JP2005146077A - Fluoropolyimide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polyimide having low dielectric constant as well as excellent properties inherent in polyimides. <P>SOLUTION: A polyamic acid is provided, being obtained by reaction between 2,2-bis(4-aminophenyl)-hexadecafluorooctane and an aromatic tetrabasic acid dianhydride. The polyimide in filmy form is obtained by dissolving the polyamic acid in a solvent followed by coating a base with the resultant solution and then drying and heating. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polyimide having a low dielectric constant and excellent mechanical, thermal and electrical properties.

Conventionally, polyimide has excellent properties in terms of mechanical properties, chemical resistance, flame retardancy, electrical properties, etc. in addition to its excellent heat resistance, so molding materials, composite materials, electrical / electronic parts, etc. It is widely used in such fields. In recent years, the development of microelectronics has been remarkable in the field of electrical and electronic components. In particular, high-speed transmission of signals is indispensable for large computers due to the use of multilayer circuit boards, etc. However, if the dielectric constant of the substrate material is large, signal transmission is delayed and becomes an obstacle to speeding up. Polyimide is used for an interlayer insulating film having a multilayer wiring structure. For these reasons, the necessity of lowering the dielectric constant has been highlighted in addition to the excellent insulating properties of conventional polyimides.
JP 05-98002 A Japanese Patent Laid-Open No. 06-340808 Japanese Patent Laid-Open No. 11-35684

  An object of the present invention is to provide a polyimide having a low dielectric constant in addition to the excellent properties inherent in polyimide.

  The inventors of the present invention have completed the present invention as a result of intensive studies in order to solve the above problems. That is, the present invention

(1) Formula 1

A polyamic acid obtained by reacting an amine component represented by the following with an aromatic tetrabasic acid dianhydride,
(2) A composition containing the polyamic acid according to (1) and a solvent,
(3) a polyimide formed by imidizing the polyamic acid described in (1) above,
(4) It is related with the film obtained by apply | coating the composition of the said Claim 2 to a base material, and heating.

The polyimide of the present invention obtained from the polyamic acid of the present invention has a low dielectric constant in addition to the excellent properties inherent in polyimide, and is extremely useful as an interlayer insulating material for a multilayer wiring structure.

  The polyamic acid of the present invention can react an amine component represented by the above formula (1) with an aromatic tetrabasic acid dianhydride. Moreover, when manufacturing the polyamic acid of this invention, you may use together other diamine as an amine component other than the compound of Formula (1). Other aromatic diamines include 4,4′-diaminodiphenylpropane, diaminodiphenylpropanes such as 3,4′-diaminodiphenylpropane; 4,4 ′-[1,3-phenylenebis (1-methylidene)] Bisanilines such as bisaniline and 4,4 ′-[1,4-phenylenebis (1-methylidene)] bisaniline; phenylenediamines such as p-phenylenediamine, m-phenylenediamine and chloro-p-phenylenediamine; Diaminodiphenyl ethers such as 4′-diaminodiphenyl ether, 2,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether; 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane Diaminodipheny Methanes; diaminodiphenyl sulfides such as 4,4′-diaminodiphenyl sulfide and 3,4′-diaminodiphenyl sulfide; diaminodiphenyl sulfones such as 4,4′-diaminodiphenyl sulfone and 3,4′-diaminodiphenyl sulfone Diaminonaphthalenes such as 1,5-diaminonaphthalene; 3,3′-dimethylbenzidine, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3′-dichlorobenzidine, 2,2′-dichloro; Benzidines such as benzidine and 3,3 ′, 5,5′-tetrachlorobenzidine; 2,4-bis (β-amino-t-butyl) toluene, bis (p-β-amino-t-butylphenyl) ether Etc. can be mentioned. When another diamine component is used in combination, the proportion of the compound of formula (1) in the amine component is preferably 70 mol% or more.

  The aromatic tetrabasic acid dianhydride is not particularly limited as long as it is a dianhydride of a compound having a structure in which four carboxyl groups are bonded to an aromatic ring. For example, 2,3,3 ′, 4′-biphenyltetra Carboxylic dianhydride, pyromellitic dianhydride; 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5 Naphthalenetetracarboxylic dianhydride such as 1,6-naphthalenetetracarboxylic dianhydride; 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyl Biphenyltetracarboxylic dianhydride such as tetracarboxylic dianhydride; 2,3,4,5-thiophenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) Lopanic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride, 2,5,6,2 ′, 5 ′, 6′-hexafluoro-3,3 ′ , 4,4′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfonic acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, and the like. Biphenyltetracarboxylic dianhydride is preferred. These aromatic tetrabasic acid dianhydrides can be used alone or in combination of two or more. In the present invention, the use ratio of the aromatic tetrabasic acid dianhydride and the amine component is usually 0.95 to 1.05 mol, preferably 0.98 to 1.03 mol, with respect to 1 mol of the former. If it is out of this range, there is a possibility that the characteristics are deteriorated due to the loss of the balance of the molar ratio, and the viscosity is also affected, which may make handling difficult.

The polyamic acid of the present invention can be prepared, for example, as follows.
First, an aromatic tetrabasic acid dianhydride and an amine component of the formula (1) are mixed in a solvent at room temperature and reacted at 40 to 80 ° C. with stirring for 8 to 15 hours. The polyamic acid of the present invention can be obtained by removing the solvent from the obtained polyamic acid-containing solution. In addition, when this solution is usually used as it is as a varnish for obtaining the film of the present invention, the solution is cooled to room temperature and then filtered through a filter such as a PTFE (poly (tetrafluoroethylene)) membrane under nitrogen pressure. To obtain the desired varnish.

  As the solvent for producing the polyamic acid, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, dimethyl sulfone, sulfolane, tetramethylene sulfoxide, dimethylimidazolidinone, Aprotic polar solvents such as hexamethylphosphoramide are suitable. These solvents can be used alone or in combination of two or more. The amount of the solvent used is not particularly limited as long as the reaction proceeds, but when considering the use as a varnish, the solid content concentration in the composition described below is usually about 2 to 50% by weight. It is good to use for.

The polyamic acid composition of the present invention contains the polyamic acid of the present invention and a solvent. As the solvent, the above solvent can be used. Various additives can be added to the polyamic acid composition of the present invention, for example, organic or inorganic pigments, dyes, leveling agents, antifoggants, antifading agents, antihalation agents, fluorescent whitening agents, surface active agents. Agents, plasticizers, flame retardants, antioxidants, fillers, antistatic agents, antifoaming agents, flow regulators, imidation catalysts such as γ-butyrolactone and pyridine, γ-valerolactone and pyridine, benzoic acid, m-hydroxy Imido accelerators such as benzoic acid, p-hydroxyphenylacetic acid, p-hydroxybenzenesulfonic acid, isoquinoline, (azeotropic) dehydrating agents such as toluene, orthodichlorobenzene, nitrobenzene, acetic anhydride / pyridine, retarder, light stability Agents, photocatalysts, fungicides, antibacterial agents, low dielectric materials, conductors, magnetic materials, layered minerals, thermal decomposable compounds, etc., especially catalysts (and imides) If an accelerating agent) or a dehydrating agent is added, subsequent imidization is promoted, and a polyimide film can be obtained under relatively mild conditions.
The composition of the present invention can be obtained by uniformly mixing the above components at a predetermined ratio. Moreover, the solution at the time of obtaining the polyamic acid of this invention can be made into the composition of this invention as it is.

The film of the present invention is coated with the composition (varnish) of the present invention on a substrate so as to have a desired imide film thickness, usually 10-30 μm, and dried at 50-150 ° C. for 5-180 minutes to form a polyamic acid film. It is prepared and then imidized by thermal treatment at 200 to 500 ° C. for 0.5 to 5 hours under a nitrogen stream to obtain the polyimide of the present invention.
The substrate is not particularly limited as long as it can withstand the above heat treatment, such as a glass substrate, copper foil, aluminum foil, stainless steel substrate, drum, endless belt, etc. can get.
The thus obtained film of the present invention has an average fluorine content of 20 to 40% by weight and a low dielectric constant.

  The film of the present invention has excellent mechanical properties, chemical resistance, flame retardancy, electrical characteristics, etc. in addition to heat resistance, so it can be widely used in the fields of electrical and electronic parts. is there. Specifically, it can be used for an interlayer insulating film having a multilayer wiring structure.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1
In a four flask equipped with a dry nitrogen gas inlet tube, a cooler, a thermometer, and a stirrer, 6.74 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter referred to as BPDA) and 2,2- Bis (4-aminophenyl) -hexadecafluorooctane (hereinafter abbreviated as APFO) 13.30 g is thoroughly mixed in a powder state, and 80 g of N, N-dimethylacetamide (hereinafter referred to as DMAc) is added thereto, and at room temperature for 17 hours, The mixture was stirred at 40 to 45 ° C. for 8 hours. After the reaction, the mixture is allowed to cool to room temperature, filtered through a poly (tetrafluoroethylene) (hereinafter referred to as PTFE) membrane (3 μm) under nitrogen pressure, and an almost colorless transparent varnish having a solid concentration of 20% by weight (the composition of the present invention). Product).

Example 2
BPDA 6.70 g and APFO 13.30 g are well mixed in a powdered state in a four flask equipped with a dry nitrogen gas inlet tube, a cooler, a thermometer, and a stirrer, and DMAc 56 g and N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 24 g. And stirred at 40-45 ° C. for 8 hours. After the reaction, the mixture was allowed to cool to room temperature, and filtered through a PTFE membrane (3 μm) under nitrogen pressure to obtain an almost colorless transparent varnish (composition of the present invention) having a solid concentration of 20% by weight.

Example 3
APFO 19.95 g was weighed into a four flask equipped with a dry nitrogen gas inlet tube, a cooler, a thermometer, and a stirrer, 49 g of DMAC and 21 g of NMP were added and dissolved, and 10.05 g of BPDA was added thereto, and 70-75 Stir at 15 ° C. for 15 hours. After the reaction, the mixture was allowed to cool, and when it reached room temperature, it was filtered through a PTFE membrane (3 μm) under nitrogen pressure to obtain an orange varnish (composition of the present invention) having a solid concentration of 30% by weight. Viscosity (25 ° C.): 16 mPa · s

Example 4
Weigh 21.84 g of APFO in a four-flask equipped with a dry nitrogen gas inlet tube, a cooler, a thermometer, and a stirrer and dissolve it in 49 g of DMAC and 21 g of NMP. Then, pyromellitic dianhydride is used instead of BPDA. (Hereinafter referred to as PMDA) 8.16 g was added and stirred at 70 to 80 ° C. for 21 hours to obtain a brown varnish. When it was allowed to cool to room temperature, it was filtered through a PTFE membrane (3 μm) under nitrogen pressure to obtain a transparent varnish (composition of the present invention) having a solid content concentration of 30% by weight. Viscosity (25 ° C.): 13 mPa · s

Example 5
Mix well with 6.29 g of 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) and 13.71 g of AFPO in a four-flask equipped with a dry nitrogen gas inlet tube, a cooler, a thermometer, and a stirrer. Then, 56 g of DMAc and 24 g of NMP were added thereto, and the mixture was stirred at 30 to 50 ° C. for 15 hours. Since insoluble matter remained, 33.3 g of NMP was further added and reacted at 60 ° C. for 15 hours. After the reaction, the mixture was allowed to cool to room temperature, and filtered through a PTFE membrane (3 μm) under nitrogen pressure to obtain a reddish brown transparent varnish (composition of the present invention) having a solid concentration of 15% by weight.

Claims (5)

Following formula (1)

A polyamic acid obtained by reacting an amine represented by the following formula with an aromatic tetrabasic dianhydride. A composition comprising the polyamic acid of claim 1 and a solvent. A polyimide obtained by imidizing the polyamic acid according to claim 1. The film obtained by apply | coating the composition of Claim 2 to a base material, and heating. An electric or electronic material comprising the film according to claim 4.