US1829258A - Process of retarding the setting of casein glue and dry glue base for use in such processes - Google Patents

Description

Patented Oct. 27, 1931 UNITED STATES PATENT OFFICE LAWRENCE BRADSHAW AND HENRY V. DUNEAM, OF BAINBRIDGE, NEW YORK, AS-

SIGNORS, BY MESNE ASSIGNMENTS, TO THE CASEIN'MANUFACTURING COMPANY OF AMERICA, IN C., OF NEW YORK, N. Y., A CORPORATION OF DELAWARE PROCESS OF RETARDING THE SETTING OF CASEIN GLUE AND DRY GLUE BASE FOR I USE IN SUCH PROCESSES No Drawing. Application filed April 2,

This invention has for its object improvements in casein waterproof glues or cements and in a novel glue base. which when prop erly incorporated with water will produce such an adhesive. It is well known that glues prepared from different commercial caseins exhibit wide variations in consistency when mixed with a given proportion of water and also difler greatly in their subsequent behavior, notably in the interval oftime which may elapse between-the initial mixing with water and the point at which the glue sets, i. e., becomes too thick to spread. Various methods have been proposed to control this interval, generally termed the life of the glue, such as the addition of animal glue or salts of the alkali or alkaline earth metals. The use of animal glue for this purpose is uneconomical, since its natural strength, which otherwise would contribute to the adhesiveness of the mixture, depreciates considerably under these conditions. The addition to casein glues of alkali metal phosphates, fluorides and other salts which by interaction with lime liberate caustic alkalies is undesirable beyond a certain point; that is to say,

peanut meal added to casein waterproof glues have a marked effect in retarding the setting of the liquid glues, thereby extending the life of such glues. As an example, the rates of change in the viscosity of a commercial casein glue (A) and of the same glue with 7% (B) and with 15% (C) respectively of pulverized cottonseed meal added are comared below. One part of each of the glue Eases was mixed with two parts of water at F., producing a slight rise in temperature. The viscosities were determined at 70 F., in all cases. The values represent readings on the Stormer viscosimeter (provided with a 500 gram weight) at regular intervals after 1926. Serial No. 99,423.

mixing. the conditions of making and testing the tlbhree liquid glues A, B and C, being identlca 1 hr. 3 hrs. 5 hrs. 7 hrs. 9 hrs 11 hrs 13 hrs.

A 26 9 2 set B 33 18 I 10 5 1 not set C 27 21 15 8 5 3 1% 1 hr. 3 hrs. 5 hrs. 7 hrs. 8 hrs.

A' 25 10 6 set P 24 20 9 2 not set;

We find that by substituting 50% of the casein in a regular third good commercial casein glue (A") by an equivalent amount of the pulverized peanut meal a glue (Q) is obtained which undergoes practically no change in viscosity over a long period, as shown in the comparison below:

1 hr. 3 hrs. 5 hrs. 7 hrs. 8 hrs.

A 20 8 23 36 set Q 20 20 21 22 25 The commercial casein glue referred to above, was in each case, a pulverulent mixture consisting of casein, hydrated lime and alkali-metal salts capable of reacting with the hydrated lime (when water is added) to produce caustic alkali and insoluble calcium salts. The proportions of said components were similar to the proportions given in the present application.

It will also be understood that by varying the proportions of the protein-rich meal added, the life of the glue can be controlled within wide limits. We prefer to use meal which has been ground to pass through a 120 mesh screen, although a coarser product of approximately 80 mesh has given good results in casein waterproof glues. With the finer meal a smoother glue is obtained.

In carrying out the inventionthe casein pressing cottonseed (a (that is, casein from milk) is mixed dry, with an appropriate amount of the vegetable meal, and to this mixture is added an alkaline earth metal hydroxide and preferably also one or more alkali metal salts capable of dissolving the proteins. The following examples of mixtures which have given satisfactory results-when applied to joints and laminated woods will serve to illustrate more particularly the character of the invention, but we do not desire to be limited to the particular compounds or proportions herein set forth. (The parts are b weight).

7 Example 1. asein 60 'parts; cottonseed meal 120 mesh, 10 parts; hydrated lime parts; sodium fluoride 5 parts, sodium carbonate 5 parts )tri-sodium phosphate 3 parts,

(98 parts in al Emmple 2.-Oasein 33 parts, cottonseed meal 33 parts, hydrated lime parts, sodium fluoride 6 parts sodium carbonate 8 parts, (100 parts 111 all).

Example 3.-Casein 50 parts, cottonseed meal 20 parts, hydrated lime 15 parts, magnesium oxide 5 parts, sodium fluoride 7 parts,

.til'i-sodium phosphate 3 parts, (100 parts in a sample 4.Casein 40 parts, peanut meal 30 parts, hydrated lime 18 parts, sodium fluoride 5 parts, sodium carbonate 5 parts, sodium arsenate 1 art, (99 parts in all). 4

Ewamle 5. asein parts, peanut meal 22 parts, hydrated lime 18 parts, sodium carbonate 10 parts, (100 parts in all).

Ewample 6-.-Casein 54 parts, peanut meal 30 parts, hydrate'd'lime 16 parts. Onepart of the dry mixture is to be incorporated with I about 3 parts of cold water.

These examples indicate the dry materials which are mixed together to form' the glue base. The dry mixture is incorporated with water (at or just before the time of use), by the methods well known to users of casein glues. We prefer to use from 2 to 2 parts of cold water to 1 part of the dry water is put into a kettle rovided with an eflicient stirring device; t e dry glue base (e. one of the above formulas) is added slow y minutes and the glue is then ready for use. The term casein is used herein in its usual significance, to denote certain coagulable phosphorus-containing roteid matter as found in milk and skim milk.

The cottonseedmeal preferably used (as re-- ferred to in Examples 1, 2 and 3) is the product obtained by grindin the cake left after r removal of the ma or (part of the hulls, and adhering fine lint if esired the oil ;-itusually-still contains some oil (perhaps -78%). It will be understood that the further removal ofoil by solvent treatment of the press cake, or the direct extraction of the oil from the seed with suitable solvents base. The l and mixed thoroughly for about 20' for the purpose of expressing.

used in aprecisely similar manner, and is accordingly considered as an equivalent, and the term protein-rich seed meal as used in the claims is intended to cover cotton seed meal and peanut meal. a

The term alkaline earth oxide as used in the appended claims is intended to embrace this material in the anhydrous or hydrated states, and also the corresponding oxide and hydroxide of magnesium. The term salt is intended to be used in the generic sense to include the singular or plural forms, i. e. one salt or several salts. The statement in any claim that the material will pass a screen of particular mesh does not mean that'the material (or some part thereof) will not pass through a finer screen. Alkaline substances, e. g. sodium carbonate, borax, etc. are capable (with Water) of dissolving casein and meal proteids.

We claim 1. A new dry base for use in making an adhesive materlal comprising casein as a substantial ingredient together with a substantial amount of a protein-rich seed meal, incorporated with an alkaline earth oxide and a Water-soluble alkali metal salt which reacts alkaline to litmus, and which salt is capable of reacting in the presence of water, with such alkaline earth oxide, which base is adapted upon being subsequently mixed with suflicient water, to produce a fluid adhesive of spreadable cons1stency. I 2. A new dry base for use in making an adhesive composition containing casein as a major ingredient together-with a relatively smaller but substantial amount of cotton seed meal from which most of the oil has been mixed with sufiicient water to reduce a fluid" adhesive of spreadable consis ncy.

3. A new dry base for the manufacture of glue and adhesive compositions, such base comprisinfg casein, a lesser but substantial amount 0 protein-rich seed meal ground to pass an 80 to meshscreen, an alkaline earth oxide in amount suificient to maintain the mixture alkaline, and a substantial amount of a water-soluble alkali metal salt which in aqueous solution will react with the said alkaline earth oxide to-produce a solvent forthe caseinand for the protein of said protein-rich seed meal, which base, upon being subsequently mixed with cold water will form a fluid adhesive.

4. A new dry base for the manufacture of glue and adhesive compositions, such base comprising casein and a protein-rich seed meal from which a large part of the hull substance has been removed, ground to pass an 80 to 120 mesh screen, such casein and seed meal both being present in substantial amount, an alkaline earth oxide, in amount sufficient to maintain the mixture alkaline and comprising casein, a lesser but substantial amount of protein-rich seed meal from which a substantial part at least of the oil has been removed, ground to pass an 80 to 120 mesh screen, an alkaline earth oxide in amount suflicient to maintain the mixture alkaline, and a substantial amount of a water-soluble alkali metal salt which in aqueous solution will react with the said alkaline earth oxide to produce a solvent for the protein, which base, upon being subsequently mixed with cold water will form a fluid adhesive.

6. Av new dry base'for the manufacture of glues and adhesive compositions, such base comprising casein and a protein-rich seed meal from which a substantial part at least of the oil has been removed, the major part at least of which meal is fine enough to pass an 80 to 100 mesh screen, and an alkaline earth oxide in amount sufficient to maintain the oxide in amount suflicient to maintain the mixture alkaline when water is added, the amount of such meal being sufiicient to substantially lengthen the life of the adhesive prepared from said base, as compared with a casein glue without such seed meal.

I 8. A new dry base for use in making an adhesive material comprising casein as a sub stantial ingredient, together with a substantial amount of a protein-rich seed meal, incorporated with an alkaline earth oxide and a water-soluble alkali .metal salt, which salt is capable of reacting, in the presence of water, with such alkaline earth oxide, which base, upon being subsequently mixed with suflicient water, will produce an adhesive of fluid spreadable consistency.

9. A novel material in the glue art, the same being an intimate dry mixturecomprising casein and a protein-rich seed meal, the former being in excess of the latter.

10. A novel material in the glue art, the same being an intimate dry mixture comprising casein and a protein-rich seed meal, the amount of casein being substantially greater than the amount of protein contained in the seed meal. I

11. A dry glue base containing about equal parts of casein and of a dry protein-rich seed meal, together with smaller amounts of an alkaline earth metal oxide and of alkaline-reacting sodium salt, the latter being in amount suflicient, by reaction with the said alkaline earth metal oxide, to form a solvent for the casein and meal proteids present.

12. A process for producing a glue of comparatively long working life from a glue base including casein, a water-soluble alkali metal salt which is alkaline to litmus, and an alkaline earth metal oxide, which process comprises incorporating a protein-rich seed meal in such glue base, and thereafter mixing this new glue base with water, the proportion of the protein-rich seed meal used being sufiicient to retard the setting of the glue produced by said admixture with water.

In testimony whereof we allix our signatures.

LAWRENCE BRADSHAW. HENRY V. DUNHAM.