U.S. patent application number 12/655136 was filed with the patent office on 2010-04-29 for derivatized polyhydroxystyrenes (dphs) with a novolak type structure and blocked dphs(bdphs) and processes for preparing the same.
Invention is credited to Hiroshi Okazaki, Michael T. Sheehan, Edward G. Zey.
Application Number | 20100105785 12/655136 |
Document ID | / |
Family ID | 35636685 |
Filed Date | 2010-04-29 |
United States Patent
Application |
20100105785 |
Kind Code |
A1 |
Sheehan; Michael T. ; et
al. |
April 29, 2010 |
Derivatized polyhydroxystyrenes (DPHS) with a novolak type
structure and blocked DPHS(BDPHS) and processes for preparing the
same
Abstract
A process for preparing a blocked derivatized
poly(4-hydroxystryrene)-DPHS having a novolak type structure which
comprises the steps of (i) supplying a solution of methanol
containing 4-hydroxyphenylmethylcarbinol, (ii) subjecting said
solution to an acid catalyzed displacement reaction for a
sufficient period of time and under suitable conditions of
temperature and pressure to convert substantially all of said
carbinol to 4-hydroxyphenylmethylcarbinol methyl ether in solution,
(iii) polymerizing said ether containing solution in the presence
of a suitable acid catalyst for a sufficient period of time and
under suitable conditions of temperature and pressure to form a
novolak type polymer; and (iv) reacting said polymer with a vinyl
ether, a dialkyl dicarbonate, or a mixture of vinyl ether and a
dialkyl dicarbonate to form the blocked DPHS. New compositions of
matter which comprise the blocked derivatized
poly(4-hydroxystyrene) prepared in the above manner and which have
application in the electronic chemicals market such as in a
photoresist composition and MEMS, and in other areas such as in
varnishes, printing inks, epoxy resins, copying paper, tackifiers
for rubber, crude oil separators, toner resins for photocopying,
antireflective coatings, and the like.
Inventors: |
Sheehan; Michael T.; (Corpus
Christi, TX) ; Zey; Edward G.; (Corpus Christi,
TX) ; Okazaki; Hiroshi; (Corpus Christi, TX) |
Correspondence
Address: |
James J. Mullen
8202 Campodolcino Drive
Corpus Christi
TX
78414
US
|
Family ID: |
35636685 |
Appl. No.: |
12/655136 |
Filed: |
December 23, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11250014 |
Oct 13, 2005 |
7662538 |
|
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12655136 |
|
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|
60625713 |
Nov 8, 2004 |
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Current U.S.
Class: |
521/25 |
Current CPC
Class: |
C08F 8/14 20130101; C08F
8/14 20130101; C08F 8/00 20130101; C08G 61/04 20130101; C08F 112/14
20130101; G03F 7/0392 20130101; C08F 112/24 20200201; G03F 7/091
20130101 |
Class at
Publication: |
521/25 |
International
Class: |
B01J 47/00 20060101
B01J047/00 |
Claims
1. A composition of matter having the following structure:
##STR00004## wherein n is from about 1 to about 10.
2. A composition of matter having the following structure:
##STR00005## wherein n is from about 1 to about 10.
3. A photoresist composition containing the composition of matter
as set forth in claim 1.
4. A photoresist composition containing the composition of matter
as set forth in claim 2.
5. A process for preparing blocked derivatized polyhydroxystyrene
(DPHS) having a novolak type structure which comprises the steps of
(a) supplying a solution of methanol containing
4-hydroxyphenylmethylcarbinol, (b) contacting said solution with an
acid ion exchange resin for a sufficient period of time and under
suitable conditions of temperature and pressure to convert
substantially all of said carbinol to 4-hydroxyphenylmethylcarbinol
methyl ether in solution, (c) polymerizing said ether containing
solution in the presence of a suitable acid catalyst for a
sufficient period of time and under suitable conditions of
temperature and pressure to form a novolak type polymer, and (d)
reacting said polymer with a vinyl ether, a dialkyl dicarbonate, or
a mixture of a vinyl ether and dialkyl dicarbonate to form said
blocked DPHS.
6. The process as set forth in claim 5 wherein said acid catalyst
is a Lewis acid.
7. The process as set forth in claim 5 wherein the temperature in
steps (b) and (c) is from about 0.degree. C. to about 100.degree.
C. and the pressure is from about 0 psig to about 10 psig.
8. The process as set forth in claim 5 wherein the acid catalyst is
a mineral acid.
9. The process as set forth in claim 8 wherein the acid catalyst is
sulfuric acid.
10. The process as set forth in claim 5 wherein the acid catalyst
is selected from the group consisting of H.sub.2SO.sub.4, HCL
AlCl.sub.3, H.sub.3PO.sub.4, oxalic acid, SnCl.sub.2, BF.sub.3,
BBr.sub.3, BCl.sub.3, para-toluene sulfonic acid, methane sulfonic
acid, trifluoroacetic acid, trichloroacetic acid and mixtures
thereof.
11. The process as set forth in claim 5 wherein the polymer formed
in step d has the structure set forth in claim 1.
12. The process as set forth in claim 5 wherein the polymer formed
in step d has the structure set forth in claim 2.
13. The process as set forth in claim 5 wherein the polymer formed
in step c is a derivatized poly(4-hydroxystyrene) characterized by
having from about 6% to about 40% linearity, a polydispersity of
less than about 2.0, and a molecular weight of less than about
10,000.
14. A primary photoresist composition for patterning electronic
circuitry based on the composition of matter formed in claim 5.
15. A curing agent for an epoxy resin based on the composition of
matter formed in claim 5.
16. A varnish incorporating the composition of matter formed in
claim 5.
17. A printing ink incorporating the composition of matter formed
in claim 5.
18. A tackifier for rubber incorporating the composition of matter
formed in claim 5.
19. A crude oil separator incorporating the composition of matter
formed in claim 5.
20. A solder mask or photoimageable coverlay for rigid or flexible
printed circuit boards incorporating the composition of matter
formed in claim 5.
21. An epoxy material which has been further derivatized by
reaction with the hydroxy groups in the composition of matter
formed in claim 5.
22. A epoxy or blocked isocyanate containing paint formulation
which also has incorporated therein the composition of matter
formed in claim 5.
23. A highly viscous polymer having incorporated therein the
composition of matter formed in claim 5 and which acts as a
viscosity modifier therefor.
24. A polymeric material having incorporated therein the
composition of matter formed in claim 5 and which acts as an
antioxidant therefor.
25. The composition of matter as formed in claim 1 wherein the mole
% blocked is from about 10% to about 90% when either the said ether
or dicarbonate is used and when both are used, the range is from
about 20% to about 70% for each compound.
26. A micro electromechanical system having incorporated therein
the composition of matter as formed in claim 5.
27. A toner resin for use in photocopying containing the
composition of matter as formed in claim 5.
28. A toner resin for use in photocopying containing the
composition of matter as formed in claim 5.
29. An antireflective coating containing the composition of matter
as formed in claim 5.
30. An antireflective coating containing the composition of matter
as formed in claim 5.
Description
RELATED U.S. APPLICATION DATA
[0001] This patent application is a divisional patent application
of pending Ser. No. 11/250,014 filed on Oct. 13, 2005 and which is
derived from provisional patent application No. 60/625,713 filed on
Nov. 8, 2004.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a new derivatized
poly(4-hydroxystyrene) (DPHS) and blocked DPHS (BDPHS) and a
process for the production of DPHS indirectly from
4-hydroxymethyl-carbinol (HPMC) and which DPHS and BDPHS have a
novolak type structure which has utility in the electronic
chemicals market such as photoresist compositions. In addition to
the use of DPHS and BDPHS in the microelectronic chemicals market,
such DPHS can be employed in standard novolak applications such as
varnishes, aniline printing inks, raw materials (e.g. curing
agents) for epoxy resins, copying paper, tackifiers for rubber,
crude oil separators, solder masks and photoimageable coverlays for
rigid and flexible printed circuit boards, and further, derivatized
epoxy resins and polyisocyanuates which have been reacted with the
hydroxy groups of the DPHS and/or BDPHS, such as paint formulations
containing the same. The DPHS and/or BDPHS may also be used as a
viscosity modifier for highly viscous polymers with the capability
of crosslinking after casting and thus providing antioxidation
protection therefore. Other applications include MEMS, micro
electromechanical systems, such as described in U.S. Pat. No.
6,801,682
[0004] 2. Description of the Prior Art
[0005] In the past, one of the ways of preparing
poly(4-hydroxystyrene) (PHS) was the use of 4-hydroxystyrene (HSM)
as the starting material; note European Patent Application No.
0-108-624. 4-Hydroxystyrene is a well-known compound in the
art.
[0006] Although there are several known ways to prepare
4-hydroxystyrene, these known methods are not commercially feasible
in the further utilization of the 4-hydroxystyrene. The
4-hydroxystyrene itself is difficult to isolate since it (1)
readily decomposes, and (2) is toxic via skin absorption and, as a
result, those skilled in the art have made numerous attempts at
finding a method of synthesizing PHS in a manner which avoids using
the 4-hydroxystyrene as the starting material.
[0007] The following prior art references are disclosed for
informational purposes.
[0008] U.S. Pat. No. 5,087,772 (issued Feb. 11, 1992) discloses the
preparation of HSM by reacting 4-acetoxystyrene (ASM) with a
suitable alcohol in the presence of a catalytic amount of a
suitable base.
[0009] U.S. Pat. No. 5,340,687 discloses the alkylation of a linear
poly(4-hydroxystyrene).
[0010] European Patent Application No. 0-128-984 (publication no.)
filed Aug. 30, 1983 discloses a process for the production of
para-vinyl phenol (HSM) by dehydrogenation of para-ethyl
phenol.
[0011] European Patent Application No. 0-108-624 (publication no.)
filed Nov. 4, 1983, discloses a process for the production of
p-vinyl phenol polymer (poly(4-hydroxystyrene) polymer--PHS) by
polymerizing p-vinyl (HSM) in the presence of water and iron.
[0012] U.S. Pat. No. 4,032,513 (issued Jun. 28, 1977) discloses a
process of producing PHS by cationically polymerizing HSM in the
presence of a nitrile such as CH.sub.3CN using a cationic
polymerization initiator in a homogeneous reaction system.
[0013] U.S. Pat. No. 5,554,719 and U.S. Pat. No. 5,565,544 disclose
a process for preparing a branched PHS directly from HPMC which
comprises the single step of polymerizing a mixture of carboxylic
acid and at least one substituted phenyl carbinol such as HPMC.
[0014] However, it is highly desirable to have a linear DPHS and a
blocked linear DPHS and the prior art does not disclose this, much
less a process for preparing the same.
[0015] Other prior art references which relate to the present
invention include U.S. Pat. No. 2,276,138; U.S. Pat. No. 3,547,858,
U.S. Pat. No. 4,544,704; U.S. Pat. No. 4,678,843; U.S. Pat. No.
4,689,371; U.S. Pat. No. 4,822,862; U.S. Pat. No. 4,857,601; U.S.
Pat. No. 4,868,256; U.S. Pat. No. 4,877,843; U.S. Pat. No.
4,898,916; U.S. Pat. No. 4,912,173; U.S. Pat. No. 4,962,147; and
U.S. Pat. No. 4,965,400.
[0016] All of the above-cited prior art and any other references
mentioned herein are incorporated herein by reference in their
entirety.
SUMMARY OF THE INVENTION
[0017] The present invention, in part, discloses a new derivatized
poly(4-hydroxystyrene) (DPHS) of the structural formula set forth
herein and which DPHS is uniquely linear in character. Another
aspect of the present invention is a process for preparing a
derivatized poly(4-hydroxystyrene) (DPHS) having a novolak type
structure which comprises the steps of (i) supplying a solution of
methanol containing HPMC, (ii) subjecting said solution to an acid
catalyzed displacement reaction for a sufficient period of time and
under suitable conditions of temperature and pressure to convert
substantially all of said HPMC to 4-hydroxyphenylmethylcarbinol
methyl ether in said solution, and (iii) polymerizing said ether
containing solution in the presence of a suitable acid catalyst for
a sufficient period of time and under suitable conditions of
temperature and pressure to form a novolak type polymer which is a
unique and new DPHS polymeric material having a molecular weight of
from about 1,000 to about 100,000, preferably from about 1,000 to
about 50,000 and more preferably from about 1,000 to about 10,000.
One of the most important characteristics of the new DPHS is the
fact that it is substantially linear (about 5% to about 40% weight
percent) compared to the prior art PHS as determined by NMR, and
has a low polydispersity, i.e. less than about 2.0.
[0018] Another part of the present invention is directed to the
blocked (or protected) DPHS, herein referred to as BDPHS, and which
is a new composition of matter. This BDPHS is prepared by the
process of reacting the DPHS with a vinyl ether compound and/or a
dialkyl dicarbonate in the presence of a catalyst in an aprotic
solvent under suitable reaction conditions to form said BDPHS.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The present invention provides, in part, a new derivatized
poly(4-hydroxystyrene) (DPHS) and blocked DPHS having the following
structures:
##STR00001## ##STR00002##
[0020] In the above structures I, II, III, and IV, n is from about
1 to about 10, and generally from about 2 to about 6.
[0021] The present invention, in part, provides a novel DPHS and a
novel process for preparing DPHS having a novolak type structure
which comprises the steps of (i) supplying a solution of methanol
containing 4-hydroxyphenylmethylcarbinol (HPMC), (ii) subjecting
said solution to an acid catalyzed displacement reaction for a
sufficient period of time and under suitable conditions of
temperature and pressure to convert substantially all of said
carbinol to 4-hydroxyphenylmethylcarbinol methyl ether in solution,
and (iii) polymerizing said ether containing solution in the
presence of a suitable acid catalyst for a sufficient period of
time and under suitable conditions of temperature and pressure to
form a novolak type polymer consisting of DPHS.
[0022] More specifically, the present invention is directed, in
part, to a unique, cost-efficient process for preparing a novolak
type polymer without any of the prior art disadvantages and wherein
the polydispersity of the new material is surprisingly low, e.g.
less than 2.0 and generally about 1.5 to about 1.9.
[0023] It has unexpectedly been found that the use of a freshly
supplied carbinol such as HPMC cannot be used'directly to form the
a DPHS having a novolak type structure, and this is contrary to the
disclosures set forth in U.S. Pat. No. 5,554,719 and U.S. Pat. No.
5,565,544. It has been found that if a freshly supplied carbinol
such as HPMC is not treated as set forth in the present invention
and before polymerization, the resultant polymer is a gummy mass
which is poor in color and hard to further treat to arrive at the
desired end product, i.e. the DPHS novolak type polymer. Thus, it
is essential and critical that HPMC be converted to its ether form
before the material is polymerized.
[0024] The carbinol such as HPMC is subject to an acid catalyzed
displacement reaction in order to convert it to its methyl ether
form. This step can be carried out by use of an acid ion exchange
resin such as Amberlyst-15 (Rohm and Haas product) or M31 (Dow
Product). The HPMC material is supplied in a methanol solvent
wherein the HPMC is dissolved therein. The concentration of HPMC in
solution is from about 1% to about 50% by weight, preferably from
about 15% to about 30% by weight. This conversion takes place by
merely contacting said HPMC containing methanol solution with, e.g.
the A-15 material either by running the solution a fixed bed of
A-15 or merely mixing the two materials together for a sufficient
period of time and under suitable conditions of temperature and
pressure. The temperature of the conversion step is not critical
and can be from about 0 C to about 10.degree. C. and the pressure
is also not critical, but can be from about 0 psig to about 10
psig, or even conducted under vacuum. The conversion time is also
not critical and is long as necessary to convert the HPMC to the
methyl ether form. This time can be as long as several days at room
temperature to as short as 24 hours at 45 C. The critical factor in
this conversion step is the conversion must convert substantially
all of the HPMC to the methyl ether form before the polymerization
step takes place. It is desirable that the conversion be at least
90% complete, preferably at least 95% complete.
[0025] The second step is the polymerization step which is carried
out with the same methanol solvent which now contains dissolved
therein the methyl ether form of HPMC. This polymerization step is
conducted with the use of a suitable acid catalyst under suitable
conditions of temperature and pressure to form the desired end
novolak product.
[0026] The catalyst employed in the present invention process is
critical and is selected from the group H.sub.2SO.sub.4, HCl,
AlCl.sub.3, H.sub.3PO.sub.4, oxalic acid, SnCl.sub.2, BF.sub.3,
BBr.sub.3, BCl.sub.3, para-toluene sulfonic acid, and methane
sulfonic acid. Thus, Lewis acids and protic acids having a pKa of
less than about 4.75 are suitable.
[0027] The catalyst is used in any amount in order to facilitate
the reaction, i.e. polymerization, to yield the DPHS which has a
novolak type structure. Such amounts generally are from about one
part per million (ppm) to about 100,000 ppm, or higher.
[0028] The temperature employed in the polymerization is generally
less than about 120.degree. C., more specifically from about
0.degree. C. to about 120.degree. C. The reaction pressure may be
subatmospheric, atmospheric, or superatmospheric.
[0029] The length of time which this polymerization step is
conducted is not critical and the only requirement is that the
polymerization be conducted for a period of time sufficient to form
PHS having a novolak type structure. Generally, this period is at
least five minutes and may be as long as 25 hours.
[0030] After the polymerization of the reaction mixture (i.e. acid
catalyst+carbinol+any nucleating agent), the desired end product
(DPHS) is recovered from the reaction product and the residual
fraction containing any unreacted carbinol methyl ether can be
recycled as part of the starting material for the next cycle. The
end product (DPHS) may be recovered from the reaction product by
any method; for example, it can be separated from the fraction
containing the unreacted carbinol methyl ether by, e.g.
precipitation in water followed by filtration, or any other
suitable technique. For example, an electronic grade of DPHS can be
produced containing low ppb metals by removal of the acid with a
basic ion exchange resin followed by removal of the metals by acid
ion exchange resin. It is also within the scope of the present
invention to utilize a nucleating agent like a seed monomer in
order to prepare the reaction mixture. Such material does not have
to be a carbinol nor does it have to contain any hydroxy groups.
Such nucleating agents may include, without limitation, the
substituted phenols and substituted triarylalkyls, and other
polyphenolics such as THPE.
[0031] It is also within the scope of the present invention to
employ a chain terminating agent after the polymerization step. Any
type of chain terminating agent may be used as long as there is no
substantial adverse effect on the novolak structure of the DPHS
formed.
[0032] It is also within the scope of the present invention that
the DPHS may be recovered by other methods in the art such as by
spray drying.
[0033] In another part of the present invention, there is provided
a process for preparing the new BDPHS. The DPHS in the alcoholic
solvent such as methanol, described above, can be subjected to a
solvent swap and then reacted with either a vinyl ether and/or a
dialkyl dicarbonate to form the BDPHS. Otherwise, the DPHS can be
recovered from the reaction medium as described above and then
reacted with a vinyl ether and/or a dialkyl dicarbonate in a
suitable solvent; in either case, the final reaction medium is a
photoresist compatible solvent. The first method utilizes a solvent
swap step.
[0034] In this step, the DPHS is solvent exchanged with an
aprotic/organic solvent which is a photoresist compatible (PC)
solvent, and the alcoholic solvent is removed by distillation. This
PC solvent is at least one member selected from glycol ethers,
glycol ether acetates and aliphatic esters having no hydroxyl or
keto group. Examples of the solvent include glycol ether acetates
such as ethylene glycol monoethyl ether acetate and propylene
glycol monomethyl ether acetate (PGMEA) and esters such as
ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, among which
PGMEA is preferred. These solvents may be used alone or in the form
of a mixture thereof.
[0035] Further examples of the third solvent include butyl acetate,
amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl
ethyl ketone, methyl amyl ketone, cyclohexanone, cyclopentanone,
3-ethoxyethyl propionate, 3-ethoxymethyl propionate,
3-methoxymethyl propionate, methyl acetoacetate, ethyl
acetoacetate, diacetone alcohol, methyl pyruvate, ethyl pyruvate,
propylene glycol monomethyl ether, propylene glycol monoethyl
ether, propylene glycol monomethyl ether propionate, propylene
glycol monoethyl ether propionate, ethylene glycol monomethyl
ether, ethylene glycol monoethyl ether, diethylene glycol
monomethyl ether, diethylene glycol monoethyl ether,
3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethylsulfoxide,
.gamma.-butyrolactone, propylene glycol methyl ether acetate,
propylene glycol ethyl ether acetate, propylene glycol propyl ether
acetate, methyl lactate, ethyl lactate, propyl lactate, and
tetramethylene sulfone. Of these, the propylene glycol alkyl ether
acetates and alkyl lactates are especially preferred. The solvents
may be used alone or in admixture of two or more. An exemplary
useful solvent mixture is a mixture of a propylene glycol alkyl
ether acetate and an alkyl lactate. It is noted that the alkyl
groups of the propylene glycol alkyl ether acetates are preferably
those of 1 to 4 carbon atoms, for example, methyl, ethyl and
propyl, with methyl and ethyl being especially preferred. Since the
propylene glycol alkyl ether acetates include 1,2- and
1,3-substituted ones, each includes three isomers depending on the
combination of substituted positions, which may be used alone or in
admixture. It is also noted that the alkyl groups of the alkyl
lactates are preferably those of 1 to 4 carbon atoms, for example,
methyl, ethyl and propyl, with methyl and ethyl being especially
preferred.
[0036] When the propylene glycol alkyl ether acetate is used as the
solvent, it preferably accounts for at least 50% by weight of the
entire solvent. Also when the alkyl lactate is used as the solvent,
it preferably accounts for at least 50% by weight of the entire
solvent. When a mixture of propylene glycol alkyl ether acetate and
alkyl lactate is used as the solvent, that mixture preferably
accounts for at least 50% by weight of the entire solvent. In this
solvent mixture, it is further preferred that the propylene glycol
alkyl ether acetate is 60 to 95% by weight and the alkyl lactate is
40 to 5% by weight. A lower proportion of the propylene glycol
alkyl ether acetate would invite a problem of inefficient coaling
whereas a higher proportion thereof would provide insufficient
dissolution and allow for particle and foreign matter formation. A
lower proportion of the alkyl lactate would provide insufficient
dissolution and cause the problem of many particles and foreign
matter whereas a higher proportion thereof would lead to a
composition which has a too high viscosity to apply and loses
storage stability.
[0037] Usually the solvent is used in amounts of about 300 to 2,000
parts, preferably about 400 to 1,000 parts by weight per 100 parts
by weight of the solids in the chemically amplified positive resist
composition. The concentration is not limited to this range as long
as film formation by existing methods is possible.
[0038] The hydroxyl containing DPHS in solution (i.e. PC solvent)
from above is then subjected to an additional reaction to provide
said polymer with protective or blocking groups (sometimes referred
to as acid labile groups) in order to protect the
functional/hydroxyl groups. In some cases, this blocking can be
either substantiality blocked or partially blocked. In this step,
the DPHS in solution is reacted with a vinyl either compound and/or
a dialkyl dicarbonate in the presence of a catalyst in the PC
solvent. When the DPHS is reacted with the vinyl ether, it is done
in the presence of an acid catalyst followed by adding a base
thereto to neutralize it and thus stop the reaction; this is
generally called an acetalization wherein an acetal derivatized
hydroxyl containing BDPHS is formed. When the DPHS is reacted with
a dialkyl dicarbonate, this is an alcoholysis by use of an
anhydride (dicarbonate) in the presence of base catalyst which is
used as a reaction catalyst. The blocking of the DPHS can be as
high as 95% with either the vinyl ether compound (VEC) or the
dialkyl dicarbonate compound (DDC), preferably from about 10% to
about 90%, and more preferably, from about 15% to about 70%. When
both compounds are used together as blocking compounds, the range
of blocking is 20% to 70% VEC and 20% to 70% DDC. The percentage
stated is based on mole % and is relative to the amount of the DPHS
compound.
[0039] The vinyl ethers suitable for use a protective group include
those falling within the formula
C(R.sub.6)(R.sub.7).dbd.C(R.sub.8)--O--R.sub.9
Wherein R.sub.6, R.sub.7 and R.sub.8 are independently represent a
hydrogen atom or a straight-chain, branched, cyclic or
hetero-cyclic alkyl group containing 1 to 6 carbon atoms, and
R.sub.9 represents a straight-chain, branched, cyclic or
hetero-cyclic alkyl or aralkyl group containing 1 to 10 carbon
atoms which may be substituted with a halogen atom, an alkoxy group
aralkyl oxycarbonyl group and/or alkyl carbonyl amino group.
[0040] The vinyl ether compounds represented by the general
formula, described above include vinyl ethers such as methyl vinyl
ether, ethyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl
ether, 2-chloro-ethyl vinyl ether, 1-methoxyethyl vinyl ether,
1-benzyloxyethyl vinyl ether etc.; and isopropenyl ethers such as
isopropenyl methyl ether, isopropenyl ethyl ether etc.
[0041] Preferable examples of cyclic vinyl ethers include 3,4
dihydro-2H-pyran etc., and preferable examples of divinyl ethers
include butanediol-1,4-divinyl ether, ethylene glycol divinyl
ether, triethylene glycol divinyl ether etc.
[0042] These vinyl ether compounds can be used alone or in
combination thereof. The vinyl ether compounds in total are used
preferably in a ratio of 0.1 to 0.7 mol equivalent to the phenolic
hydroxyl or carboxyl group of the alkali-soluble polymer having
phenolic hydroxyl or carboxyl group.
[0043] Preferable examples of the dialkyl dicarbonate used in this
part of the present invention include di-tert-butyl dicarbonate. As
with the vinyl ether compounds, the amount of the dialkyl
dicarbonate used is preferably 0.1 to 0.7 mol equivalent to the
phenolic hydroxyl or carboxyl group of the DPHS.
[0044] In this part of the present invention, at least one vinyl
ether compound and at least one dialkyl dicarbonate can be used
simultaneously for protection of the DPHS.
[0045] If the BDPHS to be synthesized is used as a component of a
resist composition exposed with e.g KrF eximer laser radiation, it
is preferable to use a catalyst showing no absorption at 248 nm
i.e. the exposure wavelength of KrF eximer laser. Accordingly, when
an acid is used as the reaction catalyst, the acid is not to have a
benzene ring preferably. Examples of acids which can be used as the
reaction catalyst in the present invention include mineral acids
such as hydrochloric acid, sulfuric acid etc., organic sulfonic
acids such as methanesulfonic acid, camphorsulfonic acid etc. or
halocarboxylic acids such as trifluoroacetic acid, trichloroacetic
acid etc. The amount of the acid used is preferably 0.1 to 10 mmol
equivalents to the phenolic hydroxyl or carboxyl group of the
DPHS.
[0046] In the case where (+/-) camphorsulfonic acid is used as the
reaction catalyst in the form of solution thereof in propylene
glycol monomethyl ether acetate, if said solution is heated or
stored for a long period of time, the propylene glycol monomethyl
ether acetate is hydrolyzed to generate propylene glycol monomethyl
ether (PGME) by which the reaction is significantly inhibited.
Accordingly, the solution of (+/-)camphorsulfonic acid in propylene
gycol monomethyl ether acetate should be prepared just before
use.
[0047] When a dialkyl dicarbonate is used as a compound to he
reacted with the DPHS, a base is used as the reaction catalyst,
while when a vinyl ether compound is used as a compound to be
reacted with the DPHS, a base is used as the reaction stopper. As
these bases, usual bases which are optically decomposable or not
decomposable and are used as conventional additives in chemically
amplified resists can be preferably used. Examples of these bases
include ammonia, organic amines such as triethylamine, dicyclohexyl
methylamine, etc.; ammonium hydroxides represented by
tetramethylammonium hydroxide (TMAH), sulfonium hydroxides
represented by triphenylsulfonium hydroxide, iodonium hydroxides
represented by diphenyliodonium hydroxide and conjugated salts of
these iodonium hydroxides, such as triphenylsulfonium acetate,
triphenylsulfonium camphonate, triphenylsulfonium camphorate etc.
These reaction base catalysts or reaction stoppers are preferably
those which when formed into a resist composition, do not have
influence on resist sensitivity, and in particular, optically
decomposable bases are preferable. When the amine is present in the
resist composition, attention should be paid because sensitivity
may be lowered. Further, inorganic bases are not preferable because
many of them contain metal ions that contaminate the substrate such
as silicon wafer etc. If the BDPHS is neither isolated nor purified
according to the method for preparing a resist composition, the
main cause for instability of the BDPHS in the step of isolation
and purification thereof can be eliminated. If a base is used as
the reaction stopper, the stability of the BDPHS is further
improved, and even in the case of the polymer having acetate as a
protective group, its stability for 2 months or more at room
temperature is confirmed.
[0048] The conditions for reacting the DPHS having a phenolic
hydroxyl or carboxyl group with the vinyl ether compound or the
dialkyl dicarbonate may be the same as in the prior art, and the
reaction may be conducted under the same conditions as in the prior
art. In this reaction, if water is present in the reaction system,
the vinyl ether is decomposed to formaldehyde and alcohol, and the
degree of protection by the vinyl ether compound becomes lower than
the set value. As the drop of the degree of DPHS has a significant
effect on the thickness loss of the resist film in developer, the
moisture content should be minimized in the reaction system
preferably. That is, if the moisture content in the reaction system
is controlled to be as low as possible, the degree of protection
can be in a certain narrow range, to significantly reduce
variations in degrees of protection as compared with the
conventional reaction. Accordingly, the moisture content of the
reaction solution before the reaction should be measured by Karl
Fischer method in order to confirm that the moisture content is
less than about 5,000 ppm, preferably less than about 1,000 ppm.
For example, if the moisture content is more than 5,000 ppm,
attention should be paid such that the degree of protection is
within a set value, for example by increasing the amount of the
vinyl other compound as necessary. The reaction temperature and
reaction time are e.g. 25.degree. C., and 6 hours respectively, but
if the protective group is ketal, are e.g. 0.degree. C. and 2 hours
respectively.
[0049] If the BDPHS is protected by both a vinyl ether compound and
a dialkyl dicarbonate, usually the BDPHS is subjected to protection
reaction with the vinyl ether compound in the presence of an acid
catalyst and then subjected to protection reaction with the dialkyl
dicarbonate in the presence of a base catalyst.
[0050] The usable base includes radiation-sensitive bases or usual
bases not sensitive to radiation. These bases are not necessarily
required for resist formulation, but because their addition can
prevent the deterioration of pattern characteristics even in the
case where the treatment step is conducted with delay, so their
addition is preferable. Further, their addition also results in
improvements in clear contrast.
[0051] Among radiation-sensitive base compounds suitable as bases,
particularly preferable examples include e.g. triphenylsulfonium
hydroxide, triphenylsulfonium acetate, triphenylsulfonium
phenolate, tris-(4-methylphenyl) sulfonium hydroxide,
tris-(4-methylphenyl)sulfonium acetate,
tris-(4-methylphenyl)sulfonium phenolate, diphenyliodonium
hydroxide, diphenyliodonium acetate, diphenyliodonium phenolate,
bis-(4-tert-butylphenyl)iodonium hydroxide,
bis-(4-tert-butylphenyl)iodonium acetate,
bis-(4-tert-butylphenyl)iodonium phenolate etc.
[0052] Further, the base compounds not sensitive to radiation
include e.g. (a) ammonium salts such as tetramethylammonium
hydroxide, tetrabutylammonium hydroxide etc., (b) amines such as
n-hexylamine, dodecylamine, aniline, dimethylaniline,
diphenylamine, triphenylamine, diazabicyclooctane,
diazabicycloundecane etc., and (c) basic heterocyclic compounds
such as 3-phenylpyridine, 4-phenylpyridine, lutidine and
2,6-di-tert-butylpyridine.
[0053] These base compounds can be used alone or in combination
thereof. The amount of the base compound added is determined
according to the amount of the photo acid-generating compound and
the photo acid-generating ability of a photoacid generator. Usually
the base compound is used in a ratio of 10 to 110 mol %, preferably
25 to 95 mole % relative to the amount of the photo acid-generating
compound.
[0054] In this step of the present invention relating to the
preparation of the BDPHS, the step of inactivating the acid
catalyst by use of the base is an important step. That is, after
the above described reaction is finished, the base (for example
triphenylsulfonium acetate or the like) is added whereby the acid
catalyst is neutralized and inactivated to stop the reaction, so
that the BDPHS solution having storage stability can be obtained.
Theoretically, addition of the base in an equivalent amount to the
acid is sufficient to inactivate the acid, but because storage
stability can be further secured by adding about 10% excess base,
addition of about 1.1 equivalents of the base to 1 equivalent of
the acid is preferable. This excess base will be taken into
consideration in order to determine the amount of another base
added as an additive for preparing the resist.
[0055] It is also feasible in this neutralization step to use an
ion exchange material as previously mentioned herein before.
[0056] If one so desires to then prepare the final resist
composition, it is prepared without isolating the resist material
by directly adding to the resist material solution (prepared as
described above), a photoacid generating compound capable of
generating an acid upon exposure to actinic radiation (photoacid
generator) and if necessary a base and additives for improvement of
optical and mechanical characteristics, a film forming property,
adhesion with the substrate, etc. optionally in the form of a
solution. The viscosity of the composition is regulated by addition
of solvent, if necessary. The solvent used in preparing the resist
composition is not necessarily limited to the type of solvent
having been used above, and it is possible to use any other solvent
which is conventionally used in preparation of a resist
composition. Further, any photo acid-generating compounds and other
additives, which are used conventionally in chemically amplified
resists, can also be used. The total solid content in the resist
composition is preferably in the range of 9 to 50% by weight, more
preferably 15 to 25% by weight, relative to the solvent.
[0057] The photoacid generator is a compound capable of generating
an acid upon exposure to high energy radiation. Preferred photoacid
generators are sulfonium salts, iodonium salts,
sulfonyldiazomethanes, and N-sulfonyloxyimides. These photoacid
generators are illustrated below while they may be used atone or in
admixture of two or more.
[0058] Sulfonium salts are salts of sulfonium cations with
sulfonates. Exemplary sulfonium cations include triphenylsulfonium,
(4-tert-butoxyphenyl)diphenylsulfonium,
bis(4-tert-butoxy-phenyl)phenylsulfonium,
tris(4-tert-butoxyphenyl)sulfonium,
(3-tert-butoxyphenyl)diphenyl-sulfonium,
bis(3-tert-butoxyphenyl)phenylsulfonium,
tris(3-tert-butoxyphenyl)sulfonium,
(3,4-di-tert-butoxyphenyl)diphenylsulfonium,
bis(3,4-di-tert-butoxyphenyl)phenylsulfonium,
tris(3,4-di-tert-butoxyphenyl)sulfonium,
diphenyl(4-thiophenoxyphenyl)sulfonium,
(4-tert-butoxycarbonyl-methyloxyphenyl)diphenylsulfonium.
tris(4-tert-butoxycarbonylmethyloxyphenyl)sulfonium,
(4-tert-butoxyphenyl)bis(4-dimethylaminophenyl)sulfonium,
tris(4-dimethylaminophenyl)sulfonium, 2-naphthyldiphenylsulfonium,
dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium,
4-methoxyphenyl-dimethylsulfonium, trimethylsulfonium,
2-oxocyclohexylcyclohexyl-methylsulfonium, trinaphthylsulfonium,
and tribenzylsulfonium. Exemplary sulfonates include
trifluoromethanesulfonate, nonafluorobutanesulfonate,
heptadecafluorooctanesulfonate, 2,2,2-trifluorooethanesulfonate,
pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate,
4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate,
4,4-toluenesulfonyloxybenzenesulfonate, naphthalenesulfonate,
camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate,
butanesulfonate, and methanesulfonate. Sulfonium salts based on
combination of the foregoing examples are included.
[0059] Iodonium salts are salts of iodonium cations with
sulfonates. Exemplary iodinium cations are arytiodonium cations
including diphenyliodinium, bis(4-tert-butylphenyl)iodonium,
4-tert-butoxyphenylphenyliodonium, and
4-methoxyphenylphenylodonium. Exemplary sulfonates include
trifluoromethanesulfonate, nonafluorobutanesulfonate,
heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,
pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate,
4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate,
4,4-toluenesulfonyloxy-benzenesulfonate, naphthalenesulfonate,
camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate,
butanesulfonate, and methanesulfonate. Iodonium salts based on
combination of the foregoing examples are included.
[0060] Exemplary sulfonyldiazomethane compounds include
bissulfonyldiazomethane compounds and sulfonylcarbonyldiazomethane
compounds such as bis(ethylsulfonyl)diazo-methane,
bis(1-methylpropylsulfonyl)diazomethane,
bis(2-methylpropylsulfonyl)diazomethane,
bis(1,1-dimethylethylsulfonyl)diazomethane,
bis(cyclohexylsulfonyl)diazomethane,
bis(perfluoroisopropylsulfonyl)diazomethane,
bis(phenylsulfonyl)diazomethane,
bis(4-methylphenylsulfonyl)diazomethane,
bis(2,4-dimethylphenylsulfonyl)diazomethane,
bis(2-naphthylsulfonyl)diazomethane,
4-methylphenylsulfonylbenzoyldiazomethane,
tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane
2-naphthylsulfonylbenzoyldiazomethane,
4-methylphenyl-sulfonyl-2-naphthoyldiazomethane,
methylsulfonylbenzoyldiazomethane, and
tert-butoxycarbonyl-4-methylphenylsulfonyldiazotmethane.
[0061] N-sulfonyloxyimide photoacid generators include combinations
of imide skeletons with sulfonates. Exemplary imide skeletons are
succinimide, naphthalene dicarboxylic acid imide, phthalimide,
cyclohexyldicarboxylic acid imide, 5-norbornene-2,3-dicarboxylic
acid imide, and 7-oxabicyclo [2,2,1]-5-heptene-2,3-dicarboxylic
acid imide. Exemplary sulfonates include trifluoromethanesulfonate,
nonafluorobutanesulfonate, heptadecafluorooctanesulfonate,
2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate,
4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate,
toluenesulfonate, benzenesulfonate, naphthalenesulfonate,
camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate,
butanesulfonate, and methanesulfonate,
[0062] Benzoinsulfonate photoacid generators include benzoin
tosylate, benzoin mesylate, and benzoin butanesulfonate.
[0063] Pyrogallol trisulfonate photoacid generators include
pyrogallol, fluoroglycine, catechol, resorcinol, hydroquinone, in
which all the hydroxyl groups are replaced by
trifluoromethanesulfonate, nonafluorobutanesulfonate,
heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,
pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate,
4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate,
naphthalenesulfonate, camphorsulfonate, octanesulfonate,
dodecylbenzenesulfonate, butanesulfonate, and methanesulfonate.
[0064] Nitrobenzyl sulfonate photoacid generators include
2,4-dinitrobenzyl sulfonate, 2-nitrobenzyl sulfonate, and
2,6-dinitrobenzyl sulfonate, with exemplary sulfonates including
trifluoromethanesulfonate, nonafluorobutanesulfonate,
heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,
pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate,
4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate,
naphthalenesulfonate, camphorsulfonate, octanesulfonate,
dodecylbenzenesulfonate, butanesulfonate, and methanesulfonate.
Also useful are analogous nitrobenzyl sulfonate compounds in which
the nitro group on the benzyl side is replaced by a trifluoromethyl
group.
[0065] Sulfone photoacid generators include
bis(phenylsulfonyl)methane, bis(4-methylphenylsulfonyl)methane,
bis(2-naphthylsulfonyl)methane, 2,2-bis(phenylsulfonyl)propane,
2,2-bis(4-methylphenylsulfonyl)propane,
2,2-bis(2-naphthylsulfonyl)propane,
2-methyl-2-(p-toluenesulfonyl)propiophenone,
2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, and
2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one.
[0066] Photoacid generators in the form of glyoxime derivatives
include bis-o-(p-toluenesulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(p-toluenesulfonyl)-.alpha.-diphenylglyoxime,
bis-o-(p-toluenesulfonyl)-.alpha.-dicyclohexylglyoxime,
bis-o-(p-toluenesulfonyl)-2,3-pentanedioneglyoxime,
bis-o-(p-toluenesulfonyl)-2-methyl-3,4-pentanedioneglyoxime,
bis-o-(n-butanesulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(n-butanesulfonyl)-.alpha.-diphenylglyoxime,
bis-o-(n-butanesulfonyl)-.alpha.-dicyclohexylglyoxime,
bis-o-(n-butanesulfonyl)-2,3-pentanedioneglyoxime,
bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedioneglyoxime,
bis-o-(methanesulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(trifluoromethanesulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(1,1,1-trifluoroethanesulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(tert-butanesulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(perfluorooctanesulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(cyclohexylsulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(benzenesulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(p-fluorobenzenesulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(p-tert-butylbenzenesulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(xylenesulfonyl)-.alpha.-dimethylglyoxime, and
bis-o-(camphorsulfonyl)-.alpha.-dimethylglyoxime.
[0067] Of these photoacid generators, the sulfonium salts,
bissulfonyldiazomethane compounds, and N-sulfonyloxyimide compounds
are preferred.
[0068] While the anion of the optimum acid to be generated differs
depending on the ease of scission of acid labile groups introduced
in the DPHS, an anion which is nonvolatile and not extremely
diffusive is generally chosen. The preferred anions include
benzenesulfonic acid anions, toluenesulfonic acid anions,
4,4-toluenesulfonyloxybenzenesulfonic acid anions,
pentafluorobenzenesulfonic acid anions,
2,2,2-trifluoroethanesulfonic acid anions, nonafluorobutanesulfonic
acid anions, heptadecafluorooctanesulfonic acid anions, and
camphorsulfonic acid anions.
[0069] In the chemically amplified positive resist composition, an
appropriate amount of the photoacid generator is 0 to 20 parts, and
especially 1 to 10 parts by weight per 100 parts by weight of the
solids in the composition. The photoacid generators may be used
alone or in a mixture of two or more. The transmittance of the
resist film can be controlled by using a photoacid generator having
a low transmittance at the exposure wavelength and adjusting the
amount of the photoacid generator added.
[0070] In conjunction with the all steps set forth above, it is
critical that all steps be conducted on an anhydrous basis, i.e.
wherein the water level is less than about 5,000 parts per million
(ppm), in order to avoid possible side reactions and provide a
mechanism to provide a convenient and direct route to a resist
composition without having to isolate the BDPHS product and then
carry out additional processing steps.
[0071] In addition to the use of DPHS (with a novolak-type
structure) and/or BDPHS, in the microelectronic chemicals market,
such DPHS and/or BDPHS can be employed in standard novolak
applications such as varnishes, aniline printing inks, raw
materials for epoxy resins, copying paper, tackifiers for rubber,
and crude oil separators and other applications as stated
herein.
[0072] The following specific examples are supplied for the purpose
of better illustrating the invention. These examples are not
intended, however, to limit or restrict the scope of the invention
in any way and should not be construed as providing conditions,
parameters, or values which must be utilized exclusively in order
to practice the present invention.
Example 1
4-Hydroxyphenylmethylcarbinol Methyl Ether (HPME) Synthesis
[0073] To 15 gms of methanolic solution containing 22.2%
4-hydroxyphenylmethylcarbinol (HPMC) was added 0.45 gms of
Amberlyst A-15 acid ion exchange resin. This mixture was allowed to
stand for 72 hours at room temperature. HPLC analysis indicates
that the resulting solution contains only 0.21% HPMC (99%
conversion) with the remainder being HPME. This material thus
produced is suitable for use as a raw material in the preparation
of the DPHS polymer.
Polymerization of 4-Hydroxyphenylmethylcarbinol Methyl Ether
(HPME), Production of DPHS Polymer in Methanol Solution.
[0074] To a 500 ml flask fitted with a nitrogen inlet, mixer,
temperature indicator and controller, and reflux condenser was
added 226 gms of methanol solution containing 30.4% HPME (68.7 gms
HPME) raw material. Using solvent distillation 131 gms of methanol
was removed rendering a solution containing 72.3% HPME in
methanol.
[0075] The resulting solution was cooled to room temperature. With
stirring and under nitrogen, 1.4 gms of aqueous 10% H.sub.2SO.sub.4
(catalyst) was added at 30.degree. C. The mixture was heated over a
30 minute period to 35.degree. C. and a second equal portion of
catalyst was added. This process was repeated three more times at
which time 7.0 gm of acid catalyst had been added with a resulting
temperature of 50.degree. C. over a two hour period. The
polymerization mixture was then increased to 65.degree. C., reflux
temperature, at which time the mixture color was noted to be pink
turning amber thereafter. Reflux was allowed to continue for
26 hours after which time the reaction mixture was cooled to
27.degree. C.
[0076] The resulting reaction mixture was diluted with methanol to
give a solids concentration of about 30% which was slowly fed into
demineralized water (1 part by weight methanol solution to 10 parts
demineralized water) to give a precipitated polymer product. The
precipitated material was filtered and washed three times with 125
gms of fresh demineralized water.
[0077] The wet-cake thus obtained was dried under vacuum at
40.degree. C. until the moisture content was about 1% or less. This
polymer was observed to have a GPC molecular weight of 4528 MW, a
polydispersity of 1.6, and was of light pink color.
Example 2 Comparative
[0078] In a similar polymerization run using a raw material
containing significant quantities of HPMC in the presence of HPME,
a polymeric material completely unsatisfactory for commercial
purposes was obtained. This undesirable material was dark blue in
color and tacky upon vacuum drying. This material was also very
difficult to filter and wash. This comparative example is similar
to those examples 1-11 set forth in U.S. Pat. No. 5,554,719 and
U.S. Pat. No. 5,565,544.
[0079] It is to be understood that the remarks above contain some
theory as to the formation of DPHS with a novolak type structure;
however, Applicant does not wish to be so limited.
Example 3
50% Acetal Blocked DPHS
[0080] To a four neck three litter round bottom flask equipped with
mechanical stirrer, nitrogen purge inlet and outlet, distillation
column, condenser and a receiver, 245 g (2.04 moles as phenol OH
equivalents) of DPHS and PGMEA, 617 g were charged. The mixture was
stirred under nitrogen at 25.degree. C. to a homogeneity and then
PGMEA was distilled at 50.degree. C. at 10 torr to remove residual
water to less than 300 ppm. The solution was cooled to 5.degree. C.
and a solution of trifluoroacetic acid, 0.5 g in PGMEA 3 g was
added under nitrogen purge and stirring. To the solution,
ethylvinylether, 73.6 g, 1.02 mole, 50 mole equivalent to phenolic
OH on DPHS was added dropwise at 5.degree. C. under nitrogen with
stirring. The mixture was stirred at 5.degree. C. for 3 hr. and at
25.degree. C. for 10 hr.
[0081] The solution was then applied to a column (25 mm diameter
and 250 mm length) containing IRA96 in PGMEA at 8 ml/min. to remove
the catalyst. The blocking level was determined to be 51 mole % by
C13 NMR, Mw=4,400, PD=1.80 by GPC, TFAA<3 ppm. 51 mole % acetal
blocked DPHS, 675 g at 43.5% solid in PGMEA (92.1% yield) was
obtained.
Example 4
40% Acetal Blocked DPHS
[0082] To a four neck three liter round bottom flask equipped with
mechanical stirrer, nitrogen purge inlet and outlet, distillation
column, condenser and a receiver, 258 g (2.15 moles as phenol OH
equivalents) of DPHS and PGMEA, 628 g were charged. The mixture was
stirred under nitrogen at 25.degree. C. to a homogeneity and then
PGMEA was distilled at 50.degree. C. at 10 torr to remove residual
water to less than 300 ppm. The solution was cooled to 5.degree. C.
and a solution of trifluoroacetic acid, 0.5 g in PGMEA 3 g was
added under nitrogen purge and stirring. To the solution,
ethylvinylether, 62 g, 0.86 mole, 40 mole equivalent to phenolic OH
on DPHS was added dropwise at 5.degree. C. under nitrogen with
stirring. The mixture was stirred at 5.degree. C. for 3 hr. and at
25.degree. C. for 10 hr.
[0083] The solution was then applied to a column (25 mm diameter
and 250 mm length) containing IRA96 in PGMEA at 8 ml/min. to remove
the catalyst. The blocking level was determined to be 43 mole % by
C13 NMR, Mw=4,400, PD=1.79 by GPC, TFAA=4.19 ppm. 43 mole % acetal
blocked DPHS, 647 g at 45.1% solid in PGMEA was obtained (91.2%
yield)
Example 5
24% t-Boc Blocked DPHS
[0084] To a four neck three liter round bottom flask equipped with
mechanical stirrer, nitrogen purge inlet and outlet, distillation
column, condenser and a receiver, 419 g (3.49 moles as phenol OH
equivalents) of DPHS, Lot 8007A and PGMEA, 1753 g were charged. The
mixture was stirred under nitrogen at 25.degree. C. to a
homogeneity and then PGMEA was distilled at 50.degree. C. at 10
torr to remove residual water to less than 300 ppm. The solution
was cooled to 40.degree. C. and a solution of Dimethylaminopyridine
(DMAP), 0.6 g in PGMEA 6 g was added under nitrogen purge and
stirring. To the solution, Di-t-butyl-di-carbonate (DBDC), 228.6 g,
1.05 mole, 30 mole equivalent to phenolic OH on DPHS was added at
once at 40.degree. C. under nitrogen with stirring. The mixture was
stirred at 40.degree. C. for 3 hr. and at 25.degree. C. for 10
hr.
[0085] The solution was then applied to a column (25 mm diameter
and 250 mm length) containing MAC-3 in PGMEA at 8 ml/min. to remove
the catalyst. The blocking level was determined to be 24 mole % by
C13 NMR, Mw=6,000, PD=1.65 by GPC, DMAP, 92 ppm. 24 mole % t-Boc
blocked DPHS 1,253 g at 39.0% solid in PGMEA (92% yield) was
obtained.
Example 6
27% t-Boc Blocked DPHS
[0086] To a four neck three litter round bottom flask equipped with
mechanical stirrer, nitrogen purge inlet and outlet, distillation
column, condenser and a receiver, 194 g (1.62 moles as phenol OH
equivalents) of DPHS and PGMEA, 1,081 g were charged. The mixture
was stirred under nitrogen at 25.degree. C. to a homogeneity and
then PGMEA was distilled at 50.degree. C. at 10 torr to remove
residual water to less than 300 ppm. The solution was cooled to
40.degree. C. and a solution of Dimethylaminopyridine (DMAP), 0.3 g
in PGMEA 3 g was added under nitrogen purge and stirring. To the
solution, Di-t-butyl-di-carbonate (DBDC), 141 g, 0.65 mole, 40 mole
equivalent to phenolic OH on DPHS was added at once at 40.degree.
C. under nitrogen with stirring. The mixture was stirred at
40.degree. C. for 3 hr. and at 25.degree. C. for 10 hr.
[0087] The solution was then applied to a column (25 mm diameter
and 250 mm length) containing MAC-3 in PGMEA at 8 ml/min. to remove
the catalyst. The blocking level was determined to be 27 mole % by
C13 NMR, Mw=6,200, PD=1.63 by GPC, DMAP, 20 ppm. 27 mole % t-Boc
blocked DPHS 776 g at 32.4% solid in PGMEA (97.2% yield) was
obtained.
Example 7
23% Acetal and 9% t-Boc Blocked DPHS
[0088] To a four neck three litter round bottom flask equipped with
mechanical stirrer, nitrogen purge inlet and outlet, distillation
column, condenser and a receiver, 413 g (3.44 moles as phenol OH
equivalents) of DPHS and PGMEA, 1967 g were charged. The mixture
was stirred under nitrogen at 25.degree. C. to a homogeneity and
then PGMEA was distilled at 50.degree. C. at 10 torr to remove
residual water to less than 300 ppm. The solution was cooled to
5.degree. C. and a solution of trifluoroacetic acid, 0.5 g in PGMEA
3 g was added under nitrogen purge and stirring. To the solution,
ethylvinylether, 66 g, 0.92 mole, 26.6 mole equivalent to phenolic
OH on DPHS was added dropwise at 5.degree. C. under nitrogen with
stirring. The mixture was stirred at 5.degree. C. for 3 hr. and at
25.degree. C. for 10 hr.
[0089] The solution was then applied to a column (25 mm diameter
and 250 mm length) containing IRA96 in PGMEA at 8 ml/min. to remove
the catalyst.
[0090] The solution was cooled to 40.degree. C. and a solution of
Dimethylaminopyridine (DMAP), 0.6 g in PGMEA 6 g was added under
nitrogen purge and stirring. To the solution,
Di-t-butyl-di-carbonate (DBDC), 80 g, 0.37 mole, 11 mole equivalent
to phenolic OH on DPHS was added at once at 40.degree. C. under
nitrogen with stirring. The mixture was stirred at 40.degree. C.
for 3 hr. and at 25.degree. C. for 10 hr.
[0091] The solution was then applied to a column (25 mm diameter
and 250 mm length) containing MAC-3 in PGMEA at 8 ml/min. to remove
the catalyst.
[0092] The blocking level was determined to be 23 mole % acetal and
9 mole % t-Boc by C13 NMR, Mw=5,800, PD=1.67 by GPC, TFAA<3 ppm.
Duo blocked DPHS, 1,035 g at 45.3% solid in PGMEA (97.3% yield) was
obtained.
[0093] Although the invention has been illustrated by certain of
the preceding examples, it is not to be construed as being limited
thereby; but rather, the invention encompasses the generic area as
hereinbefore disclosed. Various modifications and embodiments can
be made without departing from the spirit and scope thereof.
[0094] In part, the present invention covers the following
inventive ideas: [0095] 1. A process for preparing derivatized
polyhydroxystyrene having a novolak type structure which comprises
the steps of (a) supplying a solution of methanol containing
4-hydroxyphenylmethylcarbinol, (b) contacting said solution with an
acid ion exchange resin for a sufficient period of time and under
suitable conditions of temperature and pressure to convert
substantially all of said carbinol to 4-hydroxyphenylmethylcarbinol
methyl ether in solution, (c) polymerizing said ether containing
solution in the presence of a suitable acid catalyst for a
sufficient period of time and under suitable conditions of
temperature and pressure to form a novolak type polymer. [0096] 2.
The process as set forth in item 1 wherein said acid catalyst is a
Lewis acid. [0097] 3. The process as set forth in item 1 wherein
the temperature in steps (b) and (c) is from about 0.degree. C. to
about 100.degree. C. and the pressure is from about 0 psig to about
10 psig. [0098] 4. The process as set forth in item 1 wherein the
acid catalyst is a mineral acid. [0099] 5. The process as set forth
in item 4 wherein the acid catalyst is sulfuric acid. [0100] 6. The
process as set forth in item 1 wherein the acid catalyst is
selected from the group consisting of H.sub.2SO.sub.4, HCL
AlCl.sub.3, H.sub.3PO.sub.4, oxalic acid, SnCl.sub.2, BF.sub.3,
BBr.sub.3, BCl.sub.3, para-toluene sulfonic acid, methane sulfonic
acid, trifluoroacetic acid, trichloroacetic acid and mixtures
thereof. [0101] 7. A composition of matter having the following
structure:
[0101] ##STR00003## wherein n is from about 1 to about 10. [0102]
8. A composition of matter comprising a derivatized
poly(4-hydroxystyrene) characterized by having from about 6% to
about 40% linearity, a polydispersity of less than about 2.0, and a
molecular weight of less than about 10,000. [0103] 9. A primary
photoresist composition for patterning electronic circuitry based
on the composition of matter set forth in item 7. [0104] 10. A
curing agent for an epoxy resin based on the composition of matter
set forth in item [0105] 11. A varnish incorporating the
composition of matter set forth in item 7. [0106] 12. A printing
ink incorporating the composition of matter set forth in item 7.
[0107] 13. A tackifier for rubber incorporating the composition of
matter set forth in item 7. [0108] 14. A crude oil separator
incorporating the composition of matter set forth in item 7. [0109]
15. A solder mask or photoimageable coverlay for rigid or flexible
printed circuit boards incorporating the composition of matter set
forth in item 7. [0110] 16. An epoxy material which has been
further derivatized by reaction with the hydroxy groups in the
composition of matter set forth in item 7. [0111] 17. A epoxy or
blocked isocyanate containing paint formulation which also has
incorporated therein the composition of matter set forth in item 7.
[0112] 18. A highly viscous polymer having incorporated therein the
composition of matter set forth in item 7 and which acts as a
viscosity modifier therefore. [0113] 19. A polymeric material
having incorporated therein the composition of matter set forth in
item 7 and which acts as an antioxidant therefore. [0114] 20. A
process for preparing 4-hydroxyphenylmethylcarbinol methyl ether
and which comprises the steps of (i) supplying a solution of
methanol containing 4-hydrophenylmethylcarbinol and (ii) contacting
said solution with an acid ion exchange resin for a sufficient
period of time and under suitable conditions of temperature and
pressure to convert substantially all of said carbinol to the
carbinol methyl ether.
* * * * *