JPH0381368A - Crystalline polymeric material composition - Google Patents
Crystalline polymeric material compositionInfo
- Publication number
- JPH0381368A JPH0381368A JP21904589A JP21904589A JPH0381368A JP H0381368 A JPH0381368 A JP H0381368A JP 21904589 A JP21904589 A JP 21904589A JP 21904589 A JP21904589 A JP 21904589A JP H0381368 A JPH0381368 A JP H0381368A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polymeric material
- alkali metal
- fatty acid
- parts
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 title abstract description 5
- -1 alkali metal salt Chemical class 0.000 claims abstract description 44
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 13
- 239000010452 phosphate Substances 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 10
- 239000000194 fatty acid Substances 0.000 claims abstract description 10
- 229930195729 fatty acid Natural products 0.000 claims abstract description 10
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 239000002861 polymer material Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 10
- 230000008025 crystallization Effects 0.000 abstract description 10
- 238000000465 moulding Methods 0.000 abstract description 7
- 229930185605 Bisphenol Natural products 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 5
- 239000004743 Polypropylene Substances 0.000 abstract description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 4
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 4
- 229920001155 polypropylene Polymers 0.000 abstract description 4
- 239000004698 Polyethylene Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- 229920000573 polyethylene Polymers 0.000 abstract description 3
- 239000004952 Polyamide Substances 0.000 abstract description 2
- 229920002647 polyamide Polymers 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract 1
- 150000004671 saturated fatty acids Chemical class 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003484 crystal nucleating agent Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- WOOQSKAMMPIQIW-CIAFKFPVSA-N Bis(methylbenzylidene)sorbitol Chemical compound OC([C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=C(C)C=1C=CC=CC=1)=C(C)C1=CC=CC=C1 WOOQSKAMMPIQIW-CIAFKFPVSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Chemical class 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は結晶性高分子材料組成物に関し、詳しくは、ビ
スフェノール環状酸性リン酸エステ、ルおよび高級脂肪
酸のアルカリ金属塩を添加することにより、加工性、強
度、透明性などの改善された結晶性高分子材料組成物に
関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a crystalline polymer material composition, and more specifically, by adding a bisphenol cyclic acid phosphate ester and an alkali metal salt of a higher fatty acid, The present invention relates to a crystalline polymer material composition with improved processability, strength, transparency, etc.
〔従来の技術及び発明が解決しようとする課題〕ポリエ
チレン、ポリプロピレン、ポリブテン−１、ポリエチレ
ンテレフタレート、ポリブチレンテレフタレート、ボリ
アミドなどの結晶性高分子材料は、加熱成型後の結晶化
速度が遅いため、成型サイクル性が低く、金型温度を下
げなければならず、また、加熱成型後に結晶化によって
収縮する欠点があった。また、これらの結晶性高分子材
料は、大きな結晶が生成するために、強度が不充分であ
ったり透明性が劣る欠点があった。[Prior art and problems to be solved by the invention] Crystalline polymer materials such as polyethylene, polypropylene, polybutene-1, polyethylene terephthalate, polybutylene terephthalate, and polyamide have a slow crystallization rate after heat molding, so it is difficult to mold them. It has poor cycleability, requires a lower mold temperature, and has the disadvantage of shrinkage due to crystallization after hot molding. Furthermore, these crystalline polymer materials have drawbacks such as insufficient strength and poor transparency due to the formation of large crystals.
これらの欠点は、すべて、高分子材料の結晶性に由来す
るものであり、高分子材料の結晶化温度を高め、微細な
結晶を急速に生成させることができれば解消されること
が知られている。All of these drawbacks originate from the crystallinity of polymeric materials, and it is known that they can be overcome by increasing the crystallization temperature of polymeric materials and rapidly generating fine crystals. .
この目的のために、結晶核剤あるいは結晶化促進剤を添
加することが知られており、従来から、ｐ−第三ブチル
安息香酸アルミニウム塩、アジピン酸ナトリウムなどの
カルボン酸金属塩、ナトリウムビス（４−第三ブチルフ
ェニル）ホスフェート、ナトリウム−２，２゛−メチレ
ンビス（４，６−ジ第三ブチルフエニル）ホスフェート
などの酸性リン酸エステル金属塩、ジベンジリデンソル
ビトール、ビス（メチルベンジリデン）ソルビトールな
どの多価アルコール誘導体などが用いられていた。For this purpose, it is known to add a crystal nucleating agent or a crystallization accelerator. Acidic phosphate ester metal salts such as 4-tert-butylphenyl) phosphate, sodium-2,2゛-methylenebis(4,6-di-tert-butylphenyl) phosphate, and polyesters such as dibenzylidene sorbitol and bis(methylbenzylidene) sorbitol. Hydrolic alcohol derivatives were used.
これらの化合物の中でも、特開昭５８−１７３６号公報
、特開昭５９−１８４２５２号公報などに記載１された
アルキリデンビスフェノール類の環状リン酸エステルの
金属塩はその効果が比較的大きく、広く用いられている
。Among these compounds, metal salts of cyclic phosphoric acid esters of alkylidene bisphenols described in JP-A-58-1736 and JP-A-59-184252 have relatively large effects and are widely used. It is being
しかしながら、該化合物による効果もまだ不充分な場合
があり、ｐ−第三ブチル安息香酸のアルミニウム塩と高
級脂肪族カルボン酸のアルカリ金属塩または亜鉛塩を併
用する方法（特開昭６２−２６３２４４号公報、特開昭
６３−１２５５５１号公報）などが提案されたが、まだ
充分とはいえず、実用的な改良が求められていた。However, the effect of this compound may still be insufficient, and there is a method of using an aluminum salt of p-tert-butylbenzoic acid in combination with an alkali metal salt or zinc salt of a higher aliphatic carboxylic acid (Japanese Patent Laid-Open No. 62-263244). (Japanese Patent Laid-Open Publication No. 125551/1983), etc., but it was still not sufficient and practical improvements were required.
〔課題を解決するための手段〕
本発明者等はアルキリデンビスフェノール類の環状リン
酸エステルの金属塩の効果の不充分な点を解消すべく鋭
意検討を重ねた結果、アルキリデンビスフェノール類の
環状酸性リン酸エステルに、さらに高級脂肪酸のアルカ
リ金属塩を添加することにより、今までに見られなかっ
た効果が現れることを見出し本発明を完成した。[Means for Solving the Problems] The present inventors have made extensive studies to solve the insufficiency of the effects of metal salts of cyclic phosphoric acid esters of alkylidene bisphenols, and have found that cyclic acid phosphoric acid esters of alkylidene bisphenols The present invention was completed based on the discovery that by further adding an alkali metal salt of a higher fatty acid to an acid ester, an effect never seen before appears.
すなわち、本発明は、結晶性高分子材料１００重量部に
対し、次の一般式（Ｉ）で表される環状酸性リン酸エス
テル０．００５〜５重量部および高級脂肪酸のアルカリ
金属塩０．００５〜５重量部を添加してなる、結晶性高
分子材料組成物を提供するものである。That is, the present invention provides 0.005 to 5 parts by weight of a cyclic acidic phosphoric acid ester represented by the following general formula (I) and 0.005 parts by weight of an alkali metal salt of a higher fatty acid per 100 parts by weight of the crystalline polymer material. 5 parts by weight of the crystalline polymer material composition is provided.
−Ｃ４Ｈ９
（式中、Ｒ１は水素原子または炭素原子数１〜４のアル
キル基を示し、Ｒ１は炭素原子数１〜９のアルキル基を
示す、）
上記一般式（Ｉ）において、Ｒ１で表される炭素原子数
１〜４のアルキル基としては、メチル、エチル、プロピ
ル、イソプロピル、ブチル、第ニブチル、第三ブチル、
イソブチルなどがあげられ、Ｒｚで表される炭素原子数
１〜９のアルキル基としては、メチル、エチル、プロピ
ル、イソプロピル、ブチル、第ニブチル、第三ブチル、
イソブチル、アミル、第三アミル、ヘキシル、ヘプチル
、オクチル、イソオクチル、２−エチルヘキシル、第三
オクチル、ノニル、第三ノニルなどがあげられる。-C4H9 (In the formula, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R1 represents an alkyl group having 1 to 9 carbon atoms.) In the above general formula (I), R1 represents Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, nibutyl, tertiary butyl,
Examples of the alkyl group having 1 to 9 carbon atoms represented by Rz include isobutyl, methyl, ethyl, propyl, isopropyl, butyl, nibutyl, tertiary butyl,
Examples include isobutyl, amyl, tertiary amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, tertiary nonyl, and the like.
これらの化合物のうち、Ｒ１が水素原子またはメチル基
、Ｒ３が炭素原子数１〜４のアルキル基である化合物が
特に好ましい。Among these compounds, compounds in which R1 is a hydrogen atom or a methyl group and R3 is an alkyl group having 1 to 4 carbon atoms are particularly preferred.
従って、本発明で用いられる上記一般式（Ｉ）で表され
る化合物としては、次に示すものが特に好ましい。Therefore, as the compound represented by the above general formula (I) used in the present invention, the following are particularly preferable.
−ＣＪｑ
−ＣａＨｑ
ｔ−ＣＪ＊
−ＣｎＬ
ｔ−ＣａＬ
本発明で用いられる上記一般式（Ｉ）で表される環状酸
性リン酸エステル化合物は、例えば、オキシ塩化リンと
２．２°−アルキリデンビスフェノールを反応させた後
加水分解して製造後、ろ過、乾燥して目的物を得、また
必要に応じてこれを粉砕して結晶核剤として使用される
。-CJq -CaHq t-CJ* -CnL t-CaL The cyclic acidic phosphoric acid ester compound represented by the above general formula (I) used in the present invention is, for example, a combination of phosphorus oxychloride and 2.2°-alkylidene bisphenol. After reaction and hydrolysis, the target product is obtained by filtration and drying, and if necessary, it is crushed and used as a crystal nucleating agent.
また、前述の環状酸性リン酸エステル化合物と併用され
る高級脂肪酸のアルカリ金属塩としては、炭素原子数１
２〜３０の高級脂肪酸のリチウム、ナトリウム、カリウ
ム塩が好ましく、特に例えば、ラウリン酸、ξリスチン
酸、バルミチン酸、ステアリン酸、ベヘン酸、モンタン
酸などの飽和の高級脂肪酸のアルカリ金属塩が好ましい
。In addition, the alkali metal salt of higher fatty acid to be used in combination with the above-mentioned cyclic acidic phosphoric acid ester compound has a carbon atom number of 1
Lithium, sodium and potassium salts of 2-30 higher fatty acids are preferred, particularly alkali metal salts of saturated higher fatty acids such as lauric acid, ξristic acid, balmitic acid, stearic acid, behenic acid, montanic acid.
本発明の対象となる結晶性高分子材料としては、例えば
、ポリエチレン、ポリプロピレン、ポリブテン−１、ポ
リ−３−メチルブテンなとのα−オレフィン重合体、ポ
リエチレンテレフタレート、ポリブチレンテレフタレー
ト、ポリヘキサメチレンテレフタレートなどの熱可塑性
直鎖ポリエステル、ポリカプロラクタム、ポリへキサメ
チレンアジパミドなどの直鎖ボリア５ドなどを挙げるこ
とができる。Examples of crystalline polymer materials to which the present invention applies include α-olefin polymers such as polyethylene, polypropylene, polybutene-1, and poly-3-methylbutene, polyethylene terephthalate, polybutylene terephthalate, and polyhexamethylene terephthalate. Examples include thermoplastic linear polyesters, polycaprolactam, linear boria compounds such as polyhexamethylene adipamide, and the like.
本発明において、前記一般式（Ｉ）で表される化合物を
結晶性高分子材料に添加する方法は特に制限を受けず、
一般に用いられる方法をそのまま適用することができる
０例えば、結晶性高分子材料粉末あるいはペレットと、
添加剤粉末をトライブレンドする方法等を用いることが
できる。In the present invention, the method of adding the compound represented by the general formula (I) to the crystalline polymer material is not particularly limited,
Generally used methods can be applied as is. For example, with crystalline polymer material powder or pellets,
A method such as triblending additive powder can be used.
また、本発明の結晶性高分子材料組成物は、各種成型品
、繊維、二輪延伸フィルム、シートなどに使用すること
ができる。Further, the crystalline polymer material composition of the present invention can be used for various molded products, fibers, two-wheel stretched films, sheets, and the like.
本発明の組成物には、必要に応じて、フェノール系抗酸
化剤、チオエーテル系抗酸化剤、ホスファイト系抗酸化
剤、紫外線吸収剤、光安定剤、重金属不活性化剤、金属
石けん、顔料、充填剤、有機錫化合物、可塑剤、エポキ
シ化合物、発泡剤、帯電防止剤、難燃剤、滑剤、加工助
剤などを包含させることができる。The composition of the present invention may optionally contain phenolic antioxidants, thioether antioxidants, phosphite antioxidants, ultraviolet absorbers, light stabilizers, heavy metal deactivators, metallic soaps, and pigments. , fillers, organotin compounds, plasticizers, epoxy compounds, blowing agents, antistatic agents, flame retardants, lubricants, processing aids, and the like.
次に本発明を実施例によって具体的に説明する。しかし
ながら、本発明はこれらの実施例によって制限を受ける
ものではない。Next, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited to these examples.
実施例１
下記の配合により、１８０℃で５分間ロール混線後１８
０℃、２５０ ｋｇ／ｃｊの条件で５分間圧縮成型し、
次いで６０℃まで急冷して厚さ１ｍの試験片を作成した
。Example 1 With the following formulation, after roll mixing at 180°C for 5 minutes, 18
Compression molded for 5 minutes at 0°C and 250 kg/cj,
Next, it was rapidly cooled to 60° C. to prepare a test piece with a thickness of 1 m.
この試験片を用い、＾ＳＴＭ Ｄ−１００３−６１に基
づいて、霞度（Ｈａｚｅ Ｖａｌｕｅ）を測定し、また
、ＡＳＴＭＤ−２５６に基づいて、２０℃におけるアイ
ゾツト衝撃強度（ｋｇ −ｃｍ／ｃｄ）を測定した。Using this test piece, the haze value was measured based on STM D-1003-61, and the Izod impact strength (kg-cm/cd) at 20°C was measured based on ASTM D-256. It was measured.
その結果を表−１に示す。The results are shown in Table-1.
く配合〉
ポリプロピレン
（Ｐｒｏｆａｘ
６５０１）
００
重量部
ステアリン酸ナトリウム
０．１２
環状酸性リン酸エステル（表−１）
Ｏ，１
表
実施例２
下記の配合により、１６０°Ｃで５分間ロール混練後１
６０°Ｃ１２００ｋｇ／ｃｉｉの条件で５分間圧縮成型
し、次いで６０°Ｃまで急冷して厚さｌａｎの試験片を
作成した。Blend> Polypropylene (Profax 6501) 00 Part by weight Sodium stearate 0.12 Cyclic acidic phosphate ester (Table-1) O,1 Table Example 2 After roll kneading at 160°C for 5 minutes with the following formulation, 1
Compression molding was performed for 5 minutes at 60° C. at 1200 kg/cii, and then rapidly cooled to 60° C. to prepare a test piece having a thickness of 100° C.
この試験片を用い、ＡＳＴＭ Ｄ−１００３−６１に基
づいて、霞度（Ｈａｚｅ Ｖａｌｕｅ）を測定した。Using this test piece, haze value was measured based on ASTM D-1003-61.
その結果を表−２に示す。The results are shown in Table-2.
〈配合〉
環状酸性リン酸エステル（Ｎ［Ｌ４） ０．２表−２
（注）
ネ：
Ｍ４の環状酸性リン酸エステルに代えてに４の環状酸性
リン酸エステルのＮａ塩を用いた。<Formulation> Cyclic acid phosphate ester (N[L4) 0.2 Table-2 (Note) Ne: Na salt of the cyclic acid phosphate ester of 4 was used in place of the cyclic acid phosphate ester of M4.
実施例３
固有粘度０．６６のポリエチレンテレフタレート１００
重量部に対し、
ステアリン酸ナトリウム０．１
重量部および表−３に示す試料（環状酸性リン酸エステ
ル又は比較試料）０．５重量部を混合した後二軸押出機
を用いてペレットを作成した。Example 3 Polyethylene terephthalate 100 with intrinsic viscosity 0.66
After mixing 0.1 part by weight of sodium stearate and 0.5 part by weight of the sample (cyclic acid phosphate or comparative sample) shown in Table 3, pellets were created using a twin-screw extruder. .
このペレットを差動熱量計に入れ、１６°Ｃ／分で昇温
し、昇温時の結晶化温度を測定した。This pellet was placed in a differential calorimeter, heated at a rate of 16°C/min, and the crystallization temperature at the time of heating was measured.
また、３００°Ｃで５分間融解した後、１６°Ｃ／分で
降温した時の結晶化温度を測定し、降温時の吸熱ピーク
の高さＨと、ＨＩ３のところの幅Ｗとの比Ｈ／Ｗを求め
た。In addition, after melting at 300°C for 5 minutes, the crystallization temperature was measured when the temperature was lowered at 16°C/min, and the ratio H of the endothermic peak height H at the time of cooling and the width W at HI3 /W was calculated.
昇温時の結晶化温度が低いほど低温金型で底型した場合
に結晶化度の高い成型品が得られ、また、降温時の結晶
化温度が高く、Ｈ／Ｗが大きいほど結晶化速度が大きい
ことを示す。The lower the crystallization temperature when the temperature is raised, the higher the degree of crystallinity can be obtained when bottom molding is performed in a low-temperature mold, and the higher the crystallization temperature when the temperature is lowered and the larger the H/W, the faster the crystallization rate. is large.
その結果を次の表−３に示す。The results are shown in Table 3 below.
表
実施例４
ナイロン−６樹脂１００重量部にステアリン酸カリウム
０．１重量部および表−４に示す試料（環状酸性リン酸
エステル又は比較試料）０．１重量部をトライブレンド
し、３．５オンス、インラインスクリュー型射出戊型機
（シリンダー温度：２２０．２４０．２４０．２３５°
Ｃ）を使用して、成型品の肉厚１０ｍｍ、直径１００
ｍｍの円板型成型品用金型を用い、金型温度８０℃で射
出成型した。Table Example 4 100 parts by weight of nylon-6 resin was triblended with 0.1 part by weight of potassium stearate and 0.1 part by weight of the sample (cyclic acidic phosphate ester or comparative sample) shown in Table 4. ounce, in-line screw type injection machine (cylinder temperature: 220.240.240.235°
Using C), the wall thickness of the molded product is 10 mm and the diameter is 100 mm.
Injection molding was carried out at a mold temperature of 80° C. using a mold for disc-shaped molded products of mm.
射出時間１４秒、中間時間４秒とし、冷却時間を５０秒
から順次短くして３０シヨツト成型し、金型からの離型
が困難となる時または成型品にソリあるいはヒケが起こ
る時の冷却時間を測定した。The injection time is 14 seconds, the intermediate time is 4 seconds, and the cooling time is gradually shortened from 50 seconds to 30 shots. Cooling time when it becomes difficult to release from the mold or when warping or sinking occurs on the molded product. was measured.
冷却時間が短ければ短いほど成型サイクルが短縮できる
こととなり、加工作業上好ましい。The shorter the cooling time, the shorter the molding cycle, which is preferable in terms of processing operations.
その結果を表−４に示す。The results are shown in Table 4.
表
〔発明の効果〕
上記各実施例から明らかな如く、本発明の特定の環状酸
性リン酸エステルと高級脂肪酸のアルカリ金属塩を併用
することにより、結晶性高分子材料の透明性、機械的性
質を著しく改善するぽかりでなく、
成型サイクルを向
上することもできる。Table [Effects of the Invention] As is clear from the above examples, the combination of the specific cyclic acidic phosphoric acid ester of the present invention and the alkali metal salt of higher fatty acid improves the transparency and mechanical properties of the crystalline polymer material. Not only does it significantly improve the molding cycle, it can also improve the molding cycle.
Claims (1)
I ）で表される環状酸性リン酸エステル０．００５〜
５重量部および高級脂肪酸のアルカリ金属塩０．００５
〜５重量部を添加してなる、結晶性高分子材料組成物。 ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＿１は水素原子または炭素原子数１〜４のア
ルキル基を示し、Ｒ＿２は炭素原子数１〜９のアルキル
基を示す。）[Claims] For 100 parts by weight of the crystalline polymer material, the following general formula (
Cyclic acidic phosphate ester represented by I) 0.005~
5 parts by weight and 0.005 parts by weight of alkali metal salts of higher fatty acids
A crystalline polymer material composition containing ~5 parts by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R_2 represents an alkyl group having 1 to 9 carbon atoms.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21904589A JP2766330B2 (en) | 1989-08-25 | 1989-08-25 | Crystalline polymer material composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21904589A JP2766330B2 (en) | 1989-08-25 | 1989-08-25 | Crystalline polymer material composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0381368A true JPH0381368A (en) | 1991-04-05 |
| JP2766330B2 JP2766330B2 (en) | 1998-06-18 |
Family
ID=16729398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21904589A Expired - Fee Related JP2766330B2 (en) | 1989-08-25 | 1989-08-25 | Crystalline polymer material composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2766330B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5342868A (en) * | 1991-12-05 | 1994-08-30 | Asahi Denka Kogyo Kabushiki Kaisha | Crystalline synthetic resin composition |
| JPH0848838A (en) * | 1994-06-01 | 1996-02-20 | New Japan Chem Co Ltd | Polybutene-1 resin composition |
| WO2010024191A1 (en) | 2008-08-28 | 2010-03-04 | 株式会社Adeka | Polyolefin resin composition |
| JP4875229B2 (en) * | 2009-12-11 | 2012-02-15 | ジャパンスーパークォーツ株式会社 | Silica glass crucible |
| US20140005310A1 (en) * | 2011-03-17 | 2014-01-02 | Basf Se | Additive Mixture |
| US20140045980A1 (en) * | 2011-04-26 | 2014-02-13 | Basf Se | Additives for high-flow polymers |
| WO2017150662A1 (en) * | 2016-03-02 | 2017-09-08 | 株式会社Adeka | Resin additive composition, thermoplastic resin composition, and molded article thereof |
| RU2758474C1 (en) * | 2018-02-13 | 2021-10-28 | Адэка Корпорейшн | Crystallisation nucleator, polyolefin-based resin composition containing the nucleator, and moulded product made therefrom |
-
1989
- 1989-08-25 JP JP21904589A patent/JP2766330B2/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5342868A (en) * | 1991-12-05 | 1994-08-30 | Asahi Denka Kogyo Kabushiki Kaisha | Crystalline synthetic resin composition |
| JPH0848838A (en) * | 1994-06-01 | 1996-02-20 | New Japan Chem Co Ltd | Polybutene-1 resin composition |
| WO2010024191A1 (en) | 2008-08-28 | 2010-03-04 | 株式会社Adeka | Polyolefin resin composition |
| KR20110056531A (en) | 2008-08-28 | 2011-05-30 | 가부시키가이샤 아데카 | Polyolefin resin composition |
| JP4875229B2 (en) * | 2009-12-11 | 2012-02-15 | ジャパンスーパークォーツ株式会社 | Silica glass crucible |
| US20140005310A1 (en) * | 2011-03-17 | 2014-01-02 | Basf Se | Additive Mixture |
| AU2012247145B2 (en) * | 2011-04-26 | 2015-10-29 | Basf Se | Additives for high-flow polymers |
| EP2702098A4 (en) * | 2011-04-26 | 2014-10-08 | Basf Se | Additives for high-flow polymers |
| US20140045980A1 (en) * | 2011-04-26 | 2014-02-13 | Basf Se | Additives for high-flow polymers |
| WO2017150662A1 (en) * | 2016-03-02 | 2017-09-08 | 株式会社Adeka | Resin additive composition, thermoplastic resin composition, and molded article thereof |
| JPWO2017150662A1 (en) * | 2016-03-02 | 2018-05-24 | 株式会社Adeka | Resin additive composition, thermoplastic resin composition, and molded article thereof |
| CN108699291A (en) * | 2016-03-02 | 2018-10-23 | 株式会社Adeka | Resin additive composition, thermoplastic resin composition and its formed body |
| RU2771528C2 (en) * | 2016-03-02 | 2022-05-05 | Адэка Корпорейшн | Composition of resin additive, composition of thermoplastic resin and molded product from it |
| US11492461B2 (en) | 2016-03-02 | 2022-11-08 | Adeka Corporation | Resin additive composition, thermoplastic resin composition, and molded article thereof |
| TWI787175B (en) * | 2016-03-02 | 2022-12-21 | 日商Ａｄｅｋａ股份有限公司 | Resin additive composition, thermoplastic resin composition, and molded body thereof |
| RU2758474C1 (en) * | 2018-02-13 | 2021-10-28 | Адэка Корпорейшн | Crystallisation nucleator, polyolefin-based resin composition containing the nucleator, and moulded product made therefrom |
| US11306194B2 (en) | 2018-02-13 | 2022-04-19 | Adeka Corporation | Nucleating agent, polyolefin-based resin composition containing same, and molded article thereof |
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|---|---|
| JP2766330B2 (en) | 1998-06-18 |
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