JPH01126352A - Di-substituted benzylidienesorbitol composition - Google Patents
Di-substituted benzylidienesorbitol compositionInfo
- Publication number
- JPH01126352A JPH01126352A JP28433087A JP28433087A JPH01126352A JP H01126352 A JPH01126352 A JP H01126352A JP 28433087 A JP28433087 A JP 28433087A JP 28433087 A JP28433087 A JP 28433087A JP H01126352 A JPH01126352 A JP H01126352A
- Authority
- JP
- Japan
- Prior art keywords
- higher fatty
- composition
- fatty acid
- sorbitol
- solid powder
- 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 30
- 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 claims abstract description 31
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 25
- 229930195729 fatty acid Natural products 0.000 claims abstract description 25
- 239000000194 fatty acid Substances 0.000 claims abstract description 25
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 22
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 16
- 235000021357 Behenic acid Nutrition 0.000 claims abstract description 9
- 229940116226 behenic acid Drugs 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 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 8
- 239000000600 sorbitol Substances 0.000 claims description 8
- YXNWJSNQLUUFMR-ZZVYKPCYSA-N (2R,3R,4S,5R)-5-methyl-7-phenylhept-6-ene-1,2,3,4,5,6-hexol Chemical compound C[C@@](C(O)=CC1=CC=CC=C1)(O)[C@@H](O)[C@H](O)[C@H](O)CO YXNWJSNQLUUFMR-ZZVYKPCYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 229940087101 dibenzylidene sorbitol Drugs 0.000 abstract description 8
- 239000000839 emulsion Substances 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- 230000009965 odorless effect Effects 0.000 abstract description 2
- 229920000098 polyolefin Polymers 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- NWXADGGHXYSLSP-IYWMVGAKSA-N (3s,4s,5s,6r)-1,8-diphenylocta-1,7-diene-2,3,4,5,6,7-hexol Chemical class OC([C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=CC=1C=CC=CC=1)=CC1=CC=CC=C1 NWXADGGHXYSLSP-IYWMVGAKSA-N 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 229920005672 polyolefin resin Polymers 0.000 description 14
- -1 polyethylene Polymers 0.000 description 10
- 235000019645 odor Nutrition 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- 150000003935 benzaldehydes Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 229910014033 C-OH Inorganic materials 0.000 description 2
- 229910014570 C—OH Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- HZVFRKSYUGFFEJ-YVECIDJPSA-N (2r,3r,4s,5r)-7-phenylhept-6-ene-1,2,3,4,5,6-hexol Chemical class OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=CC1=CC=CC=C1 HZVFRKSYUGFFEJ-YVECIDJPSA-N 0.000 description 1
- CHMCAIRITMOPFF-CGXNFDGLSA-N (3R,4S,5R,6S)-3-methyl-1,8-diphenylocta-1,7-diene-2,3,4,5,6,7-hexol Chemical compound C[C@@](C(O)=CC1=CC=CC=C1)(O)[C@@H](O)[C@H](O)[C@H](O)C(O)=CC1=CC=CC=C1 CHMCAIRITMOPFF-CGXNFDGLSA-N 0.000 description 1
- 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 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はジベンジリデンソルビトール誘導体に基づく組
成物、殊にポリオレフィン樹脂成形品の透明性、非ブリ
ード性及び無臭性の改善に添加剤として使用した場合極
めて有用な、ジベンジリデンソルビトール誘導体に基づ
く、組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention discloses dibenzylidene sorbitol derivatives which are extremely useful when used as additives for improving the transparency, non-bleeding and odorlessness of polyolefin resin molded articles. Compositions based on sorbitol derivatives.
ジベンジリデンソルビトール並びにジベンジリデンソル
ビトール誘導体である1、3−2.4−Pメチルジベン
ジリデンソルビトール、1.3−2゜4−ジルエチルジ
ベンジリデンソルビトール、1゜3−pクロルベンジリ
デン−2,4−Pメチルベンジリデンソルビトール等は
ポリエチレン、ポリプロピレンのようなポリオレフィン
樹脂に配合することによって、それらの樹脂の成形品の
透明性が改善されることは知られている(特開昭53−
117044、特公昭51−5499及び米国特許第4
,016,118号、米国特許第4.483 。Dibenzylidene sorbitol and dibenzylidene sorbitol derivatives such as 1,3-2.4-P methyldibenzylidene sorbitol, 1.3-2゜4-diethyldibenzylidene sorbitol, 1゜3-p chlorobenzylidene-2,4- It is known that by blending P-methylbenzylidene sorbitol and the like with polyolefin resins such as polyethylene and polypropylene, the transparency of molded products of those resins is improved (Japanese Patent Application Laid-Open No. 1983-1972).
117044, Japanese Patent Publication No. 51-5499 and U.S. Patent No. 4
, 016,118, U.S. Patent No. 4.483.
952号参照)。(See No. 952).
上記の先行諸技術を改善し、より少量のジベンジリデン
ソルビトールの添加量により従来法と同等の透明性を与
え、且つ併せて剛性及び非ブリード性をも改善する技術
を本発明者は先に提案した(特開昭57−21.440
号)、この特開昭57−21440号では、ジベンジリ
デンソルビトールの固体粉末と高級脂肪酸を含有してな
り、該高級脂肪酸がジベンジリデンソルビトール固体粉
末の表面を被覆して含有される組成物が開示されている
。 上記特開昭57−21440号による組成物はポリ
オレフィン樹脂に、添加剤として配合した場合、実際の
市場において可成り高い評価を得たが、ポリオレフィン
樹脂の成形品が食品容器や化粧品容器等に用いられた場
合、僅がな異臭が該成形品の需要の伸びを著しく阻害し
ていることがその後次第に明らかとなって来た。The present inventor has previously proposed a technique that improves the above-mentioned prior art and provides transparency equivalent to the conventional method by adding a smaller amount of dibenzylidene sorbitol, and also improves rigidity and non-bleeding property. (Unexamined Japanese Patent Publication No. 57-21.440
JP-A-57-21440 discloses a composition containing a solid powder of dibenzylidene sorbitol and a higher fatty acid, the higher fatty acid coating the surface of the solid powder of dibenzylidene sorbitol. has been done. When the composition disclosed in JP-A No. 57-21440 was blended with polyolefin resin as an additive, it received a fairly high evaluation in the actual market, but molded products of polyolefin resin were used in food containers, cosmetic containers, etc. Since then, it has become increasingly clear that even slight off-odors are significantly inhibiting the growth in demand for molded products.
本発明者は、従来技術の有した上記の諸欠点を改善すべ
く研究を重ねて来た結果、本願発明を完成するに至った
ものである。The present inventor has completed the present invention as a result of repeated research to improve the above-mentioned drawbacks of the prior art.
本発明によれば、必須成分として、一般式(N■
−C−OH
H−C−OH(1)
[式中、R及びR′は、それぞれ独立して、塩素原子、
メチル基及びエチル基よりなる群より選ばれる原子また
は基を表ず]
のジベンジリデンソルビトール誘導体の固体粉末と式(
n)
CH3(CH2)ncOOH(If )[式中、nは1
4〜30好ましくは18〜22、最も好ましくは20の
数を表すコの高級脂肪酸を含有してなり、該高級脂肪酸
が該ジベンジリデンソルビトール誘導体の固体粉末の表
面を被覆して含有されているジベンジリデンソルビトー
ル誘導体組成物が提供される。According to the present invention, as an essential component, the general formula (N■ -C-OH H-C-OH (1) [wherein R and R' are each independently a chlorine atom,
represents an atom or group selected from the group consisting of a methyl group and an ethyl group] and a solid powder of a dibenzylidene sorbitol derivative with the formula (
n) CH3(CH2)ncOOH(If) [where n is 1
4 to 30, preferably 18 to 22, most preferably 20 higher fatty acids, and the higher fatty acids are contained by coating the surface of the solid powder of the dibenzylidene sorbitol derivative. Benzylidene sorbitol derivative compositions are provided.
本発明で用いられる一般式(II)のジベンジリデンソ
ルビトール誘導体としては、1.3−12゜4−ジルメ
チルベンジリデンソルビトール、]。The dibenzylidene sorbitol derivative of general formula (II) used in the present invention includes 1.3-12°4-methylbenzylidene sorbitol.
]3−12,4−ジpエチルベンジリデンソルビトール
1.3−Pメチルベンジリデン−2,4−Pクロルベン
ジリデンソルビトール、1.3−pメチルベンジリデン
−2,4−pエチルベンジリデンソルビトール及び、1
.3− Pクロルベンジリデン−2,4pメチルベンジ
リデンソルビトール等を例示することができる。]3-12,4-di p-ethylbenzylidene sorbitol 1.3-p methylbenzylidene-2,4-P chlorobenzylidene sorbitol, 1.3-p methylbenzylidene-2,4-p ethylbenzylidene sorbitol, and 1
.. Examples include 3-P chlorobenzylidene-2,4p methylbenzylidene sorbitol.
本発明の好ましい態様においては、上記一般式(1)に
おいて、R及びR′は、それぞれ独立してメチル基また
は塩素原子を表す、ジベンジリデンソルビトール誘導体
が用いられる。In a preferred embodiment of the present invention, a dibenzylidene sorbitol derivative is used in which R and R' each independently represent a methyl group or a chlorine atom in the above general formula (1).
殊に好適なジベンジリデンソルビトール誘導体は、1.
3−2.4−ジルメチルベンジリデンソルビトール、1
.3− Pメチルベンジリデン−2,4−pクロルベン
ジリデンソルビトール及び1,3−pクロルベンジリデ
ン−2,4−pメチルベンジリデンソルビトール、であ
る。Particularly preferred dibenzylidene sorbitol derivatives are: 1.
3-2.4-Zylmethylbenzylidene sorbitol, 1
.. 3-P methylbenzylidene-2,4-p chlorobenzylidene sorbitol and 1,3-p chlorobenzylidene-2,4-p methylbenzylidene sorbitol.
本発明で用いられる式(If)の高級脂肪酸の好ましい
例は、ベヘン酸、ステアリン酸およびバルミチン酸であ
り、なかでもベヘン酸が最も好ましく、ステアリン酸が
これに次ぐ。Preferred examples of the higher fatty acids of formula (If) used in the present invention are behenic acid, stearic acid and valmitic acid, of which behenic acid is most preferred, followed by stearic acid.
本発明の組成物において使用されるジベンジリデン誘導
体の固体粉末の粒径は、格別な制限は必要でなく、粒度
分布30〜100メツシユのものが好適に用いられる。There is no particular restriction on the particle size of the solid powder of the dibenzylidene derivative used in the composition of the present invention, and those having a particle size distribution of 30 to 100 mesh are preferably used.
本発明の組成物は、ジベンジリデン誘導体の95〜50
重量部、好ましくは90〜50重盪部に対し高級脂肪酸
を5〜50重景部置火ましくは10〜50重量部の範囲
において、青成分の合計が100重蓋部になる割合で含
貞する。The composition of the present invention has a dibenzylidene derivative of 95 to 50%.
The higher fatty acid is contained in an amount of 5 to 50 parts by weight, preferably 90 to 50 parts by weight, or 10 to 50 parts by weight, so that the total of the blue components is 100 parts by weight. Be faithful.
本発明の組成物は、上記割合の高級脂肪酸を含有する水
性エマルジョンに上記割合のジベンジリデンソルビトー
ル誘導体の固体粉末を添加撹拌して、ジベンジリデンソ
ルビトール誘導体の固体粉末の表面上に高級脂肪酸の被
覆層を形成させ、高級脂肪酸被覆を有するジベンジリデ
ンソルビトール誘導体粉末を炉別後、洗浄及び乾燥を行
うことによって作ることができる。The composition of the present invention is prepared by adding and stirring solid powder of a dibenzylidene sorbitol derivative in the above proportion to an aqueous emulsion containing higher fatty acids in the above proportion, and forming a coating layer of higher fatty acid on the surface of the solid powder of the dibenzylidene sorbitol derivative. It can be produced by forming a dibenzylidene sorbitol derivative powder coated with a higher fatty acid by furnace separation, followed by washing and drying.
上記方法において使用する高級脂肪酸の水性エマルジョ
ンは、例えば、高級脂肪酸の濃度5〜50重量%、好ま
しくは10〜50重量%、の有機溶媒溶液に、界面活性
剤を少量、例えば高級脂肪酸100重量部に対して1〜
10重電部、好ましくは2〜5重蓋部、を用いて水中に
分散させることによって容易に得ることができる。The aqueous emulsion of a higher fatty acid used in the above method is, for example, a solution of a higher fatty acid in an organic solvent with a concentration of 5 to 50% by weight, preferably 10 to 50% by weight, and a small amount of a surfactant, for example, 100 parts by weight of a higher fatty acid. 1 to
It can be easily obtained by dispersing it in water using 10 parts, preferably 2 to 5 parts.
また、ジベンジリデンソルビトール誘導体の固体粉末の
表面上に形成された高級脂肪酸の被覆の存在は、後記の
実施例で詳述するように、該被覆を染料で染色して観察
することによって確認することができる。In addition, the presence of a higher fatty acid coating formed on the surface of the solid powder of the dibenzylidene sorbitol derivative can be confirmed by dyeing and observing the coating with a dye, as detailed in the Examples below. Can be done.
本発明の組成物が、透明性、非ブロード性及び無臭性の
改善のために添加剤として使用される対象のポリオレフ
ィン樹脂の例は、炭素数が2〜6の脂肪族モノオレフィ
ンの数平均分子量的10.000〜約200,000、
好ましくは約30.000〜約150,000の重合体
または共重合体、例えばポリプロピレン、低密度ポリエ
チレン、高密度ポリエチレン、リニヤ−ポリエチレンお
よびエチレン−プロピレン共重合体等である。Examples of target polyolefin resins for which the composition of the present invention is used as an additive to improve transparency, non-broad properties, and odorlessness are aliphatic monoolefins having a number average molecular weight of 2 to 6 carbon atoms. Target 10,000 to about 200,000,
Preferred are polymers or copolymers of from about 30,000 to about 150,000, such as polypropylene, low density polyethylene, high density polyethylene, linear polyethylene and ethylene-propylene copolymers.
本発明の組成物においては、ポリオレフィン樹脂100
重it部に対して、ジベンジリデンソルビトール誘導体
成分として0.05〜15〜1重蓋ましくは、0.1〜
0.5置火部、に相当する高級脂肪酸で被覆されたジベ
ンジリデンソルビトール誘導体が好適に使用される。In the composition of the present invention, polyolefin resin 100
The dibenzylidene sorbitol derivative component is 0.05 to 15 to 1, or 0.1 to 1, based on the heavy it part.
A dibenzylidene sorbitol derivative coated with a higher fatty acid corresponding to 0.5 parts of heat is preferably used.
本発明の組成物は、ポリオレフィン樹脂に任意公知の混
合手段で混合することによって配合することができる。The composition of the present invention can be blended with a polyolefin resin by mixing it with any known mixing means.
また、本発明の組成物は、必要に応じて、該組成物を濃
厚量で含有するポリオレフィン樹脂中のマスターバッチ
としても用いることができる。The composition of the present invention can also be used as a masterbatch in a polyolefin resin containing a concentrated amount of the composition, if necessary.
本発明の組成物においては、ジベンジリデンソルビトー
ル誘導体の固体粒子の表面が高級脂肪酸で被覆されてい
ることが重要で、ポリオレフィン樹脂にジベンジリデン
ソルビトール誘導体及び高級脂肪酸を単に添加混合して
も本願発明の効果は達成されない。In the composition of the present invention, it is important that the surface of the solid particles of the dibenzylidene sorbitol derivative is coated with a higher fatty acid, and even if the dibenzylidene sorbitol derivative and the higher fatty acid are simply added and mixed to the polyolefin resin, the present invention can be achieved. No effect is achieved.
かくて、本発明の組成物は、従来技術に較べ、ポリオレ
フィン樹脂に配合した場合、透明性、耐ブリード性、剛
性等の諸特性を何ら損はないばかりか、場合によっては
これ等諸特性を更に向上させ、同時に優れた無臭性を有
し、併せて成形品内部に白点が出にくくなり且つ耐水失
透性が向上するといった優れた効果を奏するものである
1本発明の組成物を用いれば、ポリオレフィン樹脂の成
形品、例えばフィルム、容器等において従来実現ができ
なかった無臭性をも上記諸特性と共に同時に満足するこ
とができるもので、ポリオレフィン成形品に対し、化粧
品や食品等の分野において、更に一層広い利用分野の開
拓を始めて可能としたものである。Thus, compared to the prior art, when the composition of the present invention is blended with a polyolefin resin, it not only does not impair properties such as transparency, bleed resistance, and rigidity, but in some cases improves these properties. When using the composition of the present invention, the composition of the present invention has excellent odorlessness, reduces the appearance of white spots inside the molded product, and improves water devitrification resistance. For example, it is possible to simultaneously satisfy the above characteristics as well as odorlessness, which was previously impossible to achieve in polyolefin resin molded products such as films and containers, and it is suitable for polyolefin molded products in the fields of cosmetics and food products. This made it possible for the first time to develop an even wider field of use.
本発明の組成物が上記の優れた効果を奏する理由は必ず
しも明らかでないが、前記特開昭57−21440号の
ジベンジリデンソルビトールの製造原料であるベンズア
ルデヒド及び本発明のジベンジリデンソルビトール誘導
体の製造原料であるρ置換ベンズアルデヒド等のベンズ
アルデヒド誘導体には臭気があって、共に精製後も不可
避的にジベンジリデンソルビトール(誘導体)に微蓋残
留してポリオレフィン樹脂成形品の異臭の原因となりが
ちなこと及びジベンジリデンソルビトール(誘導体)が
ポリオレフィンの成形品の成形時にも若干分解を起こし
て異臭の原因となることが考え得る0本発明の組成物に
おいては、(1) −i式(I)の特定のジベンジリデ
ンソルビトール誘導体の固体粒子を用い、(2)該粒子
を一般式(II)の特定の高級脂肪酸で被覆する、とい
った(1)及び(2)の要件を同時に満足することによ
って、原料ベンズアルデヒド類或いは分解生成したベン
ズアルデヒド類に基づくと推定される異臭が、ポリオレ
フィン樹脂成形品において顕著に減少され且つ透明性等
の上記諸物性も同時に優れているといった効果が奏され
る。The reason why the composition of the present invention exhibits the above-mentioned excellent effects is not necessarily clear, but it is possible that benzaldehyde, which is the raw material for producing dibenzylidene sorbitol of JP-A No. 57-21440, and the raw material for producing the dibenzylidene sorbitol derivative of the present invention. Benzaldehyde derivatives such as certain ρ-substituted benzaldehydes have odors, and even after purification, a slight amount of benzaldehyde derivatives inevitably remain in dibenzylidene sorbitol (derivatives), which tends to cause off-odor in polyolefin resin molded products. In the composition of the present invention, (1) -i specific dibenzylidene sorbitol of formula (I) By simultaneously satisfying the requirements (1) and (2) of using solid particles of the derivative and (2) coating the particles with a specific higher fatty acid of general formula (II), raw benzaldehydes or decomposition products can be treated. The effects of the polyolefin resin molded article are that the off-odor that is presumed to be caused by the benzaldehydes is significantly reduced, and the above-mentioned physical properties such as transparency are also excellent.
以下に、実施例により更に詳しく本発明を説明する0部
数及びパーセントの表示は特にことわりのない限り重電
に基づく、なお、透明性(ヘイズ値)、耐ブリード性(
ブリードアウト)及び無臭性は次の方法によって測定し
た。In the following, the present invention will be explained in more detail with reference to Examples. Unless otherwise specified, the number of copies and percentages are based on heavy electrical equipment, and transparency (haze value), bleed resistance (
Bleed-out) and odorlessness were measured by the following methods.
(イ) ヘイズ値: ASTM DlooI−9T
(ロ) ブリードアウト: 実施例3のポリオレフィン
樹脂組成物を用いて射出成形
を用い、射出回数100回後の金型に
曇りがでるか否かで判定した6
(ハ) 無臭性: 20〜25才の女子10名による官
能試験を行った。即ち、午前
10時頃女子10名によって試験片に
ついて異臭の有無の程度を下記5段階
に評価させた:
1、 全く匂いはない
2、 何か判らないが臭気らしいものを感じる
3、 臭気を感じる
4゜ 強い臭気を感じる
5、 甚だ強い臭気を感じる、
実施例3の表の無臭性の欄の数値は、
10名中最も多数であった評価段階の
数値で示した。(a) Haze value: ASTM DlooI-9T (b) Bleedout: Injection molding was performed using the polyolefin resin composition of Example 3, and judgment was made based on whether fog appeared on the mold after 100 injections. 6 (c) Odorlessness: A sensory test was conducted by 10 girls aged 20 to 25. That is, around 10 a.m., 10 women evaluated the presence or absence of a strange odor on the test piece using the following 5 levels: 1. There is no odor at all 2. I don't know what it is, but I feel something like an odor 3. I feel an odor 4. I feel a strong odor. 5. I feel a very strong odor. The values in the odorless column of the table of Example 3 are shown by the value of the evaluation stage that was the most popular among the 10 people.
実施例 1(組成物の製造)
ベヘン酸40部とメチルアルコール120部をグラスラ
イニングした容器に入れて加温し、60℃の温で撹拌溶
解させる0次に、ノニオン界面活性剤を1.2部添加し
温水150部を徐々に加えて撹拌し乳化させる。得られ
た乳化液に1.3−2.4−ジ・pメチルベンジリデン
ソルビトール60部を入れてよく撹拌し白色の粘性乳状
物を得る。これを炉別し温水で洗って活性剤を除去し、
乾燥して白色粉末100部を得た。Example 1 (Production of composition) 40 parts of behenic acid and 120 parts of methyl alcohol were placed in a glass-lined container and heated, stirred and dissolved at a temperature of 60°C.Next, 1.2 parts of a nonionic surfactant was added. 150 parts of warm water was gradually added and stirred to emulsify. 60 parts of 1.3-2.4-di-p-methylbenzylidene sorbitol was added to the obtained emulsion and stirred well to obtain a white viscous emulsion. This is separated into a furnace and washed with warm water to remove the activator.
After drying, 100 parts of white powder was obtained.
得られた生成物5gを内容100ccのガラスビーカー
にとり、高級脂肪酸を染色する顕微鏡用色素ゲンケヤナ
バイオレットの0.1%水溶液20gを加えて撹拌する
と粉末は直ちに染色されて紫色の粘性液となり濾過して
乾燥すると全表面が紫色に染色された粉末をうる。When 5 g of the obtained product was placed in a 100 cc glass beaker and 20 g of a 0.1% aqueous solution of Genkeyana violet, a microscope dye that stains higher fatty acids, was added and stirred, the powder was immediately dyed and turned into a purple viscous liquid, which was filtered. When dried, a powder is obtained which is dyed purple on the entire surface.
しかし表面を被覆していないジーpメチルベンジリデン
ソルビトールは上記と同じ色素で処理しても全く染色さ
れない0以上の試験からその表面上を高級脂肪酸で完全
に被覆して入ることがわかる。However, it can be seen from the test of 0 or more that G-p methyl benzylidene sorbitol, whose surface is not coated, is completely coated with higher fatty acids even when treated with the same dye as mentioned above, showing no staining at all.
実施例 2(組成物の製造)
ベヘン酸の30部とメチルアルコール90部をグラスラ
イニングした容器に入れ60℃に加温してステアリン酸
を溶解させる。これに1部のノニオン型界面活性剤を添
加し温水150部を撹拌し乍ら徐々に加えて乳化させる
。得られた乳化液中に70部の1.3pクロルベンジリ
デン2.42メチルベンジリデンソルビトールを入れて
よく撹拌し白色の粘性乳状物を得る。これを涙別し温水
で洗って活性剤を除去し乾燥して白色粉末100部。Example 2 (Production of composition) 30 parts of behenic acid and 90 parts of methyl alcohol are placed in a glass-lined container and heated to 60°C to dissolve the stearic acid. To this was added 1 part of a nonionic surfactant, and 150 parts of warm water was gradually added while stirring to emulsify. 70 parts of 1.3p chlorobenzylidene and 2.42 methylbenzylidene sorbitol were added to the resulting emulsion and stirred thoroughly to obtain a white viscous emulsion. This was separated, washed with warm water to remove the active agent, and dried to produce 100 parts of white powder.
を得る。get.
このようにして得られた粉末を実施例1と同様にして試
験し、1,3pクロロベンジリデン2.4pメチルベン
ジリデンソルビトールの表面を完全にベヘン酸が被覆し
ていることを確かめられた。The powder thus obtained was tested in the same manner as in Example 1, and it was confirmed that the surface of 1,3p chlorobenzylidene, 2.4p methylbenzylidene sorbitol was completely coated with behenic acid.
実施例 3(組成物の応用)
エチレンプロピレン共重合のランダムコーポリマー(昭
和電工株式会社製ショウアロマ−MG410)のベレッ
トに実施例1及び実施例2で作つた組成物を下表の所定
1加えブレンダーで混合した樹脂組成物を射出温度24
0℃で射出成形して厚さ1mmの板状の試験片を作成し
た。Example 3 (Application of composition) The compositions prepared in Example 1 and Example 2 were added to a pellet of random copolymer of ethylene propylene (Showa Aroma-MG410, manufactured by Showa Denko K.K.) as specified in the table below. The resin composition mixed in a blender was heated to an injection temperature of 24
A plate-shaped test piece with a thickness of 1 mm was prepared by injection molding at 0°C.
比軟の為にジーpメチルーベンジリデンソルビトール、
1.3pクロルベンジリデン2,4pメチルベンジリデ
ンソルビトールおよびベヘン酸をそれぞれえ単味で使用
する以外は上記と同様にして作った試験片又ジベンジリ
デンソルビトール誘導体又はベヘン酸を全く配合しない
無添加のポリプロピレン樹脂を用いる以外は上記と同様
にして作った試験片についてもヘイズ値、ブリードアウ
ト及び無臭性について試験を行いその結果を下表にして
示す。Z-p methyl-benzylidene sorbitol for relative softness,
1.3p chlorobenzylidene 2,4p methylbenzylidene A test piece made in the same manner as above except that sorbitol and behenic acid were used alone, or an additive-free polypropylene resin containing no dibenzylidene sorbitol derivative or behenic acid. Test pieces prepared in the same manner as above except for using the above were also tested for haze value, bleed-out, and odorlessness, and the results are shown in the table below.
手続補正書(自発) 昭和62年12月15日Procedural amendment (voluntary) December 15, 1986
Claims (1)
メチル基及びエチル基よりなる 群より選ばれる原子または基を表す] のジベンジリデンソルビトール誘導体の固体粉末と式 CH_3(CH_2)nCOOH [式中、nは14〜30の数を表す] の高級脂肪酸を含有してなり、該高級脂肪酸が該ジベン
ジリデンソルビトール誘導体の固体粉末の表面を被覆し
て含有されているジベンジリデンソルビトール誘導体組
成物。 2、ジベンジリデンソルビトール誘導体が1,3−2,
4−ジpメチルベンジリデンソルビトールである特許請
求の範囲第1項に記載の組成物。 3、ジベンジリデンソルビトール誘導体が1,3−pメ
チルベンジリデン−2,4−pクロルベンジリデンソル
ビトールである特許請求の範囲第1項に記載の組成物。 4、ジベンジリデンソルビトール誘導体が、1,3−p
クロルベンジリデン−2,4−pメチルベンジリデンソ
ルビトールである特許請求の範囲第1項に記載の組成物
。 5、高級脂肪酸がベヘン酸である特許請求の範囲第1〜
4項の何れかに記載の組成物。[Claims] 1. As essential components, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R and R' each independently represent a chlorine atom,
represents an atom or group selected from the group consisting of a methyl group and an ethyl group] A solid powder of a dibenzylidene sorbitol derivative and a higher fatty acid of the formula CH_3(CH_2)nCOOH [where n represents a number from 14 to 30] A dibenzylidene sorbitol derivative composition comprising: the higher fatty acid coating the surface of a solid powder of the dibenzylidene sorbitol derivative. 2. Dibenzylidene sorbitol derivative is 1,3-2,
The composition according to claim 1, which is 4-di p methylbenzylidene sorbitol. 3. The composition according to claim 1, wherein the dibenzylidene sorbitol derivative is 1,3-p methylbenzylidene-2,4-p chlorobenzylidene sorbitol. 4. Dibenzylidene sorbitol derivative is 1,3-p
The composition according to claim 1, which is chlorobenzylidene-2,4-p methylbenzylidene sorbitol. 5. Claims 1 to 5, wherein the higher fatty acid is behenic acid.
The composition according to any one of Item 4.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62284330A JPH0826171B2 (en) | 1987-11-12 | 1987-11-12 | Di-substituted benzylidene sorbitol composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62284330A JPH0826171B2 (en) | 1987-11-12 | 1987-11-12 | Di-substituted benzylidene sorbitol composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01126352A true JPH01126352A (en) | 1989-05-18 |
JPH0826171B2 JPH0826171B2 (en) | 1996-03-13 |
Family
ID=17677165
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62284330A Expired - Lifetime JPH0826171B2 (en) | 1987-11-12 | 1987-11-12 | Di-substituted benzylidene sorbitol composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0826171B2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0522558A2 (en) * | 1991-07-09 | 1993-01-13 | MITSUI TOATSU CHEMICALS, Inc. | Process for stabilizing dibenzylidenesorbitols and composition thereof |
WO1998033851A1 (en) * | 1997-02-04 | 1998-08-06 | New Japan Chemical Co., Ltd. | Particulate diacetal composition, process for producing the same, and polyolefin resin composition and molding |
US6245843B1 (en) | 1997-10-03 | 2001-06-12 | New Japan Chemical Co., Ltd. | Diacetal composition, process for the preparation of the same, nucleating agent for polyolefins containing the same, polyolefin resin compositions, and moldings |
EP1505109A4 (en) * | 2002-05-02 | 2007-11-07 | New Japan Chem Co Ltd | Agent for inhibiting migration of odor and taste generated from diacetal, diacetal composition containing the agent for inhibiting odor and taste migration, nucleating agent for polyolefin comprising the composition, and polyolefin resin composition and molded object each containing the nucleating agent |
WO2019045014A1 (en) * | 2017-08-31 | 2019-03-07 | 株式会社Adeka | Clarifying agent composition, olefinic resin composition using same, and molded article thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5721440A (en) * | 1980-07-16 | 1982-02-04 | Iic Kagaku Kogyo Kk | Dibenzylidenesorbitol composition and production thereof |
-
1987
- 1987-11-12 JP JP62284330A patent/JPH0826171B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5721440A (en) * | 1980-07-16 | 1982-02-04 | Iic Kagaku Kogyo Kk | Dibenzylidenesorbitol composition and production thereof |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0522558A2 (en) * | 1991-07-09 | 1993-01-13 | MITSUI TOATSU CHEMICALS, Inc. | Process for stabilizing dibenzylidenesorbitols and composition thereof |
US5241080A (en) * | 1991-07-09 | 1993-08-31 | Mitsui Toatsu Chemicals, Inc. | Process for stabilizing dibenzylidenesorbitols and composition thereof |
WO1998033851A1 (en) * | 1997-02-04 | 1998-08-06 | New Japan Chemical Co., Ltd. | Particulate diacetal composition, process for producing the same, and polyolefin resin composition and molding |
US6417254B1 (en) | 1997-02-04 | 2002-07-09 | New Japan Chemical Co., Ltd. | Particulate diacetal composition, process for producing the same, and polyolefin resin composition and molding |
US6245843B1 (en) | 1997-10-03 | 2001-06-12 | New Japan Chemical Co., Ltd. | Diacetal composition, process for the preparation of the same, nucleating agent for polyolefins containing the same, polyolefin resin compositions, and moldings |
EP1505109A4 (en) * | 2002-05-02 | 2007-11-07 | New Japan Chem Co Ltd | Agent for inhibiting migration of odor and taste generated from diacetal, diacetal composition containing the agent for inhibiting odor and taste migration, nucleating agent for polyolefin comprising the composition, and polyolefin resin composition and molded object each containing the nucleating agent |
WO2019045014A1 (en) * | 2017-08-31 | 2019-03-07 | 株式会社Adeka | Clarifying agent composition, olefinic resin composition using same, and molded article thereof |
Also Published As
Publication number | Publication date |
---|---|
JPH0826171B2 (en) | 1996-03-13 |
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