JP2009155465A - Clearing agent composition and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a super fine powdery diacetal composition including diacetal and organosilane modified fumed silica, and having high dispersibility, and to provide a polyolefin composition to which the diacetal composition is added during polymerization of a polyolefin. <P>SOLUTION: A clearing agent composition consists of the diacetal powder and the organosilane modified fumed silica having a pH value of 5.5 to 8 as measured in 4 weight/weight% dispersed material in a 1:1 mixture of water and methanol. Diacetal is a D-sorbitol replaced with a (3-thenylidene) group, a (5-methyl-2-thenylidene) group, a (4-methyl-benzylidene) group, and a (3,4-dimethyl-benzylidene) group. A polyolefin plastic product having no visible white patches on its surface is produced with the super fine powdery diacetal composition having dispersion characteristics and its manufacturing method. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an organosilane-treated fumed silica having a pH value of 5.5 to 8 measured in a 4 wt / wt% dispersion in a 1: 1 mixture of azitol diacetal and water to methanol. % Of the improved clearing agent composition.

  The present invention also intends to provide a novel production method for producing an ultrafine powdered diacetal composition having high dispersibility.

  Finally, the invention also relates to the use of the above composition for producing a polyolefin plastic product without visible white spots on the surface of the corresponding product.

  Diacetal powders can be added to polymeric materials such as polyolefins as nucleating agents to promote crystallization, reduce molding time during melting, and improve the physical properties of the polyolefin. Diacetal powder can also be used as a clearing agent to increase the transparency of the semi-crystalline polymer.

  Basically, the mechanism of the diacetal powder as a clearing agent is described below. First, the diacetal powder is added to the polyolefin and melted at a suitable processing temperature. After the polyolefin cools, the diacetal crystallizes to form a crystallization network and many spherical nucleation sites in the polyolefin. The nucleation site is too small to reflect light and therefore becomes transparent. Thus, it is known that maintaining a small particle size and preventing agglomeration of diacetal serves as an important factor in improving polyolefin optical properties.

  As the particle size of the diacetal decreases, the amount of energy required for pulverization decreases, which generally results in reduced productivity and increased production costs. Furthermore, even if the size of the diacetal is reduced and the pulverizability is improved, the friction and aggregation of the diacetal particles are increased and the ratio of water adhering to the surface of the diacetal particles is increased under high humidity conditions. It has been pointed out that the sex decreases.

  If the particle size of the diacetal powder added to the polyolefin is too large or strongly agglomerated, the polyolefin often shows visible white spots. These white spots reject (or make defective) the production of the final plastic product. Therefore, the removal of visible white spots in polyolefins is an important issue in the art.

  US Pat. No. 5,198,484 (Mannion) described a conventional method for removing white spots in polyolefins by adding polar aliphatic additives to the polyolefin to disperse the diacetal powder. However, the aliphatic additive may migrate to the surface of the polyolefin and cause blooming. Another conventional method is to raise the processing temperature by 3 to 10 ° C. above the melting point of the diacetal. However, since the melting point of the diacetal is usually 50-100 ° C. higher than the melting point of the polyolefin, the polyolefin may be decomposed to form a yellowish odor product.

  U.S. Pat. No. 4,954,291 (Kabayashi et al.) Discloses a mixed diacetal composition comprising an acetal and a triacetal byproduct and having a low melting point. Unfortunately, this mixed diacetal composition has limited use as a clearing agent.

  Another conventional method for producing diacetals disclosed in Taiwan Patent No. 565562 (Scrivens et al.) Also creates problems for triacetals that are difficult to remove from acetal by-products and the desired diacetal. This method is also complex and limits the control of the diacetal size, which makes it difficult to disperse the diacetal in the polyolefin.

  There are common industrial approaches involving preblending powdered compounds and flow aids to improve flow characteristics. While various types of such fine powders of inorganic compounds are applicable, the use of silicon dioxide (silica) fine powders has generally been suggested.

  US Patent Application No. 2007-0060697 (Li et al.) Describes pre-blending a commercially available sorbitol acetal compound and hydrophobic silica to improve flow properties. Li et al., Aerosil ™ product line “R” series from Degussa AG and Sipernat ™ product line “D” series, Cabot. Some of the commercial quality of silica from the Cab-o-sil ™ product line “TG” series from the Include Aerosil ™ R972 and the Nanogel ™ product line and HDK ™ H15 Some samples were selected.

Commercially, the hydrophobic treatment of silica has been carried out using volatile silanes in a reactor heated at about 400 ° C. For example, a method utilizing a pyrolytic oxidation reaction in an oxyhydrogen flame of silicon tetrachloride gas has been used, where the following reaction occurs:
SiCl ₄ + H ₂ + O ₂ → SiO ₂ + 4HCl
Since it is not very easy to remove hydrogen chloride generated during this reaction, the resulting pH value of the hydrophobic silica drops to 3 or 4. In particular, the conventional organosilane-treated fumed silica obtained in the past has various problems such as the pH value and the amount to be added.

  Li et al. Disclosed a method comprising preblending acetal and hydrophobic silica having a low pH value. However, Li et al. Did not mention that the acidic state of hydrophobic silica probably caused the acetal degradation at polymer processing temperatures. Further, the hydrophobic silica Aerosil ™ R972 has a pH value of 4.2 when measured in a 4 wt / wt% dispersion in a 1: 1 mixture of water to methanol and HDK ™ H15 It is easy to obtain information from the supplier website that has a pH value of 3.8 to 4.8.

  Therefore, there is a need to provide a simple and inexpensive method for producing a clearing agent composition that has small particle size and non-aggregating properties and will not degrade at the polymer processing temperatures. The present invention provides an improved ultrafine powdered clearing agent composition and method for making it to alleviate and eliminate the above-described problems, and is further described below.

US Pat. No. 5,198,484 US Pat. No. 4,954,291 Taiwan Patent No. 565562

  The primary object of the present invention is to provide a clarifier composition that will not produce visible white spots in polyolefins.

The clearing agent according to the invention comprises an organosilane-treated fumed silica having a pH value of 5.5 to 8 measured in a 4 wt / wt% dispersion in a 1: 1 mixture of azitol diacetal and water to methanol. To 50% by weight.
The diacetal is represented by the general structural formula (I), (II), (III), (IV) or (V):

を有する。式中Ｒ^１およびＲ^２は独立して、Ｈ，Ｃ_１−Ｃ_４アルキル、Ｃ_１−Ｃ_４カルボアルコキシ，Ｆ，ＣｌおよびＢｒからなる群から選択され；ａは０，１，２または３であり；ｂは０，１，２または３であり；そしてｎは０または１である。

Have Wherein R ¹ and R ² are independently selected from the group consisting of H, C ₁ -C ₄ alkyl, C ₁ -C ₄ carboalkoxy, F, Cl and Br; a is 0, 1, 2 or 3 B is 0, 1, 2 or 3; and n is 0 or 1.

  The clearing agent of the present invention is excellent as a nucleating agent and a clearing additive for polyolefin plastic compositions.

  The present invention also relates to a polyolefin composition, characterized in that the clearing agent composition of the present invention is added during the polymerization of the polyolefin.

  The amount of clearing agent to be included in the polyolefin composition of the present invention is about 0.005 to about 2% by weight, preferably about 0.05 to 0.5% by weight, based on the weight of the polyolefin composition. Particularly preferably about 0.1 to 0.3% by weight.

  The invention also relates to a transparent polyolefin plastic product comprising the polyolefin composition of the invention.

  The term “polyolefin plastic product” as used herein is by way of example only a crystalline or semi-crystalline polyolefin product containing the above additives disclosed in the present invention for food or cosmetic containers or packaging Means.

  Preferably, the diacetal is 1,3: 2,4-di (3-tenylidene) -D-sorbitol, 1,3: 2,4-di (5-methyl-2-tenylidene) -D-sorbitol, 3: 2,4-di (4-methyl-benzylidene) -D-sorbitol, 1,3: 2,4-di (3,4-dimethyl-benzylidene) -D-sorbitol, 1,3- (3-tenylidene ) -2,4- (4-Methyl-benzylidene) -D-sorbitol, 1,3- (3-tenylidene) -2,4- (3,4-dimethyl-benzylidene) -D-sorbitol, 1,3- (5-Methyl-2-tenylidene) -2,4- (4-methyl-benzylidene) -D-sorbitol or 1,3- (5-methyl-2-tenylidene) -2,4- (3,4-dimethyl) -Benzylidene) -D- Is Rubitoru.

  Preferably, the organosilane-treated fume silica powder is 2-10% by weight of the clearing agent composition. The organosilane treated fume silica used in the present invention has a pH value of 5.5 to 8 measured in a 4 wt / wt% dispersion in a 1: 1 mixture of water to methanol.

  Conventional types of fumed silica treated with silicon halogen compounds such as dimethyldichlorosilane, methyltrichlorosilane, and trimethylchlorosilane produced hydrogen chloride during the above reaction, which was not completely removed and was about 0. 05% remains. Thus, it has a low pH value. However, in the case of fume silica treated with hexamethyldisilazane, dimethyl silicon liquid or polydimethylsiloxane in the present invention, hydrogen chloride is not produced and the problem of low pH value does not occur. During the treatment with hexamethyldisilazane, ammonia is produced in the reaction, but the resulting organosilane-treated fume silica exhibits a high pH value due to the alkalinity of the ammonia itself.

Organosilane-treated fumed silica having such properties can be readily produced by those skilled in the art according to the methods described above. PH value measured in a 4 wt / wt% dispersion in a mixture of H-2000 (fumed silica treated with hexamethyldisilazane, water to methanol 1: 1) by Wacker Chemicals East Asia Limited as a commercial product. 6.7-7.7, surface area 140 ± 30 m ² / g), TS-720 by Cabot Corporation (dimethylsilicone liquid and polydimethylsiloxane treated fume silica, 4 wt / wt% dispersion in a 1: 1 mixture of water to methanol) PH value 5.8 measured in the product, surface area 105-130 m ² / g), and TS-530 (Hexamethyldisilazane treated fume silica, water to methanol 1: 1 mixture by Cabot Corporation 4 In weight / weight% dispersion The measured pH 6.0, to no surface area 205 245m ² / g) can be used.

The polyolefin plastic compositions essentially comprise at least one homopolymer of an aliphatic mono-olefin or a copolymer of C ₂ -C ₈ alpha-mono-olefin, in particular a propylene polymer material and such a polyolefin polymer. Based on crystalline or semi-crystalline polyolefin polymer or polyolefin resin composition consisting of a mixture of coalesced (eg polypropylene). Well-known commercially available crystalline polypropylene products are usually solid and are primarily isotactic, semi-crystalline, thermoplastic homopolymers formed by the polymerization of propylene. As used herein, semi-crystalline means at least about 5-10% crystallinity as measured by X-ray diffraction.

  The clearing agent composition of the present invention comprises a condensation reaction by mixing an aromatic aldehyde, a polyol, and an acid catalyst in a polar solvent to form a reaction mixture, which is 4 wt / wt% in a 1: 1 mixture of water to methanol. Adding organosilane-treated fumed silica having a pH value of 5.5 to 8.0 measured in the dispersion to the reaction mixture, filtering, drying and grinding to form a clearing agent composition. Manufactured by. The equivalent ratio of aromatic aldehyde to polyol in the polar solvent is 2: 1 to 2: 2 (2: 1.05 to 2: 1.3 is preferred).

  The aromatic aldehyde may be thiophene carboxaldehyde or benzaldehyde and may be unsubstituted or from the group consisting of C1-C4 alkyl, C1-C4 alkoxy, C1-C4 carboxyalkoxy, F, Cl and Br. Has one, two or three selected substituents. The aromatic aldehyde may be a mixture of thiophene carboxaldehyde or benzaldehyde.

  Preferably, the thiophene carboxaldehyde may be 3-thiophene carboxaldehyde or 5-methyl-2-thiophene carboxaldehyde. The benzaldehyde can be 4-methyl-benzaldehyde or 3,4-dimethyl-benzaldehyde.

  The polyols defined here are a group of alcohols containing more than one alcohol group, referred to as sugar alcohols in food chemistry and can be sorbitol or xylitol. Preferably, the polyol is D-sorbitol.

  The acid catalyst used in the above reaction is sulfuric acid, phosphoric acid, hydrochloric acid, methanesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid or the like.

  The polar solvent used in the reaction can be methanol, ethanol, dimethylformamide (DMF) or acetonitrile.

  The condensation reaction can be performed at various temperatures. In the case of 3-thiophenecarboxaldehyde, for example, such a reaction is desirably performed at ambient or room temperature.

  An organosilane treated fume silica having a pH value of 5.5 to 8.0 measured in a 4 wt / wt% dispersion in a 1: 1 mixture of water to methanol as used in the present invention is added to the reaction mixture. Is done. Surprisingly, the freshener composition produced has a high flowability after drying and will not agglomerate. When this clarifier composition is added to a polyolefin, the clarifier composition promotes nucleation of the polyolefin and reduces haze of the polyolefin. Furthermore, the resulting polyolefin will not show visible white spots.

  Other objects, advantages and novel aspects of the present invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.

  The clarifier composition of the present invention comprises an organosilane-treated fumed silica having a pH value of 5.5 to 8 measured in a 4 wt / wt% dispersion in a 1: 1 mixture of azitol diacetal powder and water to methanol. 0.05 to 50% by weight. The diacetal is represented by the general structural formula (I), (II), (III), (IV) or (V):

を有する。式中Ｒ^１およびＲ^２は独立して、Ｈ，Ｃ_１−Ｃ_４アルキル、Ｃ_１−Ｃ_４カルボアルコキシ，Ｆ，ＣｌおよびＢｒからなる群から選択され；ａは０，１，２または３であり；ｂは０，１，２または３であり；そしてｎは０または１である。本発明で使用されるオルガノシラン処理ヒュームシリカは水対メタノール１：１の混合物中４重量／重量％分散物中で測定されたｐＨ値５．５ないし８を有し、上記透明剤組成物の０．０５ないし５０重量％である。

Have Wherein R ¹ and R ² are independently selected from the group consisting of H, C ₁ -C ₄ alkyl, C ₁ -C ₄ carboalkoxy, F, Cl and Br; a is 0, 1, 2 or 3 B is 0, 1, 2 or 3; and n is 0 or 1. The organosilane-treated fumed silica used in the present invention has a pH value of 5.5 to 8 measured in a 4 wt / wt% dispersion in a 1: 1 mixture of water to methanol, 0.05 to 50% by weight.

The method for producing the clearing agent composition includes the following steps:
Aromatic aldehyde, polyol and acid catalyst are mixed in a polar solvent to effect a condensation reaction to form a reaction mixture, wherein the equivalent ratio of aromatic aldehyde to polyol is from 2: 1 to 2: 2; And oreganosilane-treated fumed silica having a pH value of 5.5 to 8 measured in a 4 wt / wt% dispersion in a 1: 1 mixture of water to methanol was added to the reaction mixture, Filter, dry and grind to form a clearing agent composition, wherein the organosilane treated fume silica is 0.05 to 50% by weight of the clearing agent composition.

  The following examples further illustrate the invention but should not be construed as limiting the invention as defined in the appended claims. All parts and percentages in these examples are by weight unless otherwise indicated.

Preparation of 1,3: 2,4-di (3-tenylidene) -D-sorbitol A 1 liter, 4-necked cylindrical reaction flask with thermometer, nitrogen inlet and mechanical stirrer was charged with D-sorbitol (20.0 g, 0.110 mol), methanesulfonic acid (1.00 g), 3-thiophenecarboxaldehyde (25.0 g, 0.223 mol) and methanol (200 ml) were added to form a reaction mixture. The reaction mixture was stirred at room temperature for 48 hours and neutralized to pH 8-9 with 4% aqueous sodium hydroxide (NaOH) to form a precipitated product. The precipitated product is filtered, washed with 40% aqueous methanol, dried and crushed to give 1,3: 2,4-di (3-tenylidene) -D-sorbitol as a fine white powder ( 29.2 g, 72% yield): mp 237.0-239.8 ° C .; ¹ H NMR (500 MHz, d ₆ -DMSO) δ 7.49-7.48 (m, 4H), 7.13 ˜7.08 (m, 2H), 5,68 (s, 2H), 4.81 (d, 1H, J = 7.0 Hz), 4.38 (m, 1H), 4.13 to 4.09 (M, 3H), 3.89 (s, 1H), 3.81 to 3.71 (m, 1H), 3.63 to 3.57 (m, 1H), 3.483.39 (m, 1H) ). The produced powder was observed with an electron microscope at magnifications of 2000 and 5000 as shown in FIGS.

Preparation of Transparant Composition Containing 1,3: 2,4-Di (3-Tenylidene) -D-sorbitol and Organosilane-treated Fume Silica 1,3: 2,4-Di (3 -Tenylidene) -D-sorbitol is produced to form a precipitated product, to which the organosilane-treated fumed silica (3.0 g, CAB-O-SIL ™ TS720) is added to form a mixture. Formed. The mixture was dried and ground to give a white powder (33.5 g) with the following characteristics with high fluidity: melting point 237.2-240.1 ° C., ash content 8.1%. The produced powder was observed with an electron microscope at magnifications of 2000 and 5000 as shown in FIGS.

Preparation of modified 1,3: 2,4-di (3,4-dimethylbenzylidene) -D-sorbitol A 1000 liter stainless steel reaction tank equipped with a mechanical stirrer and a circulating temperature control jacket was charged with D-sorbitol (40 0.0 kg, 0.220 kg), methanesulfonic acid (0.8 kg), 3,4-dimethylbenzaldehyde (52.5 kg, 0.391 kg), 3-thiophenecarboxaldehyde (0.440 kg, 0.004 kg) ) And methanol (450 kg) to form a reaction mixture. The reaction mixture was stirred at 20-35 ° C. for 48 hours and neutralized with 4% aqueous sodium hydroxide (NaOH) to pH 8-9 to form a precipitated product. The precipitated product was collected by filtration, washed with 40% aqueous methanol, dried in a vertical dryer, crushed and modified 1,3: 2,4-di (3,4-dimethylbenzylidene) -D. -Sorbitol was obtained as a fine white powder (68.0 kg, 84% yield) with the following characteristics: melting point 257.9 ° C, crystal point 240.4 ° C and ash content 0.1%. The produced powder was observed with an electron microscope at magnifications of 2000 times and 5000 times as shown in FIGS.

Preparation of a clearer composition comprising modified 1,3: 2,4-di (3,4-dimethylbenzylidene) -D-sorbitol and organosilane-treated fumed silica Modified 1,3: 2,4 -Di (3,4-dimethylbenzylidene) -D-sorbitol was prepared as in Example 3 to form a reaction mixture and organosilane treated fumed silica (3.0 kg, CAB-O-SIL ™ TS720). ) Was added to the reaction mixture and the reaction mixture was neutralized to pH 8-9 before forming a precipitated product. The precipitated product was filtered, washed with 40% aqueous methanol, dried and crushed to give a composition (70.2 kg) having the following characteristics: melting point 269.2 ° C., crystal point 235.0 ° C. and Ash content 3.2%. The produced powder was observed with an electron microscope at magnifications of 2000 and 5000 as shown in FIGS.

Preparation of a clearer composition comprising modified 1,3: 2,4-di (3,4-dimethylbenzylidene) -D-sorbitol and organosilane-treated fumed silica Modified 1,3: 2,4 Di (3,4-dimethylbenzylidene) -D-sorbitol was prepared as in Example 3 to form a reaction mixture, and organosilane treated fumed silica (7.5 kg, CAB-O-SIL ™ TS720) ) Was added to the reaction mixture and the reaction mixture was neutralized to pH 8-9 before forming a precipitated product. The precipitated product was collected by filtration, washed with 40% aqueous methanol, dried and crushed to obtain a composition (73.7 kg) having an ash content of 9.3%. The produced powder was observed with an electron microscope at magnifications of 2000 and 5000 as shown in FIGS.

Preparation of a clarifying composition of 1,3: 2,4-di (4-methylbenzylidene) -D-sorbitol and organosilane treated fume silica in a 1000 liter stainless steel reaction tank with mechanical stirrer and circulation temperature control jacket D-sorbitol (40.0 kg, 0.220 kgol), methanesulfonic acid (1.0 kg), 4-methyl-benzaldehyde (47.9 kg, 0.399 kgol) and methanol (500 kg) are added to form a reaction mixture. did. The reaction mixture was stirred at 20-35 ° C. for 48 hours and neutralized with 4% aqueous sodium hydroxide (NaOH) to pH 8-9 to form a precipitated product. The precipitated product was collected by filtration and washed with a 40% aqueous methanol solution to obtain a wet cake (97.4 kg, solid content 71.8%).
This wet cake (collecting 1 kg) was mixed with organosilane-treated fume silica (308 g, CAB-O-SIL (trade name) TS720), dried in a vertical drying apparatus (10 liter scale), pulverized, and the above composition Product powder (987 g, ash content 29.2%) was obtained. The produced powder was observed with an electron microscope at magnifications of 2000 and 5000 as shown in FIGS.

Preparation of a clearing agent composition of 1,3: 2,4-di (4-methylbenzylidene) -D-sorbitol and organosilane-treated fume silica The above wet cake prepared in Example 6 (collecting 680 g) was treated with organosilane. It is mixed with treated fume silica (500 g, CAB-O-SIL ™ TS720), dried in a saddle dryer (10 liter scale), pulverized and powdered with the above composition (974 g, ash content 49.7). %). The produced powder was observed with an electron microscope at magnifications of 2000 and 5000 as shown in FIGS.

  The electron micrographs of FIGS. 1-14 show the above oreganosilane-treated fumed silica having a pH value of 5.5-8 measured in a 4 wt / wt% dispersion in a 1: 1 mixture of water to methanol. When added to diacetal, it shows that the clearing agent composition becomes finer. Furthermore, the addition of the organosilane-treated fume silica substantially prevents the powder produced from the clearing agent composition from agglomerating.

Polyolefin Formation and Testing Methods for adding clearing agents to polyolefins are well known in the art. Thus, the present invention shows only the components of the target polypropylene product and one method of producing the target polypropylene product. The present invention should not be limited to this method alone, but can be applied to many variations in the field.

A 1 kilogram batch of the targeted polypropylene was produced according to Table 1 below.
Table 1: Target polypropylene components

上記塩基性樹脂およびすべての添加物は計量されてから混合された。次いで、すべての試料をインゼクター中で融解し、３つの加熱ゾーンを通して約１８０℃ないし２４０℃からの勾配温度で混合した。インゼクターダイの出口での融解温度は約２２０ないし２４０℃であった。上記インゼクターのスクリューは長さ／直径比２４であった。試料のプラックは射出成形金型への射出によって製造された。該プラックは１４２×１０８×２．５４ｍｍ^３の寸法を有し、鏡面仕上げを有する金型で製造された。金型冷却エアを約２３℃の温度にコントロールした。

The basic resin and all additives were weighed and mixed. All samples were then melted in an injector and mixed with gradient temperatures from about 180 ° C. to 240 ° C. through three heating zones. The melting temperature at the exit of the injector die was about 220-240 ° C. The injector screw had a length / diameter ratio of 24. A sample plaque was produced by injection into an injection mold. The plaque had dimensions of 142 × 108 × 2.54 mm ³ and was manufactured with a mold having a mirror finish. The mold cooling air was controlled at a temperature of about 23 ° C.

  The haze was measured using the BYK Gardner XL-211 Hazemeter according to ASTM standard test method D1003-61 “Standard Test Method for Haze and Luminous Transactions of Transparent Plastics”. The plaques were visually inspected and an objective test for visible white spots in the plaques was made. Nucleation capacity is measured as the polymer recrystallization temperature (Tc), which indicates the polymer formation rate provided by the presence of the nucleation additive. The Tc of each plaque was measured using a differential scanning calorimeter (Mettler TOLEDO, DSC 821e) by first melting the target plaque and then cooling the plaque at a rate of about 10 ° C./minute. The temperature recorded when polymer reformation occurs is equal to Tc. A control plaque was also prepared in the same manner without the addition of the clearing agent composition of the present invention. The measurement results are shown in Table 2 below.

  Table 2: Results of polypropylene plaques with addition of the clearing agent composition of the present invention from the above examples

ポリプロピレンプラックの上記結果は、本発明の透明剤組成物を含有する上記ポリプロピレンプラック（実施例２，４，５，６，７）は目に見える白い斑点がないことを示し、本発明の透明剤組成物の添加は目に見える白い斑点の形成を予防することを示している。したがって、本発明の透明剤組成物を有するポリプロピレンプラックは本発明の透明剤組成物を有しないポリプロピレンプラックよりも良好な外観を有する。

The above results for the polypropylene plaques show that the above polypropylene plaques (Examples 2, 4, 5, 6, 7) containing the clearing agent composition of the present invention have no visible white spots, and the clearing agent of the present invention The addition of the composition has been shown to prevent the formation of visible white spots. Therefore, the polypropylene plaque having the clearing agent composition of the present invention has a better appearance than the polypropylene plaque not having the clearing agent composition of the present invention.

  Further, the above production method of the present invention has the following advantages over the conventional diacetal production method: 1. Triacetal non-production; 2. Effective removal of monoacetal; Ease of production; 4. 4. controllable powder size; and High transparency of the clearing agent composition.

  Although various features and advantages of the invention have been described above with details of the structure and aspects of the invention, the above disclosure is illustrative only. Changes in detail, particularly in shape, size and arrangement of parts, are possible within the scope of the principles of the invention to the full extent of the broad general meaning of the terms as set forth in the appended claims.

The electron micrograph of 2000 times of the product of Example 1 of this invention. An electron micrograph of the product of FIG. The electron micrograph of 2000 times of the product of Example 2 of this invention. FIG. 4 is an electron micrograph of the product in FIG. The electron micrograph of 2000 times of the product of Example 3 of this invention. FIG. 6 is an electron micrograph of the product shown in FIG. The electron micrograph of 2000 times of the product of Example 4 of this invention. FIG. 8 is an electron micrograph of the product shown in FIG. The electron micrograph of 2000 times of the product of Example 5 of this invention. FIG. 10 is an electron micrograph of the product of FIG. The electron micrograph of 2000 times of the product of Example 6 of this invention. An electron micrograph of the product of FIG. The electron micrograph of 2000 times of the product of Example 7 of this invention. FIG. 14 is an electron micrograph of the product of FIG.

Claims (18)

A clearing agent composition comprising:
Diacetal powder (wherein the diacetal is represented by the following general structural formula (I), (II), (III), (IV) or (V))

Wherein R ¹ and R ² are independently selected from the group consisting of H, C ₁ -C ₄ alkyl, C ₁ -C ₄ carboalkoxy, F, Cl and Br; a is 0, 1, 2 or 3 And b is 0, 1, 2 or 3 and n is 0 or 1)); and measured in a 4% w / w dispersion in a 1: 1 mixture of water to methanol. Organosilane-treated fumed silica having a pH value of 5.5 to 8 and dispersed in the diacetal powder and 0.05-50 wt / wt% of the clearing agent composition.   The diacetal is 1,3: 2,4-di (3-tenylidene) -D-sorbitol, 1,3: 2,4-di (5-methyl-2-tenylidene) -D-sorbitol, 1,3: 2 , 4-Di (4-methyl-benzylidene) -D-sorbitol, 1,3: 2,4-di (3,4-dimethyl-benzylidene) -D-sorbitol, 1,3- (3-tenylidene) -2 , 4- (4-Methyl-benzylidene) -D-sorbitol, 1,3- (3-tenylidene) -2,4- (3,4-dimethyl-benzylidene) -D-sorbitol, 1,3- (5- Methyl-2-tenylidene) -2,4- (4-methyl-benzylidene) -D-sorbitol or 1,3- (5-methyl-2-tenylidene) -2,4- (3,4-dimethyl-benzylidene) -D-sorbitol Transparent composition according to one claim 1.   The clearing agent composition according to claim 2, wherein the organosilane-treated fume silica is obtained by treatment with hexamethyldisilazane, dimethylsilicone liquid or polydimethylsiloxane.   A polyolefin composition, wherein the clearing agent composition according to claim 1 is added during polymerization of polyolefin.   1,3: 2,4-di (3-tenylidene) -D-sorbitol, 1,3: 2,4-di (5-methyl-2-tenylidene) -D-sorbitol, 1,3: 2,4- Di (4-methyl-benzylidene) -D-sorbitol, 1,3: 2,4-di (3,4-dimethyl-benzylidene) -D-sorbitol, 1,3- (3-tenylidene) -2,4- (4-Methyl-benzylidene) -D-sorbitol, 1,3- (3-tenylidene) -2,4- (3,4-dimethyl-benzylidene) -D-sorbitol, 1,3- (5-methyl-2 -Tenylidene) -2,4- (4-methyl-benzylidene) -D-sorbitol or 1,3- (5-methyl-2-tenylidene) -2,4- (3,4-dimethyl-benzylidene) -D- Clarifying agent composition containing sorbitol The polyolefin composition according to claim 4, characterized in that is added during the polymerization of the polyolefin.   6. The clearing agent composition comprising organosilane-treated fumed silica obtained by treatment with hexamethyldisilazane, dimethylsilicone liquid or polydimethylsiloxane is added during polymerization of the polyolefin. Polyolefin composition.   A transparent polyolefin plastic product comprising the polyolefin composition according to claim 4.   1,3: 2,4-di (3-tenylidene) -D-sorbitol, 1,3: 2,4-di (5-methyl-2-tenylidene) -D-sorbitol, 1,3: 2,4- Di (4-methyl-benzylidene) -D-sorbitol, 1,3: 2,4-di (3,4-dimethyl-benzylidene) -D-sorbitol, 1,3- (3-tenylidene) -2,4- (4-Methyl-benzylidene) -D-sorbitol, 1,3- (3-tenylidene) -2,4- (3,4-dimethyl-benzylidene) -D-sorbitol, 1,3- (5-methyl-2 -Tenylidene) -2,4- (4-methyl-benzylidene) -D-sorbitol or 1,3- (5-methyl-2-tenylidene) -2,4- (3,4-dimethyl-benzylidene) -D- Clarifying agent composition consisting of sorbitol Transparent polyolefin plastic product according to claim 7 comprising a polyolefin composition comprising a.   The transparent polyolefin plastic product according to claim 8, comprising a polyolefin composition containing the above-mentioned transparent agent containing organosilane-treated fume silica obtained by treatment with hexamethyldisilazane, dimethylsilicone liquid or polydimethylsiloxane. A method for producing a clearing agent composition comprising the following steps:
Aromatic aldehyde, polyol and acid catalyst are mixed in a polar solvent to effect a condensation reaction to form a reaction mixture, wherein the equivalent ratio of aromatic aldehyde to polyol is from 2: 1 to 2: 2; And oreganosilane-treated fumed silica having a pH value of 5.5 to 8 measured in a 4 wt / wt% dispersion in a 1: 1 mixture of water to methanol was added to the reaction mixture, Filter, dry and grind to form a clearing agent composition, wherein the organosilane treated fume silica is 0.05 to 50% by weight of the clearing agent composition.   The method for producing a clearing agent composition according to claim 10, wherein the aromatic aldehyde is thiophenecarboxaldehyde, benzaldehyde or a mixture thereof.   The method for producing a clearing agent composition according to claim 11, wherein the thiophene carboxaldehyde is 3-thiophene carboxaldehyde or 5-methyl-2-thiophene carboxaldehyde.   The method for producing a clearing agent composition according to claim 11, wherein the benzaldehyde is 4-methyl-benzaldehyde or 3,4-dimethyl-benzaldehyde.   The method for producing a clearing agent composition according to claim 11, wherein the polyol is sorbitol or xylitol.   The method for producing a clearing agent composition according to claim 14, wherein the polyol is D-sorbitol.   Oreganosilane-treated fumed silica having a pH value of 5.5 to 8 measured in a 4% w / w dispersion in a 1: 1 mixture of water to methanol is 2-4% by weight of the clearing agent composition. The clearing agent composition manufacturing method according to claim 15.   The method for producing a clearing agent composition according to claim 16, wherein the equivalent ratio of aromatic aldehyde to polyol is from 2: 1.05 to 2: 1.3 in the polar solvent.   The oreganosilane-treated fumed silica having a pH value of 5.5 to 8 measured in a 4 wt / wt% dispersion in a 1: 1 mixture of water to methanol is 2-10 wt of the clearing agent composition. The method for producing a clearing agent composition according to claim 17, which is%.

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