Application of Franklin W. Herrick and Louis H. Bock

WORLEY, Chief Judge

(dissenting).

Considering the state of the prior art reflected in the references cited by the Patent Office in this twice-argued appeal, it seems to me the examiner and board had ample reason for concluding that the subject matter of appellants’ claims is not patentable.

I am particularly concerned with the manner in which the majority treats claims 2 and 3. In substance, those claims recite a water insoluble, organic solvent soluble, polymethylol phenol condensate1 or heavy syrup having a com*340bined formaldehyde-phenol ratio of 2.3 to 2.52 and free of inorganic salts.

As the majority observes, the examiner found those claimed products to be “obvious to one skilled in the art having the tetramethylol-4,4'-dihydroxydiphenyl-methane disclosure of Martin” alone before him or considered further with Amann and Schrader.

The Martin reference discloses, in pertinent part:

It is now well established that in addition to the mononuclear phenol alcohols tetramethyloldihydroxydiphenylmethanes are important products of the later stages of the reaction between phenol and formaldehyde. Walker first reported the separation of 3,3', 5,5' - tetramethylol - 4,4' - dihydroxydiphenylmethane from a phenol-formaldehyde reaction mixture in 1935. A few years later Seebach made a detailed study of the compound * * *. * # * * * *
Seto has reported the synthesis of the tetramethylol derivatives of 2,2'-2 and 2,4'-dihydroxydiphenylme-thane in addition to the previously known 4,4/-isomer. The tetramethylol derivative of 2,2/-dihydroxydiphenyl-methane melts at 132-133 °C., of the 2,4'-isomer at 117-118°C., and of the 4,4'-isomer at 145-146°C. Martin had previously obtained a compound melting at 130-132 °C. which showed the correct analysis for a tetramethyloldihydroxydiphenylmethane. Although it was never proved, it would appear from the melting point that the compound obtained by Martin may have been the tetramethylol derivative of 2,2'-dihy-droxydiphenylmethane.
Tetramethyloldihydroxydiphenylmethane is formed by the self-condensation of the salts of trimethylolphenol in aqueous solution. The reaction occurs by the elimination of water and formaldehyde between 2 moles of the trialcohol and appears to be a first-order reaction dependent on the concentration of trimethylolphenol. This would mean that significant quantities of the tetraalcohol would be formed only in the later stages of a reaction between phenol and formaldehyde after appreciable quantities of the trialcohol had accumulated in the system. A high ratio of formaldehyde to phenol, e.g., in the neighborhood of 2 or 3 to *3411, also favors the formation of the compounds, but they have been detected even at a ratio of 0.8 to 1. A long reaction period would favor the tetraalcohol; a somewhat shorter reaction period would give more of the trialcohol. Many of these points are well illustrated by the data presented by Freeman and Lewis. [Emphasis supplied.]

Martin also discloses processes for the manufacture of “some of the more common resoles 3 or One-Stage resins,” stating:

CASTING RESIN. For each mole of phenol, 2.5 moles of formaldehyde as formalin solution is employed. The catalyst may be any alkali such as NaOH, KOH, or LiOH. Approximately 15 grams of 10% caustic per mole of phenol is typical with the reaction mixture being held at reflux temperature for lV^-lVz hours. The resin is then cooled and neutralized to a pH of 5.5-6.5 with lactic, citric, or tartaric acid. * * * [Emphasis supplied.]

Said the examiner:

* * * It is to be noted (and emphasized) that the tetramethylol compound relied on in Martin has 4 (four) methylol groups and a methylene bridge (joining the two phenolic nuclei) * * *, has 5 “combined” formaldehyde groups for two phenolic nuclei, this giving a “combined formaldehyde-to-phenol ratio” of 2.50 to 1. It is thus seen that the tetramethylolphenol compound of the prior art meets the quoted recitation from appealed claim 2.

With respect to the claim limitation “and having a degree of condensation such that it is water insoluble but soluble in organic solvents including methanol,” the examiner noted that appellants’ specification discloses that their “polymethylol phenol” has a “predominating chain length” of “two phenol units.” He concluded :

* * * clearly, the tetramethylol4,4/-diphenylmethane of Martin has a chain length of two phenol units and a combined formaldehyde to phenol ratio of 2.50:1. It is respectfully submitted that no novel or unobvious polymethylol phenol has been discovered or claimed; * * * [Emphasis supplied.]

The board agreed.

Disposition of this appeal has not been facilitated by certain seeming inconsistencies between the arguments made in appellants’ brief and the content of their specification and claims, and the resultant uncertainty engendered as to just what appellants are claiming. Their argument with respect to Martin is predicated on Martin’s asserted disclosure of only dimers of trimethylol phenol whereas, according to appellants’ brief, their reactants are condensed “to the point where n is equal to 2 to 5” and claims 2 and 3 are purportedly directed to a condensate mixture “consisting of dimers to pentamers.” With a condensate mixture consisting only of dimers to pentamers, it would appear, of course, quite impossible to have a combined formaldehyde to phenol ratio of greater than 2.5. Appellants have not explained how they obtain a condensate having a combined formaldehyde-phenol ratio of greater than 2.5, e. g. 2.52, without the presence of a fair proportion of trimethylol phenol monomer (at least 4% if one assumes the 2.52 ratio material contains only monomer and dimer or, if one assumes the presence of “trimers” etc. in the “mixture,” a substantially higher percentage of monomer corresponding to that required to maintain the claimed ratio at 2.52. In view of that, one also might wonder how the seemingly necessary *342presence of water-soluble trimethylol phenol in the condensate is consistent with the claim recitation that the condensate product is water insoluble. To me it is evident that:

(1) accepting appellants’ arguments in the brief at face value, their condensate product of 2.5/1 ratio contains no trimethylol phenol monomer whereupon (a) claims 2 and 3 necessarily read directly on the tetramethylol derivatives of 2,2'- or 4,4'-dihydoxydiphenylmethane which Martin discloses to be known compounds and (b) discussion of Martin’s failure to disclose specific inherent properties of those materials is wholly immaterial,4 or
(2) Following the lead of appellants’ specification, their condensate product necessarily contains a substantial portion of water-soluble trimethylol phenol and does not therefore distinguish over any conventional A-Stage or resole resin.

With respect to process claim 1 the majority seems to rely heavily on the limitation therein that the reactants are cooled to 10 °C. while adding sulfuric acid. In view of the fact that (1) most of the references in the record before us disclose that the reactants must be cooled both to arrest condensation and also during neutralization, and (2) the fact appellants’ specification attaches no particular significance to that limitation in any of its examples, it seems to me the board was correct in finding that limitation to be well within the skill of the art. Appellants certainly do not appear to be in a favorable position to argue its criticality. In re Cole, 326 F.2d 769, 51 CC PA 919 (1964).

With respect to the remaining claims, I am satisfied that the examiner and board were correct in concluding that particular subject matter is obvious in view of the prior art. I would affirm.-

. Some background will be helpful in understanding the scope of claims 2 and 3. Appellants react phenol with excess formaldehyde to prepare (at least transitorily or as an intermediate) monomeric trimethylol phenol, having the formula:

[[Image here]]

That compound, according to appellants’ specification and brief, is water soluble.

It obviously has a combined formaldehyde-phenol ratio of 3.0. During appellants’ synthesis procedure, trimethylol phenol is said to condense further to form compounds of the formula:

[[Image here]]

Where n=2, a “dimer” of trimethylol phenol is obtained, having a combined formaldehyde-phenol ratio of 2.5. Further condensation of that “dimer” with

*340other molecules of trimethylol phenol is said in appellants’ brief to lead to formation of “trímera,” “tetramers,” “pen-tamers” and the like, all possessing a combined formaldehyde-phenol ratio of less than 2.5. As appellants’ specification states:

It has been found in carrying out the reaction of phenol with formaldehyde, as practiced in this invention, that the product consists of a mixture of monomeric polymethylol phenols and loto molecular weight condensation products.

******** * * * it is difficult to obtain a combined ratio of formaldehyde to phenol above 2.5, and examples given in this specification range in value from 2.45 to 2.52. The corresponding n values, therefore, range from 2.08 to 1.92. In other words, the predominating chain length is about ttoo phenol units. ********

* * * If the degree of condensation is too low the product is too soluble in water and it is impossible to wash it free of salts without severe loss of material. However, any low condensed product can be used if the inorganic salts are removed by some other means, such as by ion exchange. On the other hand, if the condensation is carried too far the number of free methylol groups is insufficient to properly cure the lignin and form a water resistant infusible resin. We have found that the degree of condensation corresponding to a combined formaldehyde-to-phenol mole ratio of 2.3 to 2.52 is suitable for the purpose of this invention. This corresponds to an average chain length of 3.3 to 2.0. [Emphasis supplied.]

. The 2, 2'-compound corresponds to the “dimer” appellants state is obtained when n=2 in fn. 1, supra. The 2, 4'- and 4, 4'-isomers, of course, are also included within the scope of the claims.

. According to Kirk-Otlimer, Encyclopedia of Chemical Technology, Vol. 10, p. 336-337 (1953), resoles are low molecular weight phenol-formaldehyde resins “which are soluble in alkalies, alcohols, ketones, and, to some extent, water. They consist mainly of a complex mixture of phenol alcohols with a relatively high hydroxyl content.” [Emphasis supplied.]

. It is pertinent to note, as the board and solicitor point out, that appellants have presented no evidence that the prior art products disclosed by Martin do not have the claimed characteristic properties. Appellants’ argument in the brief does not take the place of evidence in the record on that score. In re Cole, infra.