Note: Descriptions are shown in the official language in which they were submitted.
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TITLE OF THE INVENTION
SOLAR CELL MODULES WITH POLY(VINYL BUTYRAL) ENCAPSULANT COMPRISING
UNSATURATED HETEROCYCLIC COMPOUND
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority under 35 U.S.C. 120 to U.S. Provisional
Appln. Nos.
61/146,535, filed on January 22, 2009, 61/221,771, filed on June 30, 2009, and
61/226,435,
filed on July 17, 2009, each of which is incorporated herein by reference in
its entirety.
FIELD OF THE INVENTION
The invention is directed to a solar cell module comprising an improved
poly(vinyl
butyral) composition useful as an encapsulant material for solar cell
assemblies. In particular,
the improved poly(vinyl butyral) composition is resistant to yellowing upon
prolonged contact
with components of the assemblies that comprise elemental silver and alloys of
elemental silver.
BACKGROUND OF THE INVENTION
Several patents and publications are cited in this description in order to
more fully
describe the state of the art to which this invention pertains. The entire
disclosure of each of
these patents and publications is incorporated by reference herein.
Because solar cells provide a sustainable energy resource, their use is
rapidly
expanding. Solar cells can typically be categorized into two types based on
the light absorbing
material used, i.e., bulk or wafer-based solar cells and thin film solar
cells.
Monocrystalline silicon (c-Si), poly- or multi-crystalline silicon (poly-Si or
me-Si) and
ribbon silicon are the materials used most commonly in forming the more
traditional wafer-
based solar cells. Solar cell modules derived from wafer-based solar cells
often comprise a
series of about 180 and about 240 pm thick self-supporting wafers (or cells)
that are soldered
together. Such a panel of solar cells, along with a layer of conductive paste
and/or connecting
wires deposited on its surface, may be referred to as a solar cell assembly
and encapsulated by
or sandwiched or laminated between polymeric encapsulants, which may be
further sandwiched
between two protective outer layers to form a weather resistant module. The
protective outer
layers may be formed of glass, metal sheets or films, or plastic sheets or
films. In general,
however, the outer layer that faces to the sunlight should be sufficiently
transparent to allow
photons reach the solar cells.
In the increasingly important alternative, thin film solar cells, the commonly
used
materials include amorphous silicon (a-Si), microcrystalline silicon (pc-Si),
cadmium telluride
(CdTe), copper indium selenide (CulnSe2 or CIS), copper indium/gallium
diselenide (CulnXGa(,_
x)Se2 or GIGS), light absorbing dyes, organic semiconductors, etc. By way of
example, thin film
solar cells are described in U.S. Patent Nos. 5,507,881; 5,512,107; 5,948,176;
5,994,163;
1
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6,040,521; 6, 123,824; 6,137,048; 6,288,325; 6,258,620; 6,613,603; and
6,784,301; and U.S.
Patent Publication Nos. 20070298590; 20070281090; 20070240759; 20070232057;
20070238285;20070227578;20070209699; 20070079866; 20080223436; and
20080271675.
Thin film solar cells with a typical thickness of less than 2 pm are produced
by depositing the
semiconductor materials onto a substrate in multi-layers. Further, connecting
wires, metal
conductive coatings, and/or metal reflector films may be deposited over the
surface of the thin
film solar cells to constitute part of the thin film solar cell assembly. The
substrate may be
formed of glass or a flexible film and may also be referred to as superstrate
in those modules in
which it faces to the sunlight. Similarly to the wafer-based solar cell
modules, the thin film solar
cell assemblies are further encapsulated by or laminated or sandwiched between
polymeric
encapsulants, which are further laminated or sandwiched between protective
outer layers. In
certain solar cell modules, the thin film solar cell assembly may be only
partially encapsulated
by the encapsulant, so that only the side of the thin film solar cell assembly
that is opposite from
the substrate (or superstrate) is laminated to a polymeric encapsulant and
then a protective
outer layer. In such a construction, the thin film solar cell assembly is
sandwiched between the
substrate (or superstrate) and the encapsulant on the opposite side.
Within the solar cell modules, some components (such as connecting wires,
conductive
paste (used in wafer-based solar cell modules), conductive coatings (used in
thin film solar
cells) and back reflector films) may comprise oxidizable silver or a silver
alloy. When in contact
with an oxidizable silver component, an encapsulant comprising poly(vinyl
butyral) (PVB) tends
to discolor over time. Discoloration is not desirable in the photovoltaic
industry, because it
decreases the transmission of light, and because it may be considered
aesthetically unpleasing.
Thus, there is a need to develop a PVB composition that is useful as an
encapsulant material
for solar cell modules and that has improved resistance to discoloration when
in prolonged
contact with oxidizable silver components.
SUMMARY OF THE INVENTION
A solar cell module comprising a solar cell assembly encapsulated by
poly(vinyl butyral)
and containing a silver component, wherein the silver component is at least
partially in contact
with the poly(vinyl butyral) and the poly(vinyl butyral) comprises about 15 to
about 45 wt% of
plasticizer and about 0.5 to about 2 wt%, preferably about 0.1 to about 2 wt%,
of unsaturated
heterocyclic compound, based on the total weight of the poly(vinyl butyral).
An assembly for preparing a solar cell module comprising a solar cell
assembly, which
comprises a silver component, and a poly(vinyl butyral) sheet having a
thickness of about 0.25
mm to about 1.2 mm and comprising about 15 to about 45 wt% of plasticizer and
about 0.5 to
about 2 wt%, preferably about 0.1 to about 2 wt%, of unsaturated heterocyclic
compound,
based on the total weight of the poly(vinyl butyral) sheet.
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A process of preventing discoloration of poly(vinyl butyral) encapsulant in a
solar cell
module comprising a solar cell assembly that comprises a silver component in
complete or
partial contact with the polyvinyl butyral) encapsulant, comprising providing
a polyvinyl butyral)
comprising about 15 to about 45 wt% of plasticizer and about 0.5 to about 2
wt%, preferably
about 0.1 to about 2 wt%, of unsaturated heterocyclic compound, based on the
total weight of
the poly(vinyl butyral), and encapsulating a solar cell assembly with the
poly(vinyl butyral).
A process of preventing discoloration of poly(vinyl butyral) encapsulant in a
solar cell
module comprising a solar cell assembly that comprises a silver component in
complete or
partial contact with the poly(vinyl butyral) encapsulant, comprising providing
a poly(vinyl butyral)
sheet having a thickness of about 0.25 mm to about 1.2 comprising about 15 to
about 45 wt% of
plasticizer and about 0.5 to about 2 wt%, preferably about 0.1 to about 2 wt%,
of unsaturated
heterocyclic compound, based on the total weight of the poly(vinyl butyral),
and forming a solar
cell module including the step of laminating the solar cell assembly to the
poly(vinyl butyral)
sheet.
DETAILED DESCRIPTION OF THE INVENTION
Unless otherwise defined, all technical and scientific terms used herein have
the same
meaning as commonly understood by one of ordinary skill in the art to which
this invention
belongs. In case of conflict, the specification, including definitions, will
control.
Although methods and materials similar or equivalent to those described herein
can be
used in the practice or testing of the invention, suitable methods and
materials are described
herein.
Unless stated otherwise, all percentages, parts, ratios, etc., are by weight.
When an amount, concentration, or other value or parameter is given as either
a range,
preferred range or a list of upper preferable values and lower preferable
values, this is to be
understood as specifically disclosing all ranges formed from any pair of any
upper range limit or
preferred value and any lower range limit or preferred value, regardless of
whether ranges are
separately disclosed. Where a range of numerical values is recited herein,
unless otherwise
stated, the range is intended to include the endpoints thereof, and all
integers and fractions
within the range. It is not intended that the scope of the invention be
limited to the specific
values recited when defining a range.
When the term "about" is used in describing a value or an end-point of a
range, the
disclosure should be understood to include the specific value or end-point
referred to.
As used herein, the terms "comprises," "comprising," "includes," "including,"
"containing,"
"characterized by," "has," "having" or any other variation thereof, are
intended to cover a non-
exclusive inclusion. For example, a process, method, article, or apparatus
that comprises a list
of elements is not necessarily limited to only those elements but may include
other elements not
expressly listed or inherent to such process, method, article, or apparatus.
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The term "or", as used herein, is inclusive; that is, the phrase "A or B"
means "A, B, or
both A and B". Exclusive "or" is designated herein by terms such as "either A
or B" and "one of
A or B", for example.
The transitional phrase "consisting essentially of' limits the scope of a
claim to the
specified materials or steps and those that do not materially affect the basic
and novel
characteristic(s) of the claimed invention.
Where applicants have defined an invention or a portion thereof with an open-
ended
term such as "comprising," it should be readily understood that unless
otherwise stated the
description should be interpreted to also describe such an invention using the
terms "consisting
essentially of and "consisting of'.
The articles "a" and "an" may be employed in connection with various elements
and
components of compositions, processes or structures described herein. This is
merely for
convenience and to give a general sense of the compositions, processes or
structures. Such a
description includes "one or at least one" of the elements or components.
Moreover, as used
herein, the singular articles also include a description of a plurality of
elements or components,
unless it is apparent from a specific context that the plural is excluded.
As used herein, the term "copolymer" refers to polymers comprising
copolymerized units
resulting from copolymerization of two or more comonomers. Such copolymers
include
dipolymers, terpolymers or higher order copolymers. In this connection, a
copolymer may be
described herein with reference to its constituent comonomers or to the
amounts of its
constituent comonomers, for example "a copolymer comprising ethylene and 18
weight % of
acrylic acid", or a similar description. Such a description may be considered
informal in that it
does not refer to the comonomers as copolymerized units; in that it does not
include a
conventional nomenclature for the copolymer, for example International Union
of Pure and
Applied Chemistry (IUPAC) nomenclature; in that it does not use product-by-
process
terminology; or for another reason. As used herein, however, a description of
a copolymer with
reference to its constituent comonomers or to the amounts of its constituent
comonomers
means that the copolymer contains copolymerized units (in the specified
amounts when
specified) of the specified comonomers. It follows as a corollary that a
copolymer is not the
product of a reaction mixture containing given comonomers in given amounts,
unless expressly
stated in limited circumstances to be such.
An improved poly(vinyl butyral) (PVB) composition useful as an encapsulant
material in
solar cell modules comprises (a) a PVB polymer at a level of about 85 wt%, or
about 80 wt%, or
about 75 to about 55 wt%, or about 65 wt%, or about 70 wt%; (b) one or more
plasticizers at a
level of about 15 wt%, or about 20 wt%, or about 25 wt% to about 45 wt%, or
about 35 wt%, or
about 30 wt%, based on the total weight of the PVB composition, and (c) one or
more
unsaturated heterocyclic compounds at a level of about 0.1 wt%, or about 0.15
wt%, or about
0.1 wt% to about 2 wt%, or about 0.2 wt% to about 1 wt%, or about 0.5 wt% to
about 2 wt%, or
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about 0.8 wt%, or about 0.75 wt%, or about 0.5 wt%, or about 0.4 wt%, or about
0.3 wt% based
on the total weight of the PVB composition. The amount of PVB resin may be
adjusted by
subtracting the weight percentage of the heterocyclic compound(s) and of any
other additives
described herein, so that the sum of the weight percentages of the components
of the improved
PVB composition is 100 wt%. The improved PVB composition exhibits reduced
yellowing after
prolonged contact with silver-containing components of the solar cell module.
PVB is a vinyl resin resulting from the condensation of poly(vinyl alcohol)
with
butyraldehyde. The PVB may be produced by aqueous or solvent acetalization. In
a solvent
process, acetalization is carried out in the presence of sufficient solvent to
dissolve the PVB and
produce a homogeneous solution at the end of acetalization. The PVB is
separated from
solution by precipitation of solid particles with water, which are then washed
and dried.
Solvents used are lower aliphatic alcohols such as ethanol. In an aqueous
process,
acetalization is carried out by adding butyraldehyde to a water solution of
poly(vinyl alcohol) at a
temperature of about 20 C to about 100 C, in the presence of an acid catalyst,
agitating the
mixture to cause an intermediate PVB to precipitate in finely divided form and
continuing the
agitation while heating until the reaction mixture has proceeded to the
desired end point,
followed by neutralization of the catalyst, separation, stabilization and
drying of the PVB. For
example, PVB can be produced as described in U.S. Patent Nos. 3,153,009 and
4,696,971.
Suitable PVB resins have a weight average molecular weight of about 30,000 Da,
or
about 45,000 Da, or about 200,000 Da to about 600,000 Da, or about 300,000 Da,
as
determined by size exclusion chromatography using low angle laser light
scattering. The PVB
may comprise about 12 wt%, or about 14 wt%, or about 15 wt%, to about 23 wt%,
or about 21
wt%, or about 19.5 wt%, or about 19 wt% of hydroxyl groups calculated as
polyvinyl alcohol
(PVOH). The hydroxyl number can be determined according to standard methods,
such as
ASTM D1396-92 (1998). In addition, the PVB used here may include up to about
10%, or up to
about 3% of residual ester groups, calculated as polyvinyl ester, typically
acetate groups, with
the balance being butyraldehyde acetal. The PVB may further comprise a minor
amount of
acetal groups other than butyral, for example, 2-ethyl hexanal, as described
in U.S. Patent No.
5,137, 954.
Plasticizers suitable for the PVB compositions may be any of those that known
within the
art (see, e.g., U.S. Patent Nos. 3,841,890; 4,144,217; 4,276,351; 4,335,036;
4,902,464;
5,013,779; and 5,886,075). Among those commonly used plasticizers are esters
of a polybasic
acid or a polyhydric alcohol. Specific examples of suitable plasticizers
include, but are not
limited to, diesters obtained from the reaction of triethylene glycol or
tetraethylene glycol with
aliphatic carboxylic acids having from 6 to 10 carbon atoms; diesters obtained
from the reaction
of sebacic acid with aliphatic alcohols having from 1 to 18 carbon atoms;
oligoethylene glycol di-
2-ethylhexanoate; tetraethylene glycol di-n-heptanoate; dihexyl adipate;
dioctyl adipate;
dibutoxy ethyl adipate; mixtures of heptyl and nonyl adipates; dibutyl
sebacate; tributoxyethyl-
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phosphate; isodecylphenylphosphate; triisopropylphosphite; polymeric
plasticizers, such as, the
oil-modified sebacid alkyds; mixtures of phosphates and adipates; mixtures of
adipates and
alkyl benzyl phthalates; and combinations of two or more of the above.
Preferred plasticizers
include triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-n-
heptanoate, dibutyl
sebacate, and combinations of two or more thereof. More preferred plasticizers
include
triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-n-heptanoate,
and combination of
two or more thereof. A plasticizer of note is triethylene glycol di-2-
ethylhexanoate.
The PVB composition further comprises one or more unsaturated heterocylic
compounds. As used herein, the term "unsaturated heterocylic compounds"
includes 1 H-
benzotriazole and non-2H substituted benzotriazole derivatives having a
formula of:
R
R N
N
R N
\
R R
1,2,3-triazole and 1,2,3-triazole derivatives having a formula of:
R
R i/N
R
1,2,4-triazole and 1,2,4-triazole derivatives having a formula of:
R
N
R'/ `11
N
R
imidazole and imidazole derivatives having a formula of:
R
R N R
{
pyrrole and pyrrole derivatives having a formula of:
R R
/
R N R
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pyrazine and pyrazine derivatives having a formula of:
R IN R
R N R
pyrimidine and pyrimidine derivatives having a formula of:
R
R N
R N' 'R
pyridine and pyridine derivatives having a formula of:
R
R R
R N R
pyridizine and pyridizine derivatives having a formula of,
R ~N
R R
R
thiazole and thiazole derivatives having a formula of:
R \ y_NR
S
R
benzoxazole and benzoxazole derivatives having a formula of:
R
R O
/ N~R
R
R
benzothiazole and benzothiazole derivatives having a formula of:
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R
R
/>-R
R \ N
R
1,3,5-triazine and 1,3,5-triazine derivatives having a formula of:
R` R
--N
NT
R
2,2'-bipyridine and 2,2'-bipyridine derivatives having a formula of:
R
R R R
R I N
N R
R
R
wherein R represents a hydrogen atom or a substituent (also referred to herein
as an "R group"
or "substituent R"); and wherein, when the unsaturated heterocyclic compound
comprises more
than one substituent, the substituents may be identical or different. Each
substituent is
independently selected from the group consisting of alkyl groups that are
branched or
unbranched, linear or cyclic; other non-aromatic hydrocarbon groups, such as
alkenyl groups
and alkynyl groups, that are also unbranched or branched, linear or cyclic,
that are singly or
multiply unsaturated and that contain C=C (double) or C=C (triple) bonds;
substituted or
unsubstituted aromatic hydrocarbon groups, including aryl groups (e.g., phenyl
and naphthyl
groups); amino groups; hydroxyl groups; alkoxy groups; and halogens (e.g., F,
Cl, Br, or I,
preferably Cl or Br). In addition, one or more of the hydrogen atoms on one or
more of the R
groups may optionally be substituted with a halogen atom or a branched or
unbranched alkyl
group comprising 1 to 4 carbon atoms. When more than one of the hydrogen atoms
of the R
group(s) are substituted, these substituents may also be the same or
different.
Preferred substituents R include branched alkyl groups, unbranched alkyl
groups, cyclic
alkyl groups, unsaturated hydrocarbon groups, substituted aryl groups,
unsubstituted aryl
groups, and halogen atoms. Branched or linear alkyl groups comprising I to 4
carbon atoms,
and in particular methyl groups, are more preferred substituents R. Other
examples of suitable
substituents R are found below in the lists of specific examples of
unsaturated heterocyclic
compounds.
More specifically with respect to benzotriazole, it is well known that this
compound exists
as two tautomers, 1 H-benzotriazole (numbered structure (1), below) and 2H-
benzotriazole
(numbered structure (ii), below). Because of symmetry, 3H-benzotriazole is
equivalent to 1 H-
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triazole; however, asymmetrical substitution with one or more non-hydrogen R
groups will
destroy this equivalence.
1
H
7 I N\N 7 `NH 2
6 4 N 2 6 4 N
3 5 3
(i) (ii)
5 Moreover, as used herein, the term "non-2H-substituted" refers to
benzotriazole
derivatives having no hydrogen atom or other substituent bound to nitrogen
atom 2. Stated
alternatively, the term "non-2H-substituted" includes the 1 H and 3H tautomers
of benzotriazole
and derivatives of these tautomers in which there is a hydrogen atom or a
substituent R bound
to nitrogen atom 1 of I H-benzotriazole or to nitrogen atom 3 of 3H-
benzotriazole. 2H-
Benzotriazole and derivatives of this tautomer in which there is a hydrogen
atom or a
substituent R bound to nitrogen atom 2 are not included. For example, 1-
propargyl-1 H-
benzotriazole (structure (i), below) is a non-2H-substituted benzotriazole;
therefore, it is within
the definition of "unsaturated heterocyclic compounds," as that term is used
herein. In contrast,
2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol (structure (ii), below)
is a 2H-substituted
benzotriazole; therefore, it is not included in the definition of "unsaturated
heterocyclic
compounds".
N He W~
N
C_zCH (i) CH3 (ii)
In summary, benzotriazole compounds are included in or excluded from the
definition of
"unsaturated heterocyclic compounds" based solely on their "non-2H
substituted" structure. In
this connection, the definition of "non-2H substituted" set forth above is not
to be superceded by
principles of nomenclature that may be inconsistent with the structural
descriptions herein.
Accordingly, examples of suitable benzotriazole derivatives include, but are
not limited
to, 1-methyl-1 H-benzotriazole, 5-methyl-1 H-benzotriazole, 1-
aminobenzotriazole, 4-hydroxy-1 H-
benzotriazole, 1-cyanobenzotriazole, 1H-benzotriazole-1-carboxaldehyde, 1,6-
dimethyl-1H-
1,2,3-benzotriazole, 1H-benzotriazole-1-methanol, 1-hydroxybenzotriazole
hydrate, 5-
chlorobenzotriazole, 1-propargyl-1 H-benzotriazole, 1 H-benzotriazol-1-
ylmethyl isocyanide, 1 H-
benzotriazole-l-acetonitrile, I-allylbenzotriazole, benzotriazole-1-
carboxamide, benzotriazole-5-
carboxylic acid, 1-(methoxymethyl)-1 H-benzotriazole, 5,6-dimethyl-1 H-
benzotriazole
monohydrate, 1-(chloromethyl)-1H-benzotriazole, 6-chloro-1-
hydroxybenzotriazole dehydrate, 1-
(2-methyl-allyl) -1 H-benzotriazole, n-(1 H-benzotriazol-1-ylmethyl)formamide,
n,n-
dimethylbenzotriazole-methanamine, 1 H-1,2,3-benzotriazole-l-ylacetic acid, 1-
methyl-5-nitro-
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1 H-1,2,3-benzotriazole, 2-methyl-4-nitro-2H-1,2,3-benzotriazole,
benzotriazole-I -carbonyl
chloride, 1-(2-butenoyl)-1H-benzotriazole, 1-(trimethylsilyl)-1H-
benzotriazole, 1-(alpha-
chloroacetyl)-1 H-benzotriazole, 1-(methylsulfonyl)-1 H-benzotriazole, 1 H-
benzotriazole-4-
sulfonic acid, 1-(1-ethoxy-2-propynyl)-1 H-benzotriazole, (1-
pyrrolidinylmethyl) benzotriazole, (1-
ethoxy-2-propenyl)benzotriazole, 1-(2,2,2-trimethylacetyl)-1 H-benzotriazole,
benzotriazole- 1-
acetic ethyl ester, 3-(1H-1,2,3-benzotriazole-1-yl)propanohydrazide, 1-
[(trimethylsilyl)methyl]
benzotriazole, 5-aminobenzotriazole dihydrochloride, 5,6-dinitro-1 H-
benzotriazole, 1-benzyl-1 H-
benzotriazole, 1-(3-chloropropionyl)-1 H-benzotriazole, 1-(2-
pyrrolecarbonyl)benzotriazole, 1-(2-
furoyl)-1 H-benzotriazole, 1 -(trifluoromethyl)acetylbenzotriazole, (4-
morpholinyl-
methyl)benzotriazole, 1-benzoyl-1 H-benzotriazole, 1-(2-pyridylcarbonyl)
benzotriazole, 1-(4-
pyridylcarbonyl)benzotriazole, N-Phenylbenzotriazole-methanamine, 1-
(phenoxymethyl)-1 H-
benzotriazole, 1-(9-amino-3H-(1,2,3)#riazolo(4,5-f)quinolin-8-yl)ethanone, 2-
benzotriazol-1-yl-
ethanesulfonyl fluoride, 1-(2-thienylcarbonyl)-1 H-benzotriazole, 1-(2,2-
dichloroacetyl)-1 H-
benzotriazole, [1-(4-morpholinyl)ethyl]benzotriazole, benzotriazol-1-
ylpyrrolidin-1-
ylmethanethione, n-(1H-1,2,3-benzotriazol-1-ylmethyl)-3-methylaniline, alpha-
methyl-n-phenyl-
1 H-benzotriazole-1-methanamine, N-(1 H-1,2,3-benzotriazol-1-ylmethyl)-2-
methylaniline, N-
methyl-N-phenylbenzotriazolemethana mine, phenyl-1 H-1,2,3-benzotriazole-5-
carboxyl ate, 1-
(benzoyloxy)-1 H-1,2,3-benzotriazole, 3-(benzotriazol-1-ylmethoxy)-
phenylamine, 1-(4-
fluorobenzoyl)-1 H-benzotriazole, 1-[(phenylthio)methyl]-1 H-benzotriazole, [1-
(4-
morpholinyl)propyl]benzotriazole, 1-(3-phenyl-2-propenoyl)-1H-1,2,3-
benzotriazole, n-(1H-
benzotriazol-1 -ylmethyl)benzamide, benzotriazol-1-ylmethyl-(2-ethyl-phenyl)-
amine, n-(1 H-
1,2,3-benzotriazol-1-ylmethyl)-2,4-dimethylaniline, 4-(1 H-1,2,3-benzotriazol-
1 -ylcarbonyl)phenyl
methyl ether, 1-(benzyloxycarbonyl)benzotriazole, 2-benzotriazol-1-yl-n-
pyridin-2-yl-acetamide,
benzotriazol-1-ylmethyl-(2-methoxy-phenyl)-amine, n-(1 H-1,2,3-benzotriazol-1 -
ylmethyl)-4-
methoxyaniline, 1-O-tolylsulfanylmethyl-1 H-benzotriazole, n'-(2-(1 H-1,2,3-
benzotriazole-1-yl)-1-
methylethylidene)-2-cyanoacetohydrazide, methyl 3-(1 H-1,2,3-benzotriazol-4-
yl(methyl) amino)-
2-cyanoacrylate, 1-(4-ohlorobenzoyl)-1 H-benzotriazole, n-(1 H-1,2,3-
benzotriazol-l-ylmethyl)-2-
chloroaniline, benzotriazol-1-ylmethyl-(3-chloro-phenyl)-amine, n-(1H-1,2,3-
benzotriazol-1-
ylmethyl)-4-chloro-aniline, 1-(phenylsulfonyl)-1H-benzotriazole, and
benzotriazol-1-ylmethyl-
(2,5-difluoro-phenyl)-amine.
Examples of suitable 1,2,3-triazole derivatives include, but are not limited
to, 5-nitro-1H-
1,2,3-triazole, 1H-1,2,3-triazolo[4,5-b]pyridine, 1-hydroxy-7-azabenzotriazole
solution, 3H-
(1,2,3)triazolo(4,5-d)pyrimidi n-7-ylamine, 8-azaadenine, 8-azaguanine, 8-
azaxanthine
monohydrate, 1,2,3-triazole-4,5-dicarboxylic acid, n-phenyl-IH-1,2,3-triazol-5-
amine, 1-acetyl-
1 H-1,2,3-triazolo[4,5-b]pyridine, 3-methyl-8-azaguanine, 3H-1,2,3,4,5,7,7a-
heptaaza-s-indacen-
8-ol, 4,6-dimethyl-I H-v-triazolo(4,5-d)pyrimidine-5,7(4H,6H)-dione, 1,2,3-
triazole-4,5-
dicarboxylic acid, monopotassium salt of 1,2,3-triazole-4,5-dicarboxylic acid,
5-amino-1,4-
diphenyl-1,2,3-triazole, 5-anilino-4-phenyl-lH-1,2,3-triazole, and rufinamide.
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Examples of suitable 1,2,4-triazole derivatives include, but are not limited
to, 3-amino-
1,2,4-triazole, 1H-1,2,4-triazol-5-amine, 1,2,4-triazolylsodium, 1 -vinyl-
1,2,4-triazole, 3,5-diamino-
1,2,4-triazole, 1H-1,2,4-triazole-3-thiol, 1,2,4-triazole-3-carboxylic acid, 3-
nitro-1H-1,2,4-triazole,
3-amino-1,2,4-triazole-5-thiol, 1,2,4-triazolo[1,5-a]pyrimidine, 3-acetamido-1
H-1,2,4-triazole,
methyl-IH-1,2,4-triazole-3-carboxylate, 5-amino-4H-(1,2,4)triazole-3-
carboxylic acid, 5-amino-
1 H-(1,2,4)triazole-3-carboxylic acid, 3-amino-1 H-1,2,4-triazole-5-carboxylic
acid, 3-amino-5-
methylthio-1H-1,2,4-triazole, 5-methyl-s-triazolo (1,5-a)pyrimidine, 1-
trimethylsilyl-1,2,4-triazole,
5-amino-1 H-[1,2,4]-triazole-3-carboxylic acid methyl ester, 3-methyl-5-(2-
oxido-2-oxohydrazino)-
1H-1,2,4-triazole, 3-amino-1,2,4-triazole-5-carboxylic acid hydrate, 1H-1,2,4-
triazole-1-
carboxamidine hydrochloride, 5,7-dimethyl-s-triazolo[1,5-a]pyrimidine, 7-
hydroxy-5-
methyl[1,2,4]triazolo[1,5-a]pyrimidine, 5-methyl(1,2,4)triazolo(4,3-
a)pyrimidin-7-ol, 7-amino-s-
triazolo(1,5-a)pyrimidin-5(4H)-one, 5-(trifluoromethyl)-4H-1,2,4-triazol-3-
ylamine, oxo(1H-1,2,4-
triazol-5-ylamino)acetic acid, 3-(1,2,4-triazol-1-yl)-L-alanine, 5-amino-1 H-
(1,2,4)triazole-3-
carboxylic acid ethyl ester, beta-(1,2,4-triazol-3-yl)-DL-alanine, 1 -amino-5-
propyl-1 H-1,2,4-
triazol-3-yl hydrosulfide, 2-(2-aminophenyl)-1 H-1,3,4-triazole, 2-chloro-n-
(4H-(1,2,4)triazol-3-yl)-
acetamide, (5-dihydroxymethyl-2H-(1,2,4)triazol-3-yl)-methanediol, 1,1'-
carbonyl-di-(1,2,4-
triazole), 5,5'-dimethyl-1H,1'H-(3,3')BI((1,2,4)triazolyl), 1H,1'H-
(3,3')Bl((1,2,4)triazolyl)-5,5'-
diamine, 2H,2'H-(3,3')BI((1,2,4)triazolyl)-5,5'-diamine, 3,3'-bis(5-amino-4H-
1,2,4-tria), 3-OXO-N-
(1H-1,2,4-triazol-5-yl)butanamide, 7-chloro-5-methyl-(1,2,4)triazolo(1,5-
a)pyrimidine, 1-(tert-
butoxycarbonyl)1 H-1,2,4-triazole, s-triazolo(4,3-a)quinoline, 6,7,8,9-
tetrahydro-5H-(1,2,4)triazolo
(1,5-a)azepin-2-yl hydrosulfide, 2-(3-nitro-(1,2,4)triazol-1-yl)-acetamide, (3-
nitro-(1,2,4)triazol-1-
yl)-acetic acid, benzylidene-(1,2,4)triazol-4-Y, 4-(benzylideneamino)-4H-1,2,4-
triazole, n-(4-
pyrid inylmethylene)-4H-1,2,4-triazol-4-amine, (4-methyl-4H-(1,2,4)triazol-3-
ylsulfanyl)-acetic
acid, 3-methylamino-5-phenyl-1,2,4-triazole, 3-(3-pyridylmethylamino)-1,2,4-
triazole,
(1,2,4)triazolo (3,4-B)(1,3)benzothiazole, 3H-1,2,3,4,5,7,7A-heptaaza-S-
indacen-8-OL, 1-
phenyl-I H-(1,2,4)triazole-3-thiol, 5-phenyl-1 H-1,2,4-triazole-3-thiol, 5-
propyl-(1,2,4)triazolo (1,5-
A)pyrimidin-7-OL, 5-(4-pyridyl)-lH-1,2,4-triazole-3-thiol, 6-nitro-
(1,2,4)triazolo (1,5-A)pyrimidin-
2-ylamine, 5-((5-amino-4H-1,2,4-triazol-3-yl)methyl)-4H-1,2,4-triazol-3-
ylamine, 3-((5-amino-1 H-
1,2,4-triazol-3-yl)methyl)-1H-1,2,4-triazol-5-ylamine, 5,7-dimethyl-
(1,2,4)triazolo (1,5-
A)pyrimidine-2-thiol, hydrochloride of 3-phenyl-4H-(1,2,4)triazole, 3-mercapto-
5-methyl-8H-
(1,2,4)triazolo(4,3-A)pyrimidin-7-one, 5-amino-1H-(1,2,4)triazole-3-carboxylic
acid butyl ester,
and 3-(4-pyridinyl)-6,7-dihydro-5H-pyrrolo (2,1-C)(1,2,4)triazole.
Examples of suitable imidazoles include, but are not limited to, 2-methyl-2-
imidazoline,
2-phenyl-2-imidazoline, 3-(4,5-dihydro-2-imidazolyl)pyridine, 8-methyl-2,3,7,8-
tetrahydroimidazo(1,2-A)pyrimidin-5(6H)-one, (4,5-dihydro-1 H-imidazol-2-
ylthio)acetic acid, 2-
benzylimidazoline, 4-(4,5-dihydro-1 H-imidazol-2-yl)phenylamine, 2-(4,5-
dihydro-1 H-imidazol-2-
yl)phenol, 4-(4,5-dihydro-1 H-imidazol-2-yl)phenol, 3-(4,5-dihydro-1 H-
imidazol-2-yl)phenol, 2-
chloro-1,3-dimethylimidazolidinium chloride, 3A,4,5,6,7,7A-hexahydro-1 H-
benzimidazol-2-yl
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methyl sulfide, hydrochloride of imidazo(1,2-A)pyridin-2-one, 2,3-dihydro-5H-
imidazo(2,1-
A)isoindol-5-one, 2-amino-5,5-bis(hydroxymethyl)-1-methyl-l,5-dihydro-4H-
imidazol-4-one, 4-
(4-methyl-4,5-dihydro-1 H-imidazol-2-yl)phenylamine, 4-(4-methyl-4,5-dihydro-1
H-imidazol-2-
yl)phenol, 2-(4-methyl-4,5-dihydro-1 H-imidazol-2-yl)phenol, 3-(4-methyl-4,5-
dihydro-1 H-
imidazol-2-yl)phenol, 2-amino-1-methyl-2-imidazoline hydrobromide, 2-mercapto-
3-phenyl-3,5-
dihydro-imidazol-4-one, 2-(4-methoxystyryl)-2-imidazoline, 2,10-dihydro-10-
ethylimidazo(2,1-
B)quinazoline-5(3H)-one, 2-methyl-4,5-di hydro-imidazole-1-carbothioic acid
phenylamide, 2-
chloro-1,3-dimethylimidazolidinium tetrafluoroborate, 2-(4-bromophenyl)-4,5-
dihydro-1 H-
imidazole, 2-(methylamino)-2-midazoline hydriodide, 2-(3-nitrophenyl)-4,5-
dihydro-1 H-imidazole
hydrochloride, 2-(4,5-dihydro-1 H-imidazol-2-yl)quinoline hydrochloride, 5-
butoxy-2-(4,5-dihydro-
I H-imidazol-2-yl)phenol, 3-(1,3-dimethyl-2,6-dioxo-1,2,3,4,5,6-hexahydro-9H-
purin-9-
yl)propanenitrile, tetrahydrozoline hydrochloride, idazoxan hydrochloride,
tetramisole
hydrochloride, levamisol hydrochloride, 1,3-diisopropylimidazolinium
tetrafluoroborate, 2-(4,5-
dihydro-IH-imidazol-2-yl)-1-benzofuran-5-yl thiocyanate, 2-methylthio-2-
imidazoline hydriodide,
4,5-dihydro-1 H-imidazol-2-yl 2-fluorobenzyl sulfide hydrochloride,
naphazoline hydrochloride, 4-
chloro-alpha-(2-imidazolin-2-yl)benzyl alcohol hydrochloride, 5A, 11A-
dihydronaphtho[2',3':4,5]imidazo[1,2-A]pyrid ine-6,11-dione, 2,3,6,7-
tetrahydro-5,7,7-trimethyl-
5H-pyrrolo(1,2-a)imidazole, 3-(4,5-dihydro-1H-imidazol-2-yl)aniline
dihydrochloride hydrate,
efaroxan hydrochloride, cirazoline hydrochloride, 1 -bityl-4,5-d i hyd ro-3-
ethyl-8-hyd roxyxa nth ine,
imidacloprid solution, 2-(4-fluorobenzylidene)-2,5,6,7,8,9-hexahydro-3H-
imidazo(1,2-a)azepin-3-
one, imidacloprid-d4, imazapyr, 9-benzyl-2-chloro-5,9-dihydro-4H-purin-6-
ylamine, 2-fluoro-1,3-
dimethylimidazolidinium hexafluorophosphate, 2-(4,5-dihydro-1H-imidazol-2-yl)-
5-
(hexyloxy)phenol, 3-phenyl-2-(4-toluidino)-3,5-dihydro-4H-imidazol-4-one,
clonidine
hydrochloride, n-(3-chlorophenyl)-n'-(i-methyl-4-oxo-4,5-dihydro-1 H-imidazol-
2-yl)urea, 2,4,5-
tri-(2-furyl)-2-imidazoline, 5-(benzyloxy)-2-(4,5-dihydro-1 H-imidazol-2-
yl)phenol, 1,3-ditert-butyl-
4,5-dihydro-1 H-imidazol-3-ium tetrafluoroborate, n-allyl-n-(2,6-
dichlorophenyl)-4,5-dihydro-1 H-
imidazol-2-amine, 2-(4,5-dihydro-1 H-imidazol-2-yl)-2,3-dihydro-l,4-
benzodioxin-2-yl methyl
ether hydrochloride, 2-(4,5-dihydro-1 H-imidazol-2-yl)-2,3-dihydro-l,4-
benzodioxin-2-yl methyl
ether, 3-(3,4-dihydroxyphenyl)-5,6-dihydroimidazo(2,1-B)thiazole
hydrochloride, 2-methyl-n-(3-
(trifluoromethyl)phenyl)-2-imidazoline-l-carboxamide, nitric acid compound
with 2-(1-
naphthylmethyl)-4,5-dihydro-1 H-imidazole (1:1), 2-benzyl-2-imidazoline
thiosulfate, 1-[3-
(triethoxysilyl)propyl]-4,5-dihydro-1 H-imidazole, 2-(4-isopropyl-4-methyl-5-
oxo-4,5-dihydro-1 H-
imidazol-2-yl)-5-methylnicotinic acid, 2-[(E)-2-(2-methylphenyl)ethenyl]-4,5-
dihydro-1 H-
imidazole ethanedioate nonahydrochtoride, 6,6-diphenyl-2,3,6,7-tetrahydro-5H-
pyrrolo(1,2-
a)imidazol-5-one, 10-benzyl-2,3-dihydroimidazo(2,1-b)quinazolin-5(10H)-one, n-
(4-chloro-6-
methoxy-2-methyl-5-pyrimidinyl)-n-(4,5-dihydro-1H-imidazol-2-yl)amine
hydrochloride, n-(4-
chloro-6-methoxy-2-methyl-5-pyrimidinyl)-n-(4,5-dihydro-1H-imidazol-2-yl)amine
hydrochloride,
2-chloro-1,3-dimethyl-4,5-dihydro-1 H-imidazol-3-ium hexafluorophosphate,
2,3,5,6,7,8-
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hexahydro-8-methylimidazo (1,2-a)pyrimidin-5-imine hydriodide, 3,7-dimethyl-1-
(5-oxo-hexyl)-
3,7-dihydro-purine-2,6-dione, 3,7-dimethyl-l-(5-oxohexyl)-3,7-dihydro-1 H-
purine-2,6-dione, 2-
(4-tert-butyl-2,6-dim ethyl benzyl)-4,5-dihydro-1 H-imidazole hydrochloride, 8-
methyl-2,3,7,8-
tetrahydroimidazo(1,2-a)pyrimidin-5(6H)-one hydriodide, 2,6-dichloro-N(1)-(4,5-
dihydro-1 H-
imidazol-2-yl)-1,4-benzenediamine hydrochloride, 3-(4-chlorophenyl)-2-ethyl-
2,3,5,6-tetra-
hydroimidazo(2, 1-b)thiazol-3-ol, 5-(4-chlorophenyl)-2,5-dihydro-3H-
imidazo[2,1-a]isoindol-5-ol,
2-(4-nitrobenzylidene}2,5,6,7,8,9-hexahydro-3H-imidazo(1,2-a)azepin-3-one, 2-
(2-
nitrobenzylidene)-2,5,6,7,8,9-hexahydro-3H-imidazo(1,2-a)azepin-3-one, 9,13b-
dihydro-1 H-
dibenzo[c,f]imidazo[1,5-a]azepin-3-ylamine hydrochloride, 2-(4,5-dihydro-1 H-
imidazol-2-ylthio)-
n-(4-methylphenyl)acetamide hydrochloride, 2-(4,5-dihydro-1H-imidazol-2-
ylthio)-n-(2-
methylphenyl)acetamide hydrochloride, methyl 2-(4-isopropyl-4-methyl-5-oxo-4,5-
dihydro-1 H-
imidazol-2-yl)-4-methylbenzoate, hydrobromide of 3-thiophen-2-yl-5,6-2H-
imidazo(2,1-
B)thiazole, 5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-
yl)nicotinic acid, n-
(5-chloro-2,1,3-benzothiadiazol-4-yl)-n-(4,5-dihydro-1 H-imidazol-2-yl)amine
hydrochloride, 2-
(4,5-dihydro-1 H-imidazol-2-yl)-5-(octyloxy)phenol, 5-bromo-N-(4,5-dihydro-1 H-
imidazol-2-yl)-6-
quinoxalinamine, 5-benzylidene-2-methylsulfanyl-3-phenyl-3,5-dihydro-imidazol-
4-one, 5-
benzyl idene-2-mercapto-3-(2-methylphenyl)-3, 5-dihydro-4H-imidazol-4-one, 6-
tert-butyl-3-(4,5-
dihydro-lH-imidazol-2-ylmethyl)-2,4-dimethylphenol hydrochloride, and DL-
isoamarine.
Examples of suitable pyrrole derivatives include, but are not limited to, I H-
pyrrole-d5, 1-
methyl-1 H-pyrrole, 3-methyl-1 H-pyrrole, 1 H-pyrrole-2-carbonitrile, 1 H-
pyrrole-2-carbaldehyde,
2,5-dimethyl-1 H-pyrrole, 2-ethyl-1 H-pyrrole, 2,4-dimethyl-1 H-pyrrole, 1 -(1
H-pyrrol-2-
yl)ethanone, 1-methyl-1 H-pyrrole-2-carbaldehyde, 1,2,5-trimethyl-1 H-pyrrole,
1 H-pyrrole-2-
carbaldehydehyde oxime, N,N-dimethyl-1 H-pyrrol-1-amine, 1 H-pyrrole-2-
carboxylic acid, 1 H-
indole, 1 H-pyrrolo[2,3-b]pyridine, 1,5-dimethyl-1 H-pyrrole-2-carbonitrile, 3-
(1 H-pyrrol-1 -
yl)propanenitrile, 3-(1 H-pyrrol-2-yl)-2-propenal, 4,5,6,7-tetrahydro-1 H-
indole, 1 H-pyrrole-2,5-
dicarbaldehyde, 1-(1-methyl-1 H-pyrrol-2-yl)ethanone, 3,5-dimethyl-1 H-pyrrole-
2-carbaldehyde,
1-(1-methyl-1 H-pyrrol-3-yl)ethanone, 1-(4-methyl-1 H-pyrrol-3-yl)ethanone, 3-
ethyl-2,4-dimethyl-
1H-pyrrole, 1-(1H-pyrrol-2-yl)ethanone oxime, 1H-indole-d7, methyl 1H-pyrrole-
1-carboxylate, 1-
methyl-1H-pyrrole-2-carboxylic acid, 2,3-dihydro-6H-[1,4]dioxino[2,3-
c]pyrrole, methyl 1 H-
pyrrole-3-carboxylate, methyl 1 H-pyrrole-2-carboxylate, 3-chloro-1 H-pyrrole-
2-carbaldehyde, 4-
methyl-1 H-indole, 2-methyl-1 H-indole, 3-methyl-1 H-indole, 1-methyl-1 H-
indole, 5-methyl-1 H-
indole, 7-methyl-1 H-indole, 6-methyl-1 H-indole, 1 H-indol-5-amine, 1 H-indol-
7-amine, 1 H-indol-
6-amine, 1 H-indol-4-amine, 1 H-indol-4-ol, I H-indol-5-ol, 1 H-indol-6-ol, 5-
fluoro-1 H-indole, 4-
fluoro-1 H-indole, 6-fluoro-1 H-indole, 1,5,6,7-tetrahydro-4H-indol-4-one, 4-
(1 H-pyrrol-2-yl)-3-
buten-2-one, formic acid (2-pyrrolylmethylene)hydrazide, 1-(2,4-dimethyl-1 H-
pyrrol-3-
yl)ethanone, 1-(4-ethyl-1 H-pyrrol-3-yl)ethanon e, ethyl I H-pyrrole-2-
carboxylate, 2-methyl-2,3-
dihydro-6H-[1,4]dioxino[2,3-c]pyrrole, 3-(1 H-pyrrol-1 -yl)propanoic acid, 2-
(1H-pyrrol-2-
yl)acetohydrazide, 1 H-indole-4-carbonitrile, 1 H-indole-5-carbonitrile, 2-(1
H-pyrrol-2-
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ylmethylene)maIononitrile, 1-phenyl-1H-pyrrole, 1H-indole-3-carbaldehyde, 1H-
indole-5-
carbaldehyde, 1 H-indole-7-carbaldehyde, 1 H-indole-2-carbaldehyde, 1 H-indole-
4-carbaldehyde,
1 H-indole-6-carbaldehyde, 2,5-dimethyl-1 H-indole, 1,3-dimethylindole, 1,2-
dimethyl-1 H-indole,
7-ethyl-1 H-indole, 2,3-dimethyl-1 H-indole, 3-chloro-1 H-pyrrole-2-carboxylic
acid, 1 H-pyrrolo[2,3-
b]pyridine-3-carbaldehyde, 2-(1H -pyrrol-2-yl m ethyl)- 1H-pyrrole, 1 H-indol-
5-ylmethanamine, 2-
methyl-1 H-indol-5-amine, 1 H-indol-3-ylmethanol, 1 H-indol-5-yl methyl ether,
1 H-indol-2-
ylmethanol, 1 H-indol-7-yl methyl ether, 1 H-indol-6-yl methyl ether, 1 H-
indol-4-yl methyl ether, 1-
(2-furylmethyl)-1 H-pyrrole, 5-formyl-3,4-dimethyl-1 H-pyrrole-2-carbonitrile,
methyl 1 H-
pyrrolo[2,3-c]pyrid in-5-yl ether, methyl 7H-pyrrolo(2,3-d)pyrimidin-4-yl
ether, 2-methyl-7H-
pyrrolo (2,3-d)pyrimidin-4-ol, 5-fluoro-2-methyl-1H-indole, 1-(1H-pyrrol-2-yl)-
1-penten-3-one, 2-
amino-7H-pyrrolo[2, 3-d]pyrimidin-4-ol, 2,5-dimethyl-1 H-pyrrole-3,4-
dicarbaldehyde, 3-(1 H-
pyrrol-3-yl)-acrylic acid methyl ester, and 3,4-dimethyl-2,5-
pyrroledicarboxaldehyde.
Examples of suitable pyrazine derivatives include, but are not limited to,
pyrazine-d4, 2-
methylpyrazine, 2-pyrazinamine, 2-pyrazinecarbonitrile, 2,3-dimethylpyrazine,
2-ethylpyrazine,
2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2-methoxypyrazine, 2-
chloropyrazine, sodium salt
of pyrazinol, imidazo[1,2-a]pyrazine, 1-(2-pyrazinyl)ethanone, 2-ethyl-3-
methylpyrazine, 2,3,5-
trimethyl pyrazine, 2-pyrazinecarboxamide, 2-pyrazinecarboxylic acid, 2-
methoxy-3-
methylpyrazine, 2-(methylsulfanyl)pyrazine, 2,3-pyrazinedicarbonitrile,
quinoxaline, 5,6,7,8-
tetrahydroquinoxaline, 5-methyl-6,7-dihydro-5H-cyclopenta[b]pyrazine, 1-(3-
methyl-2-
pyrazinyl)ethanone, 2,3,5,6-tetramethylpyrazine, 2,3-diethylpyrazine, methyl 2-
pyrazinecarboxylate, 5-methyl-2-pyrazinecarboxylic acid, 2-ethyl-3-
methoxypyrazine, 2-ethoxy-
3-methylpyrazine, 3-amino-2-pyrazinecarboxylic acid, 5-hydroxy-2-
pyrazinecarboxylic acid, 2-
methyl-3-(methylsulfanyl)pyrazine, 2-(2-pyrazinyl)ethanethiol, 3-chloro-2,5-
dimethylpyrazine, 5-
methyl-2,3-pyrazinedicarbonitrile, 2-methylquinoxaline, 5-methylquinoxaline, 2-
quinoxalinol, 2,6-
dichioropyrazine, 2,3-dichioropyrazine, furo[3,4-b]pyrazine-5,7-dione, 1-(3-
ethyl-2-
pyrazinyl)etha none, 1-(3,5-dimethyl-2-pyrazinyl)ethanone, 2,3-diethyl-5-
methylpyrazine, 2-
isobutyl-3-methylpyrazine, 2-(2-(dimethylamino)ethyl)pyrazine, 2-isopropyl-3-
methoxypyrazine,
2-methyl-6-propoxy-pyrazine, methyl 3-amino-2-pyrazinecarboxylate, 5,6-
dimethyl-2,3-
pyrazinedicarbonitrile, 2,3-dimethylquinoxaline, 6,7-dimethylquinoxa line, 2,3-
dimethylpyrido
(2,3-b)pyrazine, 5,6-diamino-2,3-pyrazinedicarbonitrile, 6,7-
dimethylpteridine, 2,3-
quinoxalinediol, pyrido[2,3-b]pyrazine-2,3-diol, 2-amino-4(3H)-pteridinone,
2,4-pteridinediol, 3-
hydroxy-5,6-dimethyl-1 H-pyrazolo-(3,4b)-pyrazine, 2-chloroquinoxaline, 2,3-
pyrazinedicarboxamide, 2-isobutyl-3-methoxypyrazine, 2-sec-butyl-3-
methoxypyrazine, 2,3-
pyrazinedicarboxylic acid, quinoxaline-2-carbaldehyde oxime, 2-
quinoxalinecarboxylic acid, 2-
methylquinoxaline-1,4-dioxide, 4-hydroxy-6,7-dimethylpteridine, hydrate of 2,3-
dimethyl-
quinoxaline, isoxanthopterin, phenazine, 3-amino-6-(chloromethyl)-2-
pyrazinecarbonitrile 4-
oxide, n-methyl-n'-quinoxalin-2-ylmethylene-hydrazine, 2,3-diethylquinoxaline,
2,3,6,7-
tetramethylquinoxa line, 1-(3,5-diamino-6-chloro-2-pyrazinyl)ethanone, 3,5-
diamino-6-chloro-2-
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pyrazinecarboxamide, 2-hydroxy-3,6,7-trimethylquinoxaline, 1,2,3,4,6,7,8,9-
octahydrophenazine, 5-bromo-2,3-pyrazinediamine, 2-(nitromethyl)quinoxaline, 3-
hydroxy-2-
quinoxalinecarboxylic acid, 6,7-dimethyl-2,3-quinoxalinediol, 2,4-diamino-6,7-
dimethylpteridine,
2-amino-6,7-dimethyl-4-pteridinol, 6,7-dimethyl-2,4-pteridinediol, (2,4-
diamino-6-
pteridinyl)methanol, 2-quinoxalinecarbonyl chloride, 2-amino-6-methyl-4,7-
pteridinediol, 2-
amino- I,5-dihydro-4,6-pteridinedione hydrate, 3-bromoimidazo[1,2-a]pyrazine,
2,6-
dichloroquinoxaline, 2,3-dichloroquinoxaline, and ethyl 2-q
uinoxalinecarboxylate.
Examples of suitable pyrimidine derivatives include, but are not limited to, 4-
methylpyrimidine, 5-methylpyrimidine, 2-methylpyrimidine, 4-pyrimidinamine, 5-
pyrimidinamine,
pyrimidine 1-oxide, 2-pyrimidine-carbonitrile, 4,6-dimethylpyrimidine, 4-
methyl-2-pyrimidinamine,
4,5-pyrimidinediamine, 2,4-pyrimidinediamine, 4,6-pyrimidinediol, 2,4-
dihydroxypyrimidine, 2-
pyrimidinethiol, 5-fluoro-2-pyrimidinol, 5-fluoro-pyrimidin-4-ol, 2-
chloropyrimidine, 2,4-
difluoropyrimidine, 9H-purine, 4-amino-5-pyrimidinecarbonitrile, n-(2-
pyrimidinyl)-formamide,
4,6-dimethyl-2-pyrimidinamine, 2,6-dimethyl-4-pyrimidinol, 4,6-diamino-2-
methylpyrimidine, 2-
amino-6-methyl-4-pyrimidinol, 4-amino-6-hydroxy-2-methylpyrimidine, 6-methoxy-
4-
pyrimidinamine, 2,4,6-pyrimidinetriamine, 6-methyl-2,4(1 H,3H)-
pyrimidinedione, 2-methyl-4,6-
pyrimidinediol, 6-methyl-pyrimidine-4,5-diol, 5-methyl-4,6-pyrimidinediol, 2,6-
diamino-4-
pyrimidinol, 6-hydrazino-4-pyrimidinol, 6-methyl-4-pyrimidinethiol, 2-amino-
4,6-pyrimidinediol,
dihydro-2,4,5(3H)-pyrimidinetrione, 5-fluoro-6-methyl-pyrimidin-4-ol, 2-thioxo-
2,3-dihydro-4(1 H)-
pyrimidinone, 4-sulfanyl-2-pyrimidinol, 2-chloro-4-pyrimidinamine, 5-chloro-2-
pyrimidinamine, 5-
fluoro-pyrimidine-4-thiol, quinazoline, 2-chloro-5-fluoropyrimidine, 2-
pyrimidinol hydrochloride,
4,5,6-trifluoropyrimidine, 2-amino-6-methyl-4(3H)-pteridinone, 4-amino-2-
methyl-pyrimidine-5-
carbonitrile, 6-methyl-9H-purine, 1H-pyrazolo[3,4-d]pyrimidin-4-amine, 7H-
purin-2-amine, 9H-
purin-6-amine, 5-cyano-2,4-diaminopyrimidine, 9H-purin-6-amine, 1,5-dihydro-4H-
pyrazolo[3,4-
d]pyrimidin-4-one, 3H-(1,2,3)triazolo(4,5-d)pyrimidin-7-ylamine, 1H-
[1,2,3]triazolo[4,5-
d]pyrimidin-7-amine, 9H-purin-6-amine, 2-acetamidopyrimidine, methyl 5-
pyrimidinecarboxylate,
4,6-diamino-5-nitrosopyrimidine, 2-amino-5,6-dimethyl-4-pyrimidinol, 4-methoxy-
6-methyl-2-
pyrimidinamine, 6-hydroxy-4-pyrimidinecarboxylic acid, 5-nitro-2-
pyrimidinamine, 5,6-dimethyl-
2,4(1 H,3H)-pyrimidinedione, 5-methyoxy-2-methyl-pyrimidin-4-ol, 2,4-
dimethoxypyrimidine, 5-
amino-4-hydroxy-6-(methylamino)pyrimidine, 4,6-dimethyl-2-pyrimidinethiol, 4-
methyl-2-
(methylsulfanyl)pyri mid ine, 2-amino-4,6-dihydroxy-5-methylpyrimidine, 2-
amino-5-methyoxy-
pyrimidin-4, 5-amino-2,4-dihydroxy-6-methylpyrimidine, 4-amino-2-hydroxy-5-
(hydroxymethyl)
pyrimidine, 2-amino-6-methyl-4,5-pyrimidinediol, 4-amino-2-mercapto-6-
methylpyrimidine, 6-
methyl-2-thioxo-2,3-dihydro-4(1 H)-pyrimidinone, 2-methylsulfanyl-pyrimidin-5-
ol, 2-
methylsulfanyl-pyrimidin-4-ol, 2,4-diamino-6-mercaptopyrimidine, 4,5-diamino-2-
mercaptopyrimidine, 2-chloro-5-ethylpyrimidine, 6-a mino-5-fluoro-2-methyl-
pyri mid in-4-ol, 4-
amino-2-hydroxy-6-mercaptopyrimidine, 4-chloro-6-methyl-2-pyrimidinamine, 2-
thioxodihydro-
4,6(1 H,5H)-pyrimidinedione, 2-chloro-5-methoxypyrimidine, 2-chloro-4-
methoxypyrimidine, 6-
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chloro-2-methyl-4-pyrimidinol, 6-chloro-2,4-pyrimidinediamine, 7H-purine-6-
carbonitrile, 5-fluoro-
6-fluoromethyl-pyrimidin-4-ol, 4(3H)-quinazolinone, and 4-methyl-2(1H)-
pyrimidinone
hydrochloride.
Examples of suitable pyridine derivatives include, but are not limited to, 2-
methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-pyridinamine, 4-
pyridinamine, 3-
pyridinamine, pyridine 1-oxide, 2-pyridinol, 3-pyridinol, 4(1 H)-pyridinone, 4-
methylpyridine-d3, 2-
fluoropyridine, 3-fluoropyridine, pyridine hydrofluoride, 2-pyridinamine-d6, 2-
methylpyridine-d7,
2-ethynylpyridine, 2-pyridinecarbonitrile, nicotinonitrile,
isonicotinonitrile, 2-vinylpyridine, 4-
vinylpyridine, 2-pyridinecarbaldehyde, nicotinaldehyde, isonicotinaldehyde,
2,5-dimethylpyridine,
4-ethylpyridine, 2,3-dimethylpyridine, 3,4-dimethylpyridine, 3-ethylpyridine,
2-ethylpyridine, 2,4-
dimethylpyridine, 3,5-dimethylpyridine, 2,6-dimethylpyridine, N-methyl-N-(4-
pyridinyl)amine, N-
methyl-N-(2-pyridinyl)a mine, 2-methyl-3-pyrid ina mine, 4-
pyridinylmethanamine, 2-methyl-4-
pyridinamine, 3-methyl-2-pyridinamine, 4-methyl-2-pyridinamine, 5-methyl-3-
pyridinamine, 3-
pyridinylmethanamine, 2-pyridinylmethanamine, 5-methyl-2-pyridinamine, 6-
methyl-2-
pyridinamine, 6-methyl-3-pyridinamine, 4-methyl-3-pyridinamine, 2-methyl-4-
pyridinamine, 3-
methyl-2(1 H)-pyridinone, 4-methoxypyridine, 5-methyl-2-pyridinol, 2-
methoxypyridine, 6-methyl-
2-pyridinol, 3-pyridinylmethanol, 2-pyridinylmethanol, 6-methyl-3-pyridinot, 4-
methyl-2-pyridinol,
4-pyridinylmethanol, 3-methoxypyridine, 2-methyl-3-pyridinol, 2,5-
pyridinediamine, 2-
hydrazinopyridine, 2,3-pyridinediamine, 3,4-pyridinediamine, 2,6-
pyridinediamine, 2-amino-3-
pyridinol, 2,4-pyridinediol, 2,3-pyridinediol, 2-fluoro-3-methylpyridine, 2-
fluoro-6-methylpyridine,
2-fluoro-5-methylpyridine, 2-fluoro-4-methylpyridine, 2-pyridinethiol, 4-
pyridinethiol, 5-fluoro-2-
pyridinamine, 3-chloropyridine, 2-chloropyridine, 2,6-difluoropyridine,
pyridine hydrochloride, 4-
methyl-2-pyridinecarbonitrile, 6-methyl-2-pyridinecarbonitrile, 3-methyl-2-
pyridinecarbonitrile,
1H-pyrrolo[2,3-b]pyridine, 3-pyridinylacetonitrile, 2-pyridinylacetonitrile, 5-
methylnicotinonitrile,
1 H-imidazo[4,5-b]pyridine, and 2-aminonicotinonitrile.
Examples of suitable pyridizine derivatives include, but are not limited to, 3-
methylpyridazine, 4-methylpyridazine, 3-pyridazinamine, pyridazine 1-oxide,
1,2-dihydro-3,6-
pyridazinedione, 3,6-pyridazinediol, 4-pyridazinecarboxylic acid, 4-methyl-3,6-
pyridazinediol, 3-
chloro-6-methylpyridazine, 3-chloro-6-methoxypyridazine, 3-chloro-6-
hydrazinopyridazine, 4-
chloro-3,6-dihydroxypyridazine, 3,6-dichloropyridazine, 3,6-
dichloropyridazine, 3-chloro-6-
ethoxypyridazine, 6-chloro-3-methoxy-4-pyridazinamine, phthalazine-1,4-
diamine, 3-chloro-6-
(methylthio)pyridazine, 3,6-dichloro-4-methylpyridazine, 3,6-dichloro-4-
pyridazinamine, 1-
chlorophthalazine, 3-amino-5,6-dimethyl-4-pyridazinecarboxamide, cinnoline
hydrochloride
hydrate, 3-chloro-5,6-dimethyl-4-pyridazinecarbonitrile, 4-cinnolinecarboxylic
acid, 5-amino-1,4-
phthalazinediol, 1,4,5-timethyl-1H-pyrazolo[3,4-c]pyridazin-3-amine, 3,6-
dichloro-N-methyl-4-
pyridazinamine, 5-chloro-8-methyl-phthalazine, benzo(C)cinnoline, 3-chloro-6-
phenylpyridazine,
3-chloro-6-(methylsulfonyl)pyridazine, 3,6-dichloro-4-pyridazinecarboxylic
acid, 6-amino-1,4-
phthalazinediol hydrate, 1,4-dichlorophthalazine, 4-amino-3-methyl-6-
nitrocinnoline, 3-chloro-6-
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methyl-4-phenylpyridazine, N-(3,6-dichloro-4-pyridazinyl)acetamide, 1-
ethoxyphthalazine
hydrochloride, 1,2,3,6,7,8-hexahydrocinnolino (5,4,3-CDE)cinnoline, 3-chloro-6-
(4-
methoxyphenyl)pyridazine, acetone O-(6-{[(1-methylethylidene) amino]oxy}-3-
pyridazinyl)oxime,
4-((6-methoxy-3-pyridazinyl)amino)-4-oxo-2-butenoic acid, 4-styrylcinnoline,
3,6-
diphenylpyridazine, 1-methyl-3H-benzo(H)pyrazolo (4,3-C)cinnoline, 1-chloro-4-
phenylphthalazine, 8-chloro-4-hydroxy-3-cinnolinecarboxylic acid hydrate, 6-
(phenylsulfinyl)
tetraazolo[1,5-b]pyridazine, 6-methyl-3,4-diphenylpyridazine, 4-methyl-3,6-
diphenylpyridazine,
4,5-dimethyl-N-[(E)-phenylmethylidene]-1H-pyrazolo[3,4-c]pyridazin-3-amine,
3,4,7-trimethyl-2-
P-tolyl-2H-pyrazolo(3,4-D)pyridazine, 1,2,5,6-tetrathia-3,4,7,8-
tetraazacyclopenta
(FG)acenaphthylene, cyclopentanone (4-chloro-1-phthalazinyl)hydrazone, 3,6-
bis(1,1,2,2-
tetramethylpropyl)pyridazin e, 3-methyl-6-[3-(trifluoromethyl)
phenyl][1,2,4]triazolo[4,3-
b]pyridazine, 3,4-dihydro-1(2H)-naphthalenone (1, 2,4)triazolo(4,3-B)pyridazin-
6-ylhydrazone, 4-
amino-N-(6-methoxy-3-pyridazinyl)benzenesulfonamide, 1,4-
dihydrazinophthalazine dihydro-
chloride monohydrate, benzaldehyde (4-chloro-1-phthalazinyl)hydrazone,
nicotinaldehyde (4-
chloro-l-phthalazinyl)hydrazone, 4-amino-N-(6-chloro-3-
pyridazinyl)benzenesulfonamide, 1-(3-
hydroxy-5,6-diphenyl-4-pyridazinyl)ethanone, 2-((6-chloro-pyridazin-3-yi)-
hydrazonomethyl)-4-
nitro-phenol, 2-((6-chloro-pyridazin-3-yl)-hydrazonomethyl)-6-nitro-phenol, 4-
amino-N-(6-ethoxy-
3-pyridazinyl)benzenesulfonamide, 4-[(1-phthal-azinylsulfanyl)methyl]benzoic
acid, 4-
methylbenzaldehyde (4-chloro-1-phthalazinyl)hydrazone, 1-phenylethanone (4-
chloro-1-
phthalazinyl) hydrazone, 2-methylbenzaldehyde (4-chloro-1 -
phthalazinyl)hydrazone, (1 R,5S)-3-
(6-chloro-3-pyridazinyl)-3,8-diazabicyclo[3.2.1 ]octane di hydrochloride, and
4-methyl-N-[2-(4-
morpholinyl)ethyl]-6-phenyl-3-pyridazinamine dihydrochloride.
Examples of suitable thiazole derivatives include, but are not limited to, 5-
methyl-1,3-
thiazole, 4-methyl-1,3-thiazole, 1,3-thiazol-2-amine, 1,3-thiazole-5-
carbaldehyde, 1,3-thiazole-2-
carbaldehyde, 4,5-dimethyl-1,3-thiazole, 2,4-dimethyl-1,3-thiazole, 4-methyl-
1,3-thiazol-2-
amine, and 5-methyl-1,3-thiazol-2-amine.
Examples of suitable benzoxazole derivatives include, but are not limited to,
2-methyl-
1,3-benzoxazole, 2-hydrazinobenzoxazole, 6-fluoro-2-methyl-1,3-benzoxazole,
1,3-benzoxazol-
2-yl hydrosulfide, 2-chloro-1,3-benzoxazole, 5-chioro-1,3-benzoxazole, 2,5,6-
trimethylbenzoxazole, 5-methyoxy-2-methylbenzoxazole, 2-
(methylthio)benzoxazole, 5-chloro-
2-methyl-1,3-benzoxazole, 5-chloro-l,3-benzoxazol-2-amine, 1-(2-benzoxazolyl)-
guanidine, 2-
methyl-6-nitrobenzoxazole, 5-chloro-2,6-dimethylbenzoxazole, 2-methylnaphth
(2,1-D)oxazole,
5-aceta m ido-2-m ethyl benzoxazole, 2-phenyl-1,3-benzoxazole, 5-phenyl-
benzooxazole, 2-
methyl-5-phenyl-1,3-benzoxazole, 2-phenyl-1,3-benzoxazol-5-amine, 4-(1,3-
benzoxazol-2-
yl)aniline, 2-(1,3-benzoxazol-2-yl)phenol, 5-cyclohexyl-2-methylbenzoxazole, 2-
(2-
methyiphenyl)-1,3-benzoxazol-5-amine, 5-(1,3-benzoxazol-2-yl)-2-methylaniline,
3-(6-methyl-
1,3-benzoxazol-2-yl)phenylamine, 3-(5-methyl-1,3-benzoxazol-2-yl)phenylamine,
4-(5-methyl-
1,3-benzoxazol-2-yl)phenylamine, 2-(5-methyl-1,3-benzoxazol-2-yl)phenol, N-
benzooxazol-2-yl-
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N'-furan-2-ylmethylene-hydrazine, 3-(5,6-dimethyl-1,3-benzoxazol-2-yl)aniline,
2-methyl-5-(6-
methyl-1,3-benzoxazol-2-yl)aniline, 2-(4-ethylphenyl)-1,3-benzoxazol-5-amine,
2-methyl-5-(5-
methyl-1,3-benzoxazol-2-yl)aniline, 2-(3-nitrophenyl)-1,3-benzoxazole, 3-(1,3-
benzoxazol-2-yl)-
4-chloroaniline, 2-(4-chlorophenyl)-1,3-benzoxazol-5-amine, 2-(2-chlorophenyl)-
1,3-benzoxazol-
5-amine, 2-(3-chlorophenyl)-1,3-benzoxazol-5-amine, 3-(5-chloro-1,3-benzoxazol-
2-
yl)phenylamine, 4-(5-chloro-1,3-benzoxazol-2-yl)phenylamine, 4-benzooxazol-2-
yl-quinoline,
methyl naphtho(1,2-D)(1,3)oxazol-2-yl sulfone, 2-(benzooxazol-2-yl-
hydrazonomethyl)-phenol,
4-(benzooxazol-2-yl-hydrazonomethyl)-phenol, 4-chloro-3-(5-methyl-1,3-
benzoxazol-2-yl)aniline,
4-chloro-3-(6-methyl-1,3-benzoxazol-2-yl)aniline, 4-benzooxazol-2-yl-2-methyl-
quinoline, 2-(1-
naphthyl)-1,3-benzoxazol-5-amine, 4-amino-2-(5-chloro-1,3-benzoxazol-2-
yl)phenol, 5-amino-2-
(5-chloro-1,3-benzoxazol-2-yl)phenol, 1,3-benzoxazol-2-yl phenoxyacetate, 2-
chloro-3-ethyl-1,3-
benzoxazol-3-ium tetrafluoroborate, ethyl 2-cyano-3-((2-methyl-1,3-benzoxazol-
5-
yl)amino)acrylate, 2-(4-methyoxy-benzylsulfanyl)-benzooxazole, 2-(((5-nitro-2-
furyl)methyl)thio)-
1,3-benzoxazole, 4-chloro-3-(5-chloro-1,3-benzoxazol-2-yl)aniline, 2-(2,4-
dichlorophenyl)-1,3-
benzoxazol-5-amine, 2-(2,5-dichlorophenyl)-1,3-benzoxazol-5-amine, 2-(3,4-
dichlorophenyl)-
1,3-benzoxazol-5-amine, 3-(1,3-benzoxazol-2-yl)-7-hydroxy-2H-chromen-2-one, N-
[3-(1,3-
benzoxazol-2-yl)phenyl}2-methylpropanamide, 4-(dimethylamino) benzaldehyde 1,3-
benzoxazol-2-ylhydrazone, N-benzooxazol-2-yl-N'-(4-nitro-benzylidene)-
hydrazine, 3-hydroxy-4-
methoxybenzaldehyde 1,3-benzoxazol-2-ylhydrazone, N-(benzooxazoi-2-
ylsulfanylmethyl)-
benzamide, 4-methyoxy-thiobenzoic acid S-benzooxazoi-2-yl ester, 2-(4-nitro-
benzylsulfanyl)-
benzooxazole, 2-(1,1'-biphenyl)-4-yl-1,3-benzoxazol-5-amine, 2-(4-bromophenyl)-
1,3-
benzoxazol-5-amine, 2-(2-bromophenyl)-1,3-benzoxazol-5-amine, 2-(3-
bromophenyl)-1,3-
benzoxazol-5-amine, 3-chloro-thiobenzoic acid S-benzooxazoi-2-yl ester, 3-(1,3-
benzoxazol-2-
yl)-N-(4-methyl phenyl)-2-oxopropanamide, 2-(1,3-benzoxazol-2-ylthio)-1-(4-
hydroxy-2-
methylphenyl)ethanone, 2-((1,3-benzoxazol-2-ylthio)methyl)-4-nitrophenol, 3-
(1,3-benzoxazol-2-
yl)-7-hydroxy-2-oxo-2H-chromene-4-carbonitrile, diethyl 2-(2-benzoxazolyl)-2-
ethyl m al on ate, 2-
(3,5-dichloro-4-methoxyphenyl)-1,3-benzoxazol-5-amine, 2-(1,3-benzoxazol-2-
yl)phenyl
benzoate, N-benzooxazol-2-yl-N'-(4-bromo-benzylidene)-hydrazine, 2-(2,4-
dinitrophenylth io)benzoxazole, toluene-4-sulfonic acid 1-benzooxazoi-2-yl-
ethyl ester, 2-(3-
bromo-4-methoxyphenyl)-1,3-benzoxazol-5-ylamine, 3-(1,3-benzoxazol-2-yl)-2-oxo-
2H-
chromen-7-yl acetate, 2-(5-bromo-2-chlorophenyl)-1,3-benzoxazol-5-ylamine, 4-
(5-(l ,3-
benzoxazol-2-yl)-1 H-benzimidazol-2-yl)phenylamine, N-(4-acetyl-phenyl)-2-
(benzooxazol-2-
yl sulfanyl)-acetamide, 4-(2-(benzooxazoi-2-ylsulfanyl)-acetylamino)-benzoic
acid, 3-(1,3-
benzoxazol-2-yl)-N-(3-chloro-2-methylphenyl)-2-oxopropanamide, 4-(5-chloro-2-
(2-
chlorophenyl)-1,3-benzoxazol-7-yl)-3-butyn-2-ol, 2-(3-phenoxy-benzylsulfanyl)-
benzooxazole,
and 2-{4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy}propanoic acid.
Examples of suitable 1,3,5-triazine derivatives include, but are not limited
to, 1,3,5-
triazine-d3, 2-amino-1,3,5-triazine, 2,4-diamino-1,3,5-triazine, 1,3,5-
triazine-2,4-diamine, 6-
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methyl-1,3,5-triazine-2,4-diamine, 1,3,5-triazine-2,4,6-triamine, 4,6-diamino-
1,3,5-triazin-2-ol,
1,3,5-triaz-inane-2,4,6-trione, 2,4,6-trifluoro-1,3,5-triazine, 4-amino-2-
dimethylamino-1,3,5-
triazine, 4-methoxy-6-methyl-1,3,5-triazin-2-amine, 6-chloro-1,3,5-triazine-
2,4-diamine, 1,3,5-
triazine-2,4,6-triamine hydrofluoride, N-(4-methoxy-6-methyl-1,3,5-triazin-2-
yi)-N-methylamine,
4-chloro-N-ethyl-6-(hydroxyamino)-1,3,5-triazin-2-amine, 1,3,5-triazine-2,4,6-
triol compound
with hydrazine (1:1), N(2)-cyclopropyl-1,3,5-triazine-2,4,6-triamine, N(2)-
ethyl-6-methoxy-1,3,5-
triazine-2,4-diamine, 4-chloro-6-(hydroxyamino)-N-isopropyl-1,3,5-triazin-2-
amine, 6-ethoxy-
N(2)-methyl-1,3,5-triazine-2,4-diamine, 2,4,6-trimethoxy-1,3,5-triazine, 2-
chloro-N-(1,3,5)triazin-
2-yl-acetamide, 6-chloro-N(2)-ethyl-1,3,5-triazine-2,4-diamine, 2-chloro-4,6-
dimethoxy-1,3,5-
triazine, 1,3,5-triazine-2,4,6-trithiol, 4,6-dichloro-1,3,5-triazine, 4,6-
dichloro-1,3,5-triazin-2-yl
methyl ether, 2,4-diamino-6-isobutyryl-1,3,5-triazine, 2,4,6-trichloro-1,3,5-
triazine, 6-phenyl-
1,3,5-triazine-2,4-diamine, 2,4,6-trichloro-1,3,5-triazine, 6-chloro-N(2)-
isopropyl-1,3,5-triazine-
2,4-diamine, 4,6-diamino-gamma-oxo-1,3,5-triazine-2-butyronitrile, N-methyl-6-
trifluoromethyl-
(1, 3,5)triazine-2,4-diamine, 2-amino-4-cyclohexylamino-1,3,5-triazine,
potassium 4,6-dioxo-
1,4,5,6-tetrahydro-1,3,5-triazine-2-carboxylate, N(2)-(tert-butyl)-6-methoxy-
1,3,5-triazine-2,4-
diamine, 2,4-diamino-6-(m-tolyl)-1,3,5-triazine, N(2)-(2-methylphenyl)-1,3,5-
triazine-2,4-diamine,
N(2)-(4-methylphenyl)-1,3,5-triazine-2,4-diamine, N(2)-(sec-butyl)-6-chloro-
1,3,5-triazine-2,4-
diamine, 6-chloro-N(2),N(4)-diethyl-1,3,5-triazine-2,4-diamine, 6-chloro-
N(2),N(4)-diethyl-1,3,5-
triazine-2,4-diamine, N(2)-(tert-butyl)-6-chloro-1,3,5-triazine-2,4-diamine, 6-
(3-fluorophenyl)-
1,3,5-triazine-2,4-diamine, 6-(4-fluorophenyl)-1,3,5-triazine-2,4-diamine, 6-
(2-fluorophenyl)-
1,3,5-triazine-2,4-diamine, N(2),N(2),N(4),N(4), N(6),N(6)-hexamethyl-1,3,5-
triazine-2,4,6-
triamine, 4,6-bis(isopropylamino)-1,3,5-triazin-2-ol, 4-(tert-butylamino)-6-
(ethylamino)-1,3,5-
triazin-2-ol, N(2)-ethyl-N(4)-isopropyl-6-methoxy-1,3,5-triazine-2,4-diamine,
6-chloro-N(2),N(4)-
diethyl-1,3,5-triazine-2,4-diamine-dl0, N(2),N(4)-diethyl-6-(methyl-sulfanyl)-
1,3,5-triazine-2,4-
diamine, 2,4-diamino-6-(2,3-xylyl)-1,3,5-triazine, 6-chloro-N(2)-ethyl-N(4)-
isopropyl-1,3,5-
triazine-2,4-diamine, 6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-
diamine, 6-chloro-
N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine, N(2)-(2-methyoxy-phenyl)-
1,3,5-triazine-
2,4-diamine, 6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diamine, 2-chloro-4-ethyl-
d5-amino-6-
isopropylamino-1,3,5-triazine, 4,6-dichloro-N,N-diethyl-1,3,5-triazin-2-amine,
2-amino-4-(4-
chloroanilino)-1,3,5-triazine, 2-(2-chlorophenyl)-4,6-diamino-1,3,5-triazine,
6-(4-chloro-phenyl)-
1,3,5-triazine-2,4-diamine, 2-N-butoxy-4,6-dichloro-l,3,5-triazine, 6-(3,5-
difluorophenyl)-1,3,5-
triazine-2,4-diamine, 2-amino-4-phenylamino-I,3,5-triazine hydrochloride, 1-[4-
amino-6-
(methylsulfanyl)-1,3,5-triazin-2-yl]-3-isopropyl-l ,2-triazadien-2-ium,
N(2),N(4)-diisopropyl-6-
methoxy-1,3,5-triazine-2,4-diamine, N(2)-(sec-butyl)-N(4)-ethyl-6-methoxy-
1,3,5-triazine-2,4-
diamine, N(2)-(tert-butyl)-N(4)-ethyl-6-methoxy-1,3,5-triazine-2,4-diamine,
N(2)-methyl-6-(2-
phenylvinyl)-1,3,5-triazine-2,4-diamine, 6-(ethylthio)-N(2)-isopropyl-N(4)-
methyl-1,3,5-triazine-
2,4-diamine, N(2)-ethyl-N(4)-isopropyl-6-(methylsulfanyl)-1,3,5-triazine-2,4-
diamine, 6-chloro-
N (2)-cyclopropyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine, 2,4-diamino-6-
phenylacetyl-1,3,5-
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triazine, N(2),N(4),N(6)-trichloro-1,3,5-triazine-2,4,6-triamine, 6-chloro-
N,N'-dipropyl-
(1,3,5)triazine -2,4-diamine, N(2)-(sec-butyl)-6-chloro-N(4)-ethyl-1,3,5-
triazine-2,4-diamine, 6-
chloro-N(2),N(4)-diisopropyl-1,3,5-triazine-2,4-diamine, 6-chloro-N(2),N(2),
N(4)-triethyl-1,3,5-
triazine-2,4-diamine, 4-(1,2,4)triazol-4-yl-6-trifluoromethyl-(1,3,5)triazin-2-
ylamine, 2,4-diamino-
6-(3-nitrophenyl)-1,3,5-triazine, 2-amino-4-anilino-6-(chloromethyl)-1,3,5-
triazine, 4-chloro-2-
(4,6-diamino-1,3,5-triazin-2-yl)phenol, 5,7-bis(ethylamino)(1,2,4)triazolo(4,3-
A)(1,3,5)triazine-3-
thiol, 2-{[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]amino}-2-m
ethylpropanenitrile, N(2),N(4)-
diisopropyl-6-(methylsulfanyl)-1,3,5-triazine-2,4-diamine, N(2)-(tert-butyl)-
N(4)-ethyl-6-
(methylsulfanyi)-1,3,5-triazine-2,4-diamine, 4,6-dichloro-1,3,5-triazin-2-yl
phenyl ether, 1,3,5-
Triazine-2,4,6-trithiol trisodium salt, N(2)-(sec-butyl)-6-chloro-N(4)-
isopropyl-1,3,5-triazine-2,4-
diamine, 2,4,6-tris(allyloxy)-1,3,5-triazine, and N(4-amino-S-triazin-2-yl)-
sulfanilic acid.
Examples of suitable 2,2'-bipyridine derivatives include, but are not limited
to, 2,2'-
bipyridine, 6-methyl-2,2'-bipyridine, 2-(2-pyridinyl)pyridine 1-oxide, 4,4'-
dimethyl-2,2'-bipyridine,
5,5'-dimethyl-2,2'-bipyridine, 6,6'-dimethyl-2,2'-bipyridine, 2,2'-bipyridine-
3,3'-diol, 2,2'-
bipyridineN,N'-dioxide, and 2-(2-pyridinyl)quinoline.
1 H-Benzotriazole, non-2H-substituted benzotriazole derivatives, imidazole,
and
imidazole derivatives are preferred unsaturated heterocyclic compounds.
Specific examples of
preferred unsaturated heterocyclic compounds include, without limitation, I H-
benzotriazole; 5-
methyl-1 H-benzotriazole; imidazole; 2-methyl imidazole; and 1 H-1,2,3-
triazole. 1H-
Benzotriazole is a more preferred unsaturated heterocyclic compound.
Moreover, the PVB composition may further comprise one or more UV absorbers at
a
level ranging from about 0.01 wt%, or about 0.05 wt%, or about 0.08 wt% to
about 1 wt%, or
about 0.8 wt%, or about 0.5 wt%, based on the total weight of the PVB
composition. UV
absorbers are well-known in the art, and any known UV absorber may find
utility within the PVB
composition. Examples of suitable UV absorbers include, but are not limited
to, benzotriazole
derivatives, hydroxybenzophenones, hydroxyphenyl triazines, esters of
substituted and
unsubstituted benzoic acids, and mixtures of any two or more of these suitable
UV absorbers.
Significantly, the benzotriazole derivatives that are useful as UV absorbers
are 2-H substituted
benzotriazole derivatives. Therefore, they are not included in the definitions
of non-2-H
substituted benzotriazole derivatives and of unsaturated heterocyclic
compounds that are set
forth above. Suitable commercially available UV absorbers include, but are not
limited to,
TinuvinTM P, TinuvinT"" 1130, TinuvinTM 326, TinuvinTM 327, TinuvinT"' 328,
TinuvinTM 571,
TinuvinTM 99-DW, or Chimassobs"d 81, manufactured by Ciba, UvinuIT" 3000,
UvinulTM 3008,
UvinuIT" 3040, or UvinuITM 3050, manufactured by BASF (Germany), and
CyasorbT"" 5411,
manufactured by Cytec Industries, Inc.
The PVB composition may further comprise one or more thermal stabilizers at a
level
ranging from about 0.01 wt%, or about 0.05 wt%, or about 0.08 wt% to about 1
wt%, or about
0.8 wt%, or about 0.5 wt%, based on the total weight of the PVB composition.
The thermal
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stabilizers used here may also be referred to as phenolic antioxidants and are
well known in the
industry. Examples of suitable thermal stabilizers include, but are not
limited to, IrganoxT'"
1010, IrganoxTM 1035, IrganoxTM 1076, IrganoxT"" 1081, IrganoxT"' 1098,
IrganoxTM 1135,
IrganoxTM 1330, IrganoxTM 1425 WL, lrganoxTM 1520, IrganoxTM 245, IrganoxTM
3114, trganoxTM
565, IrganoxTM E 201, or IrganoxTM MD 1024 manufactured by Ciba, LowinoxTM
1790,
LowinoxTM 22M46, LowinoxTM 44B25, LowinoxT"" CA22, LowinoxTM CPL, LowinoxTM HD
98,
LowinoxTM MD24, LowinoxTM TBM-6, or LowinoxTM WSP, manufactured by Chemtura
(Middlebury, CT), CyanoxTM 1741, CyanoxTM 2246, or CyanoxTM 425, manufactured
by Cytec,
or mixtures of any thereof. Thermal stabilizers of note include LowinoxTM
1790, LowinoxTM
22M46, LowinoxTM 44B25, Lowinox"'A CA22, LowinoxTM CPL, LowinoxTM HD 98,
LowinoxTM
MD24, LowinoxTM TBM-6, or LowinoxTM WSP, or mixtures of any thereof. One
preferred
thermal stabilizer is octylphenol. Another preferred thermal stabilizer is
butylated hydoxytoluene
(BHT).
The PVB composition may further comprise one or more hindered amines at a
level of
up to 1 wt %. Alternatively, the hindered amines may be present at a level
ranging from about
0.08 wt%, or about 0.1 wt%, or greater than 0.1 wt%, to about 1 wt%, to about
0.8 wt%, or up to
about 0.5 wt%, based on the total weight of the PVB composition. The hindered
amines may be
secondary or tertiary hindered amines. Examples of suitable secondary hindered
amines
include, but are not limited to, 2,2,6,6-Tetramethyl-piperadine, 2,2,6,6-
Tetramethylpiperadinol,
and mixtures thereof. Examples of suitable tertiary hindered amines include,
but are not limited
to, N-butyl piperidine, N,N-diethyl cyclohexyfamine, and mixtures of any two
or more thereof. In
some preferred PVB compositions, the hindered amines are hindered amine light
stabilizers
(HALS), which are typically secondary, tertiary, acetylated, N hydrocarbyloxy
substituted,
hydroxy substituted N-hydrocarbyloxy substituted, or other substituted cyclic
amines which
further incorporate steric hindrance, generally derived from aliphatic
substitution on the carbon
atoms adjacent to the amine function. As used herein, the terms "hindered
amines" and
"hindered amine light stabilizers" refer to compounds that are completely
saturated, except for
substituents that include a carbonyl group. Therefore, these terms do not
refer to any of the
unsaturated heterocyclic compounds described above. Hindered amine light
stabilizers are
also well known within the art and commercially available. For example,
TinuvinTM 111,
TinuvinTM 123, TinuvinTM 144, TinuvinTM 152, TinuvinTM 292, TinuvinTM 622,
TinuvinTM 765,
TinuvinTM 770, TinuvinTM 783,TinuvinTM 791, ChimassorbT"' 119, ChimassorbTM
2020, or
ChimassorbTM 944, manufactured by Ciba (Tarrytown, NY), CyasorbTM 3346 or
CyasorbTM
3853S manufactured by (Cytec Industries, Inc., Paterson, NJ), or a combination
of any two or
more thereof can be used in the PVB composition. Further information regarding
suitable
hindered amines and their use in encapsulant compositions may be found in U.S.
Provisional
Appin. No. 61/146,522, filed on January 22, 2009 (Attorney Docket No. PP0086).
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The PVB composition may further comprise one or more chelating agents at a
level
ranging from about 0.01 wt%, or about 0.05 wt%, or about 0.08 wt% to about 1
wt%, or about
0.8 wt%, or about 0.5 wt%, based on the total weight of the PVB composition.
Examples of
suitable chelating agents include, but are not limited to,
ethylenediaminetetraacetic acid (EDTA),
ethylenediamine monoacetic acid, ethylenediamine diacetic acid,
ethylenediamine triacetic acid,
ethylene diamine, tris(2-aminoethyl) amine, diethylenetriaminepentacetic acid,
or mixtures of
any thereof. As used herein, the term "chelating agent" does not include 2,2'-
bipyridine or its
derivatives. Further information regarding suitable chelating agents and their
use in
encapsulant compositions may be found in U.S. Provisional Appin. No.
61/146,547, filed on
January 22, 2009 (Attorney Docket No. PP0088).
In addition to the plasticizer and the additives listed above, the PVB
composition may
further comprise one or more of any other suitable additives, including, but
not limited to,
adhesion control additives, surface tension controlling agents, processing
aids, flow enhancing
additives, lubricants, pigments, dyes, flame retardants, impact modifiers,
nucleating agents,
anti-blocking agents such as silica, dispersants, surfactants, coupling
agents, reinforcement
additives, such as glass fiber, fillers and the like. These additives,
suitable concentrations of the
additives, and methods for incorporating them into the PVB compositions are
described in the
Kirk Othmer Encyclopedia of Chemical Technology, 51h Edition, John Wiley &
Sons (New
Jersey, 2004), for example.
Further provided herein is a solar cell module that comprises a solar cell
assembly,
wherein (A) the solar cell assembly comprises at least one solar cell and a
silver component; (B)
the solar cell assembly is fully or partially encapsulated by a PVB
encapsulant layer or layers
comprising the PVB composition described above; and (C) the silver component
is at least
partially in contact with the PVB encapsulant layer or layers.
The term "solar cell" as used herein includes any article that converts light
into electrical
energy. Solar cells useful in the solar cell assemblies and modules described
herein include,
but are not limited to, wafer-based solar cells (e.g., c-Si or me-Si based
solar cells), thin film
solar cells (e.g., a-Si, pc-Si, CdTe, or CI(G)S based solar cells), and
organic solar cells. In
principle, however, any type of solar cell known in the art is suitable for
use in the solar cell
modules described herein. The solar cells may include, but are not limited to,
those described
in U.S. Patent Nos. 4,017,332; 4,179,702; 4,292,416; 6,123,824; 6,288,325;
6,613,603; and
6,784,361, U.S. Patent Publication Nos. 2006/0213548; 2008/0185033;
2008/0223436;
2008/0251120; and 2008/0271675; and PCT Patent Application Nos. W02004/084282
and
2007/103598.
By "fully encapsulated", it is meant that the solar cell assembly is laminated
or
sandwiched between two encapsulant layers comprising the PVB composition.
Generally, the
area of the largest surface of the solar cell assembly is smaller than that of
some other
components of the solar cell module, such as, for example, the substrate or
superstrate, or the
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front or back protecting layers, or the encapsulant layer(s) before or after
lamination. Therefore,
in modules comprising fully encapsulated assemblies, the two PVB encapsulant
layers may
come in contact with each other over the edges of the solar cell assembly and
form a seal
around the edges of the solar cell module. When the area of the largest
surface of the
encapsulant layers is larger than that of the solar cell assembly, the contact
between them may
be established in the stacked, unlaminated solar cell module. Alternatively,
when the greatest
two-dimensional surface area of the encapsulant layers is smaller than that of
the solar cell
assembly, the contact between them may not be established until the
encapsulant layers melt
and flow under the heat and pressure of the solar cell module lamination
process. Those of skill
in the art will be able to take account of the changes necessitated in the
above description by
solar cell assemblies having a significant thickness.
By "partially encapsulated", it is meant that the solar cell assembly, which
comprises
solar cells (such as thin film solar cells) and is deposited on a substrate
(or superstrate), has
one side that is opposite from the substrate (or superstrate) laminated to an
encapsulant layer
comprising the PVB composition so that the solar cell assembly is sandwiched
between the
substrate (or superstrate) and the PVB encapsulant layer. In modules
comprising partially
encapsulated assemblies, the PVB encapsulant layer may come in contact with
the substrate
(or superstrate) of the solar cell assembly over the edges of the solar cell
module and form a
seal around the edges of the solar cell assembly. Again, depending on the
relative surface
areas of the substrate (superstrate), the solar cell assembly and the
encapsulant layer, the edge
seal may form before or after the lamination process that forms the solar cell
module.
In one solar cell module, for example, the PVB encapsulant layer(s) are formed
from
PVB sheets and the encapsulated solar cell assembly is formed by laminating
one or both sides
of the solar cell assemblies to the PVB sheet(s). The PVB sheets may have a
thickness of
about 0.25 to about 1.2 mm.
It has been found that, within a solar cell module, when a prior art PVB
encapsulant is in
complete or partial contact with a silver component (such as a component
comprising silver or
silver alloy), the prior art PVB encapsulant tends to discolor or yellow over
time.
Without wishing to be bound by theory, it is believed that such discoloration
results when
Ago comprised in the silver component is oxidized, under high voltage and high
moisture
conditions, to form Ag+ ions that migrate into the PVB encapsulant. Once in
the PVB
encapsulant, the Ag' ions are then reduced to metallic silver (Ag ). The
metallic silver, which
may be in the form of nano-sized silver particles, is believed to cause the
discoloration. By
adding the unsaturated heterocyclic compounds and optionally the other
additives described
above into the PVB encapsulants, however, the formation of the elemental
silver is prevented,
and the resulting discoloration of the PVB encapsulant is mitigated.
More specifically, when the PVB encapsulant described herein is in prolonged
contact
with one or more silver components, the yellowness index (YI) change of the
PVB encapsulant
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is reduced or minimized. The YI for a PVB encapsulant can be determined in
accordance with
ASTM E313-05, using a 20 observer and using Illuminant C as a light source.
These conditions
may also be described as "2 /C". The YI is reported in unitless numbers and
must be
normalized to a particular sample pathlength for direct comparison. In
general, the Yl of PVB
encapsulants described herein remains about 60 or less, or about 55 or less,
or about 50 or
less, or 40 or less, or about 30 or less, or about 20 or less, for a sample
having a pathlength of
1.0 cm.
The YI of the PVB encapsulant in a solar cell module is difficult to measure
in situ, as the
yellowness of the other components in the module, such as the coatings, is
difficult to
deconvolute from that of the encapsulant. In order to avoid this obstacle, it
is generally
necessary to delaminate the module, isolating the PVB encapsulant.
Delamination is also an
inconvenient procedure, however. Therefore, the Yl of the PVB encapsulant is
generally
measured using a model system. Both solid encapsulants and polymer solutions
may be used
as model systems for the Yl of PVB encapsulants in solar cell modules.
When a solid encapsulant is used as a model, it is laminated to the silvered
side of
silver-coated glass sheet, then held under a bias of 1,000 V for 1000 hours at
85 C and at 85%
relative humidity (RH). The solid encapsulants used as models herein have a
constant
plasticizer concentration, for the validity of the comparison of the
encapsulants' Yl. The total
amount of the other additives (unsaturated heterocyclic compound, UV absorber,
thermal
stabilizer, hindered amine and the like) is typically about 1 % or less of the
amount of plasticizer
in the solid encapsulants; accordingly, changes in Yl due to variation in the
amounts of the
additives is deemed to be insignificant.
When a polymer solution is used as a model system, a stock solution of neat
PVB resin
(10g) in methanol (100g) is combined with a stock solution of a silver salt in
methanol and with
stock solutions of any additives that are included in the solution model. The
solution samples
are incubated at 60 C in a hot water bath for 2 to 8 hours, until the yellow
color of a negative
control sample becomes apparent to the naked eye. The samples are transferred
to cuvettes
having a pathlength of 1.0 cm, and their spectra are obtained according to the
standard method.
The concentrations of the PVB and of the silver (calculated as silver ions) in
the solution
samples are held constant, again for validity of comparison of the solutions'
Yl.
The term "silver component", as used herein, refers to a constituent part or
to any sub-
combination of the constituent parts of the solar cell assembly or of the
solar cell module that
comprises elemental silver. The terms "elemental silver", "metallic silver",
and "Ag " are
synonymous and are used interchangeably herein. The elemental silver may be
present in
substantially neat or pure form, for example as it is used in a reflector
film. Alternatively, it may
be compounded, for example with a non-metallic material such as a carrier or a
filler, or it may
be present in a solid solution, in an alloy, in crystalline form, as a powder
or as a flake, as the
continuous or dispersed phase of a dispersion, or in any other morphology. For
example, the
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solder material used in some connecting wires is a silver and aluminum alloy
containing as little
as about 2 wt% of silver.
The silver component may be any one or more of the conductive paste, the
connecting
wires, the metal conductive coatings, and the metal reflector films.
The conductive paste, which is typically used in wafer-based solar cells, is a
conductive
film deposited on the front sun-facing or back non-sun-facing side of solar
cells to efficiently
contact the solar cells and transport the photo-generated current. The front
conductive paste,
for example, may comprise elemental silver.
The term "connecting wires" as used herein also includes the solder materials
used to
connect the individual wires together or to anchor the wires onto the solar
cells. The connecting
wires, which may be included in both wafer-based solar cells and thin film
solar cells, are
typically soldered on the surface of the solar cells to provide electrical
connections between
individual solar cells and to lead the photo-generated current out of the
modules. In certain
solar cell modules, the connecting wires (including its solder material), and
especially the solder
material, may comprise silver or a silver alloy.
During the construction of thin film solar cells, a first conductive layer
(e.g., a transparent
conductive oxide (TCO) or metal coating) is first coated on the substrate
before the photon
absorbing materials is deposited thereon. Further, during the construction of
the solar cells, a
second conductive layer (e.g., a TCO or metal coating) is further deposited on
the photon
absorbing materials. The silver component may be one or both of these two
metal conductive
coatings.
Metal back reflector films are often incorporated in thin film solar cells to
reflect the
photons that have passed around or through the solar cells back onto the solar
cells, thereby
improving power generating efficiency. In certain solar cell modules, the
metal back reflector
film is formed by sputtering a silver layer or a silver comprising layer on
the solar cells.
Moreover, the silver component may be completely or partially in contact with
the PVB
encapsulant. For example, "partially in contact with" indicates that the
silver at least about 3.6
x10-5% of the silver component's surface area is in contact with the PVB
encapsulant. This
amount corresponds to the calculated area of scribe lines in a thin film cell,
although it is also
used herein to indicate a minimum surface area of contact for other silver
components and in
different types of solar cell modules. In contrast, the silver component is
completely in contact
with PVB, for example in a solar cell module in which substantially 100% of
the surface area of
a reflector film is in contact with the PVB encapsulant. When used without
modification,
however, as in the term "the silver component is in contact with the PVB
encapsulant," for
example, any non-zero level of contact is indicated. Stated alternatively, any
non-zero
percentage of the component's surface area may be in contact with the PVB
encapsulant.
In one module, the solar cells are wafer-based solar cells, and the silver
component may
be a conductive paste deposited thereon, or it may be one or more connecting
wires. The silver
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component is in contact with the PVB encapsulant. Further, the solar cell
assembly, which
comprises the wafer-based solar cells and the silver component, and which is
encapsulated by
the PVB encapsulant, may be further sandwiched between two protective outer
layers (which
are also referred to as the front and back sheets).
The protective outer layers of the solar cell modules may be formed of any
suitable
sheets or films. Suitable sheets include glass sheets, metal sheets such as
aluminum, steel,
galvanized steel, ceramic plates, or plastic sheets, such as polycarbonates,
acrylics,
polyacrylates, cyclic polyolefins (e.g., ethylene norbornene polymers),
polystyrenes (preferably
polystyrenes prepared in the presence of metallocene catalysts), polyamides,
polyesters,
fluoropolymers, or combinations of two or more thereof.
Suitable films include metal films, such as aluminum foil, or polymeric films
such as
those comprising polyesters (e.g., poly(ethylene terephthalate) and
poly(ethylene naphthalate)),
polycarbonate, polyolefins (e.g., polypropylene, polyethylene, and cyclic
polyolefins),
norbornene polymers, polystyrene (e.g., syndiotactic polystyrene), styrene-
acrylate copolymers,
acrylonitrile-styrene copolymers, polysulfones (e.g., polyethersulfone,
polysulfone, etc.), nylons,
poly(urethanes), acrylics, cellulose acetates (e.g., cellulose acetate,
cellulose triacetates, etc.),
cellophane, silicones, poly(vinyl chlorides) (e.g., poly(vinylidene
chloride)), fluoropolymers (e.g.,
polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethyl en
e-tetrafl u oroethylene
copolymers, etc.), or combinations of two or more thereof. The polymeric film
may be non-
oriented, or uniaxially oriented, or biaxially oriented. Some specific
examples of suitable
polymeric films include, but are not limited to, polyester films (e.g.,
poly(ethylene terephthalate)
films), fluoropolymer films (e.g., Tedlar , Tefzel(D, and Teflon films
available from E. I. du Pont
de Nemours and Company (DuPont), Wilmington, DE). Further, the films may be in
the form of
a multi-layer film, such as a fluoropolymer/ polyester/fluoropolymer
multilayer film (e.g.,
Tedlar /PET/Tedlar or TPT laminate film available from Isovolta AG., Austria
or Madico,
Woburn, MA).
In another module, the solar cells are thin film solar cells, and the silver
component may
be selected from connecting wires, conductive coatings, or back reflector
films, or a combination
of two or more thereof. In one particular thin film solar cell, the silver
component is a conductive
coating comprising silver or silver alloy. The silver component may also be a
back reflector film
comprising silver or silver alloy. Similarly to the above described wafer-
based solar cell
modules, the thin film solar cell assembly is fully or partially encapsulated
by the PVB
encapsulant, and the silver component is in contact with the PVB encapsulant.
Again, the fully
or partially encapsulated thin film solar cell assembly may be further
sandwiched between two
additional protective outer layers, such as a front or back sheet.
Alternatively, the thin film solar
cell assembly maybe partially encapsulated by the PVB encapsulant, i.e., in
which the side that
is opposite from the substrate (or superstrate) is laminated to the PVB
encapsulant, and in
which the PVB encapsulant is further laminated to a protective outer layer.
Also preferably, the
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thin film solar cell assembly comprises a reflector film which, in turn,
comprises silver and which
is in contact with the PVB encapsulant.
In a preferred thin film solar cell module, the light absorbing materials are
deposited on a
substrate in layers. The substrate may be made of glass, or any suitable
metal, or polymeric
sheets or films as described above for the protective outer layers. The thin
film solar cells may
be single junction or multi-junction (including tandem junction) thin film
solar cells. As the
spectrum of solar radiation provides photons of varying energies, multi-
junction solar cells were
developed in which the sunlight passes serially through several solar cell
layers. Each separate
layer of the multi-junction solar cell is tailored to convert photons of a
specific wavelength
efficiently to electrical energy. The multi junction solar cells are usually
constructed with layers
of different energy gaps. The layers having greater energy gaps are adjacent
to the surface
through which the light enters the module. The layers having lesser energy
gaps are positioned
further towards the interior or back of the module.
Further provided is a solar cell array comprising two or more of the solar
cell modules
described above.
Further provided is a process for converting light energy to electricity, said
process
comprising the step of exposing a solar cell assembly or a solar cell module
to electromagnetic
radiation
Further provided is a process for converting solar energy to electricity, said
process
comprising the step of exposing a solar cell assembly or a solar cell module
to solar radiation.
Any suitable process may be used in preparing the solar cell modules described
herein.
In particular, any suitable lamination process known within the art (such as
an autoclave or a
non-autoclave process) may be used to prepare the solar cell modules. For
example, in a
typical lamination process, the solar cells are first stacked between the PVB
encapsulants (e.g.,
in the form of PVB sheets), and further between two protective films or
sheets, and this pre-
lamination assembly is then subjected to the lamination process. Further, in
the preparation of
thin film solar cell modules, the solar cells, which are deposited over a
substrate, are first
stacked over the PVB encapsulant (e.g., in the form of a PVB sheet) and then a
protective film
or sheet, to form a pre-lamination assembly.
Accordingly, further provided herein is a pre-lamination assembly for
preparing a solar
cell module. The pre-lamination assembly comprises a solar cell assembly,
which in turn
comprises a solar cell, an oxidizable metal component, and a poly(vinyl
butyral) sheet
comprising the PVB composition described herein. Preferably, the poly(vinyl
butyral) sheet has
a thickness of about 0.25 mm to about 1.2 mm and a yellowness index of about
60 or less in
accordance with ASTM E313-05 after 1000 hours at 85% relative humidity (RH)
and at 85 C
with a bias of 1,000 V. The pre-lamination assembly may further comprise one
or more
additional layers selected from the group consisting of: a second poly(vinyl
butyral) sheet that
may be the same as or different from the poly(vinyl butyral) sheet, said
second poly(vinyl
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butyral) sheet being in contact with the solar cell assembly; a protective
outer layer that is in
contact with the poly(vinyl butyral) sheet; a second protective outer layer
that may be the same
as or different from the protective outer layer, said second protective outer
layer in contact with
the second poly(vinyl butyral) sheet; and a substrate or a superstrate that is
in contact with the
solar cell assembly and with the poly(vinyl butyral) sheet.
In one suitable process, the pre-lamination assembly is placed into a bag
capable of
sustaining a vacuum ("a vacuum bag"), the air is drawn out of the bag by a
vacuum line or other
means, the bag is sealed while the vacuum is maintained (e.g., at least about
27-28 in Hg (689-
711 mm Hg)), and the sealed bag is placed in an autoclave at a pressure of
about 150 to about
250 psi (about 11.3 to about 18.8 bar), a temperature of about 130 C to about
180 C, or about
120 C to about 160 C, or about 135 C to about 160 C, or about 145 C to about
155 C, for
about 10 to about 50 min, or about 20 to about 45 min, or about 20 to about 40
min, or about 25
to about 35 min. A vacuum ring may be substituted for the vacuum bag. One type
of suitable
vacuum bag is described in U.S. Patent No. 3,311,517. Following the heat and
pressure cycle,
the air in the autoclave is cooled without adding additional gas to maintain
pressure in the
autoclave. After about 20 min of cooling, the excess air pressure is vented
and the laminates
are removed from the autoclave.
Alternatively, the pre-lamination assembly may be heated in an oven at about
80 C to
about 120 C, or about 90 C to about 100 C, for about 20 to about 40 min, and
thereafter, the
heated assembly is passed through a set of nip rolls so that the air in the
void spaces between
the individual layers may be squeezed out, and the edge of the assembly
sealed. The
assembly at this stage is referred to as a pre-press.
The pre-press may then be placed in an air autoclave where the temperature is
raised to
about 120 C to about 160 C, or about 135 C to about 160 C, at a pressure of
about 100 to
about 300 psi (about 6.9 to about 20.7 bar), or preferably about 200 psi (13.8
bar). These
conditions are maintained for about 15 to about 60 min, or about 20 to about
50 min, and after
which, the air is cooled while no more air is added to the autoclave. After
about 20 to about 40
min of cooling, the excess air pressure is vented and the laminated products
are removed from
the autoclave.
The solar cell modules may also be produced through non-autoclave processes.
Suitable non-autoclave processes are described, e.g., in U.S. Patent Nos.
3,234,062;
3,852,136; 4,341,576; 4,385,951; 4,398,979; 5,536,347; 5,853,516; 6,342,116;
and 5,415,909,
U.S. Patent Publication No. 20040182493, European Patent No. EP1235683 B1, and
PCT
Patent Publication Nos. W09101880 and W003057478. Generally, the non-autoclave
processes include heating the pre-lamination assembly and the application of
vacuum, pressure
or both. For example, the assembly may be successively passed through heating
ovens and
nip rolls.
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These examples of lamination processes are not intended to be limiting.
Essentially
any lamination process that is operative may be used.
The Examples below are provided to describe the invention in further detail.
These
Examples, which set forth a preferred mode presently contemplated for carrying
out the
invention, are intended to illustrate and not to limit the invention.
EXAMPLES
Control Example CE1
A commercially available Butacite PVB sheet from DuPont, which comprises
72.97
wt% of poly(vinyl butyral), 26.7 wt% of triethyleneglycol di-2-ethyl-
hexanoate, 0.1 wt% of
TinuvinTM P Benzotriazole UV Absorber (Ciba), 0.003 wt% of TinuvinTM 123
hindered amine
light stabilizer (HALS) (Ciba), and 0.22 wt% octylphenol, based on the total
weight of the PVB
composition, was laminated to a silver coated glass sheet at the silver coated
side. After 1000
hours of conditioning at 85% RH, 85 C and under a bias of 1000 V, the PVB
sheet changed
color from near water white to dark brown.
In connection with Control Example CE1, TinuvinTMP is a 2-H substituted
derivative of
benzotriazole. Accordingly, it is not an unsaturated heterocyclic compound as
the term is
defined herein.
Control Examples CE2 to CE7 and Examples El to E5
Solutions of dried neat PVB resin (6.9 x 10-5 mol), silver nitrate (1.2 x 10-5
mol), and
additive(s) were prepared by mixing a solution of silver nitrate and additives
in methanol with a
solution of PVB flake in methanol. The PVB resin had a residual OH level of
18.8 wt%, as
determined by ASTM E222-00(2005)el (Standard Test Methods for Hydroxyl Groups
Using
Acetic Anhydride Acetylation, Test B, Reflux Method), and a molecular weight
of greater than
125,000 Da, as determined by size exclusion chromatography.
Two control solutions (CE2 and CE3), one with PVB in methanol without
additives and
one with PVB and silver nitrate in methanol without additives, were also
prepared. The
solutions were then heated at 60 C for two to eight hours. Their color change
was monitored by
measurement with a HunterLab Ultrascan Colorimeter (Hunter Labs, Reston, VA).
Yellowness
index (YI) was calculated by ASTM E313-05, using a 2 observer and Illuminant
C (2 /C), and
normalized to a 1.0 cm pathlength. The results are summarized in Table 1.
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TABLE I
Sample Unsaturated UV Absorber Other Additives Yl
Heterocyclic Compound
CE2* --- --- -- 6*
CE3 -- -- -- 290.1
Tinuvin P
CE4 --- Benzotriazole UV --- 139.7
Absorber**
2.6 x 10-5 mol**
Tinuvin 326
CE5 Benzotriazole UV --- 175.8
Absorber"*
6.1 x 10-6 mol
CE6 - _- Octylphenol*** 197.6
2.88 x 10 mol
N,N-
CE7 -- --- Diethylcyclohexylamine*** 151.2
1.3 x 10-3 cool
E1 Benzotriazole'** -- 22.9
1.64 x 10" mol
Tinuvin P
Benzotriazole*** Benzotriazole UV
E2 Absorber** -- 7.8
1.64 x 10-3 mol
8.9 x 10-6 mol
Tinuvin 770 Low
Benzotriazole*** Molecular Weight
Hindered Amine Light
E3 1.64 x 10-3 mol Stabilizer (HALS)** 11.1
5.7 x 10-6 mol
Tinuvin P Tinuvin 770 Low
Benzotriazole UV Molecular Weight
Benzotriazole*** Hindered Amine Light
E4 Absorber** Stabilizer (HALS)** 10.2
1.1 x 10-3 mol 8.9 x 10-6 mol s
5.7x10- mol
Imidazole***
E5 8.6 x 10'4 mol -- -- 9.6
Notes: *A solution of PVB in methanol without silver nitrate;
**Ciba, Tarrytown, NY;
***Sigma Aldrich, St. Louis, MO.
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The data in Table 1 show that, as a result of the addition of silver nitrate
to the
PVB/methanol solution, the yellowness index (Yl) was changed from 6 (in
Control Example
CE2) to 290.1 (in Control Example CE3). Upon addition of an unsaturated
heterocyclic
compound (benzotriazole in Examples El to E4 and imidazole in Example E5), the
Yl was
reduced significantly compared to the PVB/silver nitrate/methanol control
solutions (Control
Examples CE3 to CE7). Addition of optional UV absorbers (e.g., TinuvinTMP, as
in Example
E2), hindered amines (e.g., TinuvinTM 770, as in Example E3), or both (as in
Example E4) can
provide a further reduction of YI.
Control Example CE8 and Example E6
In Example E6, 72.46 wt% of the dried neat PVB resin used in Examples El to E5
was
blended with a solution of 0.5 wt% 1 H-benzotriazole, 0.12 wt% TinuvinTM P,
and 0.22 wt%
octylphenol in 26.7 wt% triethylene glycol di-2-ethylhexanoate. This blend was
fed into a single
screw extruder and melted at a temperature of 200 C, nominally. The resulting
melt was
pressed into a 30 mil thick sheet, and the sheet was laminated between a first
float glass sheet
and a second float glass sheet. The second float glass sheet had a silver
coating (200 nm
thick) on the side that was laminated in contact with the PVB sheet. The
laminate of Control
Example CE8 had the same structure, except that the PVB sheet was comprised of
72.96 wt%
PVB resin, 26.7 wt% triethylene glycol di-2-ethylhexanoate, 0.12 wt% TinuvinTM
P, and 0.22
wt% octylphenol.
The laminates of Control Example CE8 and Example E6 were placed into a chamber
held at 85 C and 85% relative humidity (RH) for 1000 hours and subjected to a
bias of 1000 V.
After this exposure, the PVB sheet in the laminate of Control Example CE8 was
dark brown,
while the PVB sheet in the laminate of Example E6 was only lightly yellowed.
This result
demonstrates that the addition of the 0.5 wt% of 1 H-benzotriazole mitigates
the yellowing of a
PVB sheet that is in contact with silver.
While certain of the preferred embodiments of the present invention have been
described and specifically exemplified above, it is not intended that the
invention be limited to
such embodiments. Various modifications may be made without departing from the
scope and
spirit of the present invention, as set forth in the following claims.
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