TW202330739A - Fluororesin particle material and method for producing same, composite particle material and method for producing same, and method for producing spherical fluororesin particle material - Google Patents
Fluororesin particle material and method for producing same, composite particle material and method for producing same, and method for producing spherical fluororesin particle material Download PDFInfo
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- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims abstract description 34
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- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- C08J3/12—Powdering or granulating
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
本發明係關於氟樹脂粒子材料及其製造方法、複合粒子材料及其製造方法以及球狀氟樹脂粒子材料的製造方法。The present invention relates to a fluororesin particle material and its production method, a composite particle material and its production method, and a production method of a spherical fluororesin particle material.
作為製造以由聚四氟乙烯而成之氟樹脂形成的粒子材料之方法之一，已知有將聚四氟乙烯粉碎的方法。聚四氟乙烯由於容易因加壓而纖維化，故於粉碎操作之前會進行藉由利用電子束照射等將聚四氟乙烯之主鏈切斷而低分子量化來使之易於微細化（專利文獻1）。A method of pulverizing polytetrafluoroethylene is known as one of methods for producing a particle material made of a fluororesin made of polytetrafluoroethylene. Since polytetrafluoroethylene tends to be fibrillated by pressurization, it is easily miniaturized by cutting the main chain of polytetrafluoroethylene by electron beam irradiation or the like to lower the molecular weight before the pulverization operation (patent document 1).
『專利文獻』 《專利文獻1》日本專利公開第2020-19972號公報 《專利文獻2》日本專利再公表第2020/013336號公報 "Patent Documents" "Patent Document 1" Japanese Patent Laid-Open No. 2020-19972 "Patent Document 2" Japanese Patent Re-publication No. 2020/013336
然而，已知若將聚四氟乙烯低分子量化，則會生成全氟辛酸等全氟羧酸及其鹽。全氟羧酸及其鹽係穩定性高的物質，係其豐度受到限制的物質。However, it is known that perfluorocarboxylic acids such as perfluorooctanoic acid and salts thereof are produced when polytetrafluoroethylene is reduced in molecular weight. Perfluorocarboxylic acids and their salts are substances with high stability and are substances whose abundance is limited.
在專利文獻1之製造方法中，藉由採用在粉碎之後透過進行熱處理來去除全氟羧酸及其鹽的熱工序來將全氟羧酸及其鹽去除。In the production method of Patent Document 1, perfluorocarboxylic acid and its salt are removed by employing a thermal process of removing perfluorocarboxylic acid and its salt by performing heat treatment after pulverization.
說來，有時會採用於樹脂材料中填充有由氟樹脂而成之粒子材料作為填料的樹脂材料作為電子設備的基板材料等。隨著近年之佈線的微細化，變得要求填料的粒徑亦小者。並且，由於漿料的穩定性亦升高，故以將粒徑縮小為佳。In other words, a resin material in which a particle material made of a fluororesin is filled as a filler is sometimes used as a substrate material of an electronic device or the like. With the miniaturization of wiring in recent years, fillers having a smaller particle size are required. In addition, since the stability of the slurry also increases, it is preferable to reduce the particle size.
在專利文獻1中，透過加熱來進行全氟羧酸的去除，但若對於粒徑較專利文獻1所揭露者還要小之由氟樹脂而成之粒子材料透過相同的操作來進行全氟羧酸的去除，則會發生在專利文獻1中並未成為問題的凝集。In Patent Document 1, the removal of perfluorocarboxylic acid is carried out by heating, but if the particle size of the particle material made of fluororesin is smaller than that disclosed in Patent Document 1, perfluorocarboxylic acid is removed through the same operation. Aggregation, which is not a problem in Patent Document 1, occurs when the acid is removed.
在本發明中，有鑑於上述實情，需要解決的課題定為提供小粒徑且全氟羧酸及其鹽之豐度低的氟樹脂粒子材料以及可簡易進行全氟羧酸及其鹽之去除的氟樹脂粒子材料的製造方法。In the present invention, in view of the above facts, the problem to be solved is to provide a fluororesin particle material with a small particle size and a low abundance of perfluorocarboxylic acids and their salts, and to easily remove perfluorocarboxylic acids and their salts. The production method of the fluororesin particle material.
在解決上述課題之目的上本發明人等潛心進行研究的結果，可知若增加為了製造氟樹脂粒子材料而進行粉碎之氣體環境中的溼度，則可抑制全氟羧酸及其鹽之豐度的增加。簡言之，發現藉由控制粉碎氣體環境的溼度，可以通常之粉碎操作製造全氟羧酸及其鹽之豐度低的氟樹脂粒子材料，故與透過加熱使全氟羧酸及其鹽之豐度減少的先前技術相比，即使係小粒徑氟樹脂粒子材料亦可抑制凝集的發生。As a result of intensive studies by the inventors of the present invention to solve the above-mentioned problems, it has been found that if the humidity in the atmosphere of the atmosphere in which the fluororesin particle material is pulverized is increased, the abundance of perfluorocarboxylic acids and their salts can be suppressed. Increase. In short, it was found that by controlling the humidity of the pulverization gas environment, it is possible to produce fluororesin particle materials with a low abundance of perfluorocarboxylic acids and their salts through ordinary pulverization operations, so that the combination of perfluorocarboxylic acids and their salts by heating Compared with the prior art with reduced abundance, even small-diameter fluororesin particle materials can suppress the occurrence of aggregation.
本發明係依據上述見解完成者，解決上述課題的本發明之氟樹脂粒子材料的製造方法具有： 粉碎工序，將由聚四氟乙烯而成之原料樹脂材料在粉碎氣體環境下粉碎至成為平均粒徑為5 μm以下的粒子材料；以及 溼度控制工序，以前述粒子材料之PFOA值成為25 ppb以下之方式，將前述粉碎氣體環境所包含之水分量換算成在25℃、1 atm之條件下每1 m 3之值的換算水分含量控制在指定值以上；其中 前述溼度控制工序係將前述換算水分含量未達前述指定值的供應氣體加溼而供應至前述粉碎氣體環境或者對前述粉碎氣體環境直接加溼之任一者。在本說明書中，於不特別限制的情況下，「平均粒徑」係比表面積換算徑，係（比表面積換算徑）＝6／（密度×比表面積）。比表面積係透過使用氮的BET法量測到的值。 The present invention is completed based on the above-mentioned knowledge, and the method for producing the fluororesin particle material of the present invention that solves the above-mentioned problems includes: a pulverization step, pulverizing the raw resin material made of polytetrafluoroethylene in a pulverization gas environment until it becomes an average particle diameter Particle materials with a particle size of 5 μm or less; and the humidity control process, converting the amount of moisture contained in the aforementioned pulverization gas environment into per 1 The converted moisture content of the value of m3 is controlled to be above the specified value; wherein the aforementioned humidity control process is to humidify the supply gas whose converted moisture content does not reach the aforementioned specified value and supply it to the aforementioned pulverized gas environment or directly add to the aforementioned pulverized gas environment. either wet. In this specification, unless otherwise specified, the "average particle diameter" is a diameter converted from a specific surface area, and is (diameter converted from a specific surface area)=6/(density×specific surface area). The specific surface area is a value measured by the BET method using nitrogen.
自粉碎氣體環境中實際含有之水分量換算成在25℃、1 atm之條件下每1 m 3之值的換算水分含量係假想之數值，所算出之換算水分含量亦可無法在25℃、1 atm之條件下實際含於氣體中。簡言之，係單純將粉碎氣體環境中實際含有之水分的量在25℃、1 atm（1013.25 hPa）之情形中換算而算出之值。此外，在本說明書中，針對「換算水分含量」，在不特別規定量測條件的情況下，係在25℃、1 atm下換算時的數值。 The converted moisture content converted from the actual moisture contained in the pulverized gas environment to the value per 1 m 3 under the conditions of 25°C and 1 atm is a hypothetical value, and the calculated converted moisture content may not be available at 25°C and 1 atm. It is actually contained in the gas under the condition of atm. In short, it is a value calculated by simply converting the amount of moisture actually contained in the pulverization gas environment at 25°C and 1 atm (1013.25 hPa). In addition, in this manual, the "converted water content" is a numerical value at the time of conversion at 25°C and 1 atm unless measurement conditions are specified in particular.
藉由在已加溼之氣體環境下進行粉碎工序，可有效去除聚四氟乙烯所包含之全氟羧酸及其鹽。尤其，前述指定值以30 g／m 3以上為佳。 The perfluorocarboxylic acid and its salt contained in polytetrafluoroethylene can be effectively removed by performing the crushing process in a humidified gas environment. In particular, the aforementioned specified value is preferably 30 g/m 3 or more.
前述原料樹脂材料以熔融黏度在角頻率0.01 rad／s時為1000000 Pa·s以下為佳。用以將熔融黏度之範圍做成此範圍的方法並不特別限制，但可示例藉由照射電子束或伽瑪射線等高能量線來切斷聚四氟乙烯之主鏈使低分子量化進行的方法。The aforementioned raw resin material preferably has a melt viscosity of 1,000,000 Pa·s or less at an angular frequency of 0.01 rad/s. The method for making the range of the melt viscosity into this range is not particularly limited, but examples include cutting the main chain of polytetrafluoroethylene and reducing the molecular weight by irradiating high-energy rays such as electron beams or gamma rays. method.
前述粉碎工序以利用噴射磨機來進行且粉碎壓為0.6 MPa以上為佳。The aforementioned pulverization step is preferably performed using a jet mill, and the pulverization pressure is preferably 0.6 MPa or higher.
以更具有在前述原料樹脂材料之熔融溫度以上的加熱氣體環境下放入前述粒子材料使之軟化而球狀化的球狀化工序為佳。It is preferable to further include a spheroidization step in which the particle material is put into a heated gas atmosphere at a temperature higher than the melting temperature of the raw resin material to soften and spheroidize.
由於藉由本發明之製造方法可獲得凝集少的氟樹脂粒子材料，故變得可提供解決上述課題的氟樹脂粒子材料。亦即，解決上述課題的氟樹脂粒子材料，其平均粒徑為0.5 μm以上且2.5 μm以下，PFOA值為25 ppb以下，分散至成為一次粒子，且係由氟樹脂材料所構成。Since a fluororesin particle material with little aggregation can be obtained by the production method of the present invention, it becomes possible to provide a fluororesin particle material that solves the above-mentioned problems. That is, the fluororesin particle material that solves the above-mentioned problems has an average particle diameter of 0.5 μm to 2.5 μm, a PFOA value of 25 ppb or less, is dispersed to form primary particles, and is composed of a fluororesin material.
藉由具有上述構成，本發明之氟樹脂粒子材料的製造方法發揮「不僅在將聚四氟乙烯粉碎而做成氟樹脂粒子材料的粉碎工序中將粒徑縮小，還可減低全氟羧酸及其鹽之含量」這樣的功效。並且，藉由採用噴射磨機加溼進行粉碎，變得能夠在高壓下進行粉碎操作而粉碎效率上升。並且，本發明之氟樹脂粒子材料可提供全氟羧酸及其鹽之含量少、粒徑小且凝集少的氟樹脂粒子材料。By having the above-mentioned structure, the production method of the fluororesin particle material of the present invention exerts "not only reducing the particle size in the pulverization process of pulverizing polytetrafluoroethylene to make the fluororesin particle material, but also reducing the amount of perfluorocarboxylic acid and its salt content". In addition, by humidifying and pulverizing using a jet mill, it becomes possible to perform pulverization under high pressure, and pulverization efficiency increases. Furthermore, the fluororesin particle material of the present invention can provide a fluororesin particle material with less content of perfluorocarboxylic acid and its salt, smaller particle size and less aggregation.
針對本發明之氟樹脂粒子材料及其製造方法以及複合粒子材料及其製造方法，以下依據實施型態詳細進行說明。本實施型態之氟樹脂粒子材料係可合宜使用作為電子材料用填料的材料，舉例而言，活用源自氟樹脂之低的介電損耗正切等優異之電性特性，合宜使用於基板材料用之填料等。舉例而言，作為可使用作為填料的樹脂材料，可示例固化前之熱固性樹脂材料（樹脂前驅物：例如環氧樹脂、聚酯樹脂、脲樹脂、聚矽氧樹脂等；固化前之材料或一部分固化但具有流動性者）或熱塑性樹脂（聚苯醚樹脂、改質聚苯醚樹脂、聚醯亞胺樹脂、液晶聚合物樹脂等）之單體、由熱塑性樹脂加熱熔融而成的熔融物。本實施型態之複合粒子材料係與樹脂材料之親和性較氟樹脂粒子材料還要優異的材料，可如同氟樹脂粒子材料利用。The fluororesin particle material and its manufacturing method as well as the composite particle material and its manufacturing method according to the present invention will be described in detail below according to the embodiment. The fluororesin particle material of this embodiment can be suitably used as a filler material for electronic materials. For example, it can be suitably used as a substrate material by taking advantage of the excellent electrical properties such as low dielectric loss tangent derived from fluororesin. Filling etc. For example, as a resin material that can be used as a filler, a thermosetting resin material before curing (resin precursor: such as epoxy resin, polyester resin, urea resin, silicone resin, etc.; a material or a part thereof before curing) can be exemplified. Solidified but fluid) or thermoplastic resin (polyphenylene ether resin, modified polyphenylene ether resin, polyimide resin, liquid crystal polymer resin, etc.) monomer, melted by thermoplastic resin heating and melting. The composite particle material of this embodiment is a material having a better affinity with the resin material than the fluororesin particle material, and can be used like the fluororesin particle material.
（氟樹脂粒子材料的製造方法）(Manufacturing method of fluororesin particle material)
本實施型態之氟樹脂粒子材料的製造方法係將由氟樹脂材料而成之原料樹脂材料透過粉碎工序粉碎來做成氟樹脂粒子材料的方法。原料樹脂材料之大小並不特別限制，但使用較透過本製造方法製造之粒子材料還要大的材料。舉例而言，可採用自100 μm左右至5 mm左右之大小者。The production method of the fluororesin particle material of this embodiment is a method of pulverizing the raw resin material made of the fluororesin material through a pulverization step to produce the fluororesin particle material. The size of the raw resin material is not particularly limited, but a material larger than the particle material produced by this production method is used. For example, ones with a size from about 100 μm to about 5 mm can be used.
作為氟樹脂材料，並不特別限制，但為加熱即軟化至熔融者。作為氟樹脂材料，並不特別限制，但可示例：聚四氟乙烯（PTFE）、全氟烷氧基烷（PFA）、全氟乙烯丙烯共聚物（FEP）、乙烯―四氟乙烯共聚物（ETFE）、聚二氟亞乙烯（PVDF）、聚氯三氟乙烯（PCTFE）、乙烯―氯三氟乙烯聚合物（ECTFE）、四氟乙烯―全氟二甲基二氧呃共聚物（TFE/PDD）、聚氟乙烯（PVF），尤以採用PTFE為佳。The fluororesin material is not particularly limited, but is softened to melt upon heating. The fluororesin material is not particularly limited, but examples include: polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene-propylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer ( ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene polymer (ECTFE), tetrafluoroethylene-perfluorodimethyldioxer copolymer (TFE/ PDD), polyvinyl fluoride (PVF), especially PTFE is preferred.
氟樹脂材料容易因粉碎而纖維化進行。纖維化可藉由將氟樹脂材料低分子量化來抑制。因此，原料樹脂材料以採用低分子量的氟樹脂材料為佳。舉例而言，作為良佳之氟樹脂材料，以熔融黏度在角頻率0.01 rad／s時為1000000 Pa·s以下為佳。熔融黏度的量測條件遵循JIS K 7244，使用Discovery混合流變儀2（TA Instruments公司製）及20 mm的平行板，將預先在380℃下加熱5分鐘之2 g的試樣在0.7 MPa的荷重下保持在上述溫度而量測到的值。Fluororesin materials tend to be fibrillated by pulverization. Fibrillation can be suppressed by reducing the molecular weight of the fluororesin material. Therefore, it is better to use low-molecular-weight fluororesin material as the raw resin material. For example, a good fluororesin material should have a melt viscosity of 1,000,000 Pa·s or less at an angular frequency of 0.01 rad/s. The measurement conditions of the melt viscosity conformed to JIS K 7244. Using a Discovery Hybrid Rheometer 2 (manufactured by TA Instruments) and a 20 mm parallel plate, a 2 g sample preheated at 380°C for 5 minutes was heated at 0.7 MPa. The value measured while maintaining the above temperature under load.
低分子量的氟樹脂材料，有對於高分子量的氟樹脂材料透過照射電子束、伽瑪射線等游離輻射線來將氟樹脂材料之主鏈切斷的方法、透過加熱來將主鏈切斷的方法等。For low-molecular-weight fluororesin materials, there are methods of cutting the main chain of fluororesin materials by irradiating ionizing radiation such as electron beams and gamma rays for high-molecular-weight fluororesin materials, and methods of cutting the main chain by heating. wait.
作為游離輻射線，可列舉：電子束、紫外線、伽瑪射線、X射線、中子射線、高能量離子等，但以電子束或伽瑪射線為佳。作為游離輻射線的照射線量，以1～2500 kGy為佳，以2500 kGy以下為較佳，以2250 kGy以下為更佳。並且，以10 kGy以上為較佳，以100 kGy以上為更佳。Examples of ionizing radiation include electron beams, ultraviolet rays, gamma rays, X-rays, neutron rays, high-energy ions, and the like, but electron beams or gamma rays are preferred. The dose of ionizing radiation is preferably 1 to 2500 kGy, more preferably 2500 kGy or less, more preferably 2250 kGy or less. Furthermore, it is preferably at least 10 kGy, more preferably at least 100 kGy.
作為上述輻射線的照射溫度，只要係5℃以上且氟樹脂材料的熔點以下即不特別受限。在熔點周遭附近，亦已知氟樹脂材料的分子鏈會交聯，在獲得低分子量氟樹脂材料上，以320℃以下為佳，以300℃以下為較佳，以260℃以下為更佳。經濟上以在常溫下照射為佳。The irradiation temperature of the radiation is not particularly limited as long as it is 5° C. or higher and not higher than the melting point of the fluororesin material. Around the melting point, it is also known that the molecular chains of fluororesin materials will be cross-linked. In order to obtain low molecular weight fluororesin materials, the temperature is preferably below 320°C, more preferably below 300°C, and more preferably below 260°C. Economically, it is better to irradiate at room temperature.
游離輻射線的照射亦可在任何氣體環境中實施，舉例而言，可在空氣或氧氣等氧化氣體環境下、氮氣或氬氣等惰性氣體（inert gas）環境下、真空等實施。就可以低成本實施的觀點而言，以在空氣中的照射為佳，就不易使全氟羧酸及其鹽生成的觀點而言，以在實質上不存在氧下的照射為佳。惟本發明之製造方法由於係能夠透過粉碎工序去除全氟羧酸及其鹽的方法，故在實質上不存在氧下的照射並非必要。Irradiation of ionizing radiation can also be carried out in any gas environment, for example, it can be carried out in an oxidizing gas environment such as air or oxygen, an inert gas environment such as nitrogen or argon, or a vacuum. Irradiation in air is preferable from the viewpoint of low-cost implementation, and irradiation in the substantial absence of oxygen is preferable from the viewpoint of less formation of perfluorocarboxylic acid and its salt. However, since the production method of the present invention is a method capable of removing perfluorocarboxylic acid and its salts through a pulverization step, irradiation in the absence of oxygen is not necessary.
本實施型態之氟樹脂粒子材料的製造方法具有：粉碎工序；溼度控制工序，控制將在此粉碎工序中之粉碎氣體環境所包含之水分量換算成在25℃、1 atm之條件下每1 m 3之值的換算水分含量；以及視其他需求採用的其他工序。進行粉碎工序的氣體環境（以下有時稱為「粉碎氣體環境」）在已加溼的氣體環境下進行，亦可一邊加溼一邊進行。粉碎氣體環境的換算水分含量透過溼度控制工序來控制。作為加溼的程度，做成粉碎後之PFOA值成為25 ppb以下，以做成15 ppb以下為佳，以做成10 ppb以下為較佳，以做成5 ppb以下為更佳。 The manufacturing method of the fluororesin particle material of this embodiment has: a pulverization process; a humidity control process, which controls the amount of moisture contained in the pulverization gas environment in the pulverization process to be converted into the amount of moisture per 1 atm at 25°C. The converted moisture content of the value of m3 ; and other processes adopted according to other requirements. The gas atmosphere in which the pulverization process is performed (hereinafter sometimes referred to as "pulverization gas atmosphere") is performed in a humidified gas environment, and may be performed while humidifying. The converted moisture content of the pulverization gas environment is controlled through the humidity control process. The degree of humidification is such that the pulverized PFOA value is 25 ppb or less, preferably 15 ppb or less, more preferably 10 ppb or less, more preferably 5 ppb or less.
於此，所謂粉碎後之PFOA值，係將透過粉碎工序獲得之粒子材料所含有之PFOA的量以質量基準量測到的值。PFOA意謂全氟辛酸，有若PFOA的量多則全氟羧酸及其鹽的量多，若PFOA的量少則全氟羧酸及其鹽的量少這樣的關聯。PFOA值的量測可透過遵循關於PFOS、PFOA之量測的CEN/TS 15968之方法來進行。Here, the PFOA value after pulverization is a value measured on a mass basis by measuring the amount of PFOA contained in the particulate material obtained through the pulverization process. PFOA means perfluorooctanoic acid, and there is a relationship that when the amount of PFOA is large, the amount of perfluorocarboxylic acid and its salt is large, and when the amount of PFOA is small, the amount of perfluorocarboxylic acid and its salt is small. The measurement of PFOA value can be carried out by following the method of CEN/TS 15968 on the measurement of PFOS and PFOA.
若要示例具體之數值作為粉碎氣體環境中之換算水分含量的下限值，可採用10 g／m 3、15 g／m 3、20 g／m 3、25 g／m 3、30 g／m 3、35 g／m 3、40 g／m 3。此外，就算於在本實施型態中無法以將粉碎氣體環境中之換算水分含量之值保持在上述下限值以上之方式持續控制的情況下，即使係粉碎操作中之一部分的時間亦能夠藉由使換算水分含量上升來降低PFOA值。 To give an example of a specific value as the lower limit of the converted moisture content in the pulverized gas environment, 10 g/m 3 , 15 g/m 3 , 20 g/m 3 , 25 g/m 3 , 30 g/m 3 can be used 3 , 35 g/m 3 , 40 g/m 3 . In addition, even if it is impossible to keep the converted water content value in the pulverization gas environment at or above the above-mentioned lower limit in the present embodiment, continuous control can be achieved even if it is a part of the pulverization operation. Reduce the PFOA value by increasing the converted water content.
在控制換算水分含量之值的情況下，達到於前已述之下限值以上一事，在粉碎工序中之任一時間點上達到皆可，良佳為在粉碎工序開始時達到即可，較佳為在粉碎工序中恆常達到即可。並且，亦可採用如在一度達到下限值以上之後變成下限值以下並再度成為下限值以上的控制。In the case of controlling the value of the converted moisture content, reaching above the aforementioned lower limit can be achieved at any point in the pulverization process, preferably at the beginning of the pulverization process, preferably at the beginning of the pulverization process It is enough to achieve it constantly in the crushing process. In addition, it is also possible to employ control such that, after reaching the lower limit value once, it falls below the lower limit value and becomes more than the lower limit value again.
作為換算水分含量的上限值，並不特別限制。The upper limit of the converted water content is not particularly limited.
作為換算水分含量，至變高到某程度為止，隨著換算水分含量變高而粉碎後之PFOA值有變小的傾向。作為構成粉碎氣體環境的氣體（以下稱為「氣體環境氣體」），並不特別受限，可採用空氣、氧氣等含氧氣體環境，再者可採用氮氣或氬氣等惰性氣體環境。The value of PFOA after pulverization tends to decrease as the converted water content increases to a certain extent as the converted water content. The gas forming the pulverization gas environment (hereinafter referred to as "gas ambient gas") is not particularly limited, and an oxygen-containing gas environment such as air and oxygen, or an inert gas environment such as nitrogen or argon can be used.
作為在溼度控制工序中之加溼的方法，並不特別受限。可採用例如：將供應至粉碎氣體環境之供應氣體加溼的方法或將氣體環境氣體直接加溼的方法、於原料樹脂材料加入水分而間接加溼的方法等。再者，亦可採用藉由使在粉碎工序中因化學反應而生成水的物質存在於原料樹脂材料中或氣體環境氣體中來間接加溼的方法。作為簡易的方法，以將供應氣體直接加溼的方法為佳。The method of humidifying in the humidity control step is not particularly limited. For example, a method of humidifying the supply gas supplied to the pulverization gas environment, a method of directly humidifying the gas ambient gas, and a method of indirectly humidifying the raw resin material by adding moisture can be used. Furthermore, a method of indirectly humidifying by making a substance that generates water due to a chemical reaction in the pulverization process exist in the raw resin material or in the gaseous atmosphere can also be used. As a simple method, a method of directly humidifying the supply gas is preferable.
具體而言，亦會依採用何種操作作為粉碎操作而變化。舉例而言，在進行如「在如噴射磨機使係為進行粉碎之對象的原料分散至氣體中的狀態下與氣體一同供應至粉碎氣體環境下，於粉碎後與此氣體一同自粉碎氣體環境取出」之操作的情況下，以對於使原料分散的氣體持續進行加溼為佳，在如球磨機等的封閉空間中進行粉碎操作的情況下，亦可採用如一度使換算水分含量上升後可持續此換算水分含量的操作。Specifically, it also varies depending on which operation is used as the pulverization operation. For example, in the case of "supplying the raw material to be pulverized into the gas with the gas in the state of dispersing the raw material to be pulverized in the gas such as a jet mill, after pulverization together with the gas from the pulverized gas environment." In the case of the operation of "taking out", it is better to continuously humidify the gas that disperses the raw materials. In the case of crushing operations in a closed space such as a ball mill, it is also possible to use such as continuously increasing the converted moisture content once. This is the operation of converting moisture content.
作為將供應氣體直接加溼的方法，可使供應氣體通過水中或者將水蒸氣或液狀之水直接添加至氣體環境氣體中。在採用空氣作為供應氣體的情況下，考量空氣中所包含之水分量以成為目標之換算水分含量之方式控制加溼量。並且，對於粉碎氣體環境亦可使之含有飽和水蒸氣量以上的水蒸氣，亦可將全部做成水蒸氣。尤其在採用噴射磨機作為粉碎操作的情況下，藉由將粉碎氣體環境做成水蒸氣，粉碎效率會上升。As a method of directly humidifying the supply gas, it is possible to pass the supply gas through water or directly add water vapor or liquid water to the gas ambient gas. In the case of using air as the supply gas, the amount of humidification is controlled so that the moisture content contained in the air is considered to be a target conversion moisture content. In addition, the pulverization gas environment may contain water vapor exceeding the saturated water vapor amount, or may be made entirely of water vapor. Especially in the case of using a jet mill as the pulverization operation, the pulverization efficiency will increase by making the pulverization gas environment into water vapor.
作為粉碎氣體環境的溫度，並不特別限制，但以含有之水分不會結露的溫度以上為佳。若要示例粉碎氣體環境的溫度，可列舉：100℃以上、150℃以上、200℃以上、230℃以上。粉碎溫度的控制可藉由將供應氣體加熱來進行。The temperature of the pulverization gas environment is not particularly limited, but it is preferably a temperature above which the contained moisture does not condense. Examples of the temperature of the pulverization gas environment include: 100°C or higher, 150°C or higher, 200°C or higher, and 230°C or higher. The pulverization temperature can be controlled by heating the supplied gas.
在粉碎工序中，將原料樹脂材料粉碎做成粒徑5 μm以下的粒子材料。粒子材料的粒徑做成所需之大小即可，可採用例如3 μm以下、2 μm以下等。由於為了使全氟羧酸及其鹽的量減少而在之後積極進行加熱之工序的必要性低，故即使粒徑小，凝集之疑慮亦少。In the pulverization step, the raw resin material is pulverized into a particle material having a particle diameter of 5 μm or less. The particle diameter of the particle material may be set to a desired size, for example, 3 μm or less, 2 μm or less, or the like. Since there is little need for a subsequent positive heating step in order to reduce the amount of perfluorocarboxylic acid and its salt, there is little fear of aggregation even if the particle size is small.
作為在粉碎工序中的粉碎方法，並不特別限制。可採用例如：噴射磨機、球磨機、振動球磨機等。尤以採用噴射磨機為佳。在採用噴射磨機的情況下，可藉由一邊進行粉碎一邊進行分級來將達到所需之大小的粒子材料快速回收。The pulverization method in the pulverization step is not particularly limited. For example, a jet mill, a ball mill, a vibration ball mill, etc. can be used. It is especially preferred to use a jet mill. In the case of using a jet mill, the particulate material having a desired size can be quickly recovered by performing classification while pulverizing.
在採用噴射磨機作為在粉碎工序中的粉碎方法的情況下，以在大氣氣體環境下換算時之粉碎壓的下限值為0.6 MPa、1.0 MPa、2.0 MPa、3.0 MPa、3.7 MPa為佳。粉碎壓高者可提升粉碎效率。並且，換算水分含量高者可提升粉碎效率。將其他氣體的粉碎壓換算成大氣氣體環境下之值的方法，利用（大氣氣體環境下換算值）＝［粉碎時壓力×（粉碎氣體黏度／大氣黏度）］來算出。When a jet mill is used as the pulverization method in the pulverization step, the lower limit of the pulverization pressure in terms of atmospheric gas environment is preferably 0.6 MPa, 1.0 MPa, 2.0 MPa, 3.0 MPa, or 3.7 MPa. Those with high crushing pressure can improve the crushing efficiency. In addition, those with higher moisture content can improve the crushing efficiency. The method of converting the pulverization pressure of other gases into the value in the atmospheric gas environment is calculated by (converted value in the atmospheric gas environment) = [pressure at the time of pulverization x (crushing gas viscosity/atmospheric viscosity)].
作為其他工序，可舉出球狀化工序。球狀化工序係將透過粉碎工序獲得之粒子材料放入係為原料樹脂材料之熔融溫度以上的加熱氣體環境下使之軟化而球狀化的工序。往加熱氣體環境下的放入可藉由在使粒子材料浮游於載體氣體中的狀態下進行來獲得粒子材料間不會熔合而分別獨立的球狀粒子。所獲得之球狀粒子可為球形度為0.8以上、0.9以上、0.95以上、0.98以上、0.99以上。球形度，以SEM拍攝照片，自此觀察之粒子的面積與周長，以利用（球形度）＝［4π×（面積）÷（周長） 2］算出之值的形式算出。愈接近1，愈接近真球。具體而言，採用使用影像處理裝置（Spectris Co., Ltd.：FPIA-3000）對於100個粒子量測到的平均值。 As another step, a spheroidizing step may be mentioned. The spheroidizing step is a step of softening and spheroidizing the particle material obtained through the pulverization step in a heated gas atmosphere above the melting temperature of the raw resin material. The introduction into the heated gas environment can be carried out in a state in which the particle materials are suspended in the carrier gas, thereby obtaining independent spherical particles without fusion between the particle materials. The obtained spherical particles may have a sphericity of not less than 0.8, not less than 0.9, not less than 0.95, not less than 0.98, or not less than 0.99. The sphericity is calculated as the value calculated by (sphericity)=[4π×(area)÷(circumference) 2 ] from the area and perimeter of the particles observed by taking a picture with SEM. The closer to 1, the closer to the real ball. Specifically, an average value measured for 100 particles using an image processing device (Spectris Co., Ltd.: FPIA-3000) was used.
透過上述製造方法製造的粒子材料或球狀粒子，可分散至環氧樹脂中等基質材料中而使用於基板材料等電子材料等。The particle material or spherical particles produced by the above-mentioned production method can be dispersed in a medium matrix material such as epoxy resin to be used in electronic materials such as substrate materials and the like.
（氟樹脂粒子材料）(Fluororesin particle material)
本實施型態之氟樹脂粒子材料，其平均粒徑為0.5 μm以上且2.5 μm以下，PFOA值為25 ppb以下，分散至成為一次粒子，且係由氟樹脂材料所構成。本實施型態之氟樹脂粒子材料的平均粒徑可採用2.4 μm、2.3 μm、2.2 μm、2.1 μm、2.0 μm等作為上限值，且可採用0.6 μm、0.7 μm、0.8 μm、0.9 μm、1.0 μm等作為下限值。此等上限值及下限值能夠任意組合。The fluororesin particle material of this embodiment has an average particle diameter of 0.5 μm to 2.5 μm and a PFOA value of 25 ppb or less, is dispersed to form primary particles, and is composed of a fluororesin material. The average particle size of the fluororesin particle material in this embodiment can be 2.4 μm, 2.3 μm, 2.2 μm, 2.1 μm, 2.0 μm, etc. as the upper limit, and can be 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm etc. as the lower limit. These upper limit values and lower limit values can be combined arbitrarily.
本實施型態之氟樹脂粒子材料的PFOA值以低者為佳，針對其上限值，如同先前已述之製造方法所記載。本實施型態之氟樹脂粒子材料分散至成為一次粒子。於此，所謂分散至成為一次粒子，意謂凝集之程度少，透過乾式粒度分布量測的量測結果來判斷。乾式粒度分布的量測透過N＝3來實施。在量測結果中，將D10之N＝3的平均值定為A、將D50之N＝3的平均值定為B、將D90之N＝3的平均值定為C時，由（分散度）＝［（C－A）／B］之式算出分散度。分散度為2.5以下者視為凝集程度少而分散至成為一次粒子。The PFOA value of the fluororesin particle material of this embodiment is preferably lower, and the upper limit value is the same as that described in the production method described above. The fluororesin particle material of this embodiment is dispersed to form primary particles. Here, the so-called dispersion to become primary particles means that the degree of aggregation is small, which can be judged by the measurement results of dry particle size distribution measurement. The measurement of dry particle size distribution is carried out with N=3. In the measurement results, when the average value of N=3 in D10 is defined as A, the average value of N=3 in D50 is defined as B, and the average value of N=3 in D90 is defined as C, the (dispersion ) = [(C-A)/B] to calculate the degree of dispersion. Those with a degree of dispersion of 2.5 or less are deemed to have a small degree of aggregation and are dispersed to become primary particles.
本實施型態之氟樹脂粒子材料以球形度高為佳，可採用先前已述之製造方法所記載之範圍。The fluororesin particle material of this embodiment preferably has a high degree of sphericity, and can be used within the range described in the previously described production method.
本實施型態之氟樹脂粒子材料，在25℃溫度條件下以整體之質量為基準以50質量%分散至作為有機溶劑之甲基乙基酮中之漿料的黏度，以300 mPa·s以下為佳，以200 mPa·s以下為較佳。再者，本實施型態之氟樹脂粒子材料以在1 GHz、空腔共振器擾動法中量測到的介電損耗正切為0.004以下為佳，以0.003以下為較佳。The fluororesin particle material of this embodiment has a viscosity of 50% by mass dispersed in methyl ethyl ketone as an organic solvent based on the overall mass at a temperature of 25°C, and the viscosity is 300 mPa·s or less Preferably, it is better to be below 200 mPa·s. Furthermore, the dielectric loss tangent of the fluororesin particle material of this embodiment measured in the cavity resonator perturbation method at 1 GHz is preferably less than 0.004, more preferably less than 0.003.
（複合粒子材料及其製造方法）(Composite particle material and its manufacturing method)
本實施型態之複合粒子材料具有氟樹脂粒子材料與無機物粒子材料。氟樹脂粒子材料係先前已述之本實施型態之氟樹脂粒子材料。無機物粒子材料熔合至氟樹脂粒子材料之表面。The composite particle material of this embodiment has a fluororesin particle material and an inorganic particle material. The fluororesin particle material is the fluororesin particle material of the embodiment described above. The inorganic particle material is fused to the surface of the fluororesin particle material.
無機物粒子材料與氟樹脂粒子材料的豐度比，並不特別限制。藉由無機物粒子材料熔合至表面，氟樹脂粒子材料的表面改質。於複合粒子材料之外，亦可存在游離之無機物粒子材料或樹脂粒子材料。本實施型態之複合粒子材料的粒徑為0.5 μm～2.5 μm。尤其在分散至樹脂組成物中使用的情況下，擁有較填充此樹脂組成物之部位之最小的間隙還大之粒徑的粒子（粗粒），以實質上不含有為佳（例如以將粗粒之含量的上限做成1000 ppm、500 ppm、200 ppm、100 ppm、50 ppm為佳）。舉例而言，若為填充至50 μm之間隙的樹脂組成物，則擁有50 μm以上之粒徑的粗粒以1000 ppm以下為佳，以500 ppm以下為較佳，以200 ppm以下為更佳。The abundance ratio of the inorganic particle material to the fluororesin particle material is not particularly limited. Surface modification of fluororesin particle material by fusion of inorganic particle material to the surface. In addition to the composite particle material, free inorganic particle material or resin particle material may also exist. The particle size of the composite particle material in this embodiment is 0.5 μm to 2.5 μm. Especially in the case of being dispersed into a resin composition, it is better not to contain particles (coarse particles) having a particle size (coarse particles) that are larger than the smallest gap of the portion filled with the resin composition (for example, coarse The upper limit of grain content is preferably 1000 ppm, 500 ppm, 200 ppm, 100 ppm, 50 ppm). For example, if it is a resin composition to fill a gap of 50 μm, the coarse particles having a particle size of 50 μm or more are preferably 1000 ppm or less, more preferably 500 ppm or less, and more preferably 200 ppm or less .
在氟樹脂粒子材料之表面上，無機物粒子材料以均勻配置為佳。均勻配置與否，可以在漿料狀態下之海島結構的有無來判斷。It is preferable that the inorganic particle material is uniformly arranged on the surface of the fluororesin particle material. Whether it is uniformly arranged or not can be judged by the presence or absence of the sea-island structure in the slurry state.
存在海島結構與否，利用光學顯微鏡觀測使本實施型態之複合粒子材料以20質量%分散至甲基乙基酮（MEK）中製備的漿料來進行。透過由甲基乙基酮而成的部分與分散之複合粒子材料凝集的部分來觀測海島結構，故若均勻分散，則不會觀測到海島結構。為了海島結構的判定，作為觀測時之視野的大小，以相對於複合粒子材料之粒徑為100倍～1000倍左右進行。尤其以複合粒子材料之粒徑為基準以200倍進行。The presence or absence of the sea-island structure was observed with an optical microscope on a slurry prepared by dispersing the composite particle material of this embodiment in methyl ethyl ketone (MEK) at 20% by mass. The sea-island structure can be observed through the part made of methyl ethyl ketone and the part where the dispersed composite particle material aggregates, so if it is uniformly dispersed, the sea-island structure will not be observed. For the determination of the sea-island structure, the size of the field of view at the time of observation is about 100 to 1000 times the particle diameter of the composite particle material. In particular, it is performed by 200 times the particle diameter of the composite particle material.
無機物粒子材料熔合至氟樹脂粒子材料之表面。使之熔合的工序（熔合工序）藉由在無機物粒子材料存在於樹脂粒子材料之表面的條件下於高溫下處理來進行。透過高溫處理，於無機物粒子材料之表面產生OH基。作為存在於表面之OH基的量，可示例0.1～30 μmol／m 2。作為OH基之量的下限值，可示例0.1 μmol／m 2、0.5 μmol／m 2、1 μmol／m 2，且作為上限值，可示例30 μmol／m 2、25 μmol／m 2、20 μmol／m 2。此等上限值及下限值能夠任意組合，藉由做成此等範圍內，密合性會上升。 The inorganic particle material is fused to the surface of the fluororesin particle material. The step of fusing (fusing step) is carried out by treating at high temperature under the condition that the inorganic particle material exists on the surface of the resin particle material. Through high temperature treatment, OH groups are generated on the surface of inorganic particle materials. As the amount of OH groups present on the surface, 0.1 to 30 μmol/m 2 can be exemplified. As the lower limit of the amount of OH groups, 0.1 μmol/m 2 , 0.5 μmol/m 2 , 1 μmol/m 2 can be exemplified, and as the upper limit, 30 μmol/m 2 , 25 μmol/m 2 , 20 μmol/m 2 . These upper limit values and lower limit values can be combined arbitrarily, and the adhesiveness will increase by setting it in these ranges.
在熔合工序中的處理溫度係樹脂粒子材料之表面之至少一部分可熔融的溫度。舉例而言，做成構成樹脂粒子材料之樹脂材料的軟化點以上進一步為熔點以上的溫度。並且，可採用於無機物粒子材料之表面會生成OH基的溫度。舉例而言，在採用氧化矽作為無機物粒子材料的情況下以做成400℃以上為佳，在採用氧化鋁作為無機物粒子材料的情況下以400℃以上為佳。The processing temperature in the fusing step is a temperature at which at least a part of the surface of the resin particle material can be melted. For example, the softening point or more of the resin material constituting the resin particle material may be set at a temperature higher than the melting point. In addition, a temperature at which OH groups are generated on the surface of the inorganic particle material can be used. For example, when silicon oxide is used as the inorganic particle material, the temperature is preferably 400°C or higher, and when aluminum oxide is used as the inorganic particle material, the temperature is preferably 400°C or higher.
所謂熔合，係謂樹脂粒子材料之表面之一部分仿照無機物粒子材料之外形變形的狀態。尤其在對於複合粒子材料利用於後所述之方法量測到的無機物粒子含量之值呈指定值以上的情況下，亦可判斷為確實進行了熔合。作為指定值，可設定1 mg／m 2、3 mg／m 2、5 mg／m 2、10 mg／m 2、50 mg／m 2等，指定值尤以大者為佳。並且，良佳為即使在進行3次在於後所述之無機物粒子含量之量測方法中的清洗操作之後，亦未觀察到在於前所述之條件下的海島結構（判斷為在此情況下能夠再分散）。無機物粒子材料的粒徑小於樹脂粒子材料。作為構成無機物粒子材料的無機物，並不特別限制，但可示例氧化矽、氧化鋁、氧化鋯、二氧化鈦等無機氧化物或此等的複合氧化物。並且，無機物粒子材料亦可包含有機物。可列舉例如：矽油或矽酸水溶液、正矽酸四乙酯等的水溶液或聚矽氧樹脂等的粒子。無機物粒子材料的粒徑較樹脂粒子材料還小。作為控制無機物粒子材料之粒徑的方法，並不特別限制，但可組合粉碎、分級等機械性方法來做成目標之粒度分布，或者將構成無機物粒子材料的無機物以溶膠凝膠法、水熱法等合成後之無機物成為粒子狀的方法來做成目標之粒度分布。 Fusion refers to a state where a part of the surface of the resin particle material is deformed following the shape of the inorganic particle material. In particular, when the value of the inorganic particle content measured by the method described later for the composite particle material is greater than or equal to a specified value, it can also be judged that fusion has definitely progressed. As the specified value, 1 mg/m 2 , 3 mg/m 2 , 5 mg/m 2 , 10 mg/m 2 , 50 mg/m 2 , etc. can be set, and the specified value is preferably larger. Furthermore, it is preferable that the sea-island structure under the above-mentioned conditions was not observed even after three times of cleaning operations in the measurement method of the inorganic particle content described later (it was judged that it could be reproduced in this case). dispersion). The particle size of the inorganic particle material is smaller than that of the resin particle material. The inorganic substance constituting the inorganic particle material is not particularly limited, but examples include inorganic oxides such as silicon oxide, aluminum oxide, zirconium oxide, and titanium dioxide, or composite oxides thereof. In addition, the inorganic particle material may contain organic matter. Examples thereof include silicone oil, an aqueous solution of silicic acid, an aqueous solution such as tetraethyl orthosilicate, or particles of silicone resin or the like. The particle size of the inorganic particle material is smaller than that of the resin particle material. The method of controlling the particle size of the inorganic particle material is not particularly limited, but mechanical methods such as pulverization and classification can be combined to achieve the target particle size distribution, or the inorganic materials constituting the inorganic particle material can be sol-gel method, hydrothermal method, etc. The method of making the synthesized inorganic substances into particles to achieve the target particle size distribution.
作為無機物粒子材料之良佳之粒徑，以樹脂粒子材料的粒徑為基準為1／10～1／10000，以自1／50至1／5000為較佳。若要示例具體之數值，作為粒徑的下限值，可列舉1 nm、3 nm、5 nm、10 nm、15 nm、20 nm、30 nm、50 nm、80 nm、100 nm，且作為上限值，可列舉1 μm、800 nm、500 nm、300 nm、200 nm、150 nm、100 nm等。The preferred particle size of the inorganic particle material is 1/10 to 1/10000, more preferably from 1/50 to 1/5000, based on the particle size of the resin particle material. To give an example of a specific value, as the lower limit of the particle diameter, 1 nm, 3 nm, 5 nm, 10 nm, 15 nm, 20 nm, 30 nm, 50 nm, 80 nm, 100 nm can be cited, and as the upper limit Examples of the limit value include 1 μm, 800 nm, 500 nm, 300 nm, 200 nm, 150 nm, and 100 nm.
無機物粒子材料亦可利用具有Si－H鍵結的矽烷化合物進行表面處理。並且，表面處理亦可於做成複合粒子材料之後進行。作為矽烷化合物，亦包含矽烷耦合劑、矽氮烷類、聚矽氧（於分子中具有有機聚矽氧烷結構者）。作為矽烷化合物，以具有苯基、乙烯基、環氧基、甲基丙烯酸基、胺基、苯基胺基、脲基、巰基、異氰酸酯基、丙烯酸基、氟烷基、烷基的化合物為佳。矽烷化合物之中，作為矽氮烷類，可示例1,1,1,3,3,3-六甲基二矽氮烷。並且，亦可利用鈦酸酯類或鋁酸酯類進行表面處理。表面處理可在提升與前述樹脂粒子材料之親和性的目的上進行，或者可在提升與使用本實施型態之複合粒子材料之對象材料（樹脂材料或溶媒等）之親和性的目的上進行。由矽烷化合物所致之表面處理以做成存在於無機物粒子材料之表面的OH基可全部反應之程度的量為佳，但OH基亦可殘存。Inorganic particle materials can also be surface treated with Si-H bonded silane compounds. In addition, surface treatment can also be performed after the composite particle material is made. Silane compounds also include silane coupling agents, silazanes, and polysiloxanes (those having an organopolysiloxane structure in the molecule). As the silane compound, compounds having phenyl, vinyl, epoxy, methacrylic, amine, phenylamine, ureido, mercapto, isocyanate, acrylic, fluoroalkyl, and alkyl groups are preferred . Among silane compounds, 1,1,1,3,3,3-hexamethyldisilazane can be exemplified as silazanes. Furthermore, the surface treatment may also be performed with titanate or aluminate. The surface treatment may be performed for the purpose of improving the affinity with the aforementioned resin particle material, or may be performed for the purpose of improving the affinity with the target material (resin material or solvent, etc.) to which the composite particle material of this embodiment is used. The surface treatment by the silane compound is preferably in such an amount that all OH groups present on the surface of the inorganic particle material can react, but OH groups may remain.
本實施型態之複合粒子材料，在25℃溫度條件下以整體之質量為基準以50質量%分散至MEK中之漿料的黏度，以200 mPa·s以下為佳，以100 mPa·s以下為較佳。再者，本實施型態之複合粒子材料以在1 GHz、空腔共振器擾動法中量測到的介電損耗正切為0.004以下為佳，以0.003以下為較佳。For the composite particle material of this embodiment, the viscosity of the slurry dispersed in MEK at 50% by mass based on the overall mass at 25°C is preferably 200 mPa·s or less, preferably 100 mPa·s or less is better. Furthermore, the dielectric loss tangent of the composite particle material in this embodiment measured in the cavity resonator perturbation method at 1 GHz is preferably less than 0.004, more preferably less than 0.003.
（複合粒子材料的製造方法）(Manufacturing method of composite particle material)
本實施型態之複合粒子材料的製造方法係可合宜製造於上所述之本實施型態之複合粒子材料的製造方法。本實施型態之複合粒子材料的製造方法具有熔合工序與視其他需求採用的工序。The manufacturing method of the composite particle material of this embodiment is the manufacturing method which can conveniently manufacture the composite particle material of this embodiment mentioned above. The manufacturing method of the composite particle material in this embodiment includes a fusion process and other processes according to other requirements.
熔合工序係樹脂粒子材料變軟而附著於表面之無機物粒子材料熔合至樹脂粒子材料的工序。作為樹脂粒子材料變軟的溫度雖有熔點，但亦可採用係為熔點以下之溫度的玻璃轉移點、軟化點。在此等溫度以上的高溫氣體環境下放入無機物粒子材料與樹脂粒子材料。作為具體之良佳之溫度，如同於上已述。The fusion process is a process in which the resin particle material becomes soft and the inorganic particle material attached to the surface is fused to the resin particle material. Although there is a melting point as the temperature at which the resin particle material becomes soft, a glass transition point or a softening point which is a temperature lower than the melting point can also be used. Put the inorganic particle material and the resin particle material in the high-temperature gas environment above the above temperature. A specific preferred temperature is as described above.
高溫氣體環境係透過氣體來形成。作為可採用的氣體，並不特別限制，但可採用空氣、氧氣、氮氣、氬氣等。對於無機物粒子材料與樹脂粒子材料，由於可採用與在先前已述之本實施型態之複合粒子材料中可使用者相同者，故省略進一步的說明。The high temperature gas environment is formed through the gas. As the gas that can be used, it is not particularly limited, but air, oxygen, nitrogen, argon, etc. can be used. As for the inorganic particle material and the resin particle material, the same ones as those that can be used in the composite particle material of this embodiment described above can be used, so further description is omitted.
無機物粒子材料與樹脂粒子材料可預先做成混合物而同時放入，亦可分別放入。藉由於熔合工序之前透過複合化裝置或粉碎裝置等機械化學上的方法將無機物粒子材料埋入樹脂粒子材料之表面，可使在之後的熔合工序中之樹脂粒子材料與無機物粒子材料的鍵結強固。若透過機械化學上的方法將無機物粒子材料埋設於樹脂粒子材料之表面，則有於樹脂粒子材料產生應變之虞，但藉由在熔合工序中加熱至如樹脂材料軟化的溫度，變得可消除生成的應變。The inorganic particle material and the resin particle material may be prepared as a mixture in advance and put in at the same time, or may be put in separately. By embedding the inorganic particle material on the surface of the resin particle material through a mechanochemical method such as a composite device or a crushing device before the fusion process, the bond between the resin particle material and the inorganic particle material in the subsequent fusion process can be strengthened . If the inorganic particle material is buried on the surface of the resin particle material by a mechanochemical method, there is a risk of straining the resin particle material, but it can be eliminated by heating to the temperature at which the resin material softens in the fusion process. Generated strain.
作為實現高溫氣體環境的方法，並不特別限制，但可將構成氣體環境的氣體（空氣、氧氣、氮氣、氬氣等）加熱來使用。加熱的方法並不特別受限，可使用火焰或使用電性的手法。The method for realizing the high-temperature gas environment is not particularly limited, but the gas (air, oxygen, nitrogen, argon, etc.) constituting the gas environment may be heated and used. The heating method is not particularly limited, and a flame or an electrical method may be used.
舉例而言，作為加熱方法的熱源，亦可使用藉由使丙烷或都市煤氣、乙炔等可燃性氣體燃燒生成的火焰。並且，亦可使用將使乙醇、辛烷、煤油等有機溶劑噴霧而成之霧或者使之氣化而成之蒸氣燃燒生成的火焰。可藉由直接接觸如此操作而形成之火焰來進行加熱，亦可使用將空氣等利用火焰加熱而獲得之高溫的空氣來間接進行加熱。作為具體的燃燒裝置，可示例：預混合燃燒器、擴散燃燒式燃燒器、液體燃料燃燒器等。舉例而言，作為市售之裝置，亦可使用：NANOCREATOR FCM（細川密克朗製）、高頻感應熱電漿奈米粒子合成裝置TP-40020NPS（日本電子製）等裝置。並且，亦可以如氣流式乾燥機HIRAIWA渦輪噴射乾燥器（平岩鐵工所製）、連續瞬間氣流式乾燥機瞬間噴射乾燥器（SEISHIN ENTERPRISE CO., LTD.製）、Meteorainbow（NIPPON PNEUMATIC MFG. CO., LTD.製）、高溫乾燥用微霧噴灑乾燥器（藤崎電機製）等的電性加熱器為熱源使用已加溫的氣體類。For example, as the heat source of the heating method, a flame generated by burning a combustible gas such as propane, city gas, or acetylene can also be used. In addition, a flame produced by burning a mist obtained by spraying an organic solvent such as ethanol, octane, or kerosene or vaporizing it may be used. Heating may be performed by directly contacting the flame formed in this way, or may be heated indirectly using high-temperature air obtained by heating air or the like with a flame. As a specific combustion device, a premix burner, a diffusion combustion burner, a liquid fuel burner, and the like can be exemplified. For example, as commercially available devices, devices such as NANOCREATOR FCM (manufactured by Hosokawa Micron), high-frequency induction thermoplasma nanoparticle synthesis device TP-40020NPS (manufactured by JEOL Ltd.) can also be used. In addition, air flow dryer HIRAIWA turbo jet dryer (manufactured by Hiraiwa Iron Works Co., Ltd.), continuous instantaneous air flow dryer instant jet dryer (manufactured by SEISHIN ENTERPRISE CO., LTD.), Meteorainbow (NIPPON PNEUMATIC MFG. CO ., LTD.), electric heaters such as micro-mist spray dryers for high-temperature drying (Fujisaki Electric Co., Ltd.) use heated gases as heat sources.
於在高溫氣體環境下放入無機物粒子材料與樹脂粒子材料的情況下，以在所構成之1個1個的粒子以彼此不會熔合之方式在各自分離的狀態下放入為符合期望。作為將粒子各自分離放入的方法，採用使之浮游於由氣體或液體而成之介質中的方法。氣體與液體亦可混合使用。若於介質採用液體，則可抑制在放入前發生之粒子的凝集，故可有效防止樹脂粒子材料彼此的熔合。When putting the inorganic particle material and the resin particle material in a high-temperature gas environment, it is desirable to put them in a separated state so that the individual particles are not fused together. As a method of separately putting the particles, a method of floating them in a medium made of gas or liquid is used. Gases and liquids can also be mixed. If a liquid is used as the medium, the aggregation of the particles before putting in can be suppressed, so that the fusion of the resin particle materials can be effectively prevented.
並且，所謂將無機物粒子材料與樹脂粒子材料「放入高溫氣體環境下」，當然可藉由準備高溫氣體環境並於其中加入無機物粒子材料與樹脂粒子材料的方法來實現，亦可藉由在做成使無機物粒子材料與樹脂粒子材料浮游於介質中的狀態（例如形成有流動層的狀態）之後透過使此介質的溫度上升形成高溫氣體環境來實現。Moreover, the so-called "putting the inorganic particle material and the resin particle material into a high-temperature gas environment" can of course be realized by preparing a high-temperature gas environment and adding the inorganic particle material and the resin particle material therein, or by making a high-temperature gas environment. It is realized by making the inorganic particle material and the resin particle material float in the medium (for example, the state in which a fluidized bed is formed) and then raising the temperature of the medium to form a high-temperature gas environment.
在熔合工序中，將樹脂粒子材料與無機物粒子材料暴露於高溫氣體環境下的時間，進行至無機物粒子材料熔合至樹脂粒子材料之表面且於無機物粒子材料之表面生成OH基。熔合與否，可以樹脂粒子材料之表面是否有一部分已軟化來判斷，再者，可藉由變成於在先前已述之方法中觀測漿料狀態之複合粒子材料時未觀測到海島結構的狀態來判斷。此外，在高溫氣體環境的溫度較構成樹脂粒子材料之樹脂材料的熔點還要高的情況下，判斷為無機物粒子材料熔合至樹脂粒子材料之表面。尤其在熔合工序中暴露於高溫氣體環境下之時間的設定，可以對於所製造之複合粒子材料以於後所述之方法量測到的無機物粒子含量之值呈指定值以上之方式來進行。作為指定值，可設定1 mg／m 2、3 mg／m 2、5 mg／m 2、10 mg／m 2、50 mg／m 2等，指定值尤以大者為佳。並且，作為在熔合工序中OH基生成的量，並不特別限制，但以無機物粒子材料之表面積為基準，以做成0.1～30 μmol／m 2之範圍為符合期望。作為更良佳之OH基之量的上限值、下限值，可採用於上已述之值，可任意組合。 In the fusion process, the resin particle material and the inorganic particle material are exposed to the high-temperature gas environment until the inorganic particle material is fused to the surface of the resin particle material and OH groups are generated on the surface of the inorganic particle material. Fusion or not can be judged by whether a part of the surface of the resin particle material has been softened. Moreover, it can be judged by changing to a state where no sea-island structure is observed when observing the composite particle material in the slurry state in the method described above. judge. In addition, when the temperature of the high-temperature gas environment is higher than the melting point of the resin material constituting the resin particle material, it is determined that the inorganic particle material is fused to the surface of the resin particle material. In particular, the exposure time in the high-temperature gas environment in the fusion process can be set so that the value of the inorganic particle content measured by the method described later for the produced composite particle material is greater than or equal to a specified value. As the specified value, 1 mg/m 2 , 3 mg/m 2 , 5 mg/m 2 , 10 mg/m 2 , 50 mg/m 2 , etc. can be set, and the specified value is preferably larger. In addition, the amount of OH groups generated in the fusion process is not particularly limited, but it is desirable to make it within the range of 0.1 to 30 μmol/m 2 based on the surface area of the inorganic particle material. As the upper limit value and the lower limit value of the amount of more preferable OH groups, the above-mentioned values can be adopted, and arbitrarily combined can be used.
再者，在熔合工序中使樹脂粒子材料與無機物粒子材料在高溫氣體環境下接觸的時間，可以樹脂粒子材料加熱而球狀化的時間以上進行。若加熱時間變長，則樹脂粒子材料會加熱而軟化、熔融，已軟化、熔融的樹脂粒子材料可透過表面張力等球狀化。以本實施型態之製造方法製造之複合粒子材料的球形度為0.8以上，以0.85以上、0.9以上為更佳。以球形度高者為較佳。In addition, the time for bringing the resin particle material and the inorganic material particle material into contact in a high-temperature gas environment in the fusion process may be longer than the time for the resin particle material to be heated and spheroidized. If the heating time becomes longer, the resin particle material will be heated to soften and melt, and the softened and melted resin particle material can be spheroidized through surface tension and the like. The sphericity of the composite particle material produced by the production method of this embodiment is above 0.8, more preferably above 0.85, and above 0.9. The one with high sphericity is better.
（球形度的量測方法及無機物粒子含量的量測方法）(Measurement method of sphericity and measurement method of inorganic particle content)
將利用掃描型電子顯微鏡（SEM）觀察到的影像於電腦上使用影像分析軟體（「ImageJ」，（美國國家衛生研究院（National Institutes of Health，USA）））來進行複合粒子材料之球形度的計算。球形度，以在SEM上可觀察到100個左右之各複合粒子材料之方式拍攝照片，自此觀察之粒子的面積與周長，以利用（球形度）＝［4π×（面積）÷（周長） 2］算出之值的形式算出。愈接近1，愈接近真球。對於所有此粒子算出球形度，採用其平均值。 The image observed by scanning electron microscope (SEM) was used on the computer and image analysis software ("ImageJ", (National Institutes of Health, USA)) was used to measure the sphericity of the composite particle material calculate. For the degree of sphericity, photographs are taken in such a way that about 100 composite particle materials can be observed on the SEM, and the area and circumference of the particles observed since then can be used (sphericity) = [4π × (area) ÷ (circumference Long) 2 ] Calculated in the form of the calculated value. The closer to 1, the closer to the real ball. The sphericity is calculated for all the particles, and the average value thereof is used.
這回開發的複合粒子材料亦得在使用捏合機等混練機熔融混練後成為壓縮成形物的顆粒原料。The composite particle material developed this time must also be melted and kneaded using a kneader such as a kneader to become a pellet material for a compression molded product.
無機物粒子含量以下述方法算出。重複3次「使100 g之複合粒子材料於甲基乙基酮200 mL中混合，照射超音波（40 kHz、600 W）5分鐘之後，以10000 rpm進行離心分離5分鐘，回收上澄部分」這樣的清洗操作之後，使上澄回收液乾燥。乾燥後的殘差幾乎係無機物粒子材料，可想見係藉由於上已述之清洗操作自複合粒子材料之表面脫離者。無機物粒子含量，假定添加之無機物粒子材料全部固著或物理吸附於樹脂粒子材料，以下述式算出。The inorganic particle content was calculated by the following method. Repeat 3 times "Mix 100 g of composite particle material in 200 mL of methyl ethyl ketone, irradiate with ultrasonic waves (40 kHz, 600 W) for 5 minutes, then centrifuge at 10,000 rpm for 5 minutes, and collect the upper part" After such cleaning operation, the supernatant recovery liquid is dried. The residue after drying is almost inorganic particle material, which is conceivably detached from the surface of the composite particle material by the cleaning operation described above. The inorganic particle content is calculated by the following formula, assuming that all the added inorganic particle materials are fixed or physically adsorbed on the resin particle material.
固著量［g］＝添加量［g］－乾燥後的殘差（物理吸附量）［g］Fixed amount [g] = added amount [g] - residual after drying (physical adsorption amount) [g]
無機物粒子含量［mg／m 2］＝固著量［g］／［（清洗後的比表面積［m 2／g］×100［g］）］ Inorganic particle content [mg/m 2 ] = fixed amount [g] / [(specific surface area after cleaning [m 2 /g] × 100 [g])]
於此，乾燥條件在180℃下進行1小時。比表面積使用氮氣以BET法量測。Here, drying conditions were performed at 180° C. for 1 hour. The specific surface area is measured by the BET method using nitrogen gas.
『實施例』"Example"
茲針對本發明之氟樹脂粒子材料及其製造方法、複合粒子材料及其製造方法依據以下實施例詳細進行說明。The fluororesin particle material and its manufacturing method, the composite particle material and its manufacturing method of the present invention will be described in detail based on the following examples.
（試樣的製備）（原料的粉碎工序）・試驗例1～5(Preparation of samples) (Powdering process of raw materials)・Test examples 1 to 5
原料樹脂材料採用一次粒徑為5.0 μm、在角頻率0.01 rad／s時之熔融黏度為2.0 Pa·s的聚四氟乙烯樹脂。The raw resin material is polytetrafluoroethylene resin with a primary particle size of 5.0 μm and a melt viscosity of 2.0 Pa·s at an angular frequency of 0.01 rad/s.
對於原料樹脂材料，將供應至粉碎氣體環境之氣體環境氣體的換算水分含量做成89 g／m 3，使用噴射磨機實施粉碎，將所獲得之氟樹脂粒子材料作為本發明之氟樹脂粒子材料，作為本試驗例之試驗試樣。利用噴射磨機的粉碎條件，大氣換算時的粉碎壓為1.0 MPa，一邊透過離心分級來分離，一邊進行粉碎。 For the raw resin material, the converted moisture content of the gas atmosphere supplied to the pulverization gas environment was made 89 g/m 3 , pulverized using a jet mill, and the obtained fluororesin particle material was used as the fluororesin particle material of the present invention , as the test sample of this test example. Using the pulverization conditions of the jet mill, the pulverization pressure in atmospheric conversion is 1.0 MPa, and pulverization is performed while being separated by centrifugal classification.
量測粉碎後之粒徑與PFOA值，結果粒徑為0.2 μm，PFOA值未偵測到粉碎前之原料樹脂材料為54 ppb者（偵測下限值5 ppb以下）。The particle size and PFOA value after crushing were measured. The particle size was 0.2 μm, and the PFOA value was 54 ppb for the raw resin material before crushing (the lower limit of detection is below 5 ppb).
藉由採用相同的粉碎條件並變更分級條件，獲得擁有表1所示之平均粒徑的試驗試樣。By adopting the same crushing conditions and changing the classification conditions, test samples having the average particle diameters shown in Table 1 were obtained.
・試驗例6・Test example 6
原料樹脂材料採用一次粒徑為5.0 μm、在角頻率0.01 rad／s時之熔融黏度為2.0 Pa·s的聚四氟乙烯樹脂。The raw resin material is polytetrafluoroethylene resin with a primary particle size of 5.0 μm and a melt viscosity of 2.0 Pa·s at an angular frequency of 0.01 rad/s.
對於原料樹脂材料，將供應至粉碎氣體環境之氣體環境氣體的換算水分含量做成45 g／m 3，使用噴射磨機實施粉碎，將所獲得之氟樹脂粒子材料作為本發明之氟樹脂粒子材料，作為本試驗例之試驗試樣。利用噴射磨機的粉碎條件，大氣換算時的粉碎壓為1.0 MPa，一邊透過離心分級來分離，一邊進行粉碎。 For the raw resin material, the converted moisture content of the gas atmosphere supplied to the pulverization gas environment was made 45 g/m 3 , pulverized using a jet mill, and the obtained fluororesin particle material was used as the fluororesin particle material of the present invention , as the test sample of this test example. Using the pulverization conditions of the jet mill, the pulverization pressure in atmospheric conversion is 1.0 MPa, and pulverization is performed while being separated by centrifugal classification.
量測粉碎後之粒徑與PFOA值，結果粒徑為2.5 μm，PFOA值未偵測到粉碎前之原料樹脂材料為54 ppb者（偵測下限值5 ppb以下）。The particle size and PFOA value after crushing were measured, and the particle size was 2.5 μm, and the PFOA value was 54 ppb for the raw resin material before crushing (the lower limit of detection is below 5 ppb).
藉由採用相同的粉碎條件並變更分級條件，獲得擁有表1所示之平均粒徑的試驗試樣。By adopting the same crushing conditions and changing the classification conditions, test samples having the average particle diameters shown in Table 1 were obtained.
・試驗例7・Test example 7
原料樹脂材料採用一次粒徑為5.0 μm、在角頻率0.01 rad／s時之熔融黏度為2.0 Pa·s的聚四氟乙烯樹脂。The raw resin material is polytetrafluoroethylene resin with a primary particle size of 5.0 μm and a melt viscosity of 2.0 Pa·s at an angular frequency of 0.01 rad/s.
對於原料樹脂材料，將供應至粉碎氣體環境之氣體環境氣體的換算水分含量做成35 g／m 3，使用噴射磨機實施粉碎，將所獲得之氟樹脂粒子材料作為本發明之氟樹脂粒子材料，作為本試驗例之試驗試樣。利用噴射磨機的粉碎條件，大氣換算時的粉碎壓為1.0 MPa，一邊透過離心分級來分離，一邊進行粉碎。 For the raw resin material, the converted moisture content of the gas atmosphere supplied to the pulverization gas environment was made 35 g/m 3 , pulverized using a jet mill, and the obtained fluororesin particle material was used as the fluororesin particle material of the present invention , as the test sample of this test example. Using the pulverization conditions of the jet mill, the pulverization pressure in atmospheric conversion was 1.0 MPa, and pulverization was performed while being separated by centrifugal classification.
量測粉碎後之粒徑與PFOA值，結果粒徑為3.0 μm，PFOA值未偵測到粉碎前之原料樹脂材料為54 ppb者（偵測下限值5 ppb以下）。The particle size and PFOA value after crushing were measured, and the particle size was 3.0 μm, and the PFOA value was 54 ppb for the raw resin material before crushing (the lower limit of detection is below 5 ppb).
藉由採用相同的粉碎條件並變更分級條件，獲得擁有表1所示之平均粒徑的試驗試樣。By adopting the same crushing conditions and changing the classification conditions, test samples having the average particle diameters shown in Table 1 were obtained.
・試驗例8・Test example 8
除了在粉碎條件中將氣體環境氣體的換算水分含量做成7.0 g／m 3以外，在與試驗例1相同之條件下進行粉碎，將所獲得之氟樹脂粒子材料作為本試驗例之試驗試樣。量測粉碎後之粒徑與PFOA值，結果粒徑為1.0 μm，PFOA值之粉碎前為54 ppb者呈170 ppb。 The fluororesin particle material obtained was pulverized under the same conditions as in Test Example 1, except that the moisture content converted to ambient gas was 7.0 g/ m3 in the pulverization conditions, and the obtained fluororesin particle material was used as a test sample in this test example. . The particle size and PFOA value after crushing were measured. The particle size was 1.0 μm, and the PFOA value was 170 ppb compared to 54 ppb before crushing.
對於本試驗例之試驗試樣，為了使PFOA值減低，可藉由在230℃下加熱3小時而PFOA值減低至與試驗試樣1～7同程度（未達10 ppb）。將此試驗試樣作為供於於後所述之凝集試驗的試驗例8之試驗試樣。For the test samples in this test example, in order to reduce the PFOA value, the PFOA value can be reduced to the same level as the test samples 1-7 (less than 10 ppb) by heating at 230°C for 3 hours. This test sample was used as a test sample in Test Example 8 for an agglutination test described later.
（PFOA值減低效果）(PFOA value reduction effect)
在試驗例1～7中，藉由提高換算水分含量，可減低PFOA值。相對於此，在未進行加熱的試驗例8中，由於換算水分含量低，故無法減低PFOA值。由以上結果可知，藉由粉碎氣體環境中之換算水分含量之值變高，能夠減低PFOA值。In Test Examples 1 to 7, the PFOA value can be reduced by increasing the converted water content. On the other hand, in Test Example 8 where heating was not performed, the PFOA value could not be reduced because the converted water content was low. From the above results, it can be seen that the value of PFOA can be reduced by increasing the value of the converted water content in the pulverization gas environment.
（凝集試驗）(agglutination test)
對於本試驗例之試驗試樣1～8，透過粒度分布量測來評價凝集性。凝集性的評價藉由算出分散度來進行。分散度係以（D90－D10）／D50算出之值，大者意謂凝集性高。並且，亦以SEM觀察粒子之凝集的狀況。分散度的計算結果揭示於表1。For test samples 1 to 8 in this test example, the agglomeration was evaluated by particle size distribution measurement. The aggregation property was evaluated by calculating the degree of dispersion. The degree of dispersion is a value calculated by (D90-D10)/D50, and the larger one means higher cohesiveness. In addition, the state of particle aggregation was also observed by SEM. The calculation results of the degree of dispersion are disclosed in Table 1.
『表1』
・試驗例9～15（試樣的熔融球狀化）・Test examples 9 to 15 (molten spheroidization of samples)
將100質量份之試驗例1～7之試驗試樣與表2所示之量之作為無機物粒子材料的溼式氧化矽粒子（透過液相合成法合成的氧化矽；能夠在乾燥狀態下分散至成為一次粒子；體積平均粒徑10 nm，疏水化度：72）的混合物，做成在0.06 m 3／分鐘之空氣流以1.0 kg／小時之量供應的浮游狀態，放入由500℃之空氣而成之高溫氣體環境下（容積2 m 3）（熔合工序）。 100 parts by mass of the test samples of Test Examples 1 to 7 and wet silicon oxide particles (silicon oxide synthesized by liquid phase synthesis method; can be dispersed in a dry state to Become a primary particle; the volume average particle size is 10 nm, and the degree of hydrophobization: 72) is made into a floating state supplied at an air flow of 0.06 m 3 /min at an amount of 1.0 kg/hour, and placed in air at 500°C The resulting high-temperature gas environment (volume 2 m 3 ) (fusion process).
放入之混合物之中可回收90質量份之複合粒子材料。若要比較混合物與複合粒子材料的IR光譜，在2800～3200 cm −1附近可看到的烷基鏈之尖峰減少，在3600～3800 cm −1附近可看到的OH基之尖峰增加。將回收之複合粒子材料分別作為試驗例9～15之試驗試樣。 90 parts by mass of the composite particle material can be recovered in the mixture put into it. To compare the IR spectra of mixtures and composite particle materials, the peaks of alkyl chains that can be seen around 2800-3200 cm −1 decrease, and the peaks of OH groups that can be seen around 3600-3800 cm −1 increase. The recovered composite particle materials were used as test samples of Test Examples 9 to 15, respectively.
試驗例8之試驗試樣（供於凝集試驗者）與試驗例1～7之試驗試樣相比外觀並不光滑，未供於熔合工序。The test sample of Test Example 8 (used in the coagulation test) was not smooth in appearance compared with the test samples of Test Examples 1 to 7, and was not used in the fusion process.
（清漆黏度）(varnish viscosity)
對於試驗例9～15之試驗試樣，將作為溶媒的甲基乙基酮（MEK）與作為樹脂材料的環氧樹脂（ZX-1059）以（試驗試樣）：（溶媒）：（樹脂材料）＝40：20：30（質量比）混合做成各試驗例之樹脂組成物。混合方法使用混練機進行混練2分鐘之後，減壓除氣1分鐘來進行。對於各個樹脂組成物使用振動式黏度計量測到的黏度揭示於表2。將以（溶媒）：（樹脂材料）＝20：30（質量比）製備的樹脂組成物作為對照試樣。黏度之值小者優異。For the test samples of test examples 9 to 15, methyl ethyl ketone (MEK) as a solvent and epoxy resin (ZX-1059) as a resin material were used as (test sample): (solvent): (resin material ) = 40:20:30 (mass ratio) mixed to make the resin composition of each test example. The mixing method was kneaded for 2 minutes using a kneader, and then degassed under reduced pressure for 1 minute. Viscosities measured using a vibratory viscometer for each resin composition are disclosed in Table 2. A resin composition prepared by (vehicle):(resin material)=20:30 (mass ratio) was used as a control sample. The smaller value of viscosity is better.
『表2』
若要以4階段評價各試驗例之結果（數字小者優異。下同），試驗例9呈4，試驗例10呈2，試驗例11～15呈1。To evaluate the results of each test example in 4 stages (smaller numbers are better, the same below), test example 9 is 4, test example 10 is 2, and test examples 11-15 are 1.
（漿料黏度）(slurry viscosity)
對於試驗例9～15之試驗試樣，以（試驗試樣）：（溶媒／MEK）＝50：50（質量比）混合做成各試驗例之漿料。混合方法使用超音波槽進行分散。對於各個漿料使用振動式黏度計量測到的黏度揭示於表3。將MEK作為對照試樣。值小者優異。For the test samples of test examples 9 to 15, (test sample): (solvent/MEK) = 50:50 (mass ratio) was mixed to make a slurry for each test example. The mixing method uses an ultrasonic tank for dispersion. The viscosities measured using vibratory viscometers for the respective slurries are disclosed in Table 3. MEK was used as a control sample. Smaller values are superior.
『表3』
若要以4階段評價各試驗例之結果，試驗例9呈4，試驗例10呈2，試驗例11～15呈1。To evaluate the results of each test example in four stages, test example 9 is rated as 4, test example 10 is rated as 2, and test examples 11 to 15 are rated as 1.
（含無機氧化物漿料黏度）(Viscosity of slurry containing inorganic oxide)
對於試驗例9～15之試驗試樣，以（試驗試樣）：（溶媒／MEK）：（無機氧化物／氧化矽）＝40：60：20（質量比）混合做成各試驗例之漿料。混合方法以超音波槽進行。對於各個漿料使用振動式黏度計量測到的黏度揭示於表4。將MEK作為對照試樣。值小者優異。For the test samples of test examples 9 to 15, mix (test sample): (solvent/MEK): (inorganic oxide/silicon oxide) = 40:60:20 (mass ratio) to make slurry for each test example material. The mixing method is carried out in an ultrasonic tank. The viscosities measured using vibratory viscometers for the respective slurries are disclosed in Table 4. MEK was used as a control sample. Smaller values are superior.
『表4』
若要以4階段評價各試驗例之結果，試驗例9呈4，試驗例10呈2，試驗例11～15呈1。To evaluate the results of each test example in four stages, test example 9 is rated as 4, test example 10 is rated as 2, and test examples 11 to 15 are rated as 1.
（沉澱穩定性、再分散性）(precipitation stability, redispersibility)
製備已使試驗例9～15之試驗試樣分散於MEK的組成物。試驗試樣的濃度以整體之質量為基準以50%、55%、60%、65%、70%製備，對於此時獲得之組成物，確認是否呈有流動性的漿料狀。其結果，在試驗例9中僅50%、在試驗例10中為50%、55%、在試驗例11中於50～65%成為漿料狀，在試驗例12～15中於50～70%之範圍成為漿料狀。於是，於在所有試驗例中呈漿料狀的50%進行沉澱穩定性及再分散性的評價。A composition obtained by dispersing the test samples of Test Examples 9 to 15 in MEK was prepared. The concentration of the test sample was prepared at 50%, 55%, 60%, 65%, and 70% based on the mass of the whole. For the composition obtained at this time, it was confirmed whether it was in the form of a fluid slurry. As a result, only 50% in Test Example 9, 50% and 55% in Test Example 10, 50 to 65% in Test Example 11 became a slurry, and 50 to 70% in Test Examples 12 to 15. % range becomes a slurry. Then, the evaluation of sedimentation stability and redispersibility was performed on 50% of the slurry in all the test examples.
首先對於各試驗例之50%漿料評價沉澱穩定性。具體而言，於1小時後、3小時後、5小時後、8小時後量測於玻璃製之樣品瓶以高度35 mm放入各試驗例之漿料並將之翻轉時之於下側部生成的沉澱層之厚度。值小者優異。First, the sedimentation stability was evaluated for the 50% slurry of each test example. Specifically, after 1 hour, 3 hours, 5 hours, and 8 hours, measure the slurry of each test example in a glass sample bottle at a height of 35 mm and turn it over. The thickness of the resulting sediment layer. Smaller values are superior.
之後以振幅30 mm、振動數50 rpm沿樣品瓶的橫向進行振動，量測至沉澱層消失所需的時間，評價再分散性。值小者優異。各個結果揭示於表5。Afterwards, vibrate along the lateral direction of the sample bottle with an amplitude of 30 mm and a vibration frequency of 50 rpm, measure the time required for the precipitation layer to disappear, and evaluate the redispersibility. Smaller values are superior. The respective results are disclosed in Table 5.
『表5』
若要以4階段評價各試驗例之結果，在沉澱穩定性中試驗例9～11呈1，試驗例12、13呈2，試驗例14呈3，試驗例15呈4，在再分散性中試驗例9～12呈1，試驗例13呈2，試驗例14、15呈4。If we want to evaluate the results of each test example in four stages, test examples 9 to 11 are 1 in sedimentation stability, 2 in test examples 12 and 13, 3 in test example 14, 4 in test example 15, and 4 in redispersibility Test Examples 9 to 12 were 1, Test Example 13 was 2, and Test Examples 14 and 15 were 4.
（介電損耗正切）(dielectric loss tangent)
對於試驗例9～15之試驗試樣，使用網路分析儀（KEYSIGHT公司製，E5071C）與空腔共振器擾動法，量測在1 GHz下的相對介電常數、介電損耗正切。此量測遵循ASTMD2520（JIS C2565）進行。結果揭示於表6。值小者優異。For the test samples of Test Examples 9 to 15, the relative permittivity and dielectric loss tangent at 1 GHz were measured using a network analyzer (manufactured by KEYSIGHT, E5071C) and the cavity resonator perturbation method. This measurement is performed in accordance with ASTM D2520 (JIS C2565). The results are disclosed in Table 6. Smaller values are superior.
『表6』
若要以4階段評價各試驗例之介電分散的結果，試驗例9、10呈4，試驗例11、12呈2，試驗例13～15呈1。To evaluate the dielectric dispersion results of each test example in four stages, test examples 9 and 10 are rated as 4, test examples 11 and 12 are rated as 2, and test examples 13 to 15 are rated as 1.
（討論）(discuss)
由以上結果可知，若要匯整各試驗例之4階段評價結果，粒徑做成0.5 μm～2.0 μm之範圍尤為優異。From the above results, it can be seen that the particle size range of 0.5 μm to 2.0 μm is particularly excellent if the four-stage evaluation results of each test example are to be consolidated.
（球形度）(sphericity)
將利用掃描型電子顯微鏡（SEM）觀察到的影像於電腦上使用影像分析軟體（「ImageJ」，（美國國家衛生研究院（National Institutes of Health，USA）））來進行複合粒子材料之球形度的計算。球形度，以在SEM上可觀察到100個左右之各複合粒子材料之方式拍攝照片，自此觀察之粒子的面積與周長，以利用（球形度）＝［4π×（面積）÷（周長） 2］算出之值的形式算出。愈接近1，愈接近真球。對於所有此粒子算出球形度，採用其平均值。結果揭示於表7。此外，試驗例1～7之試驗試樣於此雖未揭露，但與進行了球狀化工序之對應的試驗例9～15相比球形度低。 The image observed by scanning electron microscope (SEM) was used on the computer and image analysis software ("ImageJ", (National Institutes of Health, USA)) was used to measure the sphericity of the composite particle material calculate. For the degree of sphericity, photographs are taken in such a way that about 100 composite particle materials can be observed on the SEM, and the area and circumference of the particles observed since then can be used (sphericity) = [4π × (area) ÷ (circumference Long) 2 ] Calculated in the form of the calculated value. The closer to 1, the closer to the real ball. The sphericity is calculated for all the particles, and the average value thereof is used. The results are disclosed in Table 7. In addition, although the test samples of Test Examples 1 to 7 are not disclosed here, their sphericity is lower than that of Test Examples 9 to 15 corresponding to the spheroidization process.
『表7』
由表明顯可知，藉由經過球狀化工序，平均球形度變高。It is clear from the table that the average sphericity becomes higher by going through the spheroidizing step.
無。none.
無。none.
無。none.
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