JP2023150831A - Composite particle material and production method of the same, composite particle material slurry, and resin composition - Google Patents
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Abstract
Description
本発明は、樹脂からなる粒子材料の表面に無機物粒子材料を融着させて形成された電子材料用樹脂組成物中などに混合して用いられる複合粒子材料及びその製造方法、更にはその複合粒子材料を含有する複合粒子材料スラリー及び樹脂組成物に関する。 The present invention relates to a composite particle material that is mixed into a resin composition for electronic materials formed by fusing an inorganic particle material to the surface of a resin particle material, a method for producing the same, and furthermore, a method for producing the composite particle material. The present invention relates to a composite particle material slurry and a resin composition containing the material.
従来、異素材添加による電気的特性向上、硬化後の寸法安定性などを目的として樹脂からなる粒子材料（本明細書中において、「樹脂粒子材料」と称する）をフィラーとして硬化前の樹脂組成物（硬化前樹脂組成物）中に用いることが行われてきた。例えばＣ－Ｆ結合をもつフッ素樹脂が電気的特性向上のために用いられている。 Conventionally, particle materials made of resin (herein referred to as "resin particle materials") have been used as fillers to improve electrical properties by adding different materials, improve dimensional stability after curing, etc., and prepare resin compositions before curing. (pre-cured resin compositions). For example, a fluororesin having a C—F bond is used to improve electrical characteristics.
通常、樹脂粒子材料は有機溶媒や有機材料などとの親和性が低いことが多く、又、表面改質も容易ではない。 Usually, resin particle materials often have low affinity with organic solvents and organic materials, and surface modification is also not easy.
そこで、本出願人は樹脂粒子材料（ポリテトラフルオロエチレン：ＰＴＦＥ製）の表面にシリカからなる無機物粒子材料を被覆させた複合粒子材料を提案している（特許文献１）。無機物粒子材料を構成する無機物はシランカップリング剤などにて表面処理することで必要な性能を付与することが容易であり混合する硬化前樹脂組成物との親和性向上などの効果が期待できる。 Therefore, the present applicant has proposed a composite particle material in which the surface of a resin particle material (made of polytetrafluoroethylene: PTFE) is coated with an inorganic particle material made of silica (Patent Document 1). The inorganic material constituting the inorganic particle material can be easily imparted with necessary performance by surface treatment with a silane coupling agent, etc., and effects such as improved compatibility with the pre-cured resin composition to be mixed can be expected.
しかしながら特許文献１に開示の複合粒子材料は、溶剤などへの分散性は向上できたものの、外力により無機物粒子材料を樹脂粒子材料の表面に押しつけて埋め込む方法であるため、得られた複合粒子材料に不要な応力が残留することがあった。また、押しつけて埋め込まれただけなので無機物粒子材料と樹脂粒子材料とが充分に接合されておらず、樹脂組成物との密着性が悪いことが分かった。その結果、電子材料用途に用いたときに配線に用いられている金属との親和性が低下することが分かった。
However, although the composite particle material disclosed in
そこで、樹脂粒子材料の表面に無機物粒子材料を均一且つ強固に接合した複合粒子材料及びその製造方法を提案している（特許文献２）。特許文献２では、樹脂粒子材料と無機物粒子材料とを樹脂粒子材料のガラス転移点、又は軟化点以上の高温雰囲気下に投入し、樹脂粒子材料の表面に無機物粒子材料を融着させることで複合粒子材料を製造する。 Therefore, a composite particle material in which an inorganic particle material is uniformly and firmly bonded to the surface of a resin particle material and a method for manufacturing the same have been proposed (Patent Document 2). In Patent Document 2, a resin particle material and an inorganic particle material are placed in an atmosphere at a high temperature higher than the glass transition point or softening point of the resin particle material, and the inorganic particle material is fused to the surface of the resin particle material to form a composite. Produce particulate material.
特許文献２に開示の複合粒子材料は、樹脂粒子の表面に無機物粒子を均一且つ強固に接合することで有機溶媒や樹脂との相性を改善し、スラリー粘度の低粘度化や密着性の向上が実現されている。しかしながら、特許文献２の方法により得られた複合粒子材料を樹脂材料中に分散させた樹脂組成物について試験を行うと以下の改善点が見つかった。具体的には、硬化した樹脂組成物の硬化物を用いてピール強度を測定すると、複合粒子材料と樹脂材料との界面にて剥離するのではなく、複合粒子材料自体が破壊されていた。 The composite particle material disclosed in Patent Document 2 improves compatibility with organic solvents and resins by uniformly and firmly bonding inorganic particles to the surface of resin particles, resulting in lower slurry viscosity and improved adhesion. It has been realized. However, when a test was conducted on a resin composition in which the composite particle material obtained by the method of Patent Document 2 was dispersed in a resin material, the following improvements were found. Specifically, when the peel strength was measured using a cured product of the cured resin composition, it was found that the composite particle material itself was destroyed, rather than peeling at the interface between the composite particle material and the resin material.
この結果からは複合粒子材料と樹脂材料との間の接着性は充分であることが示唆されるものの、複合粒子材料自体の破壊強度を向上することで更なるピール強度の向上が実現できることが示唆された。 Although this result suggests that the adhesion between the composite particle material and the resin material is sufficient, it also suggests that further improvement in peel strength can be achieved by improving the fracture strength of the composite particle material itself. It was done.
本発明は上記実情に鑑み完成したものであり、従来よりも性能が高い樹脂粒子材料の表面に無機物粒子材料を強固に接合した複合粒子材料及びその製造方法を提供することを解決すべき課題とする。 The present invention was completed in view of the above-mentioned circumstances, and the problem to be solved is to provide a composite particle material in which an inorganic particle material is firmly bonded to the surface of a resin particle material with higher performance than before, and a method for manufacturing the same. do.
本発明者らは上記課題を解決するために鋭意検討を行った結果、１０％変形強度が５ＭＰａ以下にすることで、複合粒子材料自体の破壊が抑制できることから、複合粒子材料の密着性が向上することを見出した。複合粒子材料を構成する樹脂材料はフッ素樹脂であるがフッ素樹脂を粒子化して使用する場合には、放射線照射などにより低分子量化することが行われている。
フッ素樹脂は数百万の分子量をもち高分子量の為に結晶化しにくい。結晶化度が低い状態では粉砕が難しく、分子量を低下させることで結晶化が進み粒子の圧縮強度が増して硬くなることで微粒子化しやすくなる。
The present inventors conducted intensive studies to solve the above problems, and found that by setting the 10% deformation strength to 5 MPa or less, the destruction of the composite particle material itself can be suppressed, and the adhesion of the composite particle material improves. I found out what to do. The resin material constituting the composite particle material is a fluororesin, but when the fluororesin is used in the form of particles, its molecular weight is reduced by irradiation with radiation or the like.
Fluororesin has a molecular weight of several million and is difficult to crystallize due to its high molecular weight. Grinding is difficult when the degree of crystallinity is low, and by lowering the molecular weight crystallization progresses, increasing the compressive strength of the particles and making them harder, making it easier to form fine particles.
しかしながら、フッ素樹脂は、低分子量化によって引張強度は低下する傾向にある。樹脂材料は高分子鎖の末端から破壊される性質があり、低分子量化することで高分子鎖の末端が増加することで引張強度が低下する。今回のピール強度は引張強度に由来するため低分子量化したフッ素樹脂を使用することでピール強度(密着性)が低下することになる。
本発明は、これら知見に基づき完成したものである。
However, the tensile strength of fluororesins tends to decrease as the molecular weight decreases. Resin materials have the property of being destroyed starting from the ends of the polymer chains, and as the molecular weight decreases, the number of ends of the polymer chains increases and the tensile strength decreases. Since the peel strength in this case is derived from tensile strength, using a fluororesin with a lower molecular weight will reduce the peel strength (adhesion).
The present invention was completed based on these findings.
（１）上記課題を解決する本発明の複合粒子材料は、Ｃ－Ｆ結合を有し加熱すると軟化乃至溶融するフッ素樹脂からなる樹脂粒子材料と、
前記樹脂粒子材料より粒径が小さく前記樹脂粒子材料の表面にのみ配置されるように融着しており、表面処理により疎水化された無機物粒子材料と、
を有する複合粒子材料であって、
以下の（ａ）、（ｂ）、（ｃ）の条件を満たす複合粒子材料である。
（ａ）真球度が０．８以上、
（ｂ）体積平均粒径が０．１－１００μｍ、
（ｃ）１０％変形強度が５ＭＰａ以下。
なお、本発明の複合粒子材料は、金属製の配線に接触して用いられる電子材料用樹脂組成物中に混合することに好適に用いられる。
(1) The composite particle material of the present invention that solves the above problems includes a resin particle material made of a fluororesin that has a C-F bond and softens or melts when heated;
an inorganic particle material having a smaller particle size than the resin particle material, fused so as to be disposed only on the surface of the resin particle material, and made hydrophobic by surface treatment;
A composite particle material having
This is a composite particle material that satisfies the following conditions (a), (b), and (c).
(a) Sphericity is 0.8 or more,
(b) volume average particle diameter of 0.1-100 μm;
(c) 10% deformation strength is 5 MPa or less.
The composite particle material of the present invention is suitably used for mixing into a resin composition for electronic materials used in contact with metal wiring.
１０％変形強度を低くすることで複合粒子材料の粒子割れを抑制することが可能になり、ピール強度を向上することが可能になる。無機物粒子材料が樹脂粒子材料の表面に融着されているので溶媒や硬化前樹脂組成物（更には硬化後の硬化前樹脂組成物）などの中に分散させても無機物粒子材料の脱落が起こりにくく、さらに、樹脂粒子材料の表面を無機物粒子材料で被覆することで樹脂粒子材料間の相互作用が低減して凝集や繊維化を抑制できる。また、硬化前樹脂組成物中に分散して樹脂組成物を構成し、銅材料などの金属からなる部材に接した状態で硬化して用いる場合に、硬化後の密着性に優れるという特徴を持つ。 By lowering the 10% deformation strength, it becomes possible to suppress particle cracking of the composite particle material, and it becomes possible to improve the peel strength. Since the inorganic particle material is fused to the surface of the resin particle material, the inorganic particle material may fall off even if it is dispersed in a solvent or a pre-cured resin composition (or even a pre-cured resin composition after curing). Further, by coating the surface of the resin particle material with an inorganic particle material, interaction between the resin particle materials can be reduced and aggregation and fiberization can be suppressed. In addition, when the resin composition is dispersed in a pre-cured resin composition and used after being cured in contact with a member made of metal such as copper material, it has the characteristic of excellent adhesion after curing. .
（２）上記課題を解決する本発明の複合粒子材料の製造方法は、
Ｃ－Ｆ結合を有し加熱すると軟化乃至溶融するフッ素樹脂からなる樹脂粒子材料を調製する樹脂粒子材料調製工程と、
前記樹脂粒子材料よりも粒径が小さく表面処理により疎水化された無機物粒子材料を調製する無機物粒子材料調製工程と、
前記無機物粒子材料が前記樹脂粒子材料の表面に存在する条件で気体からなる媒体中にバラバラの状態で浮遊させながら、温度が前記樹脂粒子材料の融点以上の気体からなる高温雰囲気下に投入し、前記樹脂粒子材料の表面に前記無機物粒子材料を融着させて複合粒子材料を得る融着工程と、
を有し、
下記（Ａ）及び／又は（Ｂ）の工程を備え、
前記融着工程では、前記複合粒子材料の真球度が０．８以上になるまで前記高温雰囲気に前記樹脂粒子材料を曝すものである。
（Ａ）前記無機物粒子材料調製工程における前記無機物粒子材料は、表面処理により疎水化されている、
（Ｂ）前記無機物粒子材料調製工程における前記無機物粒子材料は、式（１）：－ＯＳｉＸ１Ｘ２Ｘ３で表される官能基及び式（２）：－ＯＳｉＹ１Ｙ２Ｙ３で表される官能基と、両官能基が表面に結合している。（上記式（１）、（２）中；Ｘ１はフェニル基、ビニル基、エポキシ基、メタクリル基、アミノ基、ウレイド基、メルカプト基、イソシアネート基、又はアクリル基であり；Ｘ２、Ｘ３は－ＯＳｉＲ３及び－ＯＳｉＹ４Ｙ５Ｙ６よりそれぞれ独立して選択され；Ｙ１はＲであり；Ｙ２、Ｙ３はＲ及び－ＯＳｉＹ４Ｙ５Ｙ６よりそれぞれ独立して選択される。Ｙ４はＲであり；Ｙ５及びＹ６は、Ｒ及び－ＯＳｉＲ３からそれぞれ独立して選択され；Ｒは炭素数１～３のアルキル基から独立して選択される。なお、Ｘ２、Ｘ３、Ｙ２、Ｙ３、Ｙ５、及びＹ６の何れかは、近接する官能基のＸ２、Ｘ３、Ｙ２、Ｙ３、Ｙ５、及びＹ６の何れかと－Ｏ－にて結合しても良い。）
(2) The method for producing a composite particle material of the present invention that solves the above problems includes:
A resin particle material preparation step of preparing a resin particle material made of a fluororesin that has a C-F bond and softens or melts when heated;
an inorganic particle material preparation step of preparing an inorganic particle material that has a smaller particle size than the resin particle material and has been made hydrophobic by surface treatment;
While floating the inorganic particle material in pieces in a gaseous medium under conditions where the inorganic particle material exists on the surface of the resin particle material, the resin particle material is placed in a high-temperature atmosphere consisting of a gas having a temperature equal to or higher than the melting point of the resin particle material, a fusing step of fusing the inorganic particle material to the surface of the resin particle material to obtain a composite particle material;
has
Comprising the steps (A) and/or (B) below,
In the fusion step, the resin particle material is exposed to the high temperature atmosphere until the sphericity of the composite particle material reaches 0.8 or more.
(A) The inorganic particle material in the inorganic particle material preparation step is made hydrophobic by surface treatment.
(B) The inorganic particle material in the inorganic particle material preparation step has a functional group represented by the formula (1): -OSiX 1 X 2 X 3 and a functional group represented by the formula (2): -OSiY 1 Y 2 Y 3 Both functional groups are bonded to the surface. (In the above formulas (1) and (2); X 1 is a phenyl group, vinyl group, epoxy group, methacrylic group, amino group , ureido group, mercapto group, isocyanate group, or acrylic group; are each independently selected from -OSiR 3 and -OSiY 4 Y 5 Y 6 ; Y 1 is R; Y 2 , Y 3 are each independently selected from R and -OSiY 4 Y 5 Y 6 .Y 4 is R; Y 5 and Y 6 are each independently selected from R and -OSiR 3 ; R is independently selected from an alkyl group having 1 to 3 carbon atoms; , X 3 , Y 2 , Y 3 , Y 5 , and Y 6 are adjacent functional groups X 2 , X 3 , Y 2 , Y 3 , Y 5 , and Y 6 and -O- )
融着工程は無機物粒子材料の表面にＯＨ（以下、「表面ＯＨ基」と称することがある）が生成する条件とすることが好ましい。なお、本発明の製造にて製造される複合粒子材料は、金属製の配線に接触して用いられる電子材料用樹脂組成物中に混合することに好適に用いられる。 It is preferable that the fusion step is performed under conditions such that OH (hereinafter sometimes referred to as "surface OH group") is generated on the surface of the inorganic particle material. Note that the composite particle material produced in the production process of the present invention is suitably used for mixing into a resin composition for electronic materials used in contact with metal wiring.
樹脂粒子材料の表面を軟化乃至溶解させて無機物粒子材料を融着させることで強固な接合が実現できる。融着は外力を加えなくても進行するため、樹脂粒子材料と無機物粒子材料とは混合後の均一な状態を保ったまま融着により接合することができる。樹脂粒子材料と無機物粒子材料とは媒体中に浮遊させた状態で高温雰囲気下に投入されるため、樹脂粒子材料間の融着・凝集は進行し難い。 A strong bond can be realized by softening or melting the surface of the resin particle material and fusing the inorganic particle material. Since fusion proceeds without applying external force, the resin particle material and the inorganic particle material can be joined by fusion while maintaining a uniform state after mixing. Since the resin particle material and the inorganic particle material are suspended in a medium and placed in a high-temperature atmosphere, fusion and aggregation between the resin particle materials is difficult to proceed.
本発明の複合粒子材料及びその製造方法は、上記構成を有することにより、樹脂粒子材料の表面に無機物粒子材料を強固に接合した複合粒子材料を提供することが可能になった。特に１０％変形強度を低くすることで複合粒子材料の粒子割れを抑制することが可能になり、ピール強度を向上することが可能になる。 By having the above configuration, the composite particle material and the manufacturing method thereof of the present invention can provide a composite particle material in which an inorganic particle material is firmly bonded to the surface of a resin particle material. In particular, by lowering the 10% deformation strength, it becomes possible to suppress particle cracking of the composite particle material, and it becomes possible to improve the peel strength.
本発明の複合粒子材料及びその製造方法について以下実施形態に基づき詳細に説明を行う。本実施形態の複合粒子材料は、硬化前樹脂組成物中に分散させるフィラーとして用いることが出来る。複合粒子材料が含有する樹脂材料の性質を分散させる硬化前樹脂組成物に付与することが出来る。誘電率が低いフッ素樹脂を含む複合粒子材料は、硬化前樹脂組成物中に添加することで添加された硬化前樹脂組成物の誘電率を低下することが出来る。 The composite particle material of the present invention and its manufacturing method will be described in detail below based on embodiments. The composite particle material of this embodiment can be used as a filler to be dispersed in a pre-cured resin composition. The properties of the resin material contained in the composite particle material can be imparted to the pre-cured resin composition in which it is dispersed. A composite particle material containing a fluororesin having a low dielectric constant can lower the dielectric constant of the pre-cured resin composition by adding it to the pre-cured resin composition.
また、モノマーや樹脂前駆体などからなる硬化前樹脂組成物に本実施形態の複合粒子材料を添加・分散させることで硬化前樹脂組成物の硬化に伴う収縮を抑制することができ、精密な部材の製造が可能になる。 In addition, by adding and dispersing the composite particle material of this embodiment into a pre-cured resin composition consisting of monomers, resin precursors, etc., it is possible to suppress shrinkage accompanying curing of the pre-cured resin composition, thereby making it possible to manufacture precision parts. It becomes possible to manufacture
本実施形態の複合粒子材料が添加・分散できる硬化前樹脂組成物としては熱硬化性樹脂材料の前駆体（エポキシ樹脂、ポリエステル樹脂、ユリア樹脂、シリコン樹脂など；硬化前の材料や一部硬化しているが流動性を有するもの）や、熱可塑性樹脂（ポリフェニレンエーテル樹脂、変性ポリフェニレンエーテル樹脂、ポリイミド樹脂、液晶ポリマー樹脂など）のモノマー、熱可塑性樹脂を加熱溶融した溶融物が例示できる。本実施形態の複合粒子材料は、配線を構成する金属との密着性に優れるため、金属製の配線に接触して用いられる電子材料用樹脂組成物中に混合して用いることができる。 Pre-cured resin compositions to which the composite particle material of this embodiment can be added and dispersed include precursors of thermosetting resin materials (epoxy resins, polyester resins, urea resins, silicone resins, etc.; uncured materials and partially cured materials). Examples include monomers of thermoplastic resins (polyphenylene ether resin, modified polyphenylene ether resin, polyimide resin, liquid crystal polymer resin, etc.), and melts obtained by heating and melting thermoplastic resins. The composite particle material of this embodiment has excellent adhesion to the metal constituting the wiring, so it can be mixed into a resin composition for electronic materials used in contact with metal wiring.
本実施形態の複合粒子材料は、樹脂粒子材料と無機物粒子材料とを有する。無機物粒子材料は樹脂粒子材料の表面に融着されている。無機物粒子材料と樹脂粒子材料との存在比は特に限定しない。無機物粒子材料が表面に融着されていることで樹脂粒子材料の表面が改質される。複合粒子材料の他に遊離の無機物粒子材料や樹脂粒子材料が存在していても良い。 The composite particle material of this embodiment includes a resin particle material and an inorganic particle material. The inorganic particle material is fused to the surface of the resin particle material. The abundance ratio of the inorganic particle material and the resin particle material is not particularly limited. The surface of the resin particle material is modified by the inorganic particle material being fused to the surface. In addition to the composite particle material, free inorganic particle material or resin particle material may also be present.
本実施形態の複合粒子材料の粒径は０．１μｍ～１００μｍである。粒径の下限値としては０．２μｍ、０．５μｍ、０．８μｍ、１．０μｍ、２．０μｍ、３．０μｍ、５．０μｍ、１０μｍ、１５μｍ、２０μｍが例示でき、上限値としては８０μｍ、６０μｍ、５０μｍ、３０μｍ、２０μｍ、１５μｍ、１０μｍ、５．０μｍ、３．０μｍ、２．０μｍ、１．０μｍが例示できる。これらの上限値及び下限値は任意に組み合わせることができる。特に、樹脂組成物中に分散して用いる場合には、その樹脂組成物が充填される部位の最も小さな隙間よりも大きな粒径をもつ粒子（粗粒）は実質的に含有しないことが好ましい（例えば粗粒の含有量の上限を質量基準で１０００ｐｐｍ、５００ｐｐｍ、２００ｐｐｍ、１００ｐｐｍ、５０ｐｐｍにすることが好ましい）。例えば５０μｍの隙間に充填される樹脂組成物であれば５０μｍ以上の粒径をもつ粗粒は１０００ｐｐｍ以下で有ることが好ましく、より好ましくは５００ｐｐｍ以下、更に好ましくは２００ｐｐｍ以下である。 The particle size of the composite particle material of this embodiment is 0.1 μm to 100 μm. Examples of the lower limit of the particle size are 0.2 μm, 0.5 μm, 0.8 μm, 1.0 μm, 2.0 μm, 3.0 μm, 5.0 μm, 10 μm, 15 μm, and 20 μm, and the upper limit is 80 μm, Examples include 60 μm, 50 μm, 30 μm, 20 μm, 15 μm, 10 μm, 5.0 μm, 3.0 μm, 2.0 μm, and 1.0 μm. These upper limit values and lower limit values can be arbitrarily combined. In particular, when used dispersed in a resin composition, it is preferable that particles (coarse particles) having a particle size larger than the smallest gap in the area filled with the resin composition are not substantially contained ( For example, it is preferable to set the upper limit of the content of coarse particles to 1000 ppm, 500 ppm, 200 ppm, 100 ppm, and 50 ppm on a mass basis). For example, in the case of a resin composition to be filled into a gap of 50 μm, the amount of coarse particles having a particle size of 50 μm or more is preferably 1000 ppm or less, more preferably 500 ppm or less, and still more preferably 200 ppm or less.
本実施形態の複合粒子材料は、１０％変形強度が５ＭＰａ以下であり、４ＭＰａ以下であることが好ましく、３ＭＰａ以下であることがより好ましい。１０％変形強度とは、微小粒子圧壊力測定装置ＮＳ－Ａ１００型（ナノシーズ社製）の圧壊針により測定した値である。 The composite particle material of this embodiment has a 10% deformation strength of 5 MPa or less, preferably 4 MPa or less, and more preferably 3 MPa or less. The 10% deformation strength is a value measured using a crushing needle of a microparticle crushing force measuring device NS-A100 model (manufactured by NanoSeeds).
具体的には、測定対象の複合粒子材料をステージ上に自由落下により散布し、０．５μm/sで圧壊針を移動させた際の押し込み力の波形チャートを記録し、１０％変形時の圧壊時のピーク値とベースライン(何も力がかかっていない状態)との差を圧壊力Ｆ［Ｎ］とし、変形強度Ｓ［Ｐａ］を次式より算出した。次式中、Ｄ［ｍ］は粒子径である。
データに用いた粒子径は画像解析ソフト(WinROOF)を用いて、測定時の画像から１５個以上の粒子に対して１粒子ごとに計測した。10個の粒子の圧壊力を測定し、その平均を用いた。測定対象の粒子の選択方法はそれぞれ無作為抽出法にて行った。
Ｓ＝２．８Ｆ／（π・Ｄ２）
Specifically, the composite particle material to be measured was scattered on the stage by free fall, and the waveform chart of the pushing force was recorded when the crushing needle was moved at 0.5 μm/s, and the crushing force at 10% deformation was measured. The difference between the peak value at the time and the baseline (state where no force is applied) was defined as the crushing force F[N], and the deformation strength S[Pa] was calculated from the following formula. In the following formula, D[m] is the particle diameter.
The particle diameter used in the data was measured for each particle of 15 or more particles from the image at the time of measurement using image analysis software (WinROOF). The crushing force of 10 particles was measured and the average thereof was used. The particles to be measured were selected using a random sampling method.
S=2.8F/(π・D 2 )
１０％変形強度を低下させるには、樹脂粒子材料を構成するフッ素樹脂に対し、結晶構造を変化させたり、分子量を高くしたり、結晶化度を低くしたりすることで達成できる。特に結晶構造を変化させる方法、結晶化度を低くする方法を採用することが好ましい。 A 10% deformation strength reduction can be achieved by changing the crystal structure, increasing the molecular weight, or decreasing the crystallinity of the fluororesin constituting the resin particle material. In particular, it is preferable to adopt a method of changing the crystal structure or a method of lowering the degree of crystallinity.
結晶構造を変化させる方法の例としてはフッ素樹脂に対して一度焼成する方法がある。重合したままのフッ素樹脂は外力により線維化しやすいが、一度焼成することで、結晶構造が変化して折りたたみ結晶となるため高分子量であっても繊維化しにくくできる。フッ素樹脂を焼成する条件としては、大気雰囲気下、３３０℃から３９０℃程度で１０分間から６０分間程度処理することで行うことが好ましい。フッ素樹脂の形態としては、その後に粉砕を行い粒子化するような大きな形態で行っても良いし、ある程度の大きさにまで粒子化した状態で行っても良い。粒子化した状態で焼成を行う場合には、適正なキャリアガス中に粒子を分散させた状態で高温雰囲気下に投入することでも行うことができる。 An example of a method for changing the crystal structure is a method of once firing a fluororesin. As-polymerized fluororesin is susceptible to fibrillation due to external forces, but once fired, the crystal structure changes and becomes folded crystals, making it difficult to fibrillate even if it has a high molecular weight. As the conditions for firing the fluororesin, it is preferable to perform the firing at a temperature of about 330° C. to 390° C. for about 10 minutes to 60 minutes in an air atmosphere. As for the form of the fluororesin, it may be in a large form that is subsequently pulverized to form particles, or it may be formed into particles of a certain size. When firing in a particulate state, it can also be carried out by dispersing the particles in an appropriate carrier gas and placing them in a high-temperature atmosphere.
結晶化度を低くする方法としては、フッ素樹脂に側鎖を導入する方法が例示できる。側鎖の導入により結晶化度が低くなり、分子量が高くても繊維化しにくくなる。フッ素樹脂を低分子量化する方法としては、ガンマ線や電子線などの高エネルギー線を照射する方法や、粉砕操作や溶融状態での撹拌操作などによるメカノケミカル的な手法を採用することができる。 An example of a method for lowering the degree of crystallinity is a method of introducing side chains into a fluororesin. The introduction of side chains lowers the degree of crystallinity, making it difficult to form into fibers even if the molecular weight is high. As a method for reducing the molecular weight of the fluororesin, a method of irradiating it with high-energy rays such as gamma rays or electron beams, or a mechanochemical method such as a crushing operation or a stirring operation in a molten state can be adopted.
樹脂粒子材料の表面において、無機物粒子材料は、均一に配置されていることが好ましい。均一に配置されているかどうかは、スラリー状態での海島構造の有無にて判断できる。
海島構造が存在するかどうかは、本実施形態の複合粒子材料をメチルエチルケトン中に２０質量％で分散させて調製したスラリーを光学顕微鏡で観測して行う。メチルエチルケトンからなる部分と分散させた複合粒子材料が凝集した部分とによって海島構造が観測されるため、均一に分散されていると海島構造は観測されない。海島構造の判定のために観測するときの視野の大きさとしては複合粒子材料の粒径に対して１００倍～１０００倍程度で行う。特に複合粒子材料の粒径を基準として２００倍で行うことが好ましい。
Preferably, the inorganic particle material is uniformly arranged on the surface of the resin particle material. Whether or not they are uniformly arranged can be determined by the presence or absence of a sea-island structure in the slurry state.
The presence of a sea-island structure is determined by observing a slurry prepared by dispersing the composite particle material of this embodiment in methyl ethyl ketone at 20% by mass using an optical microscope. A sea-island structure is observed due to the part consisting of methyl ethyl ketone and the part where the dispersed composite particle material aggregates, so if it is uniformly dispersed, no sea-island structure is observed. The field of view for observation to determine the sea-island structure is approximately 100 to 1000 times the particle size of the composite particle material. In particular, it is preferable to carry out the measurement at 200 times the particle size of the composite particle material.
樹脂粒子材料は、フッ素樹脂から構成された粒子である。樹脂粒子材料を構成する樹脂は、加熱すると軟化乃至溶融するものである。フッ素樹脂としては特に限定しないが、テトラフルオロエチレン（PTFE）、パーフルオロアルコキシアルカン（PFA)、パーフルオロエチレンプロペンコポリマー（FEP)、エチレン－テトラフルオロエチレンコポリマー（ETFE)、ポリビニリデンフルオライド（PVDF)、ポリクロロトリフルオロエチレン（PCTFE)、エチレン－クロロトリフルオロエチレンポリマー（ECTFE)、テトラフルオロエチレン－パーフルオロジオキソールコポリマー（TFE/PDD)、ポリビニルフルオライド（PVF)が例示できる。2種類以上用いてもよい。 The resin particle material is a particle made of fluororesin. The resin constituting the resin particle material softens or melts when heated. Fluororesins include, but are not limited to, tetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene propene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), and polyvinylidene fluoride (PVDF). , polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene polymer (ECTFE), tetrafluoroethylene-perfluorodioxole copolymer (TFE/PDD), and polyvinyl fluoride (PVF). Two or more types may be used.
樹脂粒子材料の粒径は、用途により適正な大きさ、粒度分布が変化するため特に限定しないが得られる複合粒子材料の粒径が前述の範囲に収まるように選択される。例えば、０．０５μｍ～１００μｍ程度にすることができる。電子部品用材料に用いるフィラーとして複合粒子材料を採用する場合には、一定以上の大きさの粒径をもつ樹脂粒子材料をあらかじめ除去することも好ましい。粒径の制御方法は特に限定しないが、樹脂材料を粉砕などの物理作用により細かく切断する方法や分級により必要な粒度分布をもつ樹脂粒子材料を得たり、乳化重合・懸濁重合などにより最初から必要な粒度分布をもつように樹脂材料を製造したりすることができる。樹脂粒子材料は真球度が高い方が好ましい。本実施形態の複合粒子材料の真球度は０．８以上で有り、０．８５以上、０．９以上で有ることが更に好ましい。真球度が高い方がより好ましい。 The particle size of the resin particle material is not particularly limited since the appropriate size and particle size distribution vary depending on the application, but it is selected so that the particle size of the resulting composite particle material falls within the above range. For example, the thickness can be about 0.05 μm to 100 μm. When employing a composite particle material as a filler used in a material for electronic parts, it is also preferable to remove in advance resin particle materials having a particle size of a certain size or more. The method of controlling the particle size is not particularly limited, but there are methods such as cutting the resin material into small pieces by physical action such as pulverization, obtaining resin particle material with the required particle size distribution by classification, or obtaining resin particles from the beginning by emulsion polymerization, suspension polymerization, etc. Resin materials can be manufactured to have the required particle size distribution. It is preferable that the resin particle material has high sphericity. The sphericity of the composite particle material of this embodiment is 0.8 or more, more preferably 0.85 or more, and 0.9 or more. Higher sphericity is more preferable.
真球度を向上するためには、樹脂材料を適正な粒度分布に調整した後に高温雰囲気下に投入する方法が採用できる。高温雰囲気下への投入は後述する製造方法における融着工程で行われる樹脂粒子材料を高温雰囲気下に投入する方法と同様の方法が採用できる。また、後述の融着工程において樹脂粒子材料が充分に溶融する条件を選択することにより真球度を向上することもできる。 In order to improve the sphericity, a method can be adopted in which the resin material is adjusted to have an appropriate particle size distribution and then placed in a high temperature atmosphere. For charging into the high temperature atmosphere, a method similar to the method of charging the resin particle material into the high temperature atmosphere performed in the fusion step in the manufacturing method described later can be adopted. Moreover, the sphericity can also be improved by selecting conditions under which the resin particle material is sufficiently melted in the fusion step described below.
無機物粒子材料は、樹脂粒子材料の表面に融着している。融着させる工程（融着工程）では無機物粒子材料が樹脂粒子材料の表面に存在する条件下で高温に曝す処理を行う。高温処理により無機物粒子材料の表面にはＯＨ基が生じる。表面に存在するＯＨ基の量としては、0.1-30μmol/m2が例示できる。ＯＨ基の量の下限値としては、0.1μmol/m2、0.5μmol/m2、1μmol/m2が例示でき、上限値としては、30μmol/m2、25μmol/m2、20μmol/m2が例示できる。これらの上限値及び下限値は任意に組み合わせることが可能であり、これらの範囲内にすることにより密着性が向上する。 The inorganic particle material is fused to the surface of the resin particle material. In the fusion step (fusion step), a treatment is performed in which the inorganic particle material is exposed to high temperature under conditions where it exists on the surface of the resin particle material. The high temperature treatment produces OH groups on the surface of the inorganic particle material. An example of the amount of OH groups present on the surface is 0.1-30 μmol/m 2 . Examples of the lower limit of the amount of OH group are 0.1 μmol/m 2 , 0.5 μmol/m 2 , and 1 μmol/m 2 , and the upper limit is 30 μmol/m 2 , 25 μmol/m 2 , and 20 μmol/m 2 . I can give an example. These upper and lower limits can be arbitrarily combined, and adhesion is improved by keeping them within these ranges.
融着工程での処理温度は樹脂粒子材料の表面の少なくとも一部が溶融できる温度である。例えば、樹脂粒子材料を構成する樹脂材料の軟化点以上、更には融点以上の温度とする。また、無機物粒子材料の表面にＯＨ基が生成する温度を採用する。例えば無機物粒子材料としてシリカを採用する場合には、４００℃以上、アルミナを採用する場合には、４００℃以上とすることが好ましい。 The processing temperature in the fusion step is a temperature at which at least a portion of the surface of the resin particle material can be melted. For example, the temperature is set to be higher than the softening point, furthermore, higher than the melting point of the resin material constituting the resin particle material. Further, a temperature at which OH groups are generated on the surface of the inorganic particle material is adopted. For example, when silica is used as the inorganic particle material, the temperature is preferably 400°C or higher, and when alumina is used, the temperature is preferably 400°C or higher.
融着しているとは樹脂粒子材料の表面の一部が無機物粒子材料の外形に倣って変形している状態を言う。特に複合粒子材料について後述する方法にて測定した無機物粒子含有量の値が所定値以上となっている場合に融着が確実に行われていると判断することもできる。所定値としては、１ｍｇ／ｍ２、３ｍｇ／ｍ２、５ｍｇ／ｍ２、１０ｍｇ／ｍ２、５０ｍｇ／ｍ２などが設定でき、所定値は特に大きい方が好ましい。また、後述する無機物粒子含有量の測定方法における洗浄操作を３回行った後においても前述する条件における海島構造が観察されないこと（この場合に再分散可能であると判断する）が好ましい。 Fused means that a part of the surface of the resin particle material is deformed to follow the outer shape of the inorganic particle material. In particular, when the value of the inorganic particle content measured by the method described below for the composite particle material is equal to or higher than a predetermined value, it can be determined that the fusion is reliably performed. The predetermined value can be set to 1 mg/m 2 , 3 mg/m 2 , 5 mg/m 2 , 10 mg/m 2 , 50 mg/m 2 , etc., and it is particularly preferable that the predetermined value is large. Further, it is preferable that no sea-island structure is observed under the above-mentioned conditions even after performing the washing operation three times in the method for measuring inorganic particle content described below (in this case, it is determined that redispersion is possible).
無機物粒子材料は、樹脂粒子材料より粒径が小さい。無機物粒子材料を構成する無機物としては特に限定しないが、シリカ、アルミナ、ジルコニア、チタニアなどの無機酸化物やこれらの複合酸化物、更には混合物が例示できる。また、無機物粒子材料は有機物を含んでいてもよい。例えば、シリコーンオイルやケイ酸水溶液、オルトケイ酸テトラエチルなどの水溶液やシリコーンレジンなどの粒子が挙げられる。無機物粒子材料は粒径が樹脂粒子材料よりも小さい。無機物粒子材料の粒径を制御する方法としては特に限定しないが、粉砕、分級などの機械的方法を組み合わせて目的の粒度分布にしたり、無機物粒子材料を構成する無機物をゾルゲル法、水熱法などの合成後の無機物が粒子状になる方法で目的の粒度分布としたりすることができる。 The inorganic particle material has a smaller particle size than the resin particle material. The inorganic material constituting the inorganic particle material is not particularly limited, but examples include inorganic oxides such as silica, alumina, zirconia, and titania, composite oxides thereof, and mixtures thereof. Further, the inorganic particle material may contain organic matter. Examples include silicone oil, aqueous silicic acid solutions, aqueous solutions such as tetraethyl orthosilicate, and particles of silicone resin. The inorganic particle material has a smaller particle size than the resin particle material. Methods for controlling the particle size of the inorganic particle material are not particularly limited, but it is possible to achieve the desired particle size distribution by combining mechanical methods such as crushing and classification, or to control the inorganic material constituting the inorganic particle material by a sol-gel method, a hydrothermal method, etc. The desired particle size distribution can be achieved by a method in which the inorganic substance after synthesis becomes particulate.
無機物粒子材料の好ましい粒径としては樹脂粒子材料の粒径を基準として１／１０～１／１００００、より好ましくは１/５０から１/５０００である。具体的な数値を例示すると、粒径の下限値としては１ｎｍ、３ｎｍ、５ｎｍ、１０ｎｍ、１５ｎｍ、２０ｎｍ、３０ｎｍ、５０ｎｍ、８０ｎｍ、１００ｎｍが挙げられ、上限値としては１μｍ、８００ｎｍ、５００ｎｍ、３００ｎｍ、２００ｎｍ、１５０ｎｍ、１００ｎｍなどが挙げられる。 The preferred particle size of the inorganic particle material is 1/10 to 1/10000, more preferably 1/50 to 1/5000, based on the particle size of the resin particle material. To give specific examples of numerical values, the lower limit values of the particle size include 1 nm, 3 nm, 5 nm, 10 nm, 15 nm, 20 nm, 30 nm, 50 nm, 80 nm, and 100 nm, and the upper limit values include 1 μm, 800 nm, 500 nm, 300 nm, Examples include 200 nm, 150 nm, and 100 nm.
無機物粒子材料は、Ｓｉ－Ｈ結合を有するシラン化合物、オルガノシラザン、及び、アミノ基を有する有機化合物からなる群から選択される１つ以上の表面処理剤で表面処理されていても良い。また、表面処理は複合粒子材料にした後に行っても良い。シラン化合物としては、シランカップリング剤、シラザン類、シリコーン（オルガノポリシロキサン構造を分子中に有するもの）も含む。シラン化合物としては、フェニル基、ビニル基、エポキシ基、メタクリル基、アミノ基、フェニルアミノ基、ウレイド基、メルカプト基、イソシアネート基、アクリル基、フッ素アルキル基、アルキル基を有する化合物が好ましい。 The inorganic particle material may be surface-treated with one or more surface treating agents selected from the group consisting of silane compounds having Si—H bonds, organosilazane, and organic compounds having amino groups. Further, the surface treatment may be performed after forming the composite particle material. The silane compound also includes a silane coupling agent, silazane, and silicone (having an organopolysiloxane structure in the molecule). The silane compound is preferably a compound having a phenyl group, a vinyl group, an epoxy group, a methacrylic group, an amino group, a phenylamino group, a ureido group, a mercapto group, an isocyanate group, an acrylic group, a fluoroalkyl group, or an alkyl group.
シラン化合物の中でもシラザン類としては、１，１，１，３，３，３－ヘキサメチルジシラザンが例示できる。オルガノシラザンは、シラザンの１つ以上の水素がアルキル基などの有機基で置換された化合物である。先述したヘキサメチルジシラザンは、シラン化合物であると共にオルガノシラザンの１種である。シラザンは、分子内にケイ素－窒素結合をもつ化合物であり、特に一般式Ｈ３Ｓｉ（ＮＨＳｉＨ２）ｎＮＨＳｉＨ３で表される構造をもつ化合物である。アミノ基を有する化合物としては、アンモニア、Ｎ－アルキルアミン、ジアルキルアミン、トリアルキルアミン、第４級アンモニウム塩などが挙げられる。アルキルとしては、炭素数１、２、３、４、５、６、７、８程度のものが例示できる。また、上述の表面処理剤に代えて（又は加えて）、チタネート類やアルミネート類により表面処理が為されていても良い。 Among the silane compounds, 1,1,1,3,3,3-hexamethyldisilazane can be exemplified as the silazane. Organosilazane is a compound in which one or more hydrogens of silazane are replaced with an organic group such as an alkyl group. The aforementioned hexamethyldisilazane is a silane compound and a type of organosilazane. Silazane is a compound having a silicon-nitrogen bond in its molecule, particularly a compound having a structure represented by the general formula H 3 Si(NHSiH 2 ) n NHSiH 3 . Examples of the compound having an amino group include ammonia, N-alkylamines, dialkylamines, trialkylamines, and quaternary ammonium salts. Examples of alkyl include those having about 1, 2, 3, 4, 5, 6, 7, and 8 carbon atoms. Moreover, instead of (or in addition to) the above-mentioned surface treatment agent, the surface treatment may be performed using titanates or aluminates.
表面処理は、前述の樹脂粒子材料との親和性を向上する目的で行ったり、本実施形態の複合粒子材料が用いられる対象材料（樹脂材料や溶媒など）との親和性を向上する目的で行ったりできる。シラン化合物による表面処理は無機物粒子材料の表面に存在するＯＨ基が全て反応できる程度の量にすることが好ましいが、ＯＨ基が残存していてもよい。 The surface treatment is performed for the purpose of improving the compatibility with the aforementioned resin particle material, or for the purpose of improving the compatibility with the target material (resin material, solvent, etc.) in which the composite particle material of this embodiment is used. You can The surface treatment with the silane compound is preferably carried out in an amount that allows all of the OH groups present on the surface of the inorganic particle material to react, but some OH groups may remain.
・複合粒子材料の製造方法
本実施形態の複合粒子材料の製造方法は、上述する本実施形態の複合粒子材料を好適に製造することができる製造方法である。本実施形態の複合粒子材料の製造方法は、融着工程とその他必要に応じて採用される工程とを有する。
- Manufacturing method of composite particle material The manufacturing method of the composite particle material of this embodiment is a manufacturing method that can suitably manufacture the composite particle material of this embodiment mentioned above. The method for manufacturing a composite particle material according to the present embodiment includes a fusion step and other steps adopted as necessary.
融着工程は、樹脂粒子材料が柔らかくなって表面に付着している無機物粒子材料が樹脂粒子材料に融着される工程である。樹脂粒子材料が柔らかくなる温度としては融点があるが、融点以下の温度であるガラス転移点・軟化点も採用できる。これらの温度以上である高温雰囲気下に無機物粒子材料と樹脂粒子材料とを投入する。具体的に好ましい温度としては上述した通りである。 The fusion process is a process in which the resin particle material becomes soft and the inorganic particle material adhering to the surface is fused to the resin particle material. The melting point is the temperature at which the resin particle material becomes soft, but the glass transition point and softening point, which are temperatures below the melting point, can also be used. The inorganic particle material and the resin particle material are placed in a high temperature atmosphere that is higher than these temperatures. Specifically preferred temperatures are as described above.
高温雰囲気は気体により形成される。採用できる気体としては特に限定しないが、空気、酸素、窒素、アルゴンなどが採用できる。無機物粒子材料と樹脂粒子材料については、先述した本実施形態の複合粒子材料において使用できるものと同様のものが採用できるため、更なる説明は省略する。 The high temperature atmosphere is formed by gas. The gas that can be used is not particularly limited, but air, oxygen, nitrogen, argon, etc. can be used. Regarding the inorganic particle material and the resin particle material, the same materials as those that can be used in the composite particle material of the present embodiment described above can be employed, so further explanation will be omitted.
無機物粒子材料と樹脂粒子材料とはあらかじめ混合物にして同時に投入しても良いし、別々に投入しても良い。融着工程の前に複合化装置や粉砕装置などのメカノケミカル的な方法により樹脂粒子材料の表面に無機物粒子材料を埋め込んでおくことで、その後の融着工程における樹脂粒子材料と無機物粒子材料との結合を強固にすることができる。メカノケミカル的な方法により無機物粒子材料を樹脂粒子材料の表面に埋設すると樹脂粒子材料に歪みが生じるおそれがあるが、融着工程にて樹脂材料が軟化するような温度にまで加熱されることで生成した歪みが解消されることになる。 The inorganic particle material and the resin particle material may be mixed in advance and added at the same time, or may be added separately. By embedding the inorganic particle material into the surface of the resin particle material using a mechanochemical method such as a compositing device or a crushing device before the fusion process, the resin particle material and inorganic particle material in the subsequent fusion process can be easily separated. The bond between the two can be strengthened. If inorganic particle material is embedded on the surface of resin particle material using a mechanochemical method, there is a risk that the resin particle material may become distorted. The generated distortion will be eliminated.
高温雰囲気を実現する方法としては特に限定しないが、雰囲気を構成する気体（空気、酸素、窒素、アルゴンなど）を加熱して用いることができる。加熱の方法は特に限定されず、火炎を用いたり、電気的な手法を用いたりできる。 The method for realizing the high-temperature atmosphere is not particularly limited, but it can be used by heating the gas (air, oxygen, nitrogen, argon, etc.) that constitutes the atmosphere. The heating method is not particularly limited, and flame or electrical methods can be used.
例えば、加熱方法の熱源としてはプロパンや都市ガス、アセチレンなどの可燃性ガスを燃焼させることで生成される火炎を用いてもよい。またエタノール、オクタン、灯油などの有機溶媒を噴霧させたミスト、あるいは気化させた蒸気を燃焼して生成される火炎を用いてもよい。このようにして形成した火炎に直接接触させることにより加熱を行うこともでき、空気などを火炎により加熱して得られる高温の空気を用いて間接的に加熱を行うこともできる。具体的な燃焼装置としては予混合バーナー、拡散燃焼式バーナー、液体燃料バーナーなどが例示される。例えば、市販の装置として、ナノクリエータFCM（ホソカワミクロン製）、高周波誘導熱プラズマナノ粒子合成装置TP-40020NPS（日本電子製）などの装置を用いてもよい。また気流式乾燥機ＨＩＲＡＩＷＡターボジェットドライヤー（平岩鉄工所製）、連続瞬間気流式乾燥機フラッシュジェットドライヤー（セイシン企業製）、メテオレインボー（日本ニューマチック工業製）、高温乾燥用マイクロミストスプレードライヤ（藤崎電気製）などのような電気ヒーターを熱源として温めたガス類を用いても良い。 For example, a flame generated by burning a flammable gas such as propane, city gas, or acetylene may be used as the heat source in the heating method. Alternatively, a mist made by spraying an organic solvent such as ethanol, octane, or kerosene, or a flame generated by burning vaporized steam may be used. Heating can be performed by direct contact with the flame thus formed, or heating can be performed indirectly using high-temperature air obtained by heating air or the like with a flame. Specific examples of combustion devices include premix burners, diffusion combustion burners, and liquid fuel burners. For example, commercially available devices such as NanoCreator FCM (manufactured by Hosokawa Micron) and high frequency induction thermal plasma nanoparticle synthesis device TP-40020NPS (manufactured by JEOL Ltd.) may be used. In addition, air flow dryer HIRAIWA turbo jet dryer (manufactured by Hiraiwa Iron Works), continuous instant air flow dryer flash jet dryer (manufactured by Seishin Enterprises), Meteor Rainbow (manufactured by Nippon Pneumatic Industries), and high-temperature drying micro-mist spray dryer (Fujisaki Gas heated using an electric heater such as an electric heater as a heat source may also be used.
高温雰囲気下に無機物粒子材料と樹脂粒子材料とを投入する場合には、構成する１つ１つの粒子が互いに融着しないようにバラバラの状態で投入することが望ましい。粒子をバラバラで投入する方法としては、気体や液体からなる媒体中に浮遊させる方法を採用する。媒体中に浮遊した状態で投入した場合にバラバラの状態で投入したと判断する。気体と液体とは混合して用いても良い。媒体に液体を採用すると、投入前に生じる粒子の凝集を抑制できるため、樹脂粒子材料同士の融着が効果的に防止できる。 When introducing the inorganic particle material and the resin particle material into a high-temperature atmosphere, it is desirable to introduce them separately so that the constituent particles do not fuse to each other. As a method of introducing particles in pieces, a method of suspending them in a medium consisting of gas or liquid is adopted. If the material is thrown in a suspended state in the medium, it is determined that the material is thrown in pieces. A mixture of gas and liquid may be used. If a liquid is used as the medium, it is possible to suppress the agglomeration of particles that occurs before injection, and therefore it is possible to effectively prevent the resin particle materials from fusing together.
また、無機物粒子材料と樹脂粒子材料とを「高温雰囲気下に投入する」とは、高温雰囲気を準備し、その中に無機物粒子材料と樹脂粒子材料とを入れる方法はもちろん、無機物粒子材料と樹脂粒子材料とを媒体中に浮遊させた状態（例えば流動層が形成された状態）にした後にその媒体の温度を上昇させていくことで高温雰囲気を形成することでも実現できる。 Furthermore, "putting the inorganic particle material and the resin particle material into a high temperature atmosphere" refers to the method of preparing a high temperature atmosphere and placing the inorganic particle material and the resin particle material therein, as well as the method of putting the inorganic particle material and the resin particle material into the high temperature atmosphere. This can also be achieved by forming a high-temperature atmosphere by raising the temperature of the medium after the particle material is suspended in a medium (for example, a fluidized bed is formed).
融着工程において、樹脂粒子材料と無機物粒子材料とを高温雰囲気下に曝す時間は、樹脂粒子材料の表面に無機物粒子材料が融着するまで且つ無機物粒子材料の表面にＯＨ基が生成するまで行われる。融着したかどうかは含有する樹脂粒子材料の表面が一部でも軟化しているかどうかで判断できるし、更には先述した方法でスラリー状態の複合粒子材料を観測したときに海島構造が観測されない状態になったことで判断できる。なお、高温雰囲気の温度が樹脂粒子材料を構成する樹脂材料の融点よりも高い場合には無機物粒子材料が樹脂粒子材料の表面に融着していると判断する。特に融着工程において高温雰囲気下に曝す時間の設定は、製造された複合粒子材料について後述する方法にて測定した無機物粒子含有量の値が所定値以上となるように行うことができる。所定値としては、１ｍｇ／ｍ２、３ｍｇ／ｍ２、５ｍｇ／ｍ２、１０ｍｇ／ｍ２、５０ｍｇ／ｍ２などが設定できる。また、融着工程においてＯＨ基が生成する量としては特に限定しないが、無機物粒子材料の表面積を基準として、0.1-30μmol/m2の範囲にすることが望ましい。更に好ましいＯＨ基の量の上限値、下限値としては上述した値が採用でき、任意に組み合わせることができる。 In the fusion step, the time for exposing the resin particle material and the inorganic particle material to a high temperature atmosphere is set until the inorganic particle material is fused to the surface of the resin particle material and until OH groups are generated on the surface of the inorganic particle material. be exposed. Whether or not fusion has occurred can be determined by whether the surface of the contained resin particle material has softened at least in part, and furthermore, when the composite particle material in a slurry state is observed using the method described above, no sea-island structure is observed. You can judge by what happens. Note that if the temperature of the high-temperature atmosphere 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 time for exposure to a high temperature atmosphere in the fusion step can be set such that the value of the inorganic particle content measured by the method described below for the manufactured composite particle material is equal to or higher than a predetermined value. As the predetermined value, 1 mg/m 2 , 3 mg/m 2 , 5 mg/m 2 , 10 mg/m 2 , 50 mg/m 2 and the like can be set. Further, the amount of OH groups generated in the fusion step is not particularly limited, but it is preferably in the range of 0.1-30 μmol/m 2 based on the surface area of the inorganic particle material. The above-mentioned values can be adopted as more preferable upper and lower limits of the amount of OH groups, and can be arbitrarily combined.
更に、融着工程において、樹脂粒子材料と無機物粒子材料とを高温雰囲気下に接触させる時間は、樹脂粒子材料が加熱されて球状化する時間以上行うことができる。加熱時間が長くなると、樹脂粒子材料が加熱されて軟化・溶融することになり、軟化・溶融した樹脂粒子材料は表面張力などにより球状化することができる。本実施形態の製造方法で製造された複合粒子材料の真球度は０．８以上で有り、０．８５以上、０．９以上で有ることが更に好ましい。真球度が高い方がより好ましい。 Furthermore, in the fusion step, the resin particle material and the inorganic particle material can be brought into contact with each other in a high-temperature atmosphere for a period longer than the time required for the resin particle material to be heated and spheroidized. If the heating time becomes longer, the resin particle material will be heated and softened and melted, and the softened and melted resin particle material can become spherical due to surface tension and the like. The sphericity of the composite particle material manufactured by the manufacturing method of this embodiment is 0.8 or more, more preferably 0.85 or more, and 0.9 or more. Higher sphericity is more preferable.
・真球度の測定方法及び無機物粒子含有量の測定方法
複合粒子材料の真球度の算出は、走査型電子顕微鏡（ＳＥＭ）により観察された画像をコンピュータ上で画像解析ソフト（「ImageJ」、（アメリカ国立衛生研究所（Ｎａｔｉｏｎａｌ Ｉｎｓｔｉｔｕｔｅｓ ｏｆ Ｈｅａｌｔｈ，ＵＳＡ））を使用して行った。真球度は、各複合粒子材料がＳＥＭ上で１００個程度観察されるよう写真を撮り、その観察される粒子の面積と周囲長から、（真球度）＝｛４π×（面積）÷（周囲長）２｝で算出される値として算出する。１に近づくほど真球に近い。その粒子すべてについて真球度を算出し、その平均値を採用する。
・Method for measuring sphericity and inorganic particle content The sphericity of composite particle materials can be calculated by using image analysis software (“ImageJ”, (National Institutes of Health, USA) From the area and perimeter of the particle, it is calculated as a value calculated as (sphericity) = {4π × (area) ÷ (perimeter) 2}.The closer it is to 1, the closer it is to a true sphere. Calculate the sphericity and use the average value.
今回開発した複合粒子材料は、ニーダー等の混練機を用い溶融混練後に圧縮成形物のペレット原料にもなりえる。 The newly developed composite particle material can be used as a raw material for pellets of compression molded products after being melt-kneaded using a kneader such as a kneader.
・疎水化度
本実施形態の複合粒子材料の疎水化度は２０以上であることが好ましく、３０以上であることがより好ましく、４０以上であることが更に好ましい。
- Hydrophobic degree The hydrophobic degree of the composite particle material of this embodiment is preferably 20 or more, more preferably 30 or more, and even more preferably 40 or more.
測定方法：フラスコに攪拌子入れ、イオン交換水５０ｍｌを計量し水面に試料０．２ｇを静かに浮かせる。攪拌子を回転させ、メタノールを試料に直接かからないよう静かに滴下する。全ての試料が水面から沈降したときのメタノール量から疎水化度を算出する。
（疎水化度：％）＝１００×（メタノール滴下量（ｍＬ））÷（５０ｍＬ＋メタノール滴下量（ｍＬ））
Measurement method: Place a stirring bar in a flask, measure 50 ml of ion-exchanged water, and gently float 0.2 g of the sample on the water surface. Rotate the stirrer and gently drip methanol so as not to splash it directly onto the sample. The degree of hydrophobicity is calculated from the amount of methanol when all the samples settle from the water surface.
(Hydrophobicity: %) = 100 x (methanol dripping amount (mL)) ÷ (50 mL + methanol dripping amount (mL))
（試験試料の調製）
・実施例１
樹脂粒子材料としてポリテトラフルオロエチレン粒子（ＰＴＦＥ粒子：体積平均粒径１２μｍ）を１００質量部、無機物粒子材料としての湿式シリカ粒子（液相合成法により合成されたシリカ：乾燥状態で一次粒子にまで分散可能：体積平均粒径１０nｍ、疎水化度：７２）０．４質量部の混合物を０．０６ｍ３／分の空気の流れに１．０ｋｇ／時の量を供給し浮遊状態として、５００℃の空気からなる高温雰囲気下（容積２ｍ３）に投入した。投入した混合物の内、９０質量部の複合粒子材料が回収できた。回収した複合粒子材料を本実施例の試験試料とした。
(Preparation of test sample)
・Example 1
100 parts by mass of polytetrafluoroethylene particles (PTFE particles: volume average particle diameter 12 μm) as a resin particle material, wet silica particles (silica synthesized by liquid phase synthesis method: reduced to primary particles in a dry state) as an inorganic particle material. Dispersible: volume average particle diameter 10 nm, degree of hydrophobicity: 72) 0.4 parts by mass of the mixture was supplied in an amount of 1.0 kg/hour to a flow of air of 0.06 m 3 /min, suspended at 500°C. The sample was placed in a high-temperature atmosphere (volume: 2 m 3 ) consisting of air. Of the charged mixture, 90 parts by mass of composite particle material was recovered. The recovered composite particle material was used as a test sample in this example.
回収された複合粒子材料を熱硬化性樹脂に混錬したのち熱硬化した。ミクロトームによって切断し、TEM観察したものを図５に示す。その結果、PTFE球状粒子の最表面にシリカが均一且つ強固に接合していることを確認した。図５における粒子中の明るい部分Ａが樹脂粒子材料由来の部分であり、その周囲に無機物粒子材料が稠密且つ密着状態で層Ｂを形成していることが分かった。 The recovered composite particle material was kneaded into a thermosetting resin and then thermosetted. Fig. 5 shows the result of cutting with a microtome and observing with TEM. As a result, it was confirmed that silica was bonded uniformly and firmly to the outermost surface of the PTFE spherical particles. It was found that the bright part A in the particles in FIG. 5 was a part derived from the resin particle material, and the inorganic particle material formed a layer B around it in a dense and tightly adhered state.
・実施例２
樹脂粒子材料としてＰＴＦＥ粒子を四フッ化エチレン・パーフルオロアルコキシエチレン共重合体（ＰＦＡ）粒子（体積平均粒径４μｍ、分子量調整なし）に、無機物粒子材料としての湿式シリカ粒子の量を７．５質量部に変更したこと以外は実施例１と同様の条件で本実施例の試験試料を製造した。
・Example 2
PTFE particles were used as the resin particle material, and the amount of wet silica particles was 7.5% as the inorganic particle material. A test sample of this example was manufactured under the same conditions as in Example 1 except that the parts by mass were changed.
・実施例３
樹脂粒子材料としてＰＴＦＥ粒子をＰＦＡ粒子（体積平均粒径４μｍ、分子量調整なし）に、無機物粒子材料としての湿式シリカ粒子を体積平均粒径５０ｎｍ、３５質量部のものに変更したこと以外は実施例１と同様の条件で本実施例の試験試料を製造した。
・Example 3
Example except that the PTFE particles were changed to PFA particles (volume average particle diameter 4 μm, no molecular weight adjustment) as the resin particle material, and the wet silica particles as the inorganic particle material were changed to 35 parts by mass with a volume average particle diameter of 50 nm. A test sample of this example was manufactured under the same conditions as in Example 1.
・実施例４
樹脂粒子材料としてＰＴＦＥ粒子をＰＦＡ粒子（体積平均粒径４μｍ、分子量調整なし）に、無機物粒子材料としての湿式シリカ粒子を体積平均粒径１００ｎｍ、７０質量部のものに変更したこと以外は実施例１と同様の条件で本実施例の試験試料を製造した。
・Example 4
Example except that the PTFE particles as the resin particle material were changed to PFA particles (volume average particle diameter 4 μm, no molecular weight adjustment), and the wet silica particles as the inorganic particle material were changed to 70 parts by mass with a volume average particle diameter of 100 nm. A test sample of this example was manufactured under the same conditions as in Example 1.
・実施例５
樹脂粒子材料としてＰＴＦＥ粒子をＰＴＦＥ粒子（体積平均粒径０．５μｍ、分子量調整なし）に、無機物粒子材料としての湿式シリカ粒子の量を１０質量部に変更したこと以外は実施例１と同様の条件で本実施例の試験試料を製造した。
・Example 5
Same as Example 1 except that the PTFE particles were changed to PTFE particles (volume average particle diameter 0.5 μm, no molecular weight adjustment) as the resin particle material, and the amount of wet silica particles as the inorganic particle material was changed to 10 parts by mass. The test sample of this example was manufactured under the following conditions.
・比較例１
樹脂粒子材料としてＰＴＦＥ粒子をＰＴＦＥ粒子（体積平均粒径６μｍ、分子量調整有り）に、無機物粒子材料としての湿式シリカ粒子の量を０．８質量部に変更したこと以外は実施例１と同様の条件で本実施例の試験試料を製造した。
・Comparative example 1
Same as Example 1 except that the PTFE particles were changed to PTFE particles (volume average particle diameter 6 μm, molecular weight adjusted) as the resin particle material, and the amount of wet silica particles as the inorganic particle material was changed to 0.8 parts by mass. The test sample of this example was manufactured under the following conditions.
・比較例２
樹脂粒子材料としてＰＴＦＥ粒子をＰＴＦＥ粒子（体積平均粒径３μｍ、分子量調整有り）に、無機物粒子材料としての湿式シリカ粒子の量を１．４質量部に変更したこと以外は実施例１と同様の条件で本実施例の試験試料を製造した。
・Comparative example 2
Same as Example 1 except that the PTFE particles were changed to PTFE particles (volume average particle diameter 3 μm, molecular weight adjusted) as the resin particle material, and the amount of wet silica particles as the inorganic particle material was changed to 1.4 parts by mass. The test sample of this example was manufactured under the following conditions.
・比較例３
樹脂粒子材料としてＰＴＦＥ粒子をＰＴＦＥ粒子（体積平均粒径２μｍ、分子量調整有り）に、無機物粒子材料としての湿式シリカ粒子の量を２．７質量部に変更したこと以外は実施例１と同様の条件で本実施例の試験試料を製造した。
・Comparative example 3
Same as Example 1 except that the PTFE particles were changed to PTFE particles (volume average particle diameter 2 μm, molecular weight adjusted) as the resin particle material, and the amount of wet silica particles as the inorganic particle material was changed to 2.7 parts by mass. The test sample of this example was manufactured under the following conditions.
・実施例６
実施例１で得られた複合粒子材料の粉末100質量部にシランカップリング剤（N-フェニル-3-アミノプロピルトリメトキシシラン）を0.2質量部添加し表面処理を行った。その粉末をメチルエチルケトン（ＭＥＫ）で化学的に結合していない処理剤を洗浄したのち、乾燥してＭＥＫを除去し、洗浄粉末を100質量部回収した。その洗浄粉末のIRスペクトルを測定した。結果を図４に示す。
・Example 6
0.2 parts by mass of a silane coupling agent (N-phenyl-3-aminopropyltrimethoxysilane) was added to 100 parts by mass of the powder of the composite particle material obtained in Example 1 for surface treatment. The powder was washed with methyl ethyl ketone (MEK) to remove chemically bound processing agents, and then dried to remove MEK, and 100 parts by mass of the washed powder was recovered. The IR spectrum of the washed powder was measured. The results are shown in Figure 4.
３０００～３１００ｃｍ－１付近のフェニル基由来のピークと３４００～３５００ｃｍ－１付近のアミノ基のピークが現れていることから複合粒子材料の表面にシランカップリング剤などのシラン化合物で処理することで、複合粒子材料の表面にシラン化合物を結合させることができることが推察される。 The peak derived from the phenyl group near 3000 to 3100 cm -1 and the peak derived from the amino group near 3400 to 3500 cm -1 appear, so that by treating the surface of the composite particle material with a silane compound such as a silane coupling agent, It is speculated that the silane compound can be bonded to the surface of the composite particle material.
表面OH基量は下記の式により算出した。本明細書における表面ＯＨ量はこの方法により測定した値である。
表面OH基量（μmol/m2）＝複合粒子材料に対するシランカップリング剤添加量（mol/g）/複合粒子材料の比表面積(m2/g)×1000000
The amount of surface OH groups was calculated using the following formula. The surface OH amount in this specification is a value measured by this method.
Amount of surface OH groups (μmol/m 2 ) = Addition amount of silane coupling agent to composite particle material (mol/g) / Specific surface area of composite particle material (m 2 /g) × 1000000
実施例６の結果から、実施例１で回収された複合粒子材料の表面OH基量は５．２μmol/m2となった。 From the results of Example 6, the amount of surface OH groups of the composite particle material recovered in Example 1 was 5.2 μmol/m 2 .
なお、以上の各実施例及び比較例の樹脂粒子材料について、分子量調整有りとは、放射線照射による低分子量化を行っていることを意味する。また、各実施例及び比較例において、添加する無機物材料の量が異なるのは、製造された複合粒子材料をメチルエチルケトン（ＭＥＫ）に対して６０質量％になるよう調製したスラリー分散液について観察し、海島構造が観測されなくなる無機物粒子材料の最小限の添加量を採用した。 In addition, regarding the resin particle materials of the above-mentioned Examples and Comparative Examples, "with molecular weight adjustment" means that the molecular weight is lowered by radiation irradiation. Furthermore, in each Example and Comparative Example, the difference in the amount of the inorganic material added was observed for the slurry dispersion prepared so that the manufactured composite particle material was 60% by mass based on methyl ethyl ketone (MEK). The minimum amount of inorganic particle material added at which no sea-island structure was observed was adopted.
（評価）
・１０％変形強度の評価並びに真球度の測定
各実施例及び比較例のそれぞれについて、実施形態に記載した方法で１０％変形強度並びに真球度を測定した。
(evaluation)
-Evaluation of 10% deformation strength and measurement of sphericity For each of the examples and comparative examples, 10% deformation strength and sphericity were measured by the method described in the embodiment.
・ピール強度の評価
ワニス作成：実施例及び比較例それぞれの複合粒子材料６４質量部をＭＥＫ１５０質量部に湿式混合し、分散液２１４質量部を得た。この分散液２１４質量部に、ＭＥＫ１５０質量部、クレゾールノボラック型エポキシ樹脂（新日鉄住金化学株式会社製：ＹＤＣＮ－７０４）１００質量部、フェノールノボラック型樹脂（群栄化学工業株式会社製：ＰＳＭ－４２６１）５０質量部、イミダゾール系硬化促進剤（四国化成工業株式会社製：キュアゾール２Ｅ４ＭＺ）０．１質量部を加え混合し本評価試験の試験試料としてのワニス５１４．１質量部を得た。
-Evaluation of peel strength Varnish preparation: 64 parts by mass of the composite particle materials of each of the examples and comparative examples were wet mixed with 150 parts by mass of MEK to obtain 214 parts by mass of a dispersion liquid. To 214 parts by mass of this dispersion, 150 parts by mass of MEK, 100 parts by mass of cresol novolac epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.: YDCN-704), and phenol novolac type resin (manufactured by Gunei Chemical Co., Ltd.: PSM-4261) 50 parts by mass and 0.1 part by mass of an imidazole curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd.: Curesol 2E4MZ) were added and mixed to obtain 514.1 parts by mass of varnish as a test sample for this evaluation test.
ピール強度測定用サンプル試作：得られたワニスを１０ｃｍ×１０ｃｍ×０．８ｍｍの型に流し込み、１３０℃の熱風循環オーブンで４０分間加熱し半硬化させたシートを得た。このシートを銅箔二枚で挟み真空プレス装置（真空プレスＩＭＣ－１ＡＥＡ型）を用い、成形圧力は約２ＭＰａ、成形温度は５０℃から１７０℃に昇温速度５℃／分で昇温し、昇温後に１７０℃、２０分プレスした。プレス後、１７０℃の熱風循環オーブンで５時間加熱して各実施例及び比較例の試験試料を含むワニスの硬化物からなる樹脂付銅箔を得た。 Sample production for peel strength measurement: The obtained varnish was poured into a mold of 10 cm x 10 cm x 0.8 mm, and heated in a hot air circulation oven at 130°C for 40 minutes to obtain a semi-cured sheet. This sheet was sandwiched between two pieces of copper foil, and using a vacuum press device (vacuum press IMC-1AEA type), the molding pressure was approximately 2 MPa, and the molding temperature was raised from 50°C to 170°C at a heating rate of 5°C/min. After raising the temperature, it was pressed at 170°C for 20 minutes. After pressing, it was heated in a hot air circulation oven at 170° C. for 5 hours to obtain a resin-coated copper foil made of a cured varnish containing the test samples of each Example and Comparative Example.
ピール強度測定：この樹脂付銅箔を９０°引きはがし強さをＪＩＳＫ６８５４－１に準拠し測定を行った。測定装置として万能材料試験機５５８２型を用い、試験温度が２３℃、試験速度が５０ｍｍ／分、引きはがし幅が１０ｍｍで行った。 Peel strength measurement: The 90° peel strength of this resin-coated copper foil was measured in accordance with JIS K6854-1. Using a universal material testing machine model 5582 as a measuring device, the test was conducted at a temperature of 23° C., a test speed of 50 mm/min, and a peeling width of 10 mm.
剥離面の粒子状態の観察：ピール強度測定後の銅箔が付着していた樹脂面をＳＥＭで観察した。剥離面の粒子状態をＡ：繊維化、Ｂ：粒子の伸び、Ｃ：粒子割れのうち一番近いものとして評価した。Ａの繊維化の例としては実施例１の剥離面を図１に、Ｂの粒子の伸びの例としては実施例２の剥離面を図２に、Ｃの粒子割れの例としては比較例２の剥離面を図３に示す。以上の評価結果を表１に示す。 Observation of particle state on peeled surface: After measuring peel strength, the resin surface to which the copper foil was attached was observed using SEM. The particle condition on the peeled surface was evaluated as the closest of A: fiberization, B: particle elongation, and C: particle cracking. As an example of fiberization in A, the peeled surface of Example 1 is shown in FIG. 1, as an example of particle elongation in B, the peeled surface of Example 2 is shown in FIG. 2, and as an example of particle cracking in C, Comparative Example 2 is shown. Figure 3 shows the peeled surface. The above evaluation results are shown in Table 1.
表より明らかなように、各実施例の複合粒子材料を用いたワニスに関するピール強度は、各比較例の複合粒子材料を用いたワニスに関するピール強度よりも高いことが分かった。その理由としては、剥離面の粒子状態が各比較例のように粒子割れが生じておらず、繊維化、粒子の伸びが生じていることにあることが推測された。特に繊維化が進行した実施例１及び５については、粒子の伸びが生じた実施例２～４と比べて高いピール強度を示していた。
また、ピール強度は、１０％変形強度が低いほど高くなり、３．０ＭＰａ程度を下回ると（特に２．５ＭＰａ、更には２．３ＭＰａを下回ると）高くなることが分かった。
As is clear from the table, the peel strength of the varnish using the composite particle material of each Example was found to be higher than the peel strength of the varnish using the composite particle material of each Comparative Example. The reason for this is presumed to be that the state of the particles on the peeled surface is not cracked as in each comparative example, but fiberization and elongation of the particles occur. In particular, Examples 1 and 5 in which fiberization progressed showed higher peel strength than Examples 2 to 4 in which particle elongation occurred.
Furthermore, it was found that the peel strength increases as the 10% deformation strength decreases, and increases when it falls below about 3.0 MPa (particularly below 2.5 MPa, and even below 2.3 MPa).
Claims (9)
前記樹脂粒子材料より粒径が小さく前記樹脂粒子材料の表面にのみ配置されるように融着しており、表面処理により疎水化された無機物粒子材料と、
を有する複合粒子材料であって、
以下の（ａ）、（ｂ）、（ｃ）の条件を満たす複合粒子材料。
（ａ）真球度が０．８以上、
（ｂ）体積平均粒径が０．１μｍ～１００μｍ、
（ｃ）１０％変形強度が５ＭＰａ以下。 A resin particle material made of a fluororesin that has a C-F bond and softens or melts when heated;
an inorganic particle material having a smaller particle size than the resin particle material, fused so as to be disposed only on the surface of the resin particle material, and made hydrophobic by surface treatment;
A composite particle material having
A composite particle material that satisfies the following conditions (a), (b), and (c).
(a) Sphericity is 0.8 or more,
(b) volume average particle diameter of 0.1 μm to 100 μm;
(c) 10% deformation strength is 5 MPa or less.
前記樹脂粒子材料よりも粒径が小さく表面処理により疎水化された無機物粒子材料を調製する無機物粒子材料調製工程と、
前記無機物粒子材料が前記樹脂粒子材料の表面に存在する条件で気体からなる媒体中にバラバラの状態で浮遊させながら、温度が前記樹脂粒子材料の融点以上の気体からなる高温雰囲気下に投入し、前記樹脂粒子材料の表面に前記無機物粒子材料を融着させて複合粒子材料を得る融着工程と、
を有し、
下記（Ａ）及び／又は（Ｂ）の工程を備え、
前記融着工程では、前記複合粒子材料の真球度が０．８以上になるまで前記高温雰囲気に前記樹脂粒子材料を曝す複合粒子材料の製造方法。
（Ａ）前記無機物粒子材料調製工程における前記無機物粒子材料は、表面処理により疎水化されている、
（Ｂ）前記無機物粒子材料調製工程における前記無機物粒子材料は、式（１）：－ＯＳｉＸ１Ｘ２Ｘ３で表される官能基及び式（２）：－ＯＳｉＹ１Ｙ２Ｙ３で表される官能基と、両官能基が表面に結合している。（上記式（１）、（２）中；Ｘ１はフェニル基、ビニル基、エポキシ基、メタクリル基、アミノ基、ウレイド基、メルカプト基、イソシアネート基、又はアクリル基であり；Ｘ２、Ｘ３は－ＯＳｉＲ３及び－ＯＳｉＹ４Ｙ５Ｙ６よりそれぞれ独立して選択され；Ｙ１はＲであり；Ｙ２、Ｙ３はＲ及び－ＯＳｉＹ４Ｙ５Ｙ６よりそれぞれ独立して選択される。Ｙ４はＲであり；Ｙ５及びＹ６は、Ｒ及び－ＯＳｉＲ３からそれぞれ独立して選択され；Ｒは炭素数１～３のアルキル基から独立して選択される。なお、Ｘ２、Ｘ３、Ｙ２、Ｙ３、Ｙ５、及びＹ６の何れかは、近接する官能基のＸ２、Ｘ３、Ｙ２、Ｙ３、Ｙ５、及びＹ６の何れかと－Ｏ－にて結合しても良い。） A resin particle material preparation step of preparing a resin particle material made of a fluororesin that has a C-F bond and softens or melts when heated;
an inorganic particle material preparation step of preparing an inorganic particle material that has a smaller particle size than the resin particle material and has been made hydrophobic by surface treatment;
While floating the inorganic particle material in pieces in a gaseous medium under conditions where the inorganic particle material exists on the surface of the resin particle material, the resin particle material is placed in a high-temperature atmosphere consisting of a gas having a temperature equal to or higher than the melting point of the resin particle material, a fusing step of fusing the inorganic particle material to the surface of the resin particle material to obtain a composite particle material;
has
Comprising the steps (A) and/or (B) below,
In the method for producing a composite particle material, in the fusion step, the resin particle material is exposed to the high temperature atmosphere until the sphericity of the composite particle material reaches 0.8 or more.
(A) The inorganic particle material in the inorganic particle material preparation step is made hydrophobic by surface treatment.
(B) The inorganic particle material in the inorganic particle material preparation step has a functional group represented by the formula (1): -OSiX 1 X 2 X 3 and a functional group represented by the formula (2): -OSiY 1 Y 2 Y 3 Both functional groups are bonded to the surface. (In the above formulas (1) and (2); X 1 is a phenyl group, vinyl group, epoxy group, methacrylic group, amino group , ureido group, mercapto group, isocyanate group, or acrylic group; are each independently selected from -OSiR 3 and -OSiY 4 Y 5 Y 6 ; Y 1 is R; Y 2 , Y 3 are each independently selected from R and -OSiY 4 Y 5 Y 6 .Y 4 is R; Y 5 and Y 6 are each independently selected from R and -OSiR 3 ; R is independently selected from an alkyl group having 1 to 3 carbon atoms; , X 3 , Y 2 , Y 3 , Y 5 , and Y 6 are adjacent functional groups X 2 , X 3 , Y 2 , Y 3 , Y 5 , and Y 6 and -O- )
請求項６～８のうちの何れか１項に記載の複合粒子材料の製造方法。 A manufacturing method for manufacturing the composite particle material according to any one of claims 1 to 3, comprising:
A method for producing a composite particle material according to any one of claims 6 to 8.
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