JP4714310B2 - Non-melt processable fluororesin - Google Patents
Non-melt processable fluororesin Download PDFInfo
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- JP4714310B2 JP4714310B2 JP2004285424A JP2004285424A JP4714310B2 JP 4714310 B2 JP4714310 B2 JP 4714310B2 JP 2004285424 A JP2004285424 A JP 2004285424A JP 2004285424 A JP2004285424 A JP 2004285424A JP 4714310 B2 JP4714310 B2 JP 4714310B2
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Description
本発明は、機械加工の過程で多量に発生する切削屑・端屑等の廃材の加熱済の非溶融加工性フッ素樹脂をリサイクル・混合して、未加熱(いわゆる、重合上がり)の非溶融加工性フッ素樹脂と同等・近似の機械的特性・熱的特性を成形品に与える混合系の非溶融加工性フッ素樹脂に関する。
本発明は、具体的には、機械加工の過程で多量に発生する切削屑・端屑等の廃材を工業的規模で再原料化することを可能にする混合系の非溶融加工性フッ素樹脂に関する。The present invention recycles and mixes heated non-melt-processable fluororesin such as cutting scraps and scraps generated in a large amount in the process of machining, and performs non-heated (so-called superposition) non-melt processing. The present invention relates to a mixed non-melt-processable fluororesin that gives a molded product the same mechanical properties and thermal properties that are equivalent to or similar to those of a functional fluororesin.
More specifically, the present invention relates to a mixed non-melt processable fluororesin that makes it possible to recycle raw materials such as cutting scraps and scraps generated in a large amount in the process of machining on an industrial scale. .
熱溶融流動性による成形が可能な熱可塑性樹脂(例えば、ポリエチレン樹脂、ポリプロピレン樹脂及びポリエチレンテレフタレート樹脂等の汎用性の熱可塑性樹脂)は、いずれもが、成形品をペレット化して融点以上の加熱によって熱溶融流動性を利用する成形(例えば、押出成形、射出成形等)が可能であるところから、成形品のリサイクル・再原料化が工業的にも行われていて、リサイクルに関連する多くの提案が行われている(例えば、特許文献1〜5を参照)。 Thermoplastic resins that can be molded by hot melt fluidity (for example, general-purpose thermoplastic resins such as polyethylene resin, polypropylene resin, and polyethylene terephthalate resin) are all formed by pelletizing a molded product and heating it above its melting point. Since molding using hot melt fluidity (for example, extrusion molding, injection molding, etc.) is possible, recycling and recycling of molded products are also carried out industrially, and many proposals related to recycling (For example, refer to Patent Documents 1 to 5).
一方、超高分子量(例えば、分子量1000万以上)で結晶化度が高く融点以上で熱溶融流動性を有しない高溶融粘度(例えば、108Pa・s以上)のポリテトラフルオロエチレン樹脂(以下において、PTFE樹脂ということがある)は、300℃以上の融点の熱的特性、汎用性熱可塑性樹脂にない高機械的特性、酸、アルカリ及び有機溶剤に殆ど侵されない高耐薬品性、0.45MPa負荷での熱変形温度120℃の高耐熱性、>1018の体積抵抗率(Ω・cm(50%RH,23℃))を有する高電気絶縁性及び低摩擦性等を備えるので、IT産業その他のハイテク産業に用いる機器類、化学工業及薬品工業で用いる装置類・機器類等に不可欠な材料になっている。On the other hand, a polytetrafluoroethylene resin (hereinafter referred to as “10 8 Pa · s or higher) having a high melt viscosity that has an ultra-high molecular weight (for example, a molecular weight of 10 million or more), a high crystallinity, a melting point or higher and no thermal melt fluidity” May be referred to as PTFE resin) having a melting point of 300 ° C. or higher, high mechanical properties not found in general-purpose thermoplastic resins, high chemical resistance hardly affected by acids, alkalis and organic solvents. It has high heat resistance at a heat distortion temperature of 120 ° C. under a load of 45 MPa, high electrical insulation having a volume resistivity (Ω · cm (50% RH, 23 ° C.)) of> 10 18 , low friction, etc. It is an indispensable material for equipment used in industry and other high-tech industries, and equipment and equipment used in the chemical and pharmaceutical industries.
PTFE樹脂による成形加工は、PTFE樹脂の粉末(いわゆる、モールディンパウダー)から予備的に加工用素材を形成して、それを切削加工等の機械加工により成形品にする方法で行われていて、工業的には、フリーシンター法、フリーベーキング法、ホットコイニング法、ホットモールディング法及びアイソスタティックモールディング法等の成形加工法が用いられる(詳細は後述する)。
ただし、PTFE樹脂の成形加工では、機械加工の過程で切削屑・端屑等の廃材PTFE樹脂が多量に発生し、しかも、その廃材PTFE樹脂の処理については、下記(i)〜(vi)等の問題点が存在していた。
(i)廃材PTFE樹脂を粉末化して成形用原料として再使用すると成形品の機械的物性が約30%程度に不可逆的に低下して品質の点から成形加工の原料にはなり得ず、しかも、加熱済PTFE樹脂を未加熱のPTFE樹脂の機械的物性若しくはそれに近似の物性に戻す方法が存在しないとの問題点が存在していた。
(ii)廃材PTFE樹脂は、上記(i)等の理由から、成形用原料に使用できないとの問題点が存在していた。
(iii)廃材PTFE樹脂は、殆どが廃棄処分に付されていて、重合上がりのPTFE樹脂の約30%以上が廃材として廃棄処分されているとの問題点が存在していた。
(iv)廃材PTFE樹脂は、焼却すると有害なフッ素ガスが発生するところから殆どが埋め立てにより廃棄処分せざるを得ないとの問題点が存在していた。
(v)廃材PTFE樹脂を粉砕して低分子量化する電子線照射処理により固体潤滑剤にするリサイクル法は、電子線照射処理のための費用により固体潤滑剤のコストが上昇し、しかも、廃材PTFE樹脂の発生量に比較して固体潤滑剤の使用量が著しく少ないので、大量に発生する廃材PTFE樹脂の処理を解決するリサイクル法になり得ないとの問題点が存在していた。
(vi)廃材PTFE樹脂を化学的に分解・還元してテトラフルオロエチレン単量体(すなわち、PTFE樹脂重合用の単量体)にする方法は、PTFE樹脂重合用の高耐食性材質の大規模装置の建設が必要になるので、大量に発生する廃材PTFE樹脂の処理を解決するリサイクル法になり得ないとの問題点が存在していた。
なお、フッ素樹脂には、共重合化等による分子量及び分子構造等の調整によって一般的な熱溶融流動性を利用する成形(射出成形、押出成形等)が可能にされて、リサイクル可能なものもある。しかし、それらの共重合化フッ素樹脂は、超高分子量のPTFE樹脂とは異なる用途に使用される。The molding process using PTFE resin is performed by a method in which a material for processing is preliminarily formed from a powder of PTFE resin (so-called molding powder), and is formed into a molded product by machining such as cutting, Industrially, molding methods such as a free sintering method, a free baking method, a hot coining method, a hot molding method and an isostatic molding method are used (details will be described later).
However, in the molding process of PTFE resin, a large amount of waste material PTFE resin such as cutting scraps and scraps is generated in the process of machining, and the processing of the waste material PTFE resin is as follows (i) to (vi), etc. There was a problem.
(I) When the waste PTFE resin is powdered and reused as a molding material, the mechanical properties of the molded product are irreversibly lowered to about 30% and cannot be used as a molding material in terms of quality. However, there has been a problem that there is no method for returning the heated PTFE resin to the mechanical properties of the unheated PTFE resin or properties similar thereto.
(Ii) The waste PTFE resin has a problem that it cannot be used as a raw material for molding because of the above (i).
(Iii) Most of the waste PTFE resin has been subjected to disposal, and about 30% or more of the polymerized PTFE resin has been discarded as waste.
(Iv) The waste PTFE resin has a problem that most of it must be disposed of by landfill because it generates harmful fluorine gas when incinerated.
(V) The recycling method for converting the waste PTFE resin into a solid lubricant by electron beam irradiation treatment for pulverizing and reducing the molecular weight increases the cost of the solid lubricant due to the cost for the electron beam irradiation treatment, and the waste material PTFE. Since the amount of solid lubricant used is remarkably small compared to the amount of resin generated, there has been a problem that it cannot be a recycling method that solves the processing of waste PTFE resin generated in large quantities.
(Vi) A method of chemically decomposing and reducing waste PTFE resin to form a tetrafluoroethylene monomer (that is, a monomer for polymerizing PTFE resin) is a large-scale apparatus of high corrosion resistance material for polymerizing PTFE resin. Therefore, there is a problem that it cannot be a recycling method that solves the treatment of waste PTFE resin generated in large quantities.
Some fluororesins are recyclable because they can be molded (injection molding, extrusion molding, etc.) using general hot melt fluidity by adjusting the molecular weight and molecular structure by copolymerization. is there. However, these copolymerized fluororesins are used for different applications from ultrahigh molecular weight PTFE resins.
従来にあっては、大量に発生する廃材PTFE樹脂をリサイクル・再原料化するという発想自体が存在せず、リサイクル・再原料化についての検討及び提案も殆ど行われていなかった。
かかる状況下において、加熱済(廃材PTFE樹脂等)及び未加熱の非溶融加工性フッ素樹脂(以下において、非溶融フッ素樹脂と略称することがある)の混合物に関する特性が、本発明者により数多くの実験を通じて詳細に検討されて、それらの特性に関する新たな自然科学上の事実が見出されて本発明が創案された。
(a)本発明は、加熱済の非溶融フッ素樹脂を含有して、未加熱の非溶融フッ素樹脂と同等・近似の特性(代表的には、種々の機械的特性及び熱的特性等の特性)を成形品に与える混合系の非溶融加工性フッ素樹脂を提供すること、を目的とする。
(b)本発明は、非溶融フッ素樹脂用のいずれの成形加工法によって加工し得る混合系の非溶融加工性フッ素樹脂を提供すること、をも目的とする。
(c)本発明は、加熱済の非溶融フッ素樹脂の工業的規模でのリサイクル・再原料化を可能にする混合系の非溶融加工性フッ素樹脂を提供すること、をも目的とする。
(d)加熱済の非溶融フッ素樹脂の工業的規模のリサイクル・再原料化に際して新たな設備投資を必要としない混合系の非溶融加工性フッ素樹脂を提供すること、をも目的とする。
(e)本発明は、成形加工による成形品の品質の制御を正解に行い得る混合系の非溶融加工性フッ素樹脂を提供すること、をも目的とする。In the past, there has been no idea of recycling / recycling waste PTFE resin generated in large quantities, and there has been almost no study or proposal for recycling / recycling.
Under such circumstances, the present inventor has many characteristics relating to a mixture of heated (waste material PTFE resin and the like) and unheated non-melt-processable fluororesin (hereinafter, sometimes abbreviated as non-molten fluoro-resin). The present invention was devised by examining in detail through experiments and finding new natural scientific facts concerning these properties.
(A) The present invention contains a heated non-molten fluororesin, and has the same or similar characteristics as the non-heated non-molten fluororesin (typically, characteristics such as various mechanical characteristics and thermal characteristics). It is an object of the present invention to provide a mixed non-melt processable fluororesin that gives a molded product to a molded product.
(B) Another object of the present invention is to provide a mixed non-melt processable fluororesin that can be processed by any molding method for non-melt fluoropolymers.
(C) Another object of the present invention is to provide a mixed non-melt processable fluororesin that enables recycling and recycling of a heated non-melt fluororesin on an industrial scale.
(D) It is another object of the present invention to provide a mixed non-melt-processable fluororesin that does not require new equipment investment for recycling and re-use of raw non-melt fluororesin on an industrial scale.
(E) Another object of the present invention is to provide a mixed non-melt processable fluororesin that can accurately control the quality of a molded product by molding.
非溶融加工性フッ素樹脂は、(1)未加熱の非溶融加工性フッ素樹脂の微細体よりも最大直線長さが大きい微細体の加熱済の非溶融加工性フッ素樹脂が未加熱の非溶融加工性フッ素樹脂に含まれる非溶融加工性フッ素樹脂であって、
(2)該非溶融加工性フッ素樹脂が、未加熱の非溶融フッ素樹脂の65%以上の引張り強度にされていること、を特徴とする。
Non-melt-processable fluororesin is (1) non-melt-processed non-heat-processed non-melt-processable fluororesin that has a maximum linear length larger than that of unheated non-melt-processable fluoro-resin. A non-melt processable fluororesin contained in a functional fluororesin ,
(2) said non-melt processible fluororesin, it is the non-melt fluororesin of 65% or more of tensile strength of the resin unheated, characterized.
本発明によれば、下記(a)〜(e)に代表される種々の効果が得られる。
(a)加熱済の非溶融フッ素樹脂(例えば、廃材等)の相当量を含む状態で、未加熱の非溶融フッ素樹脂と同等・近似の物理的特性(例えば、密度)及び機械的特性(伸び、圧縮強さ、衝撃強さ、硬さ、弾性率等)等を成形品に与えることができる。
(b)加熱済の非溶融フッ素樹脂(例えば、廃材等)の工業的規模によるリサイクル・再原料化が可能になる。
(c)工業的規模のリサイクル・再原料化を行うに際しての新たな設備投資を必要としない。
(d)非溶融フッ素樹脂用の成形加工法であれば、成形加工法において制約を受けない。
(e)原料樹脂の制御(例えば、混合系の引張り強度、微細体の最大直線長さ等の制御)により成形品の品質を制御することが可能になる。According to the present invention, various effects represented by the following (a) to (e) can be obtained.
(A) Physical properties (e.g., density) and mechanical properties (elongation) equivalent to or similar to unheated non-molten fluororesin in a state that includes a considerable amount of heated non-melted fluororesin (e.g., waste material) , Compression strength, impact strength, hardness, elastic modulus, etc.) can be imparted to the molded product.
(B) Recycling and re-use of raw non-molten fluororesin (for example, waste materials) on an industrial scale becomes possible.
(C) No new capital investment is required for recycling and recycling on an industrial scale.
(D) There is no restriction in the molding method as long as it is a molding method for non-molten fluororesin.
(E) The quality of the molded product can be controlled by controlling the raw material resin (for example, controlling the tensile strength of the mixed system, the maximum linear length of the fine body, etc.).
加熱済及び未加熱の非溶融フッ素樹脂の混合系に関して本発明で見出された自然科学上の新たな事実は、下記(イ)〜(ハ)等で、本発明の基礎にされている。
(イ)加熱済の非溶融フッ素樹脂と未加熱の非溶融フッ素樹脂の混合系は、条件によって、加成性及び非加成性の特性(特に、機械的特性、物理的特性)を示すという事実である(図6を参照)。
(ロ)その混合系が非加成性領域で示す特性を、未加熱の非溶融フッ素樹脂の特性(機械的特性、物理的特性、熱的特性等)と同等・近似にすることが可能であるという事実である(図6を参照)。
(ハ)その混合系が示す未加熱の非溶融フッ素樹脂と同等・近似の特性は、加熱済及び未加熱の非溶融フッ素樹脂の微細体の形状の相対的関係により生ずる場合があるという事実である。
The new facts found in the present invention regarding the mixed system of heated and unheated non-molten fluororesin are based on the present invention in the following (a) to (c).
(A) A mixed system of a heated non-molten fluororesin and an unheated non-molten fluororesin exhibits additive properties and non-additive properties (particularly mechanical properties and physical properties) depending on conditions. It is true (see Figure 6).
(B) The characteristics of the mixed system in the non-additive region can be equivalent or approximate to the characteristics of unheated non-molten fluororesin (mechanical characteristics, physical characteristics, thermal characteristics, etc.) That is the fact (see Figure 6).
(C) The fact that the mixed system exhibits the same or approximate characteristics as the unheated non-molten fluororesin due to the fact that it may be caused by the relative relationship between the shapes of the heated and unheated non-molten fluororesin. is there.
〈本発明の概要〉:
本発明の混合系は、加熱済の非溶融フッ素樹脂の微細体が、未加熱の非溶融フッ素樹脂の微細体よりも最大直線長さを大きい形状にされて、しかも、混合系を未加熱の非溶融フッ素樹脂の65%以上の引張り強度にして、それによって、混合系に非加成性の特性を生じさせて、機械的特性(引張り強度を除く)、物理的特性及び熱的特性等を未加熱の非溶融フッ素樹脂と同等・近似にする等の様々な本発明の効果を享受可能にされている(後記実施例2の実験結果を参照)。
加熱済の非溶融フッ素樹脂の微細体の変形化及び含有量は、混合系を未加熱の非溶融フッ素樹脂の65%以上の引張り強度を与えることを基準にすると、それらの設定が容易である。
また、混合系が未加熱の非溶融フッ素樹脂の65%以上の引張り強度であると、混合系が非加成性領域の特性を示す傾向が明らかになる。混合系はその引張り強度を未加熱の非溶融フッ素樹脂の約98%程度にも設定することが可能である。
本発明の混合系は、非溶融フッ素樹脂の複合材に配合される充填剤(例えば、カーボン、グラファイト、二硫化モリブデン、ブロンズ粉若しくはガラス繊維等)を含むことが可能で、この場合には、加熱済の非溶融フッ素樹脂と、未加熱の非溶融フッ素樹脂及び充填剤との混合系と混合することにより、本発明の効果を増大させることが可能である。充填剤は、非溶融フッ素樹脂での成形加工での充填剤混合許容量が配合されても本発明の効果が維持される。
<Outline of the present invention>
Mixed system of the present invention, the fine of unmelted fluoroplastic heating already have, is the maximum linear length than the fine material unmelted fluoroplastic unheated large shape, moreover, the mixed system of unheated The tensile strength of 65% or more of the non-molten fluororesin is set, thereby creating non-additive properties in the mixed system, mechanical properties (excluding tensile strength), physical properties, thermal properties, etc. It is possible to enjoy various effects of the present invention, such as making it equivalent or approximate to an unheated non-molten fluororesin (see the experimental results of Example 2 below).
Deformation and content of the heated non-molten fluororesin fine body are easy to set when the mixed system is given a tensile strength of 65% or more of the unheated non-molten fluororesin. .
Further, when the mixed system has a tensile strength of 65% or more of the unheated non-molten fluororesin, the tendency of the mixed system to exhibit the characteristics of the non-additive region becomes clear. The mixed system can set its tensile strength to about 98% of the unheated non-molten fluororesin.
The mixed system of the present invention can include a filler (for example, carbon, graphite, molybdenum disulfide, bronze powder, glass fiber, etc.) blended in the composite material of non-melting fluororesin. The effect of the present invention can be increased by mixing with a mixed system of a heated non-molten fluororesin and an unheated non-molten fluororesin and a filler. The effect of the present invention is maintained even if the filler is blended with a filler mixing allowance in the molding process with a non-molten fluororesin.
〈非溶融フッ素樹脂〉:
本発明の「非溶融フッ素樹脂」は、融点以上に加熱されても、溶融流動性を示さず、溶融流動性によらない成形加工法に使用されるフッ素樹脂で、代表的には、PTFE樹脂ではあるが、それ以外でも、溶融流動性によらない成形加工法によるフッ素樹脂は、本発明の対象とすることが可能である。代表的には、例えば、PTFE樹脂及びCnF2n+1C=CF2(n=1〜12)、CnF2n+1O〔CF(CF3)CF2O〕mCF=CF2(n=1〜5、m=0〜10)、ClCF=CF2等の共単量体とのPTFE共重合樹脂が挙げられる。共単量体は、一般的には、少量(例えば、2%未満)であっても、成形性及び成形品の耐クリープ性を向上させて、透明性を向上させて、しかも、本発明の効果が享受される。
本発明の「未加熱の非溶融フッ素樹脂」としては、例えば、市販の重合上がり(いわゆる、バージン)の成形用の非溶融フッ素樹脂粉末を用いることが可能である。本発明の「混合系の65%以上の引張り強度」の基準となる未加熱の非溶融フッ素樹脂の引張り強度は、一般的には、本発明の実施例1の実験例2と同条件で測定する測定値及び同様の測定条件で測定される測定値が基準になる。<Non-molten fluororesin>:
The “non-molten fluororesin” of the present invention is a fluororesin that does not exhibit melt fluidity even when heated to a melting point or higher and is used in a molding process that does not depend on melt fluidity, and is typically PTFE resin. However, other than that, a fluororesin formed by a molding method that does not depend on melt fluidity can be the subject of the present invention. Typically, for example, PTFE resin and CnF 2n + 1 C═CF 2 (n = 1 to 12), C n F 2n + 1 O [CF (CF 3 ) CF 2 O] mCF═CF 2 (n = 1 to 5, m = 0 to 10) and PTFE copolymer resin with a comonomer such as ClCF═CF 2 . The comonomer generally improves the moldability and the creep resistance of the molded product to improve the transparency even in a small amount (for example, less than 2%), and further, The effect is enjoyed.
As the “unheated non-molten fluororesin” of the present invention, it is possible to use, for example, a commercially available non-molten fluororesin powder for molding after molding (so-called virgin). In general, the tensile strength of an unheated non-molten fluororesin serving as a reference for “tensile strength of 65% or more of the mixed system” of the present invention is measured under the same conditions as in Experimental Example 2 of Example 1 of the present invention. The measurement value to be measured and the measurement value measured under the same measurement conditions are used as a reference.
本発明の「加熱済の非溶融フッ素樹脂」は、成形加工法において、融点付近若しくは融点以上(融点以上が一般的)に加熱される工程を含む成形品加工法から排出される切削屑・端屑の廃材等のフッ素樹脂である。
なお、成形加工法によっては、機械加工用素材の形成工程での加熱を「焼成」と称される場合もあるが、本発明の「加熱済」には、「焼成済」も含まれる。
本発明では、加熱済の非溶融フッ素樹脂の微細体が、変形化処理されて未加熱の非溶融フッ素樹脂の微細体よりも最大直線長さ(特に、最大直線長さ及びアスペクト比)が大きい形状に変形化されている。なお、最大直線長さが大きい形状の微細体の加熱済の非溶融フッ素樹脂が混合されて、混合系が未加熱の非溶融フッ素樹脂と同等・近似の特性(機械的特性、物理的特性等)を維持することは、本発明で見出された事実である。
なお、最大直線長さが大きい形状の微細体の加熱済の非溶融フッ素樹脂が部分的に含まれる場合であっても、本発明の効果が享受可能になることがある。
なお、以下において、「未加熱の非溶融フッ素樹脂」の理解を容易にするために便宜上「重合上がりの非溶融フッ素樹脂」ということがある。但し、現存の重合法での重合上がりの非溶融フッ素樹脂に限定するものではない。
The “heated non-molten fluororesin” of the present invention is a cutting waste / end discharged from a molded product processing method including a step of heating near or above the melting point (generally higher than the melting point) in the molding method. Fluorine resin such as scrap waste.
Depending on the molding method, the heating in the forming process of the machining material may be referred to as “firing”, but “heated” in the present invention includes “firing”.
In the present invention, the heated non-molten fluororesin fine body has a maximum linear length (particularly, the maximum linear length and aspect ratio) larger than that of the non-heated non-molten fluororesin fine body that has been deformed. It has been transformed into a shape. Incidentally, are mixed maximum linear length is greater and shape unmelted fluoroplastic heating the already fine body, mixed system is non-melt fluororesin equivalent-approximation of characteristics of unheated (mechanical properties, physical properties, etc. ) Is a fact found in the present invention.
In addition, even if it is a case where the heated non-molten fluororesin of the fine body of a shape with a large maximum linear length is partially contained, the effect of this invention may be enjoyed.
Hereinafter, in order to facilitate understanding of “unheated non-molten fluororesin” , it may be referred to as “polymerized non-molten fluororesin” for convenience. However, the present invention is not limited to the non-molten fluororesin after polymerization by the existing polymerization method.
〈加熱済の非溶融フッ素樹脂の変形化〉:
加熱済の非溶融フッ素樹脂(例えば、フッ素樹脂廃材等)は、粉砕等により微細化されて、変形化処理により重合上がりの非溶融フッ素樹脂の微細体よりも最大直線長さが大きい形状にされる。ただし、フッ素樹脂廃材の粉砕化の過程で、未加熱の非溶融フッ素樹脂の微細体よりも最大直線長さが大きい形状になる場合には、変形化処理の工程が不要である。
重合上がりの成形用非溶融フッ素樹脂の粉末が、例えば、平均粒子径がおおよそ20〜100ミクロンメータで、最大粒子径がおおよそ110〜200ミクロンメータ程度ある場合には、フッ素樹脂廃材を機械的粉砕等により平均粒子径が約20〜100ミクロンメータ(好ましくは、20〜70ミクロンメータ)、最大粒子径が約110〜380ミクロンメータの粒子状に粉砕する。
ただし、非溶融フッ素樹脂は、ガラス移転温度が低いので(PTFE樹脂のガラス移転温度は−100℃)、冷凍粉砕すると所望の微細粒子に粉砕容易である。
なお、平均粒子径が約20ミクロンメータ未満では、粉砕の収率が低下して工業的実施が困難になり、平均粒子径が100ミクロンメータを超えると変形化の制御に困難を伴うようになる。また、粉砕時の粒度分布は、できるだけシャープな形状であるのが本発明の効果を享受するのに適している。
次に、粉砕したフッ素樹脂廃材の粒子状物をせん断力により変形化して重合上がり非溶融フッ素樹脂の粒子状物よりも最大直線長さが大きい形状にする。フッ素樹脂廃材の粒子状物の変形化は、少なくとも、最大直線長さが重合上がり非溶融フッ素樹脂の粒子状物よりも大きい形状であることが必要であって、例えば、最大直線長さが、非溶融フッ素樹脂の粒子状物よりも、1.2〜10.0倍であれば、本発明の効果の享受に適している。
また、フッ素樹脂廃材の粒子状物の変形化は、アスペクト比(変形化したフッ素樹脂廃材の粒子状物)/アスペクト比(重合上がり非溶融フッ素樹脂の粒子状物)の比率は、約1.7倍〜4.2倍の場合に本発明の効果が最大に享受されて(後記の実施例2を参照)、おおよそ1.1倍〜12倍程度で本発明の効果を享受することができる。
加熱済の非溶融フッ素樹脂の最大直線長さ及びアスペクト比の組み合わせを、混合系について本発明の効果を最大に享受可能に設定することが可能である。
なお、アスペクト比は、フッ素樹脂を含むプラスチック業界でも通用性が高い技術用語であって、プラスチック粒子の長い部分/短い部分の長さの比であって、必ずしも、縦・横の長さの比率ではない。
なお、重合上がりの非溶融フッ素樹脂が、工業的に異なる粒子径を使用する場合には、加熱済の非溶融フッ素樹脂もそれの平均粒子径及び最大粒子径に対応する粒子径に粉砕して、その粉砕物を重合上がり非溶融フッ素樹脂の粒子径の略同様の粒子に粉砕してせん断力により変形化するのが適している。
<Deformation of heated non-molten fluororesin>:
Heated non-molten fluororesin (for example, fluororesin waste material) is refined by pulverization and the like, and the maximum linear length is made larger by the deformation process than the non-molten fluororesin fine body after polymerization. The However, in the process of pulverizing the fluororesin waste material, when the maximum linear length is larger than that of the unheated non-molten fluororesin fine body, the step of deformation treatment is unnecessary.
When the non-molten fluororesin powder for molding after polymerization is, for example, an average particle size of about 20 to 100 microns and a maximum particle size of about 110 to 200 microns, mechanically grinding the fluororesin waste For example, the particles are pulverized into particles having an average particle diameter of about 20 to 100 micrometers (preferably 20 to 70 micrometers) and a maximum particle diameter of about 110 to 380 micrometers.
However, since the non-molten fluororesin has a low glass transition temperature (the glass transition temperature of PTFE resin is −100 ° C.), it can be easily pulverized into desired fine particles when freeze-pulverized.
If the average particle size is less than about 20 micrometer , the pulverization yield decreases and it becomes difficult to implement industrially. If the average particle size exceeds 100 micrometer, it becomes difficult to control deformation. . Moreover, it is suitable for enjoying the effects of the present invention that the particle size distribution during pulverization is as sharp as possible.
Next, the pulverized particles of the fluororesin waste material are deformed by a shearing force to be polymerized to a shape having a maximum linear length larger than that of the non-molten fluororesin particles. For the deformation of the fluororesin waste material, it is necessary that at least the maximum linear length be polymerized and larger than the non-molten fluororesin particulate, for example, the maximum linear length is If it is 1.2-10.0 times the particulate matter of a non-melting fluororesin, it is suitable for enjoying the effects of the present invention.
In addition, the deformation of the fluororesin waste material particulate matter has a ratio of aspect ratio (deformed fluororesin waste material particulate material) / aspect ratio (polymerized non-molten fluororesin particulate material) of about 1. In the case of 7 times to 4.2 times, the effect of the present invention is enjoyed to the maximum (see Example 2 described later), and the effect of the present invention can be enjoyed approximately 1.1 times to 12 times. .
The combination of the maximum linear length and aspect ratio of the heated non-molten fluororesin can be set so that the effects of the present invention can be enjoyed to the maximum with respect to the mixed system.
The aspect ratio is a technical term that is highly applicable in the plastics industry including fluororesins, and is the ratio of the length of the long part / short part of the plastic particles, and is not necessarily the ratio of the length to the length. is not.
In addition, when the non-molten fluororesin after polymerization uses an industrially different particle size, the heated non-molten fluororesin is also pulverized to a particle size corresponding to the average particle size and the maximum particle size. It is suitable that the pulverized product is polymerized and pulverized into particles having substantially the same particle diameter as the non-molten fluororesin and deformed by shearing force.
変形化に際してのせん断力負荷手段は、加熱済の非溶融フッ素樹脂の微細体を最大直線長さが重合上がり非溶融フッ素樹脂の微細体よりも大きい形状への変形が可能であれば、装置及び条件において任意である。
例えば、混練押出機によりスクリュー混練部で機械的せん断力が負荷される条件で混練して、粒子を引き伸ばして変形化すると、粒子の立体性が減少する変形により最大直線長さが大きい形状になる。
The shearing force loading means upon deformation is such that the heated non-molten fluororesin fine body can be transformed into a larger shape than the non-molten fluororesin fine body after the maximum linear length is polymerized. It is optional in the conditions.
For example, when kneading and extruding in a screw kneading section with a kneading extruder, the particles are stretched and deformed, and the maximum linear length is increased due to deformation that reduces the three-dimensionality of the particles. .
図1〜図5は、各種形状とその最大直線長さLの関係を示す説明図である。図1は、球体でその最大直線長さLは直径である。しかし、図1の球体をせん断力の負荷により変形化して図5の形状にすると、最大直線長さLは相当に大きくなる。本発明では、加熱済の非溶融フッ素樹脂の微細体が、その最大直線長さLにおいて、重合上がり非溶融フッ素樹脂粒子よりも大きい場合に本発明の効果をもたらす非加成性が生じることが見出されている。なお、本発明の「微細体の最大直線長さ」は、微細体外形の一端から他端を結ぶ直線長さが最大になる直線長さである。 1-5 is explanatory drawing which shows the relationship between various shapes and its maximum linear length L. FIG. FIG. 1 shows a sphere and its maximum straight line length L is a diameter. However, when the sphere shown in FIG. 1 is deformed by applying a shearing force to the shape shown in FIG. 5, the maximum linear length L is considerably increased. In the present invention, when the heated non-molten fluororesin fine body is larger than the non-molten fluororesin particles after polymerization in the maximum linear length L, non-additivity that brings about the effect of the present invention may occur. Has been found. The “maximum linear length of the fine body” of the present invention is a linear length that maximizes the linear length connecting one end to the other end of the external shape of the fine body.
本発明の効果をもたらす非加成性については、本発明者によって理論的根拠を予測する幾つかの案が提案されている。その一つは、本発明者による走査型電子顕微鏡による観察では、重合上がり非溶融フッ素樹脂粒子がせん断力を受けると粒子表面が繊維上に毛羽たちし易くなって(すなわち、フイブリル化しやくなって)、常温での強い圧縮でも粒子同士の密着状態により成形品の機械的特性向上に寄与することが確認できるところから、粒子同士の密着状態と他の要素との複合化を発展させた推論である。 Regarding the non-additivity that brings about the effect of the present invention, several proposals have been proposed by the present inventor to predict the theoretical basis. For example, in the observation by a scanning electron microscope by the present inventor, when the non-molten fluororesin particles after polymerization are subjected to shearing force, the particle surface tends to fluff on the fibers (that is, fibrillation is likely to occur). ) From the fact that it can be confirmed that even the strong compression at normal temperature contributes to the improvement of the mechanical properties of the molded product due to the adhesion state between the particles, the inference developed by combining the adhesion state between the particles and other elements is there.
図6は、本発明の混合系と本発明の効果をもたらす非加成性との関係を示す線図である。
図6において、横線の未加熱は未加熱の非溶融フッ素樹脂の量を表していて、横線の加熱は加熱済の非溶融フッ素樹脂の量を表している。図面右端が未加熱の非溶融フッ素樹脂が100%の場合を示して、図面左端が加熱済の非溶融フッ素樹脂が100%の場合を示している。そして、通常の両者の間に相互作用が働かない場合には、加成性領域で引っ張り強度が変化する。しかし、本発明で見出されて非加成性領域で引っ張り強度を変化させると、加熱済の非溶融フッ素樹脂が含まれていても、引っ張り強度が未加熱の非溶融フッ素樹脂と同等・近似になり(後記実施例2の実験結果を参照)、引っ張り強度以外の機械的特性及び熱的特性も未加熱の非溶融フッ素樹脂の特性と同等・近似になる。FIG. 6 is a diagram showing the relationship between the mixed system of the present invention and the non-additivity that brings about the effects of the present invention.
In FIG. 6, the unheated horizontal line represents the amount of unheated non-molten fluororesin, and the horizontal line represents the amount of heated non-molten fluororesin. The right end of the drawing shows the case where the unheated non-molten fluororesin is 100%, and the left end of the drawing shows the case where the heated non-molten fluororesin is 100%. And when an interaction does not work between normal both, tensile strength changes in an additive region. However, when the tensile strength is changed in the non-additive region as found in the present invention, even if heated non-molten fluororesin is contained, the tensile strength is equivalent to or approximate to that of unheated non-molten fluororesin (See the experimental results of Example 2 below), and mechanical and thermal characteristics other than tensile strength are equivalent to or approximate to those of the unheated non-molten fluororesin.
〈混合系の調整〉:
混合系は、重合上がりの非溶融フッ素樹脂の65%以上の引張り強度なるように加熱済の非溶融フッ素樹脂の微細体の混合量とその最大直線長さが調整される。
また、混合系は、加熱済の非溶融フッ素樹脂の微細体の混合量とその最大直線長さとアスペクト比とを重合上がりの非溶融フッ素樹脂の65%以上の引張り強度になるように調整してもよく、重合上がりの非溶融フッ素樹脂の引張り強度と、加熱済の非溶融フッ素樹脂の微細体の最大直線長さとを本発明の混合系の条件に合致させてもよい。加熱済の非溶融フッ素樹脂の微細体のアスペクト比についても同様である。
フッ素樹脂微細体の混合は、混合装置において任意であるが、ヘンシェルミキサーによる混合が混合効率の点から好適であり、常温において1000〜2500rpmの回転速度で短時間、例えば、1〜8分間、好ましくは、1〜3分間の混合で成形加工に供される。混合装置の攪拌羽根は汎用型の使用が可能である。
混合系は、加熱済の非溶融フッ素樹脂として、最大直線長さを大きくする変形化処理を施していない微細体とが部分的に含まれていてもよく、その場合であっても、本発明の条件を充足する限りにおいては、本発明の効果の享受が可能になるからである。
混合系は、量的には、例えば、未加熱の成形用溶融フッ素樹脂90〜50重量部(好ましくは、79.5〜58重量部)、加熱済の非溶融フッ素樹脂10〜40重量部(好ましくは、20〜40重量部)、未加熱の微粉状の非溶融フッ素樹脂0〜4重量部(好ましくは、0.5〜2重量部)である。ただし、これ以外の量的比率であることが可能である。
<Adjustment of mixed system>:
In the mixing system, the mixing amount of the fine body of the heated non-molten fluororesin and the maximum linear length thereof are adjusted so that the tensile strength is 65% or more of the non-molten fluororesin after polymerization.
In addition, the mixing system is adjusted so that the amount of fine particles of the heated non-molten fluororesin, the maximum linear length, and the aspect ratio are 65% or more of the tensile strength of the non-molten fluororesin after polymerization. Alternatively, the tensile strength of the unmelted fluororesin after polymerization and the maximum linear length of the heated non-molten fluororesin fine body may be matched with the conditions of the mixed system of the present invention. The same applies to the aspect ratio of the heated non-molten fluororesin fine body.
The mixing of the fluororesin fine bodies is optional in the mixing apparatus, but mixing by a Henschel mixer is preferable from the viewpoint of mixing efficiency, and it is a short time at a rotation speed of 1000 to 2500 rpm at room temperature, for example, 1 to 8 minutes, preferably Is subjected to molding by mixing for 1 to 3 minutes. A general-purpose type can be used for the stirring blade of the mixing apparatus.
The mixed system may partially contain a fine body that has not been subjected to a deformation treatment that increases the maximum linear length as a heated non-molten fluororesin. This is because the effect of the present invention can be enjoyed as long as the above condition is satisfied.
The mixed system is quantitatively, for example, 90 to 50 parts by weight (preferably 79.5 to 58 parts by weight) of an unheated molten fluororesin for molding, or 10 to 40 parts by weight of a heated non-molten fluororesin ( Preferably, it is 20 to 40 parts by weight), and 0 to 4 parts by weight (preferably 0.5 to 2 parts by weight) of unheated fine powdered non-molten fluororesin. However, other quantitative ratios are possible.
〈混合系による成形加工〉:
混合系は、非溶融フッ素樹脂用のいずれの成形加工法によってもよく、例えば、フリーシンター法、フリーベーキング法、ホットコイニング法、ホットモールディング法及びアイソスタティックモールディング法等が用いられる。
フリーシンター法は、成形用の非溶融フッ素樹脂粉末を常温の金型に均一に充填し、成形圧が例えば20〜50MPa等により圧縮成形(予備成形とも称される)して予備成形品を形成し、予備成形品を熱風循環炉等で樹脂の融点以上で一定時間(例えば、4〜10時間)焼成し、冷却によって加工用素材(切削用素材であるビレット)を形成して、それを機械加工して所望形状の成形品に仕上げる成形加工法である。
ホットコイニング法は、成形用の非溶融フッ素樹脂粉末を常温の金型に充填して熱風循環炉若しくはバンドヒータ等で金型を樹脂の融点以上に加熱し、例えば10〜20MPa等の成形圧により圧縮後、圧縮状態を維持して冷却して加工用素材を形成し、フリーシンター法と同様にそれを機械加工して所望形状の成形品に仕上げる成形加工法である。
なお、混合系による成形加工は、加熱時の昇温速度及び冷却速度の制御により混合系の非溶融フッ素樹脂の結晶化を向上させることが可能である。
なお、本発明においては、本発明の目的に沿うものであって、本発明の効果を特に害さない限りにおいては、改変あるいは部分的な変更及び付加は任意であって、いずれも本発明の範囲である。
次に、本発明を実施例に基づいて具体的に説明するが、実施例は例示であって本発明を拘束するものではない。<Molding with mixed system>:
The mixing system may be any molding method for non-molten fluororesin, for example, a free sintering method, a free baking method, a hot coining method, a hot molding method, an isostatic molding method, or the like.
In the free sinter method, a non-molten fluororesin powder for molding is uniformly filled in a normal temperature mold, and compression molding (also referred to as preforming) is performed at a molding pressure of 20 to 50 MPa, for example, to form a preformed product. Then, the preform is fired at a temperature higher than the melting point of the resin for a certain time (for example, 4 to 10 hours) in a hot air circulating furnace or the like, and a processing material (a billet that is a cutting material) is formed by cooling. This is a molding method that processes to finish a molded product of a desired shape.
In the hot coining method, a non-molten fluororesin powder for molding is filled in a normal temperature mold, and the mold is heated to a temperature higher than the melting point of the resin by a hot air circulating furnace or a band heater, for example, by a molding pressure of 10 to 20 MPa or the like. This is a molding method in which after compression, the compressed material is maintained and cooled to form a processing material, and in the same way as the free sintering method, it is machined to finish a molded product of a desired shape.
In the molding process using the mixed system, it is possible to improve the crystallization of the non-molten fluororesin of the mixed system by controlling the heating rate and the cooling rate during heating.
In the present invention, it is in accordance with the object of the present invention, and any modification or partial change and addition is optional as long as the effects of the present invention are not particularly impaired. It is.
EXAMPLES Next, although this invention is demonstrated concretely based on an Example, an Example is an illustration and does not restrain this invention.
〔実験例1〕
〈未加熱の成形用PTFE樹脂の特性〉:
市販の重合上がりの成形用PTFE樹脂粉末(商品名:テフロン7J、三井デュポンフロロケミカル(株)製)を示差走査熱量計により昇温速度10℃/分で窒素雰囲気下により測定すると、結晶融解熱が65J/g、融解ピーク温度(結晶融点)が345℃であった。
別の製造メーカの成形用PTFE樹脂粉末(商品名:ポリフロンM−12、ダイキン工業(株)製)を同様の装置・条件で測定すると、結晶融解熱が65J/g、融解ピーク温度(結晶融点)が339℃であった。
〈加熱済のPTFE粉砕粒子の調製〉:
それら製造メーカが異なるそれぞれの成形用のPTFE樹脂粉末を直径100mmで長さが100mmのロッド金型に充填し、常温において成形圧力30MPaで予備成形し、360℃で10時間焼成して機械加工用素材を形成した。この機械加工用素材を機械加工して、その際にでた加工クズを採取して冷凍粉砕して、メーカ毎の加熱済PTFE粉砕粒子を調製した。
これらの加熱済PTFE粉砕粒子は、レーザ回析/散乱式粒度分布測定装置(堀場製作所LA−910)による粒度測定によると、最大粒子径が、160ミクロンメータ(商品名:テフロン7J)、130ミクロンメータ(商品名:ポリフロンM−12)で、平均粒子径が、70ミクロンメータ(商品名:テフロン7J)、40ミクロンメータ(商品名:ポリフロンM−12)であった。
これらの加熱済のPTFE粉砕粒子は、示差走査熱量計により同条件で測定すると、結晶融解熱20〜30J/g、融解ピーク温度(結晶融点)が325〜335℃の範囲で、光学顕微鏡により200倍の倍率で観察すると、形状はほぼ等方性で、アスペクト比が平均1.2であった。
〈加熱済PTFE粉砕粒子の変形化処理〉:
加熱済のPTFE粉砕粒子をストランドダイを取り外した2軸混練押出機((株)池貝製)により溶融させずにバレル出口より直接に粒子をだして変形化した。
この変形化処理した粒子は、細長く引き伸ばされた形状で、アスペクト比が2〜5の範囲にあった。未加熱の成形用PTFE樹脂粉末は、変形化処理前の加熱済PTFE粉砕粒子と同程度のアスペクト比(すなわち、平均1.2)であった。そのために、変形化処理した粒子は、未加熱の成形用PTFE樹脂粉末の約1.7倍〜4.2倍であった。
変形化処理粒子の最大直線長さは、未加熱の成形用PTFE樹脂粉末よりも相当に大きかった。[Experimental Example 1]
<Characteristics of PTFE resin for unheated molding>
When a commercially available PTFE resin powder for molding after polymerization (trade name: Teflon 7J, manufactured by Mitsui DuPont Fluoro Chemical Co., Ltd.) was measured with a differential scanning calorimeter at a heating rate of 10 ° C./min in a nitrogen atmosphere, the heat of crystal melting Was 65 J / g and the melting peak temperature (crystal melting point) was 345 ° C.
When PTFE resin powder for molding (trade name: Polyflon M-12, manufactured by Daikin Industries, Ltd.) from another manufacturer was measured with the same apparatus and conditions, the heat of crystal fusion was 65 J / g, the melting peak temperature (crystal melting point) ) Was 339 ° C.
<Preparation of heated PTFE pulverized particles>:
Each of these different manufacturers of PTFE resin powder for molding is filled in a rod mold having a diameter of 100 mm and a length of 100 mm, preformed at room temperature at a molding pressure of 30 MPa, and fired at 360 ° C. for 10 hours for machining. Formed material. The machined material was machined, and the processing waste generated at that time was collected and frozen and pulverized to prepare heated PTFE pulverized particles for each manufacturer.
These heated PTFE pulverized particles have a maximum particle size of 160 μm (trade name: Teflon 7J), 130 μm according to particle size measurement by a laser diffraction / scattering particle size distribution measuring device (Horiba LA-910). The average particle size was 70 micrometer (trade name: Teflon 7J) and 40 micrometer (trade name: Polyflon M-12) with a meter (trade name: Polyflon M-12).
When these heated PTFE pulverized particles were measured under the same conditions with a differential scanning calorimeter, the crystal melting heat was 20 to 30 J / g, the melting peak temperature (crystal melting point) was in the range of 325 to 335 ° C., and 200 with an optical microscope. When observed at double magnification, the shape was nearly isotropic and the average aspect ratio was 1.2.
<Deformation treatment of heated PTFE pulverized particles>:
The heated PTFE pulverized particles were deformed by taking out the particles directly from the barrel outlet without melting them with a twin-screw kneading extruder (manufactured by Ikekai Co., Ltd.) with the strand die removed.
The deformed particles were elongated and had an aspect ratio in the range of 2-5. The unheated PTFE resin powder for molding had an aspect ratio (that is, an average of 1.2) comparable to that of the heated PTFE pulverized particles before the deformation treatment. Therefore, the deformed particles were about 1.7 to 4.2 times the unheated PTFE resin powder for molding.
The maximum linear length of the deformed particles was considerably larger than that of unheated PTFE resin powder for molding.
〔実験例2〕
〈混合系からの試験片の調製及び試験〉:
実験例1の成形用PTFE樹脂粉末(商品名:テフロン7J)を65%、変形化処理粒子(平均粒子径が40ミクロンメータ)35%の量的比率(全体重量を基準)にして、ヘンシェルミキサー(三井鉱山(株)製)により2000rpmで2分間混合して、次に、65mm×130mm平板金型に均一に充填し、常温において成形圧力30MPで圧縮し、厚さ3mmの板状予備成形品を形成し、それを熱風循環炉において焼成温度360℃で5時間焼成して板状成形品を形成した。この加熱済の板状成形品からASTM−D1457に準拠して、マイクロダンベル(全長:40mm、平行部寸法:20mm×4.5mm)を製作し、引張り試験(試験速度200mm/分)を行った。[Experimental example 2]
<Preparation and test of test piece from mixed system>:
Henschel mixer with 65% quantitative PTFE resin powder for molding (trade name: Teflon 7J) and 35% deformed particles (average particle size: 40 micrometer) of Experimental Example 1 (based on the total weight) (Mitsui Mine Co., Ltd.) mixed at 2000 rpm for 2 minutes, then uniformly packed into a 65 mm × 130 mm flat plate mold, compressed at a molding pressure of 30 MP at room temperature, and a 3 mm thick plate preform Was formed in a hot air circulating furnace at a baking temperature of 360 ° C. for 5 hours to form a plate-shaped molded article. In accordance with ASTM-D1457, a micro dumbbell (full length: 40 mm, parallel part size: 20 mm × 4.5 mm) was produced from this heated plate-shaped molded article, and a tensile test (test speed: 200 mm / min) was performed. .
〔実験例3〕
〈混合系からの試験片の調製及び試験〉:
実験例1の平均粒子径が70ミクロンメータ(商品名:テフロン7J)である加熱済のPTFE粉砕粒子を実験例1の変形化処理と同様の処理を行って、
それを実験例2の変形化処理粒子(平均粒子径が40ミクロンメータ)35%に代えて実験例2と量的比率を同様にし、実験例2と同条件で試験片を調製して、実験例2と同条件で引張り試験を行った。
[Experimental Example 3]
<Preparation and test of test piece from mixed system>:
Heated PTFE pulverized particles having an average particle diameter of 70 μm (trade name: Teflon 7J) in Experimental Example 1 are subjected to the same treatment as the deformation process in Experimental Example 1,
In place of 35% of the deformed particles (average particle diameter of 40 micrometer) in Experimental Example 2, the same quantitative ratio as in Experimental Example 2 was prepared, and a test piece was prepared under the same conditions as in Experimental Example 2. A tensile test was performed under the same conditions as in Example 2.
〔実験例4〕
〈混合系からの試験片の調製及び試験〉:
成形用のPTFE樹脂粉末(商品名:テフロン7J)59%と、加熱済のPTFE粉砕粒子の変形化処理粒子(平均粒子径が50ミクロンメータ)40%と、PTFE樹脂超微粉末(商品名:K−10J、三井デュポンフロロケミカル(株)製)1%との混合系から実験例2と同方法により試験片を調製して、実験例2と同条件で引張り試験を行った。[Experimental Example 4]
<Preparation and test of test piece from mixed system>:
PTFE resin powder for molding (trade name: Teflon 7J) 59%, deformed particles of PTFE ground particles that have been heated (average particle diameter is 50 microns), 40%, and PTFE resin ultrafine powder (trade name: A test piece was prepared in the same manner as in Experimental Example 2 from a mixed system of 1% with K-10J (Mitsui DuPont Fluorochemical Co., Ltd.), and a tensile test was performed under the same conditions as in Experimental Example 2.
〔実験例5〕
〈混合系からの試験片の調製及び試験〉:
重合上がりの成形用PTFE樹脂粉末(商品名:ホリフロンM−12)60%と、加熱済のPTFE粉砕粒子の変形化処理粒子(平均粒子径が30ミクロンメータ)40%との混合系から実験例2と同方法により試験片を調製して、実験例2と同条件で引張り試験を行った。[Experimental Example 5]
<Preparation and test of test piece from mixed system>:
Experimental example from a mixed system of 60% polymerized PTFE resin powder (trade name: Polyflon M-12) after polymerization and 40% deformed treated particles (average particle size of 30 microns) of heated PTFE pulverized particles A test piece was prepared by the same method as 2 and a tensile test was performed under the same conditions as in Experimental Example 2.
〔比較例1〕
重合上がりの成形用PTFE樹脂粉末のみから実験例2と同条件で板状予備成形品を形成し、実験例2と同方法により試験片を調製して、実験例2と同条件で引張り試験を行った。[Comparative Example 1]
A plate-shaped preform is formed from the polymerized PTFE resin powder after polymerization under the same conditions as in Experimental Example 2, and a test piece is prepared by the same method as in Experimental Example 2, and a tensile test is performed under the same conditions as in Experimental Example 2. went.
〔比較例2〕
加熱済のPTFE粉砕粒子(変形化処理していない)80%、残量が成形用のPTFE樹脂粉末粒子の混合系から実験例2と同条件で板状予備成形品を形成し、実験例2と同方法により試験片を調製して、実験例2と同条件で引張り試験を行った。[Comparative Example 2]
A plate-shaped preform was formed under the same conditions as in Experimental Example 2 from a mixed system of 80% heated PTFE pulverized particles (not deformed) and the remaining amount of PTFE resin powder particles for molding. A test piece was prepared by the same method as described above, and a tensile test was performed under the same conditions as in Experimental Example 2.
以下の表1及び表2は、実施例1での実験結果を示している。
表1の実験例2〜5の引張り強度の対比は、表1の比較例1の重合上がり(すなわち、未加熱)の成形用PTFE樹脂粉末のみからの試験片の引張強度との対比を示していて、実験例2の場合では、引張強度(実験例2)/引張強度(比較例1)×100で計算された数値を示している。表2の引張り破断伸びの場合も同様である。Tables 1 and 2 below show experimental results in Example 1.
The comparison of the tensile strengths of Experimental Examples 2 to 5 in Table 1 shows the comparison with the tensile strength of the test piece made only from the molded PTFE resin powder after molding (that is, unheated) in Comparative Example 1 of Table 1. In the case of Experimental Example 2, the numerical value calculated as Tensile Strength (Experimental Example 2) / Tensile Strength (Comparative Example 1) × 100 is shown. The same applies to the tensile elongation at break shown in Table 2.
そして、実験結果によれば、本発明の混合系は、加熱済の溶融フッ素樹脂の相当量を含むにもかかわらず、成形品に未加熱の非溶融フッ素樹脂が与えるのと同等・近似の特性を成形品与えている。And, according to the experimental results, the mixed system of the present invention has the same or similar characteristics as the unheated non-molten fluororesin gives to the molded product, despite containing a considerable amount of the heated molten fluororesin. The molded product is given.
上記実施例1と同様の実験を引張り強度及び引張破断伸び以外の機械的特性及物理的特性についても試験したが同様であった。 The same experiment as in Example 1 was tested for mechanical properties and physical properties other than tensile strength and tensile elongation at break.
本発明によれば、成形加工法の工程から多量に廃材として排出される加熱済の非溶融フッ素樹脂を工業的規模でリサイクルして成形用原料として活用される。また、PTFE樹脂においても、重合上がりの樹脂量の約30%以上が廃材となる大規模な資源浪費・環境保護の問題点が工業的規模で解決される。 According to the present invention, the heated non-molten fluororesin discharged as a waste material in a large amount from the step of the molding method is recycled on an industrial scale and used as a raw material for molding. Also, in PTFE resin, the problem of large-scale waste of resources and environmental protection in which about 30% or more of the amount of resin after polymerization becomes waste is solved on an industrial scale.
Claims (3)
(2)該非溶融加工性フッ素樹脂が、未加熱の非溶融フッ素樹脂の65%以上の引張り強度にされていること、を特徴とする非溶融加工性フッ素樹脂。 (1) non-melting unheated non-melt processible fluororesin non-melt processible fluororesin heating the already large fine body maximum linear length than the fine body is included in the non-melt processible fluororesin unheated A processable fluororesin ,
(2) said non-melt processible fluororesin, it is the non-melt fluororesin of 65% or more of tensile strength of the resin unheated, non-melt processible fluororesin, wherein.
(2)該非溶融加工性フッ素樹脂が、未加熱の非溶融加工性フッ素樹脂の65%以上の引張り強度にされていること、を特徴とする非溶融加工性フッ素樹脂。 (1) Heated non-melt-processable fluororesin that has a maximum linear length and aspect ratio greater than that of unheated non-melt-processable fluororesin A non-melt processable fluororesin contained in a functional fluororesin ,
(2) said non-melt processible fluororesin, it is the non-melt processability of the tensile strength more than 65% of fluorine resin unheated, non-melt processible fluororesin, wherein.
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EP1661942A1 (en) * | 2003-08-25 | 2006-05-31 | Daikin Industries, Ltd. | Mixed polytetrafluoroethylene powder, polytetrafluoroethylene porous shaped body, methods for producing those, polytetrafluoroethylene porous foam shaped body, and product for high-frequency signal transmission |
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