CA1331387C - Polyimidesiloxanes and methods for their preparation and use - Google Patents
Polyimidesiloxanes and methods for their preparation and useInfo
- Publication number
- CA1331387C CA1331387C CA 613725 CA613725A CA1331387C CA 1331387 C CA1331387 C CA 1331387C CA 613725 CA613725 CA 613725 CA 613725 A CA613725 A CA 613725A CA 1331387 C CA1331387 C CA 1331387C
- Authority
- CA
- Canada
- Prior art keywords
- polyimidesiloxane
- formula
- dianhydride
- siloxane
- carbon atoms
- 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
Abstract
(1) NOVEL SOLUBLE POLYIMIDESILOXANES AND
METHODS FOR THEIR PREPARATION AND USE
ABSTRACT
Substantially fully imidized polyimidesiloxanes which are based on a selected pyridine compound are soluble in diglyme which gives them particular utility in the micro-electronics industry.
The polymers are prepared from the dianhydride, a difunctional siloxane monomer and an organic diamine that has the formula I
wherein X is hydrogen, halogen, phenyl or combinations thereof, Z = -O-, -S-, , , , - or -Y-Ar-Y- , o Ar' is an aromatic radical of 6 to 10 carbon atoms, (2) , , , , , , , , , Y = -O-, -S-, , ,, or -.
n = 0 or 1.
Preferably formula I is wherein X, Z, Ar', Y and n are as in formula I.
(3) More specifically, the aromatic diamines are diaminoaromatic trifluoride compounds having the formula where Ar is an aromatic radical of 6 to 10 carbon atoms, and where X is hydrogen, halogen, phenyl or combinations thereof.
The preferred diamine has the formula Other diamines can be used to provide an asymmetrical structure in the polyimidesiloxane polymer chain. The polyimidesiloxane can be prepared with functional groups which render them directly curable.
The polyimidesiloxanes can also be prepared with functional groups which when reacted with an unsaturated compound renders the polymers curable. The products of the invention can be used in the form of solutions in the micro-electronic industry. The polymers can also be used in wire and cable coating and to prepare films, fibers, and molded and extruded articles.
METHODS FOR THEIR PREPARATION AND USE
ABSTRACT
Substantially fully imidized polyimidesiloxanes which are based on a selected pyridine compound are soluble in diglyme which gives them particular utility in the micro-electronics industry.
The polymers are prepared from the dianhydride, a difunctional siloxane monomer and an organic diamine that has the formula I
wherein X is hydrogen, halogen, phenyl or combinations thereof, Z = -O-, -S-, , , , - or -Y-Ar-Y- , o Ar' is an aromatic radical of 6 to 10 carbon atoms, (2) , , , , , , , , , Y = -O-, -S-, , ,, or -.
n = 0 or 1.
Preferably formula I is wherein X, Z, Ar', Y and n are as in formula I.
(3) More specifically, the aromatic diamines are diaminoaromatic trifluoride compounds having the formula where Ar is an aromatic radical of 6 to 10 carbon atoms, and where X is hydrogen, halogen, phenyl or combinations thereof.
The preferred diamine has the formula Other diamines can be used to provide an asymmetrical structure in the polyimidesiloxane polymer chain. The polyimidesiloxane can be prepared with functional groups which render them directly curable.
The polyimidesiloxanes can also be prepared with functional groups which when reacted with an unsaturated compound renders the polymers curable. The products of the invention can be used in the form of solutions in the micro-electronic industry. The polymers can also be used in wire and cable coating and to prepare films, fibers, and molded and extruded articles.
Description
Case 6037 01/25/19~9 JFM/rag ;
NOVEL POLYIMIDESILOXANES AND
METHODS FOR THEIR PREPARATION AND USE
A class of polymers known as polyimides has become known for its combination of good heat stability and high upper use tempera~
tures, as measured by glass transition temperature. A particularly useful type of such polyimides is known as polyimidesiloxanes.
Because of their combination of properties, polyimidesiloxanes . ~. .
have been used in electronic applications, particularly in micro~
electronic components 1n the 1ntegrated c1rcu1t 1ndustry.
: Because many of the previously known poly1midesiloxanes are -~ lnsoluble or d1fficultly soluble in solvents, when used 1n the ;-microelectronics industry, there is a great need for polyimide-~s~ ~ siloxanes having improved solub11ity characteristics, as well as a -better balance of heat resistance and upper use temperature.
~": ,` ~'. '~
,. ~ ' ., ~: '~ :
~ 33 ~
The chemistry for making polyimides has been well-known since about 1960. A structurally simple polyimide can be prepared by reacting a diamine with a dianhydride. `
, ~ ~
O O - -:
A, HN AANH-B~
Q~ +H2N-B-NH2~tHoJ OHJ
O O ;
lo tN~r3~ B~
r ~ The first step, or the polyaddition reaction, generates polyamide acids which are hydrolytically unstable even at room temperature. The second step, or the imidization reaction, produces the stable polyimides desired for various applications.
~`~- Polyimidesiloxanes can be prepared by reactions employing ~;
siloxane diamines or siloxane dianhydrides with organic comonomers.
Polyimidesiloxanes can also be prepared from siloxane diamines and siloxane dianhydrides without an organic comonomer.
The first polyimidesiloxane was prepared by reacting pyromellitic dianhydride (PMDA) with 1,3-bis-(aminopropyl)-1,1,3,3-.,. ~
tetramethyl disiloxane in 1966 (see V. H. Kuckertz, Macromol. Chem.
98, 1966, pp. 101-108). This polyimidesiloxane is a crystalline material and cannot be cast into flexible films from solvent.
r, ~ 2 ~,, =. ~
Polyimidesiloxanes derived from reactions of benzophenone tetra-carboxylic dianhydride (BTDA) and CY,w-diamino organo-polysiloxanes were disclosed by General Electric in 1967 in U.S. Patent No.
3,325,450. Polyimidesiloxanes containing an CX,w-diamino organo-polysiloxane and a diether dianhydride (DEDA) have also been disclosed in U.S. Patent No. 3,847,867. ~;~
A11 these BTDA and DEDA containing polyimidesiloxanes are amorphous materials. They have a glass transition temperature of no more than 100C and, therefore, have very limited upper use temperatures, despite the excellent thermal stability of these polymers up to about 200C. ; ~M~
Polyimidesiloxanes containing both organic and siloxane ;
monomers have been reported for PMDA containing copolymers (see Japan Kokai Tokkyo Koho 83/7473 and 83/13631); for BTDA containing copolymers (U.S. Patent Nos. 3,553,282 and 4,404,350) and for ~ diether dianhydride containing copolymers (U.S. Patent No.
s~ 3,847,867). These PMDA containing polyimidesiloxanes are not solu~
ble in any solvent. The BTDA containing polyimidesiloxanes are only ~?-~ soluble in high boiling or tox;c solvents such as l-methyl-2-pyrrol-~ 20 idinone, commonly known as N-methyl pyrrolidone (NMP), phenol or ~ cresol, and the like. The diether dianhydride containing polyimide-- siloxane, in addjtion, are also soluble in chlorinated solvents such ~ as dichlorobenzene and dichloromethane. Since these phenol and -s? chlorinated compounds are both corrosive and highly toxic, the polyimidesiloxanes have limited application in coating applications, ;~
~- especially in heat sensitive electronic devices. This is also due --~
- to the fact that a NMP soluble polyimidesiloxane normally has to be ;
,:,, ''5' ,'.'; ~
' ~
' ' 1331 3~7 heated to 350C for at least half an hour to remove all the residual solvent in a film having a micron-thickness film.
Only a few polyimidesiloxanes are soluble, even in high boiling and relatively toxic solvents, such as 1-methyl-2-pyrrolidinone (NMP), despite the fact that most of their polyamide acids are soluble. The usage of polyamide acids in coating applications has many drawbacks. First, a subsequent imidization reaction on ; substrates produces water. Therefore, it can only be used in very thin film coatings and where void-free property is not critical to performance. Second, the removal of high boiling, polar solvents, such as NMP, requires temperatures as high as 350C for about 30 minutes even for films of a m;cron thickness. This drying process is not only energy intensive, but also unacceptable to some heat sensitive electronic devices or substrates. In addition, the polyamide acids solution has to be stored at refrigeration temperature ( < 4C) and it still has a very short shelf life (about ~ 3 months). Finally, only the fully imidized polyimidesiloxanes are -~ thermally stable for melt processing such as extrusion and injection ~ molding. A soluble polyimidesiloxane can be fully imidized at - 20 temperatures of about 160 to 170C in a solvent~ whereas imidization ;~
for insoluble polyimidesiloxanes in the solid state may require temperatures 50$ above,theiir glass transition temperatures which can be as high as 200 to 250C. Shaping not fully imidized - ~ polyimidesiloxanes by the melt processing method produces voids in ~ 25 the products and often is not desirable.
~,, ~, ~'~
133~387 A variety of organic dianhydrides have been used in making soluble polysiloxaneimides. Some of these dianhydrides are disclosed in my copending applications as follows.
.
U!S. Patent 4,973,645, issued November 27, 1990, C.J. Lee, discloses that fully imidized polyimi-desiloxanes made from ~
oxydiphthalic anhydrides are soluble in solvents such as - - :
- diglyme, tetrahydrofuran and methyl ethyl ketone. :
U.S. Patent 4,829,131, issued May 9, 1989, C.J. Lee, discloses that substantially fully imidized polyimidesiloxanes ~
.- 10 made frcm a mixture of a biphenyl tetrac æboxylic dianhydride .;;: ;
and a benzophenone tetrac æboxylic dianhydride æ e soluble in solvents such as diglyme, tetrahydrofuran and methyl ethyl ketone.
: U.S. Patent 4,853,452, issued August 1, 1989, C.J. Lee, lS discloses that-substantially fully imidized polyimidesiloxanes made from a bis(dicarboxyphenyl)hexafluoropropene dianhydride and mixtures with other dianhydrides are soluble in solvents such as ~- d191yme, tetrahydrofuran and methyl ethyl ketone. ~ `-U.S. Patent 4,956,437, issued September 18, 1990, C.J.
; ZO Lee, discloses that substantially fully imidized polyimidesiioxanes made from sulfurdiphthalic anhydride are soluble in solvents such as diglyme, tetrahydrofuran and methyl ethyl ketone.
U.S, Patent No. 4,535,099 describes a polyimide prepared from the reaction of an organic tetracarboxylic acid or derivative thereof with a mixture of an aromatic diamine and an amine~
terminated silicone. Disclosed as suitable diamines are diamine ~- -_ 5 ; ~
,,~
~{ ::
-- 133~.~87 pyr~dines, which are d~primary monotertiary amines. The poly1mides are part~cularly useful in the preparation of flex1ble foams. ~-The above-noted U.S. Patent No. 3,553,282 discloses mak~ng polyamic acids that may include 2,6-diaminopyridine. The patent does not teach how to make fully imidized and soluble polyimide-siloxanes. More specifically, the patent does not teach how to make a fully imidized, yet soluble, polyimidesiloxane from 2,6-diamino-pyridine and dianhydrides such as BTDA and 6FDA.
U.S. Patent 4,956,437 , reissued as U.S. Reissue Patent RE 33,797, issued January 14, 1992, C.J. Lee, discloses that fully imldized polyimldesiloxanes made from diamino-trifluoro~
methyl pyridines are soluble in solvents such as diglyme.
;~ A purpose of the present invention is to make novel ;~ polyimidesiloxanes.
- 15 Another purpose of the present invention is to develop a fully - imidized polylmidesiloxane which is soluble in low boiling, f~ non-polar and non-toxic solvent such as diglyme. Another purpose of the present invent10n is to develop the desirable polyimidesiloxanes ~-~ based on less expensive and readily available organic monomers.~; Another purpose of the present invention is to develop less expensive polyimidesiloxane which can be readily scaled-up into commercially available, large scale production. Another purpose of ~ ;
the present invention is to develop less expensive polyimidesiiox-anes which can be used in price sensitive applications or in ~ 25 favorable competitive performance/cost positions in cable jacket, as -~ well as 3D molded wire board applications and where high volume and -~ low price are essential. , i -: - 6 -13313~7 Another purpose of the invent;.on ;.s to provide fully imidized polyimidesiloxanes which are soluble not only in high boiling solvents, such as NMP, but also in low boiling, low toxic, less polar solvents such as diglyme or tetrahydrofuran tTHF). A further purpose of the invention is to provide polyimidesiloxanes that are useful in microelectronic applications because they have a good balance of heat resistance and high upper use temperatures, as measured by glass transition temperatures; as well as high resistivity, good adhesion, good mechanical properties and low ;
dielectric constant.
Another purpose of this invention is to produce curable and cross-linked polyimidesiloxanes.
Summary of the Invention ~
The invention relates to polysiloxaneimides ~hat are prepared ~-from compounds of the formula~
CX CX
; 1 3 1 3 H2N-~- Ar ~ Z )n Ar' NH2 I ~;-.
wherein X is fluorine or ccmbinations of fluorine with hydrogen, ~:~ O O
Z = -0-, -S-, -S-, ,C~ , ,C(CX3)2, or -Y -Ar -Y
Ar' is an aromatic radlical of 6 to 10 carbon atoms, `
"~
~ ' .
' ' ' ' '' ' . ' '' " '~" '.' ,, -., '.':', "' ' :" ' ' " " ' ;'' . ' ' ' ' ' ~' . ' ,'' " . " ' C X , 3 ~ ~ 3 ~ 3 CX
~ ~ 3 ~ y ~ , ~ :
N N N
~ ~ ~ ~ 3Y ~ 3 o o ~ ,~
Y ~ -O-, -S-, -S-, ~C~ , ~ C ( CX3 ) 2 ~ ~C (CH3 ) 2, or ~ -n = O or 1.
-~ Preferably formula I is H2N~Z~NH2 -~ 15 - ;~
:: ~
wherein X, Z, Ar', Y and n are as in formula I.
:~
,," . ~
i'-'' ~ ,.
, ~ ... ,,~
," ~
13~87 '~
More specifically, the invention relates to polyimidesiloxanes that are prepared from d~aminoaromatic trifluoride compounds having -~
the formula H2N - Ar - NH2 where Ar is an aromatic radical of 6 to 10 carbon atoms such as benzyl, toluyl, xylyl, naphthyl, and the like, and where X is ~: fluorine. . `
Still more specifically, the invention relates to polyimidesi~ J
loxanes that are prepared from 2,5-diaminobenzotrlfluoride 2,5-(DABF) which has the formula ~ ' ~,;,~,, - ~: CF3 2 .
The diamino compounds of the invention are useful in making ~ -~ polyimidesiloxanes that have high glass transition temperatures and };-~ good thermal stability.
Substantially fullylimidized polyimidesiloxanes which are j ~ ;~
prepared from the foregoing diamino compounds are soluble in diglyme ~ ~
which gives them part1cular utility in the micro-electronics ~-industry. The latter polymers are prepared from the diamine, a difunctional siloxane monomer and an organic dianhydride.
'~
,,, _ g ` ' `; '~
133~ 3~7 The above-descr;bed dlamino compounds, which are diprimary amlnes, can be used in adm1xtures with other diamines such as the tolylene diamine. ~ -Yarious organic dianhydrides can be used such as oxydiphthalic anhydride, sulfurdiphthalic anhydride, benzophenone tetracarboxylic dianhydride, the biphenyl tetracarboxylic dianhydrides, bis(dicarboxyphenyl)hexafluoropropene dianhydride, and d1ether dianhydrides.
The polyimidesiloxanes of the invention can also be prepared with functional groups which render them directly curable. The polyimidesiloxanes can also be prepared with functional groups which when reacted with an unsaturated compound renders the polymers curable.
The products of the invention can be used in the form of solutions in the micro-electronic industry. The polymers can also I be used in wlre and cable coating and to prepare films, fibers, and molded and extruded articles.
`- Detailed Description of the Inventlon. :
l~e~rganic Diamine The organic diamine component of the polyimidesiloxanes of the invention are the compounds of the formula H2N-~- Ar'- Z ~ Ar' - NH2 I ~-~
wherein X is fluorine or combinations of fluorine with hydrogen, ' ' - 10- , ~, o o z = -o-~ -S-~ -S-~ C\ ~ ~ C(CX3)2, - or - Y - Ar - Y
Ar' is an aromatic radical of 6 to 10 carbon atoms, Ar~ y ~3_ ~ .
S ~X3~ _~3 ~3 ~N J
C X3 C X3 CX3 ~ ` :
~ ~ 10 ~Y~ ~ ~Y ~
O o ~:
y ~ _0-, -S-, -S-, C~ ~ ~ C~CX3)2' ~ C(CH3)2~ or - ~ n = O or 1. ~;~
Preferably formula I is ,- . - ..
wherein X, Z, Ar', Y and n are as in formula I. ~ ~
,' ' , '~, .
~ - 11 - , .
~. , ~ - , ,~ ~ . ' ' ~ i33~387 More spec~fically, the invention relates to polyimidesiloxanes that are prepared from diaminoaromatic trifluoride compounds havlng .
the formula ':
H2N--Ar--NH2 : where Ar is an aromatic rad1cal of 6 to 10 carbon atoms such as trisubstituted benzene, toluene, xylene and naphylene, and the like, and where X is fluorine.
Still more specifically, the invention relates to polyimide~
siloxanes that are prepared from diaminobenzotrifluorides (DABF) which have the formula CF3 ;~
~: H2N~NH2 :
: :.
. ~
"~
Suitable DABF compounds include~
2,4-diaminobenzotrifluoride .
-: 15 2,5-diaminobenzotrifluoride -~- 2,6-diaminobenzotrifluoride 3.,4-diaminobenzotrifluoride ! ~1 3,5-diaminobenzotrifluoride ::~
". . ~
~-- 3,6-diaminobenzotrifluoride -~
NOVEL POLYIMIDESILOXANES AND
METHODS FOR THEIR PREPARATION AND USE
A class of polymers known as polyimides has become known for its combination of good heat stability and high upper use tempera~
tures, as measured by glass transition temperature. A particularly useful type of such polyimides is known as polyimidesiloxanes.
Because of their combination of properties, polyimidesiloxanes . ~. .
have been used in electronic applications, particularly in micro~
electronic components 1n the 1ntegrated c1rcu1t 1ndustry.
: Because many of the previously known poly1midesiloxanes are -~ lnsoluble or d1fficultly soluble in solvents, when used 1n the ;-microelectronics industry, there is a great need for polyimide-~s~ ~ siloxanes having improved solub11ity characteristics, as well as a -better balance of heat resistance and upper use temperature.
~": ,` ~'. '~
,. ~ ' ., ~: '~ :
~ 33 ~
The chemistry for making polyimides has been well-known since about 1960. A structurally simple polyimide can be prepared by reacting a diamine with a dianhydride. `
, ~ ~
O O - -:
A, HN AANH-B~
Q~ +H2N-B-NH2~tHoJ OHJ
O O ;
lo tN~r3~ B~
r ~ The first step, or the polyaddition reaction, generates polyamide acids which are hydrolytically unstable even at room temperature. The second step, or the imidization reaction, produces the stable polyimides desired for various applications.
~`~- Polyimidesiloxanes can be prepared by reactions employing ~;
siloxane diamines or siloxane dianhydrides with organic comonomers.
Polyimidesiloxanes can also be prepared from siloxane diamines and siloxane dianhydrides without an organic comonomer.
The first polyimidesiloxane was prepared by reacting pyromellitic dianhydride (PMDA) with 1,3-bis-(aminopropyl)-1,1,3,3-.,. ~
tetramethyl disiloxane in 1966 (see V. H. Kuckertz, Macromol. Chem.
98, 1966, pp. 101-108). This polyimidesiloxane is a crystalline material and cannot be cast into flexible films from solvent.
r, ~ 2 ~,, =. ~
Polyimidesiloxanes derived from reactions of benzophenone tetra-carboxylic dianhydride (BTDA) and CY,w-diamino organo-polysiloxanes were disclosed by General Electric in 1967 in U.S. Patent No.
3,325,450. Polyimidesiloxanes containing an CX,w-diamino organo-polysiloxane and a diether dianhydride (DEDA) have also been disclosed in U.S. Patent No. 3,847,867. ~;~
A11 these BTDA and DEDA containing polyimidesiloxanes are amorphous materials. They have a glass transition temperature of no more than 100C and, therefore, have very limited upper use temperatures, despite the excellent thermal stability of these polymers up to about 200C. ; ~M~
Polyimidesiloxanes containing both organic and siloxane ;
monomers have been reported for PMDA containing copolymers (see Japan Kokai Tokkyo Koho 83/7473 and 83/13631); for BTDA containing copolymers (U.S. Patent Nos. 3,553,282 and 4,404,350) and for ~ diether dianhydride containing copolymers (U.S. Patent No.
s~ 3,847,867). These PMDA containing polyimidesiloxanes are not solu~
ble in any solvent. The BTDA containing polyimidesiloxanes are only ~?-~ soluble in high boiling or tox;c solvents such as l-methyl-2-pyrrol-~ 20 idinone, commonly known as N-methyl pyrrolidone (NMP), phenol or ~ cresol, and the like. The diether dianhydride containing polyimide-- siloxane, in addjtion, are also soluble in chlorinated solvents such ~ as dichlorobenzene and dichloromethane. Since these phenol and -s? chlorinated compounds are both corrosive and highly toxic, the polyimidesiloxanes have limited application in coating applications, ;~
~- especially in heat sensitive electronic devices. This is also due --~
- to the fact that a NMP soluble polyimidesiloxane normally has to be ;
,:,, ''5' ,'.'; ~
' ~
' ' 1331 3~7 heated to 350C for at least half an hour to remove all the residual solvent in a film having a micron-thickness film.
Only a few polyimidesiloxanes are soluble, even in high boiling and relatively toxic solvents, such as 1-methyl-2-pyrrolidinone (NMP), despite the fact that most of their polyamide acids are soluble. The usage of polyamide acids in coating applications has many drawbacks. First, a subsequent imidization reaction on ; substrates produces water. Therefore, it can only be used in very thin film coatings and where void-free property is not critical to performance. Second, the removal of high boiling, polar solvents, such as NMP, requires temperatures as high as 350C for about 30 minutes even for films of a m;cron thickness. This drying process is not only energy intensive, but also unacceptable to some heat sensitive electronic devices or substrates. In addition, the polyamide acids solution has to be stored at refrigeration temperature ( < 4C) and it still has a very short shelf life (about ~ 3 months). Finally, only the fully imidized polyimidesiloxanes are -~ thermally stable for melt processing such as extrusion and injection ~ molding. A soluble polyimidesiloxane can be fully imidized at - 20 temperatures of about 160 to 170C in a solvent~ whereas imidization ;~
for insoluble polyimidesiloxanes in the solid state may require temperatures 50$ above,theiir glass transition temperatures which can be as high as 200 to 250C. Shaping not fully imidized - ~ polyimidesiloxanes by the melt processing method produces voids in ~ 25 the products and often is not desirable.
~,, ~, ~'~
133~387 A variety of organic dianhydrides have been used in making soluble polysiloxaneimides. Some of these dianhydrides are disclosed in my copending applications as follows.
.
U!S. Patent 4,973,645, issued November 27, 1990, C.J. Lee, discloses that fully imidized polyimi-desiloxanes made from ~
oxydiphthalic anhydrides are soluble in solvents such as - - :
- diglyme, tetrahydrofuran and methyl ethyl ketone. :
U.S. Patent 4,829,131, issued May 9, 1989, C.J. Lee, discloses that substantially fully imidized polyimidesiloxanes ~
.- 10 made frcm a mixture of a biphenyl tetrac æboxylic dianhydride .;;: ;
and a benzophenone tetrac æboxylic dianhydride æ e soluble in solvents such as diglyme, tetrahydrofuran and methyl ethyl ketone.
: U.S. Patent 4,853,452, issued August 1, 1989, C.J. Lee, lS discloses that-substantially fully imidized polyimidesiloxanes made from a bis(dicarboxyphenyl)hexafluoropropene dianhydride and mixtures with other dianhydrides are soluble in solvents such as ~- d191yme, tetrahydrofuran and methyl ethyl ketone. ~ `-U.S. Patent 4,956,437, issued September 18, 1990, C.J.
; ZO Lee, discloses that substantially fully imidized polyimidesiioxanes made from sulfurdiphthalic anhydride are soluble in solvents such as diglyme, tetrahydrofuran and methyl ethyl ketone.
U.S, Patent No. 4,535,099 describes a polyimide prepared from the reaction of an organic tetracarboxylic acid or derivative thereof with a mixture of an aromatic diamine and an amine~
terminated silicone. Disclosed as suitable diamines are diamine ~- -_ 5 ; ~
,,~
~{ ::
-- 133~.~87 pyr~dines, which are d~primary monotertiary amines. The poly1mides are part~cularly useful in the preparation of flex1ble foams. ~-The above-noted U.S. Patent No. 3,553,282 discloses mak~ng polyamic acids that may include 2,6-diaminopyridine. The patent does not teach how to make fully imidized and soluble polyimide-siloxanes. More specifically, the patent does not teach how to make a fully imidized, yet soluble, polyimidesiloxane from 2,6-diamino-pyridine and dianhydrides such as BTDA and 6FDA.
U.S. Patent 4,956,437 , reissued as U.S. Reissue Patent RE 33,797, issued January 14, 1992, C.J. Lee, discloses that fully imldized polyimldesiloxanes made from diamino-trifluoro~
methyl pyridines are soluble in solvents such as diglyme.
;~ A purpose of the present invention is to make novel ;~ polyimidesiloxanes.
- 15 Another purpose of the present invention is to develop a fully - imidized polylmidesiloxane which is soluble in low boiling, f~ non-polar and non-toxic solvent such as diglyme. Another purpose of the present invent10n is to develop the desirable polyimidesiloxanes ~-~ based on less expensive and readily available organic monomers.~; Another purpose of the present invention is to develop less expensive polyimidesiloxane which can be readily scaled-up into commercially available, large scale production. Another purpose of ~ ;
the present invention is to develop less expensive polyimidesiiox-anes which can be used in price sensitive applications or in ~ 25 favorable competitive performance/cost positions in cable jacket, as -~ well as 3D molded wire board applications and where high volume and -~ low price are essential. , i -: - 6 -13313~7 Another purpose of the invent;.on ;.s to provide fully imidized polyimidesiloxanes which are soluble not only in high boiling solvents, such as NMP, but also in low boiling, low toxic, less polar solvents such as diglyme or tetrahydrofuran tTHF). A further purpose of the invention is to provide polyimidesiloxanes that are useful in microelectronic applications because they have a good balance of heat resistance and high upper use temperatures, as measured by glass transition temperatures; as well as high resistivity, good adhesion, good mechanical properties and low ;
dielectric constant.
Another purpose of this invention is to produce curable and cross-linked polyimidesiloxanes.
Summary of the Invention ~
The invention relates to polysiloxaneimides ~hat are prepared ~-from compounds of the formula~
CX CX
; 1 3 1 3 H2N-~- Ar ~ Z )n Ar' NH2 I ~;-.
wherein X is fluorine or ccmbinations of fluorine with hydrogen, ~:~ O O
Z = -0-, -S-, -S-, ,C~ , ,C(CX3)2, or -Y -Ar -Y
Ar' is an aromatic radlical of 6 to 10 carbon atoms, `
"~
~ ' .
' ' ' ' '' ' . ' '' " '~" '.' ,, -., '.':', "' ' :" ' ' " " ' ;'' . ' ' ' ' ' ~' . ' ,'' " . " ' C X , 3 ~ ~ 3 ~ 3 CX
~ ~ 3 ~ y ~ , ~ :
N N N
~ ~ ~ ~ 3Y ~ 3 o o ~ ,~
Y ~ -O-, -S-, -S-, ~C~ , ~ C ( CX3 ) 2 ~ ~C (CH3 ) 2, or ~ -n = O or 1.
-~ Preferably formula I is H2N~Z~NH2 -~ 15 - ;~
:: ~
wherein X, Z, Ar', Y and n are as in formula I.
:~
,," . ~
i'-'' ~ ,.
, ~ ... ,,~
," ~
13~87 '~
More specifically, the invention relates to polyimidesiloxanes that are prepared from d~aminoaromatic trifluoride compounds having -~
the formula H2N - Ar - NH2 where Ar is an aromatic radical of 6 to 10 carbon atoms such as benzyl, toluyl, xylyl, naphthyl, and the like, and where X is ~: fluorine. . `
Still more specifically, the invention relates to polyimidesi~ J
loxanes that are prepared from 2,5-diaminobenzotrlfluoride 2,5-(DABF) which has the formula ~ ' ~,;,~,, - ~: CF3 2 .
The diamino compounds of the invention are useful in making ~ -~ polyimidesiloxanes that have high glass transition temperatures and };-~ good thermal stability.
Substantially fullylimidized polyimidesiloxanes which are j ~ ;~
prepared from the foregoing diamino compounds are soluble in diglyme ~ ~
which gives them part1cular utility in the micro-electronics ~-industry. The latter polymers are prepared from the diamine, a difunctional siloxane monomer and an organic dianhydride.
'~
,,, _ g ` ' `; '~
133~ 3~7 The above-descr;bed dlamino compounds, which are diprimary amlnes, can be used in adm1xtures with other diamines such as the tolylene diamine. ~ -Yarious organic dianhydrides can be used such as oxydiphthalic anhydride, sulfurdiphthalic anhydride, benzophenone tetracarboxylic dianhydride, the biphenyl tetracarboxylic dianhydrides, bis(dicarboxyphenyl)hexafluoropropene dianhydride, and d1ether dianhydrides.
The polyimidesiloxanes of the invention can also be prepared with functional groups which render them directly curable. The polyimidesiloxanes can also be prepared with functional groups which when reacted with an unsaturated compound renders the polymers curable.
The products of the invention can be used in the form of solutions in the micro-electronic industry. The polymers can also I be used in wlre and cable coating and to prepare films, fibers, and molded and extruded articles.
`- Detailed Description of the Inventlon. :
l~e~rganic Diamine The organic diamine component of the polyimidesiloxanes of the invention are the compounds of the formula H2N-~- Ar'- Z ~ Ar' - NH2 I ~-~
wherein X is fluorine or combinations of fluorine with hydrogen, ' ' - 10- , ~, o o z = -o-~ -S-~ -S-~ C\ ~ ~ C(CX3)2, - or - Y - Ar - Y
Ar' is an aromatic radical of 6 to 10 carbon atoms, Ar~ y ~3_ ~ .
S ~X3~ _~3 ~3 ~N J
C X3 C X3 CX3 ~ ` :
~ ~ 10 ~Y~ ~ ~Y ~
O o ~:
y ~ _0-, -S-, -S-, C~ ~ ~ C~CX3)2' ~ C(CH3)2~ or - ~ n = O or 1. ~;~
Preferably formula I is ,- . - ..
wherein X, Z, Ar', Y and n are as in formula I. ~ ~
,' ' , '~, .
~ - 11 - , .
~. , ~ - , ,~ ~ . ' ' ~ i33~387 More spec~fically, the invention relates to polyimidesiloxanes that are prepared from diaminoaromatic trifluoride compounds havlng .
the formula ':
H2N--Ar--NH2 : where Ar is an aromatic rad1cal of 6 to 10 carbon atoms such as trisubstituted benzene, toluene, xylene and naphylene, and the like, and where X is fluorine.
Still more specifically, the invention relates to polyimide~
siloxanes that are prepared from diaminobenzotrifluorides (DABF) which have the formula CF3 ;~
~: H2N~NH2 :
: :.
. ~
"~
Suitable DABF compounds include~
2,4-diaminobenzotrifluoride .
-: 15 2,5-diaminobenzotrifluoride -~- 2,6-diaminobenzotrifluoride 3.,4-diaminobenzotrifluoride ! ~1 3,5-diaminobenzotrifluoride ::~
". . ~
~-- 3,6-diaminobenzotrifluoride -~
4,6-diaminobenzotrifluoride ~'f~ ' :."'`';
t~, ~ ~ ''"' ~' ";
"
"~
Examples of useful compounds of the above generic formula are .~
as follows: C ~ ~CF3 ~-;
~ ~ N H2 H2N~O~O~NH
~0 ~ ~
~:
H 2N ~ O ~ O ~ N H2 ~'~
H2N~}~~NH2 ' - 13 -,:
,',: ;,:
,' ' ~, 1331 387 ~:
The preferred compound is 2,5-diaminobenzotrifluoride 2,5-(DABFj, which has the formula -~
H2N~
The preparation of compounds with n = 1 Ar =
: and Z = O can be achieved, for instance, by the following reaction :~ schemes: CF
v~ 1 3 ~ 10 2 _~CI ,~OH KOH/K2C03 >
i".. ~ ~ :
2 ~
Fe/HCI > H N~ LNH2 J ~ ~ CF3 ~ : - 14 - ~:
,~,' ~' : 133~.3~7 It has been found that diamines that provide asymmetrical structure in the polyimidesiloxane chains are useful in combination with the amines such as DABF, in making polyimidesiloxanes with the desirable and superior properties of this invention.
Other suitable diamines that provide asymmetrical structure in -the polyimidesiloxane chain have the following formula:
NH2~NH2 z -~--~ 10 where x, y and z are independently selected from hydrogen, halogen, alkyl or aryl or halogenated aryl of 6 to 12 carbon atoms. The preferred diamines have at least one alkyl substituent having at ~-least one carbon atom. -Examples are: 2,4-tolyldiamine ~~ 15 2,5-tolyldiamine 2,6-tolyldiamine m-xylyldiamine 2,4-diamine-5 chloro toluene 2,4-diamine-6-chloro toluene - 20 2,4,6-trimethyl 1,3-diaminobenzene ~-~
~ ., .
~ : ~
~, '''~''"' '' ' ' ''' " "'; '"'''""'''''' ';''''''"'"''~''''''''"';'''''''''''"''' ' '' '' ~',' .' " ' ~` 133~387 : ~
Other useful diamine compounds that are asymmetr1cal 1n the polymer chain include compounds with the formula:
H ~N ~ X~jN H;7 where;n x is -CH2-, -5-, O, ,C, , ~C~
Examples are: m,m-methylene dianiline m,m-sulfone dianiline ~ ~-o,m-sulfone dianiline.
~ Another suitable diamine that is asymmetrical in the polyimide~
- 10siloxane is diaminoanthraquinone.
-~ An especial1y preferred auxiliary diamine is a mixture of ~; ~2,4-tolyldiamine and 2,6-tolyldiamine, especially the commercially available mixture of about 80 weight percent 2,4-tolyldiamine and ,., . .. ~
J'~ about 20 weight percent 2,6-tolyldiamine. -~
15Small amounts up to about 25 weight percent of diamines that ;~
are not asymetrical in the polymer chain can be employed in the polyimidesiloxane compositionis. Such other diami'nes are disclused - in U.S. Patents Nos. 4,395,527 and 4,586,997.
''' . . ',,.,"'' ~ ~
- 16 ~
. ~
Such auxiliary diamines have the formula :~
H~N ~ x ~ ~H, wherein x is preferably -5- for retaining solubili b in diglyme, THF or MEK. In addition, the x can also be C , -O-, -S- and -CH2- for achieving only solubility in NMP. Additional organic :
diamines can be employed in much smaller quantities without -~:~
affecting the favorable combinations of thermal stability glass transition temperature and solubility.
The Organic Anhydrides 10: The present invention is based on the discovery that the use ofthe above-described diamines (typified:by DABF) when reacted with : organic dianhydrides provide fully imidized polyimidesiloxanes which have~a unique combination of solubility and thermal properties.
Useful organic dianhydrides include compounds having the :~
15:: following general formula~
O
- 17 - ~`
ir' ~ i33i 387 wherein Ar is `
i ~,; ~`
~;' ; ~
~ / CF3 O .
wherein Y ~s O, C, C , CnH2n, S, S , .
o -:
Other examples of such other dianhydrldes are disclosed in U.S.
~ Patents:Nos. 4,395,527 and 4,586,997. Hcwever, even though the .
incorporation of these dianhydrides may alter only slightly thesolubility of the resulting polyimidesiloxanes in NMP or diglyme, these modified polyimidesiloxanes may become insoluble in solvents, such as MEK or THF. This limits their applications where a very low -~:
; boiling, non-toxic solvent such as MEK is required. In addition, the incorporation of the diether dianhydrides (DEDA), also reduces the glass transition temperature and thermal stability of 133~ 387 polyimidesiloxanes of the invention and limlt the;r upper use . ~.
temperatures.
Preferred organic anhydrides that can be used in the practice of the invention lnclude:
---Oxydiphthalic anhydrides (ODPA), such as disclosed in .
U. S . Patent 4, 973, 645, :. ~
~;----Sulfurdiphthalic anhydrides (SDPA), such as disclosed in .
U.S. Patent 4,956,437;
---Sulfonediphthalic anhydrides;
---Benzophenone tetracarboxylic dianhydride (BTDA);
---Biphenyl tetracarboxyljc d~anhydrides (BPDA); ;~
---Bis(dicarboxyphenyl)-hexafluoropropene dianhydride, (6FDA);
---Diether dianhydrides (DEDA); such as disclosed in U.S.
Patent No. 4,395,527.
M~xtures of the foregoing anhydrides can also be employed.
Particularly useful are the following mixtures of anhydrides:
BPDA and BTDA
6FDA and ODPA
6FDA and BPDA ;
B~DA and ODPA. ~:`
, .;~ ' -- 133~ 387 The Siloxane Monomers Siloxane diamino compounds that can be used for the present ;~
invention have the following formula~
3 . ~:
~ 5 H,N-~R ~ 5; -O ~ ~ R - N~
. ~, ; wherein m is a number from about 5 to about 200, preferably 5 to 50, Rl, R2, R3 and R4 are independently selected frcm a ~;
substituted or unsubstituted aliphatic mono-radical of 1 to 12 .
carbon atoms or substituted or unsubstituted aromatic mono-radical of 6 to 10 carbon atoms. Suitable radicals include -CH3, -CF3, -(CH2)nCF3 , -C6H5, -CF2-CHF-CF3 and -CH2-CH2-C-0-CH2CF2CF2CF3.
; R' is a di-radical of the foregoing type. Suitable di-radicals nc ude ~CH2~n' ~CF2~n' ~(CH2)n(cF2)m- and -C6H4-, wherein m and n =
1 to 10.
-~ 15 The employment of an CX,w-diaminosiloxane is important for - achieving the desired solubility in diglyme, THF or MEK in the present invention. The siloxane diamine also provides the flexi-bility or resi~liqnce ofithe polyimidesiloxanes at low tempçratures, especially when the m is an integer of more than about 5, or preferably more than about 7. When the m is more than about 50, the ;~
- incorporation of diaminosiloxane into the polyimidesiloxane becomes difficult even though it is not impossible; and a dual solvent~ ~ ;
c - - 20 - ~
:
~ e ;~
133~ 387 ::
;.~
system (one polar and one non-polar solvent) for copolymerization may have to be employed. In general, the employment of the CX,w-diaminosiloxane and CX,w-dianhydride siloxane are interchange- ;
able in the present invention. However, for making polyimide-siloxanes of high glass transition temperature, the mole percent of the mixture of dianhydrides in the total dianhydride shoùld be maximized; and therefore, it is more desirable to employ the combination of the organic dianhydride with an organic diamine and an CX,w-diaminosiloxane. ;~
Siloxane dianhydrides which can be incorporated instead of or in addition to the siloxane diamines for the practice of the present invention can have the formula:
- ' ~
~ o/ \R ~ o ~ 5 - R\ \O
;~ - 15 ~ wherein m is a number from about 5 to about 200, Rl, R2, . ,~ . .
R3 and R4 are independently selected from a substi-tuted or unsubstituted aliphatic mono-radical of 1 to 12 carbon atoms substituted or unsubstituted aromatic mono-radical of 6 to 10 carbon atoms~, SuitableOradicals include -CH3, -CF3, -(CH2)nCF3;
-CF2-CHF-CF3, -cH2-cH2-c-o-cH2cF2cF2cF3 and 6 5 ;~`
R is a tri-radical of the foregoing type. Suitable , --- tri-radicals include -CH ' , ~33~.387 ~:
It is also well-known to those skilled in the art that when the : C6H5- or CF3CH2-CH2- group is used in the siloxane block, in ;~:
replacement of the -CH3 group, the solubility of resulting ~-; 5~ polyimidesiloxanes in chlor1nated solvents, such as CH2Cl2 and ether ~;
solvent such as diglyme~and~THF will increase. In addition, the ~,S~
pol~yimidesiloxane copolymers consist of phenylated siloxane block, or fl~uorinated siloxane block~will also have higher thermal stability.~ This is due to the fact that the least thermally stable ~ ~
'''?~ ' 10 ~ , groups in the po,lyimides,iloxanes is the -CH3 grfoup on the si~oxane ~ --block. Accordingly, w1thout showing specific examples one can expect that polyimidesiloxanes of the present invention can be - further improved by incorporating the C6H5 group or CF3CH2 group s- into their siloxane~blocks in order to improve their solubility and thermal stability. 22 ~"'~ ~ ~ :',.;~
,".
-When various dianhydrides are employed, their solubility in various solvents, glass transition temperatures and thermal stability changes depending on the chemical nature of these co-monomers. For instance, when a siloxane dianhydride is incorporated in the presence of a dianhydride, the solubility of the polymer increases, while the glass transition temperature and thermal stability will be lowered. Therefore, depending on the requirements for applications, the incorporation of siloxane dianhydride may become unfavorable. On the other hand, when an organic dianhydride such as PMDA is added in small proportions of ~-less than 5 mole percent, the resulting polyimidesiloxanes still has ~7 the desirable solubility in, for instance, NMP. The incorporation of PMDA can increase the glass transition temperature and thermal stability of the resulting polyimidesiloxanes, and, therefore, can provide more favorable products for extrusion or injection molding applications. However, one may also find that even with a small amount of PMDA in the polyimidesiloxanes, the resulting copolymers .~ .
may become insoluble in solvents, such as diglyme, THF or MEK, and their applications as coating materials will be limited, for instance, in heat sensitive`electronic devices or substrates.
The Process For Soluble Polyimidesiloxanes Although the chemistry for reactions of organic diamines with ~
- organic dianhydrides has become well-known, the preparation of ~ -~ polyimidesiloxanes in the presence of the siloxane comonomers may ~ ~--~ 25 sometimes require special techniques. For instance, when the repeating unit m, of the siloxane monomer is larger ?'~ :
(i.e., > 20 to 40), it may be desirable to use a dual solvent system: i.e., a solvent system consisting not only of a polar solvent, but also a less polar solvent. (See, for instance, McGrath et al, Polymer Preprints, 27 (2), 1986, pp. 403). It is also known that in the practice of making soluble polyimides, if a polyimide is soluble in a given solvent, in which the polyam;de acid is not soluble, one can prepare the polyimide directly in a one step polymerization process, that is, by a simultaneous imidization and polycondensation process, referred to as the one-step process. This -procedure can be advantageous, especially when a desirable polymer solution for coating applications has to be made out of a given solvent in which the polyamide acids are not soluble. The problem with the simultaneous imidization and polycondensation is that the ~ ~;
depolymerization of the polyamide acid in the presence of the water which is produced during the imidization step, can be very severe.
Theoretically, the depolymerization can become an irreversible process, since it produces a dicarboxylic acid and an amino compound. The carboxylic acid reacts with amino compounds at much higher temperatures as compared to the almost instantaneous reaction ~--of the dianhydrides with the amino compounds at room temperature.
The depolymenization of polyamide acids can become very severe at high temperaturss. This oneTstep process often~produces ! ' ' polyimidesiloxanes with much lower molecular weight as compared to those produced in a good solvent, in which the polyamide acid and - 25 the imidized polymers are both soluble, and one employs a two-step process. The two-step process employs a low temperature 133~.387 polycondensation step which generates very high molecular weight polyamide acid and then a very fast heating step to imidize and remove water generated from imidization.
The two-step process produces higher molecular weight materials which have higher thermal stability and mechanical strength, -especially higher elongation at break. The polycondensation temperature for the two-step process should be below 60C, preferably below room temperature. The imidization can be carried out at temperatures from 90C to 180C, or the refluxing temperature of the solvents. When the boiling temperature of the desirable solvent for imidization is below 160C, the use of dehydrating agents and/or a base catalyst is desirable. A suitable dehydrating agent is acetic anhydride. The catalyst is a tertiary amine, such as pyridine. When the acetic anhydride is employed, lower imidiza-tion temperatures can be employed to complete the imidization. In ~, ~- addition, an azeotropic agent with water can also be added to the - reactor. The use of an azeotropic agent such as toluene can facili-tate the removal of water presented in the reactor and minimize the depolymerization of the polyamide acids. When an azeotropic agent ;~ 20 is employed, a continuous recovery of fresh azeotropic agent can be achieved by using also a Dean Stark trap under the condenser.
The degree cf polycondensation is importan~ for obtaining good thermal and mechanical properties in making polyimidesiloxanes. The ~ reaction time for making high molecular weight polyimidesiloxanes is -~ 25 normally several times longer than that-required for making ,, ~
,i,:
~- - 25 -~, ;
,~ .
133~ 387 :
~.
polyimides due to the fact that the reactivity of the ~x~w-diamino or dianhydride siloxanes is normally lower than organic monomers. ;
In general, the high molecular weight siloxane monomers react much -slower than the organic monomers in a polar solvent. Accordingly, one can also expect that the microstructure of the polyimidesiloxane depends not only on the molar ratio of the organic to siloxane monomers (or the composition of the monomers), but also on the additional sequence of these monomers during polycondensation. For ~ --instance, when a high molecular weight CY,w-diamino siloxane is employed, one sometimes finds that it is advantageous to first react the organic dianhydride without the presence of the organic diamine.
This procedure not only can overcome the need of using a dual solvent system, but also can result in a much more uniform and controllable polyimide block size and distribution. Compared to a ~-`
~ 15 polyimidesiloxane with identical chemical make-up, but prepared with r ~ a different addition sequence (i.e., add all monomer together into a solvent at once) the polyimidesiloxane with more uniform and con-trolled imide size and distribution have a more soluble characteris-~ tic toward siloxane-like solvent or non-polar solvent. On the other h,:~,' 20 hand, polyimidesiloxanes~have the identical number average molecular ~- weight of imide-block but having a broad molecular weight distribu;
tion will be less solubl,e~in the diglyme or THF. ! ! ~
Depending on the property requirements for various ~;
- ;~ applications, one can therefore design polyimidesiloxanes by their ~ 25 composition, but also control their microstructures through monomer -~ addition sequence for one's advantage. ;
~: . .
.: :
,:..;' ".,',: ,,',',"',"",,i,"; ' '. ~
1331387 `~
The solvents that can be used for the polymerization of the present invention are the phenol solvents; N,N-dialkylated carboxylamide solvents and monoalkylated or dialkylated ether type solvents. The examples of phenol solvents are phenol, o-cresol, m-cresol, o-chlorophenol, m-chlorophenol, p-fluorophenol, 2,4,6-tribromophenol; examples of N,N-dialkylated carboxylamide solvents are N,N-dimethylformamide, N,N-dimethylacetamide, NMP;
ether type solvents are tetrahydrofuran (THF), diglyme or triglyme.
Other solvents, such as ~-butyrolactone, sulfolane, dimethylsulfox-ide and chlorinated benzenes such as p-dichloro benzene which are commonly mentioned in various polyimide patents can also be used.
- Polyimidesiloxane can also be prepared in a me1t polymerization process; especially when the glass transition temperature of the imide block is lower than say about 200C; or a large proportion (> 25%) of the siloxane comonomers is employed. In practice, the melt polycondensation can be done in an extruder in which imidiza-` tion can be achieved using a vented zone situated close to the "~
outlet nozzle.
To achieve high molecular weight polyimidesiloxanes, the total moles of dianhydride component(s) should equal the total moles of diamine component(s). To reduce the molecular weight an excess of , ~: .
-~ dianhydride, diamine components or small amounts of monofunctiqnal compounds can be employed.
When the siloxane monomer is a diamine, for every 1 mole of .,., ~
siloxane diamine employed, assume that n moles of organic diamine is ~- employed. Then n + 1 moles of organic dianhydride is employed.
^"' , ,',:- ~:
~: ~
When the siloxane monomer is a dianhydride, for every 1 mole of ~h siloxane dianhydride employed, assume that n moles of organic dianhydride is employed. Then n + 1 moles of organic diamine must be employed.
In the foregoing cases, n has a value of greater than 0.01 but no more than 40, preferably 20. -~
When 0.01 ~ n ~ 0.1, the polyimidesiloxane exhibit elastomeric ~ -or rubber properties and are useful for potting, encapsulation, and -sealing applications. Especially, a cross-linking elastomeric polyimidesiloxane will have great value in the above-mentioned applications. When 0.1~ n~ 10, polyimidesiloxanes with thermoplastic elastomeric properties are obtained. These materials --~
are useful for wire, cable, injection molding and protective coating ipplications. When 10~ n~ 40, very high strength and rigid thermoplastics are produced which are useful for molding and coating applications.
; ; The Curable Polyimidesiloxanes - The soluble polyimidesiloxanes described above have many va1uable properties and uses. However, l1mitations are found in their applications, especially in areas where higher chemical or -~ creep resistance are desirable or even critical. For instance, most ~- ` of the polyimidesiloxanes show limited hydraulic fiuid or jèt fue resistance when their siloxane content lS over 30 to 40X. Even though this weakness can be largely reduced by incorporating ~` 25 fluorinated compound into their backbone structure~ in particular, "~ ' ~ - 28 -~ ~ .
into their siloxane blocks, it is still more desirable to convert these fluorinated polyimidesiloxanes into thermosets in order to achieve higher solvent and creep resistance. In general, when a cross-linkable polyimidesiloxane carries an acrylic functionally, it can be cured by either thermal or photo-method. A photosensitive or photocurable polyimidesiloxane is especially valuable for patterning applications in microchips or integrated circuit industries.
Furthermore~ these novel curable polyimidesiloxanes, as well as the soluble polyimidesiloxanes, can also find applications in passiva-tion layer, alpha particle barrier, electron beam patterning, ion implant mask or interlayer dielectric in electronics and micro-electronic industries.
The polyimidesiloxanes of the invention can be made curable by the inclusion of reactants that have functionalities that are -~
- ~ 15 capable of being cross-linked, or that have intermediate -functionalities that can be suitably modified with cross-linkable moieties after formation of the polymer. The required functionalities can be incorporated into the polymer of the 1 , invention by use of suitable diamines and/or siloxane compounds.
The diamine compounds have the characteristic described for the soluble polymers of a diamine that provide assymetrical structure in the polyimidesiloxane ch,ai!ns. The diamines further halve the follpw-ing general formula:
, H2N -Ar -NH2 ;
,, ~ I -' ' R"
, :
1331387 ::
wherein Ar is aromatic, R" is a hydroxyl, hydrothiol or carboxylic radical, preferably a hydroxyl or carboxylic radical. The metals salts of the carboxylic groups are also contemplated. Suitable metals are sodium and silver. The typical examples of these compounds are, for instance, 3,5-diaminobenzoic acid and 3,5-di-aminophenol, and the like.
The functionalized siloxane diamines or dianhydrides have the following general structure: ;
Rl IR4 ~
,~ D-Rl-(Sj-O)_Sj_Rl_D : ~, wherein D is either an amino or anhydride group and the R1 is a ~-diradical R' or a triradical R, such as described hereinbefore.
~'~2~. Radicals R1, R2, R3 and R4 are described hereinbefore, except that ,.,~" ~ .
one or more of R1, R2, R3 and R4 can be a halogen, hydride (H), vinyl or a hydroxyl group, when D is an anhydride groupj or vinyl or hydroxyl when D is an amino group.
In the functionalized siloxane diamine or dianhydride moieties, the R1, R2, R3, and R4 groups can also be selected from acetylenic-, ethylenic- or aclrylic~groups as a result of reaction o~ moieties containing hydride (H), hydroxyl, halogen and halide groups with `
acetylenic-, ethylenic- or acrylic-bearing compounds, respectively? -~
as described hereafter.
., .
,, ' .
'~
''~
1331387 ~ ~
Examples of the functiona1ized siloxane CX,w-diamino compounds can be the following~
~ I I I ;
~ 2 ( H2)n (li-O)X(Ii - O)y -li - (CH2)n-:~ 5 CH3 R"' CH3 ~:~
;l ' ~($~ o) _($i_o-) s~H2 ~
CH3 R"' CH3 wherein n is an integral from 2 to 6, preferably 3 and 4; and Rt" is a viny:l or hydroxyl group, and x + y = 1 to 100, preferably 4-40 and y is an integer of 1 to 15, preferably 1 to 5.
The examples of the functionalizedldianhydride are:
-~ ~O ICH3 fH3 fH3 . O /R --,(Sl.--O)x-(si--O)y--Si , Rl ~ ! ~ ;~
; O CH3 R "" CH3 ., ~
~'~ - 31 - ~ :
",,.
~ 133~.387 :
where Rl is ~ ~ ~ ~ ~
~~
and R "" is selected from hydride (H), hydroxyl, halogen and vinyl ~;
groups, preferably the H and vinyl groups. The x and y have the 5 ~ same meanings as above. ;
The Process For Making Curable Polyimidesiloxanes ~ The procedures for making soluble polyimidesiloxanes are ~--~ generally followed.
The comonomers are generally copolymerized in an appropriate solvent such as NMP or diglyme. The fully imidized, polyimide-,: ..
~ `siloxane which carries at least one kind of the functionalities . .
- described above, can then be further reacted or grafted with an -s ~
acetylenic, ethylenic or acrylic-bear;ng compound to provide the final products desired for this invention. The grafting reaction is preferably conducted in a non-reactive solvent, preferably in diglyme, THF or MEK. Since there are many different functional groups that can be selecjted for the functionalized polyimidesiloxane, the grafting reaction desired for this invention has to be varied accordingly. For instance, when a carboxylic or hydroxyl-containing polyimidesiloxane is first prepared, the ~, "
~331387 ~
grafting of an acrylic group can be achieved by using either an epoxy-bearing acrylate such as the O - ~:
CH / CH~ ~CH~
5/\ ,~C C
o C~3 o ~ CH, ~ CH ~ \l ~ O - C ~ (n-o~
- CH
, :, ~ 10 or an isocyanate-bearing acrylate such as ,., , . ~ .
, ~ O
. O C ~N ~ 4C~i ( 3 ::~
~ ; ~
" ~
When the functional group of the polyimidesiloxane is located ~ .
- in the siloxane blocks, the grafting reaction can be achieved using ~ n;
~'~ 15either an hydrosilylation reaction or a condensation reaction. For ~ ;
G
~- 33 .
r r~ ~
.
;~
133J 387 :: ~
f ~H~
instance, when a ~ ~; J~ group in which y is an integer o~
l to 15 is present in a polyimidesiloxane, the grafting can be achieved via hydrosilylation: i.e., reaction of a vinyl group with a Si-H
group in the presence of a catalyst, such as a Pt catalyst. Therefore grafting o~ a ca~poundo ~
in which n is 0 to 2 results in an acrylate-bearing polyimidesiloxane.
- When a -OH or epoxy group i~ present in the poly~midesiloxane, on the other hand, the grafting can be achieved via a condensation reaction. For instance, the reactions of the isocyanate-bearing acrylate or an acrylic acid or methylacrylic acid with the hydroxyl or epoxy group on the polyimidesiloxane can result in an acrylic-bearing polyimidesiloxane desired for the present invention.
.
When an acetylenic-bearing compound also bears a carboxylic, an epoxy or isocyanato functionality, it is clear that the compounds - can be grafted onto a polyimidesiloxane which carries an -OH or, a carboxylic group, respectively. ~ -When an ethylenic group is present in the siloxane block of the polyimidesiloxane, it cajn be used as such, and further be cured thermally via free radical cross-linking reactions or can be further changed into polyimidesiloxanes which carry either an acrylic or an acetylinic group. The grafting reaction of this kind is difficult to achieve, however, due to the lack of appropriate chemicals.
'B - ~
I ,, ~, . . " ". .-.. ; . .... ., , ~ .
To prepare the functionalized polyimidesiloxanes with a functional group presented in the imide block, it is preferred to ~
start with an OH or -COOH-bearing diamino compound. On the other -hand, this kind of siloxane monomer is usually not readily available. The incorporation of epoxy, silicone hydride or sil;cone hydroxyl group can be achieved via equillibration of theCX,w-diamino or CX,w- dianhydride siloxane with cyclic silicone epoxy, silicone hydride or silicone hydroxy compounds. In any event, it is preferred to graft the acrylic or ethylenic or acetylenic group rather than using an acrylic, ethylenic or acetylenic diamino or dianhydride compound for making the desired polyimidesiloxan~e. This is to avoid thermally cross-linking reactions of these functionalities during imidization of the polyimidesiloxane at high temperatures (about 160 tc 170C/2 hrs in solvent). A grafting ~" ~` : ~
~ 15 reaction of a fully imidized polyimidesiloxane with the above ., ~ ,, described functionalities can be, in general, carried out at much lower temperatures. For instance, the hydrosilylation can be carried out at temperatures as low as 25C in the presence of a platinum catalyst. The condensation between the hydroxyl or r ~
~ 20 carboxylic group with the epoxy group can be achieved at ~. ~
~, . , ,j,'b, ~ temperatures of no more than 120C, within hours with the presence ;~
-- ~ of a tertiary am,ine as a catalyst. In this invention, the pyridine ~-- compound serves as the tertiary amine. The reaction of an hydroxyl or carboxylic group with an isocyanate group needs even lower ~- 25 temperatures (RT to 80C), and the like.
~7~, 35 ~
,~
r 3 3 1. 3 8 7 ~ .
To avoid the need for isolation of the reaction product from solvent, it is desirable to conduct the grafting reaction in the solvent which is acceptable for coating operations. The desirable solvents of these kinds are solvents with low flammability and/or toxici~y, such as diglyme or MEK. The latter has been widely employed in coating industries due to its low boiling temperature.
In this specification and claims halogen shall refer to fluorine, chlorine, bromine and iodine, but preferably to fluorine and chlorine. Aromatic generally refers to hydrocarbon aromatic. -~
In the following Examples and throughout the specification and claims, parts are by weight and temperatures are in degrees Celsius, unless indicated otherwise.
~ . . .
EXAMPLES
Example 1 (A) - 15 Preparation of 2,5-diaminobenzotrifluoride 2-Amino-5-nitrobenzotrifluoride (51.6 9, 0.25 mole), ~- manufactured by Marshallton Research Laboratories, Inc., was dissolved in 95% aqueous ethanol (100 ml) and 25% aqueous sodium ; hydroxide solution (20 ml) and was heated to gentle reflux. Zinc `~ 20 dust (65 9, 1.00 9 atom) was added slowly (50 minutes) at a rate to maintain reflux without external heating. After one hour, the mixture was filtered hot and the filter cake was extracted with two 75 ml portions of hot ethanol. The filtrate, combined with the , . -~ washings, was concentrated under vacuum producing dark crystals ~
,, .
, r ~ 36 -, .
.- ... .
,~ ' '".:
133~387 (42 9, 95% yield). These were recrystallized from methanol/
methylene chloride.
Example 1 (B) Preparation of CY,w-diaminoaryl Diether Compound Two moles of 2-chloro-5-nitrobenzotrifluoride (I) and one mole of hydroquinone (II) are dehydrochlorinated by reaction at an elevated temperature, in the presence of potassium hydroxide or potassium carbonate, in a polar aprot;c solvent, such as dimethyl formamide, to yield the dinitro-diether compound III. This compound is then hydrogenated by iron and concentrated hydrochloric acid to the corresponding CX,w-diaminoaryldiether compound IV.
Example 2 Preparation of Polyimidesiloxane :. :
Nine polyimidesiloxane compositions were prepared from 2,5-diaminobenzotrifluoride, 4,4'-oxydiphthalic anhydride (ODPA) and ~- an CX-w-diaminosilane. The siloxane block size was 1, 7.5 or 12 ~ ~ ~ units and the total siloxane content in the polyimidesiloxanes was - ~20, 30 or 40 percent. The actual formulations are given in Table 1, ;;
-~ and the procedure used is given below.
To 1-methyl-2-pyrrolidinone, commonly known as N-methyl pyrrolidone (NMP? (40 ml~) was added ODPA and the mixture was stirred until the dianhydride had dissolved (5 minutes). Then, the CY-w-amino- siloxane was added and the solution stirred at ambient .:
temperature for 2 hours. Finally, the 2,5-diaminobenzotrifluoride - 25 was added and the solution was stirred for another 16 hours. The ", ~
viscous solution was cast on to a Teflon coated mold which was subsequently hea~ed at 140C for 4 hours and at 2500 for 0.5 hours to remove so,lvent and complete the imidization. ~ -Nine films prepared. Two were tested for percent elongation and tensile strength, and the results are shown in Table 2.
Table 2 Example No. Percent ElongationTensile Strength (psi) ' ;~
2C 3.5 + 0.4 6730 `,~,' 2F 1.02 1041 , Example 3 Polyimidesiloxanes Containing BTDA ;' ' Nine formulations were prepared from BTDA together with 2,5-diaminobenzotrifluoride and CX-w-diaminosiloxane using the conditions and procedures of Example 2, except substituting BTDA for, '~
ODPA. The siloxane block size was 1, 7.5 or 12 units and the total siloxane content in the polyimidesiloxanes was 20, 30 or 40 percent.
' The actual formulations are given in Table 3. Films were prepared from each formulation and the solubilities in solvents are al,so ': 20 shown in Table 3.
* trade-mark ',; - " :
-, - 38 - ~, 133l387 Example 4 Polyimidesiloxanes Containing BPDA
Nine formulations were prepared from BPDA together with 2,5-diaminobenzotrifluor;de and CY-w-diaminosiloxane using the conditions and procedures of Example 2, except substituting BPDA for ODPA. The siloxane block size was 1, 7.5 or 12 units and the tota1 ~;~
siloxane content in the polyimidesiloxanes was 20, 30 or 40 percent. ~
The actual formulations are given in Table 4. Films were prepared ~-from each formulation and the solubilities in solvents are also shown in Table 4.
In the foregoing examples, Gm has the formula~
CH, CH~ ~-~ ~ H~l o~$i~CH,~NH, CH, CW, where m indicates the average number of repeating units, as shown in Table 1, for example, G7-5 and G12. ;~
r~
- 39 ~
., ~
~, ~
~331387 59 siloxane monomer is an equilibrium product of one mole of with 2 moles of D4 at 87-90C. G1 has the following structure:
ICH3 CI H3 , ~ ' H2N,v~Si - o~ NH2 and D4 is the cyclic tetramer having the formula CH
~ i ~ . (Si - 0 -)4 ~-. .
-: ~ CH3 ;
In the formula, and in the Examples, when G has a nominal value of 9 units, experimentally G had a value of about 7.5. Similarly, when G . ;;
.-:
has:a nominal value of 13 units, experimentally G had a value of .~ about 12. The experimental measurements were done by silicon-29 ii NMR. :~
;,,~,: ' r,:
~ In general,polylmidesiloxane made with a mixture of, for instance, 2,4- and 2,6-tolyldiamine are more soluble in diglyme than polymers made from a single tolyldiamine such as 2,4-tolyldiamine. ~ ~
The solubility of the polyimidesiloxanes of the invention in ~ :
'J'. solvents, suc~ as q~IF, ND? o~ diglyme is a function of the ::
~ 20 Enoportaon of the siloxane ccmponent in the ~ ~:
~ . ' , . .
5S~
~ - 40 - -~ :
", ' ;~
1331387 :
polyimidesiloxane and is also a function of the siloxane block size.
Thus, the siloxane monomer is preferably present in a proportion and has a sufficient block size to render the polyimidesi10xane soluble in a solvent such as THF, NMP or preferably diglyme.
The polyimidesiloxanes of the invention are useful in a variety of applications in the micro-electronic industry. Such applications include use in the form of coatings as interlevel dielectrics and for encapsulation or passivations of semiconductors and hybrid integrated circuits. Coatings of the polyimidesiloxanes can be used in the fabrication of semiconductor devices in the following areas~
a) as a protective overcoat, b) as an interlayer dielectric for multi-level devices, c) as an alpha particle barrier, d) as a ;~
non-implant mask, and e) as an encapsulant. Most of these uses are :: : , .
- ~ descrlbed in detail for polyimides by Lee and Craig in Polymer ~ 15 Materials for Electronic Applicatians, ACS Symposium, Ser. 184, page s-~ 108.
,,, - .:::Other uses for the polyimidesiloxanes of the invention include - wire and cable coatings, in fibers and films, and molded and ~-extruded~articles. Other uses include uses for liquid crystal ~ alignment and for die-attach adhesives.
:; , ! , . . .
,,-, ~ ~
-~ . "
~-, , +
~ ~ I ,.
o C~ I , v~ zl ~ + + + + + + + + , ~--o ~ ~ ,~ oo o ~ Ln oo ,~ :
._ ~ ~ oo ~ ~ I~ o r~
_ o~
E
~E _ C
C~ o o o o o o o o o S N ~ ~ C~J ~ et C~.l ~) ~ q~
._ ~e c X
r !~
Ul ': ' ';'~ .
~ ~ J v r_ o Ln ~ oo~
~' CC ~ ~ ~ ~
C ~ _I O ~) N _ ~ N C~
,,~
,-:
~ ;~ 00 C~J 0 N N ~ 1~ U:l ~ 11 ~ _ ~ 0~
~ - ~ ~ N ~ ~ ~ ~ ~ N ~ E
,.: o ~a~
,~ C~ Ln ~ o L~ o ~ ~ ~ c o 3 ~ d~ ~t O Lt~ 3 o ~ C
~ X ~ o ,:-, _ O O ~ Q~
-- N _ C
- _ ~ C~ ---- _ E -- C~ O
E
E u~ t~ ~ et o oID x~:~ _ s E
O ~ In ,, _ ~ C~ ~ ' ~ -- d~ e~ O I ~ ~
~ ~ I ~0 ~0 c~ ~ ~-- C2~ C~d'~t ~ ~n E O
_ u~ o o ~
.- c~ m : ::
o o o o o o o o 0~ 0 E~ ~ z ~ ?~
, ~ ~
"''' ~- ~':;'~-"
:~ ~ E z ~c ~ ~ O ~ ~ ~ _, :~' ~ ~1 ,~ :
',: ' -,~ ~
u~ ,,~ ~
m + + ~ I I I I I ~, -.
.
. ~ I I +
.
o ~ .
c~
s ~ ~
x ~ ~e . .. . . . . . .
o o .
~
v~ . , a, ~
~ o , E E 7~ oo L~ cn ~ C~l C~J N N
o ~ oa~ ~
, ~') ~:' J
- ~ ~ CC . N ~ o o oo 1 ,:}~, ~) 00et O ~ U) t~ ~ ~ c~J c ' ~ ~. ~ E ~et :?, ~ ~ ~ O ~
. ~ cC U~ O N ~ X ~ ~ ~O O
, : E ~ o o. ~ xo ' ~ ~-~ C O ' '~
~ E ~ ,, . ~ ~ ' , C ! ~
,- o ~ E .
_ O
. ~ ~ :
~: ` E ~ T
Z
.',` ' . ~ :
:~ - 4 3 -J , ~
cn ~ ' . ~
C~ I +
o ~ , sl + + + I l + l l +
, ! .
' ~:
a~ ~ ~ ~ N 1~ ~
:~ X o ~ U~
_ ~ ~ ' ~
~ O
E ~ ~ ~ ~ ~ N N O O o~
~ ~ ¦ 2 ~ ~ N ~ ~:t 2 ~ ~ _ ~ :
t X~ ~
J C~ ~ 00 N 1~ --I U
, ~ : ¦ N _I O ~ ~ ~ N C~
-~,.
: _ ~
O N ~ ~ N ~ et c~J ~ ~t C
S O ~:
C y E . ! ~ l ~: O ~ _ E
_ --I O ~0 U~ ~N ~ - ~ODet N ~ C~
_ u~ m N
_ E occ ~ C.~ ~ ~ ~ ~ ' I -- ~
~,,', XZ ~ ~t ~ ~ d e~ d- ~ ~ ,~,;`,~
" ~ o s ~ 44 . : -:
t~, ~ ~ ''"' ~' ";
"
"~
Examples of useful compounds of the above generic formula are .~
as follows: C ~ ~CF3 ~-;
~ ~ N H2 H2N~O~O~NH
~0 ~ ~
~:
H 2N ~ O ~ O ~ N H2 ~'~
H2N~}~~NH2 ' - 13 -,:
,',: ;,:
,' ' ~, 1331 387 ~:
The preferred compound is 2,5-diaminobenzotrifluoride 2,5-(DABFj, which has the formula -~
H2N~
The preparation of compounds with n = 1 Ar =
: and Z = O can be achieved, for instance, by the following reaction :~ schemes: CF
v~ 1 3 ~ 10 2 _~CI ,~OH KOH/K2C03 >
i".. ~ ~ :
2 ~
Fe/HCI > H N~ LNH2 J ~ ~ CF3 ~ : - 14 - ~:
,~,' ~' : 133~.3~7 It has been found that diamines that provide asymmetrical structure in the polyimidesiloxane chains are useful in combination with the amines such as DABF, in making polyimidesiloxanes with the desirable and superior properties of this invention.
Other suitable diamines that provide asymmetrical structure in -the polyimidesiloxane chain have the following formula:
NH2~NH2 z -~--~ 10 where x, y and z are independently selected from hydrogen, halogen, alkyl or aryl or halogenated aryl of 6 to 12 carbon atoms. The preferred diamines have at least one alkyl substituent having at ~-least one carbon atom. -Examples are: 2,4-tolyldiamine ~~ 15 2,5-tolyldiamine 2,6-tolyldiamine m-xylyldiamine 2,4-diamine-5 chloro toluene 2,4-diamine-6-chloro toluene - 20 2,4,6-trimethyl 1,3-diaminobenzene ~-~
~ ., .
~ : ~
~, '''~''"' '' ' ' ''' " "'; '"'''""'''''' ';''''''"'"''~''''''''"';'''''''''''"''' ' '' '' ~',' .' " ' ~` 133~387 : ~
Other useful diamine compounds that are asymmetr1cal 1n the polymer chain include compounds with the formula:
H ~N ~ X~jN H;7 where;n x is -CH2-, -5-, O, ,C, , ~C~
Examples are: m,m-methylene dianiline m,m-sulfone dianiline ~ ~-o,m-sulfone dianiline.
~ Another suitable diamine that is asymmetrical in the polyimide~
- 10siloxane is diaminoanthraquinone.
-~ An especial1y preferred auxiliary diamine is a mixture of ~; ~2,4-tolyldiamine and 2,6-tolyldiamine, especially the commercially available mixture of about 80 weight percent 2,4-tolyldiamine and ,., . .. ~
J'~ about 20 weight percent 2,6-tolyldiamine. -~
15Small amounts up to about 25 weight percent of diamines that ;~
are not asymetrical in the polymer chain can be employed in the polyimidesiloxane compositionis. Such other diami'nes are disclused - in U.S. Patents Nos. 4,395,527 and 4,586,997.
''' . . ',,.,"'' ~ ~
- 16 ~
. ~
Such auxiliary diamines have the formula :~
H~N ~ x ~ ~H, wherein x is preferably -5- for retaining solubili b in diglyme, THF or MEK. In addition, the x can also be C , -O-, -S- and -CH2- for achieving only solubility in NMP. Additional organic :
diamines can be employed in much smaller quantities without -~:~
affecting the favorable combinations of thermal stability glass transition temperature and solubility.
The Organic Anhydrides 10: The present invention is based on the discovery that the use ofthe above-described diamines (typified:by DABF) when reacted with : organic dianhydrides provide fully imidized polyimidesiloxanes which have~a unique combination of solubility and thermal properties.
Useful organic dianhydrides include compounds having the :~
15:: following general formula~
O
- 17 - ~`
ir' ~ i33i 387 wherein Ar is `
i ~,; ~`
~;' ; ~
~ / CF3 O .
wherein Y ~s O, C, C , CnH2n, S, S , .
o -:
Other examples of such other dianhydrldes are disclosed in U.S.
~ Patents:Nos. 4,395,527 and 4,586,997. Hcwever, even though the .
incorporation of these dianhydrides may alter only slightly thesolubility of the resulting polyimidesiloxanes in NMP or diglyme, these modified polyimidesiloxanes may become insoluble in solvents, such as MEK or THF. This limits their applications where a very low -~:
; boiling, non-toxic solvent such as MEK is required. In addition, the incorporation of the diether dianhydrides (DEDA), also reduces the glass transition temperature and thermal stability of 133~ 387 polyimidesiloxanes of the invention and limlt the;r upper use . ~.
temperatures.
Preferred organic anhydrides that can be used in the practice of the invention lnclude:
---Oxydiphthalic anhydrides (ODPA), such as disclosed in .
U. S . Patent 4, 973, 645, :. ~
~;----Sulfurdiphthalic anhydrides (SDPA), such as disclosed in .
U.S. Patent 4,956,437;
---Sulfonediphthalic anhydrides;
---Benzophenone tetracarboxylic dianhydride (BTDA);
---Biphenyl tetracarboxyljc d~anhydrides (BPDA); ;~
---Bis(dicarboxyphenyl)-hexafluoropropene dianhydride, (6FDA);
---Diether dianhydrides (DEDA); such as disclosed in U.S.
Patent No. 4,395,527.
M~xtures of the foregoing anhydrides can also be employed.
Particularly useful are the following mixtures of anhydrides:
BPDA and BTDA
6FDA and ODPA
6FDA and BPDA ;
B~DA and ODPA. ~:`
, .;~ ' -- 133~ 387 The Siloxane Monomers Siloxane diamino compounds that can be used for the present ;~
invention have the following formula~
3 . ~:
~ 5 H,N-~R ~ 5; -O ~ ~ R - N~
. ~, ; wherein m is a number from about 5 to about 200, preferably 5 to 50, Rl, R2, R3 and R4 are independently selected frcm a ~;
substituted or unsubstituted aliphatic mono-radical of 1 to 12 .
carbon atoms or substituted or unsubstituted aromatic mono-radical of 6 to 10 carbon atoms. Suitable radicals include -CH3, -CF3, -(CH2)nCF3 , -C6H5, -CF2-CHF-CF3 and -CH2-CH2-C-0-CH2CF2CF2CF3.
; R' is a di-radical of the foregoing type. Suitable di-radicals nc ude ~CH2~n' ~CF2~n' ~(CH2)n(cF2)m- and -C6H4-, wherein m and n =
1 to 10.
-~ 15 The employment of an CX,w-diaminosiloxane is important for - achieving the desired solubility in diglyme, THF or MEK in the present invention. The siloxane diamine also provides the flexi-bility or resi~liqnce ofithe polyimidesiloxanes at low tempçratures, especially when the m is an integer of more than about 5, or preferably more than about 7. When the m is more than about 50, the ;~
- incorporation of diaminosiloxane into the polyimidesiloxane becomes difficult even though it is not impossible; and a dual solvent~ ~ ;
c - - 20 - ~
:
~ e ;~
133~ 387 ::
;.~
system (one polar and one non-polar solvent) for copolymerization may have to be employed. In general, the employment of the CX,w-diaminosiloxane and CX,w-dianhydride siloxane are interchange- ;
able in the present invention. However, for making polyimide-siloxanes of high glass transition temperature, the mole percent of the mixture of dianhydrides in the total dianhydride shoùld be maximized; and therefore, it is more desirable to employ the combination of the organic dianhydride with an organic diamine and an CX,w-diaminosiloxane. ;~
Siloxane dianhydrides which can be incorporated instead of or in addition to the siloxane diamines for the practice of the present invention can have the formula:
- ' ~
~ o/ \R ~ o ~ 5 - R\ \O
;~ - 15 ~ wherein m is a number from about 5 to about 200, Rl, R2, . ,~ . .
R3 and R4 are independently selected from a substi-tuted or unsubstituted aliphatic mono-radical of 1 to 12 carbon atoms substituted or unsubstituted aromatic mono-radical of 6 to 10 carbon atoms~, SuitableOradicals include -CH3, -CF3, -(CH2)nCF3;
-CF2-CHF-CF3, -cH2-cH2-c-o-cH2cF2cF2cF3 and 6 5 ;~`
R is a tri-radical of the foregoing type. Suitable , --- tri-radicals include -CH ' , ~33~.387 ~:
It is also well-known to those skilled in the art that when the : C6H5- or CF3CH2-CH2- group is used in the siloxane block, in ;~:
replacement of the -CH3 group, the solubility of resulting ~-; 5~ polyimidesiloxanes in chlor1nated solvents, such as CH2Cl2 and ether ~;
solvent such as diglyme~and~THF will increase. In addition, the ~,S~
pol~yimidesiloxane copolymers consist of phenylated siloxane block, or fl~uorinated siloxane block~will also have higher thermal stability.~ This is due to the fact that the least thermally stable ~ ~
'''?~ ' 10 ~ , groups in the po,lyimides,iloxanes is the -CH3 grfoup on the si~oxane ~ --block. Accordingly, w1thout showing specific examples one can expect that polyimidesiloxanes of the present invention can be - further improved by incorporating the C6H5 group or CF3CH2 group s- into their siloxane~blocks in order to improve their solubility and thermal stability. 22 ~"'~ ~ ~ :',.;~
,".
-When various dianhydrides are employed, their solubility in various solvents, glass transition temperatures and thermal stability changes depending on the chemical nature of these co-monomers. For instance, when a siloxane dianhydride is incorporated in the presence of a dianhydride, the solubility of the polymer increases, while the glass transition temperature and thermal stability will be lowered. Therefore, depending on the requirements for applications, the incorporation of siloxane dianhydride may become unfavorable. On the other hand, when an organic dianhydride such as PMDA is added in small proportions of ~-less than 5 mole percent, the resulting polyimidesiloxanes still has ~7 the desirable solubility in, for instance, NMP. The incorporation of PMDA can increase the glass transition temperature and thermal stability of the resulting polyimidesiloxanes, and, therefore, can provide more favorable products for extrusion or injection molding applications. However, one may also find that even with a small amount of PMDA in the polyimidesiloxanes, the resulting copolymers .~ .
may become insoluble in solvents, such as diglyme, THF or MEK, and their applications as coating materials will be limited, for instance, in heat sensitive`electronic devices or substrates.
The Process For Soluble Polyimidesiloxanes Although the chemistry for reactions of organic diamines with ~
- organic dianhydrides has become well-known, the preparation of ~ -~ polyimidesiloxanes in the presence of the siloxane comonomers may ~ ~--~ 25 sometimes require special techniques. For instance, when the repeating unit m, of the siloxane monomer is larger ?'~ :
(i.e., > 20 to 40), it may be desirable to use a dual solvent system: i.e., a solvent system consisting not only of a polar solvent, but also a less polar solvent. (See, for instance, McGrath et al, Polymer Preprints, 27 (2), 1986, pp. 403). It is also known that in the practice of making soluble polyimides, if a polyimide is soluble in a given solvent, in which the polyam;de acid is not soluble, one can prepare the polyimide directly in a one step polymerization process, that is, by a simultaneous imidization and polycondensation process, referred to as the one-step process. This -procedure can be advantageous, especially when a desirable polymer solution for coating applications has to be made out of a given solvent in which the polyamide acids are not soluble. The problem with the simultaneous imidization and polycondensation is that the ~ ~;
depolymerization of the polyamide acid in the presence of the water which is produced during the imidization step, can be very severe.
Theoretically, the depolymerization can become an irreversible process, since it produces a dicarboxylic acid and an amino compound. The carboxylic acid reacts with amino compounds at much higher temperatures as compared to the almost instantaneous reaction ~--of the dianhydrides with the amino compounds at room temperature.
The depolymenization of polyamide acids can become very severe at high temperaturss. This oneTstep process often~produces ! ' ' polyimidesiloxanes with much lower molecular weight as compared to those produced in a good solvent, in which the polyamide acid and - 25 the imidized polymers are both soluble, and one employs a two-step process. The two-step process employs a low temperature 133~.387 polycondensation step which generates very high molecular weight polyamide acid and then a very fast heating step to imidize and remove water generated from imidization.
The two-step process produces higher molecular weight materials which have higher thermal stability and mechanical strength, -especially higher elongation at break. The polycondensation temperature for the two-step process should be below 60C, preferably below room temperature. The imidization can be carried out at temperatures from 90C to 180C, or the refluxing temperature of the solvents. When the boiling temperature of the desirable solvent for imidization is below 160C, the use of dehydrating agents and/or a base catalyst is desirable. A suitable dehydrating agent is acetic anhydride. The catalyst is a tertiary amine, such as pyridine. When the acetic anhydride is employed, lower imidiza-tion temperatures can be employed to complete the imidization. In ~, ~- addition, an azeotropic agent with water can also be added to the - reactor. The use of an azeotropic agent such as toluene can facili-tate the removal of water presented in the reactor and minimize the depolymerization of the polyamide acids. When an azeotropic agent ;~ 20 is employed, a continuous recovery of fresh azeotropic agent can be achieved by using also a Dean Stark trap under the condenser.
The degree cf polycondensation is importan~ for obtaining good thermal and mechanical properties in making polyimidesiloxanes. The ~ reaction time for making high molecular weight polyimidesiloxanes is -~ 25 normally several times longer than that-required for making ,, ~
,i,:
~- - 25 -~, ;
,~ .
133~ 387 :
~.
polyimides due to the fact that the reactivity of the ~x~w-diamino or dianhydride siloxanes is normally lower than organic monomers. ;
In general, the high molecular weight siloxane monomers react much -slower than the organic monomers in a polar solvent. Accordingly, one can also expect that the microstructure of the polyimidesiloxane depends not only on the molar ratio of the organic to siloxane monomers (or the composition of the monomers), but also on the additional sequence of these monomers during polycondensation. For ~ --instance, when a high molecular weight CY,w-diamino siloxane is employed, one sometimes finds that it is advantageous to first react the organic dianhydride without the presence of the organic diamine.
This procedure not only can overcome the need of using a dual solvent system, but also can result in a much more uniform and controllable polyimide block size and distribution. Compared to a ~-`
~ 15 polyimidesiloxane with identical chemical make-up, but prepared with r ~ a different addition sequence (i.e., add all monomer together into a solvent at once) the polyimidesiloxane with more uniform and con-trolled imide size and distribution have a more soluble characteris-~ tic toward siloxane-like solvent or non-polar solvent. On the other h,:~,' 20 hand, polyimidesiloxanes~have the identical number average molecular ~- weight of imide-block but having a broad molecular weight distribu;
tion will be less solubl,e~in the diglyme or THF. ! ! ~
Depending on the property requirements for various ~;
- ;~ applications, one can therefore design polyimidesiloxanes by their ~ 25 composition, but also control their microstructures through monomer -~ addition sequence for one's advantage. ;
~: . .
.: :
,:..;' ".,',: ,,',',"',"",,i,"; ' '. ~
1331387 `~
The solvents that can be used for the polymerization of the present invention are the phenol solvents; N,N-dialkylated carboxylamide solvents and monoalkylated or dialkylated ether type solvents. The examples of phenol solvents are phenol, o-cresol, m-cresol, o-chlorophenol, m-chlorophenol, p-fluorophenol, 2,4,6-tribromophenol; examples of N,N-dialkylated carboxylamide solvents are N,N-dimethylformamide, N,N-dimethylacetamide, NMP;
ether type solvents are tetrahydrofuran (THF), diglyme or triglyme.
Other solvents, such as ~-butyrolactone, sulfolane, dimethylsulfox-ide and chlorinated benzenes such as p-dichloro benzene which are commonly mentioned in various polyimide patents can also be used.
- Polyimidesiloxane can also be prepared in a me1t polymerization process; especially when the glass transition temperature of the imide block is lower than say about 200C; or a large proportion (> 25%) of the siloxane comonomers is employed. In practice, the melt polycondensation can be done in an extruder in which imidiza-` tion can be achieved using a vented zone situated close to the "~
outlet nozzle.
To achieve high molecular weight polyimidesiloxanes, the total moles of dianhydride component(s) should equal the total moles of diamine component(s). To reduce the molecular weight an excess of , ~: .
-~ dianhydride, diamine components or small amounts of monofunctiqnal compounds can be employed.
When the siloxane monomer is a diamine, for every 1 mole of .,., ~
siloxane diamine employed, assume that n moles of organic diamine is ~- employed. Then n + 1 moles of organic dianhydride is employed.
^"' , ,',:- ~:
~: ~
When the siloxane monomer is a dianhydride, for every 1 mole of ~h siloxane dianhydride employed, assume that n moles of organic dianhydride is employed. Then n + 1 moles of organic diamine must be employed.
In the foregoing cases, n has a value of greater than 0.01 but no more than 40, preferably 20. -~
When 0.01 ~ n ~ 0.1, the polyimidesiloxane exhibit elastomeric ~ -or rubber properties and are useful for potting, encapsulation, and -sealing applications. Especially, a cross-linking elastomeric polyimidesiloxane will have great value in the above-mentioned applications. When 0.1~ n~ 10, polyimidesiloxanes with thermoplastic elastomeric properties are obtained. These materials --~
are useful for wire, cable, injection molding and protective coating ipplications. When 10~ n~ 40, very high strength and rigid thermoplastics are produced which are useful for molding and coating applications.
; ; The Curable Polyimidesiloxanes - The soluble polyimidesiloxanes described above have many va1uable properties and uses. However, l1mitations are found in their applications, especially in areas where higher chemical or -~ creep resistance are desirable or even critical. For instance, most ~- ` of the polyimidesiloxanes show limited hydraulic fiuid or jèt fue resistance when their siloxane content lS over 30 to 40X. Even though this weakness can be largely reduced by incorporating ~` 25 fluorinated compound into their backbone structure~ in particular, "~ ' ~ - 28 -~ ~ .
into their siloxane blocks, it is still more desirable to convert these fluorinated polyimidesiloxanes into thermosets in order to achieve higher solvent and creep resistance. In general, when a cross-linkable polyimidesiloxane carries an acrylic functionally, it can be cured by either thermal or photo-method. A photosensitive or photocurable polyimidesiloxane is especially valuable for patterning applications in microchips or integrated circuit industries.
Furthermore~ these novel curable polyimidesiloxanes, as well as the soluble polyimidesiloxanes, can also find applications in passiva-tion layer, alpha particle barrier, electron beam patterning, ion implant mask or interlayer dielectric in electronics and micro-electronic industries.
The polyimidesiloxanes of the invention can be made curable by the inclusion of reactants that have functionalities that are -~
- ~ 15 capable of being cross-linked, or that have intermediate -functionalities that can be suitably modified with cross-linkable moieties after formation of the polymer. The required functionalities can be incorporated into the polymer of the 1 , invention by use of suitable diamines and/or siloxane compounds.
The diamine compounds have the characteristic described for the soluble polymers of a diamine that provide assymetrical structure in the polyimidesiloxane ch,ai!ns. The diamines further halve the follpw-ing general formula:
, H2N -Ar -NH2 ;
,, ~ I -' ' R"
, :
1331387 ::
wherein Ar is aromatic, R" is a hydroxyl, hydrothiol or carboxylic radical, preferably a hydroxyl or carboxylic radical. The metals salts of the carboxylic groups are also contemplated. Suitable metals are sodium and silver. The typical examples of these compounds are, for instance, 3,5-diaminobenzoic acid and 3,5-di-aminophenol, and the like.
The functionalized siloxane diamines or dianhydrides have the following general structure: ;
Rl IR4 ~
,~ D-Rl-(Sj-O)_Sj_Rl_D : ~, wherein D is either an amino or anhydride group and the R1 is a ~-diradical R' or a triradical R, such as described hereinbefore.
~'~2~. Radicals R1, R2, R3 and R4 are described hereinbefore, except that ,.,~" ~ .
one or more of R1, R2, R3 and R4 can be a halogen, hydride (H), vinyl or a hydroxyl group, when D is an anhydride groupj or vinyl or hydroxyl when D is an amino group.
In the functionalized siloxane diamine or dianhydride moieties, the R1, R2, R3, and R4 groups can also be selected from acetylenic-, ethylenic- or aclrylic~groups as a result of reaction o~ moieties containing hydride (H), hydroxyl, halogen and halide groups with `
acetylenic-, ethylenic- or acrylic-bearing compounds, respectively? -~
as described hereafter.
., .
,, ' .
'~
''~
1331387 ~ ~
Examples of the functiona1ized siloxane CX,w-diamino compounds can be the following~
~ I I I ;
~ 2 ( H2)n (li-O)X(Ii - O)y -li - (CH2)n-:~ 5 CH3 R"' CH3 ~:~
;l ' ~($~ o) _($i_o-) s~H2 ~
CH3 R"' CH3 wherein n is an integral from 2 to 6, preferably 3 and 4; and Rt" is a viny:l or hydroxyl group, and x + y = 1 to 100, preferably 4-40 and y is an integer of 1 to 15, preferably 1 to 5.
The examples of the functionalizedldianhydride are:
-~ ~O ICH3 fH3 fH3 . O /R --,(Sl.--O)x-(si--O)y--Si , Rl ~ ! ~ ;~
; O CH3 R "" CH3 ., ~
~'~ - 31 - ~ :
",,.
~ 133~.387 :
where Rl is ~ ~ ~ ~ ~
~~
and R "" is selected from hydride (H), hydroxyl, halogen and vinyl ~;
groups, preferably the H and vinyl groups. The x and y have the 5 ~ same meanings as above. ;
The Process For Making Curable Polyimidesiloxanes ~ The procedures for making soluble polyimidesiloxanes are ~--~ generally followed.
The comonomers are generally copolymerized in an appropriate solvent such as NMP or diglyme. The fully imidized, polyimide-,: ..
~ `siloxane which carries at least one kind of the functionalities . .
- described above, can then be further reacted or grafted with an -s ~
acetylenic, ethylenic or acrylic-bear;ng compound to provide the final products desired for this invention. The grafting reaction is preferably conducted in a non-reactive solvent, preferably in diglyme, THF or MEK. Since there are many different functional groups that can be selecjted for the functionalized polyimidesiloxane, the grafting reaction desired for this invention has to be varied accordingly. For instance, when a carboxylic or hydroxyl-containing polyimidesiloxane is first prepared, the ~, "
~331387 ~
grafting of an acrylic group can be achieved by using either an epoxy-bearing acrylate such as the O - ~:
CH / CH~ ~CH~
5/\ ,~C C
o C~3 o ~ CH, ~ CH ~ \l ~ O - C ~ (n-o~
- CH
, :, ~ 10 or an isocyanate-bearing acrylate such as ,., , . ~ .
, ~ O
. O C ~N ~ 4C~i ( 3 ::~
~ ; ~
" ~
When the functional group of the polyimidesiloxane is located ~ .
- in the siloxane blocks, the grafting reaction can be achieved using ~ n;
~'~ 15either an hydrosilylation reaction or a condensation reaction. For ~ ;
G
~- 33 .
r r~ ~
.
;~
133J 387 :: ~
f ~H~
instance, when a ~ ~; J~ group in which y is an integer o~
l to 15 is present in a polyimidesiloxane, the grafting can be achieved via hydrosilylation: i.e., reaction of a vinyl group with a Si-H
group in the presence of a catalyst, such as a Pt catalyst. Therefore grafting o~ a ca~poundo ~
in which n is 0 to 2 results in an acrylate-bearing polyimidesiloxane.
- When a -OH or epoxy group i~ present in the poly~midesiloxane, on the other hand, the grafting can be achieved via a condensation reaction. For instance, the reactions of the isocyanate-bearing acrylate or an acrylic acid or methylacrylic acid with the hydroxyl or epoxy group on the polyimidesiloxane can result in an acrylic-bearing polyimidesiloxane desired for the present invention.
.
When an acetylenic-bearing compound also bears a carboxylic, an epoxy or isocyanato functionality, it is clear that the compounds - can be grafted onto a polyimidesiloxane which carries an -OH or, a carboxylic group, respectively. ~ -When an ethylenic group is present in the siloxane block of the polyimidesiloxane, it cajn be used as such, and further be cured thermally via free radical cross-linking reactions or can be further changed into polyimidesiloxanes which carry either an acrylic or an acetylinic group. The grafting reaction of this kind is difficult to achieve, however, due to the lack of appropriate chemicals.
'B - ~
I ,, ~, . . " ". .-.. ; . .... ., , ~ .
To prepare the functionalized polyimidesiloxanes with a functional group presented in the imide block, it is preferred to ~
start with an OH or -COOH-bearing diamino compound. On the other -hand, this kind of siloxane monomer is usually not readily available. The incorporation of epoxy, silicone hydride or sil;cone hydroxyl group can be achieved via equillibration of theCX,w-diamino or CX,w- dianhydride siloxane with cyclic silicone epoxy, silicone hydride or silicone hydroxy compounds. In any event, it is preferred to graft the acrylic or ethylenic or acetylenic group rather than using an acrylic, ethylenic or acetylenic diamino or dianhydride compound for making the desired polyimidesiloxan~e. This is to avoid thermally cross-linking reactions of these functionalities during imidization of the polyimidesiloxane at high temperatures (about 160 tc 170C/2 hrs in solvent). A grafting ~" ~` : ~
~ 15 reaction of a fully imidized polyimidesiloxane with the above ., ~ ,, described functionalities can be, in general, carried out at much lower temperatures. For instance, the hydrosilylation can be carried out at temperatures as low as 25C in the presence of a platinum catalyst. The condensation between the hydroxyl or r ~
~ 20 carboxylic group with the epoxy group can be achieved at ~. ~
~, . , ,j,'b, ~ temperatures of no more than 120C, within hours with the presence ;~
-- ~ of a tertiary am,ine as a catalyst. In this invention, the pyridine ~-- compound serves as the tertiary amine. The reaction of an hydroxyl or carboxylic group with an isocyanate group needs even lower ~- 25 temperatures (RT to 80C), and the like.
~7~, 35 ~
,~
r 3 3 1. 3 8 7 ~ .
To avoid the need for isolation of the reaction product from solvent, it is desirable to conduct the grafting reaction in the solvent which is acceptable for coating operations. The desirable solvents of these kinds are solvents with low flammability and/or toxici~y, such as diglyme or MEK. The latter has been widely employed in coating industries due to its low boiling temperature.
In this specification and claims halogen shall refer to fluorine, chlorine, bromine and iodine, but preferably to fluorine and chlorine. Aromatic generally refers to hydrocarbon aromatic. -~
In the following Examples and throughout the specification and claims, parts are by weight and temperatures are in degrees Celsius, unless indicated otherwise.
~ . . .
EXAMPLES
Example 1 (A) - 15 Preparation of 2,5-diaminobenzotrifluoride 2-Amino-5-nitrobenzotrifluoride (51.6 9, 0.25 mole), ~- manufactured by Marshallton Research Laboratories, Inc., was dissolved in 95% aqueous ethanol (100 ml) and 25% aqueous sodium ; hydroxide solution (20 ml) and was heated to gentle reflux. Zinc `~ 20 dust (65 9, 1.00 9 atom) was added slowly (50 minutes) at a rate to maintain reflux without external heating. After one hour, the mixture was filtered hot and the filter cake was extracted with two 75 ml portions of hot ethanol. The filtrate, combined with the , . -~ washings, was concentrated under vacuum producing dark crystals ~
,, .
, r ~ 36 -, .
.- ... .
,~ ' '".:
133~387 (42 9, 95% yield). These were recrystallized from methanol/
methylene chloride.
Example 1 (B) Preparation of CY,w-diaminoaryl Diether Compound Two moles of 2-chloro-5-nitrobenzotrifluoride (I) and one mole of hydroquinone (II) are dehydrochlorinated by reaction at an elevated temperature, in the presence of potassium hydroxide or potassium carbonate, in a polar aprot;c solvent, such as dimethyl formamide, to yield the dinitro-diether compound III. This compound is then hydrogenated by iron and concentrated hydrochloric acid to the corresponding CX,w-diaminoaryldiether compound IV.
Example 2 Preparation of Polyimidesiloxane :. :
Nine polyimidesiloxane compositions were prepared from 2,5-diaminobenzotrifluoride, 4,4'-oxydiphthalic anhydride (ODPA) and ~- an CX-w-diaminosilane. The siloxane block size was 1, 7.5 or 12 ~ ~ ~ units and the total siloxane content in the polyimidesiloxanes was - ~20, 30 or 40 percent. The actual formulations are given in Table 1, ;;
-~ and the procedure used is given below.
To 1-methyl-2-pyrrolidinone, commonly known as N-methyl pyrrolidone (NMP? (40 ml~) was added ODPA and the mixture was stirred until the dianhydride had dissolved (5 minutes). Then, the CY-w-amino- siloxane was added and the solution stirred at ambient .:
temperature for 2 hours. Finally, the 2,5-diaminobenzotrifluoride - 25 was added and the solution was stirred for another 16 hours. The ", ~
viscous solution was cast on to a Teflon coated mold which was subsequently hea~ed at 140C for 4 hours and at 2500 for 0.5 hours to remove so,lvent and complete the imidization. ~ -Nine films prepared. Two were tested for percent elongation and tensile strength, and the results are shown in Table 2.
Table 2 Example No. Percent ElongationTensile Strength (psi) ' ;~
2C 3.5 + 0.4 6730 `,~,' 2F 1.02 1041 , Example 3 Polyimidesiloxanes Containing BTDA ;' ' Nine formulations were prepared from BTDA together with 2,5-diaminobenzotrifluoride and CX-w-diaminosiloxane using the conditions and procedures of Example 2, except substituting BTDA for, '~
ODPA. The siloxane block size was 1, 7.5 or 12 units and the total siloxane content in the polyimidesiloxanes was 20, 30 or 40 percent.
' The actual formulations are given in Table 3. Films were prepared from each formulation and the solubilities in solvents are al,so ': 20 shown in Table 3.
* trade-mark ',; - " :
-, - 38 - ~, 133l387 Example 4 Polyimidesiloxanes Containing BPDA
Nine formulations were prepared from BPDA together with 2,5-diaminobenzotrifluor;de and CY-w-diaminosiloxane using the conditions and procedures of Example 2, except substituting BPDA for ODPA. The siloxane block size was 1, 7.5 or 12 units and the tota1 ~;~
siloxane content in the polyimidesiloxanes was 20, 30 or 40 percent. ~
The actual formulations are given in Table 4. Films were prepared ~-from each formulation and the solubilities in solvents are also shown in Table 4.
In the foregoing examples, Gm has the formula~
CH, CH~ ~-~ ~ H~l o~$i~CH,~NH, CH, CW, where m indicates the average number of repeating units, as shown in Table 1, for example, G7-5 and G12. ;~
r~
- 39 ~
., ~
~, ~
~331387 59 siloxane monomer is an equilibrium product of one mole of with 2 moles of D4 at 87-90C. G1 has the following structure:
ICH3 CI H3 , ~ ' H2N,v~Si - o~ NH2 and D4 is the cyclic tetramer having the formula CH
~ i ~ . (Si - 0 -)4 ~-. .
-: ~ CH3 ;
In the formula, and in the Examples, when G has a nominal value of 9 units, experimentally G had a value of about 7.5. Similarly, when G . ;;
.-:
has:a nominal value of 13 units, experimentally G had a value of .~ about 12. The experimental measurements were done by silicon-29 ii NMR. :~
;,,~,: ' r,:
~ In general,polylmidesiloxane made with a mixture of, for instance, 2,4- and 2,6-tolyldiamine are more soluble in diglyme than polymers made from a single tolyldiamine such as 2,4-tolyldiamine. ~ ~
The solubility of the polyimidesiloxanes of the invention in ~ :
'J'. solvents, suc~ as q~IF, ND? o~ diglyme is a function of the ::
~ 20 Enoportaon of the siloxane ccmponent in the ~ ~:
~ . ' , . .
5S~
~ - 40 - -~ :
", ' ;~
1331387 :
polyimidesiloxane and is also a function of the siloxane block size.
Thus, the siloxane monomer is preferably present in a proportion and has a sufficient block size to render the polyimidesi10xane soluble in a solvent such as THF, NMP or preferably diglyme.
The polyimidesiloxanes of the invention are useful in a variety of applications in the micro-electronic industry. Such applications include use in the form of coatings as interlevel dielectrics and for encapsulation or passivations of semiconductors and hybrid integrated circuits. Coatings of the polyimidesiloxanes can be used in the fabrication of semiconductor devices in the following areas~
a) as a protective overcoat, b) as an interlayer dielectric for multi-level devices, c) as an alpha particle barrier, d) as a ;~
non-implant mask, and e) as an encapsulant. Most of these uses are :: : , .
- ~ descrlbed in detail for polyimides by Lee and Craig in Polymer ~ 15 Materials for Electronic Applicatians, ACS Symposium, Ser. 184, page s-~ 108.
,,, - .:::Other uses for the polyimidesiloxanes of the invention include - wire and cable coatings, in fibers and films, and molded and ~-extruded~articles. Other uses include uses for liquid crystal ~ alignment and for die-attach adhesives.
:; , ! , . . .
,,-, ~ ~
-~ . "
~-, , +
~ ~ I ,.
o C~ I , v~ zl ~ + + + + + + + + , ~--o ~ ~ ,~ oo o ~ Ln oo ,~ :
._ ~ ~ oo ~ ~ I~ o r~
_ o~
E
~E _ C
C~ o o o o o o o o o S N ~ ~ C~J ~ et C~.l ~) ~ q~
._ ~e c X
r !~
Ul ': ' ';'~ .
~ ~ J v r_ o Ln ~ oo~
~' CC ~ ~ ~ ~
C ~ _I O ~) N _ ~ N C~
,,~
,-:
~ ;~ 00 C~J 0 N N ~ 1~ U:l ~ 11 ~ _ ~ 0~
~ - ~ ~ N ~ ~ ~ ~ ~ N ~ E
,.: o ~a~
,~ C~ Ln ~ o L~ o ~ ~ ~ c o 3 ~ d~ ~t O Lt~ 3 o ~ C
~ X ~ o ,:-, _ O O ~ Q~
-- N _ C
- _ ~ C~ ---- _ E -- C~ O
E
E u~ t~ ~ et o oID x~:~ _ s E
O ~ In ,, _ ~ C~ ~ ' ~ -- d~ e~ O I ~ ~
~ ~ I ~0 ~0 c~ ~ ~-- C2~ C~d'~t ~ ~n E O
_ u~ o o ~
.- c~ m : ::
o o o o o o o o 0~ 0 E~ ~ z ~ ?~
, ~ ~
"''' ~- ~':;'~-"
:~ ~ E z ~c ~ ~ O ~ ~ ~ _, :~' ~ ~1 ,~ :
',: ' -,~ ~
u~ ,,~ ~
m + + ~ I I I I I ~, -.
.
. ~ I I +
.
o ~ .
c~
s ~ ~
x ~ ~e . .. . . . . . .
o o .
~
v~ . , a, ~
~ o , E E 7~ oo L~ cn ~ C~l C~J N N
o ~ oa~ ~
, ~') ~:' J
- ~ ~ CC . N ~ o o oo 1 ,:}~, ~) 00et O ~ U) t~ ~ ~ c~J c ' ~ ~. ~ E ~et :?, ~ ~ ~ O ~
. ~ cC U~ O N ~ X ~ ~ ~O O
, : E ~ o o. ~ xo ' ~ ~-~ C O ' '~
~ E ~ ,, . ~ ~ ' , C ! ~
,- o ~ E .
_ O
. ~ ~ :
~: ` E ~ T
Z
.',` ' . ~ :
:~ - 4 3 -J , ~
cn ~ ' . ~
C~ I +
o ~ , sl + + + I l + l l +
, ! .
' ~:
a~ ~ ~ ~ N 1~ ~
:~ X o ~ U~
_ ~ ~ ' ~
~ O
E ~ ~ ~ ~ ~ N N O O o~
~ ~ ¦ 2 ~ ~ N ~ ~:t 2 ~ ~ _ ~ :
t X~ ~
J C~ ~ 00 N 1~ --I U
, ~ : ¦ N _I O ~ ~ ~ N C~
-~,.
: _ ~
O N ~ ~ N ~ et c~J ~ ~t C
S O ~:
C y E . ! ~ l ~: O ~ _ E
_ --I O ~0 U~ ~N ~ - ~ODet N ~ C~
_ u~ m N
_ E occ ~ C.~ ~ ~ ~ ~ ' I -- ~
~,,', XZ ~ ~t ~ ~ d e~ d- ~ ~ ,~,;`,~
" ~ o s ~ 44 . : -:
Claims
In a substantially fully imidized polyimidesiloxane comprising the reaction product of an organic dianhydride, a difunctional siloxane monomer, and an organic diamine, the improvement wherein the organic diamine has the formula wherein X is fluorine or combinations of fluorine with hydrogen, Z = -O-, -S-, , , , , or -Y-Ar-Y-o , , , , Y = -O-, -D-, , , , or -; and n = 0 or 1.
In a substantially fully imidized polyimidesiloxane comprising the reaction product of an organic dianhydride, a difunctional siloxane monomer, and an organic diamine, the improvement wherein the organic diamine has the formula where Ar is an aromatic radical of 6 to 10 carbon atoms, and where X is fluorine.
The polyimidesiloxane of Claim 2 wherein the organic dianhydride is an oxydiphthalic anhydride.
The polyimidesiloxane of Claim 3 wherein the organic dianhydride is 4,4'-oxydiphthalic anhydride.
The polyimidesiloxane of Claim 2 wherein the organic dianhydride is a sulfurdiphthalic anhydride or a sulfone diphthalic anhydride.
The polyimidesiloxane of Claim 3 wherein the organic dianhydride is 4,4'-sulfurdiphthalic anhydride or 4,4'-sulfone diphthalic anhydride.
The polyimidesiloxane of Claim 3 wherein the organic dianhydride is benzophenone tetracarboxylic dianhydride.
The polyimidesiloxane of Claim 3 wherein the organic dianhydride is biphenyl tetracarboxylic dianhydride.
The polyimidesiloxane of Claim 3 wherein the organic dianhydride is bis(dicarboxyphenyl)-hexafluoropropene dianhydride.
The polyimidesiloxane of Claim 3 wherein the organic dianhydride is diether dianhydride.
The polyimidesiloxane of Claim 3 wherein the organic diamine has the formula The polyimidesiloxane of Claim 12 which also comprises an asymmetrical organic diamine which provides an asymmetrical structure in the polyimidesiloxane polymer chain.
The polyimidesiloxane of Claim 13 wherein the organic diamine which provides the asymmetrical structure has the formula wherein R10, R11 and R12 are dependently selected from hydrogen, halo-gen, alkyl or aryl or halogenated aryl of 6 to 12 carbon atoms, provided that all of x, y and z are not hydrogen.
The polyimidesiloxane of Claim 14 wherein x, y and z are independently selected from hydrogen, halogen, alkyl of 1 to 12 carbon atoms or aryl of 6 to 12 carbon atoms, provided that all of x, y and z are not hydrogen.
The polyimidesiloxane of Claim 15 wherein the organic diamine is 2,4-tolyldiamine, 2,6-tolyldiamine or a mixture thereof.
The polyimidesiloxane of Claim 2, wherein the reaction product additionally includes a portion derived from an organic diamine of formula:
wherein Ar is an aromatic radical of 6 to 10 carbon atoms, and R"
is at least one of a hydroxyl, carboxyl or hydrothiol.
The polyimidesiloxane of Claim 17 wherein R" is a carboxyl group or the metal salt of said carboxyl group.
The polyimidesiloxane of Claim 2 wherein the reaction product additionally includes a portion derived from an organic diamine of the formula wherein Ar is an aromatic radical, of 6 to 10 carbon atoms, and R'"
is at least one of an acrylic-, an ethylenic- or an acetylenic-bearing radical.
The polyimidesiloxane of Claim 19 wherein the siloxane monomer is a siloxane diamine.
The polyimidesiloxane of Claim 20 wherein the siloxane diamine has the formula wherein R' is independently selected from substituted or unsubstituted aliphatic difunctional radicals of 1 to 12 carbon atoms, or substituted or unsubstituted aromatic difunctional radicals of 6 to 10 carbon atoms, and wherein one or more of R1, R2, R3 and R4 can be vinyl or hydroxyl radicals, and the remainder of R1, R2, R3 and R4 are independently selected from a substituted or unsubstituted aliphatic monofunctional radical of 1 to 12 carbon atoms, or substituted or unsubstituted aromatic monofunctional radical of 6 to 10 carbon atoms, and m is a number from about 5 to about 200.
The polyimidesiloxane according to Claim 21 wherein the remainder of R1, R2, R3 and R4 are methyl groups.
The polyimidesiloxane according to Claim 22 wherein R' is ?CH2?3.
The polyimidesiloxane of Claim 21 wherein at least a portion of the siloxane diamine of the formula comprises a diamine wherein at least one of R1, R2, R3 and R4 is a radical selected from hydroxyl or vinyl.
The polyimidesiloxane according to Claim 24 wherein at least one of R1, R2, R3 and R4 is vinyl and the remainder are methyl groups.
The polyimidesiloxane according to Claim 25 wherein the R' is ?CH2?3.
The polyimidesiloxane of Claim 24 wherein at least a portion of the siloxane diamine of the formula comprises a siloxane diamine component wherein at least one of the hydroxyl or vinyl radicals is reacted with a compound having a radical selected from acrylic-, ethylenic- or acetylenic-bearing radicals.
The polyimidesiloxane of Claim 27 comprising an acrylic-bearing radical.
The polyimidesiloxane of Claim 1 wherein the siloxane monomer is a siloxane dianhydride.
The polyimidesiloxane of Claim 29 wherein the siloxane dianhydride as the formula wherein R is substituted or unsubstituted aliphatic trifuctional radicals of 1 to 12 carbon atoms, or substituted or unsubstituted aromatic trifuctional radicals of 6 to 10 carbon atoms, and wherein one or more of R1, R2, R3 and R4 can be halogen, hydride (H), vinyl or hydroxyl radicals, and the remainder of R1, R2, R3 and R4, are independently selected from a substituted or unsubstituted aliphatic monofunc-tional radical of 1 to 12 carbon atoms, or substituted or unsubstituted aromatic monofunctional radicals of 6 to 10 carbon atoms, and wherein m is about 5 to 50.
The polyimidesiloxane of Claim 30 wherein the remainder of R1, R2, R3 and R4 are methyl groups.
The polyimidesiloxane of Claim 31 wherein R is OR The polyimidesiloxane of Claim 30 wherein at least a portion of the siloxane dianhydride of the formula comprises a dianhydride wherein at least one of R1, R2, R3 and R4 is a radical selected from hydride (H), halogen, hydroxyl or vinyl.
The polyimidesiloxane according to Claim 33 wherein at least one of R1, R2, R3 and R4 is vinyl and the remainder are methyl groups.
The polyimidesiloxane according to Claim 34 wherein R is OR The polyimidesiloxane of Claim 33 wherein at least a portion of the siloxane dianhydride component of the formula comprises a siloxane dianhydride component wherein at least one of the hydride (H), halogen, hydroxyl or vinyl radicals is reacted with a compound having a radical selected from acrylic, ethylenic or acetylenic radicals.
The polyimidesiloxane of Claim 36 comprising an acrylic-bearing radical.
A process for producing a polyimidesiloxane that is soluble in diglyme, which comprises reacting a difunctional siloxane monomer.
an organic dianhydride and an organic diamine of formula (I) of
claim 1.
The process of Claim 38 wherein the reaction is conducted in a solvent for the polyimidesiloxane.
The process of Claim 39 wherein the diamine has the formula and the solvent is selected from diglyme, triglyme, .gamma.-butyrolactone, N,N-dimethylacetamide, 1-methyl-2-pyrrolidinone, tetrahydrofuran, methyl ethyl ketone, phenols or mixtures thereof.
The process of Claim 38 wherein the siloxane monomer is a siloxane diamine.
The process of Claim 38 wherein the siloxane monomer is a siloxane diamine having the formula wherein R' is independently selected from substituted or unsubstituted aliphatic difunctional radicals of 1 to 12 carbon atoms or substituted or unsubstituted aromatic difunctional radicals of 6 to 10 carbon atoms, and wherein one or more of R1, R2, R3 and R4 can be vinyl or hydroxyl radicals, and the remainder of R1, R2, R3 and R4 are independently selected from a substituted or unsubstituted aliphatic monofunctional radical of 1 to 12 carbon atoms or substituted or unsubstituted aromatic monofunctional radicals of 6 to 10 carbon atoms, and m is an integer from about 5 to about 50.
The process of Claim 42 wherein the remainder of R1, R2, R3 and R4 are methyl groups.
The process of Claim 43 wherein R' is ?CH2?3.
The process of Claim 38 wherein the siloxane monomer is a siloxane dianhydride.
The process of Claim 45 wherein the siloxane monomer is a siloxane dianhydride having the formula wherein R is substituted or unsubstituted aliphatic trifunctional radicals of 1 to 12 carbon atoms or substituted or unsubstituted aromatic trifunctional radicals of 6 to 10 carbon atoms, and wherein one or more of R1, R2, R3 and R4 can be halogen, hydride (H), vinyl or hydroxyl radicals, and the remainder of R1, R2, R3 and R4, are independently selected from a substituted or unsubstituted aliphatic monofunc-tional radical of 1 to 12 carbon atoms or substituted or unsubstituted aromatic monofunctional radicals of 6 to 10 carbon atoms, and wherein m is about 5 to about 50.
The process of Claim 46 wherein the remainder of R1, R2, R3 and R4 are methyl groups.
The process of Claim 47 wherein R is OR The process of Claim 38, wherein said monomer, dianhydride and diamine are additionally reacted with an organic diamine of formula wherein Ar is an aromatic radical of 6 to 10 carbon atoms, and R"
is at least one of a hydroxyl, carboxyl or hydrothiol.
The process of Claim 49 wherein R" is carboxy.
The process of Claim 42 wherein at least a portion of the siloxane diamine of the formula as set forth in claim 42 comprises a diamine of said formula wherein at least one of R1, R2, R3 and R4 is a radical selected from hydroxyl or vinyl.
The process according to claim 51 wherein at least one of R1, R2, R3 and R4 is a vinyl radical, and the remainder are methyl groups.
The process according to Claim 52 where the R' is ?CH2?3.
The process of Claim 46 wherein at least a portion of the siloxane dianhydride of the formula as set forth in claim 46 com-prises a dianhydride of said formula wherein at least one of R1, R2, R3 and R4 is a radical selected from hydride (H), halogen, hydroxyl or vinyl.
The process according to Claim 54 wherein at least one of R1, R2, R3 and R4 is vinyl and the remainder are methyl groups.
The process according to Claim 55 wherein R is OR The process of Claim 49 wherein the product of the process is reacted with a compound comprising at least one of an acrylic-, an ethylenic- or an acetylenic-bearing radical.
The process of Claim 51 wherein the product of the process is reacted with a compound comprising at least one of an acrylic-, an ethylenic- or an acetylenic-bearing radical.
- 59 - i The process of Claim 54 wherein the product of the process is reacted with a compound comprising at least one of an acrylic-, an ethylenic- or an acetylenic-bearing radical.
A solution comprising the polyimidesiloxane of Claim 1 dissolved in a solvent for the polyimidesiloxane.
The solution of Claim 60 wherein the solvent is selected from diglyme, triglyme, .gamma.-butyrolactone, N,N-dimethylacetamide, 1-methyl-2-pyrrolidinone, tetrahydrofuran, methyl ethyl ketone, phenols or chlorinated solvents.
An article comprising a substrate coated with a polyimidesiloxane according to Claim 1.
An article of Claim 62 wherein the substrate is a wire or cable.
A film prepared from the polyimidesiloxane according to Claim 1.
A fiber prepared from the polyimidesiloxane according to Claim 1.
A molded article prepared from a polyimidesiloxane according to Claim 1.
An extruded article prepared from a polyimidesiloxane according to Claim 1.
A cured composition of Claim 1.
A cured composition of Claim 27.
A cured composition of Claim 36.
The process for producing a polyimidesiloxane which is soluble in diglyme, which comprises reacting an organic di-anhydride and a difunctional siloxane monomer to form an oligomer, and thereafter reacting said oligomer with an aroma-tic diamine of formula (I) of Claim 1.
The process of Claim 71 wherein the reaction is conduc-ted in a solvent for the polyimidesiloxane.
The process of Claim 72 wherein the solvent is selected from diglyme, triglyme, ?-butyrolactone, N,N-dimethyl aceta-mide, 1-methyl-2-pyrrolidinone, tetrahydrofuran, methyl ethyl ketone, phenols or mixtures thereof.
The polyimidesiloxane of Claim 1 wherein the amine has the formula The polyimidesiloxane of Claim 1 wherein the amine has the formula The polyimidesiloxane of Claim 1 wherein the amine has the formula The polyimidesiloxane of Claim 1 wherein the amine has the formula The polyimidesiloxane of Claim 1 wherein the amine has the formula The polyimidesiloxane of Claim 1 which is soluble in diglyme, ?-butyrolactone, or N-methylpyrrolidone.
The process of Claim 38 wherein the reaction is conducted in a solvent for the polyimidesiloxane.
The process of Claim 39 wherein the diamine has the formula and the solvent is selected from diglyme, triglyme, .gamma.-butyrolactone, N,N-dimethylacetamide, 1-methyl-2-pyrrolidinone, tetrahydrofuran, methyl ethyl ketone, phenols or mixtures thereof.
The process of Claim 38 wherein the siloxane monomer is a siloxane diamine.
The process of Claim 38 wherein the siloxane monomer is a siloxane diamine having the formula wherein R' is independently selected from substituted or unsubstituted aliphatic difunctional radicals of 1 to 12 carbon atoms or substituted or unsubstituted aromatic difunctional radicals of 6 to 10 carbon atoms, and wherein one or more of R1, R2, R3 and R4 can be vinyl or hydroxyl radicals, and the remainder of R1, R2, R3 and R4 are independently selected from a substituted or unsubstituted aliphatic monofunctional radical of 1 to 12 carbon atoms or substituted or unsubstituted aromatic monofunctional radicals of 6 to 10 carbon atoms, and m is an integer from about 5 to about 50.
The process of Claim 42 wherein the remainder of R1, R2, R3 and R4 are methyl groups.
The process of Claim 43 wherein R' is ?CH2?3.
The process of Claim 38 wherein the siloxane monomer is a siloxane dianhydride.
The process of Claim 45 wherein the siloxane monomer is a siloxane dianhydride having the formula wherein R is substituted or unsubstituted aliphatic trifunctional radicals of 1 to 12 carbon atoms or substituted or unsubstituted aromatic trifunctional radicals of 6 to 10 carbon atoms, and wherein one or more of R1, R2, R3 and R4 can be halogen, hydride (H), vinyl or hydroxyl radicals, and the remainder of R1, R2, R3 and R4, are independently selected from a substituted or unsubstituted aliphatic monofunc-tional radical of 1 to 12 carbon atoms or substituted or unsubstituted aromatic monofunctional radicals of 6 to 10 carbon atoms, and wherein m is about 5 to about 50.
The process of Claim 46 wherein the remainder of R1, R2, R3 and R4 are methyl groups.
The process of Claim 47 wherein R is OR The process of Claim 38, wherein said monomer, dianhydride and diamine are additionally reacted with an organic diamine of formula wherein Ar is an aromatic radical of 6 to 10 carbon atoms, and R"
is at least one of a hydroxyl, carboxyl or hydrothiol.
The process of Claim 49 wherein R" is carboxy.
The process of Claim 42 wherein at least a portion of the siloxane diamine of the formula as set forth in claim 42 comprises a diamine of said formula wherein at least one of R1, R2, R3 and R4 is a radical selected from hydroxyl or vinyl.
The process according to claim 51 wherein at least one of R1, R2, R3 and R4 is a vinyl radical, and the remainder are methyl groups.
The process according to Claim 52 where the R' is ?CH2?3.
The process of Claim 46 wherein at least a portion of the siloxane dianhydride of the formula as set forth in claim 46 com-prises a dianhydride of said formula wherein at least one of R1, R2, R3 and R4 is a radical selected from hydride (H), halogen, hydroxyl or vinyl.
The process according to Claim 54 wherein at least one of R1, R2, R3 and R4 is vinyl and the remainder are methyl groups.
The process according to Claim 55 wherein R is OR The process of Claim 49 wherein the product of the process is reacted with a compound comprising at least one of an acrylic-, an ethylenic- or an acetylenic-bearing radical.
The process of Claim 51 wherein the product of the process is reacted with a compound comprising at least one of an acrylic-, an ethylenic- or an acetylenic-bearing radical.
- 59 - i The process of Claim 54 wherein the product of the process is reacted with a compound comprising at least one of an acrylic-, an ethylenic- or an acetylenic-bearing radical.
A solution comprising the polyimidesiloxane of Claim 1 dissolved in a solvent for the polyimidesiloxane.
The solution of Claim 60 wherein the solvent is selected from diglyme, triglyme, .gamma.-butyrolactone, N,N-dimethylacetamide, 1-methyl-2-pyrrolidinone, tetrahydrofuran, methyl ethyl ketone, phenols or chlorinated solvents.
An article comprising a substrate coated with a polyimidesiloxane according to Claim 1.
An article of Claim 62 wherein the substrate is a wire or cable.
A film prepared from the polyimidesiloxane according to Claim 1.
A fiber prepared from the polyimidesiloxane according to Claim 1.
A molded article prepared from a polyimidesiloxane according to Claim 1.
An extruded article prepared from a polyimidesiloxane according to Claim 1.
A cured composition of Claim 1.
A cured composition of Claim 27.
A cured composition of Claim 36.
The process for producing a polyimidesiloxane which is soluble in diglyme, which comprises reacting an organic di-anhydride and a difunctional siloxane monomer to form an oligomer, and thereafter reacting said oligomer with an aroma-tic diamine of formula (I) of Claim 1.
The process of Claim 71 wherein the reaction is conduc-ted in a solvent for the polyimidesiloxane.
The process of Claim 72 wherein the solvent is selected from diglyme, triglyme, ?-butyrolactone, N,N-dimethyl aceta-mide, 1-methyl-2-pyrrolidinone, tetrahydrofuran, methyl ethyl ketone, phenols or mixtures thereof.
The polyimidesiloxane of Claim 1 wherein the amine has the formula The polyimidesiloxane of Claim 1 wherein the amine has the formula The polyimidesiloxane of Claim 1 wherein the amine has the formula The polyimidesiloxane of Claim 1 wherein the amine has the formula The polyimidesiloxane of Claim 1 wherein the amine has the formula The polyimidesiloxane of Claim 1 which is soluble in diglyme, ?-butyrolactone, or N-methylpyrrolidone.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/270,920 US4957993A (en) | 1987-03-31 | 1988-11-14 | Novel polyimidesiloxanes and methods for their preparation and use |
| US270,920 | 1988-11-14 | ||
| US07/307,016 US4996278A (en) | 1988-02-09 | 1989-02-07 | Novel polyimidesiloxanes and methods for their preparation and use based on diamines with pendant fluorine groups |
| US307,016 | 1989-02-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1331387C true CA1331387C (en) | 1994-08-09 |
Family
ID=26954576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 613725 Expired - Fee Related CA1331387C (en) | 1988-11-14 | 1989-09-27 | Polyimidesiloxanes and methods for their preparation and use |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1331387C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117551418A (en) * | 2024-01-12 | 2024-02-13 | 江阴苏达汇诚复合材料有限公司 | Adhesive for aluminum plastic film and preparation process thereof |
-
1989
- 1989-09-27 CA CA 613725 patent/CA1331387C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117551418A (en) * | 2024-01-12 | 2024-02-13 | 江阴苏达汇诚复合材料有限公司 | Adhesive for aluminum plastic film and preparation process thereof |
| CN117551418B (en) * | 2024-01-12 | 2024-04-02 | 江阴苏达汇诚复合材料有限公司 | Adhesive for aluminum plastic film and preparation process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1321442C (en) | Soluble polyimidesiloxanes and methods for their preparation and use | |
| CA1325075C (en) | Soluble polyimidesiloxanes and methods for their preparation and use | |
| CA1299801C (en) | Soluble polyimidesiloxanes and methods for their preparation and use | |
| US4996278A (en) | Novel polyimidesiloxanes and methods for their preparation and use based on diamines with pendant fluorine groups | |
| Wu et al. | Optically Transparent and Thermal‐Stable Polyimide Films Derived from a Semi‐Aliphatic Diamine: Synthesis and Properties | |
| KR0159287B1 (en) | Process for preparing polyimide modified by siloxane | |
| EP0349010A1 (en) | Polyimide copolymers | |
| US20030045670A1 (en) | Space environmentally durable polyimides and copolyimides | |
| EP0371313B1 (en) | Polyimide siloxanes and methods for their preparation and use | |
| US5077370A (en) | Novel polyimidesiloxanes and methods for their preparation and use | |
| CA1331387C (en) | Polyimidesiloxanes and methods for their preparation and use | |
| US5008361A (en) | Crystalline polyimidesiloxanes | |
| US5614607A (en) | Polyimide and a method of preparing polyamide from tetracarboxylic dianhydride and diisocyanate | |
| USRE33797E (en) | Novel polyimidesiloxanes and methods for their preparation and use | |
| KR20200072418A (en) | Diamine compound, polyimide precursor and polyimide film prepared by using same | |
| KR20200082278A (en) | Polyamic acid composition and transparent polyimide film using the same | |
| JP3137309B2 (en) | Heat resistant resin composition | |
| JP3578545B2 (en) | Soluble polyimide resin | |
| JP2983828B2 (en) | Resin composition with improved properties at high temperatures | |
| JP2996859B2 (en) | Heat resistant resin composition | |
| CA2008860A1 (en) | Process for the preparation of crosslinked products and novel polymers | |
| JP3137308B2 (en) | Heat resistant resin composition | |
| JPH08295734A (en) | Polyimide resin and its production | |
| JP2996858B2 (en) | Heat resistant resin composition with excellent low temperature processability | |
| JP2996857B2 (en) | Heat resistant resin composition with excellent low temperature processability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |