JP2007016222A - Polyimide powder for antistatic polyimide molded article and polyimide molded article using the same - Google Patents
Polyimide powder for antistatic polyimide molded article and polyimide molded article using the same Download PDFInfo
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Abstract
Description
本発明は、芳香族テトラカルボン酸成分とジアミン成分とからなるポリイミド粉末にカーボンブラックを添加してなり、ポリイミドの特性を損なうことなしに帯電防止性能を有するポリイミド成形体を得ることができる帯電防止ポリイミド成形体用ポリイミド粉末、およびそれを用いた帯電防止ポリイミド成形体の製法およびポリイミド成形体に関するものである。 The present invention is an antistatic material that can be obtained by adding carbon black to a polyimide powder comprising an aromatic tetracarboxylic acid component and a diamine component, and can obtain a polyimide molded body having antistatic performance without impairing the properties of the polyimide. The present invention relates to a polyimide powder for a polyimide molded body, a method for producing an antistatic polyimide molded body using the same, and a polyimide molded body.
従来、芳香族テトラカルボン酸成分、例えば３，３’，４，４’−ビフェニルテトラカルボン酸成分とパラフェニレンジアミン成分とから得られるポリイミド粉末の成形体の製法としては、例えば特許文献１、特許文献２などに記載されている。これらの文献によると、上記成形体は耐熱性、寸法安定性、圧縮強度等の機械的強度に優れていることが示されている。 Conventionally, as a method for producing a molded article of polyimide powder obtained from an aromatic tetracarboxylic acid component, for example, a 3,3 ′, 4,4′-biphenyltetracarboxylic acid component and a paraphenylenediamine component, for example, Patent Document 1 and Patent Document 2 and the like. According to these documents, it is shown that the molded body is excellent in mechanical strength such as heat resistance, dimensional stability, and compressive strength.
しかし、上記の公知文献に記載されているポリイミド粉末の成形体は、単独では摺動性、耐磨耗性あるいは帯電防止性能は持たないことが知られている。このため、ポリイミド粉末に無機質微粉末、他の樹脂およびグラファイトあるいは無機質繊維状物を添加してこれらの性能を向上させたポリイミド成形体が知られている（特許文献３〜５）。 However, it is known that the molded body of polyimide powder described in the above-mentioned known literature does not have slidability, wear resistance or antistatic performance by itself. For this reason, a polyimide molded body is known in which inorganic fine powder, other resin and graphite or inorganic fibrous material are added to the polyimide powder to improve these performances (Patent Documents 3 to 5).
一方、ポリイミドフィルムの帯電防止性能を向上させるために、ポリイミド中にスルホン酸塩を添加した帯電防止性芳香族ポリイミドフィルム（特許文献６）、ポリイミドフィルム表面に金属酸化物と導電性超微粒子との混合物を塗布法で形成する帯電防止フィルムが提案された（特許文献７）。 On the other hand, in order to improve the antistatic performance of the polyimide film, an antistatic aromatic polyimide film in which a sulfonate is added to polyimide (Patent Document 6), a metal oxide and conductive ultrafine particles on the surface of the polyimide film. An antistatic film for forming a mixture by a coating method has been proposed (Patent Document 7).
しかし、前記の各公報に記載の技術によれば、カ−ボンあるいはグラファイト等はポリイミド成形体の耐磨耗性あるいは摺動性を向上させるためにはポリイミドに対して５．５〜１００質量％添加することが必要であり、却ってポリイミド本来の特性が損なわれてしまう。
本発明の目的は、ポリイミド本来の特性を大幅に損なうことなく帯電防止機能を備えたポリイミド成形体を与える帯電防止ポリイミド成形体用ポリイミド粉末、それを用いたポリイミド成形体の製法およびそのような優れた特性を有するポリイミド成形体を提供することである。
However, according to the technology described in each of the above publications, carbon or graphite is 5.5 to 100% by mass with respect to polyimide in order to improve the wear resistance or slidability of the polyimide molded body. It is necessary to add, and on the contrary, the original characteristics of polyimide are impaired.
An object of the present invention is to provide a polyimide powder for an antistatic polyimide molded body that gives a polyimide molded body having an antistatic function without significantly deteriorating the original characteristics of the polyimide, a method for producing a polyimide molded body using the same, and such excellent properties It is providing the polyimide molded body which has the characteristic.
本発明者らは、前記の課題を達成するために鋭意検討した結果、ポリイミド粉末に特定の添加剤を少量添加することによって目的が達成されることを見出し、この発明を完成した。
本発明は、芳香族テトラカルボン酸成分とジアミン成分とから得られたポリイミド粉末にＤＢＰ吸油量が３００ｍｌ／１００ｇ以上の導電性カ−ボンブラックをポリイミド粉末に対して０．７５〜５質量％の割合で添加してなる帯電防止ポリイミド成形体用ポリイミド粉末に関する。
また、本発明は、前記に記載の帯電防止ポリイミド成形体用ポリイミド粉末を金型内に充填し、圧力および熱を同時あるいは別々に加えて成形することを特徴とする帯電防止ポリイミド成形体の製法に関する。
さらに、本発明は、前記に記載の製法によって得られる帯電防止ポリイミド成形体に関する。
As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the object can be achieved by adding a small amount of a specific additive to the polyimide powder, thereby completing the present invention.
In the present invention, a conductive carbon black having a DBP oil absorption of 300 ml / 100 g or more is added to a polyimide powder obtained from an aromatic tetracarboxylic acid component and a diamine component in an amount of 0.75 to 5% by mass with respect to the polyimide powder. It is related with the polyimide powder for antistatic polyimide moldings added in a ratio.
The present invention also provides a method for producing an antistatic polyimide molded body, comprising filling the mold with the above-described polyimide powder for an antistatic polyimide molded body and applying pressure and heat simultaneously or separately. About.
Furthermore, this invention relates to the antistatic polyimide molded object obtained by the manufacturing method as described above.
本発明によれば、少量のカ−ボンブラックを添加することによって充分な帯電防止性能を有するポリイミド成形体を与える帯電防止ポリイミド成形体用ポリイミド粉末を得ることができる。
また、本発明によれば、少量のカ−ボンブラックを添加した帯電防止ポリイミド成形体用ポリイミド粉末によって、充分な帯電防止性能を有するポリイミド成形体を製造することができる。
さらに、本発明によれば、少量のカ−ボンブラックを添加した帯電防止ポリイミド成形体用ポリイミド粉末によって、充分な帯電防止性能を有するポリイミド成形体を得ることができる。
According to the present invention, it is possible to obtain a polyimide powder for an antistatic polyimide molded body that gives a polyimide molded body having sufficient antistatic performance by adding a small amount of carbon black.
Further, according to the present invention, a polyimide molded body having sufficient antistatic performance can be produced from the polyimide powder for an antistatic polyimide molded body to which a small amount of carbon black is added.
Furthermore, according to the present invention, a polyimide molded body having sufficient antistatic performance can be obtained with the polyimide powder for an antistatic polyimide molded body to which a small amount of carbon black is added.
以下に本発明の好ましい態様を列記する。
１）ＡＳＴＭ Ｄ２４１４に従って測定したＤＢＰ吸油量が３００ｍｌ／１００ｇ以上の導電性カ−ボンブラックの添加量が、ポリイミド粉末に対して１〜３質量％である帯電防止ポリイミド成形体用ポリイミド粉末。
２）ポリイミド粉末が、芳香族テトラカルボン酸成分として３，３’，４，４’−ビフェニルテトラカルボン酸二無水物を用いたものである帯電防止ポリイミド成形体用ポリイミド粉末。
３）ポリイミド粉末が、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物と２，３，３’，４’−ビフェニルテトラカルボン酸二無水物からなる芳香族テトラカルボン酸成分およびパラフェニレンジアミンを８０モル％以上含む芳香族ジアミン成分とからなり、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物が全芳香族テトラカルボン酸成分中０．５モル％以上３０モル％未満の範囲である上記に記載の帯電防止ポリイミド成形体用ポリイミド粉末。
Preferred embodiments of the present invention are listed below.
1) A polyimide powder for an antistatic polyimide molded body, wherein the addition amount of conductive carbon black having a DBP oil absorption of 300 ml / 100 g or more measured according to ASTM D2414 is 1 to 3% by mass with respect to the polyimide powder.
2) A polyimide powder for an antistatic polyimide molded body, wherein the polyimide powder uses 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as an aromatic tetracarboxylic acid component.
3) An aromatic tetracarboxylic acid component in which the polyimide powder comprises 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, and An aromatic diamine component containing 80 mol% or more of paraphenylenediamine, and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride is 0.5 mol% or more and 30% of the total aromatic tetracarboxylic acid component. The polyimide powder for antistatic polyimide moldings as described above, which is in a range of less than mol%.
４）ポリイミド粉末が、ジアミン成分としてパラフェニレンジアミンあるいは４，４’−ジアミノジフェニルエ−テルを用いたものである帯電防止ポリイミド成形体用ポリイミド粉末。
５）前記帯電防止ポリイミド成形体用ポリイミド粉末の成形を成形温度３５０〜６００℃および成形圧力３０〜２０００ＭＰａで加熱圧縮成形、または室温〜３５０℃および成形圧力３０〜２０００ＭＰａにて得た予備成形体を非圧縮下３５０〜６００℃にて後焼結を行う帯電防止ポリイミド成形体の製法。
６）前記帯電防止ポリイミド成形体の製法で得られる、ＪＩＳ Ｋ６９１１に従って測定した表面抵抗率が１０４〜１０７Ω／□である帯電防止ポリイミド成形体。
4) A polyimide powder for an antistatic polyimide molded body, wherein the polyimide powder uses paraphenylenediamine or 4,4′-diaminodiphenyl ether as a diamine component.
5) Molding of the above-mentioned polyimide powder for an antistatic polyimide molded body by heat compression molding at a molding temperature of 350 to 600 ° C. and a molding pressure of 30 to 2000 MPa, or a preformed body obtained at room temperature to 350 ° C. and a molding pressure of 30 to 2000 MPa. A method for producing an antistatic polyimide molded body in which post-sintering is performed at 350 to 600 ° C. under non-compression.
6) The antistatic polyimide molding which is obtained by the manufacturing method of the said antistatic polyimide molding and whose surface resistivity measured according to JISK6911 is 10 < 4 > -10 < 7 > ohm / square.
本発明におけるポリイミド粉末は、芳香族テトラカルボン酸成分、例えば、芳香族テトラカルボン酸二無水物、好適には３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物とジアミン成分、例えば芳香族ジアミン、好適にはパラフェニレンジアミン、４，４’−ジアミノジフェニルエ−テルとを有機極性溶媒中で反応させて得られるポリアミック酸溶液から得られる。この場合、ポリアミック酸溶液からポリイミド前駆体粉末を単離した後、加熱乾燥してポリイミド粉末を得てもよく、あるいはポリアミック酸溶液を加熱してイミド化してポリイミド粉末を生成して単離し加熱して乾燥してポリイミド粉末を得ても良い。 The polyimide powder in the present invention contains an aromatic tetracarboxylic acid component such as aromatic tetracarboxylic dianhydride, preferably 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic acid 2 It can be obtained from a polyamic acid solution obtained by reacting an anhydride with a diamine component such as an aromatic diamine, preferably paraphenylenediamine, 4,4′-diaminodiphenyl ether in an organic polar solvent. In this case, the polyimide precursor powder may be isolated from the polyamic acid solution and then dried by heating to obtain a polyimide powder. Alternatively, the polyamic acid solution may be heated to imidize to produce a polyimide powder, which is isolated and heated. And dried to obtain polyimide powder.
また、本発明におけるポリイミド粉末は、結晶性芳香族ポリイミドを与える芳香族テトラカルボン酸成分、例えば好適には３，３’，４，４’−ビフェニルテトラカルボン酸あるいはその酸二無水物またはその酸と低級アルコ−ルとのエステル化物、および非結晶性ポリイミドを与えるテトラカルボン酸成分、例えば好適には２，３，３’，４’−ビフェニルテトラカルボン酸あるいはその酸二無水物またはその酸と低級アルコ−ルとのエステル化物（いずれも好適には酸二無水物）を主成分とし、非結晶性ポリイミドを与えるテトラカルボン酸成分（好適には２，３，３’，４’−ビフェニルテトラカルボン酸あるいはその酸二無水物またはその酸と低級アルコ−ルとのエステル化物、より好適には２，３，３’，４’−ビフェニルテトラカルボン酸二無水物）を全テトラカルボン酸成分に対して約０．５モル％以上３０モル％未満、特に１モル％以上２５モル％未満、その中でも特に１．５モル％以上２０モル％未満の割合で含む芳香族テトラカルボン酸成分と、パラフェニレンジアミンを全ジアミン成分に対して少なくとも約８０モル％以上の割合で含む芳香族ジアミン成分とを、略等モル量を公知の方法によって有機極性溶媒中で、重合およびイミド化、次いで反応系からの粉末回収によって得ることができる。
本発明におけるポリイミド粉末は、平均粒子径（一次粒子）が０．５〜１００μｍの粉末が好ましい。
In addition, the polyimide powder in the present invention is an aromatic tetracarboxylic acid component that gives a crystalline aromatic polyimide, for example, preferably 3,3 ′, 4,4′-biphenyltetracarboxylic acid or its acid dianhydride or its acid. And a tetracarboxylic acid component that gives an amorphous polyimide, for example, preferably 2,3,3 ′, 4′-biphenyltetracarboxylic acid or its acid dianhydride or its acid A tetracarboxylic acid component (preferably 2,3,3 ′, 4′-biphenyltetra) which is mainly composed of an esterified product with a lower alcohol (both preferably acid dianhydrides) and gives an amorphous polyimide. Carboxylic acid or acid dianhydride or esterified product of the acid and lower alcohol, more preferably 2,3,3 ′, 4′-biphenyltetracarboxylic acid Anhydride) with respect to the total tetracarboxylic acid component in a proportion of about 0.5 mol% or more and less than 30 mol%, particularly 1 mol% or more and less than 25 mol%, particularly 1.5 mol% or more and less than 20 mol%. An aromatic tetracarboxylic acid component and an aromatic diamine component containing paraphenylenediamine in a proportion of at least about 80 mol% or more based on the total diamine component in an organic polar solvent by a known method in an approximately equimolar amount. , Polymerization and imidization, followed by powder recovery from the reaction system.
The polyimide powder in the present invention is preferably a powder having an average particle size (primary particle) of 0.5 to 100 μm.
前記の芳香族テトラカルボン酸成分としては、３，３’４，４’−ビフェニルテトラカルボン酸類あるいはこれと２，３，３’，４’−ビフェニルテトラカルボン酸類のみを前記の割合で使用することが粉末成形体の高いレベルの物性（特に機械的強度と使用時の耐熱性）から望ましいが、ビフェニルテトラカルボン酸類の一部、好適には５０モル％以下、特に２０モル％以下を他の芳香族テトラカルボン酸類で置き換えてもよい。なお、前記テトラカルボン酸類とは、テトラカルボン酸あるいはその酸二無水物またはその酸と低級アルコ−ルとのエステル化物等をいう。 As the aromatic tetracarboxylic acid component, only 3,3′4,4′-biphenyltetracarboxylic acid or 2,3,3 ′, 4′-biphenyltetracarboxylic acid and the above-mentioned ratio should be used. Is desirable from the high level of physical properties (particularly mechanical strength and heat resistance during use) of the powder molded body, but some of the biphenyltetracarboxylic acids, preferably 50 mol% or less, particularly 20 mol% or less, are used as other fragrances. It may be replaced with a group tetracarboxylic acid. The tetracarboxylic acids refer to tetracarboxylic acids or acid dianhydrides or esterified products of the acids and lower alcohols.
これらの芳香族テトラカルボン酸類としては、ピロメリット酸あるいはその酸二無水物またはその酸と低級アルコ−ルとのエステル化物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸あるいはその酸二無水物またはその酸と低級アルコ−ルとのエステル化物、２，２’−ビス（３，４−ジカルボキシフェニル）プロパンあるいはその酸二無水物またはその酸と低級アルコ−ルとのエステル化物、ビス（３，４−ジカルボキシフェニル）メタンあるいはその酸二無水物またはその酸と低級アルコ−ルとのエステル化物、ビス（３，４−ジカルボキシフェニル）エ−テルあるいはその酸二無水物またはその酸と低級アルコ−ルとのエステル化物などを挙げることができる。 These aromatic tetracarboxylic acids include pyromellitic acid or its acid dianhydride or its esterified product with lower alcohol, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid or its acid diacid. An esterified product of an anhydride or an acid thereof and a lower alcohol, an esterified product of 2,2′-bis (3,4-dicarboxyphenyl) propane or an acid dianhydride or an acid thereof and a lower alcohol, Bis (3,4-dicarboxyphenyl) methane or its acid dianhydride or esterified product of its acid and lower alcohol, bis (3,4-dicarboxyphenyl) ether or its acid dianhydride or An esterified product of the acid and a lower alcohol can be exemplified.
また、前記のジアミンは粉末成形品の物性と重合・イミド化の操作の簡単さからパラフェニレンジアミンあるいは４，４’−ジアミノゾフェニルエ−テルを単独で使用することが望ましいが、物性を実質的に損なわない範囲でその少量部、好適には約２０モル％以下を他の芳香族ジアミンで置き換えてもよい。例えば、このようなジアミンとしては、メタフェニレンジアミン、４，４’−ジアミノジフェニルエ−テル、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルプロパン、ビス（４−アミノフェニル）ジメチルシラン、１，４−ビス（４−アミノ−フェノキシ）ベンゼン、１，３−ビス（４−アミノ−フェノキシ）ベンゼンなどを挙げることができる。 In addition, it is desirable to use paraphenylenediamine or 4,4′-diaminozophenyl ether alone as the above diamine because of the physical properties of the powder molded product and the ease of operation of polymerization and imidization. As long as the amount is not impaired, a small amount thereof, preferably about 20 mol% or less, may be replaced with other aromatic diamines. For example, such diamines include metaphenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, bis (4-aminophenyl) dimethylsilane. 1,4-bis (4-amino-phenoxy) benzene, 1,3-bis (4-amino-phenoxy) benzene, and the like.
前記の各成分をＮ，Ｎ−ジメチルアセトアミドやＮ−メチル−２−ピロリドンなどのポリアミック酸（ポリイミド前駆体）の製造に通常使用される有機極性溶媒中で、好ましくは１０〜８０℃で１〜３０時間重合して、ポリマ−の対数粘度（測定温度：３０℃、濃度：０．５ｇ／１００ｍｌ溶媒、溶媒：Ｎ−メチル−２−ピロリドン）が５以下、ポリマ−濃度が２５重量％以下であり、回転粘度（３０℃）が４５００ポイズ以下であるポリアミック酸（イミド化率：５％以下）溶液を得る。次いで、前記ポリアミック酸溶液を１６０〜３００℃、０．２〜２０時間程度加熱することによってイミド化を完了し、反応系からの粉末回収によってポリイミド粉末を得ることができる。 In the organic polar solvent normally used for manufacture of polyamic acid (polyimide precursor), such as N, N- dimethylacetamide and N-methyl-2-pyrrolidone, said each component, Preferably it is 10-80 degreeC, and is 1 When polymerized for 30 hours, the logarithmic viscosity of the polymer (measurement temperature: 30 ° C., concentration: 0.5 g / 100 ml solvent, solvent: N-methyl-2-pyrrolidone) is 5 or less, and the polymer concentration is 25% by weight or less. Yes, a polyamic acid (imidation rate: 5% or less) solution having a rotational viscosity (30 ° C.) of 4500 poise or less is obtained. Next, imidation is completed by heating the polyamic acid solution at 160 to 300 ° C. for about 0.2 to 20 hours, and a polyimide powder can be obtained by collecting the powder from the reaction system.
本発明においては、前記ポリイミド粉末に対して、０．７５〜５質量％、好適には１〜３質量％の割合でＤＢＰ吸油量が３００ｍｌ／１００ｇ以上の導電性カ−ボンブラックを添加し、好適には均一に混合して、本発明の帯電防止ポリイミド成形体用ポリイミド粉末を得ることができる。
本発明においては、導電性カ−ボンブラックとして、ＤＢＰ吸油量が３００ｍｌ／１００ｇ以上の導電性カ−ボンブラックを添加することが必要であり、ＤＢＰ吸油量が３００ｍｌ／１００ｇ未満の導電性カ−ボンブラックを添加してもポリイミド粉末成形体の表面抵抗率を１０４〜１０７Ω／□程度とするためには大量の添加が必要となり却ってポリイミド粉末成形体の物性が低下するとか均一混合が困難である。
In the present invention, a conductive carbon black having a DBP oil absorption of 300 ml / 100 g or more is added to the polyimide powder at a ratio of 0.75 to 5% by mass, preferably 1 to 3% by mass, The polyimide powder for an antistatic polyimide molded body of the present invention can be obtained by preferably mixing uniformly.
In the present invention, it is necessary to add a conductive carbon black having a DBP oil absorption of 300 ml / 100 g or more as the conductive carbon black, and a conductive carbon having a DBP oil absorption of less than 300 ml / 100 g. Even if bon black is added, in order to make the surface resistivity of the polyimide powder molded body about 10 4 to 10 7 Ω / □, it is necessary to add a large amount, and on the contrary, the physical properties of the polyimide powder molded body are lowered or uniform mixing is performed. Have difficulty.
前記のＤＢＰ吸油量が３００ｍｌ／１００ｇ以上の導電性カ−ボンブラックは、例えばライオン株式会社の各種ケッチェンブラック、例えばケッチェンブラックＥＣ−６００ＪＤ（粉末状、ＤＢＰ吸油量が４９５ｍｌ／１００ｇ）、ケッチェンブラックＥＣ（粉末状、ＤＢＰ吸油量が３６０ｍｌ／１００ｇ）を挙げることができる。前記のＤＢＰ吸油量が３００ｍｌ／１００ｇ以上の導電性カ−ボンブラックとしては、入手の容易さおよび効果の観点から、ＤＢＰ吸油量が３００〜５５０ｍｌ／１００ｇの導電性カ−ボンブラックが好適である。
ポリイミド粉末に所定量のケッチェンブラックを添加した後、それ自体公知の混合方法、好適にはボ−ルミルを用いて１〜５０時間程度混合して、本発明の帯電防止ポリイミド成形体用ポリイミド粉末を得ることができる。
The conductive carbon black having a DBP oil absorption of 300 ml / 100 g or more is, for example, various Ketjen blacks from Lion Corporation, such as Ketjen Black EC-600JD (powder, DBP oil absorption is 495 ml / 100 g), CHENBLACK EC (powder, DBP oil absorption is 360 ml / 100 g). The conductive carbon black having a DBP oil absorption of 300 ml / 100 g or more is preferably a conductive carbon black having a DBP oil absorption of 300 to 550 ml / 100 g from the viewpoint of availability and effects. .
After adding a predetermined amount of ketjen black to the polyimide powder, it is mixed for about 1 to 50 hours using a known mixing method, preferably a ball mill, and the polyimide powder for antistatic polyimide molding of the present invention. Can be obtained.
本発明において、前記帯電防止ポリイミド成形体用ポリイミド粉末を金型内に充填し、圧力および熱を同時あるいは別々に加えて成形してポリイミド粉末成形体を製造することができる。
前記製法において、成形温度３５０〜６００℃および成形圧力３０〜２０００ＭＰａで加熱圧縮成形、または室温〜３５０℃および成形圧力３０〜２０００ＭＰａにて得た予備成形体を非圧縮下３５０〜６００℃にて後焼結を行うことによって、帯電防止ポリイミド成形体を得ることが好ましい。
In the present invention, the polyimide powder molded body can be manufactured by filling the above-mentioned polyimide powder for antistatic polyimide molded body in a mold and molding it by applying pressure and heat simultaneously or separately.
In the above-mentioned manufacturing method, a preform formed at a molding temperature of 350 to 600 ° C. and a molding pressure of 30 to 2000 MPa is subjected to heat compression molding, or from room temperature to 350 ° C. and a molding pressure of 30 to 2000 MPa. It is preferable to obtain an antistatic polyimide molded body by sintering.
また、前記のポリイミド粉末成形体を製造する装置としては、例えば、４柱式油圧式プレス、高圧ホットプレスなどを挙げることができる。また、前記の予備成形体は、例えば、ロ−タリ−プレス、タブレットマシ−ンを使用する方法によって形成することが好ましい。 Examples of the apparatus for producing the polyimide powder molded body include a four-post hydraulic press and a high-pressure hot press. The preform is preferably formed by a method using, for example, a rotary press or a tablet machine.
本発明において、カーボンブラックのＤＢＰ吸油量はＡＳＴＭ Ｄ２４１４に従って測定したものである。また、ポリイミド成形体の表面抵抗率はＪＩＳ Ｋ６９１１に従って測定したものである。 In the present invention, the DBP oil absorption of carbon black is measured according to ASTM D2414. Further, the surface resistivity of the polyimide molded body is measured in accordance with JIS K6911.
以下、本発明を実施例及び比較例によって説明する。なお、以下の記載において、各略号は次の化合物を意味する。
ＮＭＰ：Ｎ−メチル−２−ピロリドン
ＰＰＤ：パラフェニレンジアミン
ａ−ＢＰＤＡ：２，３，３’，４’−ビフェニルテトラカルボン酸二無水物
ｓ−ＢＰＤＡ：３，３’，４，４’−ビフェニルテトラカルボン酸二無水物
ＯＤＡ：４，４’−ジアミノジフェニルエ−テル
Hereinafter, the present invention will be described with reference to examples and comparative examples. In the following description, each abbreviation means the following compound.
NMP: N-methyl-2-pyrrolidone PPD: paraphenylenediamine a-BPDA: 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride s-BPDA: 3,3 ′, 4,4′-biphenyl Tetracarboxylic dianhydride ODA: 4,4′-diaminodiphenyl ether
〔実施例１〕
ＮＭＰ２９８７．８９ｇと、ジアミン成分としてＰＰＤ１４０．５８ｇ（１.３００モル）とを、攪拌機と還流冷却管（水分離器付き）、温度計および窒素導入管を装着した５Ｌの４つ口セパラブルフラスコに６０℃において添加し、その混合液に窒素ガス流通と攪拌しながら、テトラカルボン酸成分としてａ−ＢＰＤＡ２６．７７ｇ（０．０９１モル）およびｓ−ＢＰＤＡ３５５．７１ｇ（１．２０９モル）をほぼ同時に添加し、２時間攪拌して各モノマ−成分をＮＭＰに均一に溶解した溶液を調製した。次いで、その溶液を窒素ガス流通と攪拌を継続しながら、溶媒と生成水とを還流させ、生成水を除去しながら、約６０分間で１９０℃まで昇温した。ポリイミド粉末の析出は内温１６５℃付近から始まった。内温が１９０℃に達した後、その温度で３時間継続し反応を完結させた。その後、反応液を冷却しポリイミド粉末を濾別し、その粉末をアセトンで洗浄し、さらに真空乾燥機により１５０℃で１０時間乾燥し、次いで３００℃にて常圧乾燥３０分行いポリイミド粉末を得た。
上記で得られたポリイミド粉末４００ｇにケッチェンブラック（ライオン社製ＥＣ−６００ＪＤ、ＤＢＰ吸油量が４９５ｍｌ／１００ｇ）を８ｇ添加しボ−ルミルで２４時間混合して、帯電防止ポリイミド成形体用ポリイミド粉末を得た。
[Example 1]
NMP 2987.89 g and PPD 140.58 g (1.300 mol) as a diamine component were placed in a 5 L four-necked separable flask equipped with a stirrer, a reflux condenser (with water separator), a thermometer and a nitrogen inlet tube. The mixture was added at 60 ° C., and 26.77 g (0.091 mol) of a-BPDA and 355.71 g (1.209 mol) of s-BPDA were added almost simultaneously as the tetracarboxylic acid component while stirring and stirring the nitrogen gas. Then, the mixture was stirred for 2 hours to prepare a solution in which each monomer component was uniformly dissolved in NMP. Next, the solution was heated to 190 ° C. in about 60 minutes while refluxing the solvent and generated water while continuing the circulation and stirring of nitrogen gas and removing the generated water. Precipitation of the polyimide powder started from around an internal temperature of 165 ° C. After the internal temperature reached 190 ° C., the temperature was continued for 3 hours to complete the reaction. Thereafter, the reaction solution is cooled and the polyimide powder is filtered off. The powder is washed with acetone, further dried at 150 ° C. for 10 hours by a vacuum dryer, and then dried at 300 ° C. under atmospheric pressure for 30 minutes to obtain a polyimide powder. It was.
8 g of Ketjen black (Lion Corporation EC-600JD, DBP oil absorption 495 ml / 100 g) was added to 400 g of the polyimide powder obtained above, and mixed for 24 hours with a ball mill to obtain polyimide powder for an antistatic polyimide molded body. Got.
〔実施例２〕
円形の金型に実施例１で得た帯電防止ポリイミド成形体用ポリイミド粉末を詰め、押し蓋をしないで３００℃で６時間かけて予備加熱した後、直ちに金型に押し蓋を重ね、３００℃に加熱したプレス機にセットして２００ＭＰａの圧力で押しながら４５０℃まで６時間かけて昇温した。その後、４５０℃になったら直ちに冷却を開始し１２時間かけ室温まで下げ、金型から直径１００ｍｍ、厚み２５ｍｍの帯電防止ポリイミド成形体を取り出した。この帯電防止ポリイミド成形体は全体が黒色で色斑は見られず分散性は良好であった。また、表面抵抗率は５×１０４Ω／□であった。
[Example 2]
After filling the circular mold with the polyimide powder for antistatic polyimide molded body obtained in Example 1 and preheating at 300 ° C. for 6 hours without pressing the lid, the mold is immediately overlaid on the mold and 300 ° C. The temperature was raised to 450 ° C. over 6 hours while being set at a pressure of 200 MPa and being pressed at a pressure of 200 MPa. Thereafter, when the temperature reached 450 ° C., cooling was started immediately and the temperature was lowered to room temperature over 12 hours, and an antistatic polyimide molded body having a diameter of 100 mm and a thickness of 25 mm was taken out from the mold. This antistatic polyimide molded body was black as a whole, no color spots were seen, and the dispersibility was good. The surface resistivity was 5 × 10 4 Ω / □.
〔実施例３〕
ケッチェンブラック（ライオン社製ＥＣ−６００ＪＤ、ＤＢＰ吸油量が４９５ｍｌ／１００ｇ）の添加量を４ｇとした以外は、実施例１と同様に行って、帯電防止ポリイミド成形体用ポリイミド粉末を得た。そして、この帯電防止ポリイミド成形体用ポリイミド粉末を使用した他は実施例２と同様にして、帯電防止ポリイミド成形体を得た。
得られた帯電防止ポリイミド成形体は、全体が黒色で色斑は見られず分散性は良好であった。また、表面抵抗率は３×１０４Ω／□であった。
Example 3
A polyimide powder for an antistatic polyimide molded body was obtained in the same manner as in Example 1 except that the addition amount of Ketjen Black (Lion Corporation EC-600JD, DBP oil absorption 495 ml / 100 g) was changed to 4 g. And the antistatic polyimide molding was obtained like Example 2 except having used this polyimide powder for antistatic polyimide moldings.
The obtained antistatic polyimide molded body was black as a whole and no discoloration was seen, and the dispersibility was good. The surface resistivity was 3 × 10 4 Ω / □.
〔実施例４〕
テトラカルボン酸成分としてｓ−ＢＰＤＡのみを３８２．４９ｇ（１.３００モル）使用してポリイミド粉末を合成した以外は、実施例１と同様に行って、帯電防止ポリイミド成形体用ポリイミド粉末を得た。そして、この帯電防止ポリイミド成形体用ポリイミド粉末を使用した他は実施例２と同様にして、帯電防止ポリイミド成形体を得た。
得られた帯電防止ポリイミド成形体は、全体が黒色で色斑は見られず分散性は良好であった。また、表面抵抗率は５×１０４Ω／□であった。
Example 4
A polyimide powder for an antistatic polyimide molded body was obtained in the same manner as in Example 1, except that s-BPDA alone was used as a tetracarboxylic acid component and 382.49 g (1.300 mol) was used to synthesize polyimide powder. . And the antistatic polyimide molding was obtained like Example 2 except having used this polyimide powder for antistatic polyimide moldings.
The obtained antistatic polyimide molded body was black as a whole and no discoloration was seen, and the dispersibility was good. The surface resistivity was 5 × 10 4 Ω / □.
〔実施例５〕
テトラカルボン酸成分としてｓ−ＢＰＤＡを３８２．４９ｇ（１.３００モル）ジアミン成分としてＯＤＡを２６０．３１ｇ（１.３００モル）使用してポリイミド粉末を合成した以外は、実施例１と同様に行なって、帯電防止ポリイミド成形体用ポリイミド粉末を得た。そして、この帯電防止ポリイミド成形体用ポリイミド粉末を使用した他は実施例２と同様にして、帯電防止ポリイミド成形体を得た。
得られた帯電防止ポリイミド成形体は、全体が黒色で色斑は見られず分散性は良好であった。また、表面抵抗率は５×１０４Ω／□であった。
Example 5
The same procedure as in Example 1 was conducted except that polyimide powder was synthesized using 238.49 g (1.300 mol) of s-BPDA as a tetracarboxylic acid component and 260.31 g (1.300 mol) of ODA as a diamine component. Thus, a polyimide powder for an antistatic polyimide molded body was obtained. And the antistatic polyimide molding was obtained like Example 2 except having used this polyimide powder for antistatic polyimide moldings.
The obtained antistatic polyimide molded body was black as a whole and no discoloration was seen, and the dispersibility was good. The surface resistivity was 5 × 10 4 Ω / □.
〔比較例１〕
カ−ボンブラックとして導電性カ−ボンブラック（三菱化学社、３３５０Ｂ、ＤＢＰ吸油量が１６５ｍｌ／１００ｇ））を用いた他は、実施例１と同様に行なって、帯電防止ポリイミド成形体用ポリイミド粉末を得た。そして、この帯電防止ポリイミド成形体用ポリイミド粉末を使用した他は実施例２と同様にして、ポリイミド成形体を得た。
得られたポリイミド成形体は、部分的に斑点が見られ分散性は不良であった。また、表面抵抗率は４×１０１５Ω／□であった。
[Comparative Example 1]
The same procedure as in Example 1 was conducted except that conductive carbon black (Mitsubishi Chemical Co., Ltd., 3350B, DBP oil absorption amount of 165 ml / 100 g)) was used as the carbon black. Got. And the polyimide molded body was obtained like Example 2 except having used this polyimide powder for antistatic polyimide molded bodies.
The obtained polyimide molding was partially spotted and poor in dispersibility. The surface resistivity was 4 × 10 15 Ω / □.
〔比較例２〕
カ−ボンブラックとしてグラファイト（日本黒鉛工業社製ＡＣＰ、ＤＢＰ吸油量が１００ｍｌ／１００ｇ）を用い、添加量を４０ｇとした以外は、実施例１と同様に行なって、帯電防止ポリイミド成形体用ポリイミド粉末を得た。そして、この帯電防止ポリイミド成形体用ポリイミド粉末を使用した他は実施例２と同様にして、ポリイミド成形体を得た。
得られたポリイミド成形体は、部分的に斑点が見られ分散性はやや不良であった。また、表面抵抗率は４×１０８Ω／□であった。
[Comparative Example 2]
The same procedure as in Example 1 was performed except that graphite (ACP manufactured by Nippon Graphite Industry Co., Ltd., DBP oil absorption amount: 100 ml / 100 g) was used as carbon black, and the addition amount was 40 g. A powder was obtained. And the polyimide molded body was obtained like Example 2 except having used this polyimide powder for antistatic polyimide molded bodies.
The obtained polyimide molded product was partially spotted and the dispersibility was somewhat poor. The surface resistivity was 4 × 10 8 Ω / □.
実施例１〜５で得られた帯電防止ポリイミド成形体用ポリイミド粉末の粒径をＳＥＭ写真（５０００倍）で測定したところ、いずれも２０μｍ以下であった。 When the particle size of the polyimide powder for antistatic polyimide molded bodies obtained in Examples 1 to 5 was measured by SEM photographs (5000 times), all were 20 μm or less.
本発明によって、少量のカ−ボンブラックを添加することによって充分な帯電防止性能を有するポリイミド成形体を与える帯電防止ポリイミド成形体用ポリイミド粉末を得ることができる。
また、本発明によって、少量のカ−ボンブラックを添加した帯電防止ポリイミド成形体用ポリイミド粉末によって、充分な帯電防止性能を有するポリイミド成形体を製造することができる。
さらに、本発明によって、少量のカ−ボンブラックを添加した帯電防止ポリイミド成形体用ポリイミド粉末によって、充分な帯電防止性能を有するポリイミド成形体を得ることができる。
According to the present invention, it is possible to obtain a polyimide powder for an antistatic polyimide molded body that gives a polyimide molded body having sufficient antistatic performance by adding a small amount of carbon black.
Further, according to the present invention, a polyimide molded body having sufficient antistatic performance can be produced from the polyimide powder for an antistatic polyimide molded body to which a small amount of carbon black is added.
Furthermore, according to the present invention, a polyimide molded body having sufficient antistatic performance can be obtained by using the polyimide powder for an antistatic polyimide molded body to which a small amount of carbon black is added.
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| JP2006158773A Expired - Fee Related JP5157087B2 (en) | 2005-06-08 | 2006-06-07 | Polyimide powder for antistatic polyimide molded body and polyimide molded body using the same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021182589A1 (en) | 2020-03-13 | 2021-09-16 | 宇部興産株式会社 | Aromatic polyimide powder for molded body, molded body using same, method for improving mechanical strength of molded body |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61281150A (en) * | 1985-06-05 | 1986-12-11 | Nitto Electric Ind Co Ltd | Polyimide powder and production thereof |
| JPS62246959A (en) * | 1986-04-21 | 1987-10-28 | Toray Ind Inc | Antistatic resin composition |
| JPH11302380A (en) * | 1998-04-24 | 1999-11-02 | Ube Ind Ltd | Polyimide powder, its production and molded product |
| JP2002096397A (en) * | 2000-07-21 | 2002-04-02 | Ube Ind Ltd | Polyimide molding and method for manufacturing the same |
-
2006
- 2006-06-07 JP JP2006158773A patent/JP5157087B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61281150A (en) * | 1985-06-05 | 1986-12-11 | Nitto Electric Ind Co Ltd | Polyimide powder and production thereof |
| JPS62246959A (en) * | 1986-04-21 | 1987-10-28 | Toray Ind Inc | Antistatic resin composition |
| JPH11302380A (en) * | 1998-04-24 | 1999-11-02 | Ube Ind Ltd | Polyimide powder, its production and molded product |
| JP2002096397A (en) * | 2000-07-21 | 2002-04-02 | Ube Ind Ltd | Polyimide molding and method for manufacturing the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021182589A1 (en) | 2020-03-13 | 2021-09-16 | 宇部興産株式会社 | Aromatic polyimide powder for molded body, molded body using same, method for improving mechanical strength of molded body |
| KR20220147139A (en) | 2020-03-13 | 2022-11-02 | 유비이 가부시키가이샤 | Aromatic polyimide powder for molded article, molded article using same, and method for improving mechanical strength of molded article |
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| Publication number | Publication date |
|---|---|
| JP5157087B2 (en) | 2013-03-06 |
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