Adhesive comprising polyvinyl acetate and a mixture of glucose and fructose

Abstract

Aqueous adhesive compositions comprising polyvinyl acetate can be extended by a) providing an adhesive polymer component wherein at least about 75% of adhesive polymer materials present in the adhesive polymer component is polyvinyl acetate; b) providing an aqueous saccharide composition comprising fructose and glucose in a fructose to glucose weight ratio of from about 3:10 to about 10:3, wherein the fructose and glucose combined are at least about 50 percent of all saccharides present in the aqueous saccharide composition. The aqueous saccharide composition has a total saccharides dry solids content of at least 70 percent by weight based on the total aqueous saccharide composition. The adhesive polymer component is mixed with the aqueous saccharide composition to form an extended aqueous adhesive composition comprising from about 5 to about 50 percent by dry weight of the saccharide composition. Compositions and methods of use are also described.

Claims

1. A method of extending an aqueous adhesive composition, the method comprising: a) providing an aqueous adhesive component wherein at least about 75% of adhesive polymer materials present in the aqueous adhesive component is polyvinyl acetate; b) providing an aqueous saccharide composition comprising fructose and glucose in a fructose to glucose weight ratio of from about 3:10 to about 10:3, wherein the fructose and glucose combined are at least about 50 percent of all saccharides present in the aqueous saccharide composition, and wherein the aqueous saccharide composition has a total saccharides dry solids content of at least 70 percent by weight based on the total aqueous saccharide composition; and c) mixing the adhesive polymer component with the aqueous saccharide composition to form an extended aqueous adhesive composition comprising from about 5 to about 50 percent by dry weight of the saccharide composition.

2. The method of claim 1, wherein the extended aqueous adhesive composition comprises from about 5 to about 40 percent by dry weight of the aqueous saccharide composition of b); or wherein the extended aqueous adhesive composition comprises from about 10 to about 40 percent by dry weight of the aqueous saccharide composition of b); or wherein the extended aqueous adhesive composition comprises from about 20 to about 40 percent by dry weight of the aqueous saccharide composition of b); or wherein the extended aqueous adhesive composition comprises from about 25 to about 40 percent by dry weight of the aqueous saccharide composition of b); or wherein the extended aqueous adhesive composition comprises from about 5 to about 35 percent by dry weight of the aqueous saccharide composition of b); or wherein the extended aqueous adhesive composition comprises from about 10 to about 35 percent by dry weight of the aqueous saccharide composition of b); or wherein the extended aqueous adhesive composition comprises from about 20 to about 35 percent by dry weight of the aqueous saccharide composition of b); or wherein the extended aqueous adhesive composition comprises from about 25 to about 35 percent by dry weight of the aqueous saccharide composition of b); or wherein the extended aqueous adhesive composition comprises from about 5 to about 20 percent by dry weight of the aqueous saccharide composition of b); or wherein the extended aqueous adhesive composition comprises from about 10 to about 20 percent by dry weight of the aqueous saccharide composition of b); or wherein the extended aqueous adhesive composition comprises from 16 to 40 percent by dry weight of the aqueous saccharide composition of b).

3. The method of claim 1, wherein the extended aqueous adhesive composition comprises from about 5 to 40 percent by dry weight of the fructose and glucose combined; or wherein the extended aqueous adhesive composition comprises from about 10 to 35 percent by dry weight of the fructose and glucose combined; or wherein the extended aqueous adhesive composition comprises from about 16 to 30 percent by dry weight of the fructose and glucose combined.

4. The method of claim 1, wherein the extended aqueous adhesive composition has a total dry solids content of from about 45 wt % to about 70 wt %.

5. The method of claim 1, wherein the extended aqueous adhesive composition comprises less than 50 percent by weight water; or wherein the extended aqueous adhesive composition comprises less than 45 percent by weight water.

6. The method of claim 1, wherein the extended aqueous adhesive composition has a water content percentage that is less than the water content percentage of the aqueous adhesive composition of a).

7. The method of claim 1, wherein the fructose and glucose combined comprise at least 70 percent by dry weight of the aqueous saccharide composition of b); or wherein the fructose and glucose combined comprise at least 75 percent by dry weight of the aqueous saccharide composition of b); or wherein the fructose and glucose combined comprise at least 80 percent by dry weight of the aqueous saccharide composition of b); or wherein the fructose and glucose combined comprises from about 70 percent to about 95 percent by dry weight of the aqueous saccharide composition of b); or wherein the fructose and glucose combined comprises from about 70 percent to about 90 percent by dry weight of the aqueous saccharide composition of b); or wherein the fructose and glucose combined comprises from about 70 percent to about 85 percent by dry weight of the aqueous saccharide composition of b).

8. The method of claim 1, wherein the aqueous saccharide composition of b) has a fructose to glucose weight ratio of from about 3:8 to about 8:3; or wherein the aqueous saccharide composition of b) has a fructose to glucose weight ratio of from about 3:7 to about 7:3; or wherein the aqueous saccharide composition of b) has a fructose to glucose weight ratio of from about 4:6 to about 6:4; or wherein the aqueous saccharide composition of b) has a fructose to glucose weight ratio of from about 4:5 to about 8:5; or wherein the aqueous saccharide composition of b) has a fructose to glucose weight ratio of from about 5:5 to about 8:5; or wherein the aqueous saccharide composition of b) has a fructose to glucose weight ratio of from about 5:5 to about 7:5; or wherein the aqueous saccharide composition of b) has a fructose to glucose weight ratio of from about 5:5 to about 6:5.

9. The method of claim 1, wherein the aqueous saccharide composition of b) has a total saccharides dry solids content of at least about 75 percent by weight; or wherein the aqueous saccharide composition of b) has a total saccharides dry solids content of at least about 80 percent by weight; or wherein the aqueous saccharide composition of b) has a total saccharides dry solids content of at least about 85 percent by weight; or wherein the aqueous saccharide composition of b) has a total saccharides dry solids content of at least about 90 percent by weight.

10. The method of claim 1, wherein the aqueous saccharide composition of b) further comprises a saccharide that is not fructose or glucose, and wherein the fructose and glucose combined is at least about 70 wt % of the saccharide present in the aqueous saccharide composition of b); or wherein the aqueous saccharide composition of b) further comprises a saccharide that is not fructose or glucose, and wherein the fructose and glucose combined is at least about 75 wt % of the saccharide present in the aqueous saccharide composition of b); or wherein the aqueous saccharide composition of b) further comprises a saccharide that is not fructose or glucose, and wherein the fructose and glucose combined is at least about 80 wt % of the saccharide present in the aqueous saccharide composition of b); or wherein the aqueous saccharide composition of b) further comprises a saccharide that is not fructose or glucose, and wherein the fructose and glucose combined is at least about 85 wt % of the saccharide present in the aqueous saccharide composition of b); or wherein the aqueous saccharide composition of b) further comprises a saccharide that is not fructose or glucose, and wherein the fructose and glucose combined is at least about 90 wt % of the saccharide present in the aqueous saccharide composition of b); or wherein the aqueous saccharide composition of b) further comprises a saccharide that is not fructose or glucose, and wherein the fructose and glucose combined is at least about 95 wt % of the saccharide present in the aqueous saccharide composition of b); or wherein the aqueous saccharide composition of b) further comprises a saccharide that is not fructose or glucose, and wherein the fructose and glucose combined is from about 70 wt % to about 95 wt % of the saccharide present in the aqueous saccharide composition of b); or wherein the aqueous saccharide composition of b) further comprises a saccharide that is not fructose or glucose, and wherein the fructose and glucose combined is from about 75 wt % to about 95 wt % of the saccharide present in the aqueous saccharide composition of b); or wherein the aqueous saccharide composition of b) further comprises a saccharide that is not fructose or glucose, and wherein the fructose and glucose combined is from about 80 wt % to about 95 wt % of the saccharide present in the aqueous saccharide composition of b); or wherein the aqueous saccharide composition of b) further comprises a saccharide that is not fructose or glucose, and wherein the fructose and glucose combined is from about 70 wt % to about 90 wt % of the saccharide present in the aqueous saccharide composition of b); or wherein the aqueous saccharide composition of b) further comprises a saccharide that is not fructose or glucose, and wherein the fructose and glucose combined is from about 75 wt % to about 90 wt % of the saccharide present in the aqueous saccharide composition of b); or wherein the aqueous saccharide composition of b) further comprises a saccharide that is not fructose or glucose, and wherein the fructose and glucose combined is from about 80 wt % to about 90 wt % of the saccharide present in the aqueous saccharide composition of b); or wherein the aqueous saccharide composition of b) further comprises a saccharide that is not fructose or glucose, and wherein the fructose and glucose combined is from about 70 wt % to about 80 wt % of the saccharide present in the aqueous saccharide composition of b).

11. The method of claim 1, wherein the aqueous saccharide composition of b) comprises from about 2 percent by dry weight to about 30 percent by dry weight disaccharides.

12. The method of claim 1, wherein the aqueous saccharide composition of b) comprises from about 0.5 percent by dry weight to about 10 percent by dry weight of trisaccharides.

13. The method of claim 1, wherein the aqueous saccharide composition of b) comprises from 73 to 85 percent by dry weight of the fructose and glucose combined, from 10 to 20 percent by dry weight disaccharides, and from 2 to 8 percent by dry weight of trisaccharides.

14. The method of claim 1, wherein the dry weight percent of the adhesive polymer component of a) present in the extended aqueous adhesive composition is from about 40 wt % to about 95 wt % of the total dry weight of the extended aqueous adhesive composition; or wherein the dry weight percent of the adhesive polymer component of a) present in the extended aqueous adhesive composition is from about 50 wt % to about 85 wt % of the total dry weight of the extended aqueous adhesive composition; or wherein the dry weight percent of the adhesive polymer component of a) present in the extended aqueous adhesive composition is from about 60 wt % to about 85 wt % of the total dry weight of the extended aqueous adhesive composition; or wherein the dry weight percent of the adhesive polymer component of a) present in the extended aqueous adhesive composition is from about 65 wt % to about 80 wt % of the total dry weight of the extended aqueous adhesive composition.

15. The method of claim 1, wherein polyvinyl acetate is present in an amount of from about 40 wt % to about 60 wt % of the total dry weight of the extended aqueous adhesive composition.

16. The method of claim 1, wherein the adhesive polymer component of a) comprises a synthetic or natural adhesive polymer other than polyvinyl acetate, and wherein at least about 80% of adhesive polymer materials present in the adhesive polymer component of a) is polyvinyl acetate; or wherein at least about 90% of adhesive polymer materials present in the adhesive polymer component of a) is polyvinyl acetate; or wherein at least about 95% of adhesive polymer materials present in the adhesive polymer component of a) is polyvinyl acetate; or wherein at least about 99% of adhesive polymer materials present in the adhesive polymer component of a) is polyvinyl acetate.

17. The method of claim 16, wherein the synthetic or natural adhesive polymer other than polyvinyl acetate is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylates, polymethacrylates, polysaccharides, and mixtures thereof.

18. The method of claim 1, wherein the adhesive polymer component of a) comprises polyvinyl alcohol, and wherein the polyvinyl acetate and polyvinyl alcohol together comprise from about 40 wt % to about 60 wt % of the aqueous adhesive composition of a); or wherein the adhesive polymer component of a) further comprises polyvinyl alcohol, and wherein the polyvinyl acetate and polyvinyl alcohol together comprise from about 45 wt % to about 55 wt % of the adhesive polymer component of a).

19. The method of claim 1, wherein the extended aqueous adhesive composition further comprises an additive selected from the group consisting of wetting agents, adhesion promoters, foam generators, defoamers, rheology modifiers, plasticizer, coalescing agents, dyes, pigments, fragrances, tackifiers, waxes, UV indicators, humectants, pH-adjusters and/or buffers, hardeners, crosslinkers, fillers and anti-caking agents.

Description

DETAILED DESCRIPTION

(1) The aspects of the present invention described below are not intended to be exhaustive or to limit the invention to the precise forms disclosed in the following detailed description. Rather a purpose of the aspects chosen and described is by way of illustration or example, so that the appreciation and understanding by others skilled in the art of the general principles and practices of the present invention can be facilitated.

(2) The adhesive polymer component used in the present method is an adhesive formulation wherein at least about 75% of adhesive polymer materials present in the adhesive polymer component is polyvinyl acetate.

(3) An example of such an adhesive is commercially available as Kestokol D-325 HF-T2547 Polyvinyl Acetate wood glue from KiiltoClean Oy, Turku, Finland.

(4) In an aspect, the adhesive polymer component of (a) may be in the form of a dispersion in water and stabilized with polyvinyl alcohol). In an aspect, the adhesive polymer component of (a) may be a vinyl acetate homopolymer, stabilized with hydroxyethylcellulose and sold under the name Fulatex by H. B. Fuller Company of St. Paul, MN. In an aspect, the adhesive polymer component of (a) may be a dextrin-stabilized polyvinyl acetate sold under the name Rhoplex 6215 from the Rohm & Haas Company of Philadelphia, Pa.

(5) In an aspect, the adhesive polymer component of (a) comprises a synthetic or natural adhesive polymer other than polyvinyl acetate, and wherein at least about 80% of adhesive polymer materials present in the adhesive polymer component of (a) is polyvinyl acetate. In an aspect, at least about 90% of adhesive polymer materials present in the adhesive polymer component of (a) is polyvinyl acetate. In an aspect, at least about 95% of adhesive polymer materials present in the adhesive polymer component of (a) is polyvinyl acetate. In an aspect, at least about 99% of adhesive polymer materials present in the adhesive polymer component of (a) is polyvinyl acetate.

(6) In an aspect, the synthetic or natural adhesive polymer other than polyvinyl acetate present in the adhesive polymer component of (a) is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylates, polymethacrylates, polysaccharides, and mixtures thereof.

(7) In an aspect, the adhesive polymer polysaccharides may be selected from cellulose, starch (amylose and amylopectin), guar, and dextrins. In an aspect, the adhesive polymer polysaccharides may be modified by, e.g., carboxymethyl, carboxyethyl, hydroxyethyl, hydroxypropyl, methyl, ethyl, propyl, or C4- to C20-alkyl groups, C4 to C20-alkyl succinimides, alginates, peptides and/or proteins such as gelatin, casein and/or soya proteins. In an aspect, the adhesive polymer polysaccharides are selected from starch ethers, hydroxyethyl and/or carboxymethyl cellulose, dextrins, gelatin and/or casein.

(8) In an aspect, the adhesive polymer component of (a) comprises polyvinyl alcohol, and wherein the polyvinyl acetate and polyvinyl alcohol together comprise from about 40 wt % to about 60 wt % of the aqueous adhesive composition of (a); or wherein the adhesive polymer component of (a) further comprises polyvinyl alcohol, and wherein the polyvinyl acetate and polyvinyl alcohol together comprise from about 45 wt % to about 55 wt % of the adhesive polymer component of (a).

(9) In an aspect, the dry weight percent of the adhesive polymer component of (a) present in the extended aqueous adhesive composition is from about 40 wt % to about 95 wt % of the total dry weight of the extended aqueous adhesive composition. In an aspect, the dry weight percent of the adhesive polymer component of (a) present in the extended aqueous adhesive composition is from about 50 wt % to about 85 wt % of the total dry weight of the extended aqueous adhesive composition. In an aspect, the dry weight percent of the adhesive polymer component of (a) present in the extended aqueous adhesive composition is from about 60 wt % to about 85 wt % of the total dry weight of the extended aqueous adhesive composition. In an aspect, the dry weight percent of the adhesive polymer component of (a) present in the extended aqueous adhesive composition is from about 65 wt % to about 80 wt % of the total dry weight of the extended aqueous adhesive composition.

(10) In an aspect, the polyvinyl acetate is present in an amount of from about 40 wt % to about 60 wt % of the total dry weight of the extended aqueous adhesive composition.

(11) The aqueous saccharide composition used in the present method comprises fructose and glucose in a fructose to glucose weight ratio of from about 3:10 to about 10:3. In an aspect, the aqueous saccharide composition is provided by obtaining fructose and glucose from separate sources and mixing the fructose with the glucose in the identified ratios. In an aspect, the aqueous saccharide composition is provided by obtaining starch from an appropriate carbohydrate source, such as maize, wheat, or potato and further breaking down the starch into glucose and converting some of the glucose to fructose to provide a mixture of glucose and fructose in the identified ratios using methods such as isomerization enzymes that convert a portion of the glucose to fructose.

(12) In an aspect, the aqueous saccharide composition is provided as a liquid composition. In an aspect, the aqueous saccharide composition is provided as a fructose/glucose containing syrup. In an aspect, the aqueous saccharide composition is provided as a high fructose corn syrup.

(13) In an aspect, the aqueous saccharide composition of b) has a total saccharides dry solids content of at least about 75 percent by weight. In an aspect, the aqueous saccharide composition of b) has a total saccharides dry solids content of at least about 80 percent by weight. In an aspect, the aqueous saccharide composition of b) has a total saccharides dry solids content of at least about 85 percent by weight. In an aspect, the aqueous saccharide composition of b) has a total saccharides dry solids content of at least about 90 percent by weight.

(14) In an aspect, the aqueous saccharide composition has a fructose to glucose weight ratio of from about 3:8 to about 8:3. In an aspect, the aqueous saccharide composition has a fructose to glucose weight ratio of from about 3:7 to about 7:3. In an aspect, the aqueous saccharide composition has a fructose to glucose weight ratio of from about 3:7 to about 7:3. In an aspect, the aqueous saccharide composition has a fructose to glucose weight ratio of from about 4:6 to about 6:4. In an aspect, the aqueous saccharide composition has a fructose to glucose weight ratio of from about 4:5 to about 8:5, or alternatively from about 2:4 to about 7:5. In an aspect, the aqueous saccharide composition has a fructose to glucose weight ratio of from about 5:5 to about 8:5, or alternatively from about 2.4:4 to 6.5:5. In an aspect, the aqueous saccharide composition has a fructose to glucose weight ratio of from about 5:5 to about 7:5, or alternatively from about 2.4:4 to 6:5. In an aspect, the aqueous saccharide composition has a fructose to glucose weight ratio of from about 5:5 to about 6:5, or in an alternative from about 2.4:4 to 5:5.

(15) In an aspect, the aqueous saccharide composition of (b) further comprises a saccharide that is not fructose or glucose, wherein the fructose and glucose combined is at least about 70 wt % of the saccharide present in the aqueous saccharide composition of (b). In an aspect, the fructose and glucose combined is at least about 75 wt % of the saccharide present in the aqueous saccharide composition of (b). In an aspect, the fructose and glucose combined is at least about 80 wt % of the saccharide present in the aqueous saccharide composition of (b). In an aspect, the fructose and glucose combined is at least about 90 wt % of the saccharide present in the aqueous saccharide composition of (b). In an aspect, the fructose and glucose combined is at least about 95 wt % of the saccharide present in the aqueous saccharide composition of (b).

(16) In an aspect, the aqueous saccharide composition of (b) further comprises a saccharide that is not fructose or glucose, wherein the fructose and glucose combined is from about 70 wt % to about 95 wt % of the saccharide present in the aqueous saccharide composition of (b). In an aspect, the fructose and glucose combined is from about 75 wt % to about 95 wt % of the saccharide present in the aqueous saccharide composition of (b). In an aspect, the fructose and glucose combined is from about 80 wt % to about 95 wt % of the saccharide present in the aqueous saccharide composition of (b). In an aspect, the fructose and glucose combined is from about 70 wt % to about 90 wt % of the saccharide present in the aqueous saccharide composition of (b). In an aspect, the fructose and glucose combined is from about 75 wt % to about 90 wt % of the saccharide present in the aqueous saccharide composition of (b). In an aspect, the fructose and glucose combined is from about 80 wt % to about 90 wt % of the saccharide present in the aqueous saccharide composition of (b). In an aspect, the fructose and glucose combined is from about 70 wt % to about 80 wt % of the saccharide present in the aqueous saccharide composition of (b). In an aspect, the fructose and glucose combined is from about 75 wt % to about 80 wt % of the saccharide present in the aqueous saccharide composition of (b). In an aspect, the fructose and glucose combined is from about 80 wt % to about 80 wt % of the saccharide present in the aqueous saccharide composition of (b).

(17) In an aspect, the aqueous saccharide composition of (b) further comprises from about 2 percent by dry weight to about 30 percent by dry weight disaccharides.

(18) In an aspect, the aqueous saccharide composition of (b) further comprises from about 0.5 percent by dry weight to about 10 percent by dry weight of trisaccharides.

(19) In an aspect, the aqueous saccharide composition of (b) further comprises from about 0.5 percent by dry weight to about 10 percent by dry weight of polysaccharides comprising three or more saccharide units.

(20) In an aspect, the aqueous saccharide composition of (b) comprises from 73 to 85 percent by dry weight of the aqueous saccharide composition of b), from 10 to 20 percent by dry weight disaccharides, and from 2 to 9 percent by dry weight trisaccharides (for example, from 2 to 8 percent by dry weight of trisaccharides.

(21) In an aspect, the extended aqueous adhesive composition comprises less than about 50 percent by weight water; or wherein the extended aqueous adhesive composition comprises less than about 45 percent by weight water.

(22) Further other components can be wetting agents, adhesion promoters, foam generators, defoamers, rheology modifiers, plasticizer, coalescing agents, dyes, pigments, fragrances, tackifiers, waxes, UV indicators, humectants, pH-adjusters and/or buffers, hardeners such as acidic metal salts such as AlCl.sub.3, FeCl, Cr(NO.sub.3).sub.3, crosslinkers such as polyisocyanates, boric acid and/or their salts or formaldehyde-urea resins and formaldehyde-phenol resins, fillers and anti-caking agents such as carbonates, clays, silicates, hydrophobic and hydrophilic silica, pyrogenic or precipitated silicic acid, microsilica, kaolin, talc, magnesium hydrosilicate, light spar, polysaccharides such as starches, mica, nut shell flours, and wood flour. Preferred fillers are calcium carbonates, clays and silica.

(23) While use of biocides and other types of preservatives can be avoided due to the powdered state of the adhesive formulation, such additives may be added if desired, for instance to prolong the shelf life after re-dispersion. Preservatives for use herein include those conventionally used in aqueous adhesives such as benzoates, amides and fluorides such as sodium fluoride.

(24) Total amounts of such additives range preferably from about 0 to 500 parts per 100 parts of organic polymeric adhesive component. More preferred amounts are from about 0 to 200 parts, and in particular from about 1 to 100 parts per 100 parts of organic polymeric adhesive component.

(25) The extended aqueous adhesive composition is prepared by mixing the adhesive polymer component a) with the aqueous saccharide composition b) so that the aqueous saccharide composition is present in the extended aqueous adhesive composition in from about 1 wt % to about 50 wt % based on total dry solids of the aqueous saccharide composition and the adhesive polymer component. In an aspect, the aqueous saccharide composition b) may be mixed with the adhesive polymer component a) in one or more successive parts. In an aspect, saccharide components other than the fructose and glucose may be provided as a conventional ingredient in the adhesive polymer component a), with additional saccharide components including the fructose and glucose in the aqueous saccharide composition b). It will be understood that for purposes of determining the relative saccharide content of the present extended aqueous adhesive composition, all saccharide components present in the composition will be deemed to be part of the aqueous saccharide composition b) regardless of timing of mixing with the adhesive polymer component a).

(26) In an aspect, the extended aqueous adhesive composition comprises from about 5 to about 40 percent by dry weight of the aqueous saccharide composition of b). In an aspect, the extended aqueous adhesive composition comprises from about 10 to about 40 percent by dry weight of the aqueous saccharide composition of b). In an aspect, the extended aqueous adhesive composition comprises from about 20 to about 40 percent by dry weight of the aqueous saccharide composition of b). In an aspect, the extended aqueous adhesive composition comprises from about 25 to about 40 percent by dry weight of the aqueous saccharide composition of b). In an aspect, the extended aqueous adhesive composition comprises from about 5 to about 35 percent by dry weight of the aqueous saccharide composition of b). In an aspect, the extended aqueous adhesive composition comprises from about 10 to about 35 percent by dry weight of the aqueous saccharide composition of b). In an aspect, the extended aqueous adhesive composition comprises from about 20 to about 35 percent by dry weight of the aqueous saccharide composition of b b). In an aspect, the extended aqueous adhesive composition comprises from about 25 to about 35 percent by dry weight of the aqueous saccharide composition of b). In an aspect, the extended aqueous adhesive composition comprises from about 5 to about 20 percent by dry weight of the aqueous saccharide composition of b). In an aspect, the extended aqueous adhesive composition comprises from about 10 to about 20 percent by dry weight of the aqueous saccharide composition of b).

(27) In an aspect, the extended aqueous adhesive composition comprises from 16 to about 40 percent by dry weight of the aqueous saccharide composition of b).

(28) In an aspect, the extended aqueous adhesive composition comprises from about 5 to 40 percent by dry weight of the fructose and glucose combined. In an aspect, the extended aqueous adhesive composition comprises from about 10 to 35 percent by dry weight of the fructose and glucose combined. In an aspect, the extended aqueous adhesive composition comprises from about 16 to 30 percent by dry weight of the fructose and glucose combined.

(29) In an aspect, the extended aqueous adhesive composition has a total dry solids content of from about 45 wt % to about 70 wt %.

(30) In an aspect, the extended aqueous adhesive composition comprises less than 50 percent by weight water. In an aspect, the extended aqueous adhesive composition comprises less than 45 percent by weight water. In an aspect, the extended aqueous adhesive composition has a water content percentage that is less than the water content percentage of the aqueous adhesive composition of a).

(31) In an aspect, the extended aqueous adhesive composition adhesive composition comprises a) an adhesive polymer component wherein at least about 75% of adhesive polymer materials present in the adhesive polymer component is polyvinyl acetate, and b) a saccharide composition comprising fructose and glucose in a fructose to glucose weight ratio of from about 3:10 to about 10:3, wherein the fructose and glucose combined are at least about 50 percent of all saccharides present in the saccharide composition, and wherein the saccharide composition has a total saccharides dry solids content of at least 70 percent by weight based on the total saccharide composition; wherein the saccharide composition is present in the extended aqueous adhesive composition in an amount of from about 5 to about 50 percent by dry weight of the saccharide composition.

(32) The extended aqueous adhesive compositions as described herein may be used to bond one substrate to a second similar or different substrate. In an aspect, the substrates to be bonded are porous substrates including paper and wood. As used herein paper means both paper and paperboard products, both single- and multi-ply (e.g., paper laminates, corrugated boards, solid fibers) sheets made from without limitation, Kraft paper, paper made from recycled fibers and the like. The term wood is meant to include wood composites and particle board and encompass chipboard, particleboard, medium density fiberboard, high density fiberboard, oriented strand board, hardboard, hardwood plywood, veneer core plywood, isocyanate or phenolic impregnated strawboard, and wood composites made from wood fiber and polymers, such as recycled polyethylene.

(33) Substrates may be bonded together by a process wherein the adhesive composition is applied to at least a first substrate, a second substrate is brought in contact with the adhesive composition applied to the first substrate, and the applied adhesive is subjected to conditions which will allow the adhesive composition to form a set bond, such conditions optionally including directing air and/or heat to the location of the bond and/or applying pressure to the substrates to provided good contact of the substrates to each other at the location of the bond.

(34) In an aspect, the extended aqueous adhesive compositions are used to adhere at least three layers of wood substrates together to form a laminate construction.

(35) In an aspect, the extended aqueous adhesive compositions are used to adhere a first surface of a first wood substrate having an end-grain surface to a second substrate.

(36) In an aspect, the extended aqueous adhesive compositions are used to adhere a first surface of a first wood substrate having a flat-grain surface to a second substrate.

EXAMPLES

(37) Test Methodology

(38) Viscosity. Viscosity measurements were obtained using a Brookfield AMETEK DV2T Viscometer from AMETEK Brookfield (Middleboro, MA) where the measurement is taken at a sample temperature of 25 C. at 10 rpm using Spindle #4. Where indicated, Viscosity was evaluated using Rapid Visco Analyzer (RVA) Method 01.05 (which is a measure of viscosity under shear conditions). Test Conditions: 25, 160 rpm, standard cup and spindle, 30 g sample weight. See https://www.perten.com/Global/Application%20notes/RVA/General%20Pasting%20Method%20-%20RVA%2001.05.pdf

(39) Dry Strength Adhesion Value is determined under dry conditions with the methodology set forth in ASTM D7998-15 cohesion test method using an ABES adhesive tester (Adhesive Evaluation Systems), with the following methodology notes.

(40) Wood test pieces were prepared with lightly-sanded, white pine blanks cut to the specified dimensions. The test pieces were conditioned at ambient conditions and humidity (21-24C and 40-50% RH). All dry bond testing was completed within one 24 hr period with a control sample included amongst the materials in use.

(41) 5 Milligrams of adhesive sample (+/1.0 mg) were placed on the end of the one of the test pieces. A corresponding blank test piece was overlapped with the piece containing the adhesive sample inside the ABES clamping mechanism. The ABES test was carried out with a 40 second pressing time at 120 degrees C. The test pieces were then air-cooled for 5 seconds and then pulled at a controlled rate of 500N/s+/25 Ns for 4 seconds to generate the corresponding pull force measurement.

(42) Wet Strength Adhesion Value is determined under wet conditions with the methodology set forth in ASTM D7998-15 cohesion test method using an ABES adhesive tester (Adhesive Evaluation Systems), with the following methodology notes.

(43) Wood test pieces were prepared the same as with the dry bond measurement with lightly sanded, white pine blanks cut to the specified dimensions. The test pieces were conditioned at ambient conditions and humidity (21-24C and 40-50% RH).

(44) 5 Milligrams of adhesive sample (+/1.0 mg) were placed on the end of the one of the test pieces. A corresponding blank test piece was overlapped with the piece containing the adhesive sample inside the ABES clamping mechanism. The ABES test was carried out with a 40 second pressing time at 120 degrees C. The test pieces were air-cooled for 5 seconds and then removed from the ABES clamping mechanism and totally submerged in an ambient tap water bath for one hour. After the requisite time period, the test pieces were then removed from the tap water bath and allowed to dry for approximately 2 hours or until the wood substrate no longer felt damp to the touch. In addition, for some adhesive formulations, a matching set of test pieces were allowed to dry for 24 hours before additional testing. The dried glued test pieces were then placed back in the ABES clamping mechanism at ambient temperatures and pulled at a controlled rate of 500N/s+/25 Ns for 4 seconds to generate the corresponding pull force measurement. This wet bond performance was then compared against the dry bond performance that was previously recorded.

(45) Materials Used

(46) TABLE-US-00001 Name used in Example tables Source K-325 PVAc Glue KiiLTO Kestokol D-325 HF-T2547 Polyvinyl Acetate wood adhesive: 50-52% dry solids 63DE Corn Syrup Cargill.sup.1 Clearsweet 63/43 Corn Syrup: 82-84% dry solids. This corn syrup does not contain fructose. Comparative Example 43DE M Corn Syrup Cargill Clearsweet 43M/43 Corn Syrup: 80-81% dry solids is a corn syrup that does not contain fructose. It has a DE of 43 and a Baum measurement of 43 with higher Maltose content than Clearsweet 43/43 Corn Syrup Comparative Example 43DE Corn Syrup Cargill Clearsweet 43/43 Corn Syrup: 80-81% dry solids. This corn syrup does not contain fructose. Comparative Example 25DE Corn Syrup Cargill Cleardex 25/42 Corn Syrup: 77- 79% dry solids. This is a corn syrup that does not contain fructose. Comparative Example 44DE Corn Syrup This is a lab-prepared corn syrup having a DE of 44 that does not contain fructose. Comparative Example 34DE Blend This is a lab-prepared corn syrup having a Corn Syrup DE of 34 that does not contain fructose. This corn syrup is prepared by blending 25 DE and 44DE syrups. Comparative Example 36DE Corn Syrup This is a lab prepared corn syrup having a DE of 36 that does not contain fructose. This corn syrup is prepared by blending 25 DE and 44DE syrups. Comparative Example Isoclear 42 42% Fructose and 52% glucose by dry Corn Syrup weight Blend syrup. 80-82% solids from Cargill This is a commercially available syrup comprising a blend of fructose and glucose. Isoclear 55 Cargill Isoclear 55 High Fructose Syrup: Corn Syrup 55% fructose and 45% glucose by dry (IC 55) weight syrup having 76-79% dry solids. This is a commercially available syrup comprising a blend of fructose and glucose. C*TruSweet Cargill C*TruSweet 01742 01742 Dextrose/Fructose Syrup: 45% glucose, 31% fructose, 15% disaccharides, and 5% trisaccharides by dry weight syrup having 81-83% dry solids C*TruSweet Cargill C*TruSweet 01743 01743 Dextrose/Fructose Syrup: 42-47% glucose, 29-33% fructose, 10-20% disaccharides, and 0-10% trisaccharides by dry weight syrup having 74.5-76.5% dry solids C*Sweet A wheat-derived Dextrose syrup that does 01521/44-47DE not contain Fructose. 71-73% solids. Available from Cargill Comparative Example C*Sweet A wheat-derived Dextrose syrup that does D-02761 not contain Fructose. 71-73% solids. Available from Cargill Comparative Example Fructose Composition prepared by dissolving dry, Syrup crystalline fructose (NOW Foods, Bloomingdale, IL) in water to prepare a 70-72% solids syrup Comparative Example .sup.1Commercially available from Cargill, Incorporated Dextrose Equivalent (DE) is a measure of the amount of reducing sugars present in a sugar product, expressed as a percentage on a dry basis relative to dextrose.

Example 1

(47) Samples prepared at 25% weight-to-weight/Carbohydrate to PVAc Glue ratios were tested at 30 and 90 days to observe viscosity changes over time. Additionally, adhesion performance was using sample formulations that were aged for the times indicated prior to adhering substrates together. Bond strengths were determined according to ASTM D7998-15.

(48) TABLE-US-00002 Initial 30-day 90-day 90-day Viscosity Viscosity Viscosity Initial 30-day 90-day N/mm2 Sample ID (cP) (cP) (cP) N/mm2 N/mm2 N/mm2 Wet Soak K-325 PVAc 5800 5680 4.9 4.2 3.4 5.3 Glue (Control) PVAc + 63DE 2780 3260 4380 4.4 6.0 4.6 4.6 Corn Syrup Comparative Example PVAc + 43DE 3220 3680 4880 5.1 4.9 4.6 M Corn Syrup Comparative Example PVAc + 43DE 3700 3820 4700 5.2 5.0 4.2 Corn Syrup Comparative Example PVAc + 25DE 42400 5.6 Corn Syrup Comparative Example PVAc + IC55 2220 2060 2960 4.9 5.5 4.5 4.6 High Fructose Corn Syrup PVAc + 34DE 8780 5460 8900 4.4 4.9 3.8 4.2 Blend Corn Syrup Comparative Example
Conclusions

(49) Viscosity of the comparative samples significantly increased over time as compared to the sample wherein the aqueous saccharide composition comprised fructose and glucose. The sample comprising 25DE Corn Syrup was not stable over time. Bond strengths of samples that could be tested was not statistically different. Lower initial viscosity and lack of significant viscosity build over time without sacrifice of bond strength properties as observed in the sample wherein the aqueous saccharide composition comprised fructose and glucose is seen to provide significant material handling properties, blendability of the materials forming the extended adhesive composition, and flexibility in selecting the desired viscosity of the ultimate extended adhesive product.

Example 2

(50) Samples prepared at 25% weight-to-weight/Carbohydrate to PVAc Glue ratios at various DE levels were tested for viscosity and bond strength in comparison with samples wherein the aqueous saccharide composition comprised fructose and glucose. Bond strengths were determined according to ASTM D7998-15.

(51) TABLE-US-00003 Brookfield Bond Sample ID-25% Blend Commercial Corn Viscosity Strength Syrups % ds (cP) (N/mm2) Sample of K-325 PVAc Glue-1 50.42 7000 3.7 gallon (Control) Sample of K-325 PVAc Glue-1 50.79 7080 5.4 gallon 1 Hour Soak (Control) 25% w/w 25DE 59.59 30500 3.8 Comparative Example 25% w/w 25DE-1 Hour Soak 60.19 38600 4.9 Comparative Example 25% w/w 36DE 57.53 3980 4.4 Comparative Example 25% w/w 36DE-1 Hour Soak 59.09 4180 3.9 Comparative Example 25% w/w 44DE 58.17 3460 4.5 Comparative Example 25% w/w 44DE-1 Hour Soak 58.56 3620 4.6 Comparative Example 25% w/w Isoclear 55 56.45 2020 4.8 25% w/w Isoclear 55-1 Hour Soak 56.61 1940 4.1
Conclusions

(52) All the samples had similar bond strength. The observed viscosity of the samples comprising with 25DE syrup/glue blend was very high and unstable. Other syrup/glue blends had lower viscosities than the glue alone. However, the sample wherein the aqueous saccharide composition comprised fructose and glucose had even lower viscosity without sacrifice of bond strength properties. It is noteworthy that the low viscosity observed in the sample wherein the aqueous saccharide composition comprised fructose and glucose was obtained even though the total solids content was in the same range as the compositions to which this extended adhesive was compared.

Example 3

(53) Samples prepared at 25% weight-to-weight/Carbohydrate to PVAc Glue ratios at various DE levels were tested for viscosity and bond strength in comparison with samples wherein the aqueous saccharide composition comprised fructose and glucose. Bond strengths were determined according to EN 205.

(54) TABLE-US-00004 Average % Brookfield Bond Sample ID-25% w/w EU Syrup Dry Viscosity Strength Blends/Wet Soak solids (cP) (N/mm2) K-325 PVAc Glue (Control) 50.84 6500 4.6 K-325 PVAc Glue 1 Hour Soak 4.6 (Control) K-325 PVAc Glue/C*TruSweet 01742 57.34 1840 5.4 K-325 PVAc Glue/C*TruSweet 5.5 01742-1 Hour Soak K-325 PVAc Glue/C*Sweet 01521/ 58.88 3060 4.7 44-47DE (Comparative) K-325 PVAc Glue/C*Sweet 4.9 01521/44-47DE/-1 Hour Soak (Comparative)
Conclusions

(55) All the samples had similar bond strength. The observed viscosity of the samples comprising with 25DE syrup/glue blend was very high and unstable. Other syrup/glue blends had lower viscosities than the glue alone. However, the sample wherein the aqueous saccharide composition comprised fructose and glucose had lower viscosity than the control and comparative examples without sacrifice of bond strength properties.

Example 4

(56) Extended adhesive samples were prepared with aqueous saccharide composition comprising fructose and glucose at increasing relative amounts to observe changes in viscosity and strength in comparison to a control adhesive sample.

(57) TABLE-US-00005 Average % Brookfield Bond Sample ID-Increasing Amount of Dry Viscosity Strength Carbohydrate solids (cP) (N/mm2) K-325 PVAc Glue-RT Bucket (Control) 50.84 6460 4.6 C*TruSweet 01742 57.34 1940 5.4 25% w/w in K-325 PVAc Glue C*TruSweet 01742 58.52 1650 4.5 30% w/w in K-325 PVAc Glue C*TruSweet 01742 59.32 1300 4.5 35% w/w in K-325 PVAc Glue
Conclusions

(58) The samples comprising fructose and glucose exhibited similar bond strength as compared to the control adhesive despite the apparent dilution of the adhesive, increase in dry solids content and decrease in viscosity. Lower viscosity without sacrifice of bond strength properties as observed in the sample wherein the aqueous saccharide composition comprised fructose and glucose is seen to provide significant material handling properties, blendability of the materials forming the extended adhesive composition, and flexibility in selecting the desired viscosity of the ultimate extended adhesive product

Example 5

(59) Adhesives were prepared with addition of various quantities of carbohydrate based extending additives.

(60) Viscosity was evaluated using Rapid Visco Analyzer (RVA) Method 01.05 (which is a measure of viscosity under shear conditions), and bond strength was evaluated according to ASTM D7998-15.

(61) Viscosity and bond strength data obtained is shown in the Tables.

(62) TABLE-US-00006 Bond Strength C*Sweet IsoClear 42 Fructose D-02761 Bond Syrup Ratio (% K-325/% Bond Strength Strength Bond Strength Carbohydrate) w/w (N/mm.sup.2) (N/mm.sup.2) (N/mm.sup.2) 100/0 5.1 5.1 5.1 75/25 5.0 4.9 5.3 70/30 5.3 4.5 4.7 65/35 5.4 4.5 4.5 60/40 4.9 4.7 3.8 55/45 4.1 3.9 3.9

(63) TABLE-US-00007 Viscosity C*Sweet Fructose Ratio (% K-325/% D-02761 IsoClear 42 Syrup Carbohydrate) w/w Viscosity(cP) Viscosity(cP) Viscosity(cP) 100/0 2745 2745 2745 75/25 1725 762 1073 70/30 1725 603 809 65/35 2800 471 656 60/40 413 413 592 55/45 343 356 557
Conclusions

(64) All the samples had similar bond strength, despite addition of carbohydrate extender. Surprisingly, the sample wherein the aqueous saccharide composition comprised fructose and glucose had even lower viscosity without sacrifice of bond strength properties. Moreover, the observed viscosity change upon increase of the relative amount of the IsoClear 42 product is predictable and effectively reduces the viscosity to a useful low level, while the observed viscosity change upon increase of the relative amount of the C*Sweet D-02761 is unpredictable.

(65) Lower viscosity without sacrifice of bond strength properties as observed in the sample wherein the aqueous saccharide composition comprised fructose and glucose is seen to provide significant material handling properties, blendability of the materials forming the extended adhesive composition, and flexibility in selecting the desired viscosity of the ultimate extended adhesive product.

Example 6

(66) Extended adhesive samples are prepared with C*TruSweet 01743 similar to those tested in Examples 4 and 5 using C*TruSweet 01742. The extended adhesive samples prepared with C*TruSweet 01743 exhibit similar properties as set forth for the extended adhesive samples prepared using C*TruSweet 01742.

(67) As used herein, the terms about or approximately mean within an acceptable range for the particular parameter specified as determined by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, e.g., the limitations of the sample preparation and measurement system. Examples of such limitations include preparing the sample in a wet versus a dry environment, different instruments, variations in sample height, and differing requirements in signal-to-noise ratios. For example, about can mean greater or lesser than the value or range of values stated by 1/10 of the stated values, but is not intended to limit any value or range of values to only this broader definition. For instance, a concentration value of about 30% means a concentration between 27% and 33%. Each value or range of values preceded by the term about is also intended to encompass the embodiment of the stated absolute value or range of values.

(68) Throughout this specification and claims, unless the context requires otherwise, the word comprise, and variations such as comprises and comprising, will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integer or step. When used herein consisting of excludes any element, step, or ingredient not specified in the claim element. When used herein, consisting essentially of does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. In the present disclosure of various embodiments, any of the terms comprising, consisting essentially of and consisting of used in the description of an embodiment may be replaced with either of the other two terms.

(69) All patents, patent applications (including provisional applications), and publications cited herein are incorporated by reference as if individually incorporated for all purposes. Unless otherwise indicated, all parts and percentages are by weight and all molecular weights are weight average molecular weights. The foregoing detailed description has been given for clarity of understanding only. No unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown and described, for variations obvious to one skilled in the art will be included within the invention defined by the claims.