Film-forming polymers

Details Film-forming polymers Film-forming polymers

1999-04-26

2001-10-23

Wu, David W. (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S271000, C526S318200, C526S318400, C526S319000, C526S322000, C526S323200, C526S328500, C526S329000, C430S192000, C430S193000, C430S270100, C522S153000

Reexamination Certificate

active

06306990

ABSTRACT:

BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
The invention relates to novel film-forming, functionalized polymers having 1,2-dicarboxylic acid monoester groups.
Film-forming, functionalized polymers which have long been known are used for coating metals, papers and textiles and in the cosmetics industry, for example in hairsprays. Such polymers are also used in the pharmaceutical industry, for example for encapsulating or for immobilizing active substances. Electronic applications are, for example, in the area of NLO polymers, i.e. nonlinear optically active polymers, and of photoresists. In the latter case, mixtures of the polymers and photoactive, i.e. radiation-sensitive, components are used, for example for structuring semiconductor components. An important requirement here is a high transparency of the polymers at the exposure wavelength. Polymers which are used in the printing plate industry or in photocuring also have to meet similar requirements.
The preparation of monoesters of maleic acid copolymers and their use in photoresists is disclosed, for example, in International Application WO 96/24621. International Application WO 97/14079 likewise discloses the use of polymers having vicinal dicarboxylic acid monoester groups in photoresists. International Application WO 89/07786 describes the alcoholysis of copolymers of maleic anhydride and cycloaliphatic hydrocarbons.
SUMMARY OF THE INVENTION
It is the object of the invention to provide novel film-forming, functionalized polymers which have 1,2-dicarboxylic acid monoester groups, are suitable for various applications and can be used in particular in photoresists.
This and related objects are achieved, according to the invention, by film-forming polymers functionalized with 1,2-dicarboxylic acid monoester groups, comprising an acid-labile, hydrolysis-stable polymer unit (A) of structure:
a thermally stable polymer unit (B) of structure:
a second thermally stable polymer unit (C) of structure
and a polymer unit (D) bearing reactive groups and having a structure
in which the amount of (A) is from 1 to 99 mol %, the amount of (B) is from 1 to 99 mol %, the amount of (C) is from 0 to 50 mol %, and the amount of (D) is from 0 to 50 mol %, provided that the amounts of (A), (B), (C), and (D) total 100 mol %; and in which
n=0, 1, 2 or 3,
R
1
is a hydrocarbon radical which is bonded via a tertiary C atom to the O atom and having a total of 4 to 10 C atoms, or a 2-tetrahydrofuranyl or 2-tetrahydropyranyl radical,
R
2
, R
3
and R
4
—independently of one another—are C
1-
to C
6-
alkyl or C
1-
to C
6-
alkoxy, C
6-
to C
18-
aryl or C
6-
to C
18-
aryloxy or aralkyl having a C
6-
to C
18-
aryl group and a C
1-
to C
4-
alkylene radical,
R
5
is H or C
1-
to C
6-
alkyl,
R
6
, R
7
, R
8
and R
9
—independently of one another—are H, C
1-
to C
6-
alkyl, C
6-
to C
18-
aryl, halogen, CN, methoxyphenyl or a radical of structure
where
R
15
is H, C
1-
to C
6-
alkyl, C
6-
to C
18-
aryl, CH
2
═CH—(vinyl), CH
2
═CH—CH
2
-(allyl), or CH
2
═CH—CO—;
R
10
is H, C
1-
to C
6-
alkyl, C
2-
to C
6-
alkenyl, C
6-
to C
18-
aryl, halogen or halogen-substituted C
1-
to C
6-
alkyl;
R
11
and R
12
—independently of one another—are linear C
1-
to C
18-
alkyl;
R
13
and R
14
—independently of one another—are linear C
1-
to C
18-
alkyl or tert-butyl;
X is Si or Sn and
Y is O or NH.
The amounts of the polymer units (A) and (B) sum to 100 mol % when only such polymer units are present. When polymer units (C) and/or (D) are present in amounts greater than 0 mol %, the amounts of polymer units (A), (B), (C) and/or (D) sum to 100 mol %. By suitable choice of amounts of these polymer units and the corresponding ratios of the unsaturated monomer source of these polymer units, the polymer properties, such as glass transition temperature and solubility, can be controlled.
The amount of polymer unit (A) of the polymer is preferably from 5 to 50 mol %. The amount of polymer units (C) and or (D) when present is in the range from
1
to 50 mol %, preferably from 5 to 15 mol % and 1 to 10 mol %, respectively.
As a feature of this invention, the hydrolytically stable and acid labile polymer units (A) are resistant to exposure to water and acidic solutions up to 70° C. As a further feature of this invention, the thermally stable polymer units (B) and (C) resist depolymerization and degradation of the polymer chain up to 230° C. under thermal conditions and the polymer units (A) decompose thermally above 150° C. and at 135° C. or more under acid-catalyzed conditions, while the film forming polymers of the invention can be selectively converted to either positive or negative photoresist by controlled heat treatment at a suitable temperature followed by development in an aqueous alkaline solution.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the polymer of this invention, the radical R
1
may be, for example, a tert-butyl radical —C(CH
3
)
3
, a tert-pentyl radical —C(CH
3
)
2
—C
2
H
5
or a 1-adamantyl radical (—C
10
H
15
). An important feature of the polymer unit (B) is its metallic component, i.e. the presence of silicon Si or tin Sn.
The polymer according to the invention can have 1,2-dicarboxylic acid monoester groups as in the structural units(1), (2), or (3), on the chain or as pendant groups. A polymer comprising units (A) and (B) having groups on the chain can be prepared, for example, by reacting a maleic anhydride copolymer with tert-butanol. The mono-tert-butyl 1,2-dicarboxylate groups can also be introduced into the polymer by homo- or copolymerization of mono-tert-butyl fumarate or maleate.
Polymers having pendant 1,2-dicarboxylic acid monoester groups, i.e. having groups which are not bonded directly to the polymer main chain but are situated outside the main chain, can be obtained, for example, by homopolymerization of or copolymerization with 1-alkyl-2-(3-alkylenesuccinic anhydride)-ethylene and subsequent reaction with tert-butanol or by homopolymerization of 1-alkyl-2-(mono-tert-butyl 3-alkylenesuccinate)-ethylene. In the case of the structural unit (3), the 1,2-dicarboxylic acid monoester groups are bonded via a norbornyl radical to the polymer main chain.
The polymers according to the invention have weight average molecular weight in the range from 5000 to 15000, typically approximately 12000, and glass transition temperatures in the range from 110 to 150° C., typically 130° C. The characteristic vibrational bands in the infra-red spectrum of the monoester moieties (polymer unit A) are at 1730 and 1710 cm
−1
. Tert-butyl succinate monoester moieties also have a characteristic band at 1150 cm
−1
. Bands characteristic of anhydride groups are found at 1750 and 1780 cm
—1
.
For the preparation of polymers according to the invention, in general an unsaturated monomer source for the polymer units (A) is copolymerized with an electron-rich monomer source for the polymer units (B). The monomer source for polymer units (a) of structure (1) is a monoester of maleic acid or fumaric acid in which the esterifying group R
1
is as defined above. The monomer source for polymer unit (A) of structure (2) can be monoester of alkylidenesuccinic acid, alkylmaleic acid or alkylfumaric acid in which the esterifying group R
1
is as defined above. The monomer source for polymer unit (A) of structure (3) can be a norbornenedicarboxylic acid monoester in which the esterifying group R
1
is as defined above. The monomer source for polymer unit (B) is an unsaturated compound with high electron density at the double bond, such as an allyl compound (leading to structure (4)) or an acrylic ester or amide (leading to structure (5)). As a result of this copolymerization, on the one hand high polymer yields are achieved and on the other hand the physical properties of the polymers can be controlled. Thus for example, a specific Si content can be realized.
In addition to the polymer units (A) and(B), the polymers according to the invention advantageously can include a further thermally stable polymer unit (C) as d

Affiliated with

Also associated with

Rating

Film-forming polymers does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Film-forming polymers, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Film-forming polymers will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2564715