Patent Description:
Historically, asphalt roofing shingles were made from organic felt mats, principally formed from randomly arranged chopped cellulose fibers that are saturated with a hot asphalt and subsequently formed into asphalt roof shingles. In contrast, for modern applications, wet laid glass fiber mats have replaced the cellulose felt mats which provide increased service life, strength and improved fire resistance.

Unfortunately, fiberglass lacks the natural inter-fiber bonding that is inherent in the natural organic fiber such as cellulose. The chopped glass fibers when randomly disposed in a mat must be bonded together by a suitable binder. The binder adhesively secures crossed glass fibers together contributing to good handling of the mats during processing into fiberglass shingles as well as providing the necessary physical performance properties such as strength, flexibility and long life that is required during roof installation and during the service life of the roof.

As with any commercial concern, when making fiberglass reinforced shingles or any other fiberglass product, it is desirable that useful binders be as cost effective as possible while also having the necessary physical properties. In some aspects, urea-formaldehyde resins are desirable for this application. They are low-cost thermoset materials having a good adhesion, a fast cure rate, desirable mechanical properties, and a lengthy shelf life.

Unfortunately, urea formaldehyde resins without some form of modification may not have sufficient mechanical properties. It has sometimes been observed that formaldehyde resins are desirable for this application. They are low-cost thermoset materials having a good adhesion, a fast cure rate, desirable mechanical properties, and a lengthy shelf life.

Unfortunately, urea formaldehyde resins without some form of modification may not have sufficient mechanical properties. It has sometimes been observed that fiberglass sheathing prepared with urea formaldehyde resin binders may break during the production of glass mats for the use in the production of shingles. This shortcoming may be overcome however, through the use of water born polymers, such as, emulsion, dispersion and water-soluble polymers. One such waterborne polymer is polyvinyl alcohol.

Polyvinyl alcohol can be readily crosslinked with urea-formaldehyde resin at elevated temperatures to improve mechanical properties of urea-formaldehyde-based binder and also improve water resistance. However, urea-formaldehyde resin and polyvinyl alcohol water solution form a two-phase system due to immiscibility or limited compatibility, depending on the molecular weight (MW), degree of hydrolysis of polyvinyl alcohol, and
solid content of the formulation. Currently, it is customary in the art of making polyvinyl alcohol resin, that less than <NUM>% by weight, is mixed with urea-formaldehyde resin to enhance the urea-formaldehyde resin performance or add the small amount of urea-formaldehyde resin into polyvinyl alcohol solution to improve polyvinyl alcohol water resistance in commercial products. It would be desirable in the art to be able to increase the amount of <NUM> polyvinyl alcohol introduced into a urea formaldehyde resin to improve its performance as a binder.

<CIT> discloses a method of preparing an urea formaldehyde resin without using of polyvinyl alcohol. <CIT> is related to the use of thickening agents which are polymeric-type materials that are at least partially water soluble. <CIT> relates to urea formaldehyde fertilizer suspensions through a process for preparing a ureaform type resin fertilizer as an aqueous suspension with is stable.

In one aspect, the invention is a method for preparing polyvinyl alcohol and urea-formaldehyde colloid including: admixing polyvinyl alcohol with a component selected from the group consisting of: a solution of formaldehyde, and a urea/formaldehyde concentrate, to form a first liquid working admixture and then admixing the first liquid working admixture with urea under reaction conditions sufficient to initiate a methylolation reaction to form an intermediate product admixture; subjecting the intermediate product <NUM> admixture to reaction conditions sufficient to initiate condensation to form a colloid.

Additionally in some embodiments the method includes completing the process by making final urea post addition to produce a polyvinyl alcohol and urea-formaldehyde resin colloid.

In another aspect, the invention is a method for preparing polyvinyl alcohol and urea-formaldehyde colloid including: admixing a component selected from the group consisting of: a solution of formaldehyde and a urea/formaldehyde concentrate, with urea under reaction conditions sufficient to initiate a methylolation reaction to form an intermediate product admixture; subjecting the intermediate product admixture to reactions conditions sufficient to initiate condensation to form a second intermediate product admixture; admixing the second intermediate product admixture with polyvinyl alcohol to from a final intermediate liquid product including a polyvinyl alcohol and urea-formaldehyde colloid. Additionally in some embodiments the method includes completing the process by making final urea post addition to produce a polyvinyl alcohol and urea-formaldehyde resin colloid.

In still another aspect, the invention is a method for preparing polyvinyl alcohol urea-formaldehyde resin colloid including: adding polyvinyl alcohol to a urea-formaldehyde resin under reaction conditions sufficient to condense the polyvinyl alcohol and the urea-formaldehyde resin to produce a polyvinyl alcohol and urea-formaldehyde resin colloid wherein the addition of polyvinyl alcohol is at a concentration sufficiently low to be compatible with the urea-formaldehyde resin solution into which it is being placed; measuring a property of the polyvinyl alcohol grafted urea-formaldehyde resin; determining whether the property of the polyvinyl alcohol grafted urea-formaldehyde resin meets a predetermined standard and taking an action selected from the group consisting of: (a) if the property of the polyvinyl alcohol grafted urea-formaldehyde resin meets the predetermined standard, stop processing; and (b) if the property of the polyvinyl alcohol grafted urea-formaldehyde resin does not meet the predetermined standard, further processing the polyvinyl alcohol grafted urea-formaldehyde resin the further processing including: adding additional polyvinyl alcohol to the polyvinyl alcohol and urea-formaldehyde resin colloid under reaction conditions, sufficient to condense the polyvinyl alcohol and the polyvinyl alcohol and urea-formaldehyde resin colloid to produce a further processed polyvinyl alcohol and urea-formaldehyde resin colloid wherein the addition of polyvinyl alcohol is at a concentration compatible with the polyvinyl alcohol and urea-formaldehyde resin colloid into which it is being placed; measuring a property of the further processed polyvinyl alcohol and urea-formaldehyde resin colloid; comparing the property of the further processed polyvinyl alcohol and urea-formaldehyde resin colloid to a predetermined standard; and repeating the further processing until the further processed polyvinyl alcohol and urea-formaldehyde resin colloid meets the predetermined standard.

Another aspect of the invention is a method for the preparation of a binder using a polyvinyl alcohol urea-formaldehyde resin colloid prepared using any of the methods described above. These binders are particularly useful for preparing shingles. The polyvinyl alcohol used in the methods according to the invention has a weight average molecular weight of from <NUM>,<NUM> to <NUM>,<NUM>.

One embodiment of the invention is a method for preparing a polyvinyl alcohol and urea-formaldehyde colloid. In the method for preparing polyvinyl alcohol and urea-formaldehyde colloid, the method includes: admixing polyvinyl alcohol with a component selected from the group consisting of: a solution of formaldehyde and a urea/formaldehyde concentrate, to form a first liquid working admixture and then admixing the first liquid working admixture with urea under reaction conditions sufficient to initiate a methylolation reaction to form an intermediate product admixture; subjecting the intermediate product admixture to reaction conditions sufficient to initiate a condensation reaction; and completing the process by making a final urea post addition to produce a polyvinyl alcohol and urea-formaldehyde resin colloid.

For the purposes of this application, the term polyvinyl alcohol (hereinafter sometimes PVA) is defined to mean compounds having the general idealized formula:
<CHM>
wherein "n" is not strictly defined. These compounds are resins containing various percentages of hydroxyl and usually acetate groups or other functional groups and are normally produced by hydrolysis of polyvinyl acetate or other polymer that is capable of being hydrolyzed. The PVA of the invention will have a weight average molecular weight of from <NUM>,<NUM> to <NUM>,<NUM>. In some embodiments the weight average molecular weight will be from <NUM>,<NUM> to <NUM>,<NUM>. In still other embodiments the weight average molecular weight will be from <NUM>,<NUM> to <NUM>,<NUM>.

In some embodiments of the application, admixing the first working admixture with urea under reaction conditions sufficient to initiate a methylolation reaction to form an intermediate product admixture is part of the method. A methylolation reaction is one where urea and formaldehyde in alkaline or slightly acidic solution (formaldehyde/urea > <NUM> - <NUM>) leads to urea-methylols or urea-hydroxymethyl species. For the purposes of the present application, the reactants are urea and formaldehyde; and/or urea and prepolymers of urea and formaldehyde. In some embodiments, the conditions for methylolation will be a temperature of <NUM> and a pH of from <NUM> to <NUM>. The pH may be adjusted using any method known to be useful to those of ordinary skill in the art. For example, triethylamine and triethanolamine may be used.

In some embodiments of the invention, the method continues to a condensation phase after methylolation. Conditions known to be useful to those of ordinary skill in the art of preparing urea formaldehyde resins may be employed with the embodiments of the application. For example, in some embodiments, the condensation may be started and controlled by lowering the pH to from <NUM> to <NUM> and then heating the reaction solution to <NUM> - <NUM>.

This reaction may then be completed by making a final urea post addition. One of ordinary skill in the art will well know how to determine the final urea addition in order to achieve a specific property or properties. These first embodiments may be described as an early addition or a "pre-mixing" approach of polyvinyl alcohol and the other components of the resin.

In a "mid mixing" approach, the colloid is prepared by admixing a component selected from the group consisting of: a solution of formaldehyde and a urea/formaldehyde concentrate, with urea under reaction conditions sufficient to initiate a methylolation reaction to form an intermediate product admixture. This embodiment continues by then subjecting the intermediate product admixture to reactions conditions sufficient to initiate a condensation reaction to form a second intermediate product admixture; admixing the second intermediate product admixture with polyvinyl alcohol to form a final intermediate product solution; and completing the process by making final urea post addition.

Another approach to the method of the application is a "post mixing" approach. In these embodiments, the polyvinyl alcohol is added to a urea-formaldehyde resin under reaction conditions sufficient to react the polyvinyl alcohol and the urea-formaldehyde resin to produce a polyvinyl alcohol and urea-formaldehyde resin colloid wherein the addition of polyvinyl alcohol is at a concentration sufficiently low to be compatible with the urea-formaldehyde resin solution into which it is being placed. This embodiment of the methods of the application continues by measuring a property of the polyvinyl alcohol grafted urea-formaldehyde resin; determining whether the property of the polyvinyl alcohol grafted urea-formaldehyde resin meets a predetermined standard and taking an action selected from the group consisting of: (a) if the property of the polyvinyl alcohol grafted urea-formaldehyde resin meets the predetermined standard, stop processing; and (b) if the property of the polyvinyl alcohol grafted urea-formaldehyde resin does not meet the predetermined standard, further processing the polyvinyl alcohol grafted urea-formaldehyde resin, the further processing including: adding additional polyvinyl alcohol to the polyvinyl alcohol and urea-formaldehyde resin colloid under reaction conditions, sufficient to condense the polyvinyl alcohol and the polyvinyl alcohol and urea-formaldehyde resin colloid to produce a further processed polyvinyl alcohol and urea-formaldehyde resin colloid wherein the addition of polyvinyl alcohol is at a concentration compatible with the polyvinyl alcohol and urea-formaldehyde resin colloid into which it is being placed. The method continues by measuring a property of the further processed polyvinyl alcohol and urea-formaldehyde resin colloid; comparing the property of the further processed polyvinyl alcohol and urea-formaldehyde resin colloid to a predetermined standard; and repeating the further processing until the further processed polyvinyl alcohol and urea-formaldehyde resin colloid meets the predetermined standard.

One predetermined standard useful with all of the methods of the application, but especially the post mixing method is turbidity. It would be desirable in the art to produce colloids that are clear to hazy or at least not too turbid. In some embodiments, the colloids produced with the methods of the application have a turbidity of less than <NUM> nephlometric turbidity units (NTU). In other embodiments, the colloids produced with the methods of the application have a turbidity of less than <NUM> NTU. For comparison, drinking water typically has a turbidity of less than <NUM> NTU.

The UF resins of the application may be prepared using urea and formaldehyde, but sometimes it is desirable to use a concentrate rather than the pure raw materials. It is common in the art use to UFC-<NUM> which is available from many vendors. Generally speaking, it is covered under <NPL> and will have a urea content of <NUM>% and a formaldehyde content of <NUM>%, the remaining material being water.

In addition to PVA, other water soluble polymers may be useful for formation of a colloid with UF. For example, hydroxyethyl cellulose could be used. These water soluble polymers can be employed just as the PVA. Water soluble polymers that can be used include, but are not limited to: hydroxyethyl cellulose (HEC), polyethylene glycol, polypropylene glycol, and polyethylene vinyl glycol. The use of HEC is illustrated below in Examples <NUM>-<NUM>.

In some embodiments of the application, polyvinyl alcohol is used to form a colloid with a urea-formaldehyde resin. One end use for this colloid is as a binder for making shingles. Advantageously, the colloids of the application have low turbidity and good shelf life.

The PVA-UF colloids prepared by the method of the application may be employed in the same manner as a conventional UF resin. For example, like UF resin, the PVA-UF colloid is compatible some acrylic and/or vinyl emulsions.

The following examples are provided to illustrate aspects of the invention. The examples are not intended to limit the scope of the invention and they should not be so interpreted. Amounts are in weight parts or weight percentages unless otherwise indicated.

Methanol (<NUM>), <NUM>% formaldehyde (<NUM>), water (<NUM>) and Selvol <NUM> (<NUM>) were charged into a <NUM>-mL flask. The mixture was heated to <NUM> for approximately <NUM> hours at initial pH of ~ <NUM> until a clear to hazy liquid was obtained. After the pH was adjusted using triethylamine and triethanolamine to <NUM>, urea granule (<NUM>) was charged into the flask. The pH was adjusted to <NUM> ~ <NUM> and the mixture was heated to <NUM> until the resin gave a cloudy appearance upon cooling to <NUM>. Next, the pH was adjusted to <NUM> ~ <NUM> and the mixture was heated to <NUM>. Thereafter, the viscosity was measured every <NUM> minutes. The temperature was reduced to <NUM> and the pH was adjusted to ~ <NUM> using NaOH solution when a desirable viscosity from <NUM> to <NUM>,<NUM> cPs was obtained and the water-based resin remained clear to hazy at ambient temperatures. Urea (<NUM>) 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 liquid. The solid content was ~ <NUM>%, and PVA content of the total solid ~ <NUM>%. The pH was ~ <NUM> and the viscosity from <NUM> cPs. Free formaldehyde content was ~ <NUM>% after <NUM> hours. Selvol <NUM> is a polyvinyl alcohol available from Sekisui Specialty Chemicals.

UFC <NUM> (<NUM>), methanol (<NUM>), water (<NUM>) and Selvol <NUM> (<NUM>) were charged into a <NUM>-mL flask. The pH was adjusted using triethylamine and triethanolamine to <NUM>. The mixture was heated to <NUM> for approximately <NUM> hours to obtain a clear to hazy liquid. Urea granules (<NUM>) were charged into the flask. The mixture was heated to <NUM> and the pH was maintained at ~ <NUM> until the resin gave a cloudy appearance upon cooling to <NUM>. Subsequently, the pH was adjusted to <NUM> ~ <NUM> and the mixture was heated to <NUM>. Thereafter, the viscosity was measured every <NUM> minutes. The temperature was reduced to <NUM> and the pH was adjusted to ~ <NUM> using NaOH solution when a desirable viscosity from <NUM> to <NUM>,<NUM> cPs was obtained and the water-based resin remained clear to hazy at ambient temperatures. Urea (<NUM>) 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 liquid. The total solid content was ~ <NUM>%, and PVA content of the total solid ~ <NUM>%. The pH was ~ <NUM>, and the viscosity ~ <NUM>,<NUM> cPs. Free formaldehyde content was ~ <NUM>%.

UFC <NUM> (<NUM>), methanol (<NUM>), water (<NUM>) and Selvol <NUM> (<NUM>) were charged into a <NUM>-mL flask. The pH was adjusted using triethylamine and triethanolamine to <NUM>. The mixture was heated to <NUM> for approximately one hour and a clear to hazy liquid was obtained. Urea granules (<NUM>) were charged into the flask. The mixture was heated to <NUM> and the pH was maintained at ~ <NUM> until the resin gave a cloudy appearance upon cooling to <NUM>. Next, the pH was adjusted to <NUM> ~ <NUM> and the mixture was heated to <NUM>. Thereafter, the viscosity was measured every <NUM> minutes. The temperature was reduced to <NUM> and the pH was adjusted to <NUM> using NaOH solution when a desirable viscosity from <NUM> to <NUM> cPs was obtained and the water-based resin remained clear to hazy at ambient temperatures. Urea (<NUM>) 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 liquid. The total solid content was ~ <NUM>%, and PVA content of the total solid ~ <NUM>%. The pH was ~ <NUM>, and the viscosity ~ <NUM> cPs. Free formaldehyde content was ~ <NUM>% after <NUM> hours.

Methanol (<NUM>), <NUM>% formaldehyde (<NUM>), water (<NUM>) and Selvol <NUM> (<NUM>) were charged into a <NUM>-mL flask. The mixture was heated to <NUM> for approximately <NUM> hours and a clear to hazy liquid was obtained. Urea (<NUM>) was charged into the flask. The mixture was heated to <NUM> and the pH was maintained at ~ <NUM> until the resin gave a cloudy appearance upon cooling to <NUM>. Next, the pH was adjusted with formic acid to from ~<NUM> to ~ <NUM> and the mixture was heated to <NUM>. Thereafter, the viscosity was measured every <NUM> minutes. The temperature was reduced to <NUM> and the pH was adjusted to <NUM> using NaOH solution when the viscosity reached ~ <NUM> cPs and the water-based resin remained clear to hazy at ambient temperatures. Urea (<NUM>) and water (<NUM>) were charged into the flask and stirred for a few minutes to obtain a clear to hazy liquid. The final product was a hazy liquid. The solid content was ~ <NUM>%, and PVA content of the total solid ~ <NUM>%. The pH was ~ <NUM>, and viscosity ~<NUM>,<NUM> cPs. Free formaldehyde content was ~ <NUM>% after <NUM> hours.

UFC <NUM> (<NUM>), methanol (<NUM>), water (<NUM>) and urea (<NUM>) were charged into a <NUM>-mL flask. The mixture was heated to <NUM> and the pH was maintained at ~ <NUM> until the resin gave a cloudy appearance upon cooling to <NUM>. Next, the pH was adjusted with formic acid to from ~ <NUM> to ~ <NUM> and the mixture was heated to <NUM>. Thereafter, the viscosity was measured every <NUM> minutes until it reached <NUM> cPs. The clear to hazy mixture was cooled down to <NUM> and then <NUM>% Selvol <NUM> (<NUM>) was charged into flask. The temperature was maintained at <NUM> and pH <NUM> until a desirable viscosity from <NUM> to <NUM> cPs was obtained and the water-based resin remained clear to hazy at ambient temperatures. Subsequently, the temperature was reduced to <NUM> and the pH was adjusted to <NUM> using NaOH solution. Urea (<NUM>) was charged into the flask and stirred for a few minutes. The final product was either a clear or a hazy liquid. The total solid content was ~<NUM>%, and PVA content of the total solid ~ <NUM>%. The pH was ~ <NUM> and the viscosity ~ <NUM> cPs. Free formaldehyde content was ~ <NUM>% after <NUM> hours. Selvol <NUM> is a ~ polyvinyl alcohol available from Sekisui Specialty Chemicals.

UFC <NUM> (<NUM>), methanol (<NUM>), water (<NUM>) and urea (<NUM>) were charged into a <NUM>-mL flask. The mixture was heated to <NUM> and the pH was maintained at ~ <NUM> until the resin gave a cloudy appearance upon cooling to <NUM>. Next, the pH was adjusted with formic acid to <NUM> ~ <NUM> and the mixture was heated to <NUM>. Thereafter, the viscosity was measured every <NUM> minutes until the viscosity reached ~ <NUM> cPs. The clear to hazy mixture was cooled down to <NUM> and then <NUM>% Selvol <NUM> (<NUM>) was charged into flask. The temperature was maintained at <NUM> and pH ~ <NUM>. The temperature was reduced to <NUM> and the pH was adjusted to <NUM> using NaOH solution when the water-based resin remained clear to hazy at ambient temperatures and the viscosity reached ~<NUM> cPs. Urea (<NUM>) was charged into the flask and stirred for a few minutes. The final product was either a clear or a hazy liquid. The total solid content was <NUM>%, the PVA content of the total solid ~ <NUM> %. The pH was ~ <NUM> and viscosity ~ <NUM> cPs. Free formaldehyde content was ~ <NUM>% after <NUM> hours.

UFC <NUM> (<NUM>), water (<NUM>) and urea (<NUM>) were charged into a <NUM>-mL flask. The mixture was heated to <NUM> and the pH was maintained at ~ <NUM> until the resin gave a cloudy appearance upon cooling to <NUM>. Next, the pH was adjusted with formic acid to from ~ <NUM> to ~ <NUM> and the mixture was heated to <NUM>. Thereafter, the viscosity was measured every <NUM> minutes until the viscosity reached ~ <NUM> cPs. The clear to hazy mixture was cooled down to <NUM> and then <NUM>% Selvol <NUM> (<NUM>) was charged into flask. The temperature was maintained at <NUM> and pH at ~ <NUM> until the viscosity reached <NUM> cPs and the water-based resin remained clear to hazy at ambient temperatures. Next, the temperature was reduced to <NUM> and the pH was adjusted to <NUM> using NaOH solution. Urea (<NUM>) 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 liquid. The solid content was ~<NUM>%, and PVA content of the total solid ~ <NUM>%. The pH was ~ <NUM> and the viscosity ~ <NUM> cPs. Free formaldehyde content was ~ <NUM>% after <NUM> hours.

UFC <NUM> (<NUM>), water (<NUM>) and urea (<NUM>) were charged into a <NUM>-mL flask. The mixture was heated to <NUM> and the pH was maintained at ~ <NUM> until the resin gave a cloudy appearance upon cooling to <NUM>. Next, the pH was adjusted with formic acid to <NUM> ~ <NUM> and the mixture was heated to <NUM>. Thereafter, the viscosity was measured every <NUM> minutes until the viscosity reached <NUM> cPs. The clear to hazy mixture was cooled down to <NUM> and then <NUM>% Selvol <NUM> (<NUM>) was charged into flask. The temperature was maintained at <NUM> and pH at ~ <NUM> until the water-based resin remained clear to hazy at ambient temperatures and the viscosity reached ~ <NUM> cPs. Next, the temperature was reduced to <NUM> and the pH was adjusted to <NUM> using NaOH solution. Urea (<NUM>) 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 liquid. The solid content was ~<NUM>%, and PVA content of the total solid ~ <NUM>%. The pH value was ~ <NUM> and the viscosity ~ <NUM> cPs. Free formaldehyde content was ~ <NUM>% after <NUM> hours. Selvol <NUM> is a polyvinyl alcohol available from Sekisui Specialty Chemicals.

UFC <NUM> (<NUM>), water (<NUM>) and urea (<NUM>) were charged into a <NUM>-mL flask. The mixture was heated to <NUM> and the pH was maintained at ~ <NUM> until the resin gave a cloudy appearance upon cooling to <NUM>. Next, the pH was adjusted with formic acid to from ~ <NUM> to ~ <NUM> and the mixture was heated to <NUM>. Thereafter, the viscosity was measured every <NUM> minutes until the viscosity reached ~ <NUM> cPs was obtained. The final product was a hazy liquid; the solid content was ~ <NUM>%.

The UF precursor (<NUM>) and <NUM>% Selvol <NUM> (<NUM>) were charged into a <NUM>-mL flask and a cloudy mixture was formed. The pH was adjusted using formic acid to ~ <NUM> and the mixture was heated to <NUM>. Thereafter, the viscosity was measured every <NUM> minutes until the viscosity <NUM> cPs was obtained and the water-based resin remained clear to hazy at ambient temperatures. Next, the temperature was reduced to <NUM> and the pH was adjusted to <NUM> using NaOH solution. Urea (<NUM>) 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 liquid. The solid content was <NUM>%, and PVA content of the total solid ~ <NUM>%. The pH value was ~ <NUM> and the viscosity ~ <NUM> cPs. Free formaldehyde content was ~ <NUM>% after <NUM> hours.

The UF precursor (<NUM>) and <NUM>% Selvol <NUM> (<NUM>) were charged into a <NUM>-mL flask and a cloudy mixture was formed. The pH was adjusted with formic acid to ~ <NUM> and the mixture was heated to <NUM>. Thereafter, the viscosity was measured every <NUM> minutes until the viscosity reached <NUM> cPs and the water-based resin remained clear to hazy at ambient temperatures. Next, the temperature was reduced to <NUM> and the pH was adjusted to <NUM> using NaOH solution. Urea (<NUM>) 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 of a hazy liquid. The solid content was <NUM>%, and PVA content of the total solid ~ <NUM>%. The pH was ~ <NUM> and the viscosity ~ <NUM> cPs. Free formaldehyde content was ~ <NUM>% after <NUM> hours. Selvol <NUM> is a polyvinyl alcohol available from Sekisui Specialty Chemicals.

The UF precursor (<NUM>) and <NUM>% Selvol <NUM> (<NUM>) were charged into a <NUM>-mL flask and a cloudy mixture was formed. The pH was adjusted with formic acid to ~ <NUM> and the mixture was heated to <NUM>. Thereafter, the viscosity was measured every <NUM> minutes until the viscosity was <NUM> cPs and the water-based resin remained clear to hazy at ambient temperatures. Next, the temperature was reduced to <NUM> and the pH was adjusted to <NUM> using NaOH solution. Urea (<NUM>) was charged into the flask and stirred for a few minutes to obtain a clear to hazy liquid. The final product was either clear or hazy liquid. The solid content was <NUM>%, and PVA content of the total solid ~ <NUM>%. The pH value was ~ <NUM> and the viscosity ~ <NUM> cPs. Free formaldehyde content was ~ <NUM>% after <NUM> hours. Selvol <NUM> is a polyvinyl alcohol available from Sekisui Specialty Chemicals.

UF precursor (<NUM>-<NUM> ) (<NUM>) and <NUM>% Selvol <NUM> (<NUM>) were charged into a <NUM>-mL flask and a cloudy mixture was formed. The pH was adjusted with formic acid to ~ <NUM> and the mixture was heated to <NUM>. Thereafter, the viscosity was measured every <NUM> minutes until the viscosity reached approximately <NUM> cPs and the water-based resin remained clear to hazy at ambient temperatures. Next, the temperature was reduced to <NUM> and the pH value was adjusted to <NUM> using NaOH solution. Urea (<NUM>) 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 liquid. The solid content was <NUM>%, and PVA content of the total solid ~ <NUM>%. The pH value was ~ <NUM> and the viscosity ~ <NUM> cPs. Free formaldehyde content was ~ <NUM>% after <NUM> hours.

UF-<NUM> (or UF-472X) is a commercial UF resin available from Momentive Specialty Materials Inc. and was used as the experimental baseline.

A mixture of UF-472X and commercial Rhoplex RL-<NUM> emulsion (<NUM>% or <NUM>% by weight of the solid based on the total solids) was used as an experimental control. Rhoplex RL-<NUM> is a commercial product produced by The Dow Chemical Company.

UFC <NUM> (<NUM>), methanol (<NUM>), water (<NUM>) and <NUM>% HEC WP-<NUM> (<NUM>) were charged into a <NUM>-mL flask. The pH was adjusted using triethylamine and triethanolamine to <NUM>. The mixture was heated to <NUM> for approximately <NUM> minutes and a clear to hazy liquid was obtained. Urea (<NUM>) was charged into the flask. The mixture was maintained at <NUM> and the pH was maintained at ~ <NUM> until it became cloudy at <NUM>. Next, the pH was adjusted to from ~ <NUM> to ~ <NUM> and the mixture was heated to <NUM>. Thereafter, the viscosity was measured every <NUM> minutes until the reaction mixture became a clear or hazy liquid. The temperature was reduced to <NUM> and the pH was adjusted to <NUM> using NaOH when a desirable viscosity reached to <NUM>,<NUM> cPs and the water-based resin remained hazy or translucent, but no phase separation at ambient temperatures. Urea (<NUM>. g) was charged into the flask and stirred for a few minutes to obtain a translucent liquid. The total solid content was ~ <NUM>%, and HEC content of the total solid ~ <NUM>%. The pH was ~ <NUM>, and the viscosity ~ <NUM>,<NUM> cPs. Free formaldehyde content ~ <NUM>% after <NUM> hours.

UFC <NUM> (<NUM>), methanol (<NUM>), water (<NUM>) and <NUM>% HEC WP-<NUM> (<NUM>) were charged into a <NUM>-mL flask. The pH was adjusted using triethylamine and triethanolamine to <NUM>. The mixture was heated to <NUM> for approximately <NUM> minutes and a clear to hazy liquid was obtained. Urea (<NUM>) was charged into the flask. The mixture was maintained at <NUM> and the pH was maintained at ~ <NUM> until it became cloudy at <NUM>. Next, the pH was adjusted to <NUM> ~ <NUM> and the mixture was heated to <NUM>. Thereafter, the viscosity was measured every <NUM> minutes until the reaction mixture became a clear or hazy liquid. The temperature was reduced to <NUM> and the pH was adjusted to <NUM> using NaOH when a desirable viscosity reached to <NUM>,<NUM> cPs and the water-based resin remained hazy or translucent, but no phase separation at ambient temperatures. Urea (<NUM>) was charged into the flask and stirred for a few minutes to obtain a translucent liquid. The total solid content was ~ <NUM>%, and HEC content of the total solid ~ <NUM>%. The pH was ~ <NUM>, and the viscosity ~ <NUM>,<NUM> cPs. Free formaldehyde content ~ <NUM>% after <NUM> hours.

UFC <NUM> (<NUM>), water (<NUM>) and <NUM>% HEC WP-<NUM> (<NUM>) were charged into a <NUM>-mL flask. The pH was adjusted using triethylamine and triethanolamine to <NUM>. The mixture was heated to <NUM> for approximately <NUM> minutes and a clear to hazy liquid was obtained. Urea granules (<NUM>) were charged into the flask. The mixture was maintained at <NUM> and the pH was maintained at ~ <NUM> until it became cloudy at <NUM>. Next, the pH was adjusted to <NUM> ~ <NUM> and the mixture was heated to <NUM>. Thereafter, the viscosity was measured every <NUM> minutes until the reaction mixture became a clear or hazy liquid. The temperature was reduced to <NUM> and the pH was adjusted to <NUM> using NaOH when a desirable viscosity reached to <NUM> cPs and the water-based resin remained haze or translucent, but no phase separation at ambient temperatures. Urea (<NUM>) was charged into the flask and stirred for a few minutes to obtain a hazy liquid. The total solid content was ~ <NUM>%, and HEC content of the total solid ~ <NUM>%. The pH was ~ <NUM>, and the viscosity ~ <NUM> cPs. Free formaldehyde content ~ <NUM>% after <NUM> hours.

Concentrated UF-PVA colloid (~<NUM>% by weight) was diluted with D. water to ~ <NUM>% by weight. The liquid binder was a clear to hazy liquid and the viscosity was less than <NUM> cPs. The diluted colloid provided approximately <NUM> days shelf life.

According to moisture content measured on Cenco moisture balance, <NUM> of wet glass fiber OC9501 (Owens Corning) with an average ¾ inch (<NUM>) length and <NUM> micron diameter were immersed in <NUM> of D. water with <NUM> of Rhodia VP-<NUM>/SPB for at least <NUM> hours.

The treated glass fiber was placed into <NUM> liters (<NUM> gallon) of warm water <NUM> in a <NUM>-liter (<NUM>-gallon) vessel equipped with a mechanical agitator under agitation at <NUM> rpm for <NUM> seconds, and then <NUM> of <NUM>% of Cytec Superfloc A-<NUM> Flocculent solution was added into the vessel under the agitation for <NUM> seconds. The glass fiber slurry was introduced onto a <NUM> × <NUM> (<NUM> × <NUM> inch) fabric mat casting mode equipped with a wire support mesh with a plastic fabric. The wet glass mat with the plastic fabric was passed through a vacuum slot to remove excess water. The liquid binder containing ~<NUM>% solid by weight was applied on the wet glass mat and passed through the vacuum slot again to remove excess binder for a desirable weight based on the certain LOI (Loss on ignition). A wet glass mat with binder was cured on Methis Labdryer at <NUM> (<NUM>°F) for <NUM> minutes or <NUM> (<NUM>°F) for <NUM> minutes.

The cured glass mat hand sheet was cut in <NUM> × <NUM> inch (<NUM> × <NUM>) rectangular specimen. Total eighteen specimens from three hand sheets were measured on Instron <NUM> to get an average tensile strength.

The cured glass mat hand sheet was cut in <NUM> × <NUM> inch (<NUM> × <NUM>) rectangular specimen. Total eighteen specimens from three hand sheets were soaked in water at <NUM> for <NUM> in a Microprocess Controlled <NUM> water bath (Precision). Excess of water in the specimen was removed with paper towel. The specimens were immediately measured on the Instron.

The cured glass mat hand sheet was cut in <NUM> × <NUM> (<NUM> × <NUM> inch) rectangular specimen. Three specimens from three hand sheets were measured on Elmendorf Tearing Tester (Thwing-Albert Instrument Co. ) in six times to get an average measurement.

The cured glass mat hand sheet was cut in <NUM> × <NUM> (<NUM> × <NUM> inch) rectangular specimen. Total twenty one sheets from three hand sheets as one specimen were measured on a Mahr Federal dial drop indicator and an average thickness of a single sheet was obtained. Average thickness for individual sheet ranged from <NUM> to <NUM> (<NUM> to <NUM> mils).

After the liquid binder was applied on <NUM> × <NUM> (<NUM> × <NUM>:<NUM> inch) square glass sheet hand sheet, the glass sheet was vacuumed to the desirable wet weight based on a certain LOI (Loss on ignition). The wet sheet was laid over a sheet of plastic with a <NUM> (<NUM>-inch) diameter hole in the center. A clear plastic sheet <NUM> (¼") thick with an identical <NUM> (<NUM>-inch) diameter hole was placed on top of the hand sheet to secure it. A <NUM> (<NUM>-<NUM>/<NUM>") diameter disc holding a paper cup was then centered over the hole and gently lowered onto the hand sheet. Water from a <NUM> burette was added at a constant rate to the cup until the web elongates a vertical distance of <NUM> and touches to the bottom plastic plate. The wet web strength in grams was the weight of the cup plus the added water at the "sag" point.

<NUM> of UF resin FG-<NUM> (<NUM>% solid) and <NUM> of <NUM>% Selvol <NUM> solution were charged into a <NUM>-mL flask to form a two-phase mixture. The mixture was heated at <NUM> for <NUM> hours at an initial pH of ~<NUM> to obtain a clear liquid. The liquid became a white opaque colloid after cool down. Total solid content was <NUM>% by weight and PVA content was <NUM>% of the total solid. Viscosity was <NUM> cPs, and the pH value was <NUM>.

<NUM> of UF resin FG-<NUM> (<NUM>% solid) and <NUM> of water were charged into a <NUM>-mL flask, <NUM> of Selvol <NUM> granules was introduced into the flask with agitation at ambient temperature. The mixture was heated at <NUM> for <NUM> hours at an initial pH of ~<NUM> to form a clear liquid. It became a white opaque colloid after cool down. The total solid content of the colloid was <NUM>% by weight and PVA content was <NUM>% of the total solid. Viscosity was <NUM> cPs, and pH was <NUM>.

<NUM> of UF resin FG-<NUM> (<NUM>% by solid) and <NUM> of water were charged into a <NUM>-mL flask, <NUM> of Selvol <NUM> granules was introduced into the flask with agitation at ambient temperature. The mixture was heated at <NUM> for <NUM> hours at initial pH ~<NUM> to form a clear liquid. It became a stable white opaque colloid after cool down. Viscosity was <NUM> cPs, and pH was <NUM>. Total solid content of the colloid was <NUM>% by weight and PVA content was <NUM>% of the total solid. The product was diluted to <NUM>% solid content prior to the use. Viscosity was <NUM> cPs, and pH was <NUM>.

<NUM> of UF resin FG-<NUM> (<NUM>% by weight) and <NUM> of water were charged into a <NUM>-mL flask, <NUM> of Selvol <NUM> was introduced into the flask with agitation at ambient temperature. The mixture was heated at <NUM> for <NUM> hours at an initial pH of ~<NUM> to form a clear liquid. The liquid became a stable white opaque colloid after cool down. Total solid content of colloid was <NUM>% by weight and PVA content was <NUM>% of the total solid. Viscosity was <NUM>,<NUM> cPs, pH was <NUM>. The product was diluted to <NUM>% solid content prior to the use. Viscosity was <NUM> cps, and pH was <NUM>.

<NUM> of UF resin FG-<NUM> (<NUM>% by solid) and <NUM> of water were charged into a <NUM>-mL flask, <NUM> of Selvol <NUM> was introduced into the flask with agitation at ambient temperature. The mixture was heated at <NUM> for <NUM> hours at initial pH ~<NUM> to form a clear liquid. The liquid became a stable white opaque colloid after cool down. Viscosity was <NUM>,<NUM> cPs, and pH was <NUM>. Total solid content of the colloid was <NUM>% by weight and PVA content was <NUM>% of the total solid. The product was diluted to <NUM>% solid content prior to use. Viscosity was <NUM> cPs, and pH was <NUM>.

<NUM> of UF resin FG-<NUM> (<NUM>% by weight) and <NUM> of water were charged into a <NUM>-mL flask, <NUM> of Selvol <NUM> was introduced into the flask with agitation at ambient temperature. The mixture was heated at <NUM> for <NUM> hours at initial pH ~<NUM> to form a clear liquid. It became a stable white opaque colloid after cool down. Total solid content of colloid was <NUM>% by weight and PVA content was <NUM>% of the total solid. Viscosity was <NUM>,<NUM> cPs, pH was <NUM>. The product was diluted to <NUM>% solid content prior to the use. Viscosity was <NUM> cps, and pH was <NUM>.

<NUM> of UF resin FG-<NUM> (<NUM>% by weight) and <NUM> of water were charged into a <NUM>-mL flask, <NUM> of HEC WP-<NUM> powder was introduced into the flask with agitation at ambient temperature. The mixture was heated at <NUM> for <NUM> hours at initial pH ~<NUM> to form a clear slightly yellow liquid. It became an off-white opaque colloid after cool down. Viscosity was <NUM>,<NUM> cps, and pH was <NUM>. The total solid content of the colloid was <NUM>% by weight and HEC content was <NUM>% of the total solid. The colloid was diluted with water to <NUM>% solid content prior to the use. Viscosity was <NUM> cPs, and pH value was <NUM>.

<NUM> of UF resin FG-<NUM> (<NUM>% by weight) and <NUM> of water were charged into a <NUM>-mL flask, <NUM> of Selvol <NUM> was introduced into the flask with agitation at ambient temperature. The mixture was heated at <NUM> for <NUM> hours at initial pH ~<NUM> to form a clear liquid. It became a white opaque colloid after cool down. The pH was adjusted with dimethylaminoethanol from <NUM> to <NUM>. Viscosity was <NUM> cPs. Total solid content of the colloid was <NUM>% by weight and PVA content was <NUM>% of the total solid. The product was diluted to <NUM>% solid content prior to the use. Viscosity was <NUM> cps, pH value was <NUM>.

<NUM> of UF resin FG-<NUM> (<NUM>% by weight), <NUM> of GL-<NUM> (<NUM>% solid), and <NUM> of D. water were mixed in a <NUM>-mL container to give a milky white liquid. Total solid content of the liquid was <NUM>%, by weight and latex RL-<NUM> was <NUM>% by weight of the total solid. Viscosity was <NUM> cPs, pH value was <NUM>.

<NUM> of UF resin FG-<NUM> (<NUM>% by weight), <NUM> of GL-<NUM> (<NUM>% solid), and <NUM> of D. water were mixed in a <NUM>-mL container to give a milky white liquid. Total solid content of the liquid was <NUM>% by weight and latex RL-<NUM> was <NUM>% by weight of the total solid. Viscosity was <NUM> cPs, pH value was <NUM>.

<NUM> of UF resin FG-<NUM> (<NUM>% by weight), <NUM> of D. water, and <NUM> of <NUM>% Selvol <NUM> solution were mixed in a <NUM>-mL flask. The liquid became two phases after stop stirring for a while. Additional water was charged into the mixture to form <NUM>% homogeneous solution. Total solid content of the solution was <NUM>% by weight and PVA was <NUM>% by weight of the total solid. Viscosity was <NUM>, and pH was <NUM>. A white precipitant was observed after a few hours.

Concentrated UF-PVA colloid (<NUM> - <NUM>% by weight) was diluted with D. water to <NUM> - <NUM>% by weight. The liquid binder is a white milky colloid with viscosity at <NUM> cps or less. The diluted colloid provided two days stability without settlement.

After a <NUM> x <NUM> inch (<NUM> x <NUM>) square glass mat hand sheet was casted, it was vacuumed to the target wet weight based on a certain LOI (Loss on ignition). The wet sheet was laid over a sheet of plastic with a <NUM>-inch (<NUM>) diameter hole in the center. A clear plastic sheet ¼" (<NUM>) thick with an identical <NUM>-inch (<NUM>) diameter hole was placed on top of the hand sheet to secure it. A <NUM>-<NUM>/<NUM>" (<NUM>) diameter disc holding a paper cup was then centered over the hole and gently lowered onto the hand sheet. Water from a <NUM> burette was added at a constant rate to the cup until the web elongates a vertical distance of <NUM> and touches to the bottom plastic plate. The wet web strength in grams was the weight of the cup plus the added water at the "Sag" point.

Claim 1:
A method for preparing a polyvinyl alcohol and urea-formaldehyde colloid comprising:
admixing polyvinyl alcohol with a component selected from the group consisting of:
a solution of formaldehyde, and
a urea/formaldehyde concentrate, to form a first liquid working admixture and then admixing the first liquid working admixture with urea under reaction conditions sufficient to initiate a methylolation reaction to form a reaction product admixture of the first liquid working admixture with urea; and
subjecting the reaction product admixture to reaction conditions sufficient to initiate a condensation to form a polyvinyl alcohol and urea-formaldehyde resin colloid, wherein the polyvinyl alcohol has a weight average molecular weight of from <NUM>,<NUM> to <NUM>,<NUM>.