JP5644151B2 - LAMINATE MANUFACTURING METHOD AND LAMINATE - Google Patents
LAMINATE MANUFACTURING METHOD AND LAMINATE Download PDFInfo
- Publication number
- JP5644151B2 JP5644151B2 JP2010066015A JP2010066015A JP5644151B2 JP 5644151 B2 JP5644151 B2 JP 5644151B2 JP 2010066015 A JP2010066015 A JP 2010066015A JP 2010066015 A JP2010066015 A JP 2010066015A JP 5644151 B2 JP5644151 B2 JP 5644151B2
- Authority
- JP
- Japan
- Prior art keywords
- polyimide foam
- laminate
- thermoplastic resin
- polyamide
- polyimide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Laminated Bodies (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明は、接着剤を使用することなく且つ積層させるポリイミド発泡体や熱可塑性樹脂シートの接合面に反応性基を導入することなく、ポリイミド発泡体と熱可塑性樹脂シートとが強固に接合された積層体の製造方法、及び該方法により製造されたポリイミド発泡体と熱可塑性樹脂シートとの積層体に関する。 In the present invention, the polyimide foam and the thermoplastic resin sheet are firmly bonded without using an adhesive and without introducing a reactive group to the bonding surface of the polyimide foam or thermoplastic resin sheet to be laminated. The present invention relates to a method for producing a laminate, and a laminate of a polyimide foam and a thermoplastic resin sheet produced by the method.
自動車などの様々な分野において、軽量、高強度で、断熱性及び耐熱性に優れた断熱材、防振材、吸音材などが嘱望されている。
このような材料として、樹脂発泡体の表面に繊維強化樹脂シートを貼り付けた積層体が知られている。例えば、特許文献１には、連続した強化繊維を一方向に整列させ熱可塑性樹脂を含浸した１枚以上のプリプレグと樹脂発泡体とを多層に重ね合わせて溶融一体化した積層体が記載されている。
また、特許文献２には、流動制御されたエポキシ樹脂を重量比で約４５％程度含有した炭素繊維強化複合材料を面板とし、ポリエーテルイミド樹脂の発泡材をコアとした複合サンドイッチ構造体が記載されている。
また、特許文献３には、Ｘ線機器用部材として、表皮材が剛性の高い繊維強化樹脂で構成され、芯材が表皮材よりも見かけ密度の小さい樹脂で構成され、さらに全体厚みを小さくした、剛性を保持したままで軽量性及びＸ線透過性に優れた繊維強化樹脂製サンドイッチパネルが記載されている。
しかし、特許文献１〜３に記載されている積層体はいずれも十分な耐熱性を実現できていない。
In various fields such as automobiles, a heat insulating material, a vibration isolating material, a sound absorbing material and the like that are lightweight, high in strength, and excellent in heat insulation and heat resistance are desired.
As such a material, a laminate in which a fiber reinforced resin sheet is attached to the surface of a resin foam is known. For example, Patent Document 1 describes a laminate in which continuous reinforcing fibers are aligned in one direction and one or more prepregs impregnated with a thermoplastic resin and a resin foam are laminated and fused together in multiple layers. Yes.
Patent Document 2 describes a composite sandwich structure using a carbon fiber reinforced composite material containing about 45% by weight of a flow-controlled epoxy resin as a face plate and a polyetherimide resin foam as a core. Has been.
Further, in Patent Document 3, as a member for X-ray equipment, the skin material is composed of a fiber-reinforced resin having high rigidity, the core material is composed of a resin having an apparent density lower than that of the skin material, and the overall thickness is further reduced. In addition, a fiber reinforced resin sandwich panel having excellent lightness and X-ray permeability while maintaining rigidity is described.
However, none of the laminates described in Patent Documents 1 to 3 can realize sufficient heat resistance.
ポリイミド発泡体と熱可塑性樹脂シートとの積層体は、従来知られていない。本発明者らは、耐熱性に優れたポリイミド発泡体と熱可塑性樹脂シートとの積層体を提供するため、射出成形機の射出装置から射出された溶融状態の熱可塑性樹脂を、ポリイミド発泡体と接合させたところ、ポリイミド発泡体が破壊されてしまい、ポリイミド発泡体と熱可塑性樹脂シートとの積層体が得られなかった。
ポリイミド発泡体と熱可塑性樹脂シートとの積層体を得る方法としては、接着剤を使用して接合する方法又は積層させるポリイミド発泡体や熱可塑性樹脂シートの接合面に反応性基を導入して該反応性基により接合する方法が考えられるが、斯かる方法はいずれも工程が煩雑でコストが掛かるなどの問題がある。
A laminate of a polyimide foam and a thermoplastic resin sheet has not been conventionally known. In order to provide a laminate of a polyimide foam excellent in heat resistance and a thermoplastic resin sheet, the present inventors used a molten thermoplastic resin injected from an injection device of an injection molding machine as a polyimide foam. When bonded, the polyimide foam was destroyed, and a laminate of the polyimide foam and the thermoplastic resin sheet could not be obtained.
As a method of obtaining a laminate of a polyimide foam and a thermoplastic resin sheet, a method of joining using an adhesive or a reactive group is introduced into the joining surface of a polyimide foam or a thermoplastic resin sheet to be laminated. Although the method of joining by a reactive group can be considered, all of these methods have problems such as complicated steps and cost.
従って、本発明の目的は、接着剤を使用することなく且つ積層させるポリイミド発泡体や熱可塑性樹脂シートの接合面に反応性基を導入することなく、ポリイミド発泡体と熱可塑性樹脂シートとが強固に接合され、しかも軽量、高強度で、断熱性及び耐熱性に優れた、ポリイミド発泡体と熱可塑性樹脂シートとの積層体が得られる、積層体の製造方法を提供することにある。 Therefore, the object of the present invention is to provide a strong bond between the polyimide foam and the thermoplastic resin sheet without using an adhesive and without introducing a reactive group into the bonding surface of the polyimide foam or thermoplastic resin sheet to be laminated. Another object of the present invention is to provide a method for producing a laminate, in which a laminate of a polyimide foam and a thermoplastic resin sheet is obtained which is bonded to the substrate and is lightweight, high in strength and excellent in heat insulation and heat resistance.
本発明は、前記目的を、下記化学式（１）で示される反復単位からなるポリイミド発泡体と、
但し、化学式（１）中のＡは、その０〜９０モル％が下記化学式（２）で示されるビフェニルテトラカルボン酸構造に基づく４価のユニットであり、その１００〜１０モル％が下記化学式（３）で示されるベンゾフェノンテトラカルボン酸構造に基づく４価のユニットであり、化学式（１）中のＢは、その５０〜９７モル％がｐ−フェニレン構造に基づく２価のユニットである。
ポリアミド６（３０％ガラス繊維強化品）のシートとの積層体の製造方法であって、ポリアミド６（３０％ガラス繊維強化品）のシートのポリイミド発泡体への接合面を、該ポリアミド６（３０％ガラス繊維強化品）の融点より５０〜８０℃高い温度に加熱した後、該ポリアミド６（３０％ガラス繊維強化品）のシートを、該ポリアミド６（３０％ガラス繊維強化品）の融点に加熱しておいた該ポリイミド発泡体に接合し、融着することを特徴とするポリイミド発泡体とポリアミド６（３０％ガラス繊維強化品）のシートとの積層体の製造方法を提供することにより達成したものである。
The present invention has the above object, and a polyimide foam comprising a repeating unit represented by the following chemical formula (1):
However, A in the chemical formula (1) is a tetravalent unit based on the biphenyltetracarboxylic acid structure represented by the following chemical formula (2) in 0 to 90 mol%, and 100 to 10 mol% thereof is represented by the following chemical formula ( 3) is a tetravalent unit based on the benzophenone tetracarboxylic acid structure represented by 3), and B in the chemical formula (1) is a divalent unit based on 50 to 97 mol% of the p-phenylene structure.
A method of manufacturing a laminate of a polyamide 6 (30% glass fiber reinforced product) sheet and a bonding surface of the polyamide 6 (30% glass fiber reinforced product) sheet to a polyimide foam. % after heating to 50 to 80 ° C. above the melting point of the glass fiber reinforced articles), heating the sheet of the polyamide 6 (30% glass fiber reinforced products), the melting point of the polyamide 6 (30% glass fiber reinforced articles) The present invention has been achieved by providing a method for producing a laminate of a polyimide foam and a sheet of polyamide 6 (30% glass fiber reinforced product), which is bonded to and fused to the polyimide foam. Is.
本発明のポリイミド発泡体と熱可塑性樹脂シートとの積層体の製造方法によれば、接着剤を使用することなく且つ積層させるポリイミド発泡体や熱可塑性樹脂シートの接合面に反応性基を導入することなく、ポリイミド発泡体と熱可塑性樹脂シートとが強固に接合され、しかも軽量、高強度で、断熱性及び耐熱性に優れたポリイミド発泡体と熱可塑性樹脂シートとの積層体が容易に得られる。そのため、本発明の製造方法により製造されたポリイミド発泡体と熱可塑性樹脂シートとの積層体は、断熱材、防振材、吸音材、遮音材、気柱共鳴防止材、衝撃吸収材などとして好適に用いることができ、特に、自動車エンジン回りの断熱材として好適なものである。 According to the method for producing a laminate of a polyimide foam and a thermoplastic resin sheet of the present invention, a reactive group is introduced into the bonding surface of the polyimide foam or thermoplastic resin sheet to be laminated without using an adhesive. In addition, the polyimide foam and the thermoplastic resin sheet are firmly bonded to each other, and a laminate of the polyimide foam and the thermoplastic resin sheet that is lightweight, high-strength and excellent in heat insulation and heat resistance can be easily obtained. . Therefore, the laminate of the polyimide foam and the thermoplastic resin sheet produced by the production method of the present invention is suitable as a heat insulating material, a vibration isolating material, a sound absorbing material, a sound insulating material, an air column resonance preventing material, an impact absorbing material, etc. In particular, it is suitable as a heat insulating material around an automobile engine.
以下、本発明のポリイミド発泡体と熱可塑性樹脂シートとの積層体の製造方法の好ましい実施形態について説明する。
本発明で用いられるポリイミド発泡体としては、芳香族ポリイミドによって形成されたポリイミド発泡体であることが好ましい。
斯かる芳香族ポリイミドとしては、特に制限されるものではないが、テトラカルボン酸成分が芳香族テトラカルボン酸類、ジアミン成分が芳香族ジアミンからなり、ガラス転移温度が２５０℃以上、好ましくは３００℃以上、より好ましくは３３０℃以上、特に好ましくは３５０℃以上の実質的に芳香族ポリイミドによって形成されたものが好適である。ガラス転移温度が低いポリイミドを用いると、ポリイミド発泡体の密度が不均一になり、形状も歪んだものになるので好ましくない。
芳香族テトラカルボン酸類と芳香族ジアミン以外の少量成分を、例えば発泡成形時の可塑性を改良する目的で用いても構わないが、得られるポリイミドのガラス転移温度が前記値以下にならないようにすることが好ましい。前記少量成分を用いる場合、その使用量は、テトラカルボン酸成分及びジアミン成分中、それぞれ独立に、１０モル％程度以下、好ましくは５モル％以下、より好ましくは２モル％以下である。
Hereinafter, preferable embodiment of the manufacturing method of the laminated body of the polyimide foam of this invention and a thermoplastic resin sheet is described.
The polyimide foam used in the present invention is preferably a polyimide foam formed from an aromatic polyimide.
The aromatic polyimide is not particularly limited, but the tetracarboxylic acid component is an aromatic tetracarboxylic acid, the diamine component is an aromatic diamine, and the glass transition temperature is 250 ° C. or higher, preferably 300 ° C. or higher. More preferably, those substantially formed of aromatic polyimide at 330 ° C. or higher, particularly preferably 350 ° C. or higher are suitable. Use of polyimide having a low glass transition temperature is not preferable because the density of the polyimide foam becomes non-uniform and the shape is distorted.
Minor components other than aromatic tetracarboxylic acids and aromatic diamines may be used for the purpose of improving plasticity during foam molding, for example, but the glass transition temperature of the resulting polyimide should not be lower than the above value. Is preferred. When using the said small amount component, the usage-amount is about 10 mol% or less each independently in a tetracarboxylic-acid component and a diamine component, Preferably it is 5 mol% or less, More preferably, it is 2 mol% or less.
前記テトラカルボン酸成分としては、２，３，３’，４’−ビフェニルテトラカルボン酸類、３，３’，４，４’−ビフェニルテトラカルボン酸類、２，２’，３，３’−ビフェニルテトラカルボン酸類などのビフェニルテトラカルボン酸類、ピロメリット酸類、３，３’，４，４’−ベンゾフェノンテトラカルボン酸類などのベンゾフェノンテトラカルボン酸類、２，３，６，７−ナフタレンテトラカルボン酸類、１，２，５，６−ナフタレンテトラカルボン酸類、１，２，４，５−ナフタレンテトラカルボン酸類、１，４，５，８−ナフタレンテトラカルボン酸類などのナフタレンテトラカルボン酸類、ビス（３，４−ジカルボキシフェニル）エーテル類などのビス（ジカルボキシフェニル）エーテル類、２，２−ビス（２，５−ジカルボキシフェニル）プロパン類などのビス（ジカルボキシフェニル）プロパン類、１，１−ビス（２，３−ジカルボキシフェニル）エタン類などのビス（ジカルボキシフェニル）エタン類、１，１−ビス（３，４−ジカルボキシフェニル）スルホン類などのビス（ジカルボキシフェニル）スルホン類などの芳香族テトラカルボン酸類を単独又は混合して好適に用いることができる。これらの中でも特にビフェニルテトラカルボン酸類が、発泡体を容易に得ることができ且つガラス転移温度が高いので、テトラカルボン酸成分の主成分（５０モル％以上、好ましくは８０モル％以上）として用いるのが好適である。
ここでテトラカルボン酸類とは、テトラカルボン酸、そのエステル化物、その無水化物などのポリイミドを形成し得るテトラカルボン酸及びその誘導体を意味する。
成形性などを考慮して用いられる少量成分としては、１，３−ビス（３，４−ジカルボキシフェニル）−１，１，３，３−テトラメチルジシロキサン類などのビス（ジカルボキシフェニル）テトラメチルジシロキサン類や、シクロペンタンテトラカルボン酸類、１，２，４，５−シクロヘキサンテトラカルボン酸、３−メチル−４−シクロヘキセン−１，２，４，５−テトラカルボン酸などのシクロヘキサンテトラカルボン酸類などの脂肪族テトラカルボン酸類が挙げられる。
Examples of the tetracarboxylic acid component include 2,3,3 ′, 4′-biphenyltetracarboxylic acids, 3,3 ′, 4,4′-biphenyltetracarboxylic acids, 2,2 ′, 3,3′-biphenyltetra Biphenyltetracarboxylic acids such as carboxylic acids, pyromellitic acids, benzophenone tetracarboxylic acids such as 3,3 ′, 4,4′-benzophenonetetracarboxylic acids, 2,3,6,7-naphthalenetetracarboxylic acids, 1,2 , 5,6-naphthalenetetracarboxylic acids, 1,2,4,5-naphthalenetetracarboxylic acids, 1,4,5,8-naphthalenetetracarboxylic acids and other naphthalenetetracarboxylic acids, bis (3,4-dicarboxyl Bis (dicarboxyphenyl) ethers such as phenyl) ether, 2,2-bis (2,5-dicarboxyphe) B) Bis (dicarboxyphenyl) propanes such as propane, bis (dicarboxyphenyl) ethanes such as 1,1-bis (2,3-dicarboxyphenyl) ethane, 1,1-bis (3 Aromatic tetracarboxylic acids such as bis (dicarboxyphenyl) sulfones such as 4-dicarboxyphenyl) sulfones can be used alone or in combination. Among these, in particular, biphenyltetracarboxylic acids can easily obtain a foam and have a high glass transition temperature, so that they are used as a main component (50 mol% or more, preferably 80 mol% or more) of a tetracarboxylic acid component. Is preferred.
Here, the tetracarboxylic acids mean tetracarboxylic acids that can form polyimides, such as tetracarboxylic acids, esterified products thereof, and anhydrides thereof, and derivatives thereof.
The minor component used in consideration of moldability and the like includes bis (dicarboxyphenyl) such as 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane. Cyclohexanetetracarboxylic acids such as tetramethyldisiloxanes, cyclopentanetetracarboxylic acids, 1,2,4,5-cyclohexanetetracarboxylic acid, 3-methyl-4-cyclohexene-1,2,4,5-tetracarboxylic acid Aliphatic tetracarboxylic acids such as acids can be mentioned.
前記ジアミン成分としては、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、２，４−ジアミノトルエン、２，６−ジアミノトルエン、３，５−ジアミノ安息香酸などのベンゼン核を１つ有する芳香族ジアミン、４，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、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スルホンなどのベンゼン核を２つ有する芳香族ジアミン、１，３−ビス（３−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）ベンゼンなどのベンゼン核を３つ有する芳香族ジアミン、ビス（４−（４−アミノフェノキシ）フェニル）スルホン、ビス（４−（３−アミノフェノキシ）フェニル）スルホン、４，４' −ビス（３−アミノフェノキシ）ビフェニル、４，４' −ビス（４−アミノフェノキシ）ビフェニル、２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパンなどのベンゼン核を４つ有する芳香族ジアミン、ジアミノナフタレン等のナフタレン環を有する芳香族ジアミン、２，６−ジアミノピリジンなどの複素環を有する芳香族ジアミンなどを単独又は混合して好適に用いることができる。これらの中でも、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、４，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、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スルホン、及び２，６−ジアミノピリジンからなる群から選択された少なくとも一つの芳香族ジアミンを主成分（５０モル％以上、好ましくは８０モル％以上）として用いることが好適である。
成形性などを考慮して用いられる少量成分としては、１，３−ビス（３−アミノプロピル）テトラメチルシランのようなジアミノシロキサンや、イソホロンジアミン、ノルボルネンジアミン、１，２−ジアミノシクロヘキサン、１，３−ジアミノシクロヘキサン、１，４−ジアミノシクロヘキサン、ビス（４−アミノシクロヘキシル）メタンなどの脂環式ジアミンや、ヘキサメチレンジアミン、ジアミノドデカンなどの脂肪族ジアミンを挙げることができる。
Examples of the diamine component include aromatic diamines having one benzene nucleus such as p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, and 3,5-diaminobenzoic acid. , 4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, aromatic diamine having two benzene nuclei such as 4,4′-diaminodiphenylsulfone, -Aminophenoxy) benzene, aromatic diamine having three benzene nuclei such as 1,3-bis (4-aminophenoxy) benzene, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3 -Aminophenoxy) phenyl) sulfone, 4,4'-bis (3-aminophenoxy) biphe Nyl, 4,4′-bis (4-aminophenoxy) biphenyl, aromatic diamine having four benzene nuclei such as 2,2-bis (4- (4-aminophenoxy) phenyl) propane, and naphthalene such as diaminonaphthalene An aromatic diamine having a ring, an aromatic diamine having a heterocyclic ring such as 2,6-diaminopyridine, and the like can be suitably used alone or in combination. Among these, p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 2, It is preferable to use at least one aromatic diamine selected from the group consisting of 6-diaminopyridine as the main component (50 mol% or more, preferably 80 mol% or more).
Minor components used in consideration of moldability and the like include diaminosiloxanes such as 1,3-bis (3-aminopropyl) tetramethylsilane, isophoronediamine, norbornenediamine, 1,2-diaminocyclohexane, 1, Examples include alicyclic diamines such as 3-diaminocyclohexane, 1,4-diaminocyclohexane, and bis (4-aminocyclohexyl) methane, and aliphatic diamines such as hexamethylenediamine and diaminododecane.
また、前記ポリイミド発泡体を形成する好ましい芳香族ポリイミドとして、下記化学式（１）で示される反復単位からなる芳香族ポリイミドが挙げられる。 Moreover, as a preferable aromatic polyimide which forms the said polyimide foam, the aromatic polyimide which consists of a repeating unit shown by following Chemical formula (1) is mentioned.
テトラカルボン酸成分中の前記化学式（２）で示されるビフェニルテトラカルボン酸構造に基づく４価のユニットの割合が多いほど、耐熱性、耐加水分解性、耐アルカリ性、ガラス転移温度、機械的強度などに優れた特性を得ることができるので好ましいが、９０モル％を越えると、ポリイミド発泡体を製造するためのテトラカルボン酸ジエステルとジアミンとからなるポリイミド前駆体が均一な溶液になり難いので好ましくない。 As the proportion of tetravalent units based on the biphenyltetracarboxylic acid structure represented by the chemical formula (2) in the tetracarboxylic acid component increases, the heat resistance, hydrolysis resistance, alkali resistance, glass transition temperature, mechanical strength, etc. However, if it exceeds 90 mol%, it is not preferable because a polyimide precursor composed of a tetracarboxylic acid diester and a diamine for producing a polyimide foam is difficult to form a uniform solution. .
ジアミン成分中の前記化学式（５）で示されるメタフェニレン構造に基づく２価のユニットが５０モル％以上であると、ガラス転移温度が３００℃以上で、且つ発泡体セルが均一で細かく、変形しても容易に亀裂が発生しない可撓性や優れたクッション性などの機械的特性を有したポリイミド発泡体を容易に得ることができるので好適である。前記化学式（５）で示されるメタフェニレン構造に基づく２価のユニットが５０モル％未満では、前記の特性を得ることが難しくなる。前記化学式（５）で示されるメタフェニレン構造に基づく２価のユニットが９７モル％を越えると、テトラカルボン酸ジエステルとジアミンとからなるポリイミド前駆体が均一な溶液になり難いので好ましくない。 When the divalent unit based on the metaphenylene structure represented by the chemical formula (5) in the diamine component is 50 mol% or more, the glass transition temperature is 300 ° C. or more, and the foam cell is uniform, fine, and deformed. However, a polyimide foam having mechanical properties such as flexibility that does not easily crack and excellent cushioning properties can be easily obtained, which is preferable. When the divalent unit based on the metaphenylene structure represented by the chemical formula (5) is less than 50 mol%, it is difficult to obtain the above characteristics. When the divalent unit based on the metaphenylene structure represented by the chemical formula (5) exceeds 97 mol%, the polyimide precursor composed of tetracarboxylic acid diester and diamine is difficult to form a uniform solution, which is not preferable.
本発明で用いられるポリイミド発泡体は、前記テトラカルボン酸成分と前記ジアミン成分とを略等モル、具体的にはモル比（テトラカルボン酸成分／ジアミン成分）が０．９５〜１．０５の範囲で用いることが好適である。 In the polyimide foam used in the present invention, the tetracarboxylic acid component and the diamine component are approximately equimolar, specifically, the molar ratio (tetracarboxylic acid component / diamine component) is in the range of 0.95 to 1.05. It is suitable to use in.
前記の芳香族ポリイミドからなる本発明で用いられるポリイミド発泡体は、従来公知の方法で好適に製造することができる。例えば、低級アルコール溶媒中でテトラカルボン酸二無水物と前記低級アルコールとを反応させてテトラカルボン酸エステル化物の溶液とし、それにジアミンを加えて混合してポリイミド前駆体溶液組成物を得、次いでその溶液組成物のアルコール溶媒を低温で蒸発除去し、粉末のポリイミド前駆体組成物を得る。この粉末のポリイミド前駆体組成物を必要に応じて予備成形してグリーン体にした後で、マイクロ波加熱などによって加熱して発泡させることで好適に得ることができる。また、前記粉末のポリイミド前駆体組成物に再度低級アルコールを加えて溶液乃至サスペンジョンのポリイミド前駆体組成物とした後で、マイクロ波加熱などによって加熱して発泡させることで好適に得ることができる。 The polyimide foam used in the present invention comprising the above aromatic polyimide can be suitably produced by a conventionally known method. For example, a tetracarboxylic dianhydride and the lower alcohol are reacted in a lower alcohol solvent to form a tetracarboxylic ester solution, and a diamine is added and mixed to obtain a polyimide precursor solution composition. The alcohol solvent of the solution composition is removed by evaporation at a low temperature to obtain a powdered polyimide precursor composition. This powder polyimide precursor composition can be suitably obtained by pre-molding as necessary to form a green body, and then heating and foaming by microwave heating or the like. Moreover, after adding a lower alcohol again to the said polyimide precursor composition of a powder to make a polyimide precursor composition of a solution thru | or a suspension, it can obtain suitably by heating by microwave heating etc. and making it foam.
ポリイミド前駆体溶液組成物の調製は、テトラカルボン酸成分とジアミン成分とが略等モルになるような組成比で混合して行われるが、発泡を均一化するために、例えばジアミノジシロキサンがジアミン成分の少量成分として好適に用いられる。溶媒の低級アルコールとしてはメタノ−ル、エタノ−ル、プロパノールなどが用いられ、他の溶媒と混合されることもある。テトラカルボン酸エステル化物の溶液にジアミンを加えて混合してポリイミド前駆体溶液組成物を得る際には、各成分の濃度はジアミンの溶解度限界以下が好適であり、不揮発成分量は全量中の３〜５０質量％程度になる。このポリイミド前駆体溶液組成物には、１，２−ジメチルイミダゾ−ル、ベンズイミダゾ−ル、イソキノリン、置換ピリジンなどのイミド化触媒、界面活性剤、或いは、他の公知の添加剤、例えば無機フィラ−、無機あるいは有機顔料などを加えてもよい。 The polyimide precursor solution composition is prepared by mixing the tetracarboxylic acid component and the diamine component at a composition ratio such that the equimolar amounts of the tetracarboxylic acid component and the diamine component. It is suitably used as a minor component of the component. As the lower alcohol of the solvent, methanol, ethanol, propanol or the like is used, and it may be mixed with other solvents. When a diamine is added to and mixed with the tetracarboxylic acid ester solution to obtain a polyimide precursor solution composition, the concentration of each component is preferably below the solubility limit of diamine, and the amount of non-volatile components is 3 in the total amount. It becomes about 50 mass%. This polyimide precursor solution composition includes 1,2-dimethylimidazole, benzimidazole, isoquinoline, substituted pyridine and other imidation catalysts, surfactants, or other known additives such as inorganic fillers. -Inorganic or organic pigments may be added.
ポリイミド前駆体溶液組成物は、実験室的にはエバポレ−タ、工業的にはスプレ−ドライヤ−などを用いて、蒸発乾固して粉末化される。この時の温度は１００℃以下特に８０℃以下が好ましい。高温で蒸発乾固するとポリイミド前駆体組成物の発泡性が極端に低下する。蒸発乾固は、常圧でも、加圧下でも、あるいは減圧下で行ってもよい。 The polyimide precursor solution composition is evaporated to dryness and pulverized using an evaporator in the laboratory and a spray dryer in the industry. The temperature at this time is preferably 100 ° C. or less, particularly preferably 80 ° C. or less. When evaporating to dryness at a high temperature, the foamability of the polyimide precursor composition is extremely lowered. Evaporation to dryness may be performed under normal pressure, under pressure, or under reduced pressure.
グリ−ン体の作成は、例えば、粉末のポリイミド前駆体組成物を室温で圧縮成形する方法、スラリ−溶液として流延乾固する方法、テフロン（登録商標）製などのマイクロ波に不活性な容器へ充填する方法などによって行うことができる。概略均一な状態のグリ−ン体を得ることができれば、発泡時の均一化は達成できる。 The green body is prepared by, for example, a method in which a powdered polyimide precursor composition is compression-molded at room temperature, a method in which it is cast and solidified as a slurry solution, and a microwave inactive to Teflon (registered trademark). It can be performed by a method of filling the container. If a green body having a substantially uniform state can be obtained, uniformization during foaming can be achieved.
ポリイミド前駆体組成物の発泡は、好適にはマイクロ波加熱による加熱によって好適に行うことができる。この際に、一般的には２．４５ＧＨｚで行う。これは日本の国内法（電波法）に基づく。粉末重量当たりのマイクロ波出力を目安とすることが好ましい。これは実験を重ねることによって定義すべきである。例えば、１００ｇ／１ｋＷ程度のマイクロ波を約１分照射すると発泡を開始し、２〜３分で発泡は収束する。
発泡した状態の発泡体は非常に脆いので、直ちにオーブンなどを用いて加熱するのが好適である。加熱は、２００℃程度から徐々に昇温（一応の目安として、１００℃／１０分程度の昇温速度）して行うのが好適である。最終的にはポリイミドのガラス転移温度＋α（１０〜１００℃位）の温度にて５〜６０分間、好適には１０分間程度加熱する。
Foaming of the polyimide precursor composition can be suitably performed by heating by microwave heating. At this time, the operation is generally performed at 2.45 GHz. This is based on Japanese domestic law (Radio Law). It is preferable to use the microwave output per weight of the powder as a guide. This should be defined by experimentation. For example, when microwaves of about 100 g / 1 kW are irradiated for about 1 minute, foaming starts, and foaming converges in 2 to 3 minutes.
Since the foamed foam is very brittle, it is preferable to immediately heat it using an oven or the like. Heating is preferably performed by gradually increasing the temperature from about 200 ° C. (as a guideline, a temperature increase rate of about 100 ° C./10 minutes). Finally, it is heated for 5 to 60 minutes, preferably about 10 minutes at a temperature of polyimide glass transition temperature + α (about 10 to 100 ° C.).
本発明で用いられるポリイミド発泡体は、発泡体セルが均一で細かなものが好ましく、断面積の８０％以上、好ましくは９０％以上の面積が、径が１００〜１５００μｍ、好ましくは１００〜１０００μｍの範囲内の発泡体セルで構成されているものが好ましい。 The polyimide foam used in the present invention preferably has a uniform and fine foam cell, and an area of 80% or more, preferably 90% or more of the cross-sectional area, has a diameter of 100 to 1500 μm, preferably 100 to 1000 μm. Those composed of foam cells within the range are preferred.
本発明で用いられるポリイミド発泡体は、その密度が、好ましくは１〜５０ｋｇ／ｍ3 、より好ましくは３〜２０ｋｇ／ｍ3 、特に好ましくは５〜１５ｋｇ／ｍ3 である。ポリイミド発泡体の密度が１ｋｇ／ｍ3 未満であると、断熱性が著しく低下し、またポリイミド発泡体の密度が５０ｋｇ／ｍ3 超であると、断熱性が密度の上昇とともに低下する。 Polyimide foam for use in the present invention, the density is preferably from 1 to 50 kg / m 3, more preferably 3~20kg / m 3, particularly preferably a 5~15kg / m 3. When the density of the polyimide foam is less than 1 kg / m 3 , the heat insulating property is remarkably lowered, and when the density of the polyimide foam is more than 50 kg / m 3 , the heat insulating property is lowered as the density is increased.
本発明で用いられる熱可塑性樹脂シートを形成する熱可塑性樹脂としては、例えば、ポリアミド６、ポリアミド６６、ポリアミド６・６６共重合、ポリアミド１２などのポリアミド樹脂；ポリアセタール、ポリエチレン、ポリプロピレンなどのポリオレフィン；ポリエチレンテレフタレート、ポリブチレンテレフタレートなどのポリエステル；ポリフェニレンスルフィド、ポリフェニレンエーテル、ポリブタジエン、ポリウレタン、ＡＢＳ樹脂などが挙げられる。これらの中でも、ポリアミド６、ポリアミド６６などのポリアミド樹脂が好ましく、特にポリアミド６が好ましい。
前記熱可塑性樹脂としては、ガラス繊維、炭素繊維、カーボンナノチューブ、タルクなどの無機フィラーなどの強化材が配合された熱可塑性樹脂を用いることができる。
Examples of the thermoplastic resin forming the thermoplastic resin sheet used in the present invention include polyamide resins such as polyamide 6, polyamide 66, polyamide 6.66 copolymer, polyamide 12; polyolefins such as polyacetal, polyethylene, and polypropylene; polyethylene Examples include polyesters such as terephthalate and polybutylene terephthalate; polyphenylene sulfide, polyphenylene ether, polybutadiene, polyurethane, and ABS resin. Among these, polyamide resins such as polyamide 6 and polyamide 66 are preferable, and polyamide 6 is particularly preferable.
As the thermoplastic resin, a thermoplastic resin containing a reinforcing material such as an inorganic filler such as glass fiber, carbon fiber, carbon nanotube, and talc can be used.
本発明の積層体は、ポリイミド発泡体と熱可塑性樹脂シートとをそれぞれ１層ずつ積層した２層構造でもよく、ポリイミド発泡体をコア層としてその両面に熱可塑性樹脂シートを積層した３層構造でもよい。２層構造の積層体の場合、ポリイミド発泡体の厚みは、好ましくは１〜３００ｍｍ、より好ましくは２〜２００ｍｍ、特に好ましくは５〜１５０ｍｍであり、熱可塑性樹脂シートの厚みは、好ましくは０．５〜１０ｍｍ、より好ましくは１〜５ｍｍ、特に好ましくは２〜４ｍｍである。また、３層構造の積層体の場合、ポリイミド発泡体の厚みは、好ましくは１〜３００ｍｍ、より好ましくは２〜１００ｍｍ、特に好ましくは５〜５０ｍｍであり、熱可塑性樹脂シートの厚みは、好ましくは０．５〜１０ｍｍ、より好ましくは１〜５ｍｍ、特に好ましくは２〜４ｍｍであり、ポリイミド発泡体の両面の熱可塑性樹脂シートの厚みは、同じでもよく、異なっていてもよい。 The laminate of the present invention may have a two-layer structure in which a polyimide foam and a thermoplastic resin sheet are laminated one by one, or a three-layer structure in which a polyimide foam is used as a core layer and thermoplastic resin sheets are laminated on both sides thereof. Good. In the case of a laminate having a two-layer structure, the thickness of the polyimide foam is preferably 1 to 300 mm, more preferably 2 to 200 mm, particularly preferably 5 to 150 mm, and the thickness of the thermoplastic resin sheet is preferably 0.00. It is 5 to 10 mm, more preferably 1 to 5 mm, and particularly preferably 2 to 4 mm. In the case of a laminate having a three-layer structure, the thickness of the polyimide foam is preferably 1 to 300 mm, more preferably 2 to 100 mm, particularly preferably 5 to 50 mm, and the thickness of the thermoplastic resin sheet is preferably It is 0.5-10 mm, More preferably, it is 1-5 mm, Most preferably, it is 2-4 mm, The thickness of the thermoplastic resin sheet of both surfaces of a polyimide foam may be the same, and may differ.
而して、本発明のポリイミド発泡体と熱可塑性樹脂シートとの積層体の製造方法を実施するには、まず、上述した熱可塑性樹脂シートのポリイミド発泡体への接合面を、該熱可塑性樹脂の融点以上、好ましくは該熱可塑性樹脂の融点より５℃以上高い温度、より好ましくは該熱可塑性樹脂の融点より１０℃以上高い温度、さらに好ましくは該熱可塑性樹脂の融点より１０〜１００℃高い温度、特に好ましくは該熱可塑性樹脂の融点より３０〜８５℃高い温度に加熱する。
熱可塑性樹脂シートとして、ポリアミド樹脂によって形成されたシートを用いる場合には、該ポリアミド樹脂シートのポリイミド発泡体への接合面を、該ポリアミド樹脂の融点より１０℃以上高い温度に加熱することが好ましく、より好ましくは該ポリアミド樹脂の融点より１５〜８５℃高い温度、さらに好ましくは該ポリアミド樹脂の融点より２０〜８０℃高い温度に加熱する。
熱可塑性樹脂シートのポリイミド発泡体への接合面の加熱温度が、該熱可塑性樹脂の融点より低いと、熱可塑性樹脂シートをポリイミド発泡体に接合することができないか、接合することができても接合強度が低く好ましくない。また、熱可塑性樹脂シートのポリイミド発泡体への接合面の加熱温度が高過ぎると、熱可塑性樹脂の熱劣化を促進し好ましくない。
Thus, in order to carry out the method for producing a laminate of a polyimide foam and a thermoplastic resin sheet according to the present invention, first, the bonding surface of the thermoplastic resin sheet to the polyimide foam is changed to the thermoplastic resin. Higher than the melting point of the thermoplastic resin, preferably higher than the melting point of the thermoplastic resin, more preferably higher than the melting point of the thermoplastic resin, more preferably higher than the melting point of the thermoplastic resin, more preferably higher than the melting point of the thermoplastic resin. Heat to a temperature, particularly preferably 30 to 85 ° C. higher than the melting point of the thermoplastic resin.
When a sheet formed of a polyamide resin is used as the thermoplastic resin sheet, it is preferable to heat the bonding surface of the polyamide resin sheet to the polyimide foam to a temperature higher by 10 ° C. or more than the melting point of the polyamide resin. More preferably, it is heated to a temperature 15 to 85 ° C. higher than the melting point of the polyamide resin, and more preferably 20 to 80 ° C. higher than the melting point of the polyamide resin.
If the heating temperature of the joining surface of the thermoplastic resin sheet to the polyimide foam is lower than the melting point of the thermoplastic resin, the thermoplastic resin sheet cannot be joined to the polyimide foam or can be joined. Bonding strength is low and not preferred. Moreover, when the heating temperature of the joining surface to the polyimide foam of a thermoplastic resin sheet is too high, the thermal deterioration of a thermoplastic resin is accelerated and it is unpreferable.
ポリイミド発泡体への接合面を前記温度に加熱した熱可塑性樹脂シートを、ポリイミド発泡体に接合し、融着することにより、本発明に係る積層体を製造することができる。
熱可塑性樹脂シートとポリイミド発泡体との接合、融着は、例えば、ポリイミド発泡体への接合面を前記温度に加熱した熱可塑性樹脂シートを、ポリイミド発泡体に重ね合わせ、空圧、油圧、水圧などを用いて、好ましくは０．１〜１０ＭＰａ、より好ましくは１〜７ＭＰａの圧力で加圧し、冷却することにより行うことができる。熱可塑性樹脂シートとポリイミド発泡体との接合、融着の際、ポリイミド発泡体は、加熱しておいてもよく、加熱しておかなくてもよいが、ポリイミド発泡体を加熱しておく場合は、熱可塑性樹脂シートの該熱可塑性樹脂の融点程度に加熱しておくのが好ましい。
The laminated body which concerns on this invention can be manufactured by joining the thermoplastic resin sheet which heated the joining surface to a polyimide foam to the said temperature to a polyimide foam, and melt | fusioning it.
Bonding and fusing of a thermoplastic resin sheet and a polyimide foam are performed by, for example, superposing a thermoplastic resin sheet having a bonded surface to the polyimide foam heated to the above temperature on the polyimide foam, air pressure, hydraulic pressure, hydraulic pressure. Etc., preferably 0.1 to 10 MPa, more preferably 1 to 7 MPa. When joining and fusing the thermoplastic resin sheet and the polyimide foam, the polyimide foam may or may not be heated, but when the polyimide foam is heated, The thermoplastic resin sheet is preferably heated to the melting point of the thermoplastic resin.
以下、本発明を実施例により更に詳細に説明するが、本発明は、これらの実施例により何ら制限されるものではない。なお以下の実施例１−６のうち、実施例３−４が本発明の範囲内の実施例である。 EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not restrict | limited at all by these Examples. Note of the following Examples 1-6, Example 3 -4 is an example within the scope of the present invention.
以下の例で記載したポリイミド発泡体、熱可塑性樹脂及び積層体の特性の測定方法及び評価方法は以下のとおりである。
（ポリイミド発泡体の密度の測定）
ＡＳＴＭ Ｄ ３５７４ ＴＥＳＴ Ａに準拠して測定した。
（熱可塑性樹脂の示差熱分析の発熱ピーク温度の測定）
差動型示差熱天秤（ＴＧ−ＤＴＡ）を用い、雰囲気：窒素、温度：常温〜３００℃、昇温速度：２０℃／分により測定した。
（積層体の接合状態の評価）
積層体を目視で観察して、ポリイミド発泡体の融着不良による著しい浮きがなく、融着部のポリイミド発泡体を手で軽く引っ張っても剥がれないものを○、融着部のポリイミド発泡体の一部が剥がれるものを△、融着部のポリイミド発泡体が容易に剥がれるものを×とした。
（積層体の接合強度の評価）
積層体を万能型引張試験機を用いて、ポリイミド発泡体及び熱可塑性樹脂シートの各両端を掴んで１ｍｍ／ｍｉｎの速度で引張り、融着部以外のポリイミド発泡体から破壊したものを○、融着部の一部を含むポリイミド発泡体から破壊したものを△、融着部から破壊したものを×とした。
（積層体の断熱性の評価）
卓上式熱板の温度設定を熱可塑性樹脂シートの該熱可塑性樹脂の融点温度に設定し、積層体を、ポリイミド発泡体側を熱板に向けて熱板に載せる。３分間放置後、熱板上で積層体の熱可塑性樹脂シートを触って、軟化や変化をしなかったものを○、軟化したものを△、変形したものを×とした。
（積層体の耐熱性の評価）
積層体を熱風式乾燥機に入れ、１５０℃の空気中に５００時間暴露し、著しい変形や剥離がないかを調べた。剥離や変形がなかったものを○、部分的に変形や剥離したものを△、全体が変形や剥離したものを×とした。
The measuring method and evaluation method of the characteristics of the polyimide foam, thermoplastic resin and laminate described in the following examples are as follows.
(Measurement of density of polyimide foam)
Measured according to ASTM D 3574 TEST A.
(Measurement of exothermic peak temperature of differential thermal analysis of thermoplastic resin)
A differential type differential thermal balance (TG-DTA) was used, and measurement was performed at atmosphere: nitrogen, temperature: normal temperature to 300 ° C., and heating rate: 20 ° C./min.
(Evaluation of bonding state of laminate)
When the laminate is visually observed, there is no significant float due to poor fusion of the polyimide foam, and it does not peel even if the polyimide foam in the fused part is pulled lightly by hand. A case where a part was peeled off was indicated by Δ, and a case where a polyimide foam at the fused part was easily peeled was indicated by ×.
(Evaluation of bonding strength of laminate)
Using a universal tensile tester, the laminate was gripped at both ends of the polyimide foam and the thermoplastic resin sheet, pulled at a speed of 1 mm / min, and broken from the polyimide foam other than the fused part. What was destroyed from the polyimide foam containing a part of the adhesion part was marked with Δ, and what was broken from the fusion part was marked with ×.
(Evaluation of thermal insulation of laminate)
The temperature setting of the tabletop hot plate is set to the melting temperature of the thermoplastic resin of the thermoplastic resin sheet, and the laminate is placed on the hot plate with the polyimide foam side facing the hot plate. After standing for 3 minutes, the thermoplastic resin sheet of the laminate was touched on the hot plate, and the softened and unchanged items were marked with ◯, the softened items with Δ, and the deformed items with x.
(Evaluation of heat resistance of laminate)
The laminate was placed in a hot air dryer and exposed to air at 150 ° C. for 500 hours to examine whether there was any significant deformation or peeling. The case where there was no peeling or deformation was marked with ◯, the case where it was partially deformed or peeled, and the case where the whole was deformed or peeled, where x.
〔参考例〕ポリイミド発泡体の調製
１ｍ3 のジャケット仕様の攪拌機付反応槽に、５５．５１９ｋｇの２，３，３',４'-ビフェニルテトラカルボン酸二無水物と１５．２０１ｋｇの３，３’，４，４' −ベンゾフェノンテトラカルボン酸二無水物と１３９．７ｋｇのメタノールとを仕込み、反応槽内を窒素置換した後、ジャケット内を９０℃の温水を循環させて加熱し、反応液が９０℃になってから９０分間還流してエステル化反応を行った。その後、反応液を３０℃以下まで冷却した後、反応液に２５．０５２ｋｇのｐ−フェニレンジアミンと０．６２８ｋｇの１，３−ビス（３- アミノプロピル）テトラメチルジシロキサンとを添加した。更に２．８９２ｋｇの1 ，２- ジメチルイミダゾールを添加し、撹拌して反応液を均一な溶液にした。次いで、スプレードライヤーを使用し、前記反応液を乾燥温度が５０℃以下となるように噴霧量を調整しながら乾燥して、発泡ポリイミド前駆体の乾燥粉を得た。次いで、この発泡ポリイミド前駆体乾燥粉の２ｋｇを２８０ｍｍφ×１００ｍｍｔの型枠に充填し、プレス機で加圧してグリーン体を圧縮成形した。得られたグリーン体は４６０ｍｍ×厚み２５ｍｍの寸法であった。このグリーン体をマイクロ波照射装置に入れ、出力１５ｋｗで７．５分間マイクロ波を照射し、発泡ポリイミド前駆体発泡物を得、これを２００℃に昇温されたオーブン中に投入し３８０℃まで昇温した後、室温まで冷却し、これを１００ｍｍ×１００ｍｍ×厚み５ｍｍの大きさに切り出し、ポリイミド発泡体を得た。得られたポリイミド発泡体は緻密で均一な発泡体であり、密度は７．５ｋｇ／ｍ3 あった。
[Reference Example] Preparation of polyimide foam In a 1 m 3 jacketed reactor equipped with a stirrer, 55.519 kg of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 15.201 kg of 3,3 ', 4,4'-Benzophenonetetracarboxylic dianhydride and 139.7 kg of methanol were charged, the inside of the reaction vessel was purged with nitrogen, and then heated by circulating 90 ° C warm water in the jacket, After reaching 90 ° C., the mixture was refluxed for 90 minutes to carry out an esterification reaction. Then, after cooling a reaction liquid to 30 degrees C or less, 25.052 kg of p-phenylenediamine and 0.628 kg of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added to the reaction liquid. Further, 2.892 kg of 1,2-dimethylimidazole was added and stirred to make the reaction solution uniform. Next, using a spray dryer, the reaction solution was dried while adjusting the spray amount so that the drying temperature was 50 ° C. or less, thereby obtaining a dry powder of a foamed polyimide precursor. Next, 2 kg of this dry dried polyimide precursor powder was filled into a 280 mmφ × 100 mmt mold and pressed with a press to compress the green body. The obtained green body had dimensions of 460 mm × thickness 25 mm. This green body is put into a microwave irradiation device, and irradiated with microwaves at an output of 15 kw for 7.5 minutes to obtain a foamed polyimide precursor foam, which is put into an oven heated to 200 ° C. and up to 380 ° C. After heating up, it cooled to room temperature, this was cut out to the magnitude | size of 100 mm x 100 mm x thickness 5mm, and the polyimide foam was obtained. The resulting polyimide foam was a dense and uniform foam with a density of 7.5 kg / m 3 .
〔実施例１〕
ポリイミド発泡体として、参考例で得られたポリイミド発泡体を用い、熱可塑性樹脂シートとして、１００ｍｍ×１００ｍｍ×厚み５ｍｍのポリアミド６からなるシートを用いた。該ポリアミド６の融点は２２０℃であった。
ポリアミド６からなるシートのポリイミド発泡体への接合面を２４０℃に加熱し、これを、２２０℃に加熱しておいたポリイミド発泡体に重ね合わせ、０．５ＭＰａの圧力で加圧し、冷却して、ポリイミド発泡体と熱可塑性樹脂シートとが融着した積層体を得た。
得られた積層体についての接合状態、接合強度、断熱性及び耐熱性の評価結果を下記表１に示す。
[Example 1]
The polyimide foam obtained in the reference example was used as the polyimide foam, and a sheet made of polyamide 6 having a size of 100 mm × 100 mm × thickness 5 mm was used as the thermoplastic resin sheet. The melting point of the polyamide 6 was 220 ° C.
The bonding surface of the sheet made of polyamide 6 to the polyimide foam is heated to 240 ° C., and this is superposed on the polyimide foam heated to 220 ° C., pressurized with a pressure of 0.5 MPa, and cooled. A laminate in which the polyimide foam and the thermoplastic resin sheet were fused was obtained.
Table 1 below shows the evaluation results of the bonding state, bonding strength, heat insulation and heat resistance of the obtained laminate.
〔実施例２〜６〕
実施例１において、熱可塑性樹脂シートを形成する熱可塑性樹脂の種類及び該シートの接合面の温度を下記表１に示すとおり変更した以外は、実施例１と同様にして、積層体をそれぞれ得た。
得られた各積層体についての接合状態、接合強度、断熱性及び耐熱性の評価結果を下記表１に示す。
[Examples 2 to 6]
In Example 1, laminates were obtained in the same manner as in Example 1 except that the type of the thermoplastic resin forming the thermoplastic resin sheet and the temperature of the joining surface of the sheet were changed as shown in Table 1 below. It was.
Table 1 below shows the evaluation results of the bonding state, bonding strength, heat insulating property, and heat resistance of each of the obtained laminates.
〔比較例１〕
宇部興産機械（株）製型締め力３５０トンの射出成形機を用い、金型温度８０℃設定で板状成形品の金型の中に参考例で得られたポリイミド発泡体を入れて、２６０℃で可塑化したポリアミド６（３０％ガラス繊維強化品）を射出プレス法で射出成形した。ポリイミド発泡体とポリアミド６は一体に貼合せた状態になったが、ポリイミド発泡体が射出成形時の射出圧力で圧縮されて潰れてしまい、ポリイミド発泡体の断熱性が著しく損なわれた積層体しか得られなかった。
[Comparative Example 1]
Using an injection molding machine with a clamping force of 350 tons manufactured by Ube Industries Co., Ltd., the polyimide foam obtained in the reference example was placed in a mold of a plate-shaped product at a mold temperature of 80 ° C., and 260 Polyamide 6 (30% glass fiber reinforced product) plasticized at 0 ° C. was injection molded by an injection press method. The polyimide foam and polyamide 6 are in a state of being bonded together, but the polyimide foam is compressed and crushed by the injection pressure at the time of injection molding, so that the heat insulation of the polyimide foam is significantly impaired. It was not obtained.
Claims (2)
A laminate for a heat insulating material around an automobile engine, in which a polyimide foam and a sheet of polyamide 6 (30% glass fiber reinforced product) are directly bonded without using an adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010066015A JP5644151B2 (en) | 2010-03-23 | 2010-03-23 | LAMINATE MANUFACTURING METHOD AND LAMINATE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010066015A JP5644151B2 (en) | 2010-03-23 | 2010-03-23 | LAMINATE MANUFACTURING METHOD AND LAMINATE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011194796A JP2011194796A (en) | 2011-10-06 |
| JP5644151B2 true JP5644151B2 (en) | 2014-12-24 |
Family
ID=44873582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010066015A Expired - Fee Related JP5644151B2 (en) | 2010-03-23 | 2010-03-23 | LAMINATE MANUFACTURING METHOD AND LAMINATE |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5644151B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5861709B2 (en) * | 2011-07-28 | 2016-02-16 | 宇部興産株式会社 | Laminated body and heat insulating material using the same |
| WO2016085984A1 (en) * | 2014-11-25 | 2016-06-02 | Polymer Technologies, Inc. | Foam insulation with thermoformable film coating and process for manufacture |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR900700292A (en) * | 1988-02-05 | 1990-08-13 | 원본미기재 | Laminated polymer sheet |
| JP3272519B2 (en) * | 1993-12-22 | 2002-04-08 | 三井化学株式会社 | Laminated body and method for producing the same |
| JP4110669B2 (en) * | 1999-05-13 | 2008-07-02 | 宇部興産株式会社 | Porous insulating material and laminate thereof |
| JP4752426B2 (en) * | 2005-09-28 | 2011-08-17 | 宇部興産株式会社 | Multilayer foam |
| JP2009012205A (en) * | 2007-07-02 | 2009-01-22 | Tosoh Corp | Composite and composite manufacturing method |
| JP2009269372A (en) * | 2008-05-12 | 2009-11-19 | Toyobo Co Ltd | Polyimide laminated board pasted with metal and printed wiring board |
| JP5245570B2 (en) * | 2008-06-25 | 2013-07-24 | 宇部興産株式会社 | Carbon porous body and method for producing the same |
| JP5055244B2 (en) * | 2008-10-29 | 2012-10-24 | 三井化学株式会社 | Polyimide metal laminate |
-
2010
- 2010-03-23 JP JP2010066015A patent/JP5644151B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011194796A (en) | 2011-10-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101920316B1 (en) | Adhesive for bonding polyimide resins | |
| JPS61219635A (en) | Laminate having improved steam stopping characteristic | |
| JP7016082B2 (en) | Semi-pregs, prepregs, resin composites and their manufacturing methods | |
| JP7566726B2 (en) | Resin composition, cured molded product, fiber-reinforced plastic molding material, fiber-reinforced plastic, fiber-reinforced plastic laminate molded product, and method for producing same | |
| JP2009274284A (en) | Heat-resistant sandwich panel comprising polyimide composite material and its method for manufacturing | |
| WO2011055530A1 (en) | Polyimide foam, polyimide powder mixture, polyimide powder, method for producing polyimide foam, method for producing multilayer molded polyimide foam body, method for producing curved molded polyimide foam body, multilayer molded polyimide foam body, and curved molded polyimide foam body | |
| CN115734871B (en) | Laminates with low dielectric constant and low dissipation factor containing aerogel layers | |
| JP5644151B2 (en) | LAMINATE MANUFACTURING METHOD AND LAMINATE | |
| JP2011218779A (en) | Method for manufacturing laminate of polyimide foam and thermoplastic resin sheet, and laminate | |
| Çakir et al. | Mechanical properties of low‐density heat‐resistant polyimide‐based advanced composite sandwich panels | |
| JP7609635B2 (en) | Fiber-reinforced resin composite and thermoplastic resin foam sheet for fiber-reinforced resin composite | |
| US12049545B2 (en) | Uncured laminate, reinforcing fiber composite material, method for producing uncured laminate, and method for producing reinforcing fiber composite material | |
| JP5310345B2 (en) | Laminated body | |
| WO2022080314A1 (en) | Multilayer polyimide film, metal-clad laminated plate, and method for producing multilayer polyimide film | |
| JP4428034B2 (en) | Foamed polyimide structure and manufacturing method thereof | |
| TWI889804B (en) | Method for producing fiber-reinforced composite | |
| US6814910B2 (en) | Aromatic polyimide foam | |
| JP7524018B2 (en) | Thermoplastic resin expanded beads, thermoplastic resin expanded bead molded product, expanded resin composite, method for producing thermoplastic resin expanded beads, and method for producing thermoplastic resin expanded bead molded product | |
| JP4752426B2 (en) | Multilayer foam | |
| US5043368A (en) | Polyetherimide/epoxy chopped fiber reinforced laminates and the preparation thereof | |
| JP7552681B2 (en) | Manufacturing method of film-like bonding material | |
| EP4190533B1 (en) | Thermoplastic resin foam, thermoplastic resin foam sheet, fiber-reinforced resin composite, method for manufacturing thermoplastic resin foam, thermoplastic resin foam molded article, method for manufacturing thermoplastic resin foam molded article, and foamed resin composite | |
| JP7416332B1 (en) | Carbon fiber base materials, prepregs, porous structures, manufacturing methods thereof, preforms, fiber reinforced resin moldings, sandwich structures, and aircraft components | |
| JPH07118625A (en) | Heat-curable polyimide adhesive composition and bonding with same adhesive composition | |
| CN102061003A (en) | Preparation method of fiber reinforced polyimide foam composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20121226 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130905 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130917 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140218 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140409 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20141007 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20141020 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5644151 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |