United States Patent [19] 

Martin et al. 

[54] AQUEOUS COMPOSITION CONTAINING 

ALDEHYDE CONDENSATE AND USE 

THEREOF 

[75] Inventors: Jeffrey E. Martin, Columbus; Albert 

F. Vozella, Worthington; Golden F. 

Watts, Delaware; Edwin R. 

Luckman, Columbus, all of Ohio 

[73] Assignee: Ashland Oil, Inc., Ashland, Ky. 

[21] Appl. No.: 187,692 

[22] Filed: Sep. 16, 1980 

[51] Int. 0.3 ....................... C08L 89/02; C08L 61/06 

[52] U.S. CI. .................................... 524/297; 524/296; 

524/704; 524/502; 524/507; 524/510; 524/541; 

524/361; 524/376; 524/378; 524/595 

[58] Field of Search ......... 260/29.3, 29.4 R, 29.2 TN, 

260/29.6 NR, 7; 525/58 

[56] References Cited 

U.S. PATENT DOCUMENTS 

3,931,088 1/1976 Sakurada et al. ........... 260/29.6 RB 

[11] 

[45] 

4,341,668 

Jul. 27, 1982 

4,110,277 8/1978 Economy et al. .................. 260/841 

4,128,695 12/1978 Kikuchi et al. .................. 428/424.8 

4,179,427 12/1979 Gardikes ..................... 260/29.2 TN 

FOREIGN PATENT DOCUMENTS 

50-69138 6/1975 Japan. 

50-69142 6/1975 Japan. 

Primary Examiner-Theodore E. Pertilla 

Attorney, Agent, or Firm-Pollock, Vande Sande & 

Priddy 

[57] ABSTRACT 

A composition containing a methylene donor, hydrophobic component containing an organic hydrophobic 

diluent and an isocyanate; and an aqueous component 

containing a water compatible aldehyde condensate and 

use thereof as an impregnant or bonding agent for cellulosic materials including paper, wood and cotton, and-

/or fibrous materials including synthetic fibers, such as 

rayon and nylon. 

41 Claims, No Drawings 
1 

4,341,668 

AQUEOUS COMPOSITION CONTAINING 

ALDEHYDE CONDENSATE AND USE THEREOF 

2 

used without benefit in the case of burning vapors unless large capital expenditures are made, wherein, heat 

generated from vapor burning is used to replace heat 

costs encountered in paper making and UB" staging the 

DESCRIPTION 

1. Technical Field 

5 saturated paper. Water solvent systems eliminating 

these capital investments are very attractive. 

The present invention is concerned with compositions containing a hydrophobic component containing 

an isocyanate compound and an aqueous component 

containing an aldehyde condensate. Moreover, the 10 

present invention is concerned with the use of such 

water containing compositions for impregnating and 

bonding cellulosic materials such as paper, wood and 

cotton, and fibrous materials including synthetic fibers, 

such as nylon and rayon. 15 

2. Background Art 

After paper is formed, it is usually saturated with a 

thermoset polymer composition such as a phenolicaldehyde condensate. Saturation places the resinous 

material in the interstices of the paper. It has been sug- 20 

gested that phenolic-aldehyde condensates are chemically reactive with hydroxyl groups in cellulosics to 

provide strength and protection for the fibers. Since 

melamine and urea aldehyde condensates contain methylol groups similar to those in phenolic-aldehyde con- 25 

densates, it is believed that melamine- and urea-formaldehyde condensates chemically react similarly to 

phenolic-aldehyde condensates. However, the final 

properties of the paper will differ. 

Paper saturated with an aldehyde condensate is par- 30 

tially heat cured or "B" staged to react only some of the 

methylol groups together and to tie in partially with the 

hydroxyl groups of the cellulosic papers; thereby, adding some physical strength to the paper. Grooving or 

corrugating is generally done at this point to provide 35 

additional strength in final use. The paper is then rolled 

and shipped to the users, who pleat, fold or otherwise 

distort the flat rolled paper. 

Pleating is accomplished before final cure. If the cure 

were completed prior to pleating, the embrittlement of 40 

the paper would cause fractures and subsequent loss of 

strength at the folds and filtration efficiency would be 

sacrificed or the filter could collapse in use. 

Fuel costs and environmental considerations have 

prompted some end paper users to buy the paper in 45 

more fully cured stages with the contained resins being 

modified to provide "pseudo-thermoplastics." These 

saturated papers require minimum heat to soften while 

pleating. This heating advances the cure of the modified 

resins minimally. Application of plastisols, which are 50 

used as adhesives, on the end caps of filters advance the 

resins to a greater extent as the plastisols are cured with 

heat. 

Filter manufacturers that have perfected such system 

usage have substantially reduced their own heating and 55 

environmental compliance costs. The paper saturators, 

Another area where water solvent systems would be 

very attractive is in the production of carpet backing 

and sound deadening insulation, such as from nonwoven cotton fabrics. For instance, in the production of 

carpet backing such as for automobiles, where sound 

deadening and insulation from excess heat and/or cold 

is required, non-woven cellulosic fabric (e.g. cotton) is 

garnetted into a mat using phenolic powder as the adhesive between the layers of the garnet. The use of a powder leaves much to be desired concerning handling of 

materials and waste. The mat is cured for about 30 

seconds using elevated temperatures on both sides so 

that the mat is easily handled. The mat is then subjected 

to a heat mold/die cut machine for forming the product. 

At this stage, it is completely cured. The ability to employ a water system in place of the powder would be 

advantageous. 

In addition, water systems which contain a hydrophobic component containing an isocyanate compound 

and an aqueous portion containing certain polymers 

reactive therewith have been previously suggested. The 

isocyanate component is present along with a hydrophobic solvent in order to retard the reaction between 

the isocyanate and aqueous component while the composition is in the liquid form. The hydrophobic solvent 

is employed to protect the isocyanate from premature 

reaction. Examples of some suggested compositions 

which employ such a system can be found in U.S. Pat. 

Nos. 3,931,088 and 4,128,695. 

DESCRIPTION OF INVENTION 

It is therefore an object of the present invention to 

provide an aqueous composition which can be used to 

impregnate and bond cellulosic and/or fibrous materials 

such as paper, wood, cotton, nylon, rayon and mixtures 

thereof, and which can be applied and cured with minimal energy requirements. 

The present invention is concerned with a composition which comprises a compound capable of providing 

reactive methylene sites at elevated temperatures; a 

hydrophobic component containing an organic hydrophobic diluent and an isocyanate and an aqueous component containing a water compatible aldehyde condensate having free methylol groups. 

The present invention is also concerned with substrates impregnated and/or bonded with the abovedefined composition and the process of coating cellulosic substrates and fibrous materials with the abovedefined composition. 

BEST AND VARIOUS MODES FOR CARRYING 

OUT INVENTION 

According to the present invention, the compositions 

include a hydrophobic component which contains an 

isocyanate. The isocyanate compound and/or polymer 

thereof is a molecule which has two or more isocyanate 

groups, such as toluene-diisocyanate, hydrogenated 

on the other hand, are being faced with using more fuel 

and emitting more volatile organic compounds (VOC) 

than previously encountered. Conversion to alcohol 

soluble, low emissions resins has cut smoke emissions 60 

from phenol, but new regulations in most areas have 

brought about concern about alcohol emissions. Under 

certain VOC regulations, limits on a yearly basis have 

been set in some states for emissions for each individual 

manufacturing location. 65 toluene-diisocyanate, trimethylolpropane-tolueneThese VOC regulations force paper makers and saturators to either burn the alcohol vapors or consider 

non-organic solvent systems (water). Additional fuel is 

diisocyanate adduct, triphenylmethane-triisocyanate, 

methylene-bis-diphenylisocyanate, hydrogenated 

methylene-bis-diphenylisocyanate, hexamethylene-
3 

4,341,668 

4 

diisocyanate, xylene-diisocyanate, 4,4' -dicyclohexyl- or most preferably a phenolic-aldehyde condensate. 

methane-diisocyanate, and polymeric MDI (Le. poly- Mixtures of such aldehyde condensates can be emmeric methylenebisphenyl-diisocyanate) such as those ployed when desired. The aldehyde condensates are 

commercially available under the trade designations preferably heat reactive and are water soluble and/or 

P API and Mondur MR. 5 water dilutable. The aldehyde condensates employed in 

Moreover, a mixture of a polyisocyanate and a accordance with the present invention are methylol 

polyol, for example, a mixture of polyols, such as poly- containing materials with at least some available sites 

ester or polyether with hydroxyl groups, and an excess filled as methylols and some reactive sites available for 

of isocyanate can be employed if desired. subsequent crosslinking via methylene addition during 

Furthermore, it is possible to employ a prepolymer 10 the pleating operation (heat applied). 

system, such as a prepolymer with NCO end groups, Examples of phenols which can be employed in prepartially polymerized from a polyol and an excess of paring the phenolic-aldehyde condensates to be used in 

polyisocyanate, or a prepolymer with OH end groups, the present invention include phenol and substituted 

partially polymerized from an excess of polyol, mixing phenols. 

it with an excess of one of the above-mentioned isocya- 15 Substituted phenols employed in the formation of the 

nates. Mixtures of isocyanates can be employed when phenolic polymers include: alkyl-substituted phenols, 

desired. aryl-substituted phenols, cyclo-alkyl-substituted pheThe hydrophobic diluent employed in the hydropho- nols, alkenyl-substituted phenols, alkoxy-substituted 

bic component according to the present invention pref- phenols, aryloxy-substituted phenols, hydroxy-suberably dissolves the isocyanate compound or polymer 20 stituted phenols, and halogen-substituted phenols, the 

and is liquid at normal room temperatures. The solubil- foregoing hydrocarbon substituents containing from 1 

ity of the diluent in water and the solubility of water in to 26, and preferably from 1 to 9 carbon atoms. Specific 

the diluent should preferably be below about 5 weight examples of suitable phenols include: phenol, resorcipercent at temperatures between 20· to 30· C. nol, catechol, hydroquinone, 2,6-xylenol, o-cresol, mSome typical examples of suitable hydrophobic dilu- 25 cresol, p-cresol, 3,5-xylenol, 3-4-xylenol, 2,3,4-trimethyl 

ents include aliphatic, cycloaliphatic, or aromatic hy- phenol, 3-ethyl phenol, 3,5-diethyl phenol, p-tertbutyl 

drocarbons or mixtures thereof as the main component. phenol, 3,5-dibutyl phenol, p-amyl phenol, pSome hydrocarbons include toluene, xylene, benzene, cyclohexyl phenol, p-octyl phenol, 3,5-dicyclohexyl 

gasoline, kerosene, ligroin, tetralin, decalin, terpentine phenol, o-phenyl phenol, p-crotyl phenol, nonyl pheoil, pine oil, liquid paraffin, and alkyl benzene. In addi- 30 nol, p-phenyl phenol, 3,5-dimethoxy phenol, 3,4,5-

tion, other diluents include halogenated hydrocarbons, trimethoxy phenol, p-ethoxy phenol, p-butoxy phenol, 

such as methylene chloride, l,l,l-trichloroethane, chlo- 3-methyl-4-methoxy phenol, and p-phenoxy phenol. In 

robenzene, chlorotoluene, bromobenzene, and chlori- addition, phenols containing multiple phenolic rings, 

nated paraffins; ketones, such as methyl-isobutyl ketone, such as bis-phenol-A, can be employed. Mixtures of 

methyl-n-amyl ketone, methyl-n-hexyl ketone, ethyl-n- 35 phenols can be used when desired. 

butyl ketone, di-n-propyl ketone and acetophenone; The preferred aldehyde employed is formaldehyde. 

ethers, such as isopropyl ether, methylphenyl ether, Such can be in aqueous solution or any of its low polyethyl-benzyl ether, and furan; lower aliphatic esters, meric forms, such as paraform or trioxane. The aldesuch as isopropyl acetate, amyl acetate, butyl acetate hydes preferably contain I to 8 carbon atoms, examples 

and butyl propionate; phthalic acid diesters, such as 40 of which include acetaldehyde, propionaldehyde, budibutyl phthalate, dioctyl phthalate, and butylbenzyl tyraldehyde, benzaldehyde, furfural, 2-ethylhexanal, 

phthalate; oleic acid esters; adipic acid esters; azelaic ethylbutyraldehyde, heptaldehyde, pentaerythrose, glyacid esters, sebacic acid esters, stearic acid esters, ben- oxal, chloral, and the like. Mixtures of aldehydes can be 

zoic acid esters, abietic acid esters, oxalic acid esters, used when desired. 

and phosphoric acid esters. Moreover, oils obtained 45 The preferred phenolic-aldehyde condensates emmainly from higher aliphatic acid esters, such as caster ployed according to the present invention are water 

oil, can be employed if desired. Mixtures of diluents can soluble and/or water dilutable and are obtained from 

be employed if desired. about 0.75 moles of aldehyde to about 3.3 moles of 

It is important to note that the hydrophobic diluent aldehyde per mole of phenolic compound, and preferashould not have amounts of active hydrogen groups, 50 bly at least about 0.95 to about 3 moles and most prefersuch as carboxy-, hydroxy-, or amino-groups in the ably about 1.5 to about 2.5 moles of aldehyde per mole 

molecule, such that upon mixing with the isocyanate of phenolic compound. In addition, the preferred phecompound or polymer it readily reacts therewith result- nolic-aldehyde condensates are prepared under basic 

ing in a significant decrease in the concentration of conditions which employ about 0.25 to 4%, and preferaactive isocyanate groups available. 55 bly about 0.75 to 2.5% by weight of a basic material, 

The isocyanate compound and/or polymer is em- such as a metallic oxide or hydroxide, ammonium hyployed in amounts of about I to about 99% by weight, droxide or basic amine based upon the amount of phenol 

preferably about 10 to about 99% by weight, and most present. Examples of some suitable metallic oxides and 

preferably about 50 to about 90% by weight based upon hydroxides include alkali metal and alkaline earth metal 

the total amount of isocyanate and hydrophobic diluent 60 oxides and hydroxides, such as sodium hydroxide, poemployed. tassium hydroxide and lithium hydroxide. Examples of 

The term "protected isocyanate" when employed in some suitable basic amines include triethyl amine and 

the present specification refers to the combination ofthe triethanol amine. The most preferred phenolic-aldeisocyanate and hydrophobic diluent of the type dis- hyde polymers employed according to the present incussed hereinabove. 65 vention contain from about 3 to about 5% by weight of 

The aqueous component of the compositions of the free phenol and a pH of about 8.5 to about 9.0. Mixtures 

present invention includes an aldehyde condensate. The of phenolic-aldehyde polymers can be employed when 

aldehyde condensate is preferably a urea-, or melamine- desired. 
5 

4,341,668 

6 

verted to hydroxyl groups for reaction with the isocyanate. 

Examples of some suitable' ethylenically unsaturated 

monomers to be employed in the polymer but which do 

A typical process for preparing the phenolic-aldehyde condensates include condensing at about 60°-105° 

C. until the aldehyde is substantially consumed. It may 

be desirable to carry out the process in the presence of 

casein such as in amounts from about 0.5 to about 10% 

by weight based upon the weight of the phenol employed in the process. 

The preferred phenolic-aldehyde condensates employed in the present invention have a pH of at least 

about 8 and most preferably at least about 8.3. The use 

of these preferred aldehyde condensates provide for 

compositions having a high degree of stability and shelf 

life. 

5 not contain groups reactive with the isocyanate include 

acrylate and methacrylate monomers, such as methylacrylate, ethylacrylate, butylacrylate, methylmethacrylate, ethylmethacrylate, butylmethacrylate, and 2-ethylhexyl acrylate; ethylene; propylene; styrene; methyl 

10 styrene; divinyl benzone; butadiene; and vinyl esters 

such as vinylacetate, vinylpropionate, and vinyl versatate. Mixtures of polymers can be employed when desired. 

The compositions of the present invention also include a compound capable of providing reactive methy- 15 

lene sites at elevated temperatures. The methylene donors are essentially non-reactive at normal room temperatures but provide reactive methylene groups at 

elevated temperatures such as at about 135° C. and 

above. Examples of some specific methylene donors 20 

include hexamethylene tetraamine and trimethylol nitromethane. Mixtures of methylene donors can be employed when desired. The methylene donors are preferably water soluble or water compatible and present in 25 

the aqueous component of the composition. The 

amount of methylene donor is usually about 1 to about 

20% by weight and preferably about 5 to about 10% by 

weight based upon the total amount of aldehyde condensate present in the composition. 30 

The aqueous component of the compositions of the 

present invention can also contain polymers in addition 

to the aldehyde condensate. This additional polymer is 

water soluble or water dispersible. The additional polymer can be non-reactive or preferably contain at least 35 

one group which is reactive with the isocyanate, such as 

reactive hydrogen groups including hydroxyl, carboxyl, amine and amide groups. Examples of some suitable polymers containing groups reactive with the isocyanate are synthetic water dispersible polyesters ob- 40 

tained from polyhydric alcohols, such as propylene 

glycol and polypropylene glycol and polycarboxylic 

acid such as adipic acid; and homopolymers or copolymers (from two or more monomers) from monomers 

containing ethylenically unsaturated groups. 'For in- 45 

stance, those polymers suggested in u.s. Pat. No. 

3,931,088 are quite suitable for the purposes of the present invention. 

Examples of some suitable ethylenically unsaturated 

monomers with groups reactive with isocyanates to be 50 

employed in the polymer include dimethylaminoethylmethacrylate, 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate, hydroxypropylmethacrylate, ethyleneglycoldimethacrylate, hydroxypropylacrylate, Nisobutoxy methylacrylamide, acrylamide, methacryl- 55 

amide, allyl alcohol, acrylic acid, methacrylic acid, 

maleic acid, fumaric acid, crotonic acid, and maleic 

anhydride. In addition, examples of some suitable copolymers containing N-methylol functional derivative 

of an allyl carbamate etherified with a CI-Cg alcohol 60 

can be found in u.s. Pat. No. 3,941,735 to Lindemann. 

The reactive groups can be provided in the monomer 

and/or the polymer by treatment subsequent to and/or 

concurrent with the polymerization of the monomers. 

For instance, polymers from vinyl acetate can be 65 

treated by saponification to provide reactive hydroxyl 

groups to provide polyvinyl alcohol. Also, the 

glycidylacrylate and glycidylmethacrylate can be conThe polymers reactive with the isocyanate generally 

contain an average of at least about two reactive functionalities per polymer chain. 

The presence of the additional polymer and especially the polymers which contain at least one group 

reactive with the isocyanate provide for enhanced 

physical strength characteristics. Those compositions 

which contain an additional polymer which contain at 

least one group reactive with the isocyanate are preferred. 

The term "polymer component which contains 

groups reactive with the isocyanate" or similar terms 

refers to the entire additional polymer component of the 

aqueous phase wherein at least one of the polymers 

contains at least one group reactive with the isocyanate. 

Accordingly, said term can encompass a mixture which 

also includes polymers which do not have groups reactive with the isocyanate. 

The compositions of the present invention can include auxiliary agents such as compounds known to 

catalyze isocyanate reactions in common urethane reactions. Examples of urethane catalysts include amines, 

divalent metal salts, alkali and alkaline earth oxides and 

hydroxides. The preferred urethane catalysts employed 

according to the present invention are tertiary amines. 

Those compositions which contain an additional polymer containing at least one group reactive with the 

isocyanate and a tertiary amine have enhanced stability 

and shelf-life when compared to such compositions 

which do not contain a tertiary amine. 

The tertiary amines which are employed according to 

a preferred aspect of the -present invention are those 

which are generally deemed to be catalysts for isocyanate reactions, and preferably tertiary amines including 

the alkanol amines and alkyl arriines wherein the alkanol 

and/or alkyl groups generally each contain 1 to 5 carbon atoms. 

The amines generally have ,up to about 20 carbon 

atoms. Examples of suitable amines include trialkyl 

amines such as trimethylamine and triethylamine; triethanolamine; dimethylethanolamine; diethylenetriamine; 

tetramethyl butane diamine; N-methyldipropylene triamine; N-diethylamino acetic acid; methylamino propionic acid; pyridine; substituted pyridines; N-alkyl morpholine compounds such as N-methyl morpholine; 

other substituted morpholine compounds such as Nacetyl morpholine and 4,4'-dithio morpholine; quiniline; 

isoquiniline; tetra-methylguanidine; cyclohexyl dimethylamine; and dimethyl aniline. 

The compositions of the present invention generally 

contain about 5 to about 97.5% by weight, and preferably about 10 to about 60% by weight of the aldehyde 

condensate; about 2 to about 75% by weight, preferably 

about 5% to about 40% by weight and more preferably 

about 5 to about 25% by weight of the isocyanate com-
7 

4,341,668 

8 

pound and/or prepolymer. The above amounts of materials are based upon the total of the aldehyde condensate, isocyanate, and methylene donor present in the 

composition. The amount of methylene donor is about 1 

to about 20% by weight and preferably about 5 to about 5 

10% by weight based upon the aldehyde condensate. 

With respect to those compositions of the present 

invention which contain one or more of the above-discussed additional polymers, such, in addition to the 

above-discussed amounts of methylene donor, generally 10 

contain from about 5 to about 50% by weight, and 

preferably about 10 to about 30% by weight of the 

aldehyde condensate; about 2 to about 75% by weight, 

preferably about 5 to about 40% by weight, and more 

preferably about 5 to about 25% by weight of the isocy- 15 

anate compound and/or prepolymer; about 25 to about 

93% by weight, preferably about 50 to about 85% by 

weight, and more preferably about 70 to about 85% by 

weight of the above-discussed polymer in addition to 

the aldehyde condensate; and when present from about 20 

0.1 to about 10% by weight, preferably about 0.1 to 

about 4% by weight, and more preferably about 0.1 to 

about 2% by weight of the tertiary amine. The above 

amounts of materials are based upon the total of the 

aldehyde condensate, isocyanate, additional polymer, 25 

and tertiary amine present in the composition. 

The compositions of the present invention generally 

contain from about 10 to about 74% by volume of nonvolatiles, preferably about 30 to about 60% by volume, 

and more preferably about 35 to about 55% by volume 30 

of non volatiles based upon the total volume of the composition. The isocyanate compound and/or polymer is 

employed in amounts of about 1 to about 99% by 

weight, preferably about 10 to about 90% by weight, 

and more preferably about 50 to about 90% by weight 35 

based upon the total amount of isocyanate and hydrophobic diluent employed in the composition. As apparent, the remainder of the composition after taking into 

account the amount of nonvolatile component and the 

amount of organic diluent is the water. 40 

In addition, the compositions can include auxiliary 

agents such as surface-active agents, water soluble 

oligomers, and fillers. The surface-active agent can be 

introduced to the compositions due to its use in the 

preparation of any of the polymers employed. The sur- 45 

face active agents can be anionic, cationic or nonionic 

surface active agents. Examples of some anionic surfactants include carboxylic acid salts such as salts of aliphatic carboxylic acids; alkyl sulfates and sulfonates; 

alkyl benzene sulfonates; alkyl naphthalene sulfonates; 50 

lignin sulfonates; and alkyl benzene sulfonates, alkyl 

naphthalene sulfonates, and the like; phosphonic ester 

salts such as phosphonic acid esters of higher fatty 

acids, and the like. The concentration of the surface-active agent when employed is usually about 0.1 to about 55 

10 weight percent, and more preferably about 0.2· to 

about 5 weight percent based upon the weight of the 

polymers present in the aqueous component of the composition. 

Suitable fillers include organic substances such as pO 

wood powder and powder of walnut shell, as well as 

inorganic substances, such as clay, kaolin, silica, calcium carbonate, and talc. 

The amount of filler, if employed, is generally about 

10 to about 50 volume percent based upon the total 65 

non volatiles of the composition. 

The preferred compositions of the present invention 

are substantially, if not completely free from acid catalysts. The aqueous component can be a solution, emulsion, or suspension, or combination thereof. 

The compositions of the present invention are preferably prepared by adding the methylene donor prior to 

the incorporation of the isocyanate portion of the composition. However, any sequence of addition of the 

components can be carried out. Also, the compositions 

are preferably prepared by adding the amine when 

present prior to the incorporation of the isocyanate 

portion of the composition. When the composition contains one or more of said additional polymers having 

groups reactive with the isocyanate, for improved stability characteristics, the preferred method of admixing 

provides for improved stability characteristics when 

said additional polymer having groups reactive with the 

isocyanate is present and includes admixing the polymer 

reactive with the isocyanate followed by the amine 

followed by the aldehyde condensate, followed by the 

methylene donor and then the isocyanate portion or 

admixing the polymer reactive with the isocyanate to 

which is added the aldehyde condensate followed by 

the amine and methylene donor and then the isocyanate 

portion. 

In addition, the compositions should be prepared by 

low speed or low shear mixing conditions, since high 

shear type mixing tends to shorten the pot life of the 

composition. It has been noted that the finer particle 

dispersions result in shorter pot life. Accordingly, ·a 

mild agitation is normally employed to form the mixtures of the present invention. 

The compositions can be subjected to an initial partial 

cure treatment which is usually carried out at room 

temperature to about 121° C. for about 5 minutes to 

about 24 hours. The composition because of the presence of the methylene donor can be post cured such as 

by heating at 135° C. to about 232° C. for about 1 minute 

to about 15 minutes. The time and temperature up to 

above cure treatments are inversely related. Thatis, as 

the temperature increases, the time needed for cure 

decreases and vice versa. 

The compositions of the present invention are particularly suitable for bonding and impregnating cellulosic 

materials and/or fibrous materials such as paper including filter papers, such as oil filter paper, industrial air 

filter paper and railroad filter paper; wood; cotton, 

including waste cotton fibers; nylon; and rayon. 

The following non-limiting examples are presented to 

further illustrate the present invention wherein all parts 

are by weight unless the contrary is stated. 

EXAMPLE 1 

To about 100 parts by weight of a polymer aqueous 

emulsion of about 35% solids are added with a slow 

speed mixing about 6.8 parts by weight of a heat reactive water dispersible aqueous phenol-formaldehyde 

polymer with 50% solids; about 1 part by weight of 

triethylamine, about 0.3 parts by weight of hexamethylene-tetraamine, and about 3.4 parts by weight of a 

protective polyisocyanate containing about 75% by 

weight of a polymeric methylene diphenyl diisocyanate 

(MDI), about 12.5% by weight of toluene, and about 

12.5% by weight of dibutylphthalate. The aqueous polymer emulsion is obtained from· about 43.04 parts by 

weight of Vinol 523, about 9.56 parts by weight of 

Vinol 425, about 693.08 parts by weight of Airflex 400, 

about 0.48 parts by weight of Dowcil 75, and sufficient 

water to provide a solids content of about 34%. Vinol 

523 is a polyvinyl alcohol commercially available from 
9 

4,341,668 

Air Products and Chemicals, Inc., and, according to the 

manufacturer, is about 87 to about 89% hydrolyzed, has 

a pH of about 5 to 7 as measured in a 4% aqueous solution, and a viscosity of about 21 to about 25 centipoise 

as measured in a 4% aqueous solution at 20° C. Vinol 5 

425 is available from Air Products and Chemicals, Inc. 

and, according to the manufacturer, is a polyvinyl aJcohoI hydrolyzed to about 95.5 to 96.5%, has a pH of 

about 5 to 7 as measured in a 4% aqueous solution, and 

a viscosity of about 26 to 30 centipoise as measured in a 10 

4% aqueous solution at 20° C. Airflex 400 is commercially available from Air Products and Chemicals, Inc. 

and is an aqueous solution emulsion of a co-polymer 

ethylene and vinyl acetate and, according to the manufacturer, has a minimum solids of about 55%, a Brook- 15 

field viscosity at 60 rpm and 77° F. of about 1400 to 

about 2000 centipoise, and a Brookfield viscosity at 20 

rpm and 77° F. of about 1900 to about 2800 centipoise, 

a pH of about 4.0 to about 5.0, and contain as protective 

colloid partially acetylated polyvinyl alcohol. A further 20 

discussion of Airflex 400 can be found in a publication 

from Air Products and Chemicals, Inc. entitled "Air 

Flex 400 Base for Adhesives", Bulletin 151-919, disclosure of which is incorporated herein by reference. 

Dowcil 75 is available from the Dow Chemical Com- 25 

pany and, according to the manufacturer, is 1-(3-

chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride 

containing a sodium bicarbonate stabilizer. Dowcil75 is 

a preservative used in adhesives. 

The phenol-formaldehyde condensate is prepared 30 

from formaldehyde and phenol in a mole ratio of about 

1.8: 1; employing about 35.2 parts by weight of phenol, 

about 2.1 parts by weight of 50% aqueous sodium hydroxide, about 15.5 parts by weight of water, aDout 3.4 

parts by weight methanol, about 41.7 parts by weight of 35 

50% formaldehyde, and about 0.09 parts by weight of 

29% aqueous ammonia at a pH of about 8.5. The phenol-formaldehyde has about 4% free phenol. 

Automotive oil filter paper is treated with the above 

composition to provide about 18 to 22% polymer 40 

pickup when cured at about 121 ° C. for about 15 minutes. The treated paper is partially cured by heating for 

5 minutes at about 177° C. The treated paper is then 

conditioned for 4 hours at about 77° F. and 50% relative 

humidity before being tested. The tests performed are 45 

for Mullen burst strength, tensile strength, and Gurley 

stiffness values. The Mullen burst strength is about 43.0 

psi, the tensile strength about 27.4 Ibs/inch, and the 

Gurley stiffness MD (machine direction) about 4445 mg 

and Gurley stiffness XD (cross direction) about 2756 50 

mg. 

Prior to post curing, the Mullen burst strength is 

about 44.6 psi, the tensile strength about 26.4 Ibs/inch, 

the Gurley stiffness MD is about 3512 mg and the Gurley stiffness XD is about 2400 mg. After 68 hours at 200° 55 

F. in lOW-40W multigrade oil, the Mullen burst 

strength is 40.1 psi, the tensile strength is about 25 

Ibs/inch, the Gurley stiffness MD is about 5218 mg, and 

the Gurley stiffness XD is about 3256 mg. 

COMPARISON EXAMPLE 2 

Example 1 is repeated except that the composition 

does not contain a methylene donor, and accordingly, is 

not subjected to post curing. The Mullen burst strength 

60 

is about 44.5 psi, the tensile strength is about 28.8 65 

1bs/inch, the Gurley stiffness MD about 2845 mg and 

the Gurley stiffness XD about 1556 mg. After 68 hours 

at 250° F. in lOW-40W multigrade oil, the Mullen burst 

10 

strength is 42.5 psi, the tensile strength is 27.5 Ibs/inch, 

the Gurley stiffness MD is 2534 mg and the Gurley 

stiffness XD is 1512 mg. 

A comparison of Examples 1 and 2 illustratys the 

significant improvement in stiffness achieved by employing a methylene donor which renders the treated 

paper practical for use as an oil filter. The burst strength 

and tensile strength when employing the methylene 

donor were only reduced slightly. 

EXAMPLE 3 

To about 100 parts by weight of a polymer aqueous 

emulsion obtained by admixing about 181.5 parts of 

water, about 3.5 parts of hexametaphosphate; about 1.35 

parts of tributylphosphate; about 3.10 parts of 80 micron 

calcium carbonate (Gamma sphere 80); about 19 parts 

of a 15% aqueous polyvinyl alcohol available under the 

trade designation PBA-EST; about 61 parts of a heatreactive water-dispersible aqueous phenol-formaldehyde polymer with 50% solids; about 396 parts of a 

noncarboxylated butadiene-styrene polymeric latex 

available under the trade designation Dow SBR Latex 

XD 30485; about 13.2 parts oftoluene; about 1.2 parts of 

Dowacil 75; and about 5 parts of a hydroxymethyl 

cellulose available under the trade designation Carbopol are added about 5 parts of a 50% aqueous solution 

of hexamethylenetetraamine and about 20 parts of a 

protective polyisocyanate containing about 75% by 

weight of a polymeric methylene diphenyl diisocyanate 

(MDI), about 12.5% by weight of toluene, and about 

12.5% by weight of dibutylphthalate. The PBA-EST is 

similar to Vinol 425 employed in Examples 1 and 2 

above and is a polyvinyl alcohol hydrolyzed to about 

95.5 to 96.5%, has a pH of about 5 to 7 as measured in 

a 4% aqueous solution, and a viscosity of about 26 to 30 

centipoise as measured in a 4% aqueous solution at 20° 

C. 

Dowcil 75 is available from the Dow Chemical Company and, according to the manufacturer, is 1-(3-

chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride 

containing a sodium bicarbonate stabilizer. Dowcil 75 is 

a preservative used in adhesives. 

The phenol-formaldehyde condensate is prepared 

from formaldehyde and phenol in a mole ratio of about 

1.8:1; employing about 35.2 parts by weight of phenol, 

about 2.1 parts by weight of 50% aqueous sodium hydroxide, about 15.5 parts by weight of water, about 3.4 

parts by weight methanol, about 41. 7 parts by weight of 

50% formaldehyde, and about 0.9 parts by weight of 

29% aqueous ammonia at a pH of about 8.5. The phenol-formaldehyde has about 5% free phenol. 

The composition is applied to one surface at 60 

. Ibs/100 sq. ft. via brushing and two surfaces of two 

pieces of Ponderosa Pine wood are bonded together 

under 125-150 psi for 16 hours. The composition is then 

post cured for 10 minutes at 325° F. The laminate is then 

subjected to 4 hours boiling water and dried overnight 

in a forced air oven at 60° C. It is then subjected to 

boiling water for another 4 hours. 

Then it is cooled with ambient water and tested wet 

to determine tensile-shear strength, according to 

ASTM 3110. The tensile-shear strength is 376 psi with 

35% wood failure. 

COMPARISON EXAMPLE 4 

Example 3 is repeated except that the composition 

does not contain a methylene donor and, accordingly, is 

not subjected to post curing. 
4,341,668 

11 12 

When subjected to the boil dry testing according to 

ASTM 3110, the tensile-strength is 328 with 25% wood 

failure. 

We claim: 

1. A composition comprising a compound capable of 5 

providing reactive methylene sites at elevated temperature of about 1350 C. and above; a hydrophobic component containing an organic hydrophobic diluent and an 

isocyanate; and an aqueous component containing a 

water soluble phenolic-aldehyde condensate having 10 

free methylol groups and a pH of at least about 8 and 

being obtained from about 0.75 to about 3.3 moles of 

aldehyde per mole of phenolic compound. 

2. The composition of claim 1 wherein said compound capable of providing reactive methylene sites is 15 

hexamethylene tetraamine or trimethylol nitromethane. 

3. The composition of claim 1 wherein said compound capable of providing reactive methylene sites is 

hexamethylene tetraamine. 

4. The composition of claim 1 wherein the aqueous 20 

component further includes a polymer in addition to 

said aldehyde condensate. 

5. The composition of claim 4 wherein said polymer 

in addition to said aldehyde condensate contains groups 

reactive with said isocyanate. 25 

6. The composition of claim 1 which further contains 

a tertiary amine. 

7. The composition of claim 1 wherein said isocyanate compound contains at least two isocyanate groups. 

8. The composition of claim 7 wherein said isocya- 30 

nate is polymeric methylene bisphenyl diisocyanate. 

9. The composition of claim 1 wherein said hydrophobic diluent is selected from the group of aliphatic 

hydrocarbons, aromatic hydrocarbons, cycloaliphatic 

hydrocarbons, halogenated hydrocarbons, ketones, 35 

ethers and esters. 

10. The composition of claim 9 wherein said hydrophobic solvent is an aliphatic, cycloaliphatic or aromatic hydrocarbon. 

11. The composition of claim 9 wherein said hydro- 40 

phobic solvent is an aromatic hydrocarbon. 

12. The composition of claim 9 wherein the hydrophobic solvent is toluene. 

13. The composition of claim 9 wherein said hydrophobic solvent is a diester of phthalic acid. 45 

14. The composition of claim 9 wherein said hydrophobic solvent is dibutyl phthalate. 

15. The composition of claim 1 wherein the isocyanate is employed in amounts of about 1 to about 99% by 

weight based upon the total amount of isocyanate and 50 

hydrophobic diluent. 

16. The composition of claim 1 wherein the isocyanate is employed in amounts of about 10 to about 90% 

21. The composition of claim 1 wherein the phenolicaldehyde condensate is obtained from about 1.5 to about 

2.5 moles of aldehyde per mole of phenolic compound. 

22. The composition of claim 1 wherein said phenolic-aldehyde condensate is prepared under basic conditions employing about 0.25 to about 4% by weight of a 

basic material based upon the amount of phenolic compound. 

23. The composition of claim 1 wherein said phenolic-aldehyde condensate is prepared under basic conditions in the presence of about 0.75 to about 2.5% by 

weight of a basic material based upon the amount of 

phenolic compound. 

24. The composition of claim 1 wherein said phenolic-aldehyde condensate contains about 3 to about 5% by 

weight of free phenolic compound. 

25. The composition of claim 1 wherein said phenolic-aldehyde condensate is a phenol-formaldehyde condensate prepared in the presence of casein at a pH of 

about 8.5 to about 9.0. 

26. The composition of claim 25 wherein the amount 

of casein present is from about 0.5 to about 10% by 

weight based upon the weight of the phenol and formaldehyde. 

27. The.composition of claim 5 wherein the aldehyde 

condensate is employed in an amount of about 5 to 

about 50% by weight; said isocyanate is employed in an 

amount of about 2 to about 75% by weight; and the 

polymer which contains groups reactive with said isocyanate is employed in an amount of about 25 to about 

90% by weight wherein the above amounts are based 

upon the total of aldehyde condensate, isocyanate, and 

the polymer which contains groups reactive with said 

isocyanate in the composition. 

28. The composition of claim 5 which contains from 

about 0.1 to about 10% by weight of a tertiary amine 

based upon the total of aldehyde condensate, isocyanate, the polymer which contains groups reactive with 

said isocyanate and amine. 

29. The composition of claim 5 wherein the aldehyde 

condensate is employed in an amount of about 10 to 

about 30% by weight, said isocyanate is employed in an 

amount of about 5 to about 40% by weight; said polymer component which contains groups reactive with 

said isocyanate is employed in an amount of about 50 to 

about 85% by weight wherein the above amounts are 

based upon the total of the phenolic-aldehyde condensate, isocyanate, and polymer reactive with said isocyanate in the composition. 

30. The composition of claim 29 which includes a 

tertiary amine of about 0.1 to about 4% by weight based 

upon the total of said phenolic-aldehyde condensate, 

by weight based upon the total amount of isocyanate said isocyanate, said amine, and said polymer compoand hydrophobic diluent. 

17. The composition of claim 1 wherein the isocyanate is employed in amounts of about 50 to about 90% 

55 nent which contains groups reactive with said isocyanate. 

by weight based upon the total amount of isocyanate 

and hydrophobic diluent. 

18. The composition of claim 6 wherein said amine is 60 

triethylamine. 

19. The composition of claim 1 wherein said phenolic-aldehyde condensate is a phenol-formaldehyde condensate. 

20. The composition of claim 1 wherein the phenolic- 65 

aldehyde condensate is obtained from about 0.95 to 

about 3 moles of aldehyde per mole of phenolic compound. 

31. The composition of claim 1, 27, 28, 29 or 30 

wherein the amount of said compound capable of providing reactive methylene sites is about 1 to about 20% 

of weight based upon the weight of said aldehyde condensate. 

32. The composition of claim 31 wherein the amount 

of said compound capable of providing reactive methylene sites is about 5 to about 10% by weight based upon 

the weight of said aldehyde condensate. 

33. The composition of claim 1 wherein the total 

nonvolatile content is about 10 to about 74% by volume. 
13 4,341,668 14 

34. The composition of claim 1 wherein the total 

nonvolatile content is about 30 to about 60% by volume. 

isocyanate have an average of at least about two reactive functionalities per polymer chain. 

35. The composition of claim 1 wherein the total 

nonvolatile content is about 35 to about 55% by vol- 5 

39. The composition of claim 4 or 5 which further 

contains about 0.1 to about 10 weight percent of a surface-active agent based upon the weight of the polymers present in the aqueous component of the composition. 

ume. 

36. The composition of claim 1 wherein the pH of 

said phenolic-aldehyde condensate is at least about 8.3. 

37. The composition of claim 5 which said groups 

reactive with said isocyanate are selected from the 

group of hydroxyl, carboxyl, amine, amide or mixtures 

thereof. 

38. The composition of claim 5 wherein said polymer 

component which contains groups reactive with said 

40. The composition of claim 1 which further in10 cludes about 10 to about 50 volume percent of a solid 

filler based upon the nonvolatiles of the composition. 

41. The composition of claim 1 which is substantially 

free from acid catalysts. 

'" '" '" '" '" 

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