Polyamideimide composition

Abstract

To provide a polyamide imide (PAI) composition that can be shaped into a polyamide imide (PAI) film to have both of a high elastic modulus and a high elongation.SOLUTION: A polyamide imide (PAI) composition comprises: polyamide imide (PAI-1) comprising trimellitic acid (TMA) as an acid component and o-tolidinediisocyanate (TODI) as an isocyanate component; and an imide elastomer. The polyamide imide (PAI) composition is shaped into a film having a tensile elongation of 60% or more and a tensile elasticity of 4.5 GPa or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyamideimide (PAI) composition which is formed into a film shape and is preferably used as an intermediate transfer belt, a fixing belt, etc. of a copying machine, a printer, etc.

Background Art

[0002] As an intermediate transfer belt and a fixing belt of a copying machine and a printer that require high speed, a film made of a polyimide-based material such as PAI having excellent heat resistance, mechanical properties, and dimensional stability is widely used. These belts can be obtained, for example, by applying a solution containing PAI to a mold and drying it, and are usually used as a seamless belt made of a PAI film with a thickness of 30 μm to 150 μm.

[0003] As a PAI film used for these belts, a film made of PAI using trimellitic acid (TMA) as an acid component and o-tolidine diisocyanate (TODI) as an isocyanate component is known. A PAI belt made of a PAI film having such a chemical structure is excellent in dimensional stability, heat resistance, and mechanical properties (especially rigidity), and is described as being preferably used for forming an intermediate transfer belt, a fixing belt, etc. of a copying machine, a printer, etc.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, a belt made of PAI using trimellitic acid (TMA) as the acid component and tolylene-2,4-diisocyanate (TODI) as the isocyanate component described in the above patent document has insufficient toughness as a belt, that is, insufficient elongation when formed into a film, and breakage or cracking may occur when the belt is attached to a copying machine and used for a long time. For these reasons, as PAI used as a belt for a copying machine, in addition to having a high elastic modulus (rigidity) when formed into a film, those having a high elongation have been demanded. That is, there has been a demand for a PAI that can achieve both a high elastic modulus and a high elongation, which are in a trade-off relationship.

[0006] Therefore, the present invention solves the above problems, and an object thereof is to provide a PAI composition capable of obtaining a PAI film having both a high elastic modulus and a high elongation when formed into a film.

Means for Solving the Problems

[0007] As a result of intensive research to solve the above problems, it has been found that by using a novel PAI composition having a specific composition and having specific mechanical properties when formed into a film, the above problems can be solved, and the present invention has been completed.

[0008] The present invention is "a polyamideimide (PAI-1) using trimellitic acid (TMA) as the acid component and o-toluidine diisocyanate (TODI) as the isocyanate component, and an imide-based elastomer As a polyimide obtained from a diamine and diphenylsulfone tetracarboxylic dianhydride and, consisting of film being 、 a polyamideimide (PAI) composition characterized in that the tensile elongation is 60% or more and the tensile elastic modulus is 4.5 GPa or more film ".

Effects of the Invention

[0009] By forming the PAI composition of the present invention into a film, a PAI film having both a high elastic modulus and a high elongation can be obtained. Therefore, the PAI belt made of this PAI film can be suitably used as an intermediate transfer belt or a fixing belt of a copying machine or a printer.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described in detail.

[0011] PAI-1 constituting the PAI composition of the present invention can be obtained as a solution, for example, by the following method. That is, it can be obtained by subjecting substantially equimolar amounts of TMA (acid component) and TODI (isocyanate component) to a polymerization reaction in a solvent. The molar ratio of the acid component to the isocyanate component is preferably 1 / 1.00 to 1.05. Here, since the homopolymer consisting only of TMA and TODI tends to be insoluble in the reaction solvent, it is preferable to substitute 10 to 60 mol% of TODI with methylene diphenyl diisocyanate (MDI) and / or toluene diisocyanate (TDI). Note that a part of TMA may be substituted with other acid components. Specifically, if it is 10 mol% or less of TMA, it may be substituted with pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, etc. If this substitution rate exceeds 10 mol%, it may be difficult to achieve both mechanical property values.

[0012] In the polymerization reaction, it is preferable to mix 0.01 to 1 mol% of a basic compound such as 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) or triethylenediamine (DABCO) as a catalyst with respect to TMA. By using such a basic catalyst, a high-viscosity PAI-1 solution can be obtained. These basic catalysts are known as polymerization catalysts during PAI polymerization, but are specifically effective in the polymerization reaction of PAI composed of TMA and TODI.

[0013] There is no restriction on the solvent used in the polymerization reaction, but it is preferable to use an amide-based solvent. Specific examples of the amide-based solvent include N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), etc. These solvents can be used alone or as a mixture. Among these, NMP, DMAc, and their mixtures are preferable. It is preferable that the water content of these polymerization solvents is dehydrated to 100 ppm or less.

[0014] The reaction temperature for carrying out the polymerization reaction is preferably 100 to 200 °C, more preferably 120 to 180 °C. In this reaction, the addition order of the monomer and the solvent is not particularly limited, and any order may be used.

[0015] The solution of PAI-1 constituting the PAI composition of the present invention preferably has a solution viscosity of 10 Pa·s or more and 200 Pa·s or less, and more preferably 80 Pa·s or more and 150 Pa·s or less. Here, the solution viscosity can be confirmed by measuring the rotational viscosity at 30 °C using a DVL-BII type digital viscometer (B-type viscometer) manufactured by Tokimec.

[0016] The concentration of the solution is preferably more than 10% by mass and less than 25% by mass, and more preferably 16% by mass or more and 22% by mass or less.

[0017] The PAI composition of the present invention can be obtained by blending an imide-based elastomer, which is another constituent of the PAI composition of the present invention, into the PAI-1 solution. Here, the "imide-based elastomer" refers to polyimide (PI), polyamide-imide (PAI), polyester-imide, and polyether-imide that are soluble in an amide-based solvent such as NMP and have a tensile elongation of 80% or more when formed into a film.In the present invention, PI is used.

[0018] These imide-based elastomers are well-known polymer compounds and are described in patent documents such as JP-A-08-217874, JP-A-11-21454, JP-A-2014-28921, and JP-A-2013-155329. Therefore, when implementing the present invention, the descriptions in these documents can be referred to. According to additional tests by the present inventors, the tensile elastic modulus of the imide-based elastomers described in these patent documents was all less than 4 GPa.

[0019] The blending ratio of the imide-based elastomer for preparing the PAI composition of the present invention is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, based on the total mass of PAI-1 and the imide-based elastomer. By setting the blending amount of the imide-based elastomer within such a range, it is possible to achieve both mechanical property values in a trade-off relationship of high elongation and high elastic modulus.

[0020] The solution containing the PAI composition of the present invention obtained as described above can be made into a film composed of the PAI composition of the present invention by coating and drying it on a substrate. There is no limitation on the substrate to be used, but metal foils such as copper foil, and organic polymer films such as polyester film and polyimide film can be preferably used. Further, the solution containing the PAI composition of the present invention can be made into a seamless belt composed of a PAI film by coating it on a cylindrical mold, drying it, and then demolding it. In addition, as the drying conditions for obtaining a film from the PAI composition solution, it is preferable to pre-dry at a temperature of 50 to 180°C and then further dry at a temperature of 200 to 300°C. Also, there is no limitation on the thickness of the formed PAI film, but it is usually about 1 to 200 μm.

[0021] The PAI composition of the present invention needs to have a tensile elongation of 60% or more and a tensile modulus of 4.5 GPa or more when formed into a film, and more preferably a tensile elongation of 70% or more and a tensile modulus of 4.8 GPa or more. By doing so, for example, it can be used as a belt for a copying machine that achieves both rigidity and toughness. The modulus of elasticity and elongation of the PAI film can be confirmed by measuring in accordance with JIS K7127:1999.

Examples

[0022] Hereinafter, the present invention will be specifically described based on examples, but it is not limited by these examples.

[0023] <Reference Example 1> (Preparation of PAI-1) In a glass reaction vessel, under a nitrogen atmosphere, 1.00 mol of TMA, 0.82 mol of TODI, 0.20 mol of TDI, and 0.001 mol of DBU were charged together with dehydrated NMP (moisture content 80 ppm), and the temperature was raised to 150 °C with stirring and reacted for 5 hours to obtain a "PAI-1a" solution with a PAI solid content concentration of 18% by mass.

[0024] <Reference Example 2> (Preparation of PAI-1) A "PAI-1b" solution with a PAI solid content concentration of 18% by mass was obtained in the same manner as in Reference Example 1, except that "0.82 mol of TODI, 0.20 mol of TDI" was changed to "0.61 mol of TODI, 0.40 mol of TDI".

[0025] <Reference Example 3> (Preparation of imide-based elastomer) An imide-based elastomer (E-1) was prepared in accordance with the description of Example 3 in JP-A-2014-28921. That is, into a glass reaction vessel, under a nitrogen atmosphere, 0.70 mol of TMA, 0.30 mol of dimer acid (manufactured by Croda Japan Co., Ltd., trade name: PRIPOL1009), and 1.00 mol of MDI were charged together with dehydrated NMP (water content: 80 ppm) so that the solid content concentration as polyamideimide was 18% by mass, and the mixture was reacted at 120°C for 2 hours with stirring. 0.01 mol of DBU was added, the temperature was raised to 180°C, and the mixture was reacted for 3 hours to obtain an imide-based elastomer (E-1) solution composed of polyamideimide.

[0026] <Reference Example 4> (Preparation of imide-based elastomer) An imide-based elastomer (E-2) was prepared in accordance with the description of Example 1 in JP-A-2013-155329. That is, into a glass reaction vessel equipped with a Dean-Stark trap and a condenser, under a nitrogen atmosphere, 0.11 mol of dimer diamine (manufactured by Croda Japan Co., Ltd., trade name: PRIAMINE1074), 0.11 mol of diphenylsulfone tetracarboxylic dianhydride, 0.012 mol of pyridine, and DMAc were placed, the temperature was raised to 200°C over 2 hours, and water was removed from the system using the Dean-Stark trap. After holding at the same temperature for 3 hours, the mixture was allowed to cool to obtain a solution of an imide-based elastomer (E-2) composed of polyimide with a solid content concentration of 18% by mass.

[0027] < Reference Example 5 > The PAI-1a solution and E-1 were mixed at 30°C with stirring to obtain a PAI composition solution (solid content concentration: 18% by mass) composed of 90% by mass of PAI-1a and 10% by mass of E-1. This PAI composition solution was applied onto a polyester film, dried at 80°C for 10 minutes and then at 130°C for 10 minutes, and the coating film was peeled off from the polyester film. Thereafter, this coating film was sandwiched between a metal frame and dried at 290°C for 60 minutes under a nitrogen gas atmosphere to obtain a PAI film with a thickness of 40 μm. Table 1 shows the results of measuring the elastic modulus and elongation of the obtained PAI film in accordance with JIS K7127:1999.

[0028] <Example 3 , 6, Reference Examples 6 to 8 > Except that the types and compounding ratios of PAI-1 and imide-based elastomers were as described in Table 1, Reference Example 5 In the same manner, after obtaining a PAI composition solution (solid content concentration: 18% by mass), a PAI film with a thickness of 40 μm was obtained using this composition solution. The elastic modulus and elongation of the obtained PAI film were Reference Example 5 Measured in the same manner as, and the results are shown in Table 1.

[0029] <Comparative Examples 1 and 2> Using only the PAI-1a solution (Comparative Example 1) or only the PAI-1b solution (Comparative Example 2), a PAI film with a thickness of 40 μm was obtained in the same manner as in Example 1. The elastic modulus and elongation of the obtained PAI film were measured in the same manner as in Example 1, and the results are shown in Table 1.

[0030]

Table 1

[0031]

Table 1

Industrial Applicability

[0032] The film made of the PAI composition of the present invention can be suitably used as a seamless PAI belt, as an intermediate transfer belt or a fixing belt of a copying machine or a printer.

Claims

【Claim 1】 A polyamideimide (PAI-1) film using trimellitic acid (TMA) as an acid component and o-tolidine diisocyanate (TODI) as an isocyanate component, and a polyimide obtained from a dimer diamine and diphenylsulfone tetracarboxylic dianhydride as an imide-based elastomer, wherein the film has a tensile elongation of 60% or more and a tensile elastic modulus of 4.5 GPa or more. A polyamideimide (PAI) composition film characterized by this.

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