USOO9499672B2

(12) United States Patent (10) Patent No.: US 9,499,672 B2

Zhang et al. (45) Date of Patent: Nov. 22, 2016
(54) METHODS FOR PREPARING STABLE UREA USPC ...................................................... 525/58, 61
FORMALDEHYDE POLYVINYLALCOHOL See application file for complete search history.
COLLOIDS
(71) Applicant: Hexion Inc., Columbus, OH (US) (56) References Cited
U.S. PATENT DOCUMENTS
(72) Inventors: Yingchao Zhang, Louisville, KY (US);
David A. Snover, Floyds Knobs, IN 3,515,581 A 6, 1970 Isaksen et al.
(US) 3,554.947 A 1/1971 Maruta et al.
3,759,736 A 9/1973 Jenny et al.
(73) Assignee: HEXION INC., Columbus, OH (US) 4,247.487 A * 1/1981 Percy ...................... C075,
4,530,713 A T. 1985 W11 tal.
(*) Notice: Subject to any disclaimer, the term of this 4,604,448 A 8, 1986 E. a
patent is extended or adjusted under 35 6,746,781 B2 6/2004 Francis et al.
U.S.C. 154(b) by 0 days. 7,927.459 B2 4/2011 Huang et al.
8,080,171 B2 12/2011 Lee et al.
2013/0337272 Al 12/2013 Zhang et al.
(21) Appl. No.: 14/943,943 2013/0337712 A1 12/2013 Zhang et al.
(22) Filed
1C
N OW. 17,
If,
2015 2014/0033950 A1 2/2014 Saha
FOREIGN PATENT DOCUMENTS
(65) Prior Publication Data
WO WO 2009/005977 A1 1, 2009
US 2016/OO68637 A1 Mar. 10, 2016 WO WO 2012/177181 A1 12/2012
O O WO WO 2013, 188541 A2 12/2013
Related U.S. Application Data WO WO 2014022654 A2 2, 2014
(62) Division of application No. 14/340,277, filed on Jul. * cited by examiner
24, 2014, now Pat. No. 9,217,046.
(51) Int. Cl. Primary Examiner — William Cheung
C08G 63/48 (2006.01)
CSF 8/00 (2006.01) (57) ABSTRACT
C08G 81/02 (2006.01)
CSF I6/06 (2006.01) The mechanical properties of urea formaldehyde resins may
CSF 8/30 (2006.01) be improved by incorporating therein polyvinyl alcohol. The
C08L 6/24 (2006.01) polyvinyl alcohol may be incorporated during pre-mixing,
(52) U.S. Cl mid mixing, and/or post mixing of the resin components.
CPC C08G 81/024 (2013.01); C08F8/30 Resins prepared using polyvinyl alcohol are particularly
(2013,01): C08F 16/06 (2013 01): cost 61/24 desirable in articles requiring improved mechanical strength
• u. fs (2013.01); C08L 2201.56 (2013.01) and water resistance, as compared to similar resins prepared
(58) Field of Classification search without the polyvinyl alcohol Such as shingles.
CPC. C08G 81/024; C08L 61/24: CO8L 2201/56;
C08F 16/06; C08F 8/30 8 Claims, No Drawings
 US 9,499,672 B2
1. 2
METHODS FOR PREPARING STABLE UREA improve polyvinyl alcohol water resistance in commercial
FORMALDEHYDE POLYVNYLALCOHOL products. It would be desirable in the art to be able to
COLLOIDS increase the amount of polyvinyl alcohol introduced into a
urea formaldehyde resin to improve its performance as a
RELATED APPLICATION DATA binder.

This application is a divisional application of U.S. patent SUMMARY OF THE INVENTION

application Ser. No. 14/340,277, filed Jul. 24, 2014, now
issued as U.S. Pat. No. 9,217,046, of which the entire In one aspect, the invention is a method for preparing
content of the application is hereby incorporated by refer 10 polyvinyl alcohol and urea-formaldehyde colloid including:
CCC. admixing polyvinyl alcohol with a component selected from
the group consisting of a solution of formaldehyde, and a
BACKGROUND OF THE INVENTION urea/formaldehyde concentrate, to form a first liquid work
ing admixture and then admixing the first liquid working
1. Field of the Invention 15 admixture with urea under reaction conditions Sufficient to
The present invention relates to urea formaldehyde col initiate a methylolation reaction to form an intermediate
loids. The present invention particularly relates to methods product admixture; Subjecting the intermediate product
of preparing urea formaldehyde polyvinyl alcohol colloids. admixture to reaction conditions sufficient to initiate con
2. Background of the Art densation to form a colloid. Additionally, in Some embodi
Historically, asphalt roofing shingles were made from ments, the method includes completing the process by
organic felt mats, principally formed from randomly making final urea post addition to produce a polyvinyl
arranged chopped cellulose fibers that are saturated with a alcohol and urea-formaldehyde resin colloid.
hot asphalt and Subsequently formed into asphalt roof In another aspect, the invention is a method for preparing
shingles. In contrast, for modern applications, wet laid glass polyvinyl alcohol and urea-formaldehyde colloid including:
fiber mats have replaced the cellulose felt mats which 25 admixing a component selected from the group consisting
provide increased service life, strength and improved fire of a solution of formaldehyde and a urea/formaldehyde
resistance. concentrate, with urea under reaction conditions sufficient to
Unfortunately, fiberglass lacks the natural inter-fiber initiate a methylolation reaction to form an intermediate
bonding that is inherent in the natural organic fiber Such as product admixture; Subjecting the intermediate product
cellulose. The chopped glass fibers when randomly disposed 30 admixture to reactions conditions sufficient to initiate con
in a mat must be bonded together by a suitable binder. The densation to form a second intermediate product admixture;
binder adhesively secures crossed glass fibers together con admixing the second intermediate product admixture with
tributing to good handling of the mats during processing into polyvinyl alcohol to from a final intermediate liquid product
fiberglass shingles as well as providing the necessary physi including a polyvinyl alcohol and urea-formaldehyde col
cal performance properties Such as strength, flexibility and 35 loid. Additionally in some embodiments the method
long life that is required during roof installation and during includes completing the process by making final urea post
the service life of the roof. addition to produce a polyvinyl alcohol and urea-formalde
As with any commercial concern, when making fiberglass hyde resin colloid.
reinforced shingles or any other fiberglass product, it is In still another aspect, the invention is a method for
desirable that useful binders be as cost effective as possible 40 preparing polyvinyl alcohol urea-formaldehyde resin colloid
while also having the necessary physical properties. In some including: adding polyvinyl alcohol to a urea-formaldehyde
aspects, urea-formaldehyde resins are desirable for this resin under reaction conditions sufficient to condense the
application. They are low-cost thermoset materials having a polyvinyl alcohol and the urea-formaldehyde resin to pro
good adhesion, a fast cure rate, desirable mechanical prop duce a polyvinyl alcohol and urea-formaldehyde resin col
erties, and a lengthy shelf life. 45 loid wherein the addition of polyvinyl alcohol is at a
Unfortunately, urea formaldehyde resins without some concentration sufficiently low to be compatible with the
form of modification may not have Sufficient mechanical urea-formaldehyde resin solution into which it is being
properties. It has sometimes been observed that fiberglass placed; measuring a property of the polyvinyl alcohol
sheathing prepared with urea formaldehyde resin binders grafted urea-formaldehyde resin; determining whether the
may break during the production of glass mats for the use in 50 property of the polyvinyl alcohol grafted urea-formaldehyde
the production of shingles. This shortcoming may be over resin meets a predetermined standard and taking an action
come however, through the use of water born polymers. Such selected from the group consisting of: (a) if the property of
as, emulsion, dispersion and water-soluble polymers. One the polyvinyl alcohol grafted urea-formaldehyde resin meets
Such waterborne polymer is polyvinyl alcohol. the predetermined standard, stop processing; and (b) if the
Polyvinyl alcohol can be readily crosslinked with urea 55 property of the polyvinyl alcohol grafted urea-formaldehyde
formaldehyde resin at elevated temperatures to improve resin does not meet the predetermined standard, further
mechanical properties of urea-formaldehyde-based binder processing the polyvinyl alcohol grafted urea-formaldehyde
and also improve water resistance. However, urea-formal resin the further processing including: adding additional
dehyde resin and polyvinyl alcohol water solution form a polyvinyl alcohol to the polyvinyl alcohol and urea-form
two-phase system due to immiscibility or limited compat 60 aldehyde resin colloid under reaction conditions, sufficient
ibility, depending on the molecular weight (MW), degree of to condense the polyvinyl alcohol and the polyvinyl alcohol
hydrolysis of polyvinyl alcohol, and solid content of the and urea-formaldehyde resin colloid to produce a further
formulation. Currently, it is customary in the art of making processed polyvinyl alcohol and urea-formaldehyde resin
polyvinyl alcohol resin, that less than 1% by weight, is colloid wherein the addition of polyvinyl alcohol is at a
mixed with urea-formaldehyde resin to enhance the urea 65 concentration compatible with the polyvinyl alcohol and
formaldehyde resin performance or add the small amount of urea-formaldehyde resin colloid into which it is being
urea-formaldehyde resin into polyvinyl alcohol solution to placed; measuring a property of the further processed poly
 US 9,499,672 B2
3 4
vinyl alcohol and urea-formaldehyde resin colloid; compar tions known to be useful to those of ordinary skill in the art
ing the property of the further processed polyvinyl alcohol of preparing urea formaldehyde resins may be employed
and urea-formaldehyde resin colloid to a predetermined with the embodiments of the application. For example, in
standard; and repeating the further processing until the Some embodiments, the condensation may be started and
further processed polyvinyl alcohol and urea-formaldehyde controlled by lowering the pH to from about 5 to about 6 and
resin colloid meets the predetermined standard. then heating the reaction solution to about 80-100° C.
Another aspect of the invention is a binder prepared using This reaction may then be completed by making a final
a polyvinyl alcohol urea-formaldehyde resin colloid pre urea post addition. One of ordinary skill in the art will well
know how to determine the final urea addition in order to
pared using any of the methods described above. These 10 achieve a specific property or properties. These first embodi
binders are particularly useful for preparing shingles. ments may be described as an early addition or a “pre
DESCRIPTION OF THE PREFERRED mixing approach of polyvinyl alcohol and the other com
EMBODIMENTS ponents of the resin.
In a “mid mixing approach, the colloid is prepared by
15 admixing a component selected from the group consisting
One embodiment of the invention is a polyvinyl alcohol of a solution of formaldehyde and a urea/formaldehyde
and urea-formaldehyde colloid. In the method for preparing concentrate, with urea under reaction conditions sufficient to
polyvinyl alcohol and urea-formaldehyde colloid, the initiate a methylolation reaction to form an intermediate
method includes: admixing polyvinyl alcohol with a com product admixture. This embodiment continues by then
ponent selected from the group consisting of a solution of Subjecting the intermediate product admixture to reactions
formaldehyde and a urea/formaldehyde concentrate, to form conditions sufficient to initiate a condensation reaction to
a first liquid working admixture and then admixing the first form a second intermediate product admixture; admixing the
liquid working admixture with urea under reaction condi second intermediate product admixture with polyvinyl alco
tions sufficient to initiate a methylolation reaction to forman hol to form a final intermediate product solution; and
intermediate product admixture; Subjecting the intermediate 25 completing the process by making final urea post addition.
product admixture to reaction conditions sufficient to initiate Another approach to the method of the application is a
a condensation reaction; and completing the process by "post mixing approach. In these embodiments, the polyvi
making a final urea post addition to produce a polyvinyl nyl alcohol is added to a urea-formaldehyde resin under
alcohol and urea-formaldehyde resin colloid. reaction conditions sufficient to react the polyvinyl alcohol
For the purposes of this application, the term polyvinyl 30 and the urea-formaldehyde resin to produce a polyvinyl
alcohol (hereinafter sometimes PVA) is defined to mean alcohol and urea-formaldehyde resin colloid wherein the
compounds having the general idealized formula: addition of polyvinyl alcohol is at a concentration suffi
ciently low to be compatible with the urea-formaldehyde
CH resin solution into which it is being placed. This embodi
35 ment of the methods of the application continues by mea
Suring a property of the polyvinyl alcohol grafted urea
OH formaldehyde resin; determining whether the property of the
polyvinyl alcohol grafted urea-formaldehyde resin meets a
predetermined standard and taking an action selected from
wherein “n” is not strictly defined. These compounds are 40 the group consisting of: (a) if the property of the polyvinyl
resins containing various percentages of hydroxyl and usu alcohol grafted urea-formaldehyde resin meets the predeter
ally acetate groups or other functional groups and are mined standard, stop processing; and (b) if the property of
normally produced by hydrolysis of polyvinyl acetate or the polyvinyl alcohol grafted urea-formaldehyde resin does
other polymer that is capable of being hydrolyzed. The PVA not meet the predetermined Standard, further processing the
useful with embodiments of the invention will have a weight 45 polyvinyl alcohol grafted urea-formaldehyde resin, the fur
average molecular weight of from about 1,000 to about ther processing including: adding additional polyvinyl alco
200,000. In some embodiments the weight average molecu hol to the polyvinyl alcohol and urea-formaldehyde resin
lar weight will be from about 10,000 to about 100,000. In colloid under reaction conditions, Sufficient to condense the
still other embodiments the weight average molecular polyvinyl alcohol and the polyvinyl alcohol and urea-form
weight will be from about 10,000 to about 50,000. 50 aldehyde resin colloid to produce a further processed poly
In some embodiments of the application, admixing the vinyl alcohol and urea-formaldehyde resin colloid wherein
first working admixture with urea under reaction conditions the addition of polyvinyl alcohol is at a concentration
sufficient to initiate a methylolation reaction to form compatible with the polyvinyl alcohol and urea-formalde
an intermediate product admixture is part of the method. hyde resin colloid into which it is being placed. The method
A methylolation reaction is one where urea and formalde 55 continues by measuring a property of the further processed
hyde in alkaline or slightly acidic solution (formaldehyde/ polyvinyl alcohol and urea-formaldehyde resin colloid;
urea > 1.8-2.4) leads to urea-methylols or urea-hydroxym comparing the property of the further processed polyvinyl
ethyl species. For the purposes of the present application, the alcohol and urea-formaldehyde resin colloid to a predeter
reactants are urea and formaldehyde; and/or urea and pre mined standard; and repeating the further processing until
polymers of urea and formaldehyde. In some embodiments, 60 the further processed polyvinyl alcohol and urea-formalde
the conditions for methylolation will be a temperature of hyde resin colloid meets the predetermined standard.
about 80° C. and a pH of from about 8.5 to about 9.5. The One predetermined standard useful with all of the meth
pH may be adjusted using any method known to be useful ods of the application, but especially the post mixing method
to those of ordinary skill in the art. For example, triethyl is turbidity. It would be desirable in the art to produce
amine and triethanolamine may be used. 65 colloids that are clear to hazy or at least not too turbid. In
In some embodiments of the invention, the method con some embodiments, the colloids produced with the methods
tinues to a condensation phase after methylolation. Condi of the application have a turbidity of less than about 200
 US 9,499,672 B2
5 6
nephlometric turbidity units (NTU). In other embodiments, formaldehyde content was -0.2% after 72 hours. Selvol 205
the colloids produced with the methods of the application is a polyvinyl alcohol available from Sekisui Specialty
have a turbidity of less than about 100 NTU. For compari Chemicals.
son, drinking water typically has a turbidity of less than
about 5 NTU. 5 Example 2
The UF resins of the application may be prepared using
urea and formaldehyde, but sometimes it is desirable to use Preparation of UF-PVA 205 (58-5) Colloid from
a concentrate rather than the pure raw materials. It is UFC 85 and Solid PVA (Pre-Mixing)
common in the art use to UFC-85 which is available from
10 UFC 85 (699.7g), methanol (11.4 g), water (356.0 g) and
many vendors. Generally speaking, it is covered under CAS
No. 9011-5-6 and will have a urea content of about 25% and Selvol 205 (40.4 g) were charged into a 2000-mL flask. The
a formaldehyde content of about 60%, the remaining mate pH was adjusted using triethylamine and triethanolamine to
rial being water. about 8.5. The mixture was heated to 60° C. for approxi
In addition to PVA, other water soluble polymers may be mately 2 hours to obtain a clear to hazy liquid. Urea granules
15 (170.7 g) were charged into the flask. The mixture was
useful for formation of a colloid with UF. For example, heated to 80° C. and the pH was maintained at -8.5 until the
hydroxyethyl cellulose could be used. These water soluble resin gave a cloudy appearance upon cooling to 25° C.
polymers can be employed just as the PVA. Water soluble Subsequently, the pH was adjusted to 5-6 and the mixture
polymers that can be used include, but are not limited to: was heated to 100° C. Thereafter, the viscosity was mea
hydroxyethyl cellulose (HEC), polyethylene glycol, poly sured every 15 minutes. The temperature was reduced to 60°
propylene glycol, and polyethylene vinyl glycol. The use of C. and the pH was adjusted to ~7.5 using NaOH solution
HEC is illustrated below in Examples 13-15. when a desirable viscosity from 800 to 1,000 cps was
In some embodiments of the application, polyvinyl alco obtained and the water-based resin remained clear to hazy at
hol is used to form a colloid with a urea-formaldehyde resin. ambient temperatures. Urea (164.1 g) was charged into the
One end use for this colloid is as a binder for making 25
flask and stirred for a few minutes to obtain a clear to hazy
shingles. Advantageously, the colloids of the application liquid. The final product was either a clear or a hazy liquid.
have low turbidity and good shelf life. The total solid content was ~58%, and PVA content of the
The PVA-UF colloids prepared by the method of the total solid -5%. The pH was ~7, and the viscosity ~1,000
application may be employed in the same manner as a cPs. Free formaldehyde content was -0.2%.
30
conventional UF resin. For example, like UF resin, the Example 3
PVA-UF colloid is compatible some acrylic and/or vinyl
emulsions.
Preparation of UF-PVA 205 (58-4.5) Colloid from
EXAMPLES UFC 85 and Solid PVA (Pre-Mixing)
35

The following examples are provided to illustrate aspects UFC 85 (287.2 g), methanol (4.9 g), water (148.6 g) and
of the invention. The examples are not intended to limit the Selvol 205 (15.2 g) were charged into a 1000-mL flask. The
scope of the invention and they should not be so interpreted. pH was adjusted using triethylamine and triethanolamine to
Amounts are in weight parts or weight percentages unless about 8.5. The mixture was heated to 60° C. for approxi
otherwise indicated.
40 mately one hour and a clear to hazy liquid was obtained.
Urea granules (71.0 g) were charged into the flask. The
Example 1 mixture was heated to 80°C. and the pH was maintained at
~8.5 until the resin gave a cloudy appearance upon cooling
to 25°C. Next, the pH was adjusted to 5-6 and the mixture
Preparation of UF-PVA 205 (58-5) Colloid from 45 was heated to 100° C. Thereafter, the viscosity was mea
Formaldehyde and PVA Solid (Pre-Mixing) sured every 15 minutes. The temperature was reduced to 60°
C. and the pH was adjusted to 7.5 using NaOH solution
Methanol (4.6 g), 50% formaldehyde (341.3 g), water when a desirable viscosity from 500 to 700 cps was obtained
(46.0 g) and Selvol 205 (16.7 g) were charged into a and the water-based resin remained clear to hazy at ambient
1000-mL, flask. The mixture was heated to 80° C. for 50 temperatures. Urea (65.0 g) was charged into the flask and
approximately 2 hours at initial pH of ~4 until a clear to hazy stirred for a few minutes to obtain a clear to hazy liquid. The
liquid was obtained. After the pH was adjusted using trieth final product was either a clear or a hazy liquid. The total
ylamine and triethanolamine to about 8.5, urea granule solid content was ~58%, and PVA content of the total solid
(141.3 g) was charged into the flask. The pH was adjusted ~4.5%. The pH was ~7, and the viscosity -500 cBs. Free
to 8-9 and the mixture was heated to 90° C. until the resin 55 formaldehyde content was -0.2% after 72 hours.
gave a cloudy appearance upon cooling to 25° C. Next, the
pH was adjusted to 5-6 and the mixture was heated to 100° Example 4
C. Thereafter, the viscosity was measured every 15 minutes.
The temperature was reduced to 60° C. and the pH was Preparation of UF-PVA 205 (44-10) Colloid from
adjusted to ~7.5 using NaOH solution when a desirable 60 Formaldehyde and Solid PVA (Pre-Mixing)
viscosity from 800 to 1,000 cps was obtained and the
water-based resin remained clear to hazy at ambient tem Methanol (4.9 g), 50% formaldehyde (341.2 g), water
peratures. Urea (69.15 g) was charged into the flask and (24.7 g) and Selvol 205 (33.6 g) were charged into a
stirred for a few minutes to obtain a clear to hazy liquid. The 1000-mL, flask. The mixture was heated to 80° C. for
final product was either a clear or a hazy liquid. The solid 65 approximately 2 hours and a clear to hazy liquid was
content was ~58%, and PVA content of the total solid -5%. obtained. Urea (71.0 g) was charged into the flask. The
The pH was -7 and the viscosity from 800 cFs. Free mixture was heated to 80°C. and the pH was maintained at
 US 9,499,672 B2
7 8
~8.5 until the resin gave a cloudy appearance upon cooling Example 7
to 25°C. Next, the pH was adjusted with formic acid to from
~5 to ~6 and the mixture was heated to 100° C. Thereafter, Preparation of UF-PVA 205 (58-5) Colloid From
the viscosity was measured every 15 minutes. The tempera UFC 85 and PVA Solution (Mid-mixing)
ture was reduced to 60° C. and the pH was adjusted to 7.5 UFC 85 (631.9 g), water (165.5 g) and urea (145.0 g) were
using NaOH solution when the viscosity reached ~600 cps charged into a 2000-mL flask. The mixture was heated to 80°
and the water-based resin remained clear to hazy at ambient C. and the pH was maintained at ~8.5 until the resin gave a
temperatures. Urea (69.1 g) and water (93.0 g) were charged cloudy appearance upon cooling to 25°C. Next, the pH was
into the flask and stirred for a few minutes to obtain a clear adjusted with formic acid to from ~5 to ~6 and the mixture
10
to hazy liquid. The final product was a hazy liquid. The solid was heated to 100° C. Thereafter, the viscosity was mea
content was ~.44%, and PVA content of the total solid ~10%. sured every 15 minutes until the viscosity reached ~150 cps.
The pH was ~7, and viscosity ~1,000 cps. Free formalde The clear to hazy mixture was cooled down to 80° C. and
hyde content was ~1.8% after 72 hours. then 20% Selvol 205 (184.2 g) was charged into flask. The
15
temperature was maintained at 80° C. and pH at ~6 until the
Example 5 viscosity reached 500 cps and the water-based resin
remained clear to hazy at ambient temperatures. Next, the
Preparation of UF-PVA 502 (52-10) Colloid from temperature was reduced to 60° C. and the pH was adjusted
UFC 85 and PVA Solution (Mid-Mixing) to 7.5 using NaOH solution. Urea (151.0 g) was charged into
the flask and stirred for a few minutes to obtain a clear to
hazy liquid. The final product was either a clear or a hazy
UFC 85 (632.6 g), methanol (13.5 g), water (178.0 g) and liquid. The solid content was ~58%, and PVA content of the
urea (156.3 g) were charged into a 2000-mL flask. The total solid -5%. The pH was ~7 and the viscosity ~500 cps.
mixture was heated to 80°C. and the pH was maintained at Free formaldehyde content was -0.2% after 72 hours.
~8.5 until the resin gave a cloudy appearance upon cooling
to 25°C. Next, the pH was adjusted with formic acid to from 25 Example 8
~5 to ~6 and the mixture was heated to 100° C. Thereafter, Preparation of UF-PVA 513 (58-2) Colloid from
the viscosity was measured every 15 minutes until it reached UFC 85 and PVA Solution (Mid-Mixing)
150 cps. The clear to hazy mixture was cooled down to 80°
C. and then 20% Selvol 502 (373.4 g) was charged into flask. UFC 85 (632.3 g), water (178.1 g) and urea (156.4 g) were
30
The temperature was maintained at 80° C. and pH about 6 charged into a 2000-mL flask. The mixture was heated to 80°
until a desirable viscosity from 300 to 500 cps was obtained C. and the pH was maintained at ~8.5 until the resin gave a
and the water-based resin remained clear to hazy at ambient cloudy appearance upon cooling to 25°C. Next, the pH was
temperatures. Subsequently, the temperature was reduced to adjusted with formic acid to 5-6 and the mixture was heated
60° C. and the pH was adjusted to 7.5 using NaOH solution. to 100° C. Thereafter, the viscosity was measured every 15
Urea (151.0 g) was charged into the flask and stirred for a
35 minutes until the viscosity reached 150 cps. The clear to
few minutes. The final product was either a clear or a hazy hazy mixture was cooled down to 80° C. and then 20%
liquid. The total solid content was ~52%, and PVA content Selvol 513 (184.2 g) was charged into flask. The temperature
of the total solid ~10%. The pH was ~7 and the viscosity was maintained at 80° C. and pH at ~6 until the water-based
-350 cBs. Free formaldehyde content was -0.2% after 72 resin remained clear to hazy at ambient temperatures and the
40 viscosity reached -250 cps. Next, the temperature was
hours. Selvol 502 is a polyvinyl alcohol available from reduced to 60° C. and the pH was adjusted to 7.5 using
Sekisui Specialty Chemicals. NaOH solution. Urea (151.0 g) was charged into the flask
Example 6 and stirred for a few minutes to obtain a clear to hazy liquid.
The final product was either a clear or a hazy liquid. The
45 solid content was ~58%, and PVA content of the total solid
Preparation of UF-PVA 502 (58-5) Colloid from ~2%. The pH value was ~7 and the viscosity -250 cps. Free
UFC 85 and PVA Solution (Mid-Mixing) formaldehyde content was -0.2% after 72 hours. Selvol 513
is a polyvinyl alcohol available from Sekisui Specialty
UFC 85 (632.5g), methanol (10.7g), water (178.0 g) and Chemicals.
urea (156.3 g) were charged into a 2000-mL flask. The 50 Preparation of UF Precursor from UFC 85
mixture was heated to 80°C. and the pH was maintained at UFC 85 (586.8 g), water (89.9 g) and urea (91.3 g) were
~8.5 until the resin gave a cloudy appearance upon cooling charged into a 1000-mL flask. The mixture was heated to 80°
to 25°C. Next, the pH was adjusted with formic acid to 5-6 C. and the pH was maintained at ~8.5 until the resin gave a
and the mixture was heated to 100° C. Thereafter, the cloudy appearance upon cooling to 25°C. Next, the pH was
Viscosity was measured every 15 minutes until the Viscosity 55 adjusted with formic acid to from ~5 to ~6 and the mixture
reached ~150 cps. The clear to hazy mixture was cooled was heated to 100° C. Thereafter, the viscosity was mea
down to 80° C. and then 20% Selvol 502 (187.4 g) was sured every 15 minutes until the viscosity reached ~200 cps
charged into flask. The temperature was maintained at 80°C. was obtained. The final product was a hazy liquid; the solid
and pH -6. The temperature was reduced to 60° C. and the content was ~60%.
pH was adjusted to 7.5 using NaOH solution when the 60
water-based resin remained clear to hazy at ambient tem Example 9
peratures and the viscosity reached -250 cps. Urea (152.0 g)
was charged into the flask and stirred for a few minutes. The Preparation of UF-PVA 502 (58-5) Colloid from
final product was either a clear or a hazy liquid. The total the UF Precursor and PVA Solution (Mid-Mixing)
solid content was 58%, the PVA content of the total solid 65
~5%. The pH was ~7 and viscosity ~200 cps. Free formal The UF precursor (107.9 g) and 20% Selvol 502 (20.5 g)
dehyde content was -0.2% after 72 hours. were charged into a 500-mL flask and a cloudy mixture was
 US 9,499,672 B2
9 10
formed. The pH was adjusted using formic acid to 6 and the temperature was reduced to 60° C. and the pH value was
mixture was heated to 80°C. Thereafter, the viscosity was adjusted to 7.5 using NaOH solution. Urea (16.3 g) was
measured every 15 minutes until the viscosity about 200 cps charged into the flask and stirred for a few minutes to obtain
was obtained and the water-based resin remained clear to a clear to hazy liquid. The final product was either a clear or
hazy at ambient temperatures. Next, the temperature was a hazy liquid. The solid content was 58%, and PVA content
reduced to 60° C. and the pH was adjusted to 7.5 using of the total solid -5%. The pH value was ~7 and the
NaOH solution. Urea (16.0 g) was charged into the flask and viscosity -380 cps. Free formaldehyde content was -0.2%
stirred for a few minutes to obtain a clear to hazy liquid. The after 72 hours.
final product was either a clear or a hazy liquid. The solid
content was 58%, and PVA content of the total solid -5%. 10 Comparative Example A
The pH value was ~7 and the viscosity ~140 cps. Free
formaldehyde content was -0.2% after 72 hours. Baseline UF

Example 10 UF-127 (or UF-472X) is a commercial UF resin available

15
from Momentive Specialty Materials Inc. and was used as
Preparation of UF-PVA 203 (58-5) Colloid from the experimental baseline.
the UF Precursor and PVA Solution (Mid-Mixing)
Comparative Example B
The UF precursor (107.0 g) and 20% Selvol 203 (20.2 g)
were charged into a 500-mL flask and a cloudy mixture was Control UF-Latex
formed. The pH was adjusted with formic acid to 6 and the
mixture was heated to 80°C. Thereafter, the viscosity was A mixture of UT-472X and commercial Rhoplex RL-720
measured every 15 minutes until the viscosity reached about emulsion (4% or 10% by weight of the solid based on the
200 cps and the water-based resin remained clear to hazy at total solids) was used as an experimental control. Rhoplex
ambient temperatures. Next, the temperature was reduced to 25 RL-720 is a commercial product produced by The Dow
60° C. and the pH was adjusted to 7.5 using NaOH solution. Chemical Company.
Urea (16.5 g) was charged into the flask and stirred for a few
minutes to obtain a clear to hazy liquid. The final product Example 13
was either a clear or a hazy liquid. The Solid content was
58%, and PVA content of the total solid -5%. The pH was 30 Preparation of UF-HEC WP-09L (60-2) Colloid
~7 and the viscosity ~150 cps. Free formaldehyde content from UFC 85 and HEC Solution (Pre-Mixing)
was -0.2% after 72 hours. Selvol 203 is a polyvinyl alcohol
available from Sekisui Specialty Chemicals. UFC 85 (632.3 g), methanol (10.3 g), water (100.2 g) and
10% HEC WP-09 (168.8 g) were charged into a 1000-mL
Example 11 35 flask. The pH was adjusted using triethylamine and trietha
nolamine to about 8.5. The mixture was heated to 60° C. for
Preparation of UF-PVA 504 (58-5)-Colloid from approximately 30 minutes and a clear to hazy liquid was
the UF Precursor and PVA Solution (Mid-Mixing) obtained. Urea (156.5 g) was charged into the flask. The
mixture was maintained at 60° C. and the pH was main
The UF precursor (106.9 g) and 20% Selvol 504 (20.7g) 40 tained at ~8.5 until it became cloudy at 25°C. Next, the pH
were charged into a 500-mL flask and a cloudy mixture was was adjusted to from ~5 to ~6 and the mixture was heated
formed. The pH was adjusted with formic acid to 6 and the to 100° C. Thereafter, the viscosity was measured every 15
mixture was heated to 80°C. Thereafter, the viscosity was minutes until the reaction mixture became a clear or hazy
measured every 15 minutes until the viscosity was about 200 liquid. The temperature was reduced to 60° C. and the pH
cPs and the water-based resin remained clear to hazy at 45 was adjusted to 7.5 using NaOH when a desirable viscosity
ambient temperatures. Next, the temperature was reduced to reached to about 1,000 cps and the water-based resin
60° C. and the pH was adjusted to 7.5 using NaOH solution. remained hazy or translucent, but no phase separation at
Urea (16.5 g) was charged into the flask and stirred for a few ambient temperatures. Urea (150.2. g) was charged into the
minutes to obtain a clear to hazy liquid. The final product flask and stirred for a few minutes to obtain a translucent
was either clear or hazy liquid. The solid content was 58%, 50 liquid. The total solid content was ~60%, and HEC content
and PVA content of the total solid -5%. The pH value was of the total solid -2%. The pH was ~7, and the viscosity
~7 and the viscosity ~180 cps. Free formaldehyde content ~1,200 cBs. Free formaldehyde content -0.2% after 72
was -0.2% after 72 hours. Selvol 504 is a polyvinyl alcohol hours.
available from Sekisui Specialty Chemicals.
55 Example 14
Example 12
Preparation of UF-HEC WP-09L (60–3) Colloid
Preparation of UF-PVA 205 (58-5) Colloid from from UFC 85 and HEC Solution (Pre-Mixing)
the UF Precursor and PVA Solution (Mid-Mixing)
60 UFC 85 (287.7 g), methanol (5.1 g), water (17.6 g) and
UF precursor (2724-157) (106.0 g) and 20% Selvol 205 10% HEC WP-09 (114.8 g) were charged into a 500-mL
(20.4 g) were charged into a 500-mL flask and a cloudy flask. The pH was adjusted using triethylamine and trietha
mixture was formed. The pH was adjusted with formic acid nolamine to about 8.5. The mixture was heated to 60° C. for
to ~6 and the mixture was heated to 80° C. Thereafter, the approximately 30 minutes and a clear to hazy liquid was
Viscosity was measured every 15 minutes until the Viscosity 65 obtained. Urea (70.9 g) was charged into the flask. The
reached approximately 400 cps and the water-based resin mixture was maintained at 80° C. and the pH was main
remained clear to hazy at ambient temperatures. Next, the tained at ~8.5 until it became cloudy at 25°C. Next, the pH
 US 9,499,672 B2
11 12
was adjusted to 5-6 and the mixture was heated to 100° C. equipped with a mechanical agitator under agitation at 500
Thereafter, the viscosity was measured every 15 minutes rpm for 30 seconds, and then 400 g of 0.23% of Cytec
until the reaction mixture became a clear or hazy liquid. The Superfloc A-130 Flocculent solution was added into the
temperature was reduced to 60° C. and the pH was adjusted vessel under the agitation for 60 seconds. The glass fiber
to 7.5 using NaOH when a desirable viscosity reached to 5
slurry was introduced onto a 12x12 inch (30.5x30.5 cm)
about 1,500 cps and the water-based resin remained hazy or fabric mat casting mode equipped with a wire Support mesh
translucent, but no phase separation at ambient tempera with a plastic fabric. The wet glass mat with the plastic
tures. Urea (68.1 g) was charged into the flask and stirred for fabric was passed through a vacuum slot to remove excess
a few minutes to obtain a translucent liquid. The total solid 10
water. The liquid binder containing ~18% solid by weight
content was ~60%, and HEC content of the total solid -2%. was applied on the wet glass mat and passed through the
The pH was ~7, and the viscosity ~1,800 cps. Free form vacuum slot again to remove excess binder for a desirable
aldehyde content -0.2% after 72 hours. weight based on the certain LOI (Loss on ignition). A wet
glass mat with binder was cured on Methis Labdryer at 375
Example 15 15
F. (190° C.) for 3 minutes or 400°F. (205°C.) for 3 minutes.
Measurement of Properties of Glass Mat Samples
Preparation of UF-HEC WP-09L (52-4) Colloid Dry Tensile Strength (DT)
from UFC 85 and HEC Solution (Pre-Mixing) The cured glass mat hand sheet was cut in 1.5x4.0 inch
(3.81x10.16 cm) rectangular specimen. Total eighteen speci
UFC 85 (258.2 g), water (74.2 g) and 10% HEC WP-09 mens from three hand sheets were measured on Instron 5566
(137.3 g) were charged into a 1000-mL flask. The pH was to get an average tensile strength.
adjusted using triethylamine and triethanolamine to about Wet Tensile Strength (WT)
8.5. The mixture was heated to 60°C. for approximately 30 The cured glass mat hand sheet was cut in 1.5x4.0 inch
minutes and a clear to hazy liquid was obtained. Urea (3.81x10.16 cm) rectangular specimen. Total eighteen speci
granules (63.9 g) were charged into the flask. The mixture mens from three hand sheets were soaked in water at 80° C.
25
was maintained at 80°C. and the pH was maintained at ~8.5 for 10 min in a Microprocess Controlled 280 water bath
until it became cloudy at 25°C. Next, the pH was adjusted (Precision). Excess of water in the specimen was removed
to 5-6 and the mixture was heated to 100° C. Thereafter, the with paper towel. The specimens were immediately mea
Viscosity was measured every 15 minutes until the reaction Sured on the Instron.
mixture became a clear or hazy liquid. The temperature was Tear Test
30
reduced to 60° C. and the pH was adjusted to 7.5 using The cured glass mat hand sheet was cut in 2.5x12.0 inch
NaOH when a desirable viscosity reached to about 500 cBs (6.35x30.48 cm) rectangular specimen. Three specimens
and the water-based resin remained haze or translucent, but from three hand sheets were measured on Elmendorf Tearing
no phase separation at ambient temperatures. Urea (62.0 g) Tester (Thwing-Albert Instrument Co.) in six times to get an
was charged into the flask and stirred for a few minutes to 35
average measurement.
obtain a hazy liquid. The total solid content was ~52%, and Caliper Test (Caliper Thickness)
HEC content of the total solid ~4%. The pH was ~7, and the The cured glass mat hand sheet was cut in 1.5x4.0 inch
viscosity 500 cps. Free formaldehyde content -0.2% after (3.81x10.16 cm) rectangular specimen. Total twenty one
72 hours. sheets from three hand sheets as one specimen were mea
40
Sured on a Mahr Federal dial drop indicator and an average
Preparation and Testing of Glass Mat Hand Sheets thickness of a single sheet was obtained. Average thickness
for Examples 1-15 for individual sheet ranged from 35 to 40 mils (0.89 to 1.02
mm).
Preparation of 18% UF-PVA Binders Wet Web Strength (WWS)
Concentrated UF-PVA colloid (-5.8% by weight) was 45
After the liquid binder was applied on 12.0x12.0 inch
diluted with D.I. water to ~18% by weight. The liquid binder (30.5x30.5 cm) square glass sheet hand sheet, the glass sheet
was a clear to hazy liquid and the Viscosity was less than 8 was vacuumed to the desirable wet weight based on a certain
cPs. The diluted colloid provided approximately 10 days LOI (Loss on ignition). The wet sheet was laid over a sheet
shelf life. of plastic with a 6-inch (15.2 cm) diameter hole in the center.
Treatment of Glass Fiber
50
A clear plastic sheet 4" (0.64 cm) thick with an identical
According to moisture content measured on Cenco mois 6-inch (15.24 cm) diameter hole was placed on top of the
ture balance, 7.7 g of wet glass fiber OC9501 (Owens hand sheet to secure it. A 2/8" (5.4 cm) diameter disc
Corning) with an average % inch (19 mm) length and 18 holding a paper cup was then centered over the hole and
micron diameter were immersed in 40 g of D.I. water with gently lowered onto the hand sheet. Water from a 250 ml
0.6 g of Rhodia VP-532/SPB for at least 2 hours. 55
burette was added at a constant rate to the cup until the web
Preparation of Glass Mat Hand Sheet elongates a vertical distance of 24 mm and touches to the
The treated glass fiber was placed into 8 gallon (30 liters) bottom plastic plate. The wet web strength in grams was the
of warm water about 50° C. in a 17-gallon (64-liter) vessel weight of the cup plus the added water at the 'sag' point.
TABLE 1.

Performance of Control (UF-Latex) and Baseline (UF resin

C- C- C- Wet- Cure
Sample LOI, 9% WT WT DT DT Tear Caliper web conditions
UF 18.9 30.3 30.2 S1.8 S1.7 266 381 82 375 F.3 min
19.4 31.9 32.7 45.3 46.6 284 37.4 400 F.3 min
 US 9,499,672 B2
TABLE 1-continued
Performance of Control (UF-Latex) and Baseline (UF resin

C- C- C- Wet- Cure
Sample LOI, 9% WT WT DT DT Tear Caliper web conditions
UF-127 GL 18.9 37.5 37.4 72.1 71.8 289 40.O 194 375 F.3 min
720 4% 18.5 SO.O 48.8 72.3 70.6 278 40.6 400°F.3 min
UF-127 GL- 19.2 49.8 S.O.6 77.4 78.6 263 40.4 173 375 F.3 min
720(10%) 18.5 52.8 S1-S 76.8 7S.O 282 39.5 400°F.3 min

C-WT Corrected Wet Tensile, lbf 1.5"

C-DT Corrected Dry Tensile, lbf 1.5"
C-Tear Corrected Tear Test, gif
Caliper Thickness, mil
WTWet Tensile, lbf 1.5"
DTDry Tensile, lbf 1.5"
W-Web Wet Web Strength, gif
LOILoss on Ignition

TABLE 2
Performance of UF-PVA Colloid on Glass Mat

C- C- C- Wet- Cure
Sample/experiment LOI 96 WT WT DT DT Tear Caliper web conditions
Example 7 19.1 51.8 S2.1. 84.7 85.2 339 38.7 212.1 375 F.3 min
19.1 52.4 52.7 81.0 81.S 344 39.4 400 F.3 min
Example 6 19.1 SO.7 51.0 80.4 80.9 305 39.4 133.8 375 F.3 min
19.0 38.7 38.8 64.9 65.1 291 39.4 400 F.3 min
Example 5 19.0 54.3 S4S 82.9 83.2 314 37.8 1838 375 F.3 min
18.9 58.2 58.2 80.3 80.2 333 37.9 400 F.3 min
Example 8 19.0 47.3 47.3 73.5 73.6 281 38.3 119.4 375 F.3 mill
18.9 51.1 S1.O 67.8 67.8 315 39.0 400 F.3 min
Example 2 19.0 62.8 62.9 88.2 88.3 449 36.3 1936 375 F.3 min
19.0 60.5 60.5 85.4 85.5 427 35.4 400 F.3 min

C-WT Corrected Wet Tensile, lbf 1.5"

C-DT Corrected Dry Tensile, lbf 1.5"
C-Tear Corrected Tear Test, gif
Caliper Thickness, mil
WTWet Tensile, lbf 1.5"
DTDry Tensile, lbf 1.5"
W-Web Wet Web Strength, gif
LOILoss on Ignition
40

The data are rounded. became a white opaque colloid after cool down. The total
solid content of the colloid was 50% by weight and PVA
Example 16 content was 13.3% of the total solid. Viscosity was 225 cFs,
45
and pH was 6.74.
Preparation of UF-PVA 502 (50-13-4) Colloid by Example 18
Grafting UF on PVA (Post Mixing)
Preparation of UF-PVA 502 (55-10-3) Colloid by
60.4 g of UF resin FG-127 (65% solid) and 30.0 g of 20% Reaction of UF with PVA (Post Mixing)
Selvol 502 solution were charged into a 250-mL flask to 50
form a two-phase mixture. The mixture was heated at 80°C. 855.0 g of UF resin FG-127 (65% by solid) and 206.1 g
for 4 hours at an initial pH of ~7.5 to obtain a clear liquid. of water were charged into a 2000-mL flask, 61.8g of Selvol
The liquid became a white opaque colloid after cool down. 502 granules was introduced into the flask with agitation at
Total solid content was 50% by weight and PVA content was ambient temperature. The mixture was heated at 80° C. for
13.3% of the total solid. Viscosity was 821 cl’s, and the pH 55 3 hours at initial pH -7.5 to form a clear liquid. It became
value was 6.69. a stable white opaque colloid after cool down. Viscosity was
790 cFs, and pH was 6.80. Total solid content of the colloid
Example 17 was 55% by weight and PVA content was 10% of the total
solid. The product was diluted to 17.6% solid content prior
Preparation of UF-PVA 502 (50-13-2) Colloid by 60
to the use. Viscosity was 5.6 cl’s, and pH was 6.75.
Reaction of UF with PVA (Post Mixing) Example 19
100.5 g of UF resin FG-127 (65% solid) and 40.0 g of Preparation of UF-PVA 513 (50-8-2) Colloid by
water were charged into a 250-mL flask, 10.0 g of Selvol 502 Reaction of UF with PVA (Post Mixing)
granules was introduced into the flask with agitation at 65
ambient temperature. The mixture was heated at 80° C. for 921.8g of UF resin FG-127 (65% by weight) and 328.4
2 hours at an initial pH of ~7.5 to form a clear liquid. It g of water were charged into a 2000-mL flask, 52.0 g of
 US 9,499,672 B2
15 16
Selvol 513 was introduced into the flask with agitation at Selvol 205 was introduced into the flask with agitation at
ambient temperature. The mixture was heated at 80° C. for ambient temperature. The mixture was heated at 80° C. for
2 hours at an initial pH of ~7.5 to form a clear liquid. The 2.5 hours at initial pH~7.5 to form a clear liquid. It became
liquid became a stable white opaque colloid after cool down. a white opaque colloid after cool down. The pH was adjusted
Total solid content of colloid was 50% by weight and PVA 5 with dimethylaminoethanol from 6.94 to 7.73. Viscosity was
content was 8.0% of the total solid. Viscosity was 1,080 cps, 374 cBs. Total solid content of the colloid was 55% by
pH was 6.95. The product was diluted to 16% solid content weight and PVA content was 5.0% of the total solid. The
prior to the use. Viscosity was 12.4 cps, and pH was 6.84. product was diluted to 17% solid content prior to the use.
Viscosity was 4.14 cps, pH value was 7.70.
Example 20 10
Comparative Example C
Preparation of UF-PVA 502 (60-5-3) Colloid by
Reaction of UF with PVA (Post Mixing) Preparation of UF-Latex RL-720 (4%) Binder as a
Control Sample
759.1 g of UF resin FG-127 (65% by solid) and 80.7 g of
water were charged into a 2000-mL flask, 26.0 g of Selvol 699.9 g of UF resin FG-127 (65% by weight), 40.6 g of
502 was introduced into the flask with agitation at ambient GL-720 (47% solid), and 1894.0 g of D.I. water were mixed
temperature. The mixture was heated at 80° C. for 3 hours in a 3000-mL container to give a milky white liquid. Total
at initial pH ~7.5 to form a clear liquid. The liquid became solid content of the liquid was 18%, by weight and latex
a stable white opaque colloid after cool down. Viscosity was RL-720 was 4% by weight of the total solid. Viscosity was
1,250 cps, and pH was 6.99. Total solid content of the 2.34 cFs, pH value was 7.23.
colloid was 60% by weight and PVA content was 5% of the
total solid. The product was diluted to 17.6% solid content Comparative Example D
prior to use. Viscosity was 3.7 cFs, and pH was 6.79. 25
Preparation of UF-Latex RL-720 (10%) Binder as a
Example 21 Control Sample
Preparation of UF-PVA 513 (55-4-3) (Colloid by 650.0 g of UF resin FG-127 (65% by weight), 100.1 g of
Reaction of UF with PVA (Post Mixing) 30 GL-720 (47% solid), and 1857.3 g of D.I. water were mixed
in a 3000-mL container to give a milky white liquid. Total
736.3 g of UF resin FG-127 (65% by weight) and 150.6 solid content of the liquid was 18% by weight and latex
g of water were charged into a 2000-mL flask, 20.0 g of RL-720 was 10% by weight of the total solid. Viscosity was
Selvol 513 was introduced into the flask with agitation at 35
2.31 cl’s, pH value was 6.82.
ambient temperature. The mixture was heated at 80° C. for
3 hours at initial pH ~7.5 to form a clear liquid. It became Comparative Example E
a stable white opaque colloid after cool down. Total solid
content of colloid was 50% by weight and PVA content was Preparation of UF-PVA 205 Solution (10%) Binder
4.0% of the total solid. Viscosity was 1,130 cps, pH was 40
as a Control Sample
6.93. The product was diluted to 16% solid content prior to
the use. Viscosity was 3.7 cps, and pH was 6.79. 600.0 g of UF resin FG-127 (65% by weight), 263.8g of
D.I. water, and 216.0 g of 20% Selvol 502 solution were
Example 22 mixed in a 3000-mL flask. The liquid became two phases
45 after stop stirring for a while. Additional water was charged
Preparation of UF-HEC WP-09L (50-8-1.5) Colloid into the mixture to form 20% homogeneous solution. Total
by Reaction of UF with HEC (Post Mixing) solid content of the solution was 20% by weight and PVA
was 10% by weight of the total solid. Viscosity was 4.14.
885.5 g of UF resin FG-127 (65% by weight) and 316.2 and pH was 7.17. A white precipitant was observed after a
g of water were charged into a 2000-mL flask, 50.0 g of HEC 50 few hours.
WP-09L powder was introduced into the flask with agitation
at ambient temperature. The mixture was heated at 80°C. for Preparation and Testing of Glass Mat Hand Sheets
1.5 hours at initial pH -7.5 to form a clear slightly yellow for Examples 16-Comparative Example E
liquid. It became an off-white opaque colloid after cool
down. Viscosity was 7,538 cps, and pH was 6.92. The total 55 Preparation of 16-18% UF-PVA Colloid
solid content of the colloid was 50% by weight and HEC
content was 8.0% of the total solid. The colloid was diluted Concentrated UF-PVA colloid (50-65% by weight) was
with water to 14% solid content prior to the use. Viscosity diluted with D.I. water to 16-18% by weight. The liquid
was 12.5 cFs, and pH value was 6.8. binder is a white milky colloid with viscosity at 10 cps or
60 less. The diluted colloid provided two days stability without
Example 23 settlement.
Treatment of Glass Fiber
Preparation of UF-PVA 205 (55-5-2.5) Colloid by Same as Above
Reaction of UF with PVA (Post Mixing) Preparation of Wet Glass Mat
65 Same as above.
877.8 g of UF resin FG-127 (65% by weight) and 184.7 Measurement of Properties of Glass Mat Samples
g of water were charged into a 2000-mL flask, 30.0 g of Dry Tensile Strength (DT)
 US 9,499,672 B2
17 18
Same as above diameter hole in the center. A clear plastic sheet /4" (0.64
Wet Tensile Strength (WT) cm) thick with an identical 6-inch (15.24 cm) diameter hole
is above was placed on top of the hand sheet to secure it. A 2/s" (5.4
Same as above cm) diameter disc holding a paper cup was then centered
Caliper Test (Caliper Thickness) over the hole and gently lowered onto the hand sheet. Water
Same as above.
Wet Web St h (WWS from a 250 ml burette was added at a constant rate to the cup
Air s SE Sios cm) Square glass mat hand until the web elongates a vertical distance of 24 mm and
sheet was casted, it was vacuumed to the target wet weight touches to the bottom plastic plate. The wet web strength in
based on a certain LOT (Loss on ignition). The wet sheet grams was the weight of the cup plus the added water at the
was laid over a sheet of plastic with a 6-inch (15.24 cm) “Sag point.
TABLE 3
Properties of Control Sample of UF-Latex (FG-127-Rhoplex' RL720
Sample LOI WT DT Tear Caliper WWS Cure Condition
FG-127/GL-720(4) 18.9 37.4 71.8 289 40.0 194 375° F (190° C.)/3 min
Comp Ex. C 18.5 48.8 70.6 278 40.6 400° F. (205 °C.)/3 min
FG-127/GL-720(10) 19.2 50.6 78.6 263 40.4 173 375° F (190° C.)/3 min
Comp Ex. D 18.5 S1-S 7SO 282 39.5 400° F. (205 °C.)/3 min
LOI: Loss on Ignition, %
DT. Dry Tensile Strength, lbf 1.5" width
Caliper: Thickness, mil
UF resin FG-127 and FG-472X are identical Momentive products.
Tear: Tear Strength, gif
WT: Wet Tensile Strength, lbf 1.5" width
WWS: Wet Web Strength, gif

TABLE 4
Properties of UF-PVA Solution
Sample LOI WT DT Caliper WWS Cure Condition
FG-127/PVA 502(10) 19.0 55.0 85.4 38.4 188 375° F (190° C.)/3 min
Solution 19.02 S6.6 8SO 35.7 400° F. (205 °C.)/3 min
Comp Ex. E)
LOI: Loss on Ignition, %
DT. Dry Tensile Strength, lbf 1.5" width
Caliper: Thickness, mil
UF resin FG-127 and FG-472X are identical Momentive products,
WT: Wet Tensile Strength, lbf 1.5" width
WWS: Wet Web Strength, gif

TABLE 5
Properties of Glass Mat with UF Derivative Colloids
Sample LOI WT DT Tear Caliper WWS Cure Condition
FG-127Selvo1502(55-10-3) 18.9 541 81.3 366 36.4 168 375°
F (190 C.)/3 min
Ex. 18 19.0 S7.6 75.6 333 35.7 400°
F. (205 C.)/3 min
FG-127/Selvols13(50-8-2) 18.6 SO.7 93.1 372 36.5 204 375°
F (190 C.)/3 min
Ex. 19 18.9 59.8 88.7 328 36.3 400°
F. (205 C.)/3 min
FG-127/Selvols02(60-5-3) 18.8 49.2. 69.8 362 34.6 194 375°
F (190 C.)/3 min
Ex. 20 18.8 55.5 75.0 382 36.6 400°
F. (205 C.)/3 min
FG-127/SelvolS13(55-4-3) 20.2 78.3 95.0 282 37.9 466 375°
F (190 C.)/3 min
Ex. 21 2O.O 75.4 94.1 329 35.3 400°
F. (205 C.)/3 min
FG-127/Selvol2O5(55-5-2.5) 18.9 52.6 91.1 390 34.0 229 375°
F (190 C.)/3 min
Ex. 22 19.0 60.7 85.7 337 35.5 400°
F. (205 C.)/3 min
FG-127/WP-09 (50-8-1.5) 18.9 32.2 65.1 336 36.9 126 375° F (190 C.)/3 min
Comp Ex. C 19.1 41.7 65.9 336 37.5 400° F. (205 C.)/3 min
LOI: Loss on Ignition, %
DT. Dry Tensile Strength, lbf 1.5" width
Caliper: Thickness, mil
UF resin FG-127 and FG-472X are an identical Momentive products.
Tear: Tear Strength, gif
WT: Wet Tensile Strength, lbf 1.5" width
WWS: Wet Web Strength, gif

The data are rounded.

 US 9,499,672 B2
19 20
What is claimed is: (b) if the property of the polyvinyl alcohol grafted
1. A binder prepared using a method selected from the urea-formaldehyde resin does not meet the prede
group consisting of termined standard, further processing the polyvi
(A) admixing polyvinyl alcohol with a component nyl alcohol grafted urea-formaldehyde resin, the
Selected from the group consisting of: further processing comprising:
a solution of formaldehyde, and adding additional polyvinyl alcohol to the poly
a urea/formaldehyde concentrate, vinyl alcohol and urea-formaldehyde resin col
to form a first liquid working admixture and then loid under reaction conditions, Sufficient to con
admixing the first liquid working admixture with urea dense the polyvinyl alcohol and the polyvinyl
under reaction conditions sufficient to initiate a 10 alcohol and urea-formaldehyde resin colloid to
methylolation reaction to form a reaction product produce a further processed polyvinyl alcohol
admixture of the first liquid working admixture with and urea-formaldehyde resin colloid wherein
urea; and the addition of polyvinyl alcohol is at a con
Subjecting the reaction product admixture to reaction centration compatible with the polyvinyl alco
conditions Sufficient to initiate a condensation to 15 hol and urea-formaldehyde resin colloid into
form a polyvinyl alcohol and urea-formaldehyde which it is being placed;
resin colloid; measuring a property of the further processed
(B) admixing a component selected from the group con polyvinyl alcohol and urea-formaldehyde resin
sisting of: colloid;
a solution of formaldehyde, and comparing the property of the further processed
a urea/formaldehyde concentrate, polyvinyl alcohol and urea-formaldehyde resin
with urea under reaction conditions sufficient to initiate
a methylolation reaction to form a reaction product colloid to a predetermined standard; and
admixture; repeating the further processing until the further
Subjecting the reaction product admixture to reactions 25 processed polyvinyl alcohol and urea-formal
conditions sufficient to initiate condensation to form dehyde resin colloid meets the predetermined
a second reaction product admixture; and standard.
admixing the second reaction product admixture with 2. The binder of claim 1 further comprising completing
polyvinyl alcohol to from a urea-formaldehyde resin the processes (A) or (B) by making a urea post addition.
colloid; and 30
3. The binder of claim 1, wherein the polyvinyl alcohol
(C) adding polyvinyl alcohol to a urea-formaldehyde resin used to prepare the binder has a weight average molecular
under reaction conditions sufficient to condense the weight of from about 1,000 to about 200,000.
polyvinyl alcohol and the urea-formaldehyde resin to
produce a polyvinyl alcohol and urea-formaldehyde 4. The binder of claim 3, wherein the polyvinyl alcohol
resin colloid wherein the addition of polyvinyl alcohol 35 has a weight average molecular weight of from about 1,000
is at a concentration sufficiently low to be compatible to about 50,000.
with the urea-formaldehyde resin solution into which it 5. The binder of claim 1, wherein the methylolation
is being placed; reactions occur at a temperature of about 80°C. and a pH of
measuring a property of the polyvinyl alcohol grafted from about 8.5 to about 9.5.
urea-formaldehyde resin: 40 6. The binder of claim 5, wherein the pH is adjusted using
determining whether the property of the polyvinyl triethylamine and triethanolamine.
alcohol grafted urea-formaldehyde resin meets a 7. An article of manufacture comprising an article pre
predetermined standard and taking an action selected pared using the binder of claim 1.
from the group consisting of 8. The article of manufacture of claim 7 wherein the
(a) if the property of the polyvinyl alcohol grafted 45
urea-formaldehyde resin meets the predetermined article of manufacture is a shingle.
standard, stop processing; and k k k k k