WO1998008675A1 - Materiaux composites prepares avec des colles en emulsion pretes a l'emploi a base de resine et de cire - Google Patents

Materiaux composites prepares avec des colles en emulsion pretes a l'emploi a base de resine et de cire Download PDF

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Publication number
WO1998008675A1
WO1998008675A1 PCT/US1996/014130 US9614130W WO9808675A1 WO 1998008675 A1 WO1998008675 A1 WO 1998008675A1 US 9614130 W US9614130 W US 9614130W WO 9808675 A1 WO9808675 A1 WO 9808675A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
wax emulsion
wax
composite
furnish
Prior art date
Application number
PCT/US1996/014130
Other languages
English (en)
Inventor
Roger Scott Johnson
Brian M. Peek
Barry W. Sewell
Daniel Di Carlo
Original Assignee
Georgia-Pacific Resins, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Georgia-Pacific Resins, Inc. filed Critical Georgia-Pacific Resins, Inc.
Priority to US08/793,731 priority Critical patent/US6132885A/en
Priority to PCT/US1996/014130 priority patent/WO1998008675A1/fr
Priority to CA002199463A priority patent/CA2199463C/fr
Priority claimed from CA002199463A external-priority patent/CA2199463C/fr
Publication of WO1998008675A1 publication Critical patent/WO1998008675A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2317/00—Animal or vegetable based
    • B32B2317/16—Wood, e.g. woodboard, fibreboard, woodchips
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials

Definitions

  • the invention is directed to a single package, ready-to-use (RTU) adhesive combining a thermosetting resin and a wax emulsion sizing agent, a process for preparing the adhesive composition and the use of the adhesive in making bonded composites such as wood products, including, parallel strand lumber, oriented strand board (OSB), wafer board and particle board, and textile products, including ceiling tiles.
  • RTU ready-to-use
  • adhesives for composites such as particle boards, fiber boards, and textile composites.
  • these adhesives are made from urea resins, urea-melamine resins, phenolic resins, and the like.
  • urea resins urea-melamine resins
  • phenolic resins phenolic resins
  • Wax solids may not remain homogeneously suspended in mixtures with water-borne resins, particularly during transport, transfer, and use.
  • the resin-wax blend needs to be used immediately or else separation occurs resulting in non-uniformity in the water-repellency and bond quality imparted to the composite by the adhesive. Further, since wood shrinks and swells as its moisture content varies, if the composite is not properly treated with a sizing agent and resin, the composite will have less integrity or debond on exposure to moisture.
  • U.S. Patent 4,407,999 attempts to provide a single component, ready-to-use (RTU), water repellant adhesive composition for wooden material, purportedly having good blendability and storage stability.
  • the adhesive consists essentially of a paraffin emulsion containing oxidized paraffin and a resin such as a phenolic resole resin.
  • This patent suggests that by using an oxidized paraffin having an acid value of from 10 to 70 and a melting point of from 30 to 90°C, with the conventional paraffin wax component, one can successfully prepare a pre-blended adhesive from the resin and wax emulsion. Too low an acid value makes emulsification of the wax difficult; too high a value reduces the water resistance of the composite.
  • the wax emulsion is prepared in the presence of a surfactant and/or a water-soluble alkali metal compound such as sodium hydroxide. Blending of wax emulsion and resin is carried out from ambient temperature to 60 °C.
  • adjusting the pH of the wax emulsion to closely match that of the resin and heating the resin prior to addition of the wax emulsion greatly improved resin/wax compatibility and handling.
  • the resultant resin/wax adhesive blend provided composites having unexpectedly improved thickness swell and water absorption properties over composites made with prior art technology, i.e. resin-wax blends not treated with the combination of pH adjustment and heating.
  • the adhesive also provided good storage life and low odor.
  • the resin/wax emulsion adhesive of the present invention eliminates the need to handle multiple raw materials at the site of use.
  • the present invention is directed to a composite prepared by combining a furnish and a ready- to-use, single package, adhesive composition.
  • the adhesive composition comprises a combination of a thermosetting resin and a wax emulsion prepared by:
  • thermosetting resin (a) heating the thermosetting resin to an initial temperature of above 40 °C, wherein the resin has a pH of about 9 to 12;
  • Figures 1, 2, and 3 depict data from a strand board study using the RTU resin/wax system of the present invention.
  • Figure 2 shows % Thickness Swell performance.
  • Figure 3 shows % Water Absorption performance.
  • Figures 4, 5, and 6 depict data from a strand board study using two different wax emulsions in the RTU resin/wax system using a 25° C or a 75° C resin-wax blending temperature.
  • Figure 5 shows % Thickness Swell performance.
  • FIG. 6 shows % Water Absorption performance.
  • the present invention combines a resin and a wax emulsion sizing agent into a single- component or ready-to-use (RTU) adhesive.
  • the RTU adhesive is then provided to the consumer in a single package.
  • the wax emulsion sizing agent (hereinafter “wax emulsion”) is used principally to impart water-resistance to the final composite construction.
  • the RTU adhesive has increased wax compatibility, substantially no foaming problems, and provides unexpected performance improvements in thickness swell and water absorption properties of the final product without degradation of other properties.
  • the resin may be any thermosetting (formaldehyde-based) resin used in preparing adhesives for bonding composite wood products such as phenol-formaldehyde resins, phenol-resorcinol- formaldehyde resins, urea-melamine-formaldehyde resins, melamine-formaldehyde resins, phenol- melamine-formaldehyde resins, melamine-urea-resorcinol-formaldehyde resins, and combinations thereof.
  • the resin is a phenol-formaldehyde resole resin (phenolic resin).
  • the resins may be prepared by any suitable method to provide an adhesive resin having a final pH of between about 9 and 12 and a sufficiently high formaldehyde mole ratio to make the resin thermosetting.
  • a phenolic resole resin is prepared to provide a formaldehyde to phenol mole ratio of about 1 : 1 to 3 : 1, preferably, about 1.8:1 to 2.7: 1.
  • the present invention is not limited to any particular process of preparing the resin and methods are well known to those skilled in the art.
  • reactants used to prepare the resin are commercially available in many forms. Any form which can react with the other reactants and which does not introduce extraneous moieties deleterious to the desired reaction and reaction product can also be used in the preparation of the resins used in the adhesives of the present invention.
  • Formaldehyde for instance, is available in many forms. Paraform (solid, polymerized formaldehyde) and formalin solutions (aqueous solutions of formaldehyde, sometimes with methanol, in 37 percent, 44 percent, or 50 percent formaldehyde concentrations) are common. Instead of formaldehyde, other aldehydes may be used such as acetaldehyde, and propionaldehyde. Typically, formalin solutions are preferred as the aldehyde source.
  • the phenol component of the resin includes any phenol typically used in preparing phenolic resole resins. Typically, ordinary phenol is used, but the phenol may be partly or completely substituted with xylenols, cresols, catechol, resorcinol, alkyl resorcinols, other naturally occurring or synthetic phenols or alkyl phenols such as cresylic acids, urea, melamine, or combinations thereof.
  • Urea is available in many forms. Solid urea, such as prill, and urea solutions, typically aqueous solutions, are common. Urea is also available in combination with formaldehyde as a UF concentrate.
  • Melamine is also commercially available and the melamine may be totally or partially replaced with other aminotriazine compounds.
  • Other suitable aminotriazine compounds include substituted melamines, or cycloaliphatic guanamines, or mixtures thereof.
  • thermosetting resin Any suitable catalyst may be used to form the thermosetting resin.
  • Phenolic resins typically use alkali metal hydroxides, alkaline earth hydroxides, ammonium hydroxide, metal carbonates, and amines.
  • the catalyst for preparing a phenolic resin is sodium hydroxide.
  • the wax emulsion may be formed from natural waxes such as slack wax, whale wax, pappy wax, honey wax, and Chinese wax, or from synthetic waxes such as esters of fatty acids, for example, n-octadecyl palmitate and cetyl stearate.
  • Slack wax a solid at ambient temperatures, is a by-product of oil refining processes, is sold as a commodity product, and is a preferred wax for reasons of economy and its high melting temperature.
  • the present invention is not limited to any particular wax so long as the wax provides the desired sizing or water-repellant properties in the end product.
  • the wax emulsion is a wax-in-water emulsion and is typically formed by, for example, stirring molten wax into water in the presence of a dispersant, emulsifier or surfactant.
  • a dispersant emulsifier or surfactant.
  • Most commercial wax emulsions may be used.
  • no additional surfactants, other than what was needed to produce a stable wax emulsion, are added to the combined resin and emulsion.
  • Some surfactants can lead to foaming problems resulting in poor handling problems.
  • any dispersant, emulsifier, or surfactant used in the emulsion must not affect the final resin/wax emulsion adhesive qualities.
  • lignosulfonate-based dispersants provide suitable wax-in-water emulsions whereas our experience indicates that fatty-acid based dispersants are less desired.
  • a sufficient amount of the wax emulsion is blended with the resin to impart the desired level of water-resistant properties to the final composite.
  • the amount will not exceed 50 wt% of the total adhesive used.
  • the preferred amount will depend on the composites intended use and target properties.
  • the wax emulsion will be used in an amount between about 4 wt% and 33 wt% based on solids of the resin/wax emulsion adhesive.
  • the pH of the wax emulsion Prior to addition of the aqueous wax emulsion to the aqueous resin, the pH of the wax emulsion is adjusted to closely match the pH of the resin. Alternatively, the pH of the resin may be adjusted to closely match that of the wax emulsion. Either way, the pH of the resin and the wax emulsion need not be identical but should be within about 1 pH unit. For example, if the pH of the resin is 10, the pH of the wax should be adjusted to between about 9 and 11 prior to mixing with the resin.
  • the pH of a phenolic resole resin prior to combining with the wax emulsion is preferably about 9 to 12, more preferably about 11.5.
  • the pH of the wax emulsion is adjusted by adding an effective amount of a suitable alkaline material or base.
  • the base must be selected so it does not, for example, negate the dispersing effect of the wax solids in the emulsion or destabilize the resin or the emulsion.
  • Suitable bases include, but are not limited to sodium hydroxide (caustic), amines, ammonium hydroxide, and carbonates. Any effect the base may have on the resin or emulsion depends on the particular resin and wax being used.
  • the resin prior to combining the resin with the wax emulsion, the resin is heated to an initial temperature above about 40°C, preferably, about 60 to 85 °C, more preferably , about 60 to 75 °C.
  • the temperature of the resin depends on the particular wax and its softening and melting properties, and also the compatibility of the wax and the resin. Adding the wax emulsion at higher temperatures generally increases the compatibility of the phenolic resole resin and wax emulsion and apparent water-soak properties of composites made using the blend.
  • the wax emulsion is combined with the resin with mixing while the resin is still hot.
  • the temperature of the combined resin and wax emulsion is preferably maintained within 5°C of the initial temperature during addition of the wax emulsion.
  • the resin and wax emulsion combination of the present invention can be used to improve the water abso ⁇ tion properties of any composite product that is prepared using a furnish, a sizing agent and a thermosetting resin.
  • the furnish may be wood, textile, or wood/textile combinations.
  • Wood furnish include fibers, particles, scrim, flakes, veneer, and the like, and combinations thereof.
  • Textile furnish include fibers of polyester, nylon, and the like. Examples of composites include, but are not limited to, oriented strand board (OSB), wafer board, particle board, hardboard, medium density fiberboard (MDF), SCRTMBER®, laminated veneer lumber (LVL), plywood, oriented strand lumber, parallel strand lumber, and textile fiber mats (e.g. for ceiling tiles and sound insulation.)
  • OSB oriented strand board
  • MDF medium density fiberboard
  • SCRTMBER® laminated veneer lumber
  • plywood oriented strand lumber
  • parallel strand lumber parallel strand lumber
  • textile fiber mats e.g. for ceiling
  • the resin and wax combination may be applied to the furnish in any suitable manner, for example, as atomized drops using a sprayer or spinning disk or by a roll coater.
  • the resinated furnish may then be formed into a mat and placed into a hot press at 350 to 450 °F for consolidation into a unitary composite.
  • a hot press at 350 to 450 °F for consolidation into a unitary composite.
  • other types of pressing equipment or heating equipment such as radio-frequency devices and steam injection presses can be used.
  • Appropriate pressure is applied to the mat to compress to the desired final thickness for a time sufficient to allow the resin to cure and bond the furnish or consolidate the composite. Examples
  • a ready-to-use adhesive can be prepared by the following procedure.
  • the mole ratios, temperatures, etc. may be modified as necessary to obtain appropriate product performance requirements.
  • a phenolic resin is prepared using known procedures from the following ingredients (parts by weight):
  • the temperature of the resin is adjusted to 60°C.
  • the pH of a wax emulsion is adjusted to within 1 pH unit of the pH of the phenolic resin, for instance with caustic, and then 8 parts by weight of the pH adjusted wax emulsion is added to 92 parts by weight of the resin and mixed.
  • the temperature of the resin is maintained at a temperature of at least 60 °C during the mixing and then the mixture is cooled.
  • Adhesive system C was prepared by conventionally cold blending a wax emulsion with a PF resin made in accordance with the process of Example 1 (excluding pH adjustment of the wax emulsion and the hot blending of the resin and wax).
  • Adhesives A and B were prepared in accordance with the process of Example 1 including pH adjustment of the wax emulsion and the hot blending of the resin and wax emulsion.
  • Emulsion A used wax emulsion BW-048 obtained from Dominion Chemical Company.
  • Emulsions B and C used wax emulsion 2057B obtained from HTI (Hopton Technologies, Inc.) Panels were manufactured using the below-listed parameters:
  • Figures 1, 2, and 3 depict the average of the samples and the 95% confidence interval of the average for the samples from strand board studies using the RTU resin/wax system.
  • Figure 1 shows that Internal Bond strength was not significantly affected by the hot blend procedure of the present invention.
  • Figure 2 shows that the % Thickness Swell performance improved using the RTU adhesive of the present invention.
  • Figure 3 shows that the % Water Abso ⁇ tion performance improved using the RTU adhesive of the present invention.
  • the resin was prepared in accordance with Example 1 and the wax emulsion was added at either cold (25 °C) or hot (75 °C) temperatures.
  • Panels were prepared and used in accordance with Example 2.
  • the wax emulsions used were Dominion Chemical Company's BW-048 and Polypro's Prowax 45. Both of the wax emulsions performed equivalently in this study and the data were combined for presentation in Figures 4, 5, and 6.
  • Figure 4 shows that wax addition temperature has no significant effect on Internal Bond. That is the RTU adhesive of the present invention performed as well as or better than traditionally prepared cold blended resin and wax emulsion.
  • Figure 5 shows that the addition of the wax emulsion at an elevated temperature provided improved % Thickness Swell performance in the composites.
  • Figure 6 shows that the addition of the wax emulsion at an elevated temperature provided improved % Water Abso ⁇ tion performance in the composites.
  • a phenol-formaldehyde resin having a mole ratio of about 2.0 was combined with a wax emulsion in the following four ways:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)

Abstract

L'invention porte sur un conditionnement unique d'une colle en émulsion prête à l'emploi à base de résine et la cire, et sur son procédé de préparation qui consiste à chauffer une résine thermodurcissable et à ajuster le pH de l'émulsion de cire avant de combiner l'émulsion de résine et de cire. L'invention porte également sur l'utilisation de la colle dans la fabrication de matériaux composites liés tels que des produits du bois: panneaux à copeaux orientés (panneaux OSB), panneaux de copeaux longs, panneaux de copeaux agglomérés et matériaux composites à panneaux de particules.
PCT/US1996/014130 1996-08-30 1996-08-30 Materiaux composites prepares avec des colles en emulsion pretes a l'emploi a base de resine et de cire WO1998008675A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US08/793,731 US6132885A (en) 1996-08-30 1996-08-30 Composites prepared with ready-to-use resin/wax emulsion adhesives
PCT/US1996/014130 WO1998008675A1 (fr) 1996-08-30 1996-08-30 Materiaux composites prepares avec des colles en emulsion pretes a l'emploi a base de resine et de cire
CA002199463A CA2199463C (fr) 1996-08-30 1996-08-30 Composites prepares avec des adhesifs a base de resine et d'emulsion de cire prets a l'emploi

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/US1996/014130 WO1998008675A1 (fr) 1996-08-30 1996-08-30 Materiaux composites prepares avec des colles en emulsion pretes a l'emploi a base de resine et de cire
CA002199463A CA2199463C (fr) 1996-08-30 1996-08-30 Composites prepares avec des adhesifs a base de resine et d'emulsion de cire prets a l'emploi

Publications (1)

Publication Number Publication Date
WO1998008675A1 true WO1998008675A1 (fr) 1998-03-05

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6846556B2 (en) 1995-09-15 2005-01-25 Saint-Gobain Glass France Substrate with a photocatalytic coating

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4361612A (en) * 1981-07-14 1982-11-30 International Paper Co. Medium density mixed hardwood flake lamina
US4407999A (en) * 1980-02-25 1983-10-04 Mitsubishi Chemical Industries Ltd. Water repellent adhesive composition for wooden material
US4758478A (en) * 1986-09-30 1988-07-19 Daisy Nick K Fast curing phenolic resins and bonding methods employing same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4407999A (en) * 1980-02-25 1983-10-04 Mitsubishi Chemical Industries Ltd. Water repellent adhesive composition for wooden material
US4361612A (en) * 1981-07-14 1982-11-30 International Paper Co. Medium density mixed hardwood flake lamina
US4758478A (en) * 1986-09-30 1988-07-19 Daisy Nick K Fast curing phenolic resins and bonding methods employing same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6846556B2 (en) 1995-09-15 2005-01-25 Saint-Gobain Glass France Substrate with a photocatalytic coating

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