US2813801A

US2813801A - Wood stains

Info

Publication number: US2813801A
Application number: US537065A
Authority: US
Inventors: Jr Harry A Toulmin
Original assignee: Chadeloid Corp
Current assignee: Chadeloid Corp
Priority date: 1955-09-27
Filing date: 1955-09-27
Publication date: 1957-11-19
Anticipated expiration: 1974-11-19

Description

surface with a filler.

WGOD STANS Harry A. Toulmin, .lra, Dayton, Ohio, assignor to Charleloid Corporation, Dayton, Ulric, a corporation of Delaware No Drawing. Application September 27, 1955, Serial No. 537,065

2 Claims. (Cl. 106-434) This invention relates to stains, especially stains for use on wood and to compositions for use in staining wood articles and the like, as well as methods for staining such articles.

This application is a continuation-in-part of application Serial No. 362,655, filed June 18, 1953, now aban- 9 doned, the latter being a division of my application Serial No. 277,919, filed March 21, 1952, now abandoned.

The art of wood staining in the past has made use of dyes which were dissolved or dispersed solvents and the like diluents so as to make the same applicable for apply- 0 'ing as a spray, dip, or by brush. The water-soluble stains "The grain raising effect of such water-soluble stains also quakes it necessary to apply a sealer coating such as shellac to the stained wood in order to stiffen the fibers of the wood so that the surface can be uniformly sanded. When an open-grain wood is used, it is necessary after the sanding operation to apply a filler to the surface over which is then applied a varnish, lacquer or other desired coatmg.

The non-aqueous stains, for example, oil stains and spirit stains, and which generally consist of an aniline dye or aniline dry base dissolved in an organic solvent such as a hydrocarbon or alcohol, have been extensively used and have certain advantages over water stains. They also have certain undesirable features. The use of hydro carbons, such as benzol, toluol or other petroleum distillates that are highly volatile when applied to the surface to be treated tends to leave the pores of the wood unimpregnated with the dye. They are also dangerous in mass application in a furniture factory. Where such composition is applied to a wood surface having open grain, it has been the practice after drying to treat the Again, before applying the finish coating of varnish or lacquer, there must be applied a coating of shellac or similar functioning coating over either the stain or the tiller in order to prevent bleeding. This application of shellac or the like is necessary, otherwise the solvents of the varnish or lacquer will penetrate into the stain and cause the color to bleed into the finish coat. The use of hydrocarbon solvents also is undesirable from the standpoint of fire hazard and the effect the volatile solvent may have on the operator applying the stain.

The spirit stains are not as useful as the water stains because they are subject to the disadvantage that such stains do not penetrate into the wood stains and they further lack permanency of color and tend to fade in use, similar as the oil type stains. Spirit stains are also subject to the bleeding effect, and in many instances, also produce the undesirable grain raising upon application to the Wood surface,

2,813,801 Patented Nov; 19, 1957 In accordance with the present invention, I have discovered that by combining citrus flavanone derivatives, for example, hesperetin, naringenin and eriodictyol as may be obtained from citrus pulp and citrus waste, with aniline or alkyl or aryl substituted aniline bases, as by coupling of the flavanone to diazotized aniline or amino compounds, and dispersing the resultant dye in water solution, an excellent wood staining composition is provided. The socalled citrns-azo dye can be readily fixed in the cellulose pores of the wood since it has an affinity for cellulose and is compatible with it. The coupled fiavanone amino-dye reaction product is capable of remaining in aqueous suspension thereby forming a coloring material compatible with the cellulose from which it is derived so that the dye solution will carry into the wood. I

It may be applied as a hot or cold aqueous solution to the wood. A hot, aqueous solution of such citrus-azo dyes, as made from these citrus flavanones and obtained from citrus waste, being derived from a cellulose source, forms a staining solution which is completely compatible with wood and cellulose products. Application of the dye solution to wood results in a highly desirable stain effect, the dye forming a dispersion of uniform character and one which deeply penetrates into the pores of the Wood without raising the grain.

The aqueous staining solutions of this invention which comprise the aforementioned citrus-azo dyes are preferably applied as a hot aqueous solution, although they are also effective as a wood stain when applied as a cold solution. Hot aqueous solutions of such dyes when applied penetrate into the Wood and the solvent evaporates before the grain of the wood is caused to raise. Upon cooling, the dye is set in the wood and forms a smooth uniformly stained wood surface which needs no sanding or other treatment to produce a desirablejsurface upon which may be applied a finish coating of varnish or lacquer.

In accordance with the invention, a Wood staining composition is provided which is very inexpensive and easy to manufacture, and wherein the use of expensive organic diluents and solvents and the like, with their attendant disadvantages may be entirely eliminated.

The formula of naringenin (as shown by Karrers Organic Chemistry, 1950-edition) is as follows:

The formula of hesperetin is given as follows:

CO H5 Eriodictyol, which is a tetrahydroxy flavanone is as follows:

O OH

- The combinationcitrus-azo dyes which are utilized in forming the wood staining composition of this invention are exemplified by the following formulae and which are illustrated graphically below:

Coupling aniline with naringenin, e. g. as recovered from grapefruitwaste, results in the production of an azo dye having the probable structural formula:

C O HO Substituting eriodictyol for naringenin the formula would Employing hesperetin as recovered from orrange waste, and coupling this compound with aniline, there results the production of an azo dye having the probable structural formula:

0 on E0 Err-Q0011 o o no Example I (1) To a solution comprising 0.1 mole of aniline in water is added 0.25 mol of hydrochloric acid. The mixture is diluted 50% by volume with water and cooled to a temperature of about 10 C.

While maintaining the temperature of the mixture at about 10 C. there is added slowly over a period of about 10 to 15 minutes a 0.1 mol aqueous solution of sodium nitrite. This mixture is then stirred for one-half hour while maintaining the temperature at about 10 C. This results in the formation of the diazonium salt CsHsNzCl.

(2) To effect the coupling action with the diazonium salt 1), an aqueous solution containing 0.1 mol of hesperetin dissolved in 0.1 mol of sodium hydroxide is employed. The resultant solution is diluted 50% by volume with water and cooled to between 5 and C. Thereafter, the diazo of (1) is stirred into the mixture over a minute period while maintaining the temperature at about l0-l5 C. and the pH of the solution above 9. After stirring the mixture for half an hour more, the dyestufi is isolated by adjusting the pH of the solution to neutral with dilute hydrochloric (0.1 N) and adding a salt, i. e., sodium chloride or sodium sulfate, until the dye precipitates from the solution. Thereafter, the mixture is filtered to recover the diazoaminohesperetin dyestufi.

Example 11 A wood stain is prepared by making up a 5% aqueous solution (5 gms. dyestuff/ gms. water) of the diazoaminohesperetin. The resultant staining solution may be applied to wood by spraying, brushing or dipping and allowed to dry. Force air drying at 250 F. may be used where separate articles of wood or pieces are to be stained.

A combination stain and filler may be formulated for use as a wood stain and filler composition as follows:

Example III To a 10% aqueous solution of the dyestufi of Example I is introduced 8% by weight of asbestine (300 mesh). The asbestine is preferably introduced as an aqueous paste containing 50% by weight asbestine, the filler being suitably ground or dispersed therein by means of a pebble mill or roller mill. To assist the dispersion of the filler particles and improve brushing properties of the stainfiller composition 1% by weight of polyethylene glycol monolaurate (based upon the liquid vehicle of the paste) is introduced. The ethylene oxide of the glycol laurate is polymerized with stannic chloride to a molecular weight of about 4500 to 4900.

In place of asbestine, there may be substituted for all or a portion thereof other suitable fillers, e. g. wood flour, infusorial earth, talc, kaolin and the like, the proportionate amount added being varied to produce a product which can be applied by brushing, dipping, or spraying.

Example IV Aniline diazotized is coupled with naringenin as in Example I, by reacting a solution of naringenin dissolved in sodium hydroxide at 15-25 C. with the mixture being kept above pH 9. After heating to 25 C. and stirring the mixture for half an hour, the dyestutf is isolated by adjusting the pH of the solution to neutral with dilute hydrochloric acid, then sodium chloride is added until the dye precipitates from the solution. The solution is then filtered to recover a diazoaminonaringenin dyestufi.

Example V A wood stain is prepared by providing an aqueous solution of the dyestutl of Example IV in water to form a 5% sodlution. The stain solution may be applied by brushing or spraying woods to stain the same.

Example VI A 50-50 mixture of naringenin and hesperetin is coupled with diazotized aniline as in Example I to produce mixed naringenin hesperetin diazoaminoflavanone dyestutl.

Example VII A wood stain is prepared by dispersing the resultant dyestufl? of Example VI in water to form a 10% solution (10 gms. dyestutf/ 100 gms. water) which may be sprayed or brushed onto wood and air dried to produce a stained wood.

Example VIII Example IV is repeated using eriodictyol in place of nar ngemn as the coupling component to produce a diazoaminoeriodictyol dyestufi.

Example IX A wood stain is prepared by making up an aqueous solution of the dyestufi of Example VIII. A 6% solution (6 gms. dyestuti in 100 gms. water) provides a staining composition. Where a filler is desired, 5% by weight of the solution may comprise wood flour. Talc especially fibrous type may also be used as the filler alone or mixed 50-50% by weight with wood flour.

In accordance with the present invention, it is possible for the first time to utilize such water soluble azo dyes made by coupling a flavanone derivative, such as naringenin, eriodictyol or hesperetin with aniline or other suitable diazotizing amino compound to form a watersoluble dye which yields, upon dispersion in an aqueous vehicle, a wood stain which is substantially fast to light, and exhibits non-fading, non-grain raising properties. A wood stain also is provided, which, when properly compounded and applied as described, does not bleed through lacquer or varnish top finishing coats. Thus, the use of intermediate sealing coats is not necessary. Where desired, of course, intermediate sealing coats of suitable type may be employed.

It will be understood that while there have been described herein specific embodiments of this invention, it is not intended thereby to have it limited to or circumscribed by the specific details given in view of the fact that this invention is susceptible to various modifications and changes which come within the spirit of this disclosure and the scope of the appended claims.

What is claimed is:

1. A combination wood staining and filling composition comprising an azo dye in which the coupling component is chosen from the group consisting of naringenin, hesperetin and eriodictyol, and containing inert organic filler and water suflicient to form at least a 5% solution, said filler comprising an aqueous paste and wherein the filler is selected from the group consisting of asbestine, fibrous talc and wood flour, and said composition containing about 1% by weight of polyethylene glycol monolaurate based upon the liquid vehicle of the paste.

2. A combination wood staining and filling composition comprising an azo dye in which the coupling component is chosen from the group consisting of naringenin, hesperetin and eriodictyol, said composition comprising a 10% aqueous solution of said dye and 8% by weight of asbestine filler consisting of aqueous paste containing 50% by weight of asbestine, and said composition containing about 1% by weight of polyethylene glycol monolaurate based upon the liquid vehicle of the paste.

References Cited in the file of this patent UNITED STATES PATENTS

Claims

1. A COMBINATION WOOD STAINING AND FILLINNG COMPOSITION COMPRISING AN AZO DYE IN WHICH THE COUPLING COMPO-NENT IS CHOSEN FROM THE GROUP CONSISTING OF NARINGENIN, HESPERETIN AND ERIODICTYOL, AND CONTAINING INERT ORGANIC FILLER AND WATER SUFFICIENT TO FORM AT LEAST A 5% SOLUTION, SAID FILLER COMPRISING AN AQUEOUS PASTE AND WHEREIN THE FILLER IS SELECTED FROM THE GROUP CONSISSTING OF ASBESTINE, FIBROUS TALC AND WOOD FLOUR, AND SAID COMPOSITION CONTAINING ABOUT 1% BY WEIGHT OF POLYETHYLENE GLYCOL MONOLAURATE BASED UPON THE LIQUID VEHICLE OF THE PASTE.