Fluorine-containing polymer composition

Details Fluorine-containing polymer composition Fluorine-containing polymer composition

1998-03-10

2001-01-16

Seidleck, James J. (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

At least one aryl ring which is part of a fused or bridged...

C524S462000, C524S544000, C524S265000, C526S245000, C526S246000, C526S247000, C526S255000, C428S421000, C428S422000

Reissue Patent

active

RE037022

ABSTRACT:

DETAILED DESCRIPTION OF THE INVENTION
1. Field of the Invention
The present invention relates to a fluorine-containing polymer composition suitable for coating, etc.
2. Prior Art
A polymer having a fluorine-containing aliphatic cyclic structure and a functional group such as a carboxyl group, a hydroxyl group, a silyl group, an amino group, a maleimide group or a nitrile group, has been proposed to improve the adhesion to various substrates or the heat resistance of the polymer having a fluorine-containing aliphatic cyclic structure (Japanese Unexamined Patent Publication No. 226177/1992 or No. 56936/1994).
However, such functional groups are usually introduced at the terminals of the polymer molecules or at the terminals of side chains of the polymer molecules and constitute associable groups in an aprotic fluorine-containing solvent, thus leading to a problem such that when the polymer having a fluorine-containing aliphatic ring structure and such a functional group, is dissolved in an aprotic fluorine-containing solvent, the viscosity of the solution tends to be remarkably high, and the solution undergoes gelletion to lose the fluidity. Therefore, filtration or coating of such a solution tends to be difficult.
A polymer having a functional group and a fluorine-containing aliphatic cyclic structure has excellent properties such as low permitivity, low water-absorptivity, heat resistance and chemical resistance, it is practically applied to a semiconductor element as e.g. an insulating material or a moisture proof coating. In such a case, a solution of the polymer having a functional group and a fluorine-containing aliphatic cyclic structure, is spin-coated on a wafer, and then the solvent is removed by evaporation to form a coating film, whereby smoothness of the coating film is questionable. Namely, there is a problem that due to the presence of associable groups in the evaporation process of the solvent, the surface of the coating film tends to be irregular and is likely to form a so-called orange peel surface.
PROBLEM TO BE SOLVING BY THE PRESENT INVENTION
The object of the present invention is to solve the above-mentioned drawbacks of the prior art.
MEANS FOR SOLVING THE PROBLEM
The present invention is a fluorine-containing polymer composition having a polymer having a functional group and a fluorine-containing aliphatic cyclic structure (hereinafter referred to simply as polymer A) dissolved in a solvent mixture of an aprotic fluorine-containing solvent and a protic fluorine-containing solvent.
In the present invention, an associable group is an atomic group consisting of a least two atoms and having a monovalent radical bond, and the interaction (attraction force) of such atomic groups is larger than their affinity to the aprotic fluorine-containing solvent, whereby a plurality of such atomic groups are likely to get together (associate). With a fluorine-containing polymer having such an associable group, a phenomenon such as gelletion or insolubilization is observed in an aprotic fluorine-containing solvent. Even if it is soluble, the viscosity tends to be high as compared with a fluorine-containing polymer having no associable group.
By using a solvent mixture of an aprotic fluorine-containing solvent and a protic fluorine-containing solvent, the protic fluorine-containing solvent will solvate at associated sites, whereby the association will be dissolved, and polymer A will disperse in the solvent at a molecular level. As a result, it becomes possible to prevent gelletion or reduction of the viscosity of the solution. It is believed that accordingly, it becomes easy to carry out precision filtration of the solution of polymer A or to control the reaction for introducing a functional group to the polymer having a fluorine-containing aliphatic cyclic structure.
As the polymer having a fluorine-containing aliphatic cyclic structure, the one obtainable by polymerizing a monomer having a fluorine-containing cyclic structure, or a polymer having a cyclic structure on its main chain, which is obtainable by cyclic polymerization of a fluorine-containing monomer having at least two polymerizable double bonds, may widely be exemplified including those which are known or well known.
The polymer having a cyclic structure on its main chain, which is obtainable by cyclic polymerization of a fluorine-containing monomer having at least two polymerizable double bonds, is known, for example, by Japanese Unexamined Patent Publication No. 238111/1988 or No. 238115/1988. Namely, it can be prepared by homopolymerization of a monomer such as perfluoro(allylvinyl ether) or perfluoro(butenylvinyl ether), or by copolymerization thereof with a radical polymerizable monomer such as tetrafluoroethylene.
Further, the polymer having a cyclic structure on its main chain, which is obtainable by polymerizing a monomer having a fluorine-containing cyclic structure, is known, for example, by Japanese Examined Patent Publication No. 18964/1988. Namely, it can be obtained by homopolymerization of a monomer having a fluorine-containing cyclic structure such as perfluoro(2,2-dimethyl-1,3-dioxole), or by copolymerization thereof with a radical polymerizable monomer such as tetrafluoroethylene.
Otherwise, it may be a polymer obtainable by copolymerizing a monomer having a fluorine-containing cyclic structure such as perfluoro(2,2-dimethyl-1,3-dioxole) with a fluorine-containing monomer having at least two polymerizable double bonds, such as perfluoro(butenylvinyl ether).
Another monomer which can be copolymerized together with the above tetrafluoroethylene or in place of tetrafluoroethylene, is not particularly limited so long as it is a monomer having radical polymerizability, and a fluorine-containing type, a hydrocarbon type, etc. can widely be exemplified.
For example, a perfluoroalkylvinyl ether such as perfluoromethylvinyl ether or perfluoropropylvinyl ether, a perfluorovinyl ether containing a functional group such as a carboxylic acid group or a sulfonic acid group, or a fluorine-containing unsaturated hydrocarbon such as vinylidene fluoride, vinyl fluoride or chlorotrifluoroethylene, may suitably be used.
As the polymer having a fluorine-containing aliphatic cyclic structure, a polymer having the cyclic structure on its main chain is suitable for use. However, from the viewpoint of the transparency, mechanical properties, etc., the one containing at least 20% of repeating units having the cyclic structure, based on the total number of repeating units, is preferred. More preferred is the one containing at least 40%.
The role of polymer A in the present invention is to improve the adhesion to various substrates of the polymer having the fluorine-containing aliphatic cyclic structure and to improve the mechanical strength of the polymer by the crosslinked structure formed by the reaction of the functional groups to one another, by itself or in combination with a coupling agent. Further, it also plays an important role to uniformly disperse various inorganic fillers or colorants in polymer A without flocculation.
For example, there is a coupling group of the formula —MR
1
n-a
R
2
a
wherein M is selected from Si, Ti, Zr, Hf, Th and Al, R
1
is selected from a halogen group, a hydroxyl group, an amino group and —OR
3
(wherein R
3
is a monovalent organic group), R
2
is a monovalent organic group, n is 2 or 3, and a is selected from 0, 1 and 2 (provided that when n is 2, a is selected from 0 and 1). Such a coupling group contains —MR
1
as a group highly reactive with an inorganic substrate, whereby an excellent adhesion is believed to be obtained.
Here, preferred examples of R
1
include a halogen atom such as chlorine or fluorine, a hydroxyl group, an alkoxy group, an alkoxy-substituted alkoxy group, a hydroxyalkyloxy group, an acyloxy group, an aminoxy group, a ketoxime group, an amino group and an amide group.
Especially when the stability of the composition, the reactivity with an organic substrate, the influence of a by-product by the reaction, etc. are taken into consideration, an alkoxy group

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