U.S. patent application number 10/546851 was filed with the patent office on 2006-08-03 for acetoacetylated polyvinyl polymers.
Invention is credited to Lorenzo Fred Pelosi, Patricia Mary Ellen Sormani.
Application Number | 20060170136 10/546851 |
Document ID | / |
Family ID | 33135262 |
Filed Date | 2006-08-03 |
United States Patent
Application |
20060170136 |
Kind Code |
A1 |
Pelosi; Lorenzo Fred ; et
al. |
August 3, 2006 |
Acetoacetylated polyvinyl polymers
Abstract
The present invention relates compositions containing
acetoacetylated polyvinyl polymers obtained from polyvinyl
polymers, such as polyvinyl butyrals. These coating compositions
are especially suitable for use as wash primers in automotive OEM
and refinish coating applications.
Inventors: |
Pelosi; Lorenzo Fred;
(Wilmington, DE) ; Sormani; Patricia Mary Ellen;
(Newark, DE) |
Correspondence
Address: |
E I DU PONT DE NEMOURS AND COMPANY;LEGAL PATENT RECORDS CENTER
BARLEY MILL PLAZA 25/1128
4417 LANCASTER PIKE
WILMINGTON
DE
19805
US
|
Family ID: |
33135262 |
Appl. No.: |
10/546851 |
Filed: |
April 7, 2004 |
PCT Filed: |
April 7, 2004 |
PCT NO: |
PCT/US04/10708 |
371 Date: |
August 24, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60462236 |
Apr 11, 2003 |
|
|
|
Current U.S.
Class: |
264/334 ;
264/328.18; 427/384; 525/191 |
Current CPC
Class: |
C08F 8/00 20130101; C08F
8/00 20130101; C08L 33/14 20130101; C08L 33/14 20130101; C09D
133/14 20130101; C08L 2666/04 20130101; C08L 2666/04 20130101; C08F
216/06 20130101; C09D 133/14 20130101 |
Class at
Publication: |
264/334 ;
525/191; 264/328.18; 427/384 |
International
Class: |
B29C 45/00 20060101
B29C045/00; C08F 8/00 20060101 C08F008/00; B05D 3/02 20060101
B05D003/02 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 9, 2004 |
US |
10/775571 |
Claims
1. A composition comprising: (a) an acetoacetylated polyvinyl
polymer having the formula: ##STR13## wherein (m) ranges from about
1.5 mole percent to about 85 mole percent, (n) ranges from about 0
mole percent to about 20.5 mole percent, (p) ranges from about 12
mole percent to about 87 mole percent and (q) ranges from about 1
mole percent to about 88 mole percent, sum of (m), (n), (p) and (q)
being 100 and wherein R.sub.1 and R.sub.2 are independently H,
substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted
or unsubstituted C.sub.6 to C.sub.14 aryl, substituted or
unsubstituted C.sub.7 to C.sub.22 aralkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 alkaryl, substituted,
unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a combination
thereof, said substituents being independently selected from the
group consisting of C.sub.1 to C.sub.12 alkoxy, acyl, carboxyl,
derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano,
and halo; (b) an acetoacetylated polyvinyl polymer having the
formula: ##STR14## wherein (m) ranges from about 1.5 mole percent
to about 85 mole percent, (n) ranges from about 0 mole percent to
about 20.5 mole percent, (p) ranges from about 12 mole percent to
about 87 mole percent, (q) ranges from about 1 mole percent to
about 88 mole percent and (x) ranges from about 0.5 to about 6 mole
percent, sum of (m), (n), (p), (q) and (x) being 100 and wherein
R.sub.1 and R.sub.2 are independently H, substituted or
unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 aryl, substituted or
unsubstituted C.sub.7 to C.sub.22 aralkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 alkaryl, substituted,
unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a combination
thereof, and wherein Z is H, or --COOH and Y is --COOH, halo,
unsubstituted phenyl or a combination thereof; said substituents
being independently selected from the group consisting of C.sub.1
to C.sub.12 alkoxy, acyl, carboxyl, derivative of carboxyl,
sulfonyl, derivative of sulfonyl, cyano, and halo; or (c) a
combination thereof.
2. The coating composition of claim 1 wherein in said
acetoacetylated polyvinyl polymer R.sub.1 is propyl and R.sub.2 is
methyl.
3. The coating composition of claim 1 wherein GPC weight average
molecular weight of said acetoacetylated polyvinyl polymer ranges
from about 20,000 to about 300,000.
4. The coating composition of claim 1 wherein Tg of the
acetoacetylated polyvinyl polymer ranges from about 40.degree. C.
to about 60.degree. C.
5. The coating composition of claim 1 wherein said acetoacetylated
polyvinyl polymer is solubilized in one or more solvents.
6. The coating composition of claim 1 wherein VOC of said
composition ranges from 0.1 to 0.72 kilograms per liter of said
composition.
7. The curable coating composition of claim 1 wherein said
acetoacetylated polyvinyl polymer is produced by the steps
comprising: (i) dissolving in one or more solvents: (a) a polyvinyl
polymer having the formula: ##STR15## wherein (m) ranges from about
1.5 mole percent to about 85 mole percent, (n) ranges from about 0
mole percent to about 20.5 mole percent and (o) ranges from about
13 mole percent to about 98.5 mole percent, sum of (m), (n) and (o)
being 100 and wherein R.sub.1 and R.sub.2 are independently H,
substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted
or unsubstituted C.sub.6 to C.sub.14 aryl, substituted or
unsubstituted C.sub.7 to C.sub.22 aralkyl, substituted or
unsubstituted C.sub.6 to C.sub.14alkaryl, substituted,
unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a combination
thereof, said substituents being independently selected from the
group consisting of C.sub.1 to C.sub.12 alkoxy, acyl, carboxyl,
derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano,
and halo; (b) a polyvinyl polymer having the formula: ##STR16##
wherein (m) ranges from about 1.5 mole percent to about 85 mole
percent, (n) ranges from about 0 mole percent to about 20.5 mole
percent and (o) ranges from about 13 mole percent to about 98.5
mole percent and (x) ranges from about 0.5 to about 6 mole percent,
sum of (m), (n), (o) and (x) being 100 and wherein R.sub.1 and
R.sub.2 are independently H, substituted or unsubstituted C.sub.1
to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.14
aryl, substituted or unsubstituted C.sub.7 to C.sub.22 aralkyl,
substituted or unsubstituted C.sub.6 to C.sub.14 alkaryl,
substituted, unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a
combination thereof, and wherein Z is H, or --COOH and Y is --COOH,
halo, unsubstituted phenyl or a combination thereof; said
substituents being independently selected from the group consisting
of C.sub.1 to C.sub.12 alkoxy, acyl, carboxyl, derivative of
carboxyl, sulfonyl, derivative of sulfonyl, cyano, and halo; or (c)
a combination of thereof to form a solution; (ii) contacting said
solution with C.sub.1 to C.sub.12 alkyl acetoacetate to produce
said acetoacetylated polyvinyl polymer.
8. The composition of claim 7 wherein said R.sub.1 is propyl and
said R.sub.2 is methyl.
9. The coating composition of claim 1 formulated as automotive
refinish or OEM wash primer composition.
10. A method of producing a coating on a substrate comprising: (i)
applying a layer over a substrate surface of a coating composition
comprising: (a) an acetoacetylated polyvinyl polymer having the
formula: ##STR17## wherein (m) ranges from about 1.5 mole percent
to about 85 mole percent, (n) ranges from about 0 mole percent to
about 20.5 mole percent, (p) ranges from about 12 mole percent to
about 87 mole percent and (q) ranges from about 1 mole percent to
about 88 mole percent, sum of (m), (n), (p) and (q) being 100 and
wherein R.sub.1 and R.sub.2 are independently H, substituted or
unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 aryl, substituted or
unsubstituted C.sub.7 to C.sub.22 aralkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 alkaryl, substituted,
unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a combination
thereof, said substituents being independently selected from the
group consisting of C.sub.1 to C.sub.12 alkoxy, acyl, carboxyl,
derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano,
and halo; (b) an acetoacetylated polyvinyl polymer having the
formula: ##STR18## wherein (m) ranges from about 1.5 mole percent
to 85 mole percent, (n) ranges from about 0 mole percent to 20.5
mole percent, (p) ranges from about 12 mole percent to about 87
mole percent, (q) ranges from about 1 mole percent to about 88 mole
percent and (x) ranges from 0.5 to 6 mole percent, sum of (m), (n),
(p), (q) and (x) being 100 and wherein R.sub.1 and R.sub.2 are
independently H, substituted or unsubstituted C.sub.1 to C.sub.12
alkyl, substituted or unsubstituted C.sub.6 to C.sub.14 aryl,
substituted or unsubstituted C.sub.7 to C.sub.22 aralkyl,
substituted or unsubstituted C.sub.6 to C.sub.14 alkaryl,
substituted, unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a
combination thereof, and wherein Z is H, or --COOH and Y is --COOH,
halo, unsubstituted phenyl or a combination thereof; said
substituents being independently selected from the group consisting
of C.sub.1 to C.sub.12alkoxy, acyl, carboxyl, derivative of
carboxyl, sulfonyl, derivative of sulfonyl, cyano, and halo; or (c)
a combination thereof; and (ii) drying said layer under ambient
conditions or at elevated cure temperatures to form said coating on
said substrate.
11. The method of claim 10 wherein said wherein said R.sub.1 is
propyl and said R.sub.2 is methyl.
12. The method of claim 10 or 11 further comprising applying a
layer of base coating composition on said layer before said drying
step.
13. The method of claim 12 further comprising applying a layer of
clear coating composition on said layer of base coating composition
before said drying step.
14. The method of claim 13 wherein said coating composition is a
wash primer composition.
15. The method of claim 14 wherein said substrate is an automotive
body.
16. A method of producing a multi-coat system on a substrate
comprising: (i) applying a layer over a substrate surface of a
coating composition comprising: (a) an acetoacetylated polyvinyl
polymer having the formula: ##STR19## wherein (m) ranges from about
1.5 mole percent to about 85 mole percent, (n) ranges from about 0
mole percent to about 20.5 mole percent, (p) ranges from about 12
mole percent to about 87 mole percent and (q) ranges from about 1
mole percent to about 88 mole percent, sum of (m), (n), (p) and (q)
being 100 and wherein R.sub.1 and R.sub.2 are independently H,
substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted
or unsubstituted C.sub.6 to C.sub.14 aryl, substituted or
unsubstituted C.sub.7 to C.sub.22 aralkyl, substituted or
unsubstituted C.sub.6 to C.sub.14alkaryl, substituted,
unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a combination
thereof, said substituents being independently selected from the
group consisting of C.sub.1 to C.sub.12 alkoxy, acyl, carboxyl,
derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano,
and halo; (b) an acetoacetylated polyvinyl polymer having the
formula: ##STR20## wherein (m) ranges from about 1.5 mole percent
to 85 mole percent, (n) ranges from about 0 mole percent to 20.5
mole percent, (p) ranges from about 12 mole percent to about 87
mole percent, (q) ranges from about 1 mole percent to about 88 mole
percent and (x) ranges from 0.5 to 6 mole percent, sum of (m), (n),
(p), (q) and (x) being 100 and wherein R.sub.1 and R.sub.2 are
independently H, substituted or unsubstituted C.sub.1 to C.sub.12
alkyl, substituted or unsubstituted C.sub.6 to C.sub.14 aryl,
substituted or unsubstituted C.sub.7 to C.sub.22 aralkyl,
substituted or unsubstituted C.sub.6 to C.sub.14 alkaryl,
substituted, unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a
combination thereof, and wherein Z is H, or --COOH and Y is --COOH,
halo, unsubstituted phenyl or a combination thereof; said
substituents being independently selected from the group consisting
of C.sub.1 to C.sub.12 alkoxy, acyl, carboxyl, derivative of
carboxyl, sulfonyl, derivative of sulfonyl, cyano, and halo; or (c)
a combination thereof; (ii) applying a layer of a base coating
composition on said composition layer; (iii) applying a layer of a
clear coating composition on said layer of base coating composition
to form a multi-layer system on said substrate; and (iv) drying
said multi-layer system under ambient conditions or at elevated
cure temperatures to form said multi-coat system on said
substrate.
17. The method of claim 16 wherein said substrate is an automotive
body.
18. A method of producing a molded article comprising: (i) mixing
fibrids, floc, pulp, micropulp or a combination thereof with a
composition to form a moldable component, said composition
comprising: (a) an acetoacetylated polyvinyl polymer having the
formula: ##STR21## wherein (m) ranges from about 1.5 mole percent
to about 85 mole percent, (n) ranges from about 0 mole percent to
about 20.5 mole percent, (p) ranges from about 12 mole percent to
about 87 mole percent and (q) ranges from about 1 mole percent to
about 88 mole percent, sum of (m), (n), (p) and (q) being 100 and
wherein R.sub.1 and R.sub.2 are independently H, substituted or
unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 aryl, substituted or
unsubstituted C.sub.7 to C.sub.22 aralkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 alkaryl, substituted,
unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a combination
thereof, said substituents being independently selected from the
group consisting of C.sub.1 to C.sub.12 alkoxy, acyl, carboxyl,
derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano,
and halo; (b) an acetoacetylated polyvinyl polymer having the
formula: ##STR22## wherein (m) ranges from about 1.5 mole percent
to 85 mole percent, (n) ranges from about 0 mole percent to 20.5
mole percent, (p) ranges from about 12 mole percent to about 87
mole percent, (q) ranges from about 1 mole percent to about 88 mole
percent and (x) ranges from 0.5 to 6 mole percent, sum of (m), (n),
(p), (q) and (x) being 100 and wherein R.sub.1 and R.sub.2 are
independently H, substituted or unsubstituted C.sub.1 to C.sub.12
alkyl, substituted or unsubstituted C.sub.6 to C.sub.14 aryl,
substituted or unsubstituted C.sub.7 to C.sub.22 aralkyl,
substituted or unsubstituted C.sub.6 to C.sub.14 alkaryl,
substituted, unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a
combination thereof, and wherein Z is H, or --COOH and Y is --COOH,
halo, unsubstituted phenyl or a combination thereof; said
substituents being independently selected from the group consisting
of C.sub.1 to C.sub.12 alkoxy, acyl, carboxyl, derivative of
carboxyl, sulfonyl, derivative of sulfonyl, cyano, and halo; or (c)
a combination thereof; (ii) heating said moldable component into a
melt; (iii) conveying a desired amount of said melt into a cavity
of an article mold; (iv) cooling said desired amount of melt to
form said article; and (v) removing said article from said
cavity.
19. The method of claim 18 wherein said molded article is a safety
helmet.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority under 35 U.S.C. .sctn.119
from U.S. Provisional Application Ser. No. 60/456,236 (filed Apr.
11, 2002), which is incorporated by reference herein as if fully
set forth.
FIELD OF INVENTION
[0002] The present invention generally relates to polyvinyl
polymers and their various uses, such as coating compositions and
molded products.
BACKGROUND OF THE INVENTION
[0003] Polyvinyl polymers, such as polyvinyl butyrals have been
used since the 1930s in various compositions, such as lacquers,
primers for metals and anti-corrosive paints, printing inks,
temporary binders, adhesives and as films for shatterproof safety
glass. The need still exists for polyvinyl polymer-containing
compositions having improved coating properties, such as adhesion
to metal substrates, improved corrosion resistance, and lower
solution viscosity.
STATEMENT OF THE INVENTION
[0004] The present invention is directed to a composition
comprising:
[0005] (a) an acetoacetylated polyvinyl polymer having the formula:
##STR1## wherein (m) ranges from about 1.5 mole percent to about 85
mole percent, (n) ranges from about 0 mole percent to about 20.5
mole percent, (p) ranges from about 12 mole percent to about 87
mole percent and (q) ranges from about 1 mole percent to about 88
mole percent, sum of (m), (n), (p) and (q) being 100 and wherein
R.sub.1 and R.sub.2 are independently H, substituted or
unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 aryl, substituted or
unsubstituted C.sub.7 to C.sub.22 aralkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 alkaryl, substituted,
unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a combination
thereof, said substituents being independently selected from the
group consisting of C.sub.1 to C.sub.12 alkoxy, acyl, carboxyl,
derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano,
and halo;
[0006] (b) an acetoacetylated polyvinyl polymer having the formula:
##STR2## wherein (m) ranges from about 1.5 mole percent to about 85
mole percent, (n) ranges from about 0 mole percent to about 20.5
mole percent, (p) ranges from about 12 mole percent to about 87
mole percent, (q) ranges from about 1 mole percent to about 88 mole
percent and (x) ranges from about 0.5 to about 6 mole percent, sum
of (m), (n), (p), (q) and (x) being 100 and wherein R.sub.1 and
R.sub.2 are independently H, substituted or unsubstituted C.sub.1
to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.14
aryl, substituted or unsubstituted C.sub.7 to C.sub.22 aralkyl,
substituted or unsubstituted C.sub.6 to C.sub.14 alkaryl,
substituted, unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a
combination thereof, and wherein Z is H, or --COOH and Y is --COOH,
halo, unsubstituted phenyl or a combination thereof; said
substituents being independently selected from the group consisting
of C.sub.1 to C.sub.12 alkoxy, acyl, carboxyl, derivative of
carboxyl, sulfonyl, derivative of sulfonyl, cyano, and halo; or
[0007] (c) a combination thereof.
[0008] The present invention is also directed to a method of
producing a coating on a substrate comprising:
[0009] (i) applying a layer over a substrate surface of a coating
composition comprising:
[0010] (a) an acetoacetylated polyvinyl polymer having the formula:
##STR3## wherein (m) ranges from about 1.5 mole percent to about 85
mole percent, (n) ranges from about 0 mole percent to about 20.5
mole percent, (p) ranges from about 12 mole percent to about 87
mole percent and (q) ranges from about 1 mole percent to about 88
mole percent, sum of (m), (n), (p) and (q) being 100 and wherein
R.sub.1 and R.sub.2 are independently H, substituted or
unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 aryl, substituted or
unsubstituted C.sub.7 to C.sub.22 aralkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 alkaryl, substituted,
unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a combination
thereof, said substituents being independently selected from the
group consisting of C.sub.1 to C.sub.12 alkoxy, acyl, carboxyl,
derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano,
and halo;
[0011] (b) an acetoacetylated polyvinyl polymer having the formula:
##STR4## wherein (m) ranges from about 1.5 mole percent to 85 mole
percent, (n) ranges from about 0 mole percent to 20.5 mole percent,
(p) ranges from about 12 mole percent to about 87 mole percent, (q)
ranges from about 1 mole percent to about 88 mole percent and (x)
ranges from 0.5 to 6 mole percent, sum of (m), (n), (p), (q) and
(x) being 100 and wherein R.sub.1 and R.sub.2 are independently H,
substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted
or unsubstituted C.sub.6 to C.sub.14 aryl, substituted or
unsubstituted C.sub.7 to C.sub.22 aralkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 alkaryl, substituted,
unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a combination
thereof, and wherein Z is H, or --COOH and Y is --COOH, halo,
unsubstituted phenyl or a combination thereof; said substituents
being independently selected from the group consisting of C.sub.1
to C.sub.12 alkoxy, acyl, carboxyl, derivative of carboxyl,
sulfonyl, derivative of sulfonyl, cyano, and halo; or
[0012] (c) a combination thereof; and
[0013] (ii) drying said layer under ambient conditions or at
elevated cure temperatures to form said coating on said
substrate.
[0014] The present invention is further directed to a method of
producing a multi-coat system on a substrate comprising:
[0015] (i) applying a layer over a substrate surface of a coating
composition comprising:
[0016] (a) an acetoacetylated polyvinyl polymer having the formula:
##STR5## wherein (m) ranges from about 1.5 mole percent to about 85
mole percent, (n) ranges from about 0 mole percent to about 20.5
mole percent, (p) ranges from about 12 mole percent to about 87
mole percent and (q) ranges from about 1 mole percent to about 88
mole percent, sum of (m), (n), (p) and (q) being 100 and wherein
R.sub.1 and R.sub.2 are independently H, substituted or
unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 aryl, substituted or
unsubstituted C.sub.7 to C.sub.22 aralkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 alkaryl, substituted,
unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a combination
thereof, said substituents being independently selected from the
group consisting of C.sub.1 to C.sub.12 alkoxy, acyl, carboxyl,
derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano,
and halo;
[0017] (b) an acetoacetylated polyvinyl polymer having the formula:
##STR6## wherein (m) ranges from about 1.5 mole percent to 85 mole
percent, (n) ranges from about 0 mole percent to 20.5 mole percent,
(p) ranges from about 12 mole percent to about 87 mole percent, (q)
ranges from about 1 mole percent to about 88 mole percent and (x)
ranges from 0.5 to 6 mole percent, sum of (m), (n), (p), (q) and
(x) being 100 and wherein R.sub.1 and R.sub.2 are independently H,
substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted
or unsubstituted C.sub.6 to C.sub.14 aryl, substituted or
unsubstituted C.sub.7 to C.sub.22 aralkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 alkaryl, substituted,
unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a combination
thereof, and wherein Z is H, or --COOH and Y is --COOH, halo,
unsubstituted phenyl or a combination thereof; said substituents
being independently selected from the group consisting of C.sub.1
to C.sub.12 alkoxy, acyl, carboxyl, derivative of carboxyl,
sulfonyl, derivative of sulfonyl, cyano, and halo; or
[0018] (c) a combination thereof;
[0019] (ii) applying a layer of a base coating composition on said
composition layer;
[0020] (iii) applying a layer of a clear coating composition on
said layer of base coating composition to form a multi-layer system
on said substrate; and
[0021] (iv) drying said multi-layer system under ambient conditions
or at elevated cure temperatures to form said multi-coat system on
said substrate.
[0022] The present invention is also directed to a method of
producing a molded article, such as a safety helmet, said method
comprising:
[0023] (i) mixing fibrids, floc, pulp, micropulp or a combination
thereof with a composition to form a moldable component, said
composition comprising:
[0024] (a) an acetoacetylated polyvinyl polymer having the formula:
##STR7## wherein (m) ranges from about 1.5 mole percent to about 85
mole percent, (n) ranges from about 0 mole percent to about 20.5
mole percent, (p) ranges from about 12 mole percent to about 87
mole percent and (q) ranges from about 1 mole percent to about 88
mole percent, sum of (m), (n), (p) and (q) being 100 and wherein
R.sub.1 and R.sub.2 are independently H, substituted or
unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 aryl, substituted or
unsubstituted C.sub.7 to C.sub.22 aralkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 alkaryl, substituted,
unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a combination
thereof, said substituents being independently selected from the
group consisting of C.sub.1 to C.sub.12 alkoxy, acyl, carboxyl,
derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano,
and halo;
[0025] (b) an acetoacetylated polyvinyl polymer having the formula:
##STR8## wherein (m) ranges from about 1.5 mole percent to 85 mole
percent, (n) ranges from about 0 mole percent to 20.5 mole percent,
(p) ranges from about 12 mole percent to about 87 mole percent, (q)
ranges from about 1 mole percent to about 88 mole percent and (x)
ranges from 0.5 to 6 mole percent, sum of (m), (n), (p), (q) and
(x) being 100 and wherein R.sub.1 and R.sub.2 are independently H,
substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted
or unsubstituted C.sub.6 to C.sub.14 aryl, substituted or
unsubstituted C.sub.7 to C.sub.22 aralkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 alkaryl, substituted,
unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a combination
thereof, and wherein Z is H, or --COOH and Y is --COOH, halo,
unsubstituted phenyl or a combination thereof; said substituents
being independently selected from the group consisting of C.sub.1
to C.sub.12 alkoxy, acyl, carboxyl, derivative of carboxyl,
sulfonyl, derivative of sulfonyl, cyano, and halo; or
[0026] (c) a combination thereof;
[0027] (ii) heating said moldable component into a melt;
[0028] (iii) conveying a desired amount of said melt into a cavity
of an article mold;
[0029] (iv) cooling said desired amount of melt to form said
article; and
[0030] (v) removing said article from said cavity.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0031] As used herein:
[0032] "Low VOC coating composition" means a coating composition
that includes in the range of from 0.1 kilograms (1.0 pounds per
gallon) to 0.72 kilograms (6.0 pounds per gallon), preferably from
0.3 kilograms (2.6 pounds per gallon) to 0.6 kilograms (5.0 pounds
per gallon) and more preferably from 0.34 kilograms (2.8 pounds per
gallon) to 0.53 kilograms (4.4 pounds per gallon) of the solvent
per liter of the coating composition. All VOC's determined under
the procedure provided in ASTM D3960.
[0033] "High solids composition" means a coating composition having
solid component of above 30 percent, preferably in the range of
from 35 to 90 percent and more preferably in the range of from 40
to 80 percent, all in weight percentages based on the total weight
of the composition.
[0034] "GPC weight average molecular weight" means a weight average
molecular weight measured by utilizing gel permeation
chromatography, such as high performance liquid chromatograph
(HPLC) supplied by Hewlett-Packard, Palo Alto, Calif. Unless stated
otherwise, polystyrene standards were employed and tetrahydrofuran
was used as the liquid phase.
[0035] "Tg" (glass transition temperature) measured in .degree. C.
determined by DSC (Differential Scanning Calorimetry).
[0036] "(Meth)acrylate" means acrylate and methacrylate.
[0037] "Polymer solids" or "composition solids" means a polymer or
composition in its dry state.
[0038] "Ambient cure condition" is defined as the temperature range
of 12.degree. C. to 45.degree. C. (55.degree. F. to 110.degree. F.)
and a humidity range of 15% to 90% that is present in the spraying
area.
Acetoacetylated Polyvinyl Polymer
[0039] Polyvinyl polymer suitable for producing the acetoacetylated
polyvinyl polymers of the present invention is represented by the
following formula (I): ##STR9## wherein (m) ranges from about 1.5
mole percent to about 85 mole percent, preferably from about 36
mole percent to about 68 mole percent, and more preferably from
about 40 mole percent to about 64 mole percent, (n) ranges from
about 0 mole percent to about 20.5 mole percent, preferably from
about 1 mole percent to about 6 mole percent, and more preferably
from about 2 mole percent to about 4 mole percent and (o) ranges
from about 13 mole percent to about 98.5 mole percent, preferably
from about 32 mole percent to about 63 mole percent, and more
preferably from about 34 mole percent to about 55 mole percent. All
the foregoing mole percentages are based on the sum of (m), (n) and
(o) being 100. It should be noted that the aforementioned groups,
(m), (n) and (o) are typically randomly distributed on the polymer
backbone. R.sub.1 and R.sub.2 are independently H, substituted or
unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 aryl, substituted or
unsubstituted C.sub.7 to C.sub.22 aralkyl, substituted or
unsubstituted C.sub.6 to C.sub.14 alkaryl, substituted,
unsubstituted C.sub.4 to C.sub.14 carbocyclyl or a combination
thereof, said substituents being independently selected from the
group consisting of C.sub.1 to C.sub.12 alkoxy, acyl, carboxyl,
derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano,
and halo. Some of the examples of the foregoing for R.sub.1 include
propyl, phenyl and alkyl-substituted phenyl (preferably tolyl and
xylyl). Some of the examples of the foregoing for R.sub.2 include
methyl, ethyl, propyl, butyl and phenyl. More preferred is
polyvinyl butyral having R.sub.1 as propyl and R.sub.2 as
methyl.
[0040] More preferred polyvinyl polymers having R.sub.1 as propyl
and R.sub.2 as methyl are typically supplied in the form of fine
grained free flowing powder by Clariant Corporation, Charlotte,
N.C. under the trademark Mowital.RTM.. Some examples of polyvinyl
butyrals suitable for use in the present invention include
Mowital.RTM. B20H [(m) at 49 to 55 mole percent, (n) at 1 to 5 mole
percent and (o) at 40 to 46 mole percent], B30T [(m) at 41 to 46
mole percent, (n) at 1 to 5 mole percent and (o) at 49 to 55 mole
percent] and B30H [(m) at 50 to 55 mole percent, (n) at 1 to 5 mole
percent and (o) at 40 to 46 mole percent].
[0041] The polyvinyl polymers suitable for use in the present
invention can include copolymers of vinyl acetates with one or more
of the following comonomers:
[0042] Monocarboxylic acids, such as acrylic, methacrylic, crotonic
acids, preferably acrylic, methacrylic acids;
[0043] Ethylenically unsaturated dicarboxylic acids, such as
maleic, fumaric, itaconic acids, preferably maleic acid;
[0044] Anhydride monomers such as, maleic anhydride;
[0045] Glycidyl-containing monomers, such as allylglycidyl ether,
glycidyl (meth) acrylate, preferably glycidyl (meth) acrylate;
[0046] Halogen-containing monomers, such as vinyl chloride, vinyl
fluoride and vinyl bromide, preferably vinyl chloride;
[0047] C.sub.2 to C.sub.12 alkylenes, preferably ethylene and
propylene; and
[0048] Phosphate derivatives, preferably vinyl phosphate, and vinyl
diphosphate.
[0049] The aforedescribed polymers, containing both vinyl acetate
and one or more of the aforedescribed comonomers, are
conventionally prepared by the hydrolysis of the vinyl acetate
groups to vinyl alcohol groups followed by reaction, in the
presence of acid catalyst, such as phosphoric acid or hydrochloric
acid, with one or more aldehydes, such as acetaldehyde,
propanaldehyde, butyraldehyde, or a combination thereof to produce
the polyvinyl polymer of the following formula (II): ##STR10##
wherein R.sub.1, R.sub.2 (m), (n) and (o) are the same as those
stated in the formula (I) above and wherein Z is H, or --COOH and Y
is --COOH, halo, unsubstituted phenyl or a combination thereof and
(x) ranges from about 0.5 to about 6 mole percent, preferably from
about 1 mole percent to about 5 mole percent, more preferably from
about 2 mole percent to about 4 mole percent, sum of (m), (n), (o)
and (x) being 100.
[0050] By adjusting the proportions of (m) groups, (n) groups and
hydroxyl (o) groups on the backbone of polyvinyl polymer of
foregoing formulas (I), (II), or a combination thereof, the
physical and chemical properties of the resulting polyvinyl polymer
can be controlled. The degree of polymerization can also influence
the thermal and mechanical properties of the resulting polyvinyl
polymer. Thus, properties of a coating, such as, hardness,
toughness, elasticity and water resistance of a resulting coating
composition can be suitably adjusted.
[0051] The applicants of the present invention have unexpectedly
discovered that by providing polyvinyl polymer with acetoacetate
functionalities, a composition containing the resulting
acetoacetylated polyvinyl polymer not only has desired substrate
adhesion, but it also has lower solution viscosity. As a result,
the VOC of the resulting composition can be lowered without
adversely affecting coating properties.
[0052] The acetoacetylated polyvinyl polymer of the present
invention results from the substitution of about 10 mole percent to
about 90 mole percent, preferably of about 15 mole percent to about
55 mole percent, more preferably of about 25 mole percent to about
50 mole percent of hydroxy ethylenyl (o) groups on the polyvinyl
polymer backbone of the formula (I) with acetoacetate groups. The
resulting acetoacetylated polyvinyl polymer of the present
invention has the following formula (III): ##STR11## wherein (p)
ranges from about 12 mole percent to about 87 mole percent,
preferably from about 5 mole percent to about 45 mole percent and
more preferably from about 7 mole percent to about 35 mole percent;
and (q) ranges from about 1 mole percent to about 88 mole percent,
preferably from about 5 mole percent to about 40 mole percent and
more preferably from about 10 mole percent to about 30 mole
percent. All the foregoing mole percentages are based on the sum of
(m), (n), (p) and (q) being 100.
[0053] Alternatively, the acetoacetylated polyvinyl polymer of the
present invention can also result from the substitution of about 10
mole percent to about 90 mole percent, preferably of about 15 mole
percent to about 55 mole percent, more preferably of about 25 mole
percent to about 50 mole percent of hydroxy ethylenyl groups (o) on
the polyvinyl polymer backbone of the formula (II) with
acetoacetate groups. The resulting acetoacetylated polyvinyl
polymer of the present invention has the following formula (IV):
##STR12## wherein all the functionalities and mole percentages of
the acetoacetylated polyvinyl of formula (IV) are those described
in formulas, (I), (II), and (III) above. It is understood that a
combination of the acetoacetylated polyvinyl polymers of formulas
(III) and (IV) can also be utilized.
[0054] The GPC weight average molecular weight of the
acetoacetylated polyvinyl polymer of formulas (III) and (IV) ranges
from about 10,000 to about 300,000, preferably from about 20,000 to
about 200,000, more preferably from about 30,000 to about 120,000.
The Tg of the acetoacetylated polyvinyl polymer ranges from about
0.degree. C. to about 150.degree. C., preferably from about
20.degree. C. to about 90.degree. C., more preferably from about
40.degree. C. to about 60.degree. C. as determined by DSC.
[0055] The acetoacetylated polyvinyl polymers of formulas (III) and
(IV) are produced by contacting the aforedescribed polyvinyl
polymer of formulas (I) or (II) with C.sub.1 to C.sub.12 alkyl
acetoacetate, preferably t-butyl acetoacetate, to convert about 10
mole percent to about 90 mole percent of hydroxyl on said polyvinyl
polymer into acetoacetate-groups. The foregoing contacting step
preferably takes place at a temperature ranging from about
75.degree. C. to about 135.degree. C., preferably from about
80.degree. C. to about 125.degree. C. and more preferably from
about 90.degree. C. to about 120.degree. C. It should be understood
that one of ordinary skill in the art could conduct the foregoing
reaction at elevated or preferably at atmospheric pressure.
Depending upon the reaction temperature, the reaction time can
range from 2 minutes to 15 hours. The suitable process is a
solution process in which polyvinyl polymer is first dissolved in a
solvent, such as butyl acetate, n-methyl pyrolidone, methyl ethyl
ketone, methyl propyl ketone, methyl amyl ketone; or a combination
thereof followed by contacting the polyvinyl polymer solution with
C.sub.1 to C.sub.12 alkyl acetoacetate. The resulting
acetoacetylated polyvinyl polymer can be separated into a free
flowing powder or stored as a solution in the solvent described
above.
[0056] A clear extruded film of the acetoacetylated polyvinyl
polymer can be laminated to glass panels, such as those used in
automotive windshields, to produce shatter-resistant safety
glass.
Composition
[0057] The composition of the present invention includes the
acetoacetylated polyvinyl polymer of the present invention
solubilized in the solvent described earlier. The acetoacetylated
polyvinyl polymer can also be provided in the form of a dried
powder. The amount of the acetoacetylated polyvinyl polymer
utilized in the present invention typically ranges from about 3
weight percent to about 100 weight percent, preferably from about
35 weight percent to about 70 weight percent, more preferably from
about 40 weight percent to about 45 weight percent, all weight
percentages based on the total weight of composition solids.
[0058] The composition can further contain from about 0.1% to 50%
by weight, based on the total weight of composition solids, of an
acrylic polymer having a GPC weight average molecular weight of
about 1,000 to 35,000.
[0059] The acrylic polymers are prepared from one or more monomers
in the following group, such as, for example, acrylic ester monomer
including methyl acrylate, ethyl acrylate, butyl acrylate,
2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl
methacrylate, butyl methacrylate, lauryl (meth)acrylate, isobornyl
(meth)acrylate, isodecyl (meth)acrylate, oleyl (meth)acrylate,
palmityl (meth)acrylate, stearyl (meth)acrylate, hydroxyethyl
(meth)acrylate, acetoacetoxy ethyl (meth)acrylate, and
hydroxypropyl (meth)acrylate; acrylamide or substituted
acrylamides; styrene or alkyl substituted styrenes; butadiene;
ethylene; vinyl acetate; vinyl ester of "Versatic" acid (a tertiary
monocarboxylic acid having C.sub.9, C.sub.10 and C.sub.11 chain
length, the vinyl ester is also known as "vinyl versataten), or
other vinyl esters; vinyl monomers, such as, for example, vinyl
chloride, vinylidene chloride, vinyl pyridine, N-vinyl pyrrolidone;
amino monomers, such as, for example, N,N'-dimethylamino
(meth)acrylate; chloroprene and acrylonitrile or methacrylonitrile.
Acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
fumaric acid, maleic acid, monometlyl itaconate, monomethyl
fumarate, monobutyl fumarate, maleic anhydride,
2-acrylamido-2-methyl-1-propanesulfonic acid, sodium vinyl
sulfonate, and phosphoethyl methacrylate.
[0060] The composition of the present invention can also contain
from about 0.01% to 40% by weight, based on the total weight of
composition solids, of a polyester polymer which is the
esterification product of an aliphatic or aromatic dicarboxylic
acid, a polyol having at least three reactive hydroxyl groups, a
diol, an aromatic or aliphatic cyclic anhydride and a cyclic
alcohol. One preferred polyester is the esterification product of
adipic acid, trimethylol propane, hexanediol, hexahydrophathalic
anhydride and cyclohexane dimethylol.
[0061] The composition can optionally contain, in the range of from
0.1 weight percent to 50 weight percent of a modifying resin, such
as a well-known non-aqueous dispersion (NAD), all percentages being
based on the total weight of composition solids.
[0062] The non-aqueous dispersion-type polymer is prepared by
dispersion polymerizing at least one vinyl monomer in the presence
of a polymer dispersion stabilizer and an organic solvent. The
polymer dispersion stabilizer may be any of the known stabilizers
used commonly in the field of non-aqueous dispersions.
[0063] If desired, the composition can include in the range of from
2 weight percent to 10 weight percent, preferably in the range of 3
weight percent to 8 weight percent, more preferably 3.5 weight
percent to 6 weight percent of zinc tetroxychromate, wherein all
weight ranges are based on the weight of the composition. Zinc
tetroxychromate supplied by Rockwood Chemicals, Beltsville, Md.,
under the trademark J-1345 Basic zinc chromate, can be used in the
present invention.
[0064] If desired, the coating composition can include in the range
of from 0.1% to 6%, preferably in the range of from 0.5% to 4.0%
and more preferably 0.8 to 3 wt % of phosphoric acid, all weight
percentage are by weight based on the weight of the coating
composition. When used, phosphoric acid is kept separate from the
composition and it is mixed with the composition just prior to use.
Phosphoric acid supplied by Rhodia, Cranbury, N.J., under the name
Phosphoric Acid NF 85%, can be used in the present invention.
[0065] The composition of the present invention can also contain
conventional additives, such as pigments, stabilizers, rheology
control agents, flow agents, toughening agents and fillers.
Selection of such additional additives will, obviously, depend on
the intended use of the coating composition.
[0066] In use, a layer of the composition is typically applied over
a substrate by conventional techniques, such as spraying,
electrostatic spraying, roller coating, dipping or brushing. The
layer of the composition then dries under ambient conditions in the
range of 10 minutes to 4 hours, preferably in the range of 30
minutes to 60 minutes to form a coating on the substrate having the
desired coating properties. It is understood that the actual drying
time depends upon the thickness of the applied layer or the
presence or absence of suitable drying devices, such as fans that
assist in continuously flowing air over the coated substrate to
accelerate the dry rate. Generally, the composition applied as a
wash primer layer having a thickness in the range of from 6
micrometers to 25 micrometers over a metal substrate, such as
automotive body, dries in 10 to 60 minutes under ambient conditions
in the absence of any suitable drying devices and generally, a
primer layer having a thickness in the range of from 25 micrometers
to 300 micrometers applied over a metal substrate, such as
automotive body, dries in 2 hours to 4 hours under ambient
conditions in the absence of any suitable drying devices. If
desired, baking the coated substrate at a temperature of about
60.degree. C. for about 30 minutes may further accelerate the dry
rate. The foregoing baking step is particularly useful under OEM
(Original Equipment Manufacture) conditions.
[0067] It is also contemplated that the composition can be
conventionally produced in the form of a free flowing powder, which
can be conventionally applied over a substrate through a fluidized
bed. Alternatively, aqueous slurry of the powder can be utilized,
which can then be conventionally applied over a substrate. An
applied layer of the powder can then be typically subjected to
elevated temperatures to melt the powder and form a coating on the
substrate.
[0068] The present invention is also directed to a method of
producing a multi-coat system, preferably multi-coat automotive OEM
or refinish systems that includes the coating composition of the
present invention as a wash primer. In such a method, a layer of
the composition of the present invention is applied over a bare
metal substrate to produce a wash primer coating by using the steps
described earlier. The wash primer coating is then followed by the
conventional application of a coating of a conventional base
coating composition, which can be pigmented, followed by the
conventional application of a coating of a conventional clear
coating composition. If desired, an additional coating from a
conventional primer coating composition can be applied over the
wash primer coating before the application of the layer of the base
coating composition.
[0069] The composition of the present invention is suitable for use
as coating compositions, especially in wash primers or primers, for
automotive OEM and refinish industries; industrial coatings, such
as coiled coatings; flow agent in powder coatings; paper lacquers,
plastic surface finishes; spot-weldable paints; strippable
packaging lacquers; wood sealing varnishes; zinc-rich primers;
flexographic inks; gravure inks; inkjet inks; thermo-transfer inks;
temporary binders for abrasives, ceramics, metal powder pellets;
rheology agents in adhesives and hot-melt adhesives; binders for
sand papers; candle coatings; impregnating agent for card packaging
material, welding rods, underwater welding rods, particle boards,
such as orientated strand boards; coating compositions for magnetic
recording tapes; adhesives for laminated printed circuit boards;
safety helmets for work and sports; shatter-resistant safety glass;
binders for extruded, stamped, or molded floor panels and
insulating boards; as thermoset and thermoplastic injection molded
compounds suitable for making consumer products; and in industrial
coatings, such as coil coatings, adhesives and sealants.
[0070] The composition of the present invention is also suitable
for use as coating compositions on:
[0071] Woven or non-woven cellulosic or non-cellulosic fabrics;
leather or non-leather goods, such as shoes, boots, sandals,
sneakers, gloves, hats and upholstery; various sports and athletics
related footwear, such as sneakers, running shoes, roller blade
shoes; foot ball shoes; sports and recreation equipment, such as
golf clubs, balls, tees, skis, jet skis, wet bikes, snowmobiles,
skates, hockey rink surfaces, hockey pucks and hockey sticks,
bowling alley lanes, bowling pins and balls; fake fruits and dry
flowers; fiber optics; packaging materials, such as bottles,
beverage cases, food bags and boxes; finger nails and fake finger
nails; safety glass, shatter-proof glass and eye wear glasses;
plasticizer migration resistant coating over vinyl surfaces;
furniture, including lawn furniture; roof and roof tiles; textured
and soft-feel wall coverings; toys, such as Nerf.RTM.balls; light
fixtures and bulbs; communications equipment, such as phones,
pagers and fax machines; credit cards; luggage and attaches; touch
screen television tubes, cathode ray tubes and radar screens,
liquid crystal and flat panel displays; mirrors; non-skid
floorings; sound absorbent acoustical walls, ceilings and seats,
acoustical equipment; marine surfaces, such as boat hulls, buoys,
jetties, ship decks, sail canvas; office equipment, such as
computers, photocopying machines, computer printers; musical
instruments, such as piano, guitars, organs; costume jewelry; and
bright metallic surfaces.
[0072] Due to their durable nature, the coating from the
composition of the present invention may be used as durable long
life traffic markings on road surfaces, including reflective road
markings.
[0073] Due to improved chip and impact resistance offered by the
acetoacetylated polyvinyl polymer of the present invention, woven
mats or fibrous mats of the high strength materials, such as floc,
pulp, fibrids, micropulp, and a combination thereof described
below, can be impregnated with the coating composition of the
present invention and then conventionally compression molded,
extruded or pultrusion molded to produce a variety of products,
such as light weight ladders, and crash resistant safety helmets,
such as those described in U.S. Pat. Nos. 2,413,823; 3,946,441; and
4,466,138, all of which are incorporated herein by reference.
[0074] Floc comprises generally short fibers made by cutting
continuous filament fibers into short lengths without significant
fibrillation; and the lengths of short fibers can be of almost any
length, but typically they vary from about 1 mm to 12 mm for a
reinforcing fiber and up to several centimeters for a staple fiber
that is spun into a yarn, such as 1.5 mm Kevlar.RTM. 6F561 Floc
supplied by DuPont Company of Wilmington, Del. Short fibers
suitable for use in the present invention are the reinforcing
fibers disclosed in U.S. Pat. No. 5,474,842, which is incorporated
herein by reference.
[0075] Pulp can be made by refining fibers to fibrillate the short
pieces of the fiber material. Pulp can be also made by casting a
polymerizing solution of polymer material and grinding and refining
the solution, once solidified. Such a process is disclosed in U.S.
Pat. No. 5,028,372. Pulp particles differ from short fibers by
having a multitude of fibrils or tentacles extending from the body
of each pulp particle such as Keviar.RTM. 1F361 supplied by DuPont
Company of Wilmington, Del. These fibrils or tentacles provide
minute hair-like anchors for reinforcing composite materials and
cause the pulp to have a very high surface area.
[0076] Fibrids are substantially sheet-like structures, which can
be made in accordance with the process disclosed in U.S. Pat. Nos.
5,209,877; 5,026,456; 3,018,091; and 2,999,788, which are all
incorporated herein by reference. The process includes adding a
solution of organic polymer, with vigorous, agitation, to a liquid,
which is a non-solvent for the polymer and is miscible with the
solvent of the solution, to cause coagulation of fibrids; the
coagulated fibrids are wet milled and separated from the liquid;
the separated fibrids are dried, by means appropriate, to yield
clumps of fibrids having a high surface area; and the clumps are
opened to yield a particulate fibrid product. The Product
Information brochure identified as H-67192 10/98 published DuPont
Canada Inc in Mississauga, Ontario, Canada illustrates the film
like physical structure of typical fibrids known as F20W DuPont
fibrids.
[0077] Micropulp having a volume average length ranging from 0.01
micrometers to 100 micrometers, preferably ranging from 1
micrometer to 50 micrometers and more preferably from ranging from
0.1 micrometers to 10 micrometers are also suitable for use in the
present invention.
[0078] The aforementioned floc, fibrid, pulp or micropulp suitable
for use in the present invention can be made from organic fibers
from aliphatic polyamides, polyesters, polyacrylonitriles,
polyvinyl alcohols, polyolefins, polyvinyl chlorides,
polyvinylidene chlorides, polyurethanes, polyfluorocarbons,
phenolics, polybenzimidazoles, polyphenylenetriazoles,
polyphenylene sulfides, polyoxadiazoles, polyimides, aromatic
polyamides, or a mixture thereof. More preferred polymers are made
from aromatic polyamides, polybenzoxadiazole, polyben-zimidazole,
or a mixture thereof. Still more preferred organic fibers are
aromatic polyamides ((p-phenylene terephthalamide),
poly(m-phenylene isophthalamide), or a mixture thereof).
[0079] More particularly, the aromatic polyamide organic fibers
disclosed in U.S. Pat. Nos. 3,869,430; 3,869,429; 3,767,756; and
2,999,788, all of which are incorporated herein by reference, are
preferred. Such aromatic polyamide organic fibers and various forms
of these fibers are available from DuPont Company, Wilmington, Del.
under the trademark Kevlar.RTM. fibers, such as Kevlar.RTM. Aramid
Pulp, 1F543, 1.5 mm Kevlar.RTM. Aramid Floc 6F561, DuPont
Nomex.RTM. aramid Fibrids F25W. Other suitable commercial polymer
fibers include:
[0080] Zylon.RTM. PBO-AS (Poly(p-phenylene-2,6-benzobisoxazole)
fiber, Zylon.RTM. PBO-HM (Poly(p-phenylene-2,6-benzobisoxazole))
fiber, Dyneema.RTM. SK60 and SK71 ultra high strength polyethylene
fiber, all supplied by Toyobo, Japan. Celanese Vectran.RTM. HS
pulp, EFT 1063-178, supplied by Engineering Fibers Technology,
Shelton, Conn. CFF Fibrillated Acrylic Fiber supplied by Sterling
Fibers Inc, Pace, Fla. Tiara Aramid KY-400S Pulp supplied by Daicel
Chemical Industries, Ltd, 1 Teppo-Cho, Sakai City Japan.
[0081] The organic fibers suitable for use in the present invention
can also include natural fibers, such as cellulose, cotton and wool
fibers.
EXAMPLES
[0082] The following test procedures were used for generating data
reported in the examples below.
Solids Measurement
[0083] The non-volatile content of polymer solutions was measured
by removing the solvent of a polymer sample in down draft oven at
110.degree. C. A known quantity of the polymer was mixed with
tricresyl phosphate and acetone, and placed in a down draft oven
maintained at 110.+-.10.degree. C. for one hour. The weight of the
residue was used to calculate the wt % solids.
.sup.13C NMR (Mole Percentage Determination)
[0084] The mole percentages of groups on the acetoacetylated
polyvinyl polymer samples were determined through a Bruker DRX-400
NMR spectrometer equipped with a 10 mm broad banded probe. The
polymer samples were vacuum dried at 50.degree. C., dissolved in
deuterated methanol at approximately 5-10 weight percent and run
through the spectrometer at about 34.degree. C. using a 30 second
relaxation delay and a 90.degree. flip pulse to insure
quantitation.
[0085] From the ratio of the acetoacetate carbonyl to the carbon in
the butyral ring between the oxygen atoms, and knowing the molar
ratio of vinyl alcohol to butyral in the polymer backbone, the mole
percentages of vinyl alcohol that was substituted by acetoacetate
group was calculated.
Adhesion Test
[0086] The coated panels were tested for dry, wet and recovered
adhesion. For dry adhesion a cross cut and a grid hatch were made
on the panel, tape was applied and removed. The panel was then
given two ratings. The first rating was from a visual scale of 0 to
10 based on the amount of coating removed, 0 being total failure
and 10 being no coating removed. The second rating was the
point-of-failure that occurred as describer above. The panels were
then placed in a humidity cabinet maintained in compliance with
ASTM D-1735-02 for 96 hours. The panels were removed from the
humidity cabinet and the wet adhesion was measured within one hour.
The panels were then stored at 25.degree. C. and 50% relative
humidity for 24 hours and then retested to measure the recovered
adhesion.
Example 1
[0087] To a glass reactor equipped with an agitator, condenser, and
under nitrogen atmosphere, 500 parts of Pioloform.RTM. LL4150 (GPC
weight average molecular weight about 35,000) polyvinyl butyral
supplied by Wacker GmbH, Munich, Germany were added to 611 parts of
methyl ethyl ketone. The solution was heated to 75.degree. C. and
80.8 parts of t-butyl acetoacetate were added over a period of
several minutes. The batch was held 3 hours at 75.degree. C. and
then cooled to produce acetoacetylated polyvinyl butyral of formula
(III) above wherein (p) was 28 and (q) was 8. The polymer was
isolated by precipitation into cold water, (0.473 liter (1 pint) of
water to 150 g of polymer solution), filtered, washed with cold
water, filtered, and dried at room temperature under vacuum at room
temperature for about 7 hours, and then under vacuum at about
55.degree. C. for about 7 hours.
Example 2
[0088] To a glass reactor equipped with an agitator, condenser, and
under nitrogen atmosphere, 500 parts of Pioloform.RTM. LL4150 (GPC
weight average molecular weight about 35,000) polyvinyl butyral
supplied by Wacker Polymer System were added to 611 parts of methyl
ethyl ketone. The solution was heated to 75.degree. C. and 255.9
parts of t-butyl acetoacetate were added over a period of several
minutes. The batch was held for 3 hours at 75.degree. C. and then
cooled to produce acetoacetylated polyvinyl butyral wherein (p) was
14 and (q) was 22. The polymer was isolated by precipitation into
cold water, (0.473 liter (1 pint) of water to 150 g of polymer
solution), filtered, washed twice with cold water, filtered, and
dried at room temperature under vacuum at room temperature for
about 7 hours, and then under vacuum at about 55.degree. C. for
about 7 hours.
Example 3
[0089] To a glass reactor equipped with an agitator, condenser,
distillation head, and under nitrogen atmosphere, 500 parts of
Pioloform.RTM. LL4150 (GPC weight average molecular weight about
35,000) polyvinyl butyral supplied by Wacker GmbH, Munich, Germany
were added to 611 parts of n-methylpyrrolidone. The solution was
heated to 130.degree. C. and 255.9 parts of t-butyl acetoacetate
were added over a period of several minutes. The batch was held for
3 hours at 130.degree. C. and then cooled to produce
acetoacetylated polyvinyl butyral of formula (III) above wherein
(p) was 9 and (q) was 27. The polymer was isolated by precipitation
in cold water, (0.473 liter (1 pint) of water to 150 g of polymer
solution), filtered, washed with cold water, filtered, and dried at
room temperature under vacuum at room temperature for about 7
hours, and then under vacuum at about 55.degree. C. for about 7
hours. Final sample weight percent solids was 98.2%.
Example 4
[0090] To a glass reactor equipped with an agitator, condenser,
distillation head, and under nitrogen atmosphere, 150 parts of
Mowital.RTM. B20H (GPC weight average molecular weight of about
35,000 to 45,000) polyvinyl butyral supplied by Clariant
Corporation were added to 606 parts of n-methyl pyrolidone. The
solution was heated to 190.degree. C. to remove any low boiling
solvent. The solution was then cooled to between 140.degree. C. and
145.degree. C. and 25.6 parts of t-butyl acetoacetate were added
over a period of several minutes. The batch was held 30 minutes at
temperature and then was heated to about 195.degree. C. to remove
t-butanol by-product to produce acetoacetylated polyvinyl butyral
of formula (III) above wherein (p) is 39 and (q) is 4. The polymer
was isolated by precipitation into cold water, (0.473 liter (1
pint) of water to 150 g of polymer solution), filtered, and dried
under vacuum at 45.degree. C.
Example 5
[0091] To a glass reactor equipped with an agitator, condenser,
distillation head, and under nitrogen atmosphere, 200 parts of
Mowital.RTM. B20H (GPC weight average molecular weight of about
35,000 to 45,000) polyvinyl butyral supplied by Clariant
Corporation were added to 606 parts of n-methyl pyrolidone. The
solution was heated to 190.degree. C. to remove any low boiling
solvent. The solution was then cooled to between 140.degree. C. and
145.degree. C. and 68.2 parts of t-butyl acetoacetate were added
over a period of several minutes. The batch was held 30 minutes at
temperature and then was heated to about 195.degree. C. to remove
t-butanol by-product to produce acetoacetylated polyvinyl butyral
of formula (III) above wherein (p) is 32 and (q) is 11. The polymer
was isolated by precipitation into cold water, (0.473 liter (1
pint) of water to 150 g of polymer solution), filtered, and dried
under vacuum at 45.degree. C.
Example 6
[0092] To a glass reactor equipped with an agitator, condenser,
distillation head, and under nitrogen atmosphere, 200 parts of
Mowital.RTM. B20H (GPC weight average molecular weight of about
35,000 to 45,000) polyvinyl butyral supplied by Clariant
Corporation were added to 606 parts of n-methylpyrolidone. The
solution was heated to 190.degree. C. to remove any low boiling
solvent. The solution was then cooled to between 140.degree. C. and
145.degree. C. and 102.3 parts of t-butyl acetoacetate were added
over a period of several minutes. The batch was held 30 minutes at
temperature and then was heated to about 195.degree. C. to remove
t-butanol by-product to produce acetoacetylated polyvinyl butyral
of formula (III) above wherein (p) is 16 and (q) is 27. The polymer
was isolated by precipitation into cold water, (0.473 liter (1
pint) of water to 150 g of polymer solution), filtered, and dried
under vacuum at 60.degree. C.
Example 7
[0093] To a glass reactor equipped with an agitator, condenser,
distillation head, and under nitrogen atmosphere, 300 parts of
Butvar.RTM. B90 (GPC weight average molecular weight about 90,000)
polyvinyl butyral supplied by Solutia Inc., Springfield, Mass. were
added to 2000 parts of n-methyl pyrolidone. The solution was heated
to 190.degree. C. to remove any low boiling solvent. The solution
was then cooled to between 140.degree. C. and 145.degree. C. and
102.3 parts of t-butyl acetoacetate were added over a period of
several minutes. The batch was held 30 minutes at temperature and
then was heated to about 195.degree. C. to remove t-butanol
by-product and to produce acetoacetylated polyvinyl butyral of
formula (III) above wherein (p) is 35 and (q) is 8. The polymer was
isolated by precipitation into cold water, (0.473 liter (1 pint) of
water to 150 g of polymer solution), filtered, and dried under
vacuum at 45.degree. C.
Example 8
[0094] To a glass reactor equipped with an agitator, condenser,
distillation head, and under nitrogen atmosphere, 150 parts of
Butvar.RTM. B90 (GPC weight average molecular weight about 90,000)
polyvinyl butyral supplied by Solutia Inc., Springfield, Mass. were
added to 1000 parts of n-methyl pyrolidone. The solution was heated
to 190.degree. C. to remove any low boiling solvent. The solution
was then cooled to between 140.degree. C. and 145.degree. C. and
76.8 parts of t-butyl acetoacetate were added over a period of
several minutes. The batch was held 30 minutes at temperature and
then was heated to about 195.degree. C. to remove t-butanol
by-product and to produce acetoacetylated polyvinyl butyral of
formula (III) above wherein (p) is 29 and (q) is 14. The polymer
was isolated by precipitation into cold water, (0.473 liter (1
pint) of water to 150 g of polymer solution), filtered, and dried
under vacuum at 45.degree. C.
Coating Compositions
[0095] The examples, shown in Table 1 below, were prepared by
sequentially adding the components in Table 1, to compare the
coating properties of unmodified polyvinyl polymer against the
acetoacetylated polyvinyl polymer of the present invention. All the
compositions below were adjusted to 30 weight percent solids.
TABLE-US-00001 TABLE 1 Comp. Ctng Ex. 1 Ctng Ex. 1 Ctng Ex. 2 Ctng
Ex. 3 Poly Vinyl 30.0 Butyral.sup.1 Example 1 30.0 Example 2 30.0
Example 3 30.6 ethanol 39.9 39.9 39.9 39.6 toluene 30.1 30.1 30.1
29.9 Total 100 100 100 100 .sup.1Pioloform .RTM. LL4150 polyvinyl
butyral supplied by Wacker Polymer System.
[0096] The layers of coating compositions described in Table 1
above were applied with a draw-down bar over electro-coated steel
test panels to a dry film thickness of 1.5 to 2 mils (38 to 50
micrometers). The layers were then dried for at least 14 days and
then adhesion was tested to the indicated substrates.
TABLE-US-00002 TABLE 2 Under Dry Under Wet After Conditions
Conditions Recovery # X # X # X Hatch hatch Hatch hatch Hatch hatch
Adhesion over unsanded electrocoated steel substrates Comp. 3 8 7 9
5 10 Ctng Ex. 1 Ctng Ex. 1 3 10 8 8 9 9 Ctng Ex. 2 8 9 9 9 10 9
Ctng Ex. 3 8 9 8 9 9 9 Adhesion over galvanized steel substrates
Comp. 10 10 8 8 10 10 Ctng Ex. 1 Ctng Ex. 1 10 10 8 10 10 10 Ctng
Ex. 2 10 10 9 10 10 10 Ctng Ex. 3 10 10 8 8 10 10 Adhesion over
cold rolled steel (CRS) substrates Comp. 9 10 8 9 10 10 Ctng Ex. 1
Ctng Ex. 1 9 10 8 9 10 10 Ctng Ex. 2 10 10 9 10 10 10 Ctng Ex. 3 10
10 9 10 10 10 Adhesion over Aluminum substrates Comp. 10 10 10 10
10 10 Ctng Ex. 1 Ctng Ex. 1 10 10 1 1 1 1 Ctng Ex. 2 10 10 1 7 1 2
Ctng Ex. 3 10 10 3 10 10 10 Cold rolled steel panels coated with
Powercron .RTM. 590 E-coat supplied by ACT Laboratories, Inc,
Hillsdale, Illinois.
[0097] From Table 2, it can be seen that the coating compositions
of the present invention can be suitably used over various types of
substrates. Unmodified Polyvinyl butyral (Comp. Ctng Ex. 1) showed
poor adhesion to unsanded electrocoated steel panels. The
acetoacetylated polyvinyl butyral of the present invention, which
contain acetoacetate groups, showed much improved adhesion to
unsanded electrocoated panels. While the adhesion of these polymers
to Aluminum was less than desired at low levels of
acetoacetylation, it improved dramatically at higher levels of
acetoacetylation (Gtng Ex. 3 vs. Ctng Ex. 1 and 2). Therefore, the
acetoacetylated polyvinyl butyrals of the present invention have
improved adhesion to unsanded electrocoated steel panels, without
sacrificing adhesion to other substrates.
[0098] The examples, shown in Table 3 below, were prepared by
sequentially adding the components in Table 3, to compare the
coating properties of acetoacetylated polyvinyl butyral against the
acetoacetylated polyvinyl butyral of the present invention.
TABLE-US-00003 TABLE 3 Comp. Ctg. Ex Ctg. Ex Ctg. Ex Ctg. Ex. Ctg.
Ex Ctg. 4 5 6 2 7 Ex. 8 Ethanol 37.0 37.0 37.0 37.0 37.0 37.0
Toluene 28.7 28.7 28.7 28.7 28.7 28.7 Deionized 1.1 1.1 1.1 1.1 1.1
1.1 water Example 4 10 Example 5 10 Example 6 10 Comm. Poly* 10
Example 7 10 Example 8 10 Ethanol 22.5 22.5 22.5 22.5 22.5 22.5
Toluene 15 15 15 15 15 15 Total 114.31 114.31 114.31 114.31 114.31
114.31 *Butvar .RTM. B90 polyvinyl butyral supplied by Solutia,
Inc.
[0099] The layers of coating compositions described in Table 3
above were applied with a draw-down bar over test panels indicated
below to a dry film thickness of 13 to 25.4 micrometers (0.5 to 1.0
mil). The layers were then dried for at least 14 days and then
adhesion was tested. TABLE-US-00004 TABLE 4 Under Dry Under Wet
Conditions Conditions After Recovery # X # X # X Hatch Hatch Hatch
Hatch Hatch Hatch Adhesion over aluminum substrates. Ctg. Ex. 4 10
10 10 10 10 10 Ctg. Ex. 5 10 10 10 10 10 10 Ctg. Ex. 6 10 10 10 10
10 10 Comp. Ctg. Ex 2 10 10 10 10 10 10 Ctg. Ex. 7 10 10 10 10 10
10 Ctg. Ex. 8 10 10 10 10 10 10 Adhesion over cold rolled steel
(CRS) substrates. Ctg. Ex. 4 10 10 10 10 10 10 Ctg. Ex. 5 10 10 10
10 10 10 Ctg. Ex. 6 10 10 10 10 10 10 Comp. Ctg. Ex 2 10 5 5 2 6 2
Ctg. Ex. 7 10 10 10 7 10 10 Ctg. Ex. 8 10 10 10 9 10 10 Adhesion
over sanded electrocoated substrates*. Ctg. Ex. 4 10 10 10 10 10 10
Ctg. Ex. 5 10 10 10 10 10 10 Ctg. Ex. 6 10 10 10 10 10 10 Comp.
Ctg. Ex 2 10 10 8 2 10 10 Ctg. Ex. 7 10 10 10 10 10 10 Ctg. Ex. 8
10 10 10 10 10 10 Adhesion over unsanded electrocoated substrates*
Ctg. Ex. 4 10 3 10 1 10 4 Ctg. Ex. 5 10 10 10 10 10 10 Ctg. Ex. 6
10 10 10 10 10 10 Comp. Ctg. Ex 2 0 0 0 0 3 2 Ctg. Ex. 7 6 2 1 8 3
10 Ctg. Ex. 8 10 2 10 10 10 10 Adhesion over galvanized steel
substrates Ctg. Ex. 4 10 10 10 10 10 10 Ctg. Ex. 5 10 10 10 10 10
10 Ctg. Ex. 6 10 10 10 10 10 10 Comp. Ctg. Ex 2 10 10 1 1 1 1 Ctg.
Ex. 7 10 10 6 10 6 2 Ctg. Ex. 8 10 10 10 10 10 10 *Cold rolled
steel panels coated with Powercron .RTM. 590 E-coat supplied by ACT
Laboratories, Inc. Hillsdale, Illinois.
[0100] From Table 4, it can be readily seen that the presence of
the acetoacetylated polyvinyl butyral of the present invention in a
coating composition resulted in excellent adhesion to a variety of
substrates. Performance of the acetoacetylated polyvinyl butyral of
the present invention in a coating composition was particularly
good on cold rolled steel (CRS) substrates, on galvanized steel
substrates and on unsanded e-coated substrates, as compared to the
unmodified polyvinyl butyral (Comp. Ctg. Ex. 2). The test on
unsanded electrocoated substrates was very demanding, but the
presence of acetoacetylated polyvinyl butyral at higher levels of
acetoacetylation showed dramatically better adhesion as compared to
that containing the unmodified polyvinyl butyral (Ctg. Ex. 5, 6, 8
compared to Comp. Ctg. Ex. 2) It can also be readily seen that the
presence of the acetoacetylated polyvinyl butyral of the present
invention in a coating composition showed no weakness in adhesion
to the sanded electrocoated substrates, as compared to that
containing the unmodified polyvinyl butyral. This improvement in
performance is achieved without sacrificing adhesion to
aluminum.
* * * * *