree of transparency but also no generation of odor due to thermal decomposition during molding. Moreover, since the melting point of the nucleating agent composition is 250 ° C. or lower, which is remarkably low as compared with the melting points of the conventional DBSs having excellent performance, the molding temperature can be reduced.

【0070】更に、ポリエチレン等の比較的低温で成形
する樹脂に適用する場合においても、核剤としてのDB
S類が完全に融解しないことに起因するフィッシュアイ
の生成を抑制することが容易である。
Further, even when applied to a resin such as polyethylene which is molded at a relatively low temperature, DB as a nucleating agent is used.
It is easy to suppress the formation of fish eyes due to the fact that Ss are not completely melted.

【0071】本発明に係る核剤組成物は、従来公知の核
剤組成物と比較して極めて少量で上記所定の効果を得る
ことができる。
The nucleating agent composition according to the present invention can obtain the above-mentioned predetermined effects in an extremely small amount as compared with conventionally known nucleating agent compositions.

【表1】 [Table 1]

【表2】 [Table 2]

Claims (6)

【特許請求の範囲】[Claims] 【請求項1】 下記のA成分及びB成分を含有すること
を特徴とする核剤組成物。 A成分:一般式(1)で表されるジアセタール化合物 【化1】 [式中、X1が3,4−ジメチルベンジリデン基を表すと
き、X2は一般式(2)で表される基又は5,6,7,8−テト
ラヒドロ−2−ナフチル基を表す。X2が3,4−ジメチル
ベンジリデン基を表すとき、X1は一般式(2)で表さ
れる基又は5,6,7,8−テトラヒドロ−2−ナフチル基を表
す。] 【化2】 [式中、R1は炭素数1〜3のアルキル基、クロル基又
はメチルオキシメチル基を表す。] B成分:ビス(O−3,4−ジメチルベンジリデン)ソル
ビトール
1. A nucleating agent composition comprising the following components A and B: Component A: diacetal compound represented by the general formula (1) [In the formula, when X 1 represents a 3,4-dimethylbenzylidene group, X 2 represents a group represented by the general formula (2) or a 5,6,7,8-tetrahydro-2-naphthyl group. When X 2 represents a 3,4-dimethylbenzylidene group, X 1 represents a group represented by the general formula (2) or a 5,6,7,8-tetrahydro-2-naphthyl group. ] [Chemical 2] [In the formula, R 1 represents an alkyl group having 1 to 3 carbon atoms, a chloro group or a methyloxymethyl group. ] Component B: Bis (O-3,4-dimethylbenzylidene) sorbitol
【請求項2】 A成分/B成分が、4/1〜1/9(重
量基準)である請求項1に記載の核剤組成物。
2. The nucleating agent composition according to claim 1, wherein the A component / B component is 4/1 to 1/9 (weight basis).
【請求項3】 更に、C成分として、一般式(3)で表
されるアセタール化合物を配合してなる核剤組成物。 【化3】 [式中、X3は前記一般式(2)で表される基又は5,6,
7,8−テトラヒドロ−2−ナフチル基を表す。]
3. A nucleating agent composition further comprising, as the component C, an acetal compound represented by the general formula (3). [Chemical 3] [In the formula, X 3 is a group represented by the general formula (2) or 5, 6,
It represents a 7,8-tetrahydro-2-naphthyl group. ]
【請求項4】 C成分/(A成分+B成分+C成分)
が、0.4以下(重量基準)である請求項3に記載の核
剤組成物。
4. C component / (A component + B component + C component)
Is 0.4 or less (weight basis), The nucleating agent composition according to claim 3.
【請求項5】 ポリオレフィン系樹脂及び請求項1〜4
の何れかの請求項に記載の核剤組成物を含有してなるポ
リオレフィン系樹脂組成物。
5. A polyolefin resin and claims 1 to 4.
A polyolefin resin composition containing the nucleating agent composition according to claim 1.
【請求項6】 ポリオレフィン系樹脂100重量部に対
し、請求項1〜4の何れかの請求項に記載の核剤組成物
0.05〜3重量部を含有してなるポリオレフィン系樹
脂組成物。
6. A polyolefin resin composition comprising 0.05 to 3 parts by weight of the nucleating agent composition according to any one of claims 1 to 4 with respect to 100 parts by weight of the polyolefin resin.
JP10605094A 1994-04-20 1994-04-20 Nucleator composition and polyolefin resin composition Pending JPH07286066A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP10605094A JPH07286066A (en) 1994-04-20 1994-04-20 Nucleator composition and polyolefin resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP10605094A JPH07286066A (en) 1994-04-20 1994-04-20 Nucleator composition and polyolefin resin composition

Publications (1)

Publication Number Publication Date
JPH07286066A true JPH07286066A (en) 1995-10-31

Family

ID=14423807

Family Applications (1)

Application Number Title Priority Date Filing Date
JP10605094A Pending JPH07286066A (en) 1994-04-20 1994-04-20 Nucleator composition and polyolefin resin composition

Country Status (1)

Country Link
JP (1) JPH07286066A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6495620B1 (en) 2001-03-23 2002-12-17 Milliken & Company Asymmetric substituted benzaldehyde alditol derivatives and compositions and articles containing same
US6548581B2 (en) 2001-03-23 2003-04-15 Milliken & Company Asymmetric halogen-alkyl alditol derivatives as nucleators and clarifiers for polyolefins, and polyolefin plastic compositions containing same
US6547988B2 (en) 2001-03-23 2003-04-15 Milliken & Company Symmetrical halogenated and alkylated alditol derivatives and compositions and articles containing same
US6555696B2 (en) 2001-03-23 2003-04-29 Milliken & Company Asymmetric dipolar multi-substituted alditol derivatives, methods of making thereof, and compositions and articles containing same
US6599964B2 (en) 2001-03-23 2003-07-29 Milliken & Company Symmetric substituted benzaldehyde alditol derivatives and compositions and articles containing same
KR100418564B1 (en) * 2001-04-30 2004-02-14 선구케미칼(주) Nucleating agent containing metaparadimethylbenzylidene paramethylbenzylidene sorbitol and the preparation method thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6495620B1 (en) 2001-03-23 2002-12-17 Milliken & Company Asymmetric substituted benzaldehyde alditol derivatives and compositions and articles containing same
US6548581B2 (en) 2001-03-23 2003-04-15 Milliken & Company Asymmetric halogen-alkyl alditol derivatives as nucleators and clarifiers for polyolefins, and polyolefin plastic compositions containing same
US6547988B2 (en) 2001-03-23 2003-04-15 Milliken & Company Symmetrical halogenated and alkylated alditol derivatives and compositions and articles containing same
US6555696B2 (en) 2001-03-23 2003-04-29 Milliken & Company Asymmetric dipolar multi-substituted alditol derivatives, methods of making thereof, and compositions and articles containing same
US6599964B2 (en) 2001-03-23 2003-07-29 Milliken & Company Symmetric substituted benzaldehyde alditol derivatives and compositions and articles containing same
US6844382B2 (en) 2001-03-23 2005-01-18 Milliken & Company Gels comprising asymmetric dipolar multi-substituted alditol derivatives
US6894176B2 (en) 2001-03-23 2005-05-17 Milliken & Company Reaction product mixtures including both symmetric compounds and asymmetric dipolar multi-substituted alditol derivatives
US6972306B2 (en) 2001-03-23 2005-12-06 Milliken & Company Compositions and articles comprising asymmetric dipolar multi-substituted alditol derivatives
US6984740B2 (en) 2001-03-23 2006-01-10 Milliken & Company Symmetrical halogenated and alkylated alditol derivatives and compositions and articles containing same
KR100418564B1 (en) * 2001-04-30 2004-02-14 선구케미칼(주) Nucleating agent containing metaparadimethylbenzylidene paramethylbenzylidene sorbitol and the preparation method thereof

Similar Documents

Publication Publication Date Title
JPH089679B2 (en) Diacetal composition for resin modification and crystalline resin composition
EP0948563B1 (en) Modifying agents for polyolefins
JP5239869B2 (en) Novel polyolefin resin composition and resin molded body thereof
JPH0770134A (en) 1,3-2,4-di(arylidene/heteroarylidene)-d- sorbitol derivative and polyolefin composition containing same
JP2012233149A (en) Diacetal composition, nucleating agent for polyolefin-based resin containing the diacetal composition, polyolefin-based resin composition containing the nucleating agent, and molded article of the resin composition
JP3430626B2 (en) Polypropylene resin composition
TW202222775A (en) Trisamide compounds and compositions comprising the same
TW202222777A (en) Trisamide compounds and compositions comprising the same
JPWO2005037770A1 (en) Amide compound, polyolefin resin composition and molded article
JPH08199003A (en) Nucleator composition and polyolefin resin composition
JPH07286066A (en) Nucleator composition and polyolefin resin composition
JPH08325415A (en) Nucleator composition and polyolefin resin composition
JP3367200B2 (en) Nucleating agent composition and polyolefin resin composition
WO2007106330A1 (en) Metal carboxylate salt nucleating or clarifying agent compounds and related polymer compositions and methods
JP5183561B2 (en) Propylene-based molded products
JPH0827323A (en) Nucleator composition and polyolefin resin composition
JPH0372544A (en) Polypropylene resin composition
JP2007022924A (en) Agent for suppressing transfer of odor and taste generated from diacetal and diacetal composition containing the same agent
JPH09286788A (en) Dibenzylidenesorbitol composition and polyolefin-based resin composition containing the same
JP4526830B2 (en) Polyolefin molded body for sodium chloride filling
JP2793642B2 (en) Diacetal composition and crystalline resin composition
JP7417082B2 (en) Crystal nucleating agent composition for polyolefin resin, and polyolefin resin composition containing the crystal nucleating agent composition
JP2826152B2 (en) Diacetal composition and crystalline resin composition
JPWO2002040587A1 (en) Dibenzylidene sorbitol composition and polyolefin resin composition containing the same
JPS60195141A (en) Crystalline propylene polymer composition