WO2016088767A1 - Manufacturing method for granular resin additive, granular resin additive obtained by said manufacturing method, thermoplastic resin composition, and molded article - Google Patents
Manufacturing method for granular resin additive, granular resin additive obtained by said manufacturing method, thermoplastic resin composition, and molded article Download PDFInfo
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- WO2016088767A1 WO2016088767A1 PCT/JP2015/083796 JP2015083796W WO2016088767A1 WO 2016088767 A1 WO2016088767 A1 WO 2016088767A1 JP 2015083796 W JP2015083796 W JP 2015083796W WO 2016088767 A1 WO2016088767 A1 WO 2016088767A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
Definitions
- the present invention relates to a method for producing an additive for granular resin, an additive for granular resin obtained by the production method, a thermoplastic resin composition, and a molded article.
- a stabilizer for preventing thermal degradation and oxidative degradation during molding processing a stabilizer for imparting storage stability against light, heat, oxidation, etc. of the molded product after molding processing
- Various additives such as a modifier, a crystallization nucleating agent, and a catalyst deactivator for imparting strength, transparency, color tone and the like of the molded body are used.
- the additive is added to the thermoplastic resin by a method of using the additive as a master batch, a method of melting and pelletizing the additive, or a method of granulating with a compression granulator. .
- the amount of the masterbatch resin tends to be increased.
- the additive content is low and the masterbatch resin to be used is different from the thermoplastic resin, the target physical properties There is a problem of affecting the etc. Further, when the master batch resin is reduced as much as possible and the concentration of the additive is increased, there is a problem that the additive cannot be uniformly mixed in the thermoplastic resin.
- the method of pelletizing by melting the additive a combination of low melting point additives is required for pellet granulation, the degree of freedom in selecting the additive is small, and a molten pellet for each formulation is required. It becomes. And in the method of using granules and tablets using a compression granulator such as a roller compactor, there is a problem that the additives are aggregated and not uniformly dispersed in the resin.
- Patent Document 1 discloses a granular additive for synthetic resin in which a resin additive is granulated and the surface thereof is coated with a thermoplastic resin. Since the thermoplastic resin is used, the various properties of the resulting thermoplastic resin composition may be adversely affected.
- Patent Document 2 it is known that when the crystallization nucleating agent is granulated, it is granulated using a binder composed of a metal soap such as calcium stearate and an organic compound such as stearic acid monoglyceride. Yes.
- the present invention uses the additive for resin as an additive for granular resin by a specific production method.
- a method for producing an additive for a granular resin which can efficiently obtain a thermoplastic resin composition, and less likely to cause deterioration in quality, with respect to a molded product after molding the obtained thermoplastic resin composition, It is an object to provide an additive for granular resin obtained by this production method, a thermoplastic resin composition using the additive for granular resin, and a molded article formed by molding the thermoplastic resin composition. To do.
- the present inventors have found that the above object can be achieved by using water and a wetting agent as a resin additive to complete the present invention. I came to let you. That is, the present invention relates to the following [1] to [11].
- a method for producing an additive for granular resin according to claim 1. [5] The method for producing an additive for granular resin according to any one of the above [1] to [4], wherein the additive for resin is a crystallization nucleating agent.
- thermoplastic resin composition obtained by adding the additive for granular resin according to [7] or [8] to a thermoplastic resin.
- thermoplastic resin composition according to the above [9] wherein the thermoplastic resin is a crystalline thermoplastic resin.
- thermoplastic resin composition according to [10] above, wherein the crystalline thermoplastic resin is a polyolefin resin.
- the method for producing an additive for a granular resin of the present invention can efficiently produce an additive for a granular resin by a simple process, and the resulting additive for a granular resin is excellent in fluidity. It is excellent in quantitative supply, and a thermoplastic resin composition can be obtained efficiently. Moreover, since the obtained thermoplastic resin composition is excellent in the dispersibility of the resin additive, the resin additive can be uniformly dispersed. Therefore, a molded product formed by molding this thermoplastic resin composition can provide a molded product having excellent quality.
- a wet product is obtained by adding water and a wetting agent to the resin additive, and then the wet product is granulated by a granulator and wetted. In the form of a granulated product, the wet granulated product is dried.
- the manufacturing method of the additive for granular resins of this invention is demonstrated in detail. In the present specification, it is possible to arbitrarily adopt provisions that are preferable, and it can be said that a combination of preferable ones is more preferable.
- the additive for resin used in the method for producing the additive for granular resin of the present invention is not particularly limited as long as it is an additive used for a thermoplastic resin.
- a crystallization nucleating agent examples thereof include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, slip agents, inorganic fillers, organic pigments, inorganic pigments, and coloring agents such as dyes and pigments. These additives can be used alone or in combination of two or more.
- Water to be added to resin additive In the method for producing an additive for granular resin of the present invention, water is used for addition to the additive for resin. Water is used to wet the resin additive to obtain a wet product.
- the amount of water added is 3 to 150 parts by weight, preferably 5 to 100 parts by weight, and more preferably 50 to 70 parts by weight with respect to 100 parts by weight of the resin additive.
- a wetting agent added to resin additives In the method for producing an additive for granular resin of the present invention, a wetting agent is added together with water to be added to the additive for resin. By adding a wetting agent, the granulation property can be improved when the wet product is granulated to obtain a wet granulated product.
- the wetting agent used in the present invention it is preferable to use a compound selected from polyoxyalkylene sorbitan alkylate, polyoxyalkylene glycol, sodium alkylsulfosuccinate, and propanediol.
- polyoxyalkylene sorbitan alkylate examples include polyoxyethylene sorbitan mono (or di, tri) laurate, polyoxyethylene sorbitan mono (or di, tri) stearate, polyoxyethylene sorbitan mono (or di, tri) oleate, etc. Is mentioned.
- polyoxyalkylene glycol examples include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyethylene / polypropylene glycol; methoxy polyethylene glycol, ethoxy polyethylene glycol, propoxy polyethylene glycol, butoxy polyethylene glycol, pentyloxy polyethylene glycol, hexyloxy Oxyethylene adducts of lower alcohols and higher alcohols having 8 or more carbon atoms such as pentyloxypolyethylene glycol, octyloxypentyloxypolyethylene glycol, nonylalkoxypolyethylene glycol; methoxypolyethylene / polypropyleneglycol, methoxypolyethylene / polybutyleneglycol, etho Si polyethylene / polypropylene glycol, ethoxy polyethylene / polybutylene glycol, propoxy polyethylene / polypropylene glycol, propoxy polyethylene / polybutylene glycol, butoxy polyethylene / polypropy
- oxyethylene adducts of lower alcohols such as polyethylene glycol, polypropylene glycol, methoxy polyethylene glycol, and ethoxy polyethylene glycol are preferable, and polyoxyethylene polyoxypropylene glycol, polypropylene glycol, and polyethylene glycol are preferable.
- sodium alkylsulfosuccinate examples include compounds such as sodium dialkylsulfosuccinate and sodium monoalkylsulfosuccinate, and sodium dialkylsulfosuccinate is preferred.
- sodium dialkylsulfosuccinates include octyl (2-ethylhexyl) compounds in which the alkyl group has 8 (C8) carbon atoms.
- propanediol include 1,3-propanediol and 2,3-propanediol.
- the wetting agent is preferably added in an amount of 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of water. Is more preferable.
- 0.01 part by mass or more of a wetting agent By adding 0.01 part by mass or more of a wetting agent, the granulation property can be improved, and by adding 15 parts by mass or less, the molded product obtained from the thermoplastic resin composition obtained as a final product is moistened. The agent can be prevented from bleeding out.
- the maximum diameter is 0.1 to 7 mm, preferably 0.3 to 5 mm, so that dispersibility and drying properties can be made preferable.
- the wet granulation product thus obtained can be dried to remove moisture, thereby obtaining an additive for granular resin.
- the dryer used for drying is not particularly limited, and a dryer such as a hot air dryer or a vacuum dryer can be used.
- the drying temperature is not particularly limited as long as it is equal to or lower than the decomposition temperature of the resin additive to be used.
- the moisture content after drying is desirably 5% by mass or less, preferably 3% by mass or less.
- the granular resin additive thus obtained can have an angle of repose of 45 ° or less, preferably 40 ° or less, so that an additive for granular resin having excellent fluidity can be obtained.
- the lower limit of the angle of repose is not particularly limited, but is usually about 30 °.
- thermoplastic resin composition and molded product The additive for granular resins obtained by the method for producing an additive for granular resins of the present invention can be added to a thermoplastic resin to obtain a thermoplastic resin composition.
- thermoplastic resin include a crystalline thermoplastic resin and an amorphous thermoplastic resin.
- crystalline thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, aromatic polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyesters such as polycaprolactone, nylon-6, nylon-66, and nylon-12.
- Aliphatic polyamides such as aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines
- polyacetal resins such as polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropylene aldehyde, polybutyraldehyde, polyphenylene Examples thereof include sulfide resin (PPS).
- Amorphous thermoplastic resins include styrene resins such as polystyrene (PS), AS, and ABS, polyvinyl chloride resins, acrylic resins, polycarbonate resins, ethylene-vinyl acetate copolymer resins, polyimide resins, polysulfone resins, A polyphenylene ether resin etc.
- thermoplastic resins may be used alone or in combination of two or more.
- a crystalline thermoplastic resin such as a polyolefin resin, a polyester resin, or a polyamide resin is used for the purpose of improving the transparency, the rigidity, the heat resistance, etc. as described above.
- a crystallization nucleating agent is used as an additive.
- the crystallization nucleating agents described below can be mentioned.
- crystallization nucleating agent for the polyolefin resin (a) benzoic acid metal salt, (b) polyhydric alcohol derivative such as sorbitol derivative, nonitol derivative, (c) organic phosphate metal salt, (d) branched A olefin or the like can be used.
- crystallization nucleating agents When these crystallization nucleating agents are added to polyolefin-based resins, the flowability of the crystallization nucleating agent is not good, so the quantitative supply is inferior.
- sorbitol derivatives, nonitol derivatives, and metal benzoates are used as crystallization nuclei.
- meterability can be improved by using the production method of the present invention, and a thermoplastic resin composition can be obtained efficiently.
- crystallization nucleating agent for the polyolefin resin trade names such as NA-21 and NA-11 (registered trademark) manufactured by Asahi Denka, Gelall MD (registered trademark) manufactured by Shin Nippon Chemical Co., Ltd.
- examples include Millard 3988 (registered trademark), NX8000 (registered trademark), and NC-4 (registered trademark) manufactured by Mitsui Chemicals.
- nonitol derivatives represented by Millard NX8000 (registered trademark) manufactured by Milliken and sorbitol derivatives represented by Millard 3988 (registered trademark) are excellent in the effect of improving transparency, and polyolefins having excellent transparency.
- a resin sheet and a film can be obtained.
- the amount of crystallization nucleating agent added to the crystalline thermoplastic resin is usually 0.01 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, per 100 parts by mass of the crystalline thermoplastic resin. Is preferred. By adding the crystallization nucleating agent to the crystalline thermoplastic resin within this range, the effect as the crystallization nucleating agent can be exerted, and the transparency due to the aggregation of the crystallization nucleating agent is hardly impaired. .
- thermoplastic resin composition In order to obtain the thermoplastic resin composition by adding the additive for granular resin obtained by the method for producing the additive for granular resin of the present invention to the thermoplastic resin, a uniaxial kneading extruder or a biaxial kneading extruder
- a thermoplastic resin composition can be produced by melt-kneading using an extruder such as the above, and pelletizing.
- a certain amount of additive for granular resin is continuously added from a popper or the like to the continuously supplied thermoplastic resin.
- thermoplastic resin in advance, supply the thermoplastic resin containing the additive for the granular resin to the extruder, melt kneaded and pelletized, or for the thermoplastic resin in the molten state in the extruder, A certain amount of the additive for granular resin can be added quantitatively by side-feeding continuously from a popper or the like, and melt-kneaded to be pelletized.
- the additive for granular resin obtained by the method for producing an additive for granular resin of the present invention has a low angle of repose, so it has excellent fluidity and may be blocked in a container such as a popper. There are few, and when it supplies continuously, it has the effect excellent in quantitative supply.
- the thermoplastic resin in addition to the additive for granular resin, is fibrous material such as glass fiber, carbon fiber, inorganic filler such as talc, mica, titanium dioxide, and coloring agent.
- Additives such as ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, slip agents and the like can be pelletized to produce a thermoplastic resin composition.
- the thermoplastic resin composition of the present invention thus obtained can be obtained by a known molding method such as injection molding, extrusion molding, blow molding, inflation molding, compression molding, or the like, as a sheet, film, pipe, home appliance, mobile phone, Various molded products used for electronic devices such as OA devices, automobile parts, and the like can be obtained.
- Example 1 A crystallization nucleating agent [manufactured by Milliken: sorbitol-based nucleating agent, Millard 3988] as a resin additive, 100 parts by mass of sodium di (2-ethylhexyl) sulfosuccinate as a wetting agent and 2,3-propane 60 parts by mass of an aqueous solution in which 0.4 part by mass of diol was added to 58.8 parts by mass of water and dissolved therein was charged into a Henschel mixer to obtain a wet mixture. This mixture was put into a wet extrusion granulator (Fuji Paudal, ec pelleter) to produce a wet granulated product having a diameter of 1 mm.
- a wet extrusion granulator Fruji Paudal, ec pelleter
- the granulated product was dried at 90 ° C. for 8 hours with a box dryer to produce an additive for granular resin having a water content of 1.2% by mass.
- the angle of repose was measured in a transparent container by the tilt method, and the fluidity of the additive for granular resin was evaluated.
- 0.4 parts by mass of the obtained crystallization nucleating agent for granular resin is added to 100 parts by mass of polypropylene (prime polymer J700GP), and then molded at a set temperature of 230 ° C. with an injection molding machine. Then, a sheet-like molded product having a thickness of 2 mm was molded, and the transparency was evaluated. It shows in Table 1 about each component used when manufacturing the additive for granular resins. Moreover, the granulation property of the granular resin additive, the angle of repose, and the transparency of the sheet-like molded product were evaluated. The results are shown in Table 2.
- Example 2 As the crystallization nucleating agent for the resin additive used in Example 1, Millitol NX8000J, a nonitol nucleating agent manufactured by Milliken Corporation, 0.6 parts by mass of polyoxyethylene sorbitan monolaurate as a wetting agent, and water was carried out in the same manner as in Example 1 except that the content was changed to 59.4 parts by mass to produce an additive for granular resin having a water content of 0.8% by mass. Using the obtained additive for granular resin, the granularity of the additive for granular resin, the angle of repose, and the transparency of the sheet-like molded product were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
- Example 3 As a crystallization nucleating agent for the resin additive used in Example 1, AL-PTBBA [chemical name: hydroxy-di (p-tert-butylbenzoic acid) aluminum] manufactured by Japan Chemtech Co., Ltd. was used as a wetting agent. As in Example 1, except that 0.4 parts by mass of polyoxyethylene sorbitan monolaurate, 2.0 parts by mass of polyoxyethylene polyoxypropylene glycol, and 57.6 parts by mass of water were used. An additive for granular resin having a water content of 1.0% by mass was produced. Using the obtained additive for granular resin, the granularity of the additive for granular resin, the angle of repose, and the transparency of the sheet-like molded product were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
- Comparative Example 1 Without using the resin additive crystallization nucleating agent used in Example 2 as a granular resin additive, 0.4 part by mass is added to 100 parts by mass of polypropylene (Prime Polymer J700GP) to form a sheet. This was carried out in the same manner as in Example 2 except that the product was molded. The results are shown in Tables 1 and 2.
- Example 2 a granular resin additive having a water content of 0.7% by mass was produced in the same manner without adding a wetting agent. It could not pass through the mesh of the granulator and a good additive for granular resin could not be produced.
- Example 3 water was not used and 10 parts by mass of calcium stearate was used instead of 0.6 parts by mass of polyoxyethylene sorbitan monolaurate used as a wetting agent.
- An additive for granular resin was produced in the same manner as in Example 2 except that a dry granulator (manufactured by Freund Turbo, roller compactor) was used instead. Using the obtained additive for granular resin, the granularity of the additive for granular resin, the angle of repose, and the transparency of the sheet-like molded product were evaluated in the same manner as in Example 2. The results are shown in Tables 1 and 2.
- the granular resin additives obtained by the production methods of the present invention of Examples 1 to 3 have good granulation properties and small repose angles, and thus have excellent fluidity.
- the transparency of the sheet-like molded product produced using this granular resin additive was good without any aggregates.
- Comparative Example 1 since the crystallization nucleating agent of the resin additive was used as it was, there was an aggregate in the sheet-like molded product, and the transparency was lowered.
- Comparative Example 2 since no wetting agent was used, the additive for granular resin could not be obtained.
- Comparative Example 3 since water was not used, the sheet-like molded product had a large number of aggregates, and transparency was lowered.
- thermoplastic resin composition By using the method for producing an additive for granular resin of the present invention, a thermoplastic resin composition can be efficiently produced, and the additive for resin in a molded product obtained from the thermoplastic resin composition Can be uniformly dispersed, which is useful for the production of thermoplastic resin compositions and molded articles thereof.
Abstract
Provided is a manufacturing method for a granular resin additive, wherein, by converting a resin additive into a granular resin additive, the granular resin additive has excellent quantitative supply properties, can efficiently yield a thermoplastic resin composition, and is not likely to cause a deterioration of quality in a molded article produced by molding the thermoplastic resin composition. Also provided are: a granular resin additive obtained by said manufacturing method; a thermoplastic resin composition in which the granular resin additive is used; and a molded article produced by molding the thermoplastic resin composition. In the manufacturing method for a granular resin additive, a resin additive is wetted by adding water thereto, thereby creating a wetted product; next, the wetted product is granulated using a granulator, thereby creating a wet granulated product; and the wet granulated product is dried.
Description
本発明は、顆粒状樹脂用添加剤の製造方法、その製造方法により得られる顆粒状樹脂用添加剤、熱可塑性樹脂組成物、及び成形品に関する。
The present invention relates to a method for producing an additive for granular resin, an additive for granular resin obtained by the production method, a thermoplastic resin composition, and a molded article.
各種の熱可塑性樹脂には、成形加工時の熱劣化や酸化劣化を防止するための安定剤、成形加工後の成形体の光、熱、酸化等に対する保存安定性を付与するための安定剤、そして、成形体の強度、透明性、色調等を付与するための改質剤、結晶化核剤、触媒失活剤等の各種添加剤が使用されている。
For various thermoplastic resins, a stabilizer for preventing thermal degradation and oxidative degradation during molding processing, a stabilizer for imparting storage stability against light, heat, oxidation, etc. of the molded product after molding processing, Various additives such as a modifier, a crystallization nucleating agent, and a catalyst deactivator for imparting strength, transparency, color tone and the like of the molded body are used.
通常これらの各種添加剤は、粉末状の添加剤であることが多く、粉末状のままでの使用は、浮遊粉塵による作業環境を悪化させる問題点がある。また、粉末状添加剤の性状や形状等の影響により添加剤を原体のままで定量的に供給することが困難となる添加剤が多く存在する。このため、添加剤をマスターバッチとする方法、添加剤を溶融してペレット化する方法、あるいは圧縮型造粒機による顆粒状とする方法等により、熱可塑性樹脂に添加することが行なわれている。しかし、マスターバッチ方法では、マスターバッチ樹脂の使用量が多くなりがちであり、したがって、添加剤の含有率が低くなり、使用するマスターバッチ樹脂と熱可塑性樹脂とが相違する場合、目標とする物性等に影響を与えるという問題点がある。また、マスターバッチ樹脂をできるだけ少なくし、添加剤を高濃度化すると、添加剤を熱可塑性樹脂中に均一に混合することができなくなるという問題点がある。
また、添加剤を溶融してペレット化する方法では、ペレットの造粒に当り、低融点の添加剤の組み合わせが必要となり、添加剤の選択の自由度が少なく、さらに処方毎の溶融ペレットが必要となる。そして、ローラーコンパクターなどの圧縮型造粒機を用いて顆粒状や錠剤とする方法では、添加剤が凝集して均一に樹脂に分散しないという問題点がある。 Usually, these various additives are often powdery additives, and their use in the powdery state has a problem of deteriorating the working environment due to suspended dust. Further, there are many additives that make it difficult to quantitatively supply the additive as it is due to the influence of the properties and shape of the powdered additive. For this reason, the additive is added to the thermoplastic resin by a method of using the additive as a master batch, a method of melting and pelletizing the additive, or a method of granulating with a compression granulator. . However, in the masterbatch method, the amount of the masterbatch resin tends to be increased. Therefore, when the additive content is low and the masterbatch resin to be used is different from the thermoplastic resin, the target physical properties There is a problem of affecting the etc. Further, when the master batch resin is reduced as much as possible and the concentration of the additive is increased, there is a problem that the additive cannot be uniformly mixed in the thermoplastic resin.
In addition, in the method of pelletizing by melting the additive, a combination of low melting point additives is required for pellet granulation, the degree of freedom in selecting the additive is small, and a molten pellet for each formulation is required. It becomes. And in the method of using granules and tablets using a compression granulator such as a roller compactor, there is a problem that the additives are aggregated and not uniformly dispersed in the resin.
また、添加剤を溶融してペレット化する方法では、ペレットの造粒に当り、低融点の添加剤の組み合わせが必要となり、添加剤の選択の自由度が少なく、さらに処方毎の溶融ペレットが必要となる。そして、ローラーコンパクターなどの圧縮型造粒機を用いて顆粒状や錠剤とする方法では、添加剤が凝集して均一に樹脂に分散しないという問題点がある。 Usually, these various additives are often powdery additives, and their use in the powdery state has a problem of deteriorating the working environment due to suspended dust. Further, there are many additives that make it difficult to quantitatively supply the additive as it is due to the influence of the properties and shape of the powdered additive. For this reason, the additive is added to the thermoplastic resin by a method of using the additive as a master batch, a method of melting and pelletizing the additive, or a method of granulating with a compression granulator. . However, in the masterbatch method, the amount of the masterbatch resin tends to be increased. Therefore, when the additive content is low and the masterbatch resin to be used is different from the thermoplastic resin, the target physical properties There is a problem of affecting the etc. Further, when the master batch resin is reduced as much as possible and the concentration of the additive is increased, there is a problem that the additive cannot be uniformly mixed in the thermoplastic resin.
In addition, in the method of pelletizing by melting the additive, a combination of low melting point additives is required for pellet granulation, the degree of freedom in selecting the additive is small, and a molten pellet for each formulation is required. It becomes. And in the method of using granules and tablets using a compression granulator such as a roller compactor, there is a problem that the additives are aggregated and not uniformly dispersed in the resin.
このような問題点を改善するために、例えば、特許文献１では、樹脂用添加剤を粒状化し、その表面を熱可塑性樹脂で被覆した合成樹脂用粒状添加剤が知られているが、被覆用熱可塑性樹脂を使用するために、得られる熱可塑性樹脂組成物の各種性質に対して悪影響を与えることがあった。また、特許文献２では、結晶化核剤を顆粒状とするに当り、ステアリン酸カルシウム等の金属石鹸とステアリン酸モノグリセリド等の有機化合物からなる結着剤を用いて顆粒状とすることが知られている。この方法では、結晶化核剤１００質量部に対して、金属石鹸を１０～１００質量部及び有機化合物からなる結着剤を１０質量部以上使用する必要があり、多量の金属石鹸や結着剤の使用により、得られる熱可塑性樹脂組成物を成形した後の成形品に対して、透明性等の性質に悪影響を及ぼす可能性があった。
In order to improve such a problem, for example, Patent Document 1 discloses a granular additive for synthetic resin in which a resin additive is granulated and the surface thereof is coated with a thermoplastic resin. Since the thermoplastic resin is used, the various properties of the resulting thermoplastic resin composition may be adversely affected. In Patent Document 2, it is known that when the crystallization nucleating agent is granulated, it is granulated using a binder composed of a metal soap such as calcium stearate and an organic compound such as stearic acid monoglyceride. Yes. In this method, it is necessary to use 10 to 100 parts by weight of a metal soap and 10 parts by weight or more of a binder composed of an organic compound with respect to 100 parts by weight of a crystallization nucleating agent. , There is a possibility that the properties such as transparency may be adversely affected on the molded product after molding the thermoplastic resin composition obtained.
本発明は、熱可塑性樹脂に添加される樹脂用添加剤を使用して熱可塑性樹脂組成物を得るに当り、該樹脂用添加剤を特定の製造方法によって顆粒状樹脂用添加剤とすることにより、効率よく熱可塑性樹脂組成物を得ることができ、得られる熱可塑性樹脂組成物を成形した後の成形品に対して、品質の低下を招く恐れの少ない顆粒状樹脂用添加剤の製造方法、この製造方法により得られる顆粒状樹脂用添加剤、この顆粒状樹脂用添加剤を用いた熱可塑性樹脂組成物、及びこの熱可塑性樹脂組成物を成形してなる成形品を提供することを目的とするものである。
In obtaining a thermoplastic resin composition using an additive for resin added to a thermoplastic resin, the present invention uses the additive for resin as an additive for granular resin by a specific production method. , A method for producing an additive for a granular resin, which can efficiently obtain a thermoplastic resin composition, and less likely to cause deterioration in quality, with respect to a molded product after molding the obtained thermoplastic resin composition, It is an object to provide an additive for granular resin obtained by this production method, a thermoplastic resin composition using the additive for granular resin, and a molded article formed by molding the thermoplastic resin composition. To do.
本発明者等は、鋭意検討を進めた結果、樹脂用添加剤に水及び湿潤剤を用いて顆粒状樹脂用添加剤とすることにより、上記目的が達成されることを見出し、本発明を完成させるに至った。
すなわち、本発明は、下記［１］～［１１］に関する。 As a result of diligent investigations, the present inventors have found that the above object can be achieved by using water and a wetting agent as a resin additive to complete the present invention. I came to let you.
That is, the present invention relates to the following [1] to [11].
すなわち、本発明は、下記［１］～［１１］に関する。 As a result of diligent investigations, the present inventors have found that the above object can be achieved by using water and a wetting agent as a resin additive to complete the present invention. I came to let you.
That is, the present invention relates to the following [1] to [11].
［１］樹脂用添加剤に水及び湿潤剤を添加することによりウェット化させてウェット化物とし、次いで、該ウェット化物を造粒機により顆粒化してウェット状の顆粒化物とし、該ウェット状の顆粒化物を乾燥させる、顆粒状樹脂用添加剤の製造方法。
［２］樹脂用添加剤１００質量部に対して、水を３～１５０質量部添加する、上記［１］に記載の顆粒状樹脂用添加剤の製造方法。
［３］水１００質量部に対して、湿潤剤を０．０１～１５質量部添加する、上記［１］又は［２］に記載の顆粒状樹脂用添加剤の製造方法。
［４］前記湿潤剤が、ポリオキシアルキレンソルビタンアルキレート、ポリオキシアルキレングリコール、アルキルスルフォコハク酸ナトリウム、及びプロパンジオールから選ばれた少なくとも１種である、上記［１］～［３］のいずれかに記載の顆粒状樹脂用添加剤の製造方法。
［５］前記樹脂用添加剤が、結晶化核剤である、上記［１］～［４］のいずれかに記載の顆粒状樹脂用添加剤の製造方法。
［６］前記造粒機が、円筒造粒機又は湿式押出造粒機である、上記［１］～［５］のいずれかに記載の顆粒状樹脂用添加剤の製造方法。
［７］上記［１］～［６］のいずれかに記載の製造方法により得られる、顆粒状樹脂用添加剤。
［８］安息角が、４０°以下である、上記［７］に記載の顆粒状樹脂用添加剤。
［９］上記［７］又は［８］に記載の顆粒状樹脂用添加剤を熱可塑性樹脂に添加してなる、熱可塑性樹脂組成物。
［１０］前記熱可塑性樹脂が、結晶性熱可塑性樹脂である、上記［９］に記載の熱可塑性樹脂組成物。
［１１］前記結晶性熱可塑性樹脂が、ポリオレフィン系樹脂である、上記［１０］に記載の熱可塑性樹脂組成物。
［１２］上記［９］～［１１］のいずれかに記載の熱可塑性樹脂組成物を成形してなる成形品。 [1] Adding water and a wetting agent to a resin additive to make it wet to obtain a wet product, and then granulating the wet product using a granulator to form a wet granulated product, the wet granule The manufacturing method of the additive for granular resin which dries a chemical compound.
[2] The method for producing an additive for granular resin according to the above [1], wherein 3 to 150 parts by mass of water is added to 100 parts by mass of the additive for resin.
[3] The method for producing an additive for granular resin according to [1] or [2] above, wherein 0.01 to 15 parts by mass of a wetting agent is added to 100 parts by mass of water.
[4] Any of the above [1] to [3], wherein the wetting agent is at least one selected from polyoxyalkylene sorbitan alkylate, polyoxyalkylene glycol, sodium alkylsulfosuccinate, and propanediol. A method for producing an additive for granular resin according to claim 1.
[5] The method for producing an additive for granular resin according to any one of the above [1] to [4], wherein the additive for resin is a crystallization nucleating agent.
[6] The method for producing an additive for granular resin according to any one of the above [1] to [5], wherein the granulator is a cylindrical granulator or a wet extrusion granulator.
[7] An additive for granular resin obtained by the production method according to any one of [1] to [6] above.
[8] The additive for granular resin according to [7], wherein the angle of repose is 40 ° or less.
[9] A thermoplastic resin composition obtained by adding the additive for granular resin according to [7] or [8] to a thermoplastic resin.
[10] The thermoplastic resin composition according to the above [9], wherein the thermoplastic resin is a crystalline thermoplastic resin.
[11] The thermoplastic resin composition according to [10] above, wherein the crystalline thermoplastic resin is a polyolefin resin.
[12] A molded product obtained by molding the thermoplastic resin composition according to any one of [9] to [11].
［２］樹脂用添加剤１００質量部に対して、水を３～１５０質量部添加する、上記［１］に記載の顆粒状樹脂用添加剤の製造方法。
［３］水１００質量部に対して、湿潤剤を０．０１～１５質量部添加する、上記［１］又は［２］に記載の顆粒状樹脂用添加剤の製造方法。
［４］前記湿潤剤が、ポリオキシアルキレンソルビタンアルキレート、ポリオキシアルキレングリコール、アルキルスルフォコハク酸ナトリウム、及びプロパンジオールから選ばれた少なくとも１種である、上記［１］～［３］のいずれかに記載の顆粒状樹脂用添加剤の製造方法。
［５］前記樹脂用添加剤が、結晶化核剤である、上記［１］～［４］のいずれかに記載の顆粒状樹脂用添加剤の製造方法。
［６］前記造粒機が、円筒造粒機又は湿式押出造粒機である、上記［１］～［５］のいずれかに記載の顆粒状樹脂用添加剤の製造方法。
［７］上記［１］～［６］のいずれかに記載の製造方法により得られる、顆粒状樹脂用添加剤。
［８］安息角が、４０°以下である、上記［７］に記載の顆粒状樹脂用添加剤。
［９］上記［７］又は［８］に記載の顆粒状樹脂用添加剤を熱可塑性樹脂に添加してなる、熱可塑性樹脂組成物。
［１０］前記熱可塑性樹脂が、結晶性熱可塑性樹脂である、上記［９］に記載の熱可塑性樹脂組成物。
［１１］前記結晶性熱可塑性樹脂が、ポリオレフィン系樹脂である、上記［１０］に記載の熱可塑性樹脂組成物。
［１２］上記［９］～［１１］のいずれかに記載の熱可塑性樹脂組成物を成形してなる成形品。 [1] Adding water and a wetting agent to a resin additive to make it wet to obtain a wet product, and then granulating the wet product using a granulator to form a wet granulated product, the wet granule The manufacturing method of the additive for granular resin which dries a chemical compound.
[2] The method for producing an additive for granular resin according to the above [1], wherein 3 to 150 parts by mass of water is added to 100 parts by mass of the additive for resin.
[3] The method for producing an additive for granular resin according to [1] or [2] above, wherein 0.01 to 15 parts by mass of a wetting agent is added to 100 parts by mass of water.
[4] Any of the above [1] to [3], wherein the wetting agent is at least one selected from polyoxyalkylene sorbitan alkylate, polyoxyalkylene glycol, sodium alkylsulfosuccinate, and propanediol. A method for producing an additive for granular resin according to claim 1.
[5] The method for producing an additive for granular resin according to any one of the above [1] to [4], wherein the additive for resin is a crystallization nucleating agent.
[6] The method for producing an additive for granular resin according to any one of the above [1] to [5], wherein the granulator is a cylindrical granulator or a wet extrusion granulator.
[7] An additive for granular resin obtained by the production method according to any one of [1] to [6] above.
[8] The additive for granular resin according to [7], wherein the angle of repose is 40 ° or less.
[9] A thermoplastic resin composition obtained by adding the additive for granular resin according to [7] or [8] to a thermoplastic resin.
[10] The thermoplastic resin composition according to the above [9], wherein the thermoplastic resin is a crystalline thermoplastic resin.
[11] The thermoplastic resin composition according to [10] above, wherein the crystalline thermoplastic resin is a polyolefin resin.
[12] A molded product obtained by molding the thermoplastic resin composition according to any one of [9] to [11].
本発明の顆粒状樹脂用添加剤の製造方法は、簡単な工程により、効率よく顆粒状樹脂用添加剤を製造することができ、得られる顆粒状樹脂用添加剤は、流動性に優れるので、定量供給性に優れており、熱可塑性樹脂組成物を効率よく得ることができる。また、得られる熱可塑性樹脂組成物は、樹脂用添加剤の分散性が優れているので、樹脂用添加剤を均一に分散化させることができる。したがって、この熱可塑性樹脂組成物を成形してなる成形品は、品質に優れる成形品を提供することができる。
The method for producing an additive for a granular resin of the present invention can efficiently produce an additive for a granular resin by a simple process, and the resulting additive for a granular resin is excellent in fluidity. It is excellent in quantitative supply, and a thermoplastic resin composition can be obtained efficiently. Moreover, since the obtained thermoplastic resin composition is excellent in the dispersibility of the resin additive, the resin additive can be uniformly dispersed. Therefore, a molded product formed by molding this thermoplastic resin composition can provide a molded product having excellent quality.
本発明の顆粒状樹脂用添加剤の製造方法は、樹脂用添加剤に水及び湿潤剤を添加することによりウェット化させてウェット化物とし、次いで、該ウェット化物を造粒機により顆粒化してウェット状の顆粒化物とし、該ウェット状の顆粒化物を乾燥させてなるものである。
以下、本発明の顆粒状樹脂用添加剤の製造方法について詳細に説明する。なお、本明細書において、好ましいとされている規定は任意に採用することができ、好ましいもの同士の組み合わせはより好ましいと言える。 In the method for producing an additive for granular resin of the present invention, a wet product is obtained by adding water and a wetting agent to the resin additive, and then the wet product is granulated by a granulator and wetted. In the form of a granulated product, the wet granulated product is dried.
Hereinafter, the manufacturing method of the additive for granular resins of this invention is demonstrated in detail. In the present specification, it is possible to arbitrarily adopt provisions that are preferable, and it can be said that a combination of preferable ones is more preferable.
以下、本発明の顆粒状樹脂用添加剤の製造方法について詳細に説明する。なお、本明細書において、好ましいとされている規定は任意に採用することができ、好ましいもの同士の組み合わせはより好ましいと言える。 In the method for producing an additive for granular resin of the present invention, a wet product is obtained by adding water and a wetting agent to the resin additive, and then the wet product is granulated by a granulator and wetted. In the form of a granulated product, the wet granulated product is dried.
Hereinafter, the manufacturing method of the additive for granular resins of this invention is demonstrated in detail. In the present specification, it is possible to arbitrarily adopt provisions that are preferable, and it can be said that a combination of preferable ones is more preferable.
［樹脂用添加剤］
本発明の顆粒状樹脂用添加剤の製造方法に使用される樹脂用添加剤は、熱可塑性樹脂に使用される添加剤であれば、特に限定されるものではなく、例えば、結晶化核剤、紫外線吸収剤、光安定剤、酸化防止材、帯電防止剤、難燃剤、スリップ剤、無機フィラー、有機顔料、無機顔料、染料や顔料等の着色剤等を挙げることができる。これらの添加剤は、１種を、又は２種以上を混合して用いることができる。 [Additives for resins]
The additive for resin used in the method for producing the additive for granular resin of the present invention is not particularly limited as long as it is an additive used for a thermoplastic resin. For example, a crystallization nucleating agent, Examples thereof include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, slip agents, inorganic fillers, organic pigments, inorganic pigments, and coloring agents such as dyes and pigments. These additives can be used alone or in combination of two or more.
本発明の顆粒状樹脂用添加剤の製造方法に使用される樹脂用添加剤は、熱可塑性樹脂に使用される添加剤であれば、特に限定されるものではなく、例えば、結晶化核剤、紫外線吸収剤、光安定剤、酸化防止材、帯電防止剤、難燃剤、スリップ剤、無機フィラー、有機顔料、無機顔料、染料や顔料等の着色剤等を挙げることができる。これらの添加剤は、１種を、又は２種以上を混合して用いることができる。 [Additives for resins]
The additive for resin used in the method for producing the additive for granular resin of the present invention is not particularly limited as long as it is an additive used for a thermoplastic resin. For example, a crystallization nucleating agent, Examples thereof include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, slip agents, inorganic fillers, organic pigments, inorganic pigments, and coloring agents such as dyes and pigments. These additives can be used alone or in combination of two or more.
［樹脂用添加剤に添加する水］
本発明の顆粒状樹脂用添加剤の製造方法には、樹脂用添加剤に添加するために水が使用される。水は、樹脂用添加剤をウェット化させてウェット化物を得るために使用される。水の添加量は、樹脂用添加剤１００質量部に対して、３～１５０質量部、好ましくは５～１００質量部、更に好ましくは５０～７０質量部が添加される。水の添加量を３質量部以上とすることにより樹脂用添加剤を適度にウェット化させることができ、１５０質量部以下とすることにより樹脂用添加剤をウェット化させて得られるウェット化物の乾燥を効率よく行うことができるので、顆粒状樹脂用添加剤の流動性を低下させる恐れが少なくなる。 [Water to be added to resin additive]
In the method for producing an additive for granular resin of the present invention, water is used for addition to the additive for resin. Water is used to wet the resin additive to obtain a wet product. The amount of water added is 3 to 150 parts by weight, preferably 5 to 100 parts by weight, and more preferably 50 to 70 parts by weight with respect to 100 parts by weight of the resin additive. By making the additive amount of water 3 parts by mass or more, it is possible to appropriately wet the resin additive, and by making it 150 parts by mass or less, drying the wet product obtained by wetting the resin additive Can be performed efficiently, so that the possibility of reducing the fluidity of the additive for granular resin is reduced.
本発明の顆粒状樹脂用添加剤の製造方法には、樹脂用添加剤に添加するために水が使用される。水は、樹脂用添加剤をウェット化させてウェット化物を得るために使用される。水の添加量は、樹脂用添加剤１００質量部に対して、３～１５０質量部、好ましくは５～１００質量部、更に好ましくは５０～７０質量部が添加される。水の添加量を３質量部以上とすることにより樹脂用添加剤を適度にウェット化させることができ、１５０質量部以下とすることにより樹脂用添加剤をウェット化させて得られるウェット化物の乾燥を効率よく行うことができるので、顆粒状樹脂用添加剤の流動性を低下させる恐れが少なくなる。 [Water to be added to resin additive]
In the method for producing an additive for granular resin of the present invention, water is used for addition to the additive for resin. Water is used to wet the resin additive to obtain a wet product. The amount of water added is 3 to 150 parts by weight, preferably 5 to 100 parts by weight, and more preferably 50 to 70 parts by weight with respect to 100 parts by weight of the resin additive. By making the additive amount of water 3 parts by mass or more, it is possible to appropriately wet the resin additive, and by making it 150 parts by mass or less, drying the wet product obtained by wetting the resin additive Can be performed efficiently, so that the possibility of reducing the fluidity of the additive for granular resin is reduced.
［樹脂用添加剤に添加する湿潤剤］
本発明の顆粒状樹脂用添加剤の製造方法には、樹脂用添加剤に添加するための水とともに、湿潤剤が添加される。湿潤剤を添加することにより、ウェット化物を造粒してウェット状の顆粒化物を得る際に、造粒性を改善することができる。
本発明で使用される湿潤剤としては、ポリオキシアルキレンソルビタンアルキレート、ポリオキシアルキレングリコール、アルキルスルフォコハク酸ナトリウム、及びプロパンジオールから選ばれる化合物を用いることが好ましい。 [Wetting agent added to resin additives]
In the method for producing an additive for granular resin of the present invention, a wetting agent is added together with water to be added to the additive for resin. By adding a wetting agent, the granulation property can be improved when the wet product is granulated to obtain a wet granulated product.
As the wetting agent used in the present invention, it is preferable to use a compound selected from polyoxyalkylene sorbitan alkylate, polyoxyalkylene glycol, sodium alkylsulfosuccinate, and propanediol.
本発明の顆粒状樹脂用添加剤の製造方法には、樹脂用添加剤に添加するための水とともに、湿潤剤が添加される。湿潤剤を添加することにより、ウェット化物を造粒してウェット状の顆粒化物を得る際に、造粒性を改善することができる。
本発明で使用される湿潤剤としては、ポリオキシアルキレンソルビタンアルキレート、ポリオキシアルキレングリコール、アルキルスルフォコハク酸ナトリウム、及びプロパンジオールから選ばれる化合物を用いることが好ましい。 [Wetting agent added to resin additives]
In the method for producing an additive for granular resin of the present invention, a wetting agent is added together with water to be added to the additive for resin. By adding a wetting agent, the granulation property can be improved when the wet product is granulated to obtain a wet granulated product.
As the wetting agent used in the present invention, it is preferable to use a compound selected from polyoxyalkylene sorbitan alkylate, polyoxyalkylene glycol, sodium alkylsulfosuccinate, and propanediol.
前記ポリオキシアルキレンソルビタンアルキレートとしては、ポリオキシエチレンソルビタンモノ（またはジ、トリ）ラウレート、ポリオキシエチレンソルビタンモノ（またはジ、トリ）ステアレート、ポリオキシエチレンソルビタンモノ（またはジ、トリ）オレエート等が挙げられる。
Examples of the polyoxyalkylene sorbitan alkylate include polyoxyethylene sorbitan mono (or di, tri) laurate, polyoxyethylene sorbitan mono (or di, tri) stearate, polyoxyethylene sorbitan mono (or di, tri) oleate, etc. Is mentioned.
前記ポリオキシアルキレングリコールとしては、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリエチレン／ポリプロピレングリコールなどのポリアルキレングリコール類；メトキシポリエチレングリコール、エトキシポリエチレングリコール、プロポキシポリエチレングリコール、ブトキシポリエチレングリコール、ペンチルオキシポリエチレングリコール、ヘキシルオキシペンチルオキシポリエチレングリコール、オクチルオキシペンチルオキシポリエチレングリコール、ノニルアルコキシポリエチレングリコールなどの低級アルコールおよび炭素原子数８以上の高級アルコールのオキシエチレン付加物；メトキシポリエチレン／ポリプロピレングリコール、メトキシポリエチレン／ポリブチレングリコール、エトキシポリエチレン／ポリプロピレングリコール、エトキシポリエチレン／ポリブチレングリコール、プロポキシポリエチレン／ポリプロピレングリコール、プロポキシポリエチレン／ポリブチレングリコール、ブトキシポリエチレン／ポリプロピレングリコール、ペンチルオキシポリエチレン／ポリプロピレングリコール、ブトキシポリエチレン／ポリブチレングリコール、ヘキシルオキシポリエチレン／ポリプロピレングリコール、ヘキシルオキシポリエチレン／ポリブチレングリコール、オクチルオキシポリエチレン／ポリプロピレングリコール、オクチルオキシポリエチレン／ポリブチレングリコール、ノニルアルコキシポリエチレン／ポリプロピレングリコール、ノニルアルコキシポリエチレン／ポリブチレングリコールなどの低級アルコールおよび炭素原子数８以上の高級アルコールのオキシエチレンを必須とする２種以上のオキシアルキレン付加物などが挙げられる。これらの中でも、ポリエチレングリコール、ポリプロピレングリコール、メトキシポリエチレングリコール、エトキシポリエチレングリコールなどの低級アルコールのオキシエチレン付加物が好ましく、ポリオキシエチレンポリオキシプロピレングリコール、ポリプロピレングリコール、ポリエチレングリコールが好ましい。
Examples of the polyoxyalkylene glycol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyethylene / polypropylene glycol; methoxy polyethylene glycol, ethoxy polyethylene glycol, propoxy polyethylene glycol, butoxy polyethylene glycol, pentyloxy polyethylene glycol, hexyloxy Oxyethylene adducts of lower alcohols and higher alcohols having 8 or more carbon atoms such as pentyloxypolyethylene glycol, octyloxypentyloxypolyethylene glycol, nonylalkoxypolyethylene glycol; methoxypolyethylene / polypropyleneglycol, methoxypolyethylene / polybutyleneglycol, etho Si polyethylene / polypropylene glycol, ethoxy polyethylene / polybutylene glycol, propoxy polyethylene / polypropylene glycol, propoxy polyethylene / polybutylene glycol, butoxy polyethylene / polypropylene glycol, pentyloxy polyethylene / polypropylene glycol, butoxy polyethylene / polybutylene glycol, hexyloxy polyethylene / Lower grades such as polypropylene glycol, hexyloxypolyethylene / polybutylene glycol, octyloxypolyethylene / polypropylene glycol, octyloxypolyethylene / polybutylene glycol, nonylalkoxypolyethylene / polypropyleneglycol, nonylalkoxypolyethylene / polybutyleneglycol Alcohol and two or more kinds of oxyalkylene adducts of the essential oxyethylene 8 or more carbon atoms of the higher alcohol and the like. Among these, oxyethylene adducts of lower alcohols such as polyethylene glycol, polypropylene glycol, methoxy polyethylene glycol, and ethoxy polyethylene glycol are preferable, and polyoxyethylene polyoxypropylene glycol, polypropylene glycol, and polyethylene glycol are preferable.
前記アルキルスルフォコハク酸ナトリウムとしては、ジアルキルスルフォコハク酸ナトリウム、モノアルキルスルフォコハク酸ナトリウム等の化合物を挙げることができ、ジアルキルスルフォコハク酸ナトリウムが好ましい。ジアルキルスルフォコハク酸ナトリウムは、通常、アルキル基の炭素原子数が８（Ｃ８）のオクチル系（２エチルヘキシル系）の化合物が挙げられる。また、前記プロパンジオールとしては、１，３－プロパンジオール、２，３－プロパンジオールが挙げられる。
Examples of the sodium alkylsulfosuccinate include compounds such as sodium dialkylsulfosuccinate and sodium monoalkylsulfosuccinate, and sodium dialkylsulfosuccinate is preferred. Examples of sodium dialkylsulfosuccinates include octyl (2-ethylhexyl) compounds in which the alkyl group has 8 (C8) carbon atoms. Examples of the propanediol include 1,3-propanediol and 2,3-propanediol.
前記湿潤剤は、水１００質量部に対して、０．０１～１５質量部添加することが好ましく、０．１～１０質量部添加することがより好ましく、０．５～５質量部添加することが更に好ましい。湿潤剤を０．０１質量部以上添加することにより、造粒性を改善することができ、１５質量部以下添加することにより、最終製品として得られる熱可塑性樹脂組成物から得られる成形品から湿潤剤がブリードアウトするのを防止することができる。
The wetting agent is preferably added in an amount of 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of water. Is more preferable. By adding 0.01 part by mass or more of a wetting agent, the granulation property can be improved, and by adding 15 parts by mass or less, the molded product obtained from the thermoplastic resin composition obtained as a final product is moistened. The agent can be prevented from bleeding out.
[顆粒化方法]
本発明の顆粒状樹脂用添加剤の製造方法では、ヘンシェルミキサー等の混合機に、樹脂用添加剤、所定量の水、及び所定量の湿潤剤を投入し、均一に混合してウェット化させ、ウェット化物を得る。次いで、得られたウェット化物を造粒機により顆粒化して、ウェット状の顆粒化物を得る。造粒機としては特に限定されるものではないが、円筒造粒機や湿式押出造粒機を用いることが好ましい。ウェット状の顆粒化物のサイズとしては、最大径が０．１～７ｍｍ、好ましくは、０．３～５ｍｍとすることにより、分散性と乾燥性を好ましいものとすることができる。
このようにして得られたウェット状の顆粒化物から水分を除去するために乾燥して、顆粒状樹脂用添加剤を得ることができる。乾燥するために使用する乾燥機としては、特に限定されるものではなく、熱風乾燥機、減圧乾燥機等の乾燥機を用いることができる。乾燥温度は、使用する樹脂用添加剤の分解温度以下であれば、特に限定されるものではないが、水分含有率、ウェット状の顆粒化物のサイズ、乾燥時間から、任意の温度に設定して乾燥することができる。通常は、５０～１５０℃で、３０分～２４時間の範囲内で乾燥すればよい。乾燥後の水分含有率は、５質量％以下、好ましくは３質量％以下となるようにすることが望ましい。このようにして得られる顆粒状樹脂用添加剤は、安息角を４５°以下、好ましくは４０°以下とすることができるので、流動性に優れる顆粒状樹脂用添加剤を得ることができる。なお、安息角の下限値については、特に限定されるものではないが、通常は、３０°程度である。 [Granulation method]
In the method for producing an additive for granular resin of the present invention, a resin additive, a predetermined amount of water, and a predetermined amount of wetting agent are charged into a mixer such as a Henschel mixer, and the mixture is uniformly mixed and wetted. Get wet. Next, the obtained wet product is granulated with a granulator to obtain a wet granulated product. Although it does not specifically limit as a granulator, It is preferable to use a cylindrical granulator and a wet extrusion granulator. With respect to the size of the wet granulated product, the maximum diameter is 0.1 to 7 mm, preferably 0.3 to 5 mm, so that dispersibility and drying properties can be made preferable.
The wet granulation product thus obtained can be dried to remove moisture, thereby obtaining an additive for granular resin. The dryer used for drying is not particularly limited, and a dryer such as a hot air dryer or a vacuum dryer can be used. The drying temperature is not particularly limited as long as it is equal to or lower than the decomposition temperature of the resin additive to be used. Can be dried. Usually, it may be dried at 50 to 150 ° C. for 30 minutes to 24 hours. The moisture content after drying is desirably 5% by mass or less, preferably 3% by mass or less. The granular resin additive thus obtained can have an angle of repose of 45 ° or less, preferably 40 ° or less, so that an additive for granular resin having excellent fluidity can be obtained. The lower limit of the angle of repose is not particularly limited, but is usually about 30 °.
本発明の顆粒状樹脂用添加剤の製造方法では、ヘンシェルミキサー等の混合機に、樹脂用添加剤、所定量の水、及び所定量の湿潤剤を投入し、均一に混合してウェット化させ、ウェット化物を得る。次いで、得られたウェット化物を造粒機により顆粒化して、ウェット状の顆粒化物を得る。造粒機としては特に限定されるものではないが、円筒造粒機や湿式押出造粒機を用いることが好ましい。ウェット状の顆粒化物のサイズとしては、最大径が０．１～７ｍｍ、好ましくは、０．３～５ｍｍとすることにより、分散性と乾燥性を好ましいものとすることができる。
このようにして得られたウェット状の顆粒化物から水分を除去するために乾燥して、顆粒状樹脂用添加剤を得ることができる。乾燥するために使用する乾燥機としては、特に限定されるものではなく、熱風乾燥機、減圧乾燥機等の乾燥機を用いることができる。乾燥温度は、使用する樹脂用添加剤の分解温度以下であれば、特に限定されるものではないが、水分含有率、ウェット状の顆粒化物のサイズ、乾燥時間から、任意の温度に設定して乾燥することができる。通常は、５０～１５０℃で、３０分～２４時間の範囲内で乾燥すればよい。乾燥後の水分含有率は、５質量％以下、好ましくは３質量％以下となるようにすることが望ましい。このようにして得られる顆粒状樹脂用添加剤は、安息角を４５°以下、好ましくは４０°以下とすることができるので、流動性に優れる顆粒状樹脂用添加剤を得ることができる。なお、安息角の下限値については、特に限定されるものではないが、通常は、３０°程度である。 [Granulation method]
In the method for producing an additive for granular resin of the present invention, a resin additive, a predetermined amount of water, and a predetermined amount of wetting agent are charged into a mixer such as a Henschel mixer, and the mixture is uniformly mixed and wetted. Get wet. Next, the obtained wet product is granulated with a granulator to obtain a wet granulated product. Although it does not specifically limit as a granulator, It is preferable to use a cylindrical granulator and a wet extrusion granulator. With respect to the size of the wet granulated product, the maximum diameter is 0.1 to 7 mm, preferably 0.3 to 5 mm, so that dispersibility and drying properties can be made preferable.
The wet granulation product thus obtained can be dried to remove moisture, thereby obtaining an additive for granular resin. The dryer used for drying is not particularly limited, and a dryer such as a hot air dryer or a vacuum dryer can be used. The drying temperature is not particularly limited as long as it is equal to or lower than the decomposition temperature of the resin additive to be used. Can be dried. Usually, it may be dried at 50 to 150 ° C. for 30 minutes to 24 hours. The moisture content after drying is desirably 5% by mass or less, preferably 3% by mass or less. The granular resin additive thus obtained can have an angle of repose of 45 ° or less, preferably 40 ° or less, so that an additive for granular resin having excellent fluidity can be obtained. The lower limit of the angle of repose is not particularly limited, but is usually about 30 °.
[熱可塑性樹脂組成物及び成形品]
本発明の顆粒状樹脂用添加剤の製造方法によって得られる顆粒状樹脂用添加剤は、熱可塑性樹脂に添加して、熱可塑性樹脂組成物とすることができる。熱可塑性樹脂としては、結晶性熱可塑性樹脂及び非晶性熱可塑性樹脂を挙げることができる。結晶性熱可塑性樹脂としては、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂、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等の芳香族系ポリエステル系樹脂、ポリカプロラクトン等のポリエステル、ナイロン－６、ナイロン－６６、ナイロン－１２等の脂肪族ポリアミド、芳香族ジカルボン酸と脂肪族ジアミンより製造される芳香族ポリアミド等のポリアミド系樹脂、ポリホルムアルデヒド（ポリオキシメチレン）、ポリアセトアルデヒド、ポリプロピレンアルデヒド、ポリブチルアルデヒド等のポリアセタール系樹脂、ポリフェニレンサルファイド樹脂（ＰＰＳ）等を挙げることができる。また、非晶性熱可塑性樹脂としては、ポリスチレン（ＰＳ）、ＡＳ、ＡＢＳ等のスチレン系樹脂、ポリ塩化ビニル樹脂、アクリル樹脂、ポリカーボネート樹脂、エチレン－酢酸ビニル共重合樹脂、ポリイミド樹脂、ポリサルフォン樹脂、ポリフェニレンエーテル樹脂等を挙げることができる。これらの熱可塑性樹脂は、単独で使用してもよいし、２種以上として使用してもよい。特に、熱可塑性樹脂として、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂等の結晶性熱可塑性樹脂は、前述したように、透明性を向上させる目的や、剛性、耐熱性等を向上させる目的で、添加剤として結晶化核剤が使用される。特に、ポリオレフィン系樹脂に対しては、以下に記載する結晶化核剤を挙げることができる。 [Thermoplastic resin composition and molded product]
The additive for granular resins obtained by the method for producing an additive for granular resins of the present invention can be added to a thermoplastic resin to obtain a thermoplastic resin composition. Examples of the thermoplastic resin include a crystalline thermoplastic resin and an amorphous thermoplastic resin. Examples of the crystalline thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, aromatic polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyesters such as polycaprolactone, nylon-6, nylon-66, and nylon-12. Aliphatic polyamides, polyamide resins such as aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines, polyacetal resins such as polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropylene aldehyde, polybutyraldehyde, polyphenylene Examples thereof include sulfide resin (PPS). Amorphous thermoplastic resins include styrene resins such as polystyrene (PS), AS, and ABS, polyvinyl chloride resins, acrylic resins, polycarbonate resins, ethylene-vinyl acetate copolymer resins, polyimide resins, polysulfone resins, A polyphenylene ether resin etc. can be mentioned. These thermoplastic resins may be used alone or in combination of two or more. In particular, as a thermoplastic resin, a crystalline thermoplastic resin such as a polyolefin resin, a polyester resin, or a polyamide resin is used for the purpose of improving the transparency, the rigidity, the heat resistance, etc. as described above. A crystallization nucleating agent is used as an additive. In particular, for polyolefin resins, the crystallization nucleating agents described below can be mentioned.
本発明の顆粒状樹脂用添加剤の製造方法によって得られる顆粒状樹脂用添加剤は、熱可塑性樹脂に添加して、熱可塑性樹脂組成物とすることができる。熱可塑性樹脂としては、結晶性熱可塑性樹脂及び非晶性熱可塑性樹脂を挙げることができる。結晶性熱可塑性樹脂としては、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂、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等の芳香族系ポリエステル系樹脂、ポリカプロラクトン等のポリエステル、ナイロン－６、ナイロン－６６、ナイロン－１２等の脂肪族ポリアミド、芳香族ジカルボン酸と脂肪族ジアミンより製造される芳香族ポリアミド等のポリアミド系樹脂、ポリホルムアルデヒド（ポリオキシメチレン）、ポリアセトアルデヒド、ポリプロピレンアルデヒド、ポリブチルアルデヒド等のポリアセタール系樹脂、ポリフェニレンサルファイド樹脂（ＰＰＳ）等を挙げることができる。また、非晶性熱可塑性樹脂としては、ポリスチレン（ＰＳ）、ＡＳ、ＡＢＳ等のスチレン系樹脂、ポリ塩化ビニル樹脂、アクリル樹脂、ポリカーボネート樹脂、エチレン－酢酸ビニル共重合樹脂、ポリイミド樹脂、ポリサルフォン樹脂、ポリフェニレンエーテル樹脂等を挙げることができる。これらの熱可塑性樹脂は、単独で使用してもよいし、２種以上として使用してもよい。特に、熱可塑性樹脂として、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂等の結晶性熱可塑性樹脂は、前述したように、透明性を向上させる目的や、剛性、耐熱性等を向上させる目的で、添加剤として結晶化核剤が使用される。特に、ポリオレフィン系樹脂に対しては、以下に記載する結晶化核剤を挙げることができる。 [Thermoplastic resin composition and molded product]
The additive for granular resins obtained by the method for producing an additive for granular resins of the present invention can be added to a thermoplastic resin to obtain a thermoplastic resin composition. Examples of the thermoplastic resin include a crystalline thermoplastic resin and an amorphous thermoplastic resin. Examples of the crystalline thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, aromatic polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyesters such as polycaprolactone, nylon-6, nylon-66, and nylon-12. Aliphatic polyamides, polyamide resins such as aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines, polyacetal resins such as polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropylene aldehyde, polybutyraldehyde, polyphenylene Examples thereof include sulfide resin (PPS). Amorphous thermoplastic resins include styrene resins such as polystyrene (PS), AS, and ABS, polyvinyl chloride resins, acrylic resins, polycarbonate resins, ethylene-vinyl acetate copolymer resins, polyimide resins, polysulfone resins, A polyphenylene ether resin etc. can be mentioned. These thermoplastic resins may be used alone or in combination of two or more. In particular, as a thermoplastic resin, a crystalline thermoplastic resin such as a polyolefin resin, a polyester resin, or a polyamide resin is used for the purpose of improving the transparency, the rigidity, the heat resistance, etc. as described above. A crystallization nucleating agent is used as an additive. In particular, for polyolefin resins, the crystallization nucleating agents described below can be mentioned.
前記ポリオレフィン系樹脂に対する結晶化核剤としては、（ａ）安息香酸金属塩、（ｂ）ソルビトール誘導体、ノニトール誘導体等の多価アルコール誘導体、（ｃ）有機機リン酸エステル金属塩、（ｄ）分岐状オレフィン等を使用することができる。具体的には（ａ）ｐ－tert－ブチル安息香酸アルミニウム等、（ｂ）ジベンジリデンソルビトール、ビス（４－メチルベンジリデン）ソルビトール、１，２，３－トリデオキシ－４，６：５，７－ビス－［（４－プロピルフェニル）メチレン］－ノニトール等、（ｃ）ナトリウム－２，２－メチレンビス（４，６－ジ－tert－ブチルフェニル）ホスフェート等、（ｄ）３－メチル－１－ブテン、３，３－ジメチル－１－ブテン、３－メチル－１－ペンテン、４－メチル－１－ペンテン、３－メチル－１－ペンテン等の単独重合体または共重合体等が挙げられる。これらの結晶化核剤をポリオレフィン系樹脂に添加する場合、結晶化核剤の流動性が良くないので定量供給性に劣るが、特に、ソルビトール誘導体、ノニトール誘導体、及び安息香酸金属塩を結晶化核剤として用いる場合、本発明の製造方法を用いることにより計量性を改善することができ、熱可塑性樹脂組成物を効率よく得ることができる。
As the crystallization nucleating agent for the polyolefin resin, (a) benzoic acid metal salt, (b) polyhydric alcohol derivative such as sorbitol derivative, nonitol derivative, (c) organic phosphate metal salt, (d) branched A olefin or the like can be used. Specifically, (a) aluminum p-tert-butylbenzoate, etc., (b) dibenzylidene sorbitol, bis (4-methylbenzylidene) sorbitol, 1,2,3-trideoxy-4,6: 5,7-bis -[(4-propylphenyl) methylene] -nonitol, etc., (c) sodium-2,2-methylenebis (4,6-di-tert-butylphenyl) phosphate, etc., (d) 3-methyl-1-butene, Examples include homopolymers or copolymers of 3,3-dimethyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene, and the like. When these crystallization nucleating agents are added to polyolefin-based resins, the flowability of the crystallization nucleating agent is not good, so the quantitative supply is inferior. In particular, sorbitol derivatives, nonitol derivatives, and metal benzoates are used as crystallization nuclei. When used as an agent, meterability can be improved by using the production method of the present invention, and a thermoplastic resin composition can be obtained efficiently.
前記ポリオレフィン系樹脂に対する結晶化核剤の具体例としては、商品名として旭電化製のＮＡ－２１やＮＡ－１１（登録商標）、新日本理化製のゲルオールＭＤ（登録商標）、ミリケン社製のミラード３９８８（登録商標）、ＮＸ８０００（登録商標）、三井化学製のＮＣ－４（登録商標）などが例示される。なかでもミリケン社製のミラードＮＸ８０００（登録商標）に代表されるノニトール誘導体やミラード３９８８（登録商標）に代表されるソルビトール誘導体は透明性の改質効果に優れており、透明性に優れたポリオレフィン系樹脂シート、フィルムを得ることができる。結晶性熱可塑性樹脂に結晶化核剤を添加する場合の添加量としては、通常、結晶性熱可塑性樹脂１００質量部あたり０．０１～５質量部、より好ましくは０．０５～２質量部が好適である。この範囲内で結晶化核剤を結晶性熱可塑性樹脂に添加することにより、結晶化核剤としての効果を発揮させることができ、また、結晶化核剤の凝集による透明性が損なわれにくくなる。
As specific examples of the crystallization nucleating agent for the polyolefin resin, trade names such as NA-21 and NA-11 (registered trademark) manufactured by Asahi Denka, Gelall MD (registered trademark) manufactured by Shin Nippon Chemical Co., Ltd. Examples include Millard 3988 (registered trademark), NX8000 (registered trademark), and NC-4 (registered trademark) manufactured by Mitsui Chemicals. Among them, nonitol derivatives represented by Millard NX8000 (registered trademark) manufactured by Milliken and sorbitol derivatives represented by Millard 3988 (registered trademark) are excellent in the effect of improving transparency, and polyolefins having excellent transparency. A resin sheet and a film can be obtained. The amount of crystallization nucleating agent added to the crystalline thermoplastic resin is usually 0.01 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, per 100 parts by mass of the crystalline thermoplastic resin. Is preferred. By adding the crystallization nucleating agent to the crystalline thermoplastic resin within this range, the effect as the crystallization nucleating agent can be exerted, and the transparency due to the aggregation of the crystallization nucleating agent is hardly impaired. .
本発明の顆粒状樹脂用添加剤の製造方法によって得られる顆粒状樹脂用添加剤を熱可塑性樹脂に添加して、熱可塑性樹脂組成物とするには、一軸混練押出機や二軸混練押出機等の押出機を使用して溶融混練させ、ペレット化して熱可塑性樹脂組成物を製造することができる。押出機を使用して溶融混練させペレット化した熱可塑性樹脂組成物を製造する際は、連続的に供給する熱可塑性樹脂に対して一定量の顆粒状樹脂用添加剤をポッパー等から連続的に事前に熱可塑性樹脂に添加し、顆粒状樹脂用添加剤を含む熱可塑性樹脂を押出機に供給して溶融混練させてペレット化したり、又は押出機中の溶融状態の熱可塑性樹脂に対して、ポッパー等から連続的に一定量の顆粒状樹脂用添加剤をサイドフィードすることにより定量的に添加し、溶融混練させてペレット化することができる。前述したとおり、本発明の顆粒状樹脂用添加剤の製造方法によって得られる顆粒状樹脂用添加剤は、安息角が低いので、流動性に優れ、ポッパー等内の容器内でブロッキング化する恐れが少なく、連続的に供給する際に、定量供給性に優れた効果を有する。熱可塑性樹脂組成物を製造するに当たっては、前記顆粒状樹脂用添加剤以外に、熱可塑性樹脂にガラス繊維、炭素繊維等の繊維状物、タルク、マイカ、二酸化チタン等の無機充填材、着色剤、紫外線吸収剤、光安定剤、酸化防止材、帯電防止剤、難燃剤、スリップ剤等の添加剤を添加してペレット化して熱可塑性樹脂組成物を製造することができる。このようにして得られる本発明の熱可塑性樹脂組成物は、射出成形、押出成形、ブロー成形、インフレーション成形、圧縮成形等の公知の成形方法により、シート、フィルム、パイプ、家電製品、携帯電話やＯＡ機器等の電子機器、自動車部品等に使用される各種の成形品を得ることができる。
In order to obtain the thermoplastic resin composition by adding the additive for granular resin obtained by the method for producing the additive for granular resin of the present invention to the thermoplastic resin, a uniaxial kneading extruder or a biaxial kneading extruder A thermoplastic resin composition can be produced by melt-kneading using an extruder such as the above, and pelletizing. When producing a thermoplastic resin composition that is melt-kneaded and pelletized using an extruder, a certain amount of additive for granular resin is continuously added from a popper or the like to the continuously supplied thermoplastic resin. Add to the thermoplastic resin in advance, supply the thermoplastic resin containing the additive for the granular resin to the extruder, melt kneaded and pelletized, or for the thermoplastic resin in the molten state in the extruder, A certain amount of the additive for granular resin can be added quantitatively by side-feeding continuously from a popper or the like, and melt-kneaded to be pelletized. As described above, the additive for granular resin obtained by the method for producing an additive for granular resin of the present invention has a low angle of repose, so it has excellent fluidity and may be blocked in a container such as a popper. There are few, and when it supplies continuously, it has the effect excellent in quantitative supply. In producing the thermoplastic resin composition, in addition to the additive for granular resin, the thermoplastic resin is fibrous material such as glass fiber, carbon fiber, inorganic filler such as talc, mica, titanium dioxide, and coloring agent. Additives such as ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, slip agents and the like can be pelletized to produce a thermoplastic resin composition. The thermoplastic resin composition of the present invention thus obtained can be obtained by a known molding method such as injection molding, extrusion molding, blow molding, inflation molding, compression molding, or the like, as a sheet, film, pipe, home appliance, mobile phone, Various molded products used for electronic devices such as OA devices, automobile parts, and the like can be obtained.
以下に実施例及び比較例を挙げて、本発明をさらに詳しく説明するが、本発明はこれらの例示に限定されるものではない。なお、文中の配合比率は、質量基準である。
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the mixture ratio in a sentence is a mass reference | standard.
実施例１
樹脂用添加剤として結晶化核剤[ミリケン社製：ソルビトール系核剤、ミラード３９８８]１００質量部に、湿潤剤としてジ（２－エチルヘキシル）スルホコハク酸ナトリウム０．８質量部と２，３－プロパンジオール０．４質量部を５８．８質量部の水に添加して溶解させた水溶液６０質量部をヘンシェルミキサーに投入混合してウェット化された混合物を得た。この混合物を湿式押出造粒機[不二パウダル社製、エックペレッター]に投入して、直径１ｍｍの湿潤した顆粒化物を製造した。この顆粒化物を箱形乾燥機にて９０℃で８時間乾燥して、水分含有率が１．２質量％の顆粒状樹脂用添加剤を製造した。得られた顆粒状樹脂用添加剤の定量供給性を評価する為に、透明容器中にて傾斜法による安息角を測定し、顆粒状樹脂用添加剤の流動性を評価した。ついで、ポリプロピレン（プライムポリマーＪ７００ＧＰ）１００質量部に対して、得られた結晶化核剤の顆粒状樹脂用添加剤を０．４質量部添加して、射出成形機にて設定温度２３０℃で成型して厚さ２ｍｍのシート状成形物を成形し、透明性を評価した。顆粒状樹脂用添加剤を製造する際に使用した各成分について、表１に示す。また、顆粒状樹脂用添加剤の造粒性、安息角、及びシート状成形物の透明性について評価した。その結果を表２に示す。 Example 1
A crystallization nucleating agent [manufactured by Milliken: sorbitol-based nucleating agent, Millard 3988] as a resin additive, 100 parts by mass of sodium di (2-ethylhexyl) sulfosuccinate as a wetting agent and 2,3-propane 60 parts by mass of an aqueous solution in which 0.4 part by mass of diol was added to 58.8 parts by mass of water and dissolved therein was charged into a Henschel mixer to obtain a wet mixture. This mixture was put into a wet extrusion granulator (Fuji Paudal, ec pelleter) to produce a wet granulated product having a diameter of 1 mm. The granulated product was dried at 90 ° C. for 8 hours with a box dryer to produce an additive for granular resin having a water content of 1.2% by mass. In order to evaluate the quantitative supply of the obtained additive for granular resin, the angle of repose was measured in a transparent container by the tilt method, and the fluidity of the additive for granular resin was evaluated. Next, 0.4 parts by mass of the obtained crystallization nucleating agent for granular resin is added to 100 parts by mass of polypropylene (prime polymer J700GP), and then molded at a set temperature of 230 ° C. with an injection molding machine. Then, a sheet-like molded product having a thickness of 2 mm was molded, and the transparency was evaluated. It shows in Table 1 about each component used when manufacturing the additive for granular resins. Moreover, the granulation property of the granular resin additive, the angle of repose, and the transparency of the sheet-like molded product were evaluated. The results are shown in Table 2.
樹脂用添加剤として結晶化核剤[ミリケン社製：ソルビトール系核剤、ミラード３９８８]１００質量部に、湿潤剤としてジ（２－エチルヘキシル）スルホコハク酸ナトリウム０．８質量部と２，３－プロパンジオール０．４質量部を５８．８質量部の水に添加して溶解させた水溶液６０質量部をヘンシェルミキサーに投入混合してウェット化された混合物を得た。この混合物を湿式押出造粒機[不二パウダル社製、エックペレッター]に投入して、直径１ｍｍの湿潤した顆粒化物を製造した。この顆粒化物を箱形乾燥機にて９０℃で８時間乾燥して、水分含有率が１．２質量％の顆粒状樹脂用添加剤を製造した。得られた顆粒状樹脂用添加剤の定量供給性を評価する為に、透明容器中にて傾斜法による安息角を測定し、顆粒状樹脂用添加剤の流動性を評価した。ついで、ポリプロピレン（プライムポリマーＪ７００ＧＰ）１００質量部に対して、得られた結晶化核剤の顆粒状樹脂用添加剤を０．４質量部添加して、射出成形機にて設定温度２３０℃で成型して厚さ２ｍｍのシート状成形物を成形し、透明性を評価した。顆粒状樹脂用添加剤を製造する際に使用した各成分について、表１に示す。また、顆粒状樹脂用添加剤の造粒性、安息角、及びシート状成形物の透明性について評価した。その結果を表２に示す。 Example 1
A crystallization nucleating agent [manufactured by Milliken: sorbitol-based nucleating agent, Millard 3988] as a resin additive, 100 parts by mass of sodium di (2-ethylhexyl) sulfosuccinate as a wetting agent and 2,3-propane 60 parts by mass of an aqueous solution in which 0.4 part by mass of diol was added to 58.8 parts by mass of water and dissolved therein was charged into a Henschel mixer to obtain a wet mixture. This mixture was put into a wet extrusion granulator (Fuji Paudal, ec pelleter) to produce a wet granulated product having a diameter of 1 mm. The granulated product was dried at 90 ° C. for 8 hours with a box dryer to produce an additive for granular resin having a water content of 1.2% by mass. In order to evaluate the quantitative supply of the obtained additive for granular resin, the angle of repose was measured in a transparent container by the tilt method, and the fluidity of the additive for granular resin was evaluated. Next, 0.4 parts by mass of the obtained crystallization nucleating agent for granular resin is added to 100 parts by mass of polypropylene (prime polymer J700GP), and then molded at a set temperature of 230 ° C. with an injection molding machine. Then, a sheet-like molded product having a thickness of 2 mm was molded, and the transparency was evaluated. It shows in Table 1 about each component used when manufacturing the additive for granular resins. Moreover, the granulation property of the granular resin additive, the angle of repose, and the transparency of the sheet-like molded product were evaluated. The results are shown in Table 2.
実施例２
実施例１で使用した樹脂用添加剤の結晶化核剤として、ミリケン社製のノニトール系核剤ミラードＮＸ８０００Ｊを使用し、湿潤剤としてポリオキシエチレンソルビタンモノラウレートを０．６質量部、及び水を５９．４質量部とした以外は、実施例１と同様にして実施して、水分含有率が０．８質量％の顆粒状樹脂用添加剤を製造した。得られた顆粒状樹脂用添加剤を用いて、実施例１と同様にして顆粒状樹脂用添加剤の造粒性、安息角、及びシート状成形物の透明性について評価した。その結果を表１及び表２に示す。 Example 2
As the crystallization nucleating agent for the resin additive used in Example 1, Millitol NX8000J, a nonitol nucleating agent manufactured by Milliken Corporation, 0.6 parts by mass of polyoxyethylene sorbitan monolaurate as a wetting agent, and water Was carried out in the same manner as in Example 1 except that the content was changed to 59.4 parts by mass to produce an additive for granular resin having a water content of 0.8% by mass. Using the obtained additive for granular resin, the granularity of the additive for granular resin, the angle of repose, and the transparency of the sheet-like molded product were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
実施例１で使用した樹脂用添加剤の結晶化核剤として、ミリケン社製のノニトール系核剤ミラードＮＸ８０００Ｊを使用し、湿潤剤としてポリオキシエチレンソルビタンモノラウレートを０．６質量部、及び水を５９．４質量部とした以外は、実施例１と同様にして実施して、水分含有率が０．８質量％の顆粒状樹脂用添加剤を製造した。得られた顆粒状樹脂用添加剤を用いて、実施例１と同様にして顆粒状樹脂用添加剤の造粒性、安息角、及びシート状成形物の透明性について評価した。その結果を表１及び表２に示す。 Example 2
As the crystallization nucleating agent for the resin additive used in Example 1, Millitol NX8000J, a nonitol nucleating agent manufactured by Milliken Corporation, 0.6 parts by mass of polyoxyethylene sorbitan monolaurate as a wetting agent, and water Was carried out in the same manner as in Example 1 except that the content was changed to 59.4 parts by mass to produce an additive for granular resin having a water content of 0.8% by mass. Using the obtained additive for granular resin, the granularity of the additive for granular resin, the angle of repose, and the transparency of the sheet-like molded product were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
実施例３
実施例１で使用した樹脂用添加剤の結晶化核剤として、ジャパンケムテック社製のＡＬ－ＰＴＢＢＡ［化学名：ヒドロキシ－ジ（ｐ－ｔｅｒｔ－ブチル安息香酸）アルミニウム］を使用し、湿潤剤としてポリオキシエチレンソルビタンモノラウレート０．４質量部及びポリオキシエチレンポリオキシプロピレングリコール２．０質量部、並びに水を５７．６質量部とした以外は、実施例１と同様にして実施して、水分含有率が１．０質量％の顆粒状樹脂用添加剤を製造した。得られた顆粒状樹脂用添加剤を用いて、実施例１と同様にして顆粒状樹脂用添加剤の造粒性、安息角、及びシート状成形物の透明性について評価した。その結果を表１及び表２に示す。 Example 3
As a crystallization nucleating agent for the resin additive used in Example 1, AL-PTBBA [chemical name: hydroxy-di (p-tert-butylbenzoic acid) aluminum] manufactured by Japan Chemtech Co., Ltd. was used as a wetting agent. As in Example 1, except that 0.4 parts by mass of polyoxyethylene sorbitan monolaurate, 2.0 parts by mass of polyoxyethylene polyoxypropylene glycol, and 57.6 parts by mass of water were used. An additive for granular resin having a water content of 1.0% by mass was produced. Using the obtained additive for granular resin, the granularity of the additive for granular resin, the angle of repose, and the transparency of the sheet-like molded product were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
実施例１で使用した樹脂用添加剤の結晶化核剤として、ジャパンケムテック社製のＡＬ－ＰＴＢＢＡ［化学名：ヒドロキシ－ジ（ｐ－ｔｅｒｔ－ブチル安息香酸）アルミニウム］を使用し、湿潤剤としてポリオキシエチレンソルビタンモノラウレート０．４質量部及びポリオキシエチレンポリオキシプロピレングリコール２．０質量部、並びに水を５７．６質量部とした以外は、実施例１と同様にして実施して、水分含有率が１．０質量％の顆粒状樹脂用添加剤を製造した。得られた顆粒状樹脂用添加剤を用いて、実施例１と同様にして顆粒状樹脂用添加剤の造粒性、安息角、及びシート状成形物の透明性について評価した。その結果を表１及び表２に示す。 Example 3
As a crystallization nucleating agent for the resin additive used in Example 1, AL-PTBBA [chemical name: hydroxy-di (p-tert-butylbenzoic acid) aluminum] manufactured by Japan Chemtech Co., Ltd. was used as a wetting agent. As in Example 1, except that 0.4 parts by mass of polyoxyethylene sorbitan monolaurate, 2.0 parts by mass of polyoxyethylene polyoxypropylene glycol, and 57.6 parts by mass of water were used. An additive for granular resin having a water content of 1.0% by mass was produced. Using the obtained additive for granular resin, the granularity of the additive for granular resin, the angle of repose, and the transparency of the sheet-like molded product were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
比較例１
実施例２で使用した樹脂用添加剤の結晶化核剤を顆粒状樹脂用添加剤としないで、ポリプロピレン（プライムポリマーＪ７００ＧＰ）１００質量部に対して、０．４質量部添加してシート状成形物を成形した以外は、実施例２と同様にして実施した。その結果を表１及び表２に示す。 Comparative Example 1
Without using the resin additive crystallization nucleating agent used in Example 2 as a granular resin additive, 0.4 part by mass is added to 100 parts by mass of polypropylene (Prime Polymer J700GP) to form a sheet. This was carried out in the same manner as in Example 2 except that the product was molded. The results are shown in Tables 1 and 2.
実施例２で使用した樹脂用添加剤の結晶化核剤を顆粒状樹脂用添加剤としないで、ポリプロピレン（プライムポリマーＪ７００ＧＰ）１００質量部に対して、０．４質量部添加してシート状成形物を成形した以外は、実施例２と同様にして実施した。その結果を表１及び表２に示す。 Comparative Example 1
Without using the resin additive crystallization nucleating agent used in Example 2 as a granular resin additive, 0.4 part by mass is added to 100 parts by mass of polypropylene (Prime Polymer J700GP) to form a sheet. This was carried out in the same manner as in Example 2 except that the product was molded. The results are shown in Tables 1 and 2.
比較例２
実施例１において、湿潤剤を添加せずに同様にして、水分含有率が０．７質量％の顆粒状樹脂用添加剤を製造したが、混合物の流動性が低下して凝集状態となり、押出造粒機のメッシュを通過することができず、良好な顆粒状樹脂用添加剤を製造することができなかった。 Comparative Example 2
In Example 1, a granular resin additive having a water content of 0.7% by mass was produced in the same manner without adding a wetting agent. It could not pass through the mesh of the granulator and a good additive for granular resin could not be produced.
実施例１において、湿潤剤を添加せずに同様にして、水分含有率が０．７質量％の顆粒状樹脂用添加剤を製造したが、混合物の流動性が低下して凝集状態となり、押出造粒機のメッシュを通過することができず、良好な顆粒状樹脂用添加剤を製造することができなかった。 Comparative Example 2
In Example 1, a granular resin additive having a water content of 0.7% by mass was produced in the same manner without adding a wetting agent. It could not pass through the mesh of the granulator and a good additive for granular resin could not be produced.
比較例３
実施例２において、水を使用せず、かつ、湿潤剤として使用したポリオキシエチレンソルビタンモノラウレート０．６質量部に変えて、カルシウムステアレート１０質量部を使用し、湿式押出造粒機に変えて乾式造粒機[フロイントターボ社製、ローラーコンバクター]を使用した以外は、実施例２と同様にして、顆粒状樹脂用添加剤を製造した。得られた顆粒状樹脂用添加剤を用いて、実施例２と同様にして顆粒状樹脂用添加剤の造粒性、安息角、及びシート状成形物の透明性について評価した。その結果を表１及び表２に示す。 Comparative Example 3
In Example 2, water was not used and 10 parts by mass of calcium stearate was used instead of 0.6 parts by mass of polyoxyethylene sorbitan monolaurate used as a wetting agent. An additive for granular resin was produced in the same manner as in Example 2 except that a dry granulator (manufactured by Freund Turbo, roller compactor) was used instead. Using the obtained additive for granular resin, the granularity of the additive for granular resin, the angle of repose, and the transparency of the sheet-like molded product were evaluated in the same manner as in Example 2. The results are shown in Tables 1 and 2.
実施例２において、水を使用せず、かつ、湿潤剤として使用したポリオキシエチレンソルビタンモノラウレート０．６質量部に変えて、カルシウムステアレート１０質量部を使用し、湿式押出造粒機に変えて乾式造粒機[フロイントターボ社製、ローラーコンバクター]を使用した以外は、実施例２と同様にして、顆粒状樹脂用添加剤を製造した。得られた顆粒状樹脂用添加剤を用いて、実施例２と同様にして顆粒状樹脂用添加剤の造粒性、安息角、及びシート状成形物の透明性について評価した。その結果を表１及び表２に示す。 Comparative Example 3
In Example 2, water was not used and 10 parts by mass of calcium stearate was used instead of 0.6 parts by mass of polyoxyethylene sorbitan monolaurate used as a wetting agent. An additive for granular resin was produced in the same manner as in Example 2 except that a dry granulator (manufactured by Freund Turbo, roller compactor) was used instead. Using the obtained additive for granular resin, the granularity of the additive for granular resin, the angle of repose, and the transparency of the sheet-like molded product were evaluated in the same manner as in Example 2. The results are shown in Tables 1 and 2.
表２の結果から、実施例１～３の本願発明の製造方法で得られた顆粒状樹脂用添加剤は、造粒性が良好であり、その安息角も小さいので流動性に優れている。この顆粒状樹脂用添加剤を用いて製造されたシート状成形物の透明性は、凝集物等もなく良好であった。一方、比較例１では、樹脂用添加剤の結晶化核剤をそのまま使用したため、シート状成形物に凝集物があり、透明性は低下していた。比較例２では、湿潤剤を使用しなかったため、顆粒状樹脂用添加剤とすることができなかった。比較例３では、水を使用しなかったため、シート状成形物に多数の凝集物があり、透明性は低下していた。
From the results shown in Table 2, the granular resin additives obtained by the production methods of the present invention of Examples 1 to 3 have good granulation properties and small repose angles, and thus have excellent fluidity. The transparency of the sheet-like molded product produced using this granular resin additive was good without any aggregates. On the other hand, in Comparative Example 1, since the crystallization nucleating agent of the resin additive was used as it was, there was an aggregate in the sheet-like molded product, and the transparency was lowered. In Comparative Example 2, since no wetting agent was used, the additive for granular resin could not be obtained. In Comparative Example 3, since water was not used, the sheet-like molded product had a large number of aggregates, and transparency was lowered.
本発明の顆粒状樹脂用添加剤の製造方法を用いることにより、熱可塑性樹脂組成物を効率よく製造することができ、また、該熱可塑性樹脂組成物から得られる成形品中に樹脂用添加剤を均一に分散させることができるので、熱可塑性樹脂組成物及びその成形品の製造に有用である。
By using the method for producing an additive for granular resin of the present invention, a thermoplastic resin composition can be efficiently produced, and the additive for resin in a molded product obtained from the thermoplastic resin composition Can be uniformly dispersed, which is useful for the production of thermoplastic resin compositions and molded articles thereof.
Claims (12)
- 樹脂用添加剤に水及び湿潤剤を添加することによりウェット化させてウェット化物とし、次いで、該ウェット化物を造粒機により顆粒化してウェット状の顆粒化物とし、該ウェット状の顆粒化物を乾燥させる、顆粒状樹脂用添加剤の製造方法。 Water and a wetting agent are added to a resin additive to make it wet to be a wet product, and then the wet product is granulated by a granulator to form a wet granulated product, and the wet granulated product is dried. A method for producing an additive for granular resin.
- 樹脂用添加剤１００質量部に対して、水を３～１５０質量部添加する、請求項１に記載の顆粒状樹脂用添加剤の製造方法。 The method for producing an additive for granular resin according to claim 1, wherein 3 to 150 parts by mass of water is added to 100 parts by mass of the additive for resin.
- 水１００質量部に対して、湿潤剤を０．０１～１５質量部添加する、請求項１又は２に記載の顆粒状樹脂用添加剤の製造方法。 The method for producing an additive for granular resin according to claim 1 or 2, wherein 0.01 to 15 parts by mass of a wetting agent is added to 100 parts by mass of water.
- 前記湿潤剤が、ポリオキシアルキレンソルビタンアルキレート、ポリオキシアルキレングリコール、アルキルスルフォコハク酸ナトリウム、及びプロパンジオールから選ばれた少なくとも１種である、請求項１～３のいずれかに記載の顆粒状樹脂用添加剤の製造方法。 The granular form according to any one of claims 1 to 3, wherein the wetting agent is at least one selected from polyoxyalkylene sorbitan alkylate, polyoxyalkylene glycol, sodium alkylsulfosuccinate, and propanediol. A method for producing an additive for resin.
- 前記樹脂用添加剤が、結晶化核剤である、請求項１～４のいずれかに記載の顆粒状樹脂用添加剤の製造方法。 The method for producing an additive for granular resin according to any one of claims 1 to 4, wherein the additive for resin is a crystallization nucleating agent.
- 前記造粒機が、円筒造粒機又は湿式押出造粒機である、請求項１～５のいずれかに記載の顆粒状樹脂用添加剤の製造方法。 The method for producing an additive for granular resin according to any one of claims 1 to 5, wherein the granulator is a cylindrical granulator or a wet extrusion granulator.
- 請求項１～６のいずれかに記載の製造方法により得られる、顆粒状樹脂用添加剤。 An additive for granular resin obtained by the production method according to any one of claims 1 to 6.
- 安息角が、４０°以下である、請求項７に記載の顆粒状樹脂用添加剤。 The additive for granular resin according to claim 7, wherein the repose angle is 40 ° or less.
- 請求項７又は８に記載の顆粒状樹脂用添加剤を熱可塑性樹脂に添加してなる、熱可塑性樹脂組成物。 A thermoplastic resin composition obtained by adding the additive for granular resin according to claim 7 or 8 to a thermoplastic resin.
- 前記熱可塑性樹脂が、結晶性熱可塑性樹脂である、請求項９に記載の熱可塑性樹脂組成物。 The thermoplastic resin composition according to claim 9, wherein the thermoplastic resin is a crystalline thermoplastic resin.
- 前記結晶性熱可塑性樹脂が、ポリオレフィン系樹脂である、請求項１０に記載の熱可塑性樹脂組成物。 The thermoplastic resin composition according to claim 10, wherein the crystalline thermoplastic resin is a polyolefin resin.
- 請求項９～１１のいずれかに記載の熱可塑性樹脂組成物を成形してなる成形品。
A molded article formed by molding the thermoplastic resin composition according to any one of claims 9 to 11.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018052010A1 (en) * | 2016-09-16 | 2018-03-22 | 新日本理化株式会社 | Crystal nucleator for polyolefin resins, method for producing crystal nucleator for polyolefin resins, and method for improving fluidity of crystal nucleator for polyolefin resins |
| EP3492519A4 (en) * | 2016-07-29 | 2020-03-18 | New Japan Chemical Co., Ltd. | Crystal nucleating agent for polyolefin resin, method for producing crystal nucleating agent for polyolefin resin, and method for improving fluidity of crystal nucleating agent for polyolefin resin |
| US10894874B2 (en) | 2016-08-25 | 2021-01-19 | New Japan Chemical Co., Ltd. | Crystal nucleator for polyolefin resins, method for producing crystal nucleator for polyolefin resins, and method for improving fluidity of crystal nucleator for polyolefin resins |
| US11702514B2 (en) | 2016-10-28 | 2023-07-18 | Giovanni Broggi | Universal pigmentary preparations for colouring and reenforcing plastics |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60212466A (en) * | 1984-04-05 | 1985-10-24 | Denki Kagaku Kogyo Kk | Acetylene black |
| JPH01167357A (en) * | 1987-11-24 | 1989-07-03 | Sandoz Ag | Polymer composition containing fire retardant agent and light stabilizer |
| JPH04122341A (en) * | 1990-09-14 | 1992-04-22 | Matsushita Electric Ind Co Ltd | Vacuum cleaner |
| JPH10510313A (en) * | 1994-11-28 | 1998-10-06 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Products with persistent coloring and / or fluorescent properties |
| JP2001164132A (en) * | 1999-12-07 | 2001-06-19 | Shingo Hishida | Granular additive for synthetic resin and production method thereof |
| JP2005526867A (en) * | 2002-02-01 | 2005-09-08 | ビーエーエスエフ アクチェンゲゼルシャフト | Pigment granules |
| JP2007524740A (en) * | 2004-01-23 | 2007-08-30 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Process for producing low dust granules from polymer additives |
| JP2008138170A (en) * | 2006-11-09 | 2008-06-19 | Sharp Corp | Method for manufacturing resin particle |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3006060B2 (en) * | 1990-09-13 | 2000-02-07 | 住友化学工業株式会社 | Method for granulating 2,2,6,6-tetramethylpiperidine-based light stabilizer |
-
2015
- 2015-12-01 WO PCT/JP2015/083796 patent/WO2016088767A1/en active Application Filing
- 2015-12-01 JP JP2016562642A patent/JP6346305B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60212466A (en) * | 1984-04-05 | 1985-10-24 | Denki Kagaku Kogyo Kk | Acetylene black |
| JPH01167357A (en) * | 1987-11-24 | 1989-07-03 | Sandoz Ag | Polymer composition containing fire retardant agent and light stabilizer |
| JPH04122341A (en) * | 1990-09-14 | 1992-04-22 | Matsushita Electric Ind Co Ltd | Vacuum cleaner |
| JPH10510313A (en) * | 1994-11-28 | 1998-10-06 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Products with persistent coloring and / or fluorescent properties |
| JP2001164132A (en) * | 1999-12-07 | 2001-06-19 | Shingo Hishida | Granular additive for synthetic resin and production method thereof |
| JP2005526867A (en) * | 2002-02-01 | 2005-09-08 | ビーエーエスエフ アクチェンゲゼルシャフト | Pigment granules |
| JP2007524740A (en) * | 2004-01-23 | 2007-08-30 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Process for producing low dust granules from polymer additives |
| JP2008138170A (en) * | 2006-11-09 | 2008-06-19 | Sharp Corp | Method for manufacturing resin particle |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3492519A4 (en) * | 2016-07-29 | 2020-03-18 | New Japan Chemical Co., Ltd. | Crystal nucleating agent for polyolefin resin, method for producing crystal nucleating agent for polyolefin resin, and method for improving fluidity of crystal nucleating agent for polyolefin resin |
| US11634427B2 (en) | 2016-07-29 | 2023-04-25 | New Japan Chemical Co., Ltd. | Crystal nucleating agent for polyolefin resin, method for producing crystal nucleating agent for polyolefin resin, and method for improving fluidity of crystal nucleating agent for polyolefin resin |
| US10894874B2 (en) | 2016-08-25 | 2021-01-19 | New Japan Chemical Co., Ltd. | Crystal nucleator for polyolefin resins, method for producing crystal nucleator for polyolefin resins, and method for improving fluidity of crystal nucleator for polyolefin resins |
| WO2018052010A1 (en) * | 2016-09-16 | 2018-03-22 | 新日本理化株式会社 | Crystal nucleator for polyolefin resins, method for producing crystal nucleator for polyolefin resins, and method for improving fluidity of crystal nucleator for polyolefin resins |
| US11746211B2 (en) | 2016-09-16 | 2023-09-05 | New Japan Chemical Co., Ltd. | Crystal nucleator for polyolefin resins, method for producing crystal nucleator for polyolefin resins, and method for improving fluidity of crystal nucleator for polyolefin resins |
| US11702514B2 (en) | 2016-10-28 | 2023-07-18 | Giovanni Broggi | Universal pigmentary preparations for colouring and reenforcing plastics |
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