JP2978457B2 - Adhesive for bonding melamine treated paper to particleboard - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a decorative solid color (solid c) treated with a melamine formaldehyde resin.
olor) and an adhesive based on polyvinyl acetate emulsion for bonding printed paper to particleboard. The adhesive based on the polyvinyl acetate emulsion must have sufficient wet adhesive strength to hold the melamine resin-treated paper sheet on the upper and lower surfaces of the particle board sheet. This is because these panels are moved through the heating and pressurizing zones. The adhesive substantially eliminates stress cracking of the melamine treated paper cured on these panels. The adhesive substantially eliminates wrinkle formation and edge and corner delamination that occur during the movement of these panels through the heating and pressing zones. The adhesive also bonds the melamine formaldehyde resin treated paper to the particle board with a strength exceeding the internal strength of the particle board. Thus, the melamine formaldehyde resin treated paper will not be able to separate from the particleboard unless sufficient force is applied to tear the component from the particleboard.

[0002]

BACKGROUND OF THE INVENTION High-pressure laminates are adhesively bonded to substrate materials such as plywood, hardboard, particleboard, cement-asbestos board, etc., to provide additional strength and rigidity to the substrate material for the intended structural application. It is possible to grant. In this bonding step, usually as an initial stage, the back surface of the laminate is polished to ensure a sufficient bonding force between the laminate and the adhesive used to bond the laminate to the substrate material. Need to do. This polishing step increases the manufacturing cost of the laminate. During the lamination process, the laminate is
After the resin contained therein is cured, it is relatively inferior in flexibility. Thin laminates (for example, simply overlay sheets,
Decorative sheets and laminates comprising a piece of kraft paper or linerboard) are particularly susceptible to damage during the polishing process because of their fragility after lamination. This need for polishing can be eliminated by coating the backing sheet with a thermosetting adhesive. The resulting laminate can be easily bonded with a known adhesive (Hosmer, USP No. 4,2,
58,103). Useful adhesive compositions include a copolyester elastomer and a compatible low molecular weight thermoplastic.
The copolyester elastomer has improved adhesion, especially under high temperature and high stress conditions. The copolyester elastomer consists essentially of a number of single-chain ester units and long-chain ester units linked via ester bonds. These adhesive compositions have been demonstrated to have improved adhesion to many substrates, including substrates that are difficult to adhere to, such as melamine formaldehyde laminated plastic. The adhesive is also available from EI du Pont de Nmours & Company.
emours and Company, Inc.) and may also include Tyzor brand tetrabutyl titanate (Edinger, USP No. 4,247,427).

[0003] Pressure sensitive adhesives formulated to include organofunctional silane adhesives have improved adhesion, especially to silane modified acrylic / melamine paint systems (Fisher et al., USP No. 5,354,600). Solid color and printed decorative paper can be manufactured with a coating of melamine formaldehyde resin on the wear surface. Solid color and printed decorative paper useful in the manufacture of high and low pressure decorative laminates are useful in the manufacture of melamine formaldehyde coated paper. It is impregnated with resin for strength. It can be adhesively bonded to a substrate such as a particle board. The overlay is impregnated with a melamine formaldehyde resin and partially cured by passing the resin impregnated overlay through an oven. Place this overlay on a decorative solid color or printed paper that is not impregnated with resin and apply it at approximately 300-2000 psi (20
-136 bar) and preferably under pressure of about 750-1500 psi (51-102 bar). This resin composition is prepared to have limited fluidity. This is because the partially cured resin in the overlay is laminated with decorative paper that is not impregnated with resin. The resin in the overlay must flow through the decorative paper to impregnate the decorative paper and impart strength thereto. The flow needs to be restricted so that the decorative side of the laminate has predetermined wear and decorative properties. The amount of resin on the opposite side of the laminate that must be adhesively bonded to the substrate is limited.

[0004] Solid color and printed decorative paper coated with melamine formaldehyde resin is adhesively bonded to particle board with commercially available wood adhesive, vinyl acetate-ethylene copolymer adhesive. The adhesive is available under the trade name Airflex 400H Emulsion from Air Products and Chemicals, 7201 Hamilton Boulevard, Aalentown, PA 18195-1501.
icals) as a commercial product. The laminate of structural elements is prepared using an adhesive comprising an organic compound of ethylene and vinyl acetate, a free radical source, and a silicon source. If necessary, various auxiliaries, such as tints (color control agents), heat stabilizers, UV stabilizers, UV absorbers, fillers and / or plasticizers, reduce the adhesion to the structural element laminate. Without having to be incorporated into the vinyl acetate-ethylene copolymer adhesive (Snedeker)
Et al., USP No. 3,622,440). When using auxiliary agents,
These must be materials that are physicochemically compatible with each of the other components of the adhesive composition under the operating conditions described. The adjuvant is used in an amount effective for the intended purpose. Thus, for example, an effective amount of a plasticizer is a plasticizing amount, ie, an amount that will significantly increase the flexibility, processability, workability and / or extensibility of the copolymer-based system. The stabilizer is used in a stabilizing effective amount, and the filler is used in an effective amount therefor;
For example, if a reinforcing filler is used, the filler will be used in an amount to provide the desired reinforcing effect.

[0005] Not only are polyvinyl alcohols important as emulsifiers / protective colloids in the manufacture of polyvinyl acetate emulsions, but they can also be added as modifiers to adjust certain properties of the adhesive. Some binding properties can be affected, the release time can be increased, and the viscosity decreases as a function of the viscosity of the polyvinyl alcohol solution. Thermal stability can be improved. Curing time can be improved by optimizing the polyvinyl alcohol content. The storage stability is better with partially hydrolyzed polyvinyl acetate than with fully hydrolyzed polyvinyl acetate. Further, the tackifying polyvinyl alcohol is useful for an adhesive containing polyvinyl acetate as a main component, and is also available as a commercial product. An adhesion promoter can be used as a primer and can be incorporated into the adhesive. Examples of non-peroxide type organosilicon compounds that can be used as an adhesion promoter include alkoxysilane, aminoalkoxysilane, vinylalkoxysilane, epoxyalkylalkoxysilane, aminoalkylalkoxysilane, cyanoalkylalkoxysilane, hydroxyalkylalkoxysilane, and the like. (Snedeker et al., USP No. 3,622,44
0).

In preparing the laminate, the ethylene-
A layer of an adhesive based on vinyl acetate copolymer is applied between each pair of laminates to be bonded together, and the resulting laminates are stacked on top of each other and then subjected to each other under high temperature and pressure conditions. Join. This binding is preferably carried out at a temperature of about 80-205 ° C and most preferably at
300psi (0.14 ~21kg / cm ²⁾ and most preferably from about 150
It carried out at a pressure of ^{~250psi (10.5 ~17.5kg / cm 2)} . In the case where a free radical generating compound or the like is used, the bonding is performed at a temperature equal to or lower than the decomposition temperature of all the components of the laminate except the compound. The joining operation can be carried out in any commonly used pressurizing equipment used by those skilled in the art for the preparation of structural element laminates, such as autoclaves and hydraulic presses and rolls (Snadecker ( Snedeker) et al., USP No. 3,622,440).
Binding systems comprising fillers dispersed or suspended in a resin or adhesive material are improved by improving the bonding or associative interaction between the filler particles and the resin polymer. Improvements are made to the resin / filler suspension or mixture,
This is achieved by using a coupling agent. These improvements are achieved by including a silane-, titanate-, or zircoaluminate-coupling agent in the resin / filler suspension. The coupling agent acts to apparently improve the resin / filler interaction. In many instances, the results are reduced viscosity of the suspension, improved retention of the filler in the suspension, and / or improved strength and / or non-water sensitivity of the binding system throughout the product. It is to show. Various silane-, titanate-, or zircoaluminate-coupling agents can be used (DeWald, USP N
o. 4,871,376).

[0007] Coupling agents typically act through two different reactive functional groups, an organic functional moiety and an inorganic functional moiety. The applied adhesive bond system (ie,
If the adhesive / filler mixture) is modified by a coupling agent, the organic functional groups of the coupling agent will either bind to the adhesive / filler matrix when the adhesive polymerizes or otherwise Attach or associate with it. It is believed that the inorganic functional moiety forms a bond with the dispersed inorganic filler or produces a similar bond. Thus, the coupling agent functions as a bridge between the organic resinous adhesive and the inorganic filler (DeWald, USP No. 4,871,376). The adhesive based on polyvinyl acetate emulsion must have sufficient wet adhesive strength to hold the melamine resin treated paper sheet on the upper and lower surfaces of the particleboard sheet. This is because these panels are moved through the heating and pressurizing zones. This polyvinyl acetate emulsion-based adhesive is used to bond a sheet of melamine resin-treated paper onto these panels.
It is cured in a heating and pressing zone. There is a need to substantially eliminate stress cracking of the melamine resin cured on these panels. It is also necessary to substantially eliminate the formation of wrinkles and peeling of edges and corners that occur during the movement of these panels through the heating and pressing zones. The adhesive containing a polyvinyl acetate emulsion as a main component also needs to adhesively bond melamine formaldehyde resin-treated paper to a particle board with a strength exceeding the internal strength of the particle board. Thus, the melamine formaldehyde resin treated paper applies sufficient force,
Unless the member is torn from the particle board, it will not be able to separate from the particle board.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide adhesives based on polyvinyl acetate emulsions for bonding papers treated with melamine formaldehyde resin, such as decorative solid colors and printed papers, to particle boards. To provide an agent.

[0009]

SUMMARY OF THE INVENTION A sheet of melamine treated paper is effectively bonded to the upper and lower surfaces of a particle board using a tackifying polyvinyl alcohol, starch, a tackifying agent and a coupling agent. It has been found that it can be formulated as an adhesive. Stress cracks were virtually eliminated. It also substantially eliminates wrinkle formation and edge and corner delamination that occur during the movement of these panels through the heating and pressurizing zones. The adhesive based on the polyvinyl acetate emulsion of the present invention is about 1.5-4.
It is formulated using 5%, preferably about 2-4% and most preferably about 3.5% by weight of a tackifying polyvinyl alcohol. The adhesive also has about 20 of the adhesive.
Formulated using -35% by weight starch solids. Preferably, the starch is corn starch having a particle size of about 5-25μ and a mean particle size (median particle size) of about 15μ. The adhesive of the present invention may also contain about 0-15% by weight of the adhesive, preferably about 5-
Formulated using 10% by weight of a tackifier solid. Preferably, the tackifier is butylbenzyl phthalate. Further, the adhesives of the present invention are formulated using about 1-5%, preferably about 1.5-2.5%, by weight of the adhesive, of a coupling agent solid. Suitable coupling agents are water-soluble or water-dispersible silane, titanate or zircoaluminate coupling agents or mixtures thereof,
Preferred are titanate or zircoaluminate coupling agents or mixtures thereof. The most preferred coupling agent is DuPont Chemicals (DuPowell Chemicals, 988, Delaware, 1007 Market Street, Wilmington).
Tyzor 131 brand coupling agent, a mixed titanium orthoester complex, commercially available from Pont Chemicals. A preferred embodiment of the present invention has the following formula:

[0010]

[Table 1] Ingredient Amount ^* Chemical name Manufacturer XX-240 60.25 Vinyl acetate resin Air Products & Chemicals, Mopolymere POBox 538, Ahrentown, Marshon PA 18105 (Company 1) Airbol (Air-3.6 Polyvinyl Air Products & Chemicals, vol) 523 PA18105 Pearl Starch 25.7 Corn Starch AE Star Ray Mfg., 2200E (Pearl Starch) Stoel Dorado, Decatur, IL 62525 (company 2) Santisizer 8.6 Butylbenzyl Monsanto Company 800 No (Santicizer) 160 Phthalate Sledberg Boulevard, Cent Louis, MO 63167 (Company 3) Tysol 1.85 Mixed Titanium DuPont Chemicals, 1007mer (Tyzor) 131 Estrecket Street, Wilming Complex Ton, DE 19898 (Company 4) *: The amount is the solids in the adhesive Based on the weight, the weight percent of solids. (Company 1): Air Products & Chemicals, PO Box 538, Allentown, PA 18105 (Company 2): AE Sraley Mfg. Co., 2200 East Eldorado, Decatur, IL 62525 (Company 3): Monsanto Company, 800 North Lindbergh Blvd ., St. Louis, MO 63167 (Company 4): Du Pont Chemicals, 1007 Market Street, Wilmington, DE 19898.

[0011] The adhesive based on polyvinyl acetate emulsion according to this preferred embodiment has sufficient wet bond strength to maintain the sheet of melamine resin treated paper on the top and bottom surfaces of the particle board. Here the sheets are moved through the heating and pressing zones. This adhesive substantially eliminates stress cracks in panels made of melamine treated paper bonded to particleboard. The adhesive also eliminates wrinkles and edge and corner peeling as these panels move through the heating and pressing zones. The adhesive also allows bonding of the melamine resin treated paper to the particle board with a bond strength greater than the internal strength of the particle board. Thus,
Melamine formaldehyde resin treated paper cannot be separated from the particle board unless sufficient force is applied to tear the member from the particle board. According to this preferred embodiment, the tackifying polyvinyl alcohol is prepared by stirring about 837 g of water, 8 g of boric acid and
Add 3.2 g of phosphoric acid, then 150 g of Airvol
Manufactured by adding 523. Then, about 1.8g
Of Mazu DF 132 (antifoam) is added to the mixture.
The mixture is then heated to about 200 ° F (93.3 ° C) and
Maintain at 200 ° F (93.3 ° C) for minutes. The mixture is cooled to ambient temperature before use. Airvol 523 brand polyvinyl alcohol is a polyvinyl acetate obtained by hydrolyzing about 78-89% of polyvinyl alcohol. Airvol 523 is Air Products & Chemicals, POBox 538, Ahrentown, PA 18105 (Air
Products & Chemicals, PO Box 538, Allentown, PA
18105). Mazu DF 1
32 Defoaming agent with the trade name of PPG Industries (PPG
Industries, Inc.), PPG Place, Pittsburgh, PA
Commercially available from 15272.

Tackifying Polyvinyl Alcohol The preparation of a polyvinyl acetate emulsion adhesive using two different amounts of tackifying polyvinyl alcohol is described.
This will be described with the following example. The tackifying polyvinyl alcohol used in these examples was made using the procedure already described for the preferred embodiment. The adhesive of these examples was applied to a 0.01-0.02 cm (0.004-0.008 in) thick adhesive coating at 4-8 g / ft ² (929.03 cm ² ) of 4 × 8 feet (121.9 × 243 in) of particle board. .8 cm) on both sides of the sheet. 4x8 feet of melamine treated paper
A sheet of (121.9 × 243.8 cm) was placed on each of the adhesive treated surfaces, and the resulting panel was moved along the heating zone. The residence time in the heating zone was about 40 seconds. These panels entered the heating zone at ambient temperature and exited at a temperature of about 180-200 ° F (82.2-93.3 ° C). 30-40p as the panel passes through the heating zone
A pressure of si (2.1-2.8 Kg / cm ² ) was applied by a nip roller. The adhesives of these examples, having two concentrations of tackifying polyvinyl alcohol, have the following formula:

[0013]

[Table 2] Ingredient Amount ^* Chemical name Manufacturer XX-240 60.25 / Vinyl acetate plastic Air Products & Chemicals, 62.05 Mopolymere POBox 538, Ahrentown, Marshon PA 18105 Airbol (Air-1.8 / Polyvinyl Air Products & Chemicals, vol) 523 ( Adhesive 3.6 Alcohol POBox 538, Arlentown, imparting properties) PA 18105 Pearl Starch 25.7 / Corn Starch AE Star Ray Mfg., 2200-E (Pearl Starch) 25.7 Stoerdorado, Decatur, IL 62525 Santisizer 8.6 / Butylbenzyl Monsanto Company, 800 No (Santicizer) 160 8.6 Phthalate Sledberg Boulevard, St. Louis, MO 63167 Tysol 1.85 / Mixed Titanium Dupont Chemicals, 1007mer (Tyzor) 131 1.85 Wiltester Complex Street, Wilming Complex Ton, DE 19898 *: Based on the weight of solids in the adhesive It represents the percent by weight of the solids.

The corner peeling was measured by measuring 4 × 8 feet (121.9 × 243.8 cm) of melamine resin treated paper on both the upper and lower surfaces of a 4 × 8 feet (121.9 × 243.8 cm) sheet of particle board.
m) were based on ten or more panels, which were produced by bonding the adhesives of these examples while moving them through the heating and pressing zones. Was. Any of the stripped corners indicates a defective product. 12x12 inch (30.5x30.5 c) cut from each of these panels
Form two notches along each end of the sample in m). Thereafter, the sample is placed in a 65 ° C. oven for 24 hours. After removing the sample from the oven and cooling to ambient temperature, the sample is inspected for the presence of cracks. Cracks only occur at notches along the sides of the sample, representing the machine direction with respect to the paper. The machine direction for the paper is the side of the paper generated along the forming screen on the paper machine. "Good" for stress cracking
A rating of no means that no cracks were observed in more than 95% of the notched area in the cross direction of the sample. A rating of "passive" means that no cracks were observed in more than 90% of the notched area in the cross direction of the sample. Cracks in these samples were 4 notches along the edge of the panel.
It did not extend beyond inches (10.2 cm). No cracks were formed outside the notch. Notch formation represents severe test conditions.

[0015]

[Table 3] Peeling of corners of PVOH with% tackiness Stress cracking 3.60-10% Good 1.8 10-20%

The formulation of a polyvinyl acetate emulsion adhesive using three different amounts of tackifying polyvinyl alcohol is shown in the following example. The tackifying polyvinyl alcohol used in these examples was prepared by the procedure described for the preferred embodiment above. The adhesive in these examples, with respect to coating of the adhesive thickness 0.01~0.02cm (0.004~0.008in), at ^{4~8g / ft 2 (929.03cm 2)} , 4x8 foot particle board (121.9X243. 8cm) on both sides of the sheet. 4x8 feet of melamine treated paper (1
21.9 x 243.8 cm) was placed on each of the adhesive treated surfaces and the resulting panel was moved along the heating zone. The residence time in the heating zone was about 40 seconds. These panels enter the heating zone at ambient temperature,
It came out of it at a temperature of about 180-200 ° F (82.2-93.3 ° C). 30-40p as the panel passes through the heating zone
A pressure of si (2.1-2.8 Kg / cm ² ) was applied by a nip roller. The adhesives of these examples, having three concentrations of tackifying polyvinyl alcohol, have the following formula:

[0017]

[Table 4] Ingredient Amount ^* Chemical name Manufacturer XX-240 64.5 / Vinyl acetate air products & chemicals, 67.6 / Mopolymere POBox 538, Ahrentown, 70.9 Marshon PA 18105 Airbol (Air-5.6 / Polyvinyl air products & chemicals, vol) 523 (adhesive 3.7 / alcohol POBox 538, Arlentown, imparting properties) 1.8 PA 18105 pearl starch 27.9 / corn starch AE Star Ray Mfg., 2200 e (Pearl Starch) 26.7 / stouerdorado, deca tool, 25.5 IL 62525 tysol 2 / mixed Titanium DuPont Chemicals, 1007 Mer (Tyzor) 131 1.9 / Tolesterket Street, Wilming 1.8 Complex Ton, DE 19898 *: The amounts are weight percent solids, based on the weight of solids in the adhesive .

Corner peeling and stress cracking were measured according to the procedure described for the above examples.

[0019]

[Table 5] Peeling of corner of PVOH with% tackiness Stress cracking 5.6 Remarkably good 3.7 10-20% Good 1.8 10-20% Fair

Polyvinyl Alcohol An example of the formulation of a polyvinyl acetate emulsion adhesive containing two different polyvinyl alcohols is shown below. The polyvinyl alcohol used in the following examples is Air Products & Chemicals, POBox 538, Ahrentown,
PA 18105 (Air Products & Chemicals, PO Box 538, A
Airvor 540 1,709 pounds (775.2 kg) commercially available from Llentown, PA 18105) and Maz (commercially available from PPG Industries, Inc., PPG Place, Pittsburgh, PA 15272) Mazu) DF 132 Exclusive antifoam agent with the trade name of 34 lbs.
(15.4kg) and Huls America Inc.,
17 lb (7.71) Nuosept 95 brand preservative (tetrahydroxy-3,5-dimethyl-2H-1,3,5-thiadiazin-2-thio) commercially available from PO Box 365, Piscataway, NJ 08854 kg) and 15,328 pounds of water (695
3 kg). Adhesives of these examples, with respect to coating of the adhesive thickness 0.01~0.02cm (0.004~0.008in), at ^{4~8g / ft 2 (929.03cm 2)} , 4x8 foot particleboard (121.9X243 .8 cm) on both sides of the sheet. 4x8 feet of melamine treated paper (1
21.9 x 243.8 cm) was placed on each of the adhesive treated surfaces and the resulting panel was moved along the heating zone. The residence time in the heating zone was about 40 seconds.
These panels enter the heating zone at ambient temperature and
It came out of it at a temperature of 0-200 ° F (82.2-93.3 ° C).
As the panel passes through the heating zone, 30-40 psi (2.1
A pressure of -2.8 Kg / cm ² ) was applied by a nip roller. The adhesives of these examples, having two concentrations of polyvinyl alcohol, have the following formula:

[0021]

[Table 6] Ingredient Amount ^* Chemical name Manufacturer XX-240 58 / Vinyl acetate plastic Air Products & Chemicals, 62.9 Mopolymere POBox 538, Ahrentown, Marshon PA 18105 Airbol (Air-3.6 / Polyvinyl Air Products & Chemicals, vol) 540 ( 1.7 Alcohol POBox 538, Aalentown, N.D.) PA 18105 Pearl Starch 27.3 / Corn Starch AE Star Ray Mfg., 2200 E (Pearl Starch) 25.2 Stoerdorado, Decatur, IL 62525 Santisizer 9.1 / Butylbenzyl Monsanto Company, 800 No (Santicizer) 160 8.4 Phthalate (viscosity Sulindberg Boulevard, adhesion-imparting agent) Neuluis, MO 63167 Tysol 2 / Mixed titanium oxide Dupont Chemicals, 1007mer (Tyzor) 131 1.8 Luster ester cake street, Wilming composite ton, DE 19898 *: The amount is the weight of solids in the adhesive It is the weight percentage of solids, based on the amount.

Corner peeling and stress cracking were measured by the procedure described for the previous example.

[0023]

[Table 7] % PVOH% tackifier corner peeling stress cracking 3.65 remarkable good 1.75 remarkable good or reasonable

The following are examples of formulations of polyvinyl acetate emulsion adhesives containing polyvinyl alcohol in two different amounts. The polyvinyl alcohol used in the following examples is Air Products & Chemicals, POBox 538,
Aalentown, PA 18105 (Air Products & Chemicals,
PO Box 538, Allentown, PA 18105) Commercially available Airvor 540 1,709 lbs (77
5.2 kg) and PPG Industries,
Inc.), PPG Place, Pittsburgh, PA 15272, a proprietary anti-foaming agent 34 pounds (15.4 kg) under the trade name Mazu DF 132, and Hulse America, Inc.
s America Inc.), PO Box 365, Piscataway, NJ 0
Nuosept, commercially available from 8854
95 brand preservatives (tetrahydroxy-3,5-dimethyl-2
H-1,3,5-thiadiazine-2-thi (17) 17 lb (7.71 kg)
And 15,328 pounds (6953 kg) of water. The adhesive of these examples has a thickness of 0.01 to 0.02 cm.
(0.004-0.008in) 4-8g / ft
² (929.03cm ² ) 4x8 feet of particleboard
(121.9X243.8cm) applied to both sides of the sheet. A 4x8 ft (121.9x243.8cm) sheet of melamine treated paper
Placed on each of the adhesive treated surfaces, the resulting panel was moved along the heating zone. The residence time in the heating zone was about 40 seconds. The panels entered the heating zone at ambient temperature and exited at a temperature of about 180-200 ° F (82.2-93.3 ° C). As the panel passed through the heating zone, a pressure of 30-40 psi (2.1-2.8 Kg / cm ² ) was applied by a nip roller. The adhesives of these examples, having two concentrations of polyvinyl alcohol, have the following formula:

[0025]

[Table 8] Ingredient Amount ^* Chemical Name Manufacturer XX-240 65.7 / Vinyl Acetate Air Products & Chemicals, 70.2 Mopolymere POBox 538, Ahrentown, Marshon PA 18105 Airbol (Air-3.8 / Polyvinyl Air Products & Chemicals, vol) 540 ( Brew 1.7 Alcohol POBox 538, Aalentown, Nd) PA 18105 Pearl Starch 28.05 / Corn Starch AE Star Ray Mfg., 2200E (Pearl Starch) 26.2 Stoerdorado, Deca Tool, IL 62525 Tysol 2 / Mixed Titanium Dupont Chemicals, 1007mer (Tyzor) 131 1.9 crude ester street, Wilming Complex Ton, DE 19898 *: Amounts are weight percent solids based on the weight of solids in the adhesive.

Corner peeling and stress cracking were measured by the procedure described for the previous example.

[0027]

[Table 9] % PVOH corner peeling stress cracking 3.8 remarkable good 1.7 remarkable good or reasonable

Starch Various amounts of starch and various basis weights of decorative paper were used.
The formulation of the polyvinyl acetate emulsion adhesive is illustrated by the following example. The adhesives of these examples have a thickness of 0.01 to
For a 0.02cm (0.004-0.008in) adhesive coating, 4 ~
8 g / ft ² (929.03 cm ² ) was applied to both sides of a 4 × 8 foot (121.9 × 243.8 cm) sheet of particleboard. A 4 x 8 ft (121.9 x 243.8 cm) sheet of melamine resin treated paper was placed on each of the adhesive treated surfaces and the resulting panel was moved along the heating zone. The residence time in the heating zone was about 40 seconds. These panels enter the heating zone at ambient temperature and are exposed to about 180-200 ° F (82.2-93.3
° C) came out of it. As the panel passed through the heating zone, a pressure of 30-40 psi (2.1-2.8 Kg / cm ² ) was applied by a nip roller. The adhesives in these examples have the following formula:

[0029]

[Table 10] Ingredient Amount ^* Chemical Name Manufacturer XX-240 69-88 Vinyl Acetate Air Products & Chemicals, Mopolymere POBox 538, Allentown, Marshon PA 18105 Pearl Starch 5-24 Corn Starch AE Starley Mfg., 2200 e ( Pearl Starch) Stoeldorado, Decatur, IL 62525 Santisizer 5-Butylbenzyl Monsanto Company, 800 No (Santicizer) 160 Phthalate (viscous Sulindberg Boulevard, adhesion-imparting agent) Montluis, MO 63167 Tysol 2 Mixed Titanium DuPont Chemicals, 1007mer (Tyzor) 131 Tortesterk Street, Wilming Complex Ton, DE 19898 *: Amounts are weight percent of solids in the adhesive.

A 12x1 cut from each of these panels
Along each edge of the 2 inch (30.5 x 30.5 cm) sample,
Two notches were formed. Thereafter, the sample was placed in a 65 ° C. oven for 24 hours. After removing the sample from the oven and cooling to ambient temperature, the sample was inspected for cracks. The longest crack length was reported. The frequency of cracks extending from the notch along the machine direction of the paper was reported. Each sample had two notches along each of its machine direction sides. No cracks were observed on the notches along the sides of the sample, representing the cross direction to the paper. The machine direction of the paper is the side of the paper formed along the forming screen of the paper machine, and the cross direction is the direction across the forming screen. No cracks occurred outside the notch. Notch formation represents severe test conditions.

[0031]

[Table 11] Starch ^{* 85lb (39kg) ** 75lb (} 34kg) ** 62lb (28kg) ** 50lb (23kg) ** 43lb (20kg) ** 5 3/4 '' (1.9cm) 3/4 '' (1.9cm) 1 3/8 '' (3.5cm) 3/4 '' (1.9 1/2 '' (1.3cm) (8/8) (4/8) (2/4) cm) ( 5/8) (4/8) 10 1/2 '' (1.3cm) 1/2 '' (1.3cm) 1/2 '' (1.3cm) 5/16 '' (0.8 5/16 '' ( 0.8 (5/8) (1/8) (7/8) cm) (6/8) cm) (5/8) 15 5/16 '' (0.8 0 (0) (0/16) 1/4 '' (0.64 1/8 '' (0.32 1/8 '' (0.32 cm) (11/16) cm) (8/16) cm) (11/16) cm) (9/16) 18 3/8 '' (0.95 0 (0) (0/16) 1/4 '' (0.64 1/4 '' (0.64 3/16 '' (0.45 cm) (3/16) cm) (2/16) cm) (11/16) cm) (13/16) 20 1/8 '' (0.32 1/16 '' (0.16 1/8 '' (0.32 3/16 '' (0.45 1/16 '' (0.16 cm) (1/16) cm) (1/16) cm) (3/16) cm) (5/16) cm) (3/16) 22 5/16 '' (0.8 3/16 '' (0.45 1 / 4 '' (0.64 3/16 '' (0.45 1/16 '' (0.16 cm) (11/16) cm) (2/16) cm) (6/16) cm) (12/16) cm) ( 5/16) 24 1/4 '' (0.64 7/16 '' (1.11 1/8 '' (0.32 1/4 '' (0.64 1/8 '' (0.32 cm) (3/16) cm) ( 1/16) cm) (3/16) cm) (10/16) cm) (6/16) *: Starch is% by weight based on the adhesive. **: The basis weight of decorative paper in pounds / 3000 ft ² (279 m ² ).

The formulation of a polyvinyl acetate emulsion adhesive using various amounts of starch and various basis weights of decorative paper is illustrated by the following examples. The adhesive of these examples was applied to a 0.01-0.02 cm (0.004-0.008 in) thick adhesive coating at 4-8 g / ft ² (929.03 cm ² ) of 4 × 8 feet (121.9 × 243 in) of particle board. .8 cm) on both sides of the sheet. 4x8 feet (121.9X2) of melamine treated paper
43.8 cm) of a sheet was placed on each of the adhesive treated surfaces and the resulting panel was moved along the heating zone. The residence time in the heating zone was about 40 seconds. These panels enter the heating zone at ambient temperature and
It came out of it at a temperature of 0 ° F (82.2-93.3 ° C). As the panel passes through the heating zone, 30-40 psi (2.1-
A pressure of 2.8 kg / cm ² ) was applied by a nip roller. The adhesives in these examples have the following formula:

[0033]

[Table 12] Ingredient Amount ^* Chemical Name Manufacturer XX-240 70-89 Vinyl Acetate Air Products & Chemicals, Mopolymere POBox 538, Allentown, Marshon PA 18105 Pearl Starch 5-24 Corn Starch AE Starley Mfg., 2200E ( Pearl Starch) Stouerdorado, Decatur, IL 62525 Santisizer 5-Butylbenzyl Monsanto Company, 800 No (Santicizer) 160 Phthalate (viscous Sulindberg Boulevard, adhesion-imparting agent) Treuis, MO 63167 Tysol 1 Mixed Titanium DuPont Chemicals, 1007 Mer (Tyzor) 131 Toluquette Street, Wilming Complex Ton, DE 19898 *: Amounts are by weight based on the adhesive.

A 12x1 cut from each of these panels
Along each edge of the 2 inch (30.5 x 30.5 cm) sample,
Two notches were formed. Thereafter, the sample was placed in a 65 ° C. oven for 24 hours. After removing the sample from the oven and cooling to ambient temperature, the sample was inspected for cracks. The longest crack length was reported. The frequency of cracks extending from the notch along the machine direction of the paper was reported. Each sample had two notches along each of its machine direction sides. No cracks were observed on the notches along the sides of the sample, representing the cross direction to the paper. The machine direction of the paper is the side of the paper formed along the forming screen of the paper machine, and the cross direction is the direction across the forming screen. No cracks occurred outside the notch. Notch formation represents severe test conditions.

[0035]

[Table 13] Starch ^{* 85lb (39kg) ** 75lb (} 34kg) ** 62lb (28kg) ** 50lb (23kg) ** 43lb (20kg) ** 15 5/8 '' (1.6 0 (0) ( 0/16) 1/4 '' (0.64 1/4 '' (0.64 1/16 '' (0.16 cm) (12/16) cm) (12/16) cm) (11/16) cm) (11 / 16) 18 3/8 '' (0.95 0 (0) (0/16) 3/4 '' (1.9cm) 1/4 '' (0.64 1/4 '' (0.645 cm) (1/16) (5/16) cm) (14/16) cm) (14/16)) 20 0 (0) (0/16) 0 (0) (0/16) 0 (0) (0/16) 3 / 16 '' (0.45 1/16 '' (0.16 cm) (7/16) cm) (7/16) 22 3/8 '' (0.95 1/4 '' (0.64 5/16 '' (0.8 1 / 4 '' (0.64 1/8 '' (0.32 cm) (12/16) cm) (7/16) cm) (8/16) cm) (15/16)) cm) (6/16) 24 1 / 2 '' (1.3cm) 1/4 '' (0.64 5/16 '' (0.8 3/16 '' (0.45 3/16 '' (0.45 (11/16) cm) (4/16) cm) (6/16) cm) (8/16) cm) (6/16) *: Starch is% by weight based on the adhesive. **: The basis weight of decorative paper in pounds / 3000 ft ² (279 m ² ).

Coupling Agents Water-soluble or water-dispersible silane, titanium and zircoaluminate coupling agents are used in polyvinyl acetate emulsion adhesives to bond between melamine formaldehyde resin treated paper and particleboard. Strength can be increased. Preferred coupling agents are titanate and zircoaluminate coupling agents.
Also, the melamine treated paper may shrink under heat and pressure conditions as it hardens further during bonding between the melamine formaldehyde treated paper and the particle board. Useful in the adhesive of the present invention, titanium coupling agent and zircoaluminate coupling agent,
It is water-soluble or water-dispersible and can be used in a pH range of 2-6. DuPont C
Chemicals), Tyzor LA Titanate-dihydroxybis (ammonium lactate) titanium and Taisol 131 titanate
(Tyzor 131 Titanate) -mixed titanium orthoester complex increases adhesive bond strength. Rhone Poulenc (Rho
ne-Poulenc Inc.)
chem) CPG-carboxyzircoaluminate and Manchem APO-X-aminozircoaluminate solutions also increase the adhesive bond strength. OSI Special Deeds
Silquest A-187 Silane-γ-glycidoxypropyltrimethoxy-silane, Silquest A-Supplied by (OSI Specialties, Inc.)
1100 silane (Silquest A-1101 Silane) -γ-aminopropyltriethoxy-silane, Silquest A-1128 silane (S
ilquest A-1128 Silane)-A silane coupling agent containing an amino-modified organic silane ester also increases the bond strength.
However, silane coupling agents may not have sufficient stability in polyvinyl acetate emulsion adhesives for long-term storage before use.

The coupling agent is effective in the range of 0.5-5% by weight, preferably 0.5-4% by weight and most preferably 1.5-3% by weight, based on the adhesive formulation.
High concentrations of coupling agents can reduce the binding capacity of the adhesive formulation. The effectiveness of the adhesive containing polyvinyl acetate emulsion as a main component for bonding decorative solid colors and printed paper treated with melamine formaldehyde resin to particle board will be described with reference to the following examples. In these examples, titanate, zircoaluminate and a silane coupling agent were compounded in an adhesive containing a polyvinyl acetate emulsion and polyvinyl alcohol. This adhesive has the following formula:

[0038]

[Table 14] Ingredient Amount ^* Chemical Name Manufacturer XX-240 26.05 Vinyl Acetate Air Products & Chemicals, Mopolymer POBox 538, Ahrentown, PA 18105 Pearl Starch 23.68 Corn Starch AE Starley Mfg., 2200E (Pearl Starch) , DecaTool, IL 62525 Air Vol (Air-4.74 Polyvinyl Air Products & Chemicals, vol.) 540 Alcohol POBox 538, Ahrentown, PA 18105 Ethylene Gri 1.77 Ethylene Celanese Chemicals, 1250 Wacoal (Ethy-Recall Stoking Bird, Dallas, lene Glycol) TX 75247 (Company 5) Tectamer 0.29 1,2-Dibromo-Calgon Corp., PO (Tektamer) 2,4-dicyano Box 1346, Pittsburgh, PA 38AD Butane 15230 (Company 6) Nuocept 0.32 Bicyclic Hals America , PO Box 365 (Nuosept) 95 Oxazolidine piscataway Mazu DF 0.40 Proprietary defoamer PPG Industries, PPG 132, Pittsburgh, PA 15272 (Company 8) Nuocept 0.09 Tetrahydroxyhalus America, PO Box 365 (Nuosept) 120 -3,5-Dimethyl-piscataway, NJ 08854 2H-1,3,5-Thiaziazine-2-tin Water 42.66 *: Amounts are expressed in weight percent based on the adhesive. (Company 5): Celanese Chemical Co., 1250 West Mockingbird, Dallas, TX 75247 (Company 6): Calgon Corporation, PO Box 1346, Pittsburgh, PA 15230 (Company 7): Huls America Inc., PO Box 365, Piscataway, NJ 08854 (company 8): PPG Industries, Inc., PPG Place, Pittsburgh, PA 15272

Cross Hatch Test Melamine formaldehyde-treated paper was inscribed using a universal knife with a pattern similar to the number sign, #.
The melamine formaldehyde treated paper was separated from the particleboard using the tip of the knife. If the particleboard is removed with the melamine formaldehyde treated paper bound, the bond is considered good (P). If the particleboard was not removed with the melamine formaldehyde treated paper,
The binding is considered to be poor (F). The crosshatch test was performed twice. First, at room temperature, 24 hours after assembling the sample (before) and a second time, placing the product in an oven at 70 ° C. for 24 hours and cooling to room temperature (after ). Thermal stress cracks Cracks occur at the panel edges and are placed in an oven at 70 ° C for 24 hours.
Placed in time and then inspected for crack growth behind the pre-notch point. To pass this test,
The crack growth must be less than 1/4 inch (0.635 cm) in length. Tyzor 131 titanate was mixed with the adhesive of this example at the concentrations shown in the table below. Concentrations are given in weight percent based on the adhesive of this example. Tysol 131 is a mixed titanium orthoester complex and is available from Du Pont Chemi
cals), 1007 Market Street, Wilmington,
Available commercially from Delaware 19898.

[0040]

[Table 15] Concentration Cross hatch (before) Cross hatch (after) No stress crack PFF 0.1 PPP 0.5 PPP 1.0 PPP 2.0 PPP 4.0 PPP

Tyzor® LA titanate was mixed with the adhesive of this example at the concentrations indicated in the table below. Concentrations are given in weight percent based on the adhesive of this example. Tysol LA is dihydroxybis (ammonium lactate) titanium, manufactured by DuPont Chemical
(Du Pont Chemicals), 1007 Market Street, Wilmington, Del.

[0042]

[Table 16] Concentration Cross hatch (before) Cross hatch (after) No stress crack PFF 0.1 PPP 0.5 PPP 1.0 PPP2.0 PPP 4.0 PPP

Tyzor® GBA titanate was mixed with the adhesive of this example. The adhesive exhibited a viscosity that was too high to bond the melamine formaldehyde treated decorative paper to the particleboard. Tysol GBA is a registered trademark of NJ Trade Secret Registry (NJ
Trade Secret Registry) as # 008502010015522P and Du Pont Chemi
cals), 1007 Market Street, Wilmington,
Available from Delaware 19898. Tyzor:
® TE titanate was mixed with the adhesive of this example. The adhesive exhibited a viscosity that was too high to bond the melamine formaldehyde treated decorative paper to the particleboard. Tysol TE is isopropoxy (triethanol aminato) titanium and is commercially available from DuPont Chemicals, 1007 Market Street, Wilmington, Del. 19898.

[0044]

[Table 17] Concentration Cross hatch (before) Cross hatch (after) No stress crack PFF 0.1 PPP 0.5 PPP 1.0 PPP 2.0 PPP 4.0 PPP

Manchem® CPG was mixed with the adhesive of this example at the concentrations indicated in the table below. Concentrations are given in weight percent based on the adhesive of this example. Manchem CPG is a carboxyzircoaluminate solution, available from Rhone-Poulenc Incorporated.
c.), commercially available from Metal Organics, 275 Keystone Drive, Bethleam, PA 18017.

[0046]

[Table 18] Concentration Cross hatch (before) Cross hatch (after) No stress crack PFF 0.1 PPP 0.5 PPP 1.0 PPP 2.0 PPP 4.0 PPP

Manchem (registered trademark) APG-X was
The adhesives of this example were mixed at the concentrations indicated in the table below.
Concentrations are given in weight percent based on the adhesive of this example. Manchem APG-X is an aminozircoaluminate solution, available from Rhone-Poulenc Inc.,
Available commercially from Metal Organics, 275 Keystone Drive, Bethleam, PA 18017.

[0048]

[Table 19] Concentration Cross hatch (before) Cross hatch (after) No stress crack PFF 0.1 PPP 0.5 PPP 1.0 PPP 2.0 PPP 4.0 PPP

Silquest® A-1100
Was mixed with the adhesive of this example at the concentrations indicated in the table below. Concentrations are given in weight percent based on the adhesive of this example. Silquest A-1100 is γ-aminopropyl-triethoxysilane and is available from OSI Specialties, Inc.
Specialties, Inc.), 39 Available from Oldridge Valley Road, Danbury, CT 06810-5121.

[0050]

[Table 20] Concentration Cross hatch (before) Cross hatch (after) No stress crack PFF 0.1 PPP 0.5 PPP 1.0 PPP 2.0 PPP 4.0 PPP

Silquest (registered trademark) A-1128
Was mixed with the adhesive of this example at the concentrations indicated in the table below. Concentrations are given in weight percent based on the adhesive of this example. Silquest A-1128 is an amino-functional silane ester and is available from OSI Specialties, Inc.
s, Inc.), 39, available from Oldridge Valley Road, Danbury, CT 06810-5121.

[0052]

[Table 21] Concentration Cross hatch (before) Cross hatch (after) No stress cracking P PF 0.1 P P P 0.5 P P P 1.0 P P P 2.0 P F F 4.0 F F F

Silquest (registered trademark) A-187
Was mixed with the adhesive of this example at the concentrations indicated in the table below. Concentrations are given in weight percent based on the adhesive of this example. Silquest A-187 is glycidoxypropyltrimethoxy-silane and is available from OSI Specialties, Inc.
I Specialties, Inc.), 39 Available from Oldridge Valley Road, Danbury, CT 06810-5121.

[0054]

[Table 22] Concentration Cross hatch (before) Cross hatch (after) No stress crack PFF 0.1 PPP 0.5 PPP 1.0 PPP 2.0 PPP 4.0 PPP

In the following comparative examples, titanate, zircoaluminate and a silane coupling agent were blended in a vinyl acetate adhesive containing polyvinyl acetate as a main component. Melamine formaldehyde treated paper was bonded to the particleboard using these polyvinyl acetate based adhesives. However, they have not eliminated stress cracking. It is considered that the adhesives of these comparative examples do not have sufficient flexibility to reduce the accumulated shrinkage of the decorative paper when the decorative paper treated with melamine formaldehyde is bonded to the particle board. Was.

[0056]

[Table 23] Ingredient Amount ^* Chemical Name Manufacturer XX-240 79.59 Vinyl Acetate Air Products & Chemicals, Mopolymer POBox 538, Aalentown, PA 18105 Pearl Starch 14.97 Corn Starch AE Starley Mfg., 2200 E (Pearl Starch) , Decatur, IL 62525 Santisizer 4.97 Butylbenzyl Monsanto Company, 800 No (Santicizer) 160 Phthalate Sledberg Boulevard, St. Louis, MO 63167 Nuocept 0.20 Bicyclic Hals America, PO Box 365 (Nuosept) 95 Oxazolidine piscataway, NJ 08854 Similar solutions Tectamer 0.20 1,2-Dibromo-calgon coboration, PO (Tektamer) 2,4-dicyano Box 1346, Pittsburgh, PA 38AD Butane 15230 Maz (Mazu) DF 0.07 Proprietary defoamer PPG Industries, PPG 132 , Pittsburgh, PA 15272 *: It is expressed in% by weight based on the adhesive.

Tyzor® 131 titanate was mixed with the adhesive of this comparative example at the concentrations shown in the following table. Concentrations are given in weight percent based on the adhesive of this comparative example. Tysol 131 is a mixed titanium orthoester complex, available from Dupont Chemical Company (D
u Pont Chemicals), 1007 Market Street, Wilmington, Del.

[0058]

[Table 24] Concentration Cross hatch (before) Cross hatch (after) No stress cracking PPF 0.1 PPP 0.5 PPP 1.0 PPP 2.0 PPP 4.0 PPP

Tyzor® LA titanate was mixed with the adhesive of this comparative example at the concentrations shown in the table below. Concentrations are given in weight percent based on the adhesive of this comparative example. Tysol LA is a dihydroxybis (ammonium lactate) titanium, commercially available from DuPont Chemicals, 1007 Market Street, Wilmington, Del. 19898.

[0060]

[Table 25] Concentration Cross hatch (before) Cross hatch (after) No stress cracking PPF 0.1 PPF 0.5 PPF 1.0 PPF 2.0 PPF 4.0 PPF

Manchem® CPG was mixed with the adhesive of this comparative example at the concentrations shown in the table below. Concentrations are given in weight percent based on the adhesive of this comparative example. Manchem CPG is a carboxyzircoaluminate solution and is available from Rhone-Poule
nc Inc.), Metal Organics, 275 Keystone Drive, Bethleam, PA 18017.

[0062]

[Table 26] Concentration Cross hatch (before) Cross hatch (after) No stress cracking PPP 0.1 PPP 0.5 PPP 1.0 PPP 2.0 PPP 4.0 PPP

Manchem® APG-X was
It was mixed with the adhesive of this comparative example at the concentrations shown in the following table. Concentrations are given in weight percent based on the adhesive of this comparative example. Manchem APG-X is an aminozircoaluminate solution, available from Rhone-Poulenc.
Inc.), Metal Organics, 275 Keystone Drive, Bethleam, PA 18017.

[0064]

[Table 27] Concentration Cross hatch (before) Cross hatch (after) No stress cracking PPF 0.1 PPP 0.5 PPP 1.0 PPP 2.0 PPP 4.0 PPP

[0065] Silquest (registered trademark) A-1100
Was mixed with the adhesive of this comparative example at the concentrations shown in the following table. Concentrations are given in weight percent based on the adhesive of this comparative example. Silquest A-1100 is gamma-aminopropyl-triethoxysilane and is commercially available from OSI Specialties, Inc., 39 Oldridge Valley Road, Danbury, CT 06810-5121.

[0066]

[Table 28] Concentration Cross hatch (before) Cross hatch (after) No stress cracking PPF 0.1 PPF 0.5 PPF 1.0 PPF

[0069] Silquest (registered trademark) A-1128
Was mixed with the adhesive of this comparative example at the concentrations shown in the following table. Concentrations are given in weight percent based on the adhesive of this comparative example. Silquest A-1128 is an amino-functional silane ester and is available from OSI Specialties, Inc.
cialties, Inc.), 39 Oldridge Valley Road, Danbury, CT 06810-5121.

[0068]

[Table 29] Concentration Cross hatch (before) Cross hatch (after) No stress cracking PPF 0.1 PPF 0.5 PPP 1.0 PFF 2.0 PFP 4.0 FFP

[0069] Silquest (registered trademark) A-187
Was mixed with the adhesive of this comparative example at the concentrations shown in the following table. Concentrations are given in weight percent based on the adhesive of this comparative example. Silquest A-187 is glycidoxypropyltrimethoxy-silane and is commercially available from OSI Specialties, Inc., 39 Oldridge Valley Road, Danbury, CT 06810-5121.

[0070]

[Table 30] Concentration Cross hatch (before) Cross hatch (after) No stress cracking PPF 0.1 PPF 0.5 PPP 1.0 PPP 2.0 PPF 4.0 PPF

In the following comparative examples, titanate, zircoaluminate and a silane coupling agent were blended in a vinyl acetate adhesive containing a vinyl acetate-ethylene copolymer as a main component. Melamine formaldehyde treated paper was bonded to the particleboard using these vinyl acetate-ethylene copolymer based adhesives. However, they did not eliminate stress cracking. It is considered that the adhesives of these comparative examples do not have sufficient flexibility to reduce the shrinkage accumulated in the decorative paper when the decorative paper treated with melamine formaldehyde is bonded to the particle board. Was.

[0072]

[Table 31] Ingredient Amount ^* Chemical name Manufacturer Airfreight 85.72 Vinyl acetate-Air Products & Chemicals, Airflex Ethylene Copo POBox 538, Arlentown, 400 Rimmer PA 18105 Santisizer 5.53 Butylbenzyl Monsanto Company, 800 No (Santicizer) 160 Phthalate Sledberg Boulevard, Cent Louis, MO 63167 Ethylene Gly 1.86 Ethylene Celanese Chemicals, 1250 Ekole (Ethy-Recall Stroking Bird, Dallas, lene Glycol) TX 75247 Mazu DF 0.14 Exclusive foaming agent PPG Industries, PPG Program 132 Race, Pittsburgh, PA 15272 Triton 0.01 Octylphenoki Union Carbide, Specialty (Triton) Polypolyethoxy Chemical Chemicals, Danbury X-100 Tanol CT 06817-0001 (Company 9) Toluene 6.74 Toluene Fibroene Ghee USA, Inc., 500 Dallas Avenue, soot 3200 Houston, TX 77002 (company 10) *: The amount is expressed in weight percent based on the adhesive. (Company 9): Union Carbide Corporation Specialty Chemicals, Danbuty, CT 06817 -0001 (Company 10): Phibro Energy USA, Inc., 500 Dallas Avenue, Suite 3200, Houston, TX 77002

Tyzor® 131 titanate was mixed with the adhesive of this comparative example at the concentrations shown in the following table. Concentrations are given in weight percent based on the adhesive of this comparative example. Tysol 131 is a mixed titanium orthoester complex, available from Dupont Chemical Company (D
u Pont Chemicals), 1007 Market Street, Wilmington, Del.

[0074]

[Table 32] Concentration Cross hatch (before) Cross hatch (after) No stress cracking PPF 0.1 PPF 0.5 PPF 1.0 PPF 2.0 PPP 4.0 PPP

Tyzor® LA titanate was mixed with the adhesive of this comparative example at the concentrations indicated in the table below. Concentrations are given in weight percent based on the adhesive of this comparative example. Tysol LA is a dihydroxybis (ammonium lactate) titanium, commercially available from DuPont Chemicals, 1007 Market Street, Wilmington, Del. 19898.

[0076]

[Table 33] Concentration Cross hatch (before) Cross hatch (after) No stress cracking PPF 0.1 PPF 0.5 PPF 1.0 PPF 2.0 PPF 4.0 PPF

[0077] Manchem® CPG was mixed with the adhesive of this comparative example at the concentrations indicated in the table below. Concentrations are given in weight percent based on the adhesive of this comparative example. Manchem CPG is a carboxyzircoaluminate solution and is available from Rhone-Poule
nc Inc.), Metal Organics, 275 Keystone Drive, Bethleam, PA 18017.

[0078]

[Table 34] Concentration Cross hatch (before) Cross hatch (after) No stress cracking PPF 0.1 PPF 0.5 PPF 1.0 PPF 2.0 PPF 4.0 PPF

Manchem® APG-X was
It was mixed with the adhesive of this comparative example at the concentrations shown in the following table. Concentrations are given in weight percent based on the adhesive of this comparative example. Manchem APG-X is an aminozircoaluminate solution, available from Rhone-Poulenc.
Inc.), Metal Organics, 275 Keystone Drive, Bethleam, PA 18017.

[0080]

[Table 35] Concentration Cross hatch (before) Cross hatch (after) No stress cracking PPF 0.1 PPF 0.5 PPF 1.0 PPF 2.0 PPF 4.0 PPF

Silquest (registered trademark) A-1100
Was mixed with the adhesive of this comparative example at the concentrations shown in the following table. Concentrations are given in weight percent based on the adhesive of this comparative example. Silquest A-1100 is gamma-aminopropyl-triethoxysilane and is commercially available from OSI Specialties, Inc., 39 Oldridge Valley Road, Danbury, CT 06810-5121.

[0082]

[Table 36] Concentration Crosshatch (before) Crosshatch (after) No stress cracking PPF 0.1 PPF 0.5 PPF 1.0 PPF 2.0 PPF 4.0 PPF

Silquest (registered trademark) A-1128
Was mixed with the adhesive of this comparative example at the concentrations shown in the following table. Concentrations are given in weight percent based on the adhesive of this comparative example. Silquest A-1128 is an amino-functional silane ester and is available from OSI Specialties, Inc.
cialties, Inc.), 39 Oldridge Valley Road, Danbury, CT 06810-5121.

[0084]

[Table 37] Concentration Cross hatch (before) Cross hatch (after) No stress cracking PPF 0.1 PPF 0.5 PPF 1.0 PPF 2.0 PPF 4.0 PPF

[0085] Silquest (registered trademark) A-187
Was mixed with the adhesive of this comparative example at the concentrations shown in the following table. Concentrations are given in weight percent based on the adhesive of this comparative example. Silquest A-187 is glycidoxypropyltrimethoxy-silane and is commercially available from OSI Specialties, Inc., 39 Oldridge Valley Road, Danbury, CT 06810-5121.

[0086]

[Table 38] Concentration Cross hatch (before) Cross hatch (after) No stress cracking PPF 0.1 PPF 0.5 PPF 1.0 PPF 2.0 PPF 4.0 PPF

In the following comparative examples, the air flex
400H is a vinyl acetate-ethylene copolymer and is available from Air Products & Chemicals.
s), Hamilton Boulevard, Allentown, PA 181
It is commercially available from 96-1501 and was used to bind melamine formaldehyde treated paper to particle board. However, they did not eliminate stress cracking. It is considered that the adhesives of these comparative examples do not have sufficient flexibility to reduce the shrinkage accumulated in the decorative paper when the decorative paper treated with melamine formaldehyde is bonded to the particle board. Was.

[0088]

[Table 39] Cross Hatch Cross Hatch Stress Adhesive (Before) (After) Crack Air Flex 400H P F

The vinyl acetate-ethylene copolymer functions to bond the melamine formaldehyde treated paper with the particle board in the adhesive. However,
The example in this application did not eliminate stress cracking. It is considered that the adhesive of this example does not have sufficient flexibility to reduce the contraction force accumulated in the decorative paper when the decorative paper treated with the melamine formaldehyde resin is bonded to the particle board. Was done. While the exemplary embodiments of the invention have been described in detail, various other modifications will be apparent to those skilled in the art and may be made without departing from the spirit and scope of the invention. Should be easy for a person skilled in the art. Therefore, the claims appended hereto are not limited to the examples and description set forth herein, but rather by the skilled artisan to which the present invention pertains. It should be understood that the present invention includes all patentable novel features that exist in this invention, including all features that would be treated as such.

────────────────────────────────────────────────── (5) References JP-A-59-142269 (JP, A) JP-A-56-81380 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09J 1/00-201/10 B32B 21/06 CA (STN) REGISTRY (STN)

Claims (11)

(57) [Claims] 1. A polyvinyl acetate polymer emulsion,
Mainly polyvinyl acetate for bonding melamine formaldehyde resin treated paper and particle board, characterized by containing tackifying polyvinyl alcohol, starch, tackifier and water-soluble or water-dispersible coupling agent. Adhesive as a component. 2. An adhesive comprising polyvinyl acetate as a main component for bonding paper treated with melamine formaldehyde resin and particle board, comprising a polyvinyl acetate polymer emulsion and 2-4 weight of the adhesive. % Tackified polyvinyl alcohol solids and 20-35 of the adhesive
Polyacetic acid comprising: by weight of starch solids, 5-10% by weight of the adhesive, a tackifier solid, and 1.5-3% by weight of the adhesive, a water-soluble or water-dispersible coupling agent. Vinyl adhesive. 3. The starch has a particle size of 5-25 μm and an average particle size of 15 μm.
The vinyl acetate adhesive according to claim 2, which is a corn starch having the following. 4. The vinyl acetate adhesive according to claim 2, wherein said tackifier is butylbenzyl phthalate. 5. The vinyl acetate adhesive according to claim 2, wherein said coupling agent is a silane, titanate or zircoaluminate coupling agent or a mixture thereof. 6. The vinyl acetate adhesive according to claim 2, wherein said coupling agent is a titanate or zircoaluminate coupling agent or a mixture thereof. 7. The vinyl acetate adhesive according to claim 2, wherein the coupling agent is dihydroxybis (ammonium lactate) titanium or a mixed titanium orthoester complex, or a mixture thereof. 8. The vinyl acetate adhesive according to claim 2, wherein the coupling agent is carboxy zirco aluminate or amino zirco aluminate or a mixture thereof. 9. The vinyl acetate adhesive according to claim 2, wherein the coupling agent is γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, an amino-modified organosilane ester or a mixture thereof. 10. The vinyl acetate adhesive according to claim 2, wherein said coupling agent is a mixed titanium orthoester complex. 11. An adhesive comprising polyvinyl acetate as a main component for bonding melamine formaldehyde resin-treated paper and particle board, comprising: a polyvinyl acetate polymer emulsion; and 2-4% by weight of the adhesive. % Of polyvinyl alcohol solid having tackiness and 20-3 of the adhesive.
5% by weight of a corn starch solid having a particle size of 5-25μ and an average particle size of 15μ, 5-10% by weight of the adhesive butylbenzyl phthalate tackifier solid, and 1.5-
The above polyvinyl acetate adhesive comprising 3% by weight of the mixed titanium orthoester complex.