WO1997015541A1 - CYCLIC ALPHA-PERFLUORO-DI-p-XYLYLENES FOR USE IN THE FORMATION OF LOW DIELECTRIC CONSTANT ALPHA-PERFLUORO-p-XYLYLENE POLYMERS - Google Patents

CYCLIC ALPHA-PERFLUORO-DI-p-XYLYLENES FOR USE IN THE FORMATION OF LOW DIELECTRIC CONSTANT ALPHA-PERFLUORO-p-XYLYLENE POLYMERS Download PDF

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Publication number
WO1997015541A1
WO1997015541A1 PCT/US1996/017030 US9617030W WO9715541A1 WO 1997015541 A1 WO1997015541 A1 WO 1997015541A1 US 9617030 W US9617030 W US 9617030W WO 9715541 A1 WO9715541 A1 WO 9715541A1
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WIPO (PCT)
Prior art keywords
perfluoro
xylylenes
cyclic
dielectric constant
alpha
Prior art date
Application number
PCT/US1996/017030
Other languages
French (fr)
Inventor
William F. Beach
John Wary
Roger A. Olson
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Specialty Coating Systems, Inc.
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Filing date
Publication date
Application filed by Specialty Coating Systems, Inc. filed Critical Specialty Coating Systems, Inc.
Publication of WO1997015541A1 publication Critical patent/WO1997015541A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/025—Polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
    • C07C23/18—Polycyclic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C07C25/22—Polycyclic aromatic halogenated hydrocarbons with condensed rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/342—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3424—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms non-conjugated, e.g. paracyclophanes or xylenes

Definitions

  • Parylene conformal polymer coatings are obtained from their associated parylene dimers by means of a well-known vapor deposition process in which the dimer is vaporized, pyrolized, i.e. cleaved into a monomer molecules deposit and polymerize into a thin film onto a substrate disposed within the vacuum chamber. The process occurs according to the following reaction:
  • Parylene AF4 polymer coatings which are derived from the AF4 dimer by the vapor deposition process have a very high melting temperature (about 500° C), and a relatively low dielectric constant (about 2.3). These characteristics make parylene AF4 ideally suite for a variety of applications within the electronics industry. While Parylene AF4 has a relatively low dielectric constant, which is desirable in almost all electronics applications, thee is nevertheless a continuing need in the electronics industry for coating and/or dielectric materials having still lower dielectric constants.
  • the instant invention provides a plurality of cyclic ⁇ -perfluoro-di-p-xylylenes which are believed to be effective in producing parylene polymer films having equal, if not better, dielectric characteristics, i.e. lower dielectric constant, than the basic AF4 polymer, More specifically, the instant invention provides a first group of cyclic ⁇ -perfluoro-di-p-xylylenes having the structure:
  • the invention still further provides a second group of cyclic ⁇ -perfluoro-di-p-xylylenes having the structure:
  • the selected substitute groups are believed to provide the resulting polymer films with desirable dielectric characteristics.
  • cyclic ⁇ -perfluoro-di-p-xylylenes for use in the formation of ⁇ -perfluoro-p-xylylene polymer films having highly desirable dielectric properties, i.e. low dielectric constant.
  • the instant invention provides cyclic ⁇ -perfluoro-di-p-xylylenes which are effective for producing ⁇ -perfluoro-di-p-xylylene polymer film having highly desirable dielectric properties, i.e. low dielectric constants. More specifically, the instant invention provides a first group of cyclic ⁇ -perfluoro-di-p-xylylenes having the structure:
  • the invention further provides a second group of cyclic ⁇ -perfluoro-di-p-xylylenes having the structure:
  • the basic cyclic ⁇ -perfluoro-di-p-xylylene i.e. the parylene AF4 dimer
  • the basic cyclic ⁇ -perfluoro-di-p-xylylene i.e. the parylene AF4 dimer
  • the parylene AF4 dimer is well known in the art, and can be readily produced by methods known in the art.
  • the U.S. Patent to Dolbeir No. 5,210,341 describes a method for producing the AF4 dimer.
  • the methods of producing the above-described, ring-substituted AF4 dimers are not critical to the instant invention, as such methods could be implemented by those skilled in the art.
  • the instant invention provides highly desirable cyclic ⁇ -perfluoro-di-p-xylylenes which are effective for the production of a-perfluoro-p-xylylene polymer films having low dielectric constants.
  • the instant invention is believed to represent a significant advancement in the art which has substantial commercial merit.

Abstract

Cyclic α-perfluoro-di-p-xylylenes having the structure (I), wherein G is an aromatic nuclear substituent group selected from the group consisting of chlorine and fluorine (m = 4), and perfluoroalkyl groups having the formula CnF2n+1 (m = 1 to 4), are effective for the production of low dielectric constant α-perfluoro-p-xylylene polymer films.

Description

CYCLIC ALPHA-PERFLUORO-DI-p-XYLYLENES FOR USE IN THE FORMATION OF LOW DIELECTRIC CONSTANT ALPHA-PERFLUORO-p-XYLYLENE
POLYMERS
Background and Summary of the Invention
The instant invention relates to poly-p-xylylene (Parylene) polymers, and more particularly to a plurality of unique, low dielectric constant α-perfluoro-p-xylylene polymers which are formed from their associated cyclic α-perfluoro-di-p-xylylenes.
The outstanding physical properties of the poly-p-xylylene (Parylene) polymer family, including their ability to conformally coat objects of varied geometric shape, have prompted extensive coating applications within the automotive, electronics, and medical industries.
Parylene is a generic term used to describe a class of poly-p-xylylene polymers which are derived from a dimer having the structure:
Figure imgf000003_0001
wherein X is typically a hydrogen. Parylene conformal polymer coatings are obtained from their associated parylene dimers by means of a well-known vapor deposition process in which the dimer is vaporized, pyrolized, i.e. cleaved into a monomer molecules deposit and polymerize into a thin film onto a substrate disposed within the vacuum chamber. The process occurs according to the following reaction:
Figure imgf000003_0002
Although thee polymers have excellent thermal and chemical stability, the presence of -CH2- groups adjacent to the aromatic ring provide potentially vulnerable sites for atmospheric attack. In order to strengthen these weak molecular bonds, it has been found desirable to replace the active hydrogen atoms with a more stable substituent group, such as fluorine, resulting in α-perfluoro-di-p-xylylene, otherwise referred to as Parylene AF4 dimer. The AF4 dimer has the structure:
Figure imgf000004_0002
It is known that Parylene AF4 polymer coatings which are derived from the AF4 dimer by the vapor deposition process have a very high melting temperature (about 500° C), and a relatively low dielectric constant (about 2.3). These characteristics make parylene AF4 ideally suite for a variety of applications within the electronics industry. While Parylene AF4 has a relatively low dielectric constant, which is desirable in almost all electronics applications, thee is nevertheless a continuing need in the electronics industry for coating and/or dielectric materials having still lower dielectric constants.
Accordingly, the instant invention provides a plurality of cyclic α-perfluoro-di-p-xylylenes which are believed to be effective in producing parylene polymer films having equal, if not better, dielectric characteristics, i.e. lower dielectric constant, than the basic AF4 polymer, More specifically, the instant invention provides a first group of cyclic α-perfluoro-di-p-xylylenes having the structure:
Figure imgf000004_0001
wherein G is an aromatic nuclear substituent group selected from the group consisting of fluorine and chlorine, and further wherein m=4.
The invention still further provides a second group of cyclic α-perfluoro-di-p-xylylenes having the structure:
Figure imgf000005_0001
wherein G is an aromatic number substituent group selected from the group consisting of perfluoroalkyl groups having the formula CnF2n+1 for n=1, 2, 3 . . . , and further wherein m=1 to 4.
The selected substitute groups are believed to provide the resulting polymer films with desirable dielectric characteristics.
Accordingly, among the objects of the instant invention are the provision of cyclic α-perfluoro-di-p-xylylenes for use in the formation of α-perfluoro-p-xylylene polymer films having highly desirable dielectric properties, i.e. low dielectric constant.
Other objects, features and advantages of the invention shall become apparent as the description thereof process when considered in connection with the accompanying illustrative drawings.
Description of the Preferred Embodiment
As will hereinafter be more fully described, the instant invention provides cyclic α-perfluoro-di-p-xylylenes which are effective for producing α-perfluoro-di-p-xylylene polymer film having highly desirable dielectric properties, i.e. low dielectric constants. More specifically, the instant invention provides a first group of cyclic α-perfluoro-di-p-xylylenes having the structure:
Figure imgf000006_0001
wherein G is an aromatic nuclear substituent group selected from the group consisting of chlorine and fluorine, and further wherein m=4.
The invention further provides a second group of cyclic α-perfluoro-di-p-xylylenes having the structure:
Figure imgf000006_0002
wherein G is an aromatic nuclear substituent group selected from the group consisting of perfluoroalkyl groups having the formula CnF2n+ 1, for n=1, 2, 3, . . ., and further wherein m=1 to 4, inclusive.
The basic cyclic α-perfluoro-di-p-xylylene, i.e. the parylene AF4 dimer, is well known in the art, and can be readily produced by methods known in the art. For example, the U.S. Patent to Dolbeir No. 5,210,341 describes a method for producing the AF4 dimer. The methods of producing the above-described, ring-substituted AF4 dimers are not critical to the instant invention, as such methods could be implemented by those skilled in the art.
The ring-substituted cyclic α-perfluoro-di-p-xylylenes as described above are readily converted into their polymer forms by the above-described vapor deposition process resulting in polymer chain films having the structure:
Figure imgf000007_0001
wherein G is a nuclear substituent group selected from the group consisting of chlorine and fluorine (m=4), and perfluoroalkyl groups having the formula CnF 2n+1, for n=1, 1, 3 (m=1 to 4, inclusive), and x is an integer greater than 1.
It is believed that the selected nuclear substituent groups as defined above, will provide highly desirable physical and electrical properties to the polymer films. One such desirable property comprises an expected lower dielectric constant than the currently available parylene materials. Such low dielectric constant materials are highly desirable in the art, and will provide a new generation of materials for the preparation of electronic circuit structures, and coatings for such structures.
It can therefore be seen that the instant invention provides highly desirable cyclic α-perfluoro-di-p-xylylenes which are effective for the production of a-perfluoro-p-xylylene polymer films having low dielectric constants. For these reasons, the instant invention is believed to represent a significant advancement in the art which has substantial commercial merit.
While there is described herein certain specific structures embodying the invention, it will be manifest to those skilled in the art that various modifications and rearrangements of the parts may be made without departing from the spirit and scope of the underlying inventive concept and that the same is not limited to the particular forms herein described except insofar as indicated by the scope of the appended claims.

Claims

Cyclic a-perfluoro-di-p-xylylene having the structure:
Figure imgf000008_0001
wherein G is a nuclear substituent group selected from the group consisting of chlorine and fluorine, and further wherein m=4.
2. Cyclic α-perfluoro-di-p-xylylene having the structure:
Figure imgf000008_0002
wherein G is a nuclear substituent group selected from the group consisting of perfluoroalkyl groups having the formula CnF2n+1 for n=1, 2, 3 . . . , and further wherein m=1 to 4.
3. An α-perfluoro-p-xylylene polymer having the structure:
Figure imgf000008_0003
wherein G is an aromatic nuclear substituent group selected from the group consisting of perfluoroalkyl groups having the formula CnF2n+ 1, m is an integer having a value of from 1 to 4. and x is an integer greater than 1.
PCT/US1996/017030 1995-10-27 1996-10-24 CYCLIC ALPHA-PERFLUORO-DI-p-XYLYLENES FOR USE IN THE FORMATION OF LOW DIELECTRIC CONSTANT ALPHA-PERFLUORO-p-XYLYLENE POLYMERS WO1997015541A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US54912595A 1995-10-27 1995-10-27
US08/549,125 1995-10-27

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001213818A (en) * 2000-01-31 2001-08-07 Nippon Shokubai Co Ltd Method of production for cyclophane derivative
JP2001213819A (en) * 2000-01-31 2001-08-07 Nippon Shokubai Co Ltd Method of production for cyclophane derivative
US6291072B1 (en) * 1998-06-15 2001-09-18 Kishimoto Sangyo Co., Ltd. Insulating film for semiconductor device and semiconductor device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3332891A (en) * 1963-09-23 1967-07-25 Union Carbide Corp Process for the preparation of alpha-per-fluoro-p-xylylene polymers
GB1146005A (en) * 1965-06-25 1969-03-19 Union Carbide Corp Gaseous electrical glow discharge etching of para-xylene polymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3332891A (en) * 1963-09-23 1967-07-25 Union Carbide Corp Process for the preparation of alpha-per-fluoro-p-xylylene polymers
GB1146005A (en) * 1965-06-25 1969-03-19 Union Carbide Corp Gaseous electrical glow discharge etching of para-xylene polymers

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6291072B1 (en) * 1998-06-15 2001-09-18 Kishimoto Sangyo Co., Ltd. Insulating film for semiconductor device and semiconductor device
JP2001213818A (en) * 2000-01-31 2001-08-07 Nippon Shokubai Co Ltd Method of production for cyclophane derivative
JP2001213819A (en) * 2000-01-31 2001-08-07 Nippon Shokubai Co Ltd Method of production for cyclophane derivative

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