JPH0512388B2 - - Google Patents
Info
- Publication number
- JPH0512388B2 JPH0512388B2 JP63206291A JP20629188A JPH0512388B2 JP H0512388 B2 JPH0512388 B2 JP H0512388B2 JP 63206291 A JP63206291 A JP 63206291A JP 20629188 A JP20629188 A JP 20629188A JP H0512388 B2 JPH0512388 B2 JP H0512388B2
- Authority
- JP
- Japan
- Prior art keywords
- dmbs
- present
- polypropylene resin
- resin composition
- weight
- 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.)
- Expired - Lifetime
Links
- -1 polypropylene Polymers 0.000 claims description 20
- 239000004743 Polypropylene Substances 0.000 claims description 17
- 229920001155 polypropylene Polymers 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 11
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 7
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 claims description 7
- 229960002401 calcium lactate Drugs 0.000 claims description 7
- 235000011086 calcium lactate Nutrition 0.000 claims description 7
- 239000001527 calcium lactate Substances 0.000 claims description 7
- 239000000600 sorbitol Substances 0.000 claims description 7
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 238000010828 elution Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000008395 clarifying agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000007922 dissolution test Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 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
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005673 polypropylene based resin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
本発明は改良された透明性のポリプロピレン系
樹脂組成物に関し特に透明化剤の水または熱水へ
の逃失逃失が防止された、食品容器包装材および
医療用器具などに有用なポリプロピレン系樹脂組
成物に関する。
ポリプロピレン系樹脂の透明性を向上させる方
法として特開昭53−117044号にはポリプロピレン
又はその共重合体に１・３，２・４−ジ（メチル
ベンジリデン）ソルビトール（以下、単に
DMBSと略記する）を配合し、加熱成形するこ
とが提案されている。一方、ポリプロピレン系樹
脂の触媒残渣中の塩素捕捉剤として、又該樹脂の
流動性をよくしたり、金型からの離型性を改善す
るため、並びに他の添加剤及び顔料等の分散剤と
して、一般に安定剤あるいは滑剤としてステアリ
ン酸カルシウム、ステアリン酸亜鉛などの高級脂
肪酸の金属塩が添加される。しかしながら、ポリ
プロピレン系樹脂に上記した透明化剤のDMBS
と滑剤あるいは安定剤の高級脂肪酸の金属塩を併
用した場合、得られる該ポリプロピレン系樹脂の
組成物は水、熱水、あるいは蒸気に対して
DMBSが流失または逃失し易いために特に食品
容器包装材や医療用器具などの分野において安全
衛生上の問題を生じるばかりでなくさらに透明性
の長期持続性を損う欠点もある。
本発明者等は、DMBSを用いたポリプロピレ
ン系樹脂組成物の上述したような問題を解決する
ために鋭意検討した結果、ポリプロピレン系樹脂
とDMBSの混合物に特定化合物を混合すること
を見い出し、本発明を提案するに至つた。
即ち、本発明はポリプロピレン系樹脂、１・
３，２・４ジ（メチルベンジリデン）ソルビトー
ル及び乳酸カルシウムよりなるポリプロピレン系
樹脂組成物である。本発明の樹脂組成物は従来公
知の高級脂肪酸の金属塩を配合しないで乳酸カル
シウムを配合するだけで、従来のDMBS配合品
からのDMBSの溶出又は逃失を完全に防止する
ことが出来る。又、これらの該組成物は従来公知
の高級脂肪酸金属塩配合品の成形性、流動性、離
型性及び熱安定性等を損うものではない。本発明
に用いるポリプロピレン系樹脂は、プロピレンの
単独重合体（ホモポリマー）、或いは、プロピレ
ン含量が70重量％以上であるポリプロピレンとエ
チレン、ブテン、ペンテン、酢酸ビニル、塩化ビ
ニル等の一種又は複数のものよりなる共重合体、
及びこれらのポリマーのブレンド物である。
本発明に用いられる１・３，２・４−ジ（メチ
ルベンジリデン）ソルビトールは、トルアルデヒ
ドとソルビトールとの縮合物で、該製造方法等
は、公知のものが特に制限なく用いられる。
上記樹脂組成物の配合割合は、用途により適宜
選定すればよいが、特に、ポリプロピレン系樹脂
100重量部に対して、DMBS0.01〜１重量部と乳
酸カルシウム0.01〜１重量部の割合で配合したも
のは、本発明の効果が極めて顕著に発揮されるた
め好ましい。
また、本発明樹脂組成物は、必要に応じて酸化
防止剤、帯電防止剤、滑剤、分散剤、顔料、螢光
剤、殺菌剤、光安定剤、紫外線吸収剤、金属不活
性化剤、及び光劣化防止剤の添加剤を本発明の効
果を著しく減少させない範囲で配合することも出
来る。
本発明の樹脂組成物は常法により混練、成形す
ることにより所望の成形品を得ることができる。
以下実施例に基づき具体的に説明するが、本発
明は以下の実施例に特に限定されるものではな
い。
尚、以下の実施例及び比較例において使用した
測定法を次に示した。
(1) 曇り度：ASTM D1003−61に準拠（射出成
形板３mmtを測定）
(2) 溶出試験：厚生省告示の医療用器具試験法に
準拠。（但し、ペレツト溶出試験は、121℃−
1hr処理、射出成形板は100℃−24hr処理）
(3) 溶出量分析：IR分析法
試料（20〜50mg／粒のペレツト）40ｇをガラ
ス容器に入れ、蒸留水200mlを加え、蒸気釜に
て121℃−1hr処理。その溶出液50mlにあらかじ
め調整された微粉CaCO3（平均粉径1μ以下）10
mgとKBr200mgのブレンド物から10mgを取り、
KBr錠剤法でIR分析し、1020cm-1log Io／I870
cm-1log I1／Ｉの強度比を算出し、あらかじめ
作成している検量線より透明化剤のDMBSの
溶出量（ppm）を求める。
備考 1020cm-1：DMBSの特性吸収帯
870cm-1：CaCO3の特性吸収帯
(4) 成形性試験8oz射出成形機の一般的成形条件
（250℃）で連続100シヨツト以上、テストピー
ス（３mmt）を成形し、主として金型からの離
型性を比較評価。
(5) 熱安定性試験：JIS K7212に準拠。
0.5mmtシートの150℃オーブンでの1/3面積劣
化時間。
実施例 １〜２
ポリプロピレン系樹脂100重量部に対しDMBS
と乳酸カルシウムの第１表記載量を配合し、ヘン
シエルミサーで十分混合した。
得られた混合物40ｍ／ｍφ押出機を用いて、樹
脂温度260℃でペレツト化し、テストピースを射
出成形した。
次に得られたペレツト用いて前述の溶出試験を
実施し、溶出量分析を行つた。又、これらペレツ
トを0.5mmシートに溶融プレス成形し、熱安定性
試験を行つた。
得られた射出テストピースについては、水中に
没した状態で、100℃−24hr処理前後の曇り度を
測定した。
これらの結果はいずれも次に示す比較例に比べ
DMBSの溶出量及び曇り度低下がいちじるしく
少なく、且つ良好な成形性及び熱安定性であつ
た。
比較例 １〜７
実施例１〜２において乳酸カルシウムの代りに
代表的な脂肪酸の第族金属塩を配合した場合、
並びに配合しなかつた他は、実施例１〜２と全く
同様に行つた。
従来公知のDMBSと脂肪酸第族金属塩の配
合試料はDMBSの溶出量が多く、曇り度低下も
大なるものであり、実施例１〜２に比較し、劣る
ものであつた。
一方、配合しないものは、成形性及び熱安定性
が配合したものに比し、不良であつた。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved transparent polypropylene resin composition, and in particular to food containers and packaging materials and medical instruments, which prevent the transparency agent from escaping into water or hot water. The present invention relates to a polypropylene resin composition useful for, etc. As a method for improving the transparency of polypropylene-based resins, JP-A-53-117044 describes adding 1,3,2,4-di(methylbenzylidene) sorbitol (hereinafter simply referred to as sorbitol) to polypropylene or its copolymer.
It has been proposed to blend DMBS (abbreviated as DMBS) and heat-form it. On the other hand, it can be used as a chlorine scavenger in the catalyst residue of polypropylene resins, to improve the fluidity of the resins, to improve the releasability from molds, and as a dispersant for other additives and pigments. Generally, metal salts of higher fatty acids such as calcium stearate and zinc stearate are added as stabilizers or lubricants. However, DMBS, the above-mentioned clarifying agent, is used in polypropylene resins.
When a metal salt of a higher fatty acid as a lubricant or stabilizer is used in combination, the resulting polypropylene resin composition is resistant to water, hot water, or steam.
Since DMBS is easily washed away or escaped, it not only causes health and safety problems particularly in the fields of food containers and packaging materials and medical equipment, but also has the disadvantage of impairing the long-term sustainability of transparency. As a result of intensive studies to solve the above-mentioned problems of polypropylene resin compositions using DMBS, the present inventors discovered that a specific compound can be mixed into a mixture of polypropylene resin and DMBS, and the present invention I have come to propose this. That is, the present invention provides polypropylene resin, 1.
This is a polypropylene resin composition consisting of 3,2,4 di(methylbenzylidene) sorbitol and calcium lactate. The resin composition of the present invention can completely prevent elution or escape of DMBS from conventional DMBS-blended products simply by blending calcium lactate without blending the conventionally known metal salts of higher fatty acids. Furthermore, these compositions do not impair the moldability, fluidity, mold releasability, thermal stability, etc. of conventionally known products containing higher fatty acid metal salts. The polypropylene resin used in the present invention is a propylene homopolymer, or one or more of polypropylene with a propylene content of 70% by weight or more and ethylene, butene, pentene, vinyl acetate, vinyl chloride, etc. A copolymer consisting of
and blends of these polymers. 1,3,2,4-di(methylbenzylidene) sorbitol used in the present invention is a condensate of tolualdehyde and sorbitol, and any known method for producing the same can be used without particular limitation. The blending ratio of the above resin composition may be appropriately selected depending on the application, but in particular, polypropylene resin
It is preferable to mix 0.01 to 1 part by weight of DMBS and 0.01 to 1 part by weight of calcium lactate to 100 parts by weight, since the effects of the present invention are exhibited very markedly. The resin composition of the present invention may also contain antioxidants, antistatic agents, lubricants, dispersants, pigments, fluorescent agents, bactericides, light stabilizers, ultraviolet absorbers, metal deactivators, and Additives such as photodegradation inhibitors can also be added within a range that does not significantly reduce the effects of the present invention. A desired molded article can be obtained from the resin composition of the present invention by kneading and molding using conventional methods. The present invention will be specifically explained below based on Examples, but the present invention is not particularly limited to the Examples below. The measurement methods used in the following Examples and Comparative Examples are shown below. (1) Haze: Conforms to ASTM D1003-61 (measured on 3mm t of injection molded plate) (2) Elution test: Conforms to the medical device testing method announced by the Ministry of Health and Welfare. (However, the pellet dissolution test was conducted at 121℃-
(1 hour treatment, 100℃-24 hour treatment for injection molded plates) (3) Elution amount analysis: IR analysis method Put 40 g of sample (20-50 mg/granule pellets) into a glass container, add 200 ml of distilled water, and heat in a steam pot. Treatment at 121°C for 1 hour. Pre-adjusted fine powder CaCO 3 (average powder diameter 1 μ or less) in 50 ml of the eluate 10
Take 10mg from a blend of mg and KBr200mg,
IR analysis using KBr tablet method, 1020cm -1 log Io/I870
The intensity ratio of cm -1 log I 1 /I is calculated, and the elution amount (ppm) of the clarifying agent DMBS is determined from a calibration curve prepared in advance. Remarks 1020cm -1 : Characteristic absorption band of DMBS 870cm -1 : Characteristic absorption band of CaCO 3 (4) Molding test 100 continuous shots or more under general molding conditions (250℃) of 8oz injection molding machine, test piece (3mm t) ) was molded, and the comparative evaluation was mainly performed on the releasability from the mold. (5) Thermal stability test: Compliant with JIS K7212. 1/3 area deterioration time of 0.5mm T sheet in 150℃ oven. Examples 1-2 DMBS for 100 parts by weight of polypropylene resin
and calcium lactate in the amounts listed in Table 1 and thoroughly mixed in a Henschel mixer. The resulting mixture was pelletized using a 40 m/mφ extruder at a resin temperature of 260° C., and test pieces were injection molded. Next, the above-mentioned dissolution test was carried out using the obtained pellets, and the dissolution amount was analyzed. In addition, these pellets were melt press-molded into 0.5 mm sheets and a thermal stability test was conducted. The obtained injection test piece was submerged in water, and its haze level was measured before and after treatment at 100°C for 24 hours. All of these results are compared to the comparative example shown below.
The amount of DMBS eluted and the decrease in haze were significantly small, and the moldability and thermal stability were good. Comparative Examples 1 to 7 In Examples 1 to 2, when typical group metal salts of fatty acids were blended instead of calcium lactate,
The same procedure as in Examples 1 and 2 was carried out except that the ingredients were not blended. The conventionally known blended sample of DMBS and fatty acid group metal salt had a large amount of DMBS eluted and a large decrease in haze, and was inferior to Examples 1 and 2. On the other hand, the moldability and thermal stability of those without the mixture were poorer than those with the mixture. 【table】
Claims (1)
（メチルベンジリデン）ソルビトール及び乳酸カ
ルシウムよりなるポリプロピレン系樹脂組成物。 ２ ポリプロピレン系樹脂100重量部に対して、
１・３，２・４−ジ（メチルベンジリデン）ソル
ビトール0.01〜１重量部と乳酸カルシウム0.01〜
１重量部を配合した特許請求の範囲第１項記載の
樹脂組成物。[Scope of Claims] 1. A polypropylene resin composition comprising a polypropylene resin, 1,3,2,4-di(methylbenzylidene)sorbitol, and calcium lactate. 2 For 100 parts by weight of polypropylene resin,
0.01 to 1 part by weight of 1,3,2,4-di(methylbenzylidene)sorbitol and 0.01 to 1 part by weight of calcium lactate
The resin composition according to claim 1, containing 1 part by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20629188A JPS6479241A (en) | 1983-05-19 | 1988-08-22 | Polypropylene resin composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58086653A JPS59213747A (en) | 1983-05-19 | 1983-05-19 | Polypropylene resin composition |
| JP20629188A JPS6479241A (en) | 1983-05-19 | 1988-08-22 | Polypropylene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6479241A JPS6479241A (en) | 1989-03-24 |
| JPH0512388B2 true JPH0512388B2 (en) | 1993-02-17 |
Family
ID=26427760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20629188A Granted JPS6479241A (en) | 1983-05-19 | 1988-08-22 | Polypropylene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6479241A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58104933A (en) * | 1981-12-18 | 1983-06-22 | New Japan Chem Co Ltd | Polyolefin resin composition |
-
1988
- 1988-08-22 JP JP20629188A patent/JPS6479241A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58104933A (en) * | 1981-12-18 | 1983-06-22 | New Japan Chem Co Ltd | Polyolefin resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6479241A (en) | 1989-03-24 |
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