JPH11323029A - Crystallization nucleating agent - Google Patents
Crystallization nucleating agentInfo
- Publication number
- JPH11323029A JPH11323029A JP13000798A JP13000798A JPH11323029A JP H11323029 A JPH11323029 A JP H11323029A JP 13000798 A JP13000798 A JP 13000798A JP 13000798 A JP13000798 A JP 13000798A JP H11323029 A JPH11323029 A JP H11323029A
- Authority
- JP
- Japan
- Prior art keywords
- nucleating agent
- anhydride
- crystallization
- halogen
- crystallization nucleating
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、結晶ポリオレフィ
ン用の新規な結晶化核剤に関する。TECHNICAL FIELD The present invention relates to a novel crystallization nucleating agent for crystalline polyolefin.
【０００２】[0002]
【従来の技術】ポリプロピレン、ポリエチレン等の結晶
性ポリオレフィン樹脂の透明性、曲げ弾性率、熱変形温
度等の物性を改良する目的で、種々の結晶化核剤を添加
することが行われている。これらの目的で使用される結
晶化核剤のうち、その効果が高いものとしてジベンジリ
デンソルビトール系核剤が知られており、実際に多くの
用途で使用されている。しかしながら、該ジベンジリデ
ンソルビトール系核剤は価格が高く、より安価で提供可
能な新規な核剤が求められている。2. Description of the Related Art Various crystallization nucleating agents have been added for the purpose of improving the properties of crystalline polyolefin resins such as polypropylene and polyethylene, such as transparency, flexural modulus and heat deformation temperature. Among the crystallization nucleating agents used for these purposes, dibenzylidene sorbitol-based nucleating agents are known as having high effects, and are actually used in many applications. However, the dibenzylidene sorbitol-based nucleating agent is expensive and a new nucleating agent that can be provided at a lower cost is demanded.
【０００３】ジベンジリデンソルビトール系核剤と全く
異なる基本骨格で且つ比較的単純な構造を有する有機化
合物が造核効果（或いは結晶化促進効果）を示せば、該
化合物は安価な結晶化核剤となる可能性が有ると言え
る。このような例として特公昭４５−２３４１６号公報
には、特定の３成分系高分子混合物、即ちポリプロピレ
ン／ポリエチレン／エチレン-プロピレン共重合物に非
置換のフタル酸無水物をカルボン酸塩と共に添加すると
若干の造核効果が認められることが記載されている。し
かしながら、上記公報に記載されている系では２種類の
化合物を併用する必要が有るばかりでなく、その効果は
低く、充分なものではなかった。[0003] If an organic compound having a basic skeleton completely different from that of a dibenzylidenesorbitol-based nucleating agent and having a relatively simple structure exhibits a nucleating effect (or crystallization promoting effect), the compound can be used as an inexpensive crystallization nucleating agent. It can be said that there is a possibility. For example, Japanese Patent Publication No. 45-23416 discloses a method in which an unsubstituted phthalic anhydride is added together with a carboxylate to a specific three-component polymer mixture, that is, a polypropylene / polyethylene / ethylene-propylene copolymer. It is described that a slight nucleation effect is observed. However, the system described in the above publication not only requires the use of two kinds of compounds in combination but also has a low effect and is not sufficient.
【０００４】従来、フタル酸のモノあるいはジエステル
誘導体は、高分子可塑剤として広く利用されているが、
上記の非置換のフタル酸無水物の類似化合物について
は、結晶性ポリオレフィン樹脂に配合した例は殆ど知ら
れておらず、例えば、ハロゲン原子の置換したフタル酸
無水物の樹脂への添加の例としては、２官能性のアルコ
ールであるグリセリンやエチレングリコールと反応させ
て得られる樹脂についての難燃性の評価あるいはセルロ
ースエステル、ポリスチレン、ポリメタクリレートへの
可塑剤としての利用が提案されているのみであった（ I
ndustrial Engineering Chemistry，39巻，1419頁，194
7年）。Heretofore, mono- or diester derivatives of phthalic acid have been widely used as polymer plasticizers.
Regarding the above-mentioned analogous compounds of unsubstituted phthalic anhydride, examples of blending in crystalline polyolefin resin are hardly known, for example, as an example of adding a phthalic anhydride substituted with a halogen atom to a resin. It has only been proposed to evaluate the flame retardancy of a resin obtained by reacting with a bifunctional alcohol such as glycerin or ethylene glycol, or to use it as a plasticizer for cellulose esters, polystyrene and polymethacrylate. (I
ndustrial Engineering Chemistry, 39, 1419, 194
7 years).
【０００５】[0005]
【発明が解決しようとする課題】本発明は、ジベンジリ
デンソルビトール系核剤と全く別の構造を有し、結晶性
ポリオレフィン樹脂に添加したときに優れた造核効果
（結晶化促進効果）を発現する有機系結晶化核剤を提供
することを目的とする。DISCLOSURE OF THE INVENTION The present invention has a completely different structure from a dibenzylidene sorbitol-based nucleating agent, and exhibits an excellent nucleating effect (crystallization promoting effect) when added to a crystalline polyolefin resin. It is an object of the present invention to provide an organic crystallization nucleating agent.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、上記課題
を解決するために、種々の化合物を結晶性ポリオレフィ
ンに添加し、その核剤としての効果を調べた。その結
果、特定のハロゲン置換フタル酸無水物を結晶性ポリオ
レフィンに添加したときに優れた造核効果（結晶化促進
効果）を示すことを見出し、本発明を完成するに至っ
た。Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have added various compounds to crystalline polyolefin and examined the effects as nucleating agents. As a result, they have found that when a specific halogen-substituted phthalic anhydride is added to a crystalline polyolefin, an excellent nucleating effect (crystallization promoting effect) is exhibited, and the present invention has been completed.
【０００７】即ち、本発明は、下記式（１）That is, the present invention provides the following formula (1)
【０００８】[0008]
【化２】 Embedded image
【０００９】（式中、Ｘ1、Ｘ2、Ｘ3、及びＸ4はそれぞ
れ独立に水素原子又はハロゲン原子であり、かつ、それ
らのうちの少なくとも２つはハロゲン原子である。）で
示されるハロゲン置換フタル酸無水物よりなる結晶化核
剤である。Wherein X 1 , X 2 , X 3 and X 4 are each independently a hydrogen atom or a halogen atom, and at least two of them are halogen atoms. It is a crystallization nucleating agent consisting of halogen-substituted phthalic anhydride.
【００１０】また、他の発明は、結晶性ポリオレフィン
樹脂１００重量部、及び上記の結晶化核剤０．００１〜
１重量部を含んでなることを特徴とする樹脂組成物であ
る。In another aspect, the present invention relates to 100 parts by weight of a crystalline polyolefin resin, and from 0.001 to 0.001 of the above-mentioned crystallization nucleating agent.
A resin composition comprising 1 part by weight.
【００１１】[0011]
【発明の実施の形態】本発明の結晶化核剤は、前記式
（１）で示されるハロゲン置換フタル酸無水物よりな
る。前記式中Ｘ1、Ｘ2、Ｘ3、及びＸ4はそれぞれ独立に
水素原子又はハロゲン原子であり、かつ、それらのうち
の少なくとも２つはハロゲン原子である。DESCRIPTION OF THE PREFERRED EMBODIMENTS The crystallization nucleating agent of the present invention comprises a halogen-substituted phthalic anhydride represented by the above formula (1). In the above formula, X 1 , X 2 , X 3 and X 4 are each independently a hydrogen atom or a halogen atom, and at least two of them are halogen atoms.
【００１２】本発明の結晶化核剤として、好適に使用で
きる化合物を具体的に例示すると、３，６−ジクロロ無
水フタル酸、４，５−ジクロロ無水フタル酸、３，６−
ジブロモ無水フタル酸、３，４−ジブロモ無水フタル
酸、３−クロロー５−フルオロ無水フタル酸、テトラク
ロロ無水フタル酸、テトラブロモ無水フタル酸、テトラ
ヨード無水フタル酸等が挙げられる。これら化合物の中
でも、３，６−ジクロロ無水フタル酸や３，４−ジブロ
モ無水フタル酸等の、ジハロゲン置換無水フタル酸は結
晶性ポリオレフィン樹脂に添加したときの造核効果が高
く特に好適である。Specific examples of compounds which can be suitably used as the crystallization nucleating agent of the present invention include 3,6-dichlorophthalic anhydride, 4,5-dichlorophthalic anhydride, and 3,6-dichlorophthalic anhydride.
Examples thereof include dibromophthalic anhydride, 3,4-dibromophthalic anhydride, 3-chloro-5-fluorophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, and tetraiodophthalic anhydride. Among these compounds, dihalogen-substituted phthalic anhydrides such as 3,6-dichlorophthalic anhydride and 3,4-dibromophthalic anhydride are particularly preferable because of their high nucleating effect when added to a crystalline polyolefin resin.
【００１３】前記式（１）で示されるハロゲン置換フタ
ル酸無水物は、一般的に対応するハロゲン置換フタル酸
を高温で加熱するか、もしくは無水酢酸等を用いて脱水
環化させることにより容易に合成できることが広く知ら
れており、また、それらのうちのいくつかは、試薬とし
て購入することもできる。例えば、４，５ージクロロフ
タル酸（２０．０ｇ．）と無水酢酸（３５．０ｇ．）の
混合物を油浴中で加熱し、カルボン酸が完全に溶解する
まで穏やかに還流し、その後さらに同温度で約１時間加
熱して反応させ、減圧下に揮発分を留去して、残留した
固体をトルエンから再結晶することにより白色結晶とし
て融点１９８℃の４，５ージクロロ無水フタル酸（１
２．５ｇ．）が得られる。The halogen-substituted phthalic anhydride represented by the above formula (1) can be easily prepared by heating the corresponding halogen-substituted phthalic acid at a high temperature or by subjecting the corresponding halogen-substituted phthalic anhydride to dehydration cyclization using acetic anhydride or the like. It is widely known that they can be synthesized, and some of them can also be purchased as reagents. For example, a mixture of 4,5 dichlorophthalic acid (20.0 g.) And acetic anhydride (35.0 g.) Is heated in an oil bath, gently refluxed until the carboxylic acid is completely dissolved, and then further heated at the same temperature. The reaction was conducted by heating for about 1 hour, the volatiles were distilled off under reduced pressure, and the remaining solid was recrystallized from toluene to obtain white crystals of 4,5-dichlorophthalic anhydride (1) having a melting point of 198 ° C.
2.5 g. ) Is obtained.
【００１４】また、テトラクロロ無水フタル酸等のテト
ラハロゲン置換無水フタル酸は、例えば「高分子化学、
８巻、２２頁（１９５１年）」に記載されているよう
に、非置換の無水フタル酸を、無水硫酸を含む発煙硫酸
中で、充分な量の塩素等のハロゲン化剤で処理すること
によっても容易に合成することができる。具体的には、
無水フタル酸（２０．０ｇ．）を５０％の無水硫酸を含
む発煙硫酸（２００ｍｌ）に溶かし、少量のヨードを触
媒として添加し、当初反応容器内の温度を４０℃に保っ
て撹拌下に塩素ガスを通じ、反応液中に結晶が析出し始
めた段階で、反応温度を徐々に上昇させ、最終的には２
００℃まで上げて生成したクロロスルホン酸を除去し、
反応混合物を注意深く氷水に注ぎ、析出した固体をトル
エンから再結晶することにより、融点２５６℃のテトラ
クロロ無水フタル酸（２６.8ｇ．）を白色結晶として得
ることができる。Further, tetrahalogen-substituted phthalic anhydrides such as tetrachlorophthalic anhydride are described, for example, in "Polymer Chemistry,
8, page 22 (1951) "by treating unsubstituted phthalic anhydride with a sufficient amount of a halogenating agent such as chlorine in fuming sulfuric acid containing sulfuric anhydride. Can also be easily synthesized. In particular,
Phthalic anhydride (20.0 g.) Is dissolved in fuming sulfuric acid (200 ml) containing 50% sulfuric anhydride, a small amount of iodine is added as a catalyst, and the temperature in the reaction vessel is kept at 40 ° C. and chlorine is stirred. At the stage where crystals began to precipitate in the reaction solution through the gas, the reaction temperature was gradually increased,
Remove the chlorosulfonic acid generated by raising the temperature to 00 ° C,
The reaction mixture is carefully poured into ice water, and the precipitated solid is recrystallized from toluene to give tetrachlorophthalic anhydride (26.8 g.) Having a melting point of 256 ° C as white crystals.
【００１５】前記本発明の結晶化核剤は、結晶性ポリオ
レフィン樹脂に添加し溶融成形したときに良好な造核効
果（結晶化促進効果）を示す。ここで、本発明の結晶化
核剤が添加される結晶性ポリオレフィン樹脂とは、エチ
レン、プロピレン、１−ブテン、等のα−オレフィンの
単独重合体、若しくは共重合体、またはこれらの混合物
である。本発明の結晶化核剤は、これら結晶性ポリオレ
フィン樹脂の中でも一般にホモＰＰ、ランダムＰＰ、ブ
ロックＰＰと称されるプロピレン系樹脂に対して使用し
たときにその効果が顕著である。The crystallization nucleating agent of the present invention exhibits a good nucleating effect (crystallization promotion effect) when added to a crystalline polyolefin resin and melt-molded. Here, the crystalline polyolefin resin to which the crystallization nucleating agent of the present invention is added is a homopolymer, a copolymer, or a mixture thereof of α-olefins such as ethylene, propylene, and 1-butene. . The effect of the crystallization nucleating agent of the present invention is remarkable when the crystallization nucleating agent is used for a propylene-based resin generally called homo PP, random PP, or block PP among these crystalline polyolefin resins.
【００１６】本発明の結晶化核剤を結晶性ポリオレフィ
ン樹脂に添加するときの添加量は特に制限されないが、
一般に結晶性ポリオレフィン樹脂１００重量部に対して
０．００１〜１重量部、特に０．０１〜１重量部が好適
である。 ０．００１重量部未満の添加量では結晶性改
良効果が小さく、１重量部を超える添加量では一般に結
晶性改良効果が飽和し、コスト的な面で好ましくなく、
また、逆に結晶性改良効果を損なったりブリードアウト
して他の物性を損なう場合がある。The amount of the crystallization nucleating agent of the present invention to be added to the crystalline polyolefin resin is not particularly limited.
Generally, 0.001 to 1 part by weight, particularly 0.01 to 1 part by weight, is suitable for 100 parts by weight of the crystalline polyolefin resin. If the amount is less than 0.001 part by weight, the effect of improving crystallinity is small, and if the amount exceeds 1 part by weight, the effect of improving crystallinity is generally saturated, which is not preferable in terms of cost.
Conversely, the crystallinity improving effect may be impaired or bleed out to impair other physical properties.
【００１７】本発明の結晶化核剤は、タルクやジベンジ
リデンソルビトール等の他の結晶化核剤と併用すること
もでき、さらに、分散剤、殺菌剤、紫外線防止剤、中和
剤、滑剤、帯電防止剤、酸化防止剤等の添加剤を発明の
効果を損なわない範囲で配合することもできる。The crystallization nucleating agent of the present invention can be used in combination with other crystallization nucleating agents such as talc and dibenzylidene sorbitol, and further include a dispersant, a bactericide, an ultraviolet ray inhibitor, a neutralizing agent, a lubricant, Additives such as an antistatic agent and an antioxidant can be added in a range that does not impair the effects of the present invention.
【００１８】本発明の結晶化核剤の結晶性ポリオレフィ
ン樹脂への添加は、任意の混合方法で行うことができ
る。例えば、粉末状またはペレット状の結晶性ポリオレ
フィン樹脂、所定量の本発明の結晶化核剤、及び必要に
応じて他の添加剤をタンブラー、ヘンシェルミキサー等
の公知の手段で混合することにより行うことが出来る。
この様にして得られた混合物はそのまま、或いは、さら
にスクリュー押出機やロール等で加熱混練してペレット
化した後、溶融成形して成形体とされる。溶融成形方法
は特に限定されず、圧縮成形、射出成形、押出成形、中
空成形等の公知の方法が採用できる。The crystallization nucleating agent of the present invention can be added to the crystalline polyolefin resin by any mixing method. For example, by mixing a powdery or pellet-like crystalline polyolefin resin, a predetermined amount of the crystallization nucleating agent of the present invention, and if necessary, other additives with a known means such as a tumbler or a Henschel mixer. Can be done.
The mixture obtained in this manner is used as it is, or after further heating and kneading with a screw extruder or a roll to form pellets, and then melt-molded to obtain a molded body. The melt molding method is not particularly limited, and known methods such as compression molding, injection molding, extrusion molding, and hollow molding can be employed.
【００１９】[0019]
【実施例】以下に本発明の実施例及び比較例を示すが、
本発明はこれらに制限されるものではない。EXAMPLES Examples and comparative examples of the present invention are shown below.
The present invention is not limited to these.
【００２０】各実施例及び比較例で結晶性ポリオレフィ
ンに添加した化合物の略号を以下に示す。The abbreviations of the compounds added to the crystalline polyolefin in each of Examples and Comparative Examples are shown below.
【００２１】｛前記式（１）で示されるハロゲン置換フ
タル酸無水物｝ Ａ：３，６−ジクロロフタル酸無水物 Ｂ：４，５−ジクロロフタル酸無水物 Ｃ：３，６−ジブロモフタル酸無水物 Ｄ：３，４−ジブロモフタル酸無水物 Ｅ：３−クロロ−５−フルオロフタル酸無水物 Ｆ：テトラクロロフタル酸無水物 Ｇ：テトラブロモフタル酸無水物 Ｈ：テトラアイオドフタル酸無水物 ｛前記式（１）で示されるハロゲン置換フタル酸無水物
以外のフタル酸誘導体｝ Ｉ：無水フタル酸 Ｊ：４−クロロフタル酸無水物 Ｋ：４−ブロモフタル酸無水物 ｛従来の有機結晶化核剤｝ ＢＳ：ジベンジリデンソルビトール 実施例１ （株）トクヤマ製のホモアイソタクチックポリプロピレ
ン粉末（PN １２０）１００重量部対し、本発明の結晶
化核剤として化合物 Ａをそれぞれ０．０１重量部、
０．０３重量部、０．１重量部、０．３重量部、及び
１．０重量部となる割合で混合し、各混合物についてブ
ラベンダー・プラスチコーダーで２００℃の温度、６０
ｒｐｍの回転数で５分間溶融混練した。{Halogen-substituted phthalic anhydride represented by the above formula (1)} A: 3,6-dichlorophthalic anhydride B: 4,5-dichlorophthalic anhydride C: 3,6-dibromophthalic acid Anhydride D: 3,4-dibromophthalic anhydride E: 3-chloro-5-fluorophthalic anhydride F: tetrachlorophthalic anhydride G: tetrabromophthalic anhydride H: tetraiodophthalic anhydride Compounds {phthalic acid derivatives other than the halogen-substituted phthalic anhydride represented by the above formula (1)} I: phthalic anhydride J: 4-chlorophthalic anhydride K: 4-bromophthalic anhydride {conventional organic crystal nuclei Ingredient｝ BS: dibenzylidene sorbitol Example 1 100 parts by weight of homoisotactic polypropylene powder (PN 120) manufactured by Tokuyama Corporation was compounded as a crystallization nucleating agent of the present invention. 0.01 parts by weight of material A,
0.03 parts by weight, 0.1 parts by weight, 0.3 parts by weight, and 1.0 parts by weight were mixed, and each mixture was heated at a temperature of 200 ° C. and 60 ° C. with a Brabender plastic coder.
The mixture was melt-kneaded at 5 rpm for 5 minutes.
【００２２】得られた混練物の一部を切り取り、ホット
プレート上で厚さ約０．３ｍｍのシートに成形した。こ
のシートを示差走査熱量計のパンの中に入れ、窒素気流
中２３０℃で１０分間溶融した後、毎分１０℃の速度で
降温し、発熱曲線がピークを示す温度（結晶化温度）を
測定した。上記各試料の結晶化温度（C.T.）はそれぞ
れ、１１８．２℃、１２５．１℃、１２６．６℃、１２
３．３℃、及び１２２．０℃であった。A part of the kneaded material was cut out and formed into a sheet having a thickness of about 0.3 mm on a hot plate. This sheet is placed in a pan of a differential scanning calorimeter, melted in a nitrogen stream at 230 ° C. for 10 minutes, and then cooled at a rate of 10 ° C. per minute to measure the temperature at which the exothermic curve shows a peak (crystallization temperature). did. The crystallization temperatures (CT) of the respective samples were 118.2 ° C, 125.1 ° C, 126.6 ° C, and 12 ° C, respectively.
3.3 ° C and 122.0 ° C.
【００２３】後述する比較例１に示すように、結晶化核
剤無添加の場合の結晶化温度（C.T.）は１１３．２℃で
あり、化合物Ａのハロゲン置換フタル酸無水物を添加す
ることにより結晶化温度が上昇していることが分かる。
結晶化温度（C.T.）が高いことは溶融状態からの冷却過
程において高い温度で結晶化が始まることを意味し、造
核効果（或いは結晶化促進効果）が高いことを意味す
る。また、後述する比較例５の結果との比較から分かる
ように、該ハロゲン置換フタル酸無水物の造核効果は、
添加量によって若干異なるが、結晶化核剤として一般に
使用されているジベンジリデンソルビトールとほぼ同等
である。As shown in Comparative Example 1 described below, the crystallization temperature (CT) in the case where no crystallization nucleating agent was added was 113.2 ° C., and the addition of the halogen-substituted phthalic anhydride of Compound A was carried out. It can be seen that the crystallization temperature has increased.
A high crystallization temperature (CT) means that crystallization starts at a high temperature in a cooling process from a molten state, and means that a nucleation effect (or a crystallization promoting effect) is high. Further, as can be seen from comparison with the results of Comparative Example 5 described later, the nucleation effect of the halogen-substituted phthalic anhydride is
Although slightly different depending on the amount added, it is almost equivalent to dibenzylidene sorbitol generally used as a crystallization nucleating agent.
【００２４】実施例２〜８ 実施例１において使用する本発明の結晶化核剤を表１に
示す化合物に変える他は同様にして混合、混練を行い、
得られた混練物の一部を切り取ってシートに成形した。
このシートにつき実施例１と同様に示差走査熱量計を用
いて結結晶化温度（C.T.）を測定した。その結果を表１
に示す。Examples 2 to 8 Mixing and kneading were carried out in the same manner except that the crystallization nucleating agent of the present invention used in Example 1 was changed to the compounds shown in Table 1.
A part of the obtained kneaded material was cut out and formed into a sheet.
The crystallization temperature (CT) of this sheet was measured using a differential scanning calorimeter in the same manner as in Example 1. Table 1 shows the results.
Shown in
【００２５】[0025]
【表１】 [Table 1]
【００２６】比較例１ 結晶化核剤を加えない他は実施例１と同様にして混合、
混練を行い、得られた混練物の一部を切り取ってシート
に成形した。このシートにつき実施例１と同様に示差走
査熱量計を用いて結晶化温度を測定したところ、結晶化
温度は１１３．２℃であった。Comparative Example 1 A mixture was prepared in the same manner as in Example 1 except that no crystallization nucleating agent was added.
Kneading was performed, and a part of the obtained kneaded material was cut out and formed into a sheet. When the crystallization temperature of this sheet was measured using a differential scanning calorimeter in the same manner as in Example 1, the crystallization temperature was 113.2 ° C.
【００２７】比較例２〜５ 実施例１において添加する結晶化核剤を、表２に示す化
合物に変える他は実施例１と同様にして混合、混練を行
い、得られた混練物の一部を切り取ってシートに成形し
た。このシートにつき実施例１と同様に示差走査熱量計
を用いて結晶化温度（C.T.）を測定した。結果を表２に
示す。Comparative Examples 2-5 Mixing and kneading were carried out in the same manner as in Example 1 except that the crystallization nucleating agent added in Example 1 was changed to the compounds shown in Table 2, and a part of the obtained kneaded product was obtained. Was cut out and formed into a sheet. The crystallization temperature (CT) of this sheet was measured using a differential scanning calorimeter in the same manner as in Example 1. Table 2 shows the results.
【００２８】[0028]
【表２】 [Table 2]
【００２９】比較例２〜４の結果に示されるように、本
発明の結晶化核剤として使用するハロゲン置換フタル酸
無水物と類似の構造を有する各化合物を添加した場合の
結晶化温度（C.T.）は低く、本発明の結晶化核剤に比べ
て造核効果（結晶化促進効果）が低いことが分かる。As shown in the results of Comparative Examples 2 to 4, the crystallization temperature (CT) when each compound having a structure similar to the halogen-substituted phthalic anhydride used as the crystallization nucleating agent of the present invention was added. ) Is low, indicating that the nucleating effect (crystallization promoting effect) is lower than that of the crystallization nucleating agent of the present invention.
【００３０】[0030]
【発明の効果】本発明の結晶化核剤は少量の添加でポリ
プロピレン等の結晶化ポリオレフィン樹脂の結晶化温度
（C.T.）を上昇させる。即ち、本発明の結晶化核剤を含
有する結晶性ポリオレフィン樹脂は、結晶化温度（C.
T.）が上昇し、早く結晶固化するので高速成形性が改良
される。また、得られた成形品は、結晶が微細になり、
結晶化度が増大するため、透明性、剛性、耐熱性等の物
性が向上する。The crystallization nucleating agent of the present invention increases the crystallization temperature (CT) of a crystallized polyolefin resin such as polypropylene by addition of a small amount. That is, the crystalline polyolefin resin containing the crystallization nucleating agent of the present invention has a crystallization temperature (C.
T.) rises and crystallizes quickly, improving high-speed moldability. Also, the obtained molded product has fine crystals,
Since the degree of crystallinity increases, physical properties such as transparency, rigidity and heat resistance are improved.
Claims (2)
原子又はハロゲン原子であり、かつ、それらのうちの少
なくとも２つはハロゲン原子である。）で示されるハロ
ゲン置換フタル酸無水物よりなる結晶化核剤。[Claim 1] The following formula (1) Wherein X 1 , X 2 , X 3 and X 4 are each independently a hydrogen atom or a halogen atom, and at least two of them are halogen atoms. A crystallization nucleating agent consisting of an acid anhydride.
部、及び請求項１記載の結晶化核剤０．００１〜１重量
部を含んでなることを特徴とする樹脂組成物。2. A resin composition comprising 100 parts by weight of a crystalline polyolefin resin and 0.001 to 1 part by weight of a crystallization nucleating agent according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13000798A JPH11323029A (en) | 1998-05-13 | 1998-05-13 | Crystallization nucleating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13000798A JPH11323029A (en) | 1998-05-13 | 1998-05-13 | Crystallization nucleating agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11323029A true JPH11323029A (en) | 1999-11-26 |
Family
ID=15023851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13000798A Pending JPH11323029A (en) | 1998-05-13 | 1998-05-13 | Crystallization nucleating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11323029A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002265709A (en) * | 2001-03-07 | 2002-09-18 | Tosoh Corp | Composition for cap liner material and cap |
| JP2004530803A (en) * | 2001-05-17 | 2004-10-07 | ミリケン・アンド・カンパニー | Low-shrink polypropylene fiber, fabric produced therefrom and method for producing same |
| WO2020241503A1 (en) * | 2019-05-24 | 2020-12-03 | 株式会社Adeka | Resin composition and molded article thereof |
-
1998
- 1998-05-13 JP JP13000798A patent/JPH11323029A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002265709A (en) * | 2001-03-07 | 2002-09-18 | Tosoh Corp | Composition for cap liner material and cap |
| JP2004530803A (en) * | 2001-05-17 | 2004-10-07 | ミリケン・アンド・カンパニー | Low-shrink polypropylene fiber, fabric produced therefrom and method for producing same |
| WO2020241503A1 (en) * | 2019-05-24 | 2020-12-03 | 株式会社Adeka | Resin composition and molded article thereof |
| JP2021001356A (en) * | 2019-05-24 | 2021-01-07 | 株式会社Adeka | Resin composition, molded article thereof, and method for producing resin composition |
| JP2021001357A (en) * | 2019-05-24 | 2021-01-07 | 株式会社Adeka | Resin composition, molded article thereof, and method for producing resin composition |
| JP6824482B1 (en) * | 2019-05-24 | 2021-02-03 | 株式会社Adeka | Crystallinity inhibitor for polyolefin resin, crystallinity inhibitor of polyolefin resin, and method for producing polyolefin resin composition |
| CN113874431A (en) * | 2019-05-24 | 2021-12-31 | 株式会社Adeka | Resin composition and molded article thereof |
| CN113874431B (en) * | 2019-05-24 | 2025-03-25 | 株式会社Adeka | Resin composition and molded product thereof |
| US12435205B2 (en) | 2019-05-24 | 2025-10-07 | Adeka Corporation | Resin composition and molded article thereof |
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