TW200815556A - Adhesive system - Google Patents

Abstract

The invention relates to an adhesive system comprising a protein and one or more polymers containing acetoacetoxy groups. It also relates to a method of producing a laminated wood based product and a particle board.

Description

200815556 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to an adhesive system and a method of making a wood based product. [Prior Art]

Furfural-based resins such as phenol-furfural resins, melamine-formaldehyde resins, and urea-methyl resins have been widely used as binders in the manufacture of wood-based products. Embodiments of this wood-based product have composite products comprising several layers glued together, such as plywood (plyW〇〇d), laminated flooring products, veneered flooring, and use in, for example, home Other inlay products in the enamel. A further embodiment is a plate-like product such as a pellet board, a chipboard, and a fiberboard that pressurize the chips and/or fibers together with the binder to form a panel. After hardening the resin based on 曱骏, formaldehyde is released during the manufacture of the wood-based product and during the subsequent use of the product. Since a few years ago, formaldehyde, which was released into indoor air, has been a major concern for health reasons. There is an increasing demand for Yijiajun wood adhesives that provide sufficient bond strength and overall end product quality. The formaldehyde-free wood adhesive: suitable as a prior art adhesive for a resin based on Ajun. Product. Water repellency and bond strength are generally important qualities of anti-quality. In general, there are specific quality parameter criteria in order to meet the needs of wood-based products established for specific end products. For example, plywoods need to meet certain criteria in terms of, for example, internal bonding, thickness and water absorption; while composite flooring products require, for example, delaminating to meet certain criteria. The protein-based binder has been used in plywood • clothing for ten years ago but has been replaced by the excellent properties of formaldehyde-based resins. Recently, different types of protein-based adhesives have been suggested. WO 2005/1 13700 A1, Us 2〇〇4/(10)379〇6 and us 2〇〇4/〇〇89418 I disclose a soy protein-based adhesive composition. Further examples of protein-based binders disclose a soy-based binder t in Li et al. containing bismuth dichloro-2.propanol as a hardener (Wood and Fiber Science, 36 ( 2), 2004, pp. 186-194). US 2002/0005251 does not disclose a soy protein isolate-based adhesive. US 2 〇〇 5/〇 166 796 discloses a binder composition comprising soy protein isolate. U.S. Patent No. 6,790,271 and U.S. Patent Application Publication No. 2005/0234156, the entire disclosure of which is incorporated herein by reference. M〇ri et al., "Honeymoon Type Adhesives for 1 Wood Products...", Applied Polymer Science Journal (applied p〇lymer science), Vol. 91, 296, 2972 (2〇〇4) reveals a kind of wood Ethylene glycolated polyethylene glycol in the binder, but

It is not combined with any protein. US 4,350,788, US and US 2005/0197441 A1 disclose the use of an ethyl acetylated polyvinyl alcohol in a wood adhesive, but which does not combine with any protein 0 for providing high adhesion strength and high product quality. Protein-based wood adhesives are still in demand. 6 200815556 Accordingly, the present invention provides a protein-based adhesive composition that provides excellent bond strength and product quality (as for example, water repellency). As such, the present invention provides a method of making a wood based product. SUMMARY OF THE INVENTION The present invention provides an adhesive system comprising a protein and one or more polymers (P) comprising an ethyl ethoxylate. • "Adhesion system" as used herein means two or more combinations of components that form and act as wood adhesives. The name "adhesive" also includes the name "binder,,. This syllabus also relates to a method of making a wood-based product comprising providing an adhesive system comprising a protein, one or more polymers comprising an ethyl ethoxylate (P) to one or more pieces of wood On the basis of the materials, and combining the pieces of wood with one or more additional sheets of material, preferably on a wood basis. • The weight ratio of Shibaibei to one or more polymers (p) suitably ranges from about 1 · 2 to about 100 : i, preferably from about 丨: 丨 to about 丨 (8): 1, more preferably from about 1 · 1 To about 20: 1, the best from about 2: i to about 丨〇: i. In a specific embodiment, the adhesive system comprises an adhesive implant. σ The adhesive composition suitably comprises from about i to about 99 weight: preferably from about 3 to about 75% by weight, most preferably from about 5 to about 5. : Set %. The adhesive composition suitably comprises from about 1 to about % by weight of 7 200815556 one or more polymers (p), preferably from about to about 50 weights or even more preferably from about 5 to about 15 weights / Hey. Up to about 80% by weight, more preferably from 2 2 to about 25 % by weight, most preferably from the adhesive composition herein. Body 3! suitably from about 1 Torr to about 95 cc. 20 to about weight%. Preferably, the force 75 is from about 30 to about 50. In one embodiment, the adhesive system comprises - protein and one

A plurality of polymers (P) are used as individual components, and these individual components are preferably kept away until they are actually used in the gluing process. ^, the knife can also be mixed before the money is used in the gluing method - the short phase of the segment, thus the shape = the adhesive composition of the invention. "short time " suitably meant herein to mean about 1 hour, preferably less than about 30 minutes, and preferably less than about "in a particular embodiment of the method of the invention, The adhesive system is applied in a fixed set to one or more wood-based materials, one of which comprises protein and the additional component comprises one or more polymers (p). The protein-containing component may include a protein solution or dispersion, or a protein such as a dry material. This protein solution or dispersion is preferably aqueous. The component comprising one or more polymers (P) is suitably a solution or dispersion' preferably an aqueous solution or dispersion, or a solid material. As an individual component of the adhesive system, the polymer (P) is suitably present in the aqueous composition, the composition comprising from about 0.11 to about 99% by weight of the polymer (p), preferably from about 1 to about 80% by weight, more preferably from about 2 to about 5% by weight, even more preferably from about 2 to about 25% by weight, most preferably from about 3 to about 15% by weight. 200815556 When the adhesive system is provided as an individual component to one or more wood-based materials, it is preferred to successively apply the components of the adhesive system comprising the first coating component and the second coating component. . In a specific embodiment of the method of the present invention, the first coating component 匕S is a /liquid or dispersion or a protein of a dry material, and the second coating component comprises one or more polymers (P a solution or dispersion. In a specific embodiment of the method of the present invention, the first coating component | comprises a solution or dispersion of one or more polymers (P), and the second coating component is contained as a 'liquid or dispersion Or a protein that is a dry material. In a specific embodiment of the method of the present invention, the first coating component comprises one or more polymers (p) which are solid materials and the second coating component is a liquid/dispersion or Protein for drying materials. In a specific embodiment of the method of the present invention, a composite of a polymer (P) having a solid material/B and a protein as a dry material is applied. In a specific embodiment of the method of the present invention, the dispersion is opened, and the second coating component is dried after coating the second component. In this case, the first coating component is preferably a solution or dispersion of one or more polymers (P). Examples of δ-suitable proteins are natural proteins derived from, for example, milk (road protein), Dali, Ma Lingmo, :j: water - jade, wheat, rice, peas, etc.,

Give the protein of the shell) and the modified protein. Suitable soy protein I include soy protein concentrate, soy meai, Da Li water TL V -, large denier 7 knife protein. This protein is preferably soy protein isolate 9 200815556 (SPI). This protein is suitably used in the form of a protein such as a protein meal or as an exoprotein for use in the present. The protein content of the protein powder or protein isolate is suitably from about 3 Torr to about 100% by weight, preferably from about 5 () to about 1% by weight, most preferably from about 7 Torr to about 100%. weight%. The aqueous composition of the compound 12% protein has suitably a viscosity of from about 500 to about 5,000,000 mPa*s (Br〇〇kfieid, 12 rpm, spindle 4, at 20C), preferably from about! , 〇〇〇 to about 2, 〇〇〇, 〇〇〇,

More preferably from about 50, 〇〇〇 to about 15 〇〇 pa mpa*s, preferably from about (10), just to about 1,000,000 mpa*s. "Xuan or oxime extract (p) suitably has a weight average molecular weight of from about 丨, 〇〇〇 to about 5, 〇〇〇, 000 g / mol, preferably from about 1 〇, _ to about 200 〇, 〇〇〇克/莫耳. The acetamethyleneoxy group content in the one or more polymers (p) is suitably from about 〇.5 to about 50% by mole, preferably from about 丄 to about 〇% by mole, most preferably from From about 5 to about 20 mole percent. The one or more polymers (P) preferably comprise an ethyl acetylated polyethylene glycol (AAPVA). The adhesive system suitably further comprises one or more polymers (P1) comprising an amine or a guanamine group, preferably as individual components or as a mixture with a protein component. This guanamine group is preferably a pendant guanamine group. The name "amine group" includes a formamide group herein. The one or more polymers (P1) preferably comprise a primary amine group or a formamidine group. Preferably, the one or more polymers (P1) comprise polyvinylamine, polyvinylformamide, poly(vinyl alcohol-co-vinylamine), poly(vinyl alcohol-co-ethyl 200815556 alkenylcarboxamide ), polyallylamine, polyethyleneimine or polyamidamine. Most preferably, the one or more polymers (P1) comprise polyvinylamine or polyethyleneimine. The cerium or polymer (P1) suitably has a weight average molecular weight of from 1,000 to about 5,000,000 g/mole, preferably from about (10) to about 2,000,000 g/mole. As a separate component of the adhesive system, the polymer (p丨) is suitably present in an aqueous combination comprising from about 〇1 to about 99% by weight of the polymer (P1), preferably from about 1 Up to about 80% by weight, more preferably from about 2 to about 50 psi, even more preferably from about 2 to about 25% by weight, most preferably from about 3 to about! 5 wt%. The aqueous composition comprising one or more polymers (P1) may further comprise inorganic- or organic salts. A portion of the one or more polymers (ρι) may carry an ionic charge, preferably a cationic charge. The amount of the negative counterion of the salt in the aqueous composition suitably ranges from about 50 to about 50% by weight, preferably from about 约 to about 30 s s 。 。 from about 2 to about 2 〇 by weight. _ Each of these contains one or more components of the adhesion system of protein, polymer (P) and selective polymer (P1), or a combination of binders comprising protein and polymer and selective polymer (P1) The additive may further comprise an additive and a filler such as mulberry. In a specific embodiment of the method, the adhesive composition is dried after application of the adhesive composition, and thereafter by the addition of water or a water-containing composition comprising one or more poly(P) or comprises a Or an aqueous composition of a plurality of polymers (p1) to be activated. In a specific embodiment, the adhesive system comprises a protein, a 11 200815556 or a plurality of polymers (P) and/or a plurality of polymers (P1) as individual components, which are kept separate until they are actually used in the gluing method. in. The adhesive system can also be mixed for a short period of time prior to actual use in the gluing process, thus forming the adhesive composition of the present invention. "Short time" as used herein suitably means less than about 1 hour', preferably less than about 3 minutes, and most preferably less than about 15 minutes.

A specific embodiment of the method of the present invention, which applies the adhesive system to one or more wood-based materials with individual components, wherein the components comprise proteins, further components comprise - or Polymer (8): The further component comprises one or more polymers (P1). Protein-containing components: including protein solutions or dispersions, including eggs such as dry materials. The component comprising - or a plurality of polymers (P) is suitably a solution or dispersion. & The component comprising - or a plurality of polymers (P1) is suitably a solution or dispersion. / In a specific embodiment of the method, 'the first coating component comprises a solution or dispersion of a white shell and or a polymer (p), and it comprises - or a plurality of polymers (P1) The solution or dispersion of the solution is dried. And in the specific embodiment of the method, the first coating component comprises a solution or dispersion of protein and/or a plurality of polymers (P1), and the cloth comprises - or a plurality of polymers ( a solution or dispersion of p), the first coating component comprising one and coating a solution or dispersion comprising a protein in a specific embodiment of the method or a plurality of polymers (P), 12 200815556 The two-component precursor and/or the liquid I or the dispersion of the plurality of polymers (P1) are dried. In a specific embodiment of the method, the first coating component comprises a solution or dispersion of one or more polymers (P1), and the coating of the coating white matter and/or the plurality of polymers (P) Or second of the dispersion

It is dried. J protein and/or multiple polymers (p) and optionally one or more polymerizations

The amount of the substance (P1) in the binder composition suitably constitutes at least 75 weights: / has a molecular weight equal to or greater than the fraction of the touch/mol, and is also suitably = from about 75 to @ wo wt%. It is at least 85% by weight 'more preferably from about ... just % by weight' optimally at least 95% by weight, and most preferably from about 95 to about 1 weight 〇/〇. The present invention is directed to the use of an adhesive system according to the present invention to bond wood-based pieces of material to form a wood-based product. In a particular embodiment of the invention, the wood based material: the sheet is a sheet or sheet. In this example, the wood based product is suitably a composite flooring material, a veneered floor, an inlaid furniture material, a glued backboard, a roofing sheet or a laminated beam. In a specific embodiment of the invention, the wood-based material sheet is wood chips or wood chips, such as chips, shavings, flakes, sawn chips, and the like, which are finely divided by U wood. . In this case, the wood based product is suitably chipboard, plywood or fiberboard, or oriented strand b〇ard. The moisture content of the wood granules to be used in the present invention is suitably from about 13 200815556 〇 to about 20% by weight, and the car is about 5% to about 5% by weight. …1…. The center of gravity 'better from about!.5 The weight ratio of the wood pellet to the adhesive system has been suitably from about 1 〇〇:1 to about 1:1, preferably from about 5 〇:1 to about 2 1/2.仏攸 about 3〇·1 to about 2'5: 1, best from about 15:1 to about 3: i. The method according to the invention suitably comprises contacting one or more pieces of the base material with the adhesive system according to the invention, pressurizing and thus 2 wood-based material sheets and further wood-based materials = ^ this plus The pressure is suitably carried out at a high temperature. This wood-based material; any type and form of U-based material, such as fibers, slabs, thin layers, reclinings, fragments, and the like. This method suitably comprises the application of the adhesive composition according to the invention to a wood based material: the butt joint is pressurized. The pressurization temperature is based on the wood-based product that is intended to be manufactured: it is not fixed. However, suitably from about 5 Torr to about fiber and preferably from about 7 Torr to a force of 200 C. For plywood, chipboard and fiberboard products, the pressurization temperature is preferably from about just 225 to about 225. Hey, the best is from about i5G to about 2 generations. For knower layer products such as plywood, laminate flooring or veneer flooring products, the pressurization temperature is preferably from about 7 Torr to about 17 passages, preferably from about % to about 5%. Adding time and adding temperature are related, so it often takes longer to add time. The wood-based production to be manufactured also determines the appropriate temperature and time. Suitably, the dusting time is at least about 10 seconds, suitably from about 1 " less to about 60 minutes, preferably at least about 30 seconds, and more preferably from about % seconds to about % is at least ... minutes, Good from W to about 15 minutes. 14 200815556 In a specific implementation of the method, the method suitably comprises applying a binder composition according to the present invention to a surface to make a binder. The joint will contain u 3 nucleus ΐ ΐ to an original coating amount of about 500 g/sq. Depending on the amount of coating

Depending on the product of Ik: from about 50 to about 200 杳/巫+ for compression molded finishes, from about 160 == ruler for materials, and square meters for laminate flooring. The appropriate upper limit depends on the type of wood-based material (4) depending on the solution.

The binder composition can be applied to one or both surfaces to be bonded. The sum of the amounts applied to the surface of each side when flooding the surface of the two sides will be in accordance with the preferred amount of the joint of all the adhesives specified. In another embodiment of the method, when manufacturing the laminated product, the method suitably comprises applying the adhesive system according to the present invention to the surface as a separate component of the protein and/or the plurality of polymers (P) on. Both the protein and the polymer (P) are suitably coated with an aqueous composition. In addition, protein two and one or more polymers (P) can be applied to individual surfaces intended to be combined. The total amount of the adhesive system applied to one or both surfaces is the original coating amount of the adhesive joint 2 to about York/m2. The amount of coating depends on the product to be manufactured: from about 5 〇 to York/m2 for compression molded finishes and from about 1 约克 to York/m2 for composite flooring. good. The appropriate upper limit also depends on the type of wood-based material to be coated with this solution. In another embodiment of the method, when manufacturing a plywood, chipboard or fiberboard and similar products, the method suitably comprises the adhesion system according to the invention as a protein and one or more polymers (p) Individual groups 15 200815556 were applied to the wood chips in the form. When coated separately, the protein may be applied in dry form or in the presence of the aqueous composition in the manufacture of plywood, chipboard or fiberboard and similar products. It is preferred that the protein is coated in a dry form. The one or more polymers (P) may be coated either as a solid or as an aqueous composition. One or more polymers (p) are first added to the chips followed by the addition of the protein. In a specific embodiment, in the manufacture of plywood, chipboard or fiberboard and similar products, one or more polymers (P) are coated with an aqueous composition followed by the addition of protein in a dry form. In a particular embodiment, in the manufacture of plywood, chipboard or fiberboard and similar products, one or more polymers (p) are coated as a solid simultaneously and in dry form. The invention also relates to a wood based product obtainable by the process of making a wood based product therefrom. Things such as plywood, laminate flooring or veneer flooring products.摅太太路日日&制祝,_心,.

This wood based product is suitably a plywood, chipboard or fiberboard product. In addition, this wood-based product is suitably a laminate 16 200815556 Occurrence and percentage Other percentages are described. Parts by weight and weight [Embodiment] EXAMPLES Example 1 : The article product straw was prepared by coating different compositions onto a plywood plate of 1 5 X 1 5 8 and then drying 5 。. Then, re-run

The adhesive layer' then inlaid a layer of -0.6 mm beech onto the board. Press this combination for a few minutes at 130 °C. Test the fiber to tear the tear) (chisel). The compositions tested were: 1) 14 grams of soy protein isolate (SPI) (SUpro® 500E from Solae), 100 ml of water. 2) 8 g of soy protein isolate (SPI) (Supro® 500E from Solay), 50 g of acetaminolated polyvinyl alcohol solution (AAPVA) (Gohsefimer® Z-220 from sputum synthesis) Chemical (Nippon Gohsei)) (5 wt%). 3) 8 grams of soy protein isolate (SPI) (Supro®500E from Solay), 50 grams of ethyl acetylated polyvinyl alcohol solution (AAPVA) (Gohsefimer® Z-220, from Japanese synthetic chemistry ) (10% by weight). 17 200815556 Table i First coating component First coating amount Rewetting fiber tearing (%) Hot cold SPI 2.7 g 1 g water 20-30 〜5 SP1 2·7 g 1 g AAPVA (12 wt%) 50-60 50-60 SPI+AAPVA (5 wt%) 3.7 g 1.4 g water ~90 〜30 SPI+AAPVA (10 wt%) 3.7 g 1.4 g water 100 100 SPI+AAPVA (10 wt%) 3.7 g U g Polyvinylamine (11% by weight) 100 100 Example 2: Plywood by mixing 864 grams of wood chips with a moisture content of 2% by weight with 205 grams of about 11% by weight of acetylated polyvinyl alcohol (AAPVA) An aqueous solution (Gohsefimer® Z-220 from Synthetic Chemistry Japan) was then prepared by mixing in about 85 grams of soy protein isolate (SPI) (Prisolate® 601 EM from Food Partner). SPI has a protein content > 90% by weight and a dry content of 94% by weight. The chip mixture was formed into a 30 x 30 cm sheet and pressed at 185 ° C for three minutes and pressed into a 16 mm thick plate. The pressurization procedure is 30 seconds during 160 kg/cm 2 , 2.5 minutes during 40 kg/cm 2 and no pressure during the last 30 seconds. Tensile strength (internal bond, IB), expanded thickness (TSW), and water absorption (ABS) were measured. Further plywood was produced in the same manner as before by mixing 994 g of wood chips having a moisture content of 2% by weight with about 85 g of soy protein isolate (Supro® 500E from Solay). SPI has a protein content > 90% by weight and a dry content of 94% by weight. Measuring tensile strength (internal bonding, 200815556

$Not measured Example 3:

Table 2 Wood chips (g) Protein protein (g) AAPVA (11%) (g) Moisture content before pressurization (%) IB (kPa) TSW 24 hours (%) ABS 24 hours (%) 864 SPI 85.3 205 14.6 490 30.2 93.7 994 SPI 79.6 7.8 10 Plywood on a smaller scale by mixing 50.7 g of wood chips with 2% by weight moisture content and 1 g of polyvinyl alcohol (AAPVA) (Gohsenmer®) Z-220, from Sakamoto Synthetic Chemistry, presented as an aqueous solution of about 16.5% by weight, was then prepared by mixing in different amounts of soy protein isolate (SPI) (Supi: o® 500E from Solay). SPI has a protein content > 90% by weight and a dry content of 94% by weight. Reference sets without SPI and reference groups without AAPV A were also prepared. The debris mixture was pressed into a 10 mm thick plate. The press was carried out at 9 kg/cm 2 for 5 minutes at 1 80 - 1 85 °C. The internal bond strength (IB) was measured by gluing a 5 x 5 cm piece onto two metal anvil plates and tearing them apart. Table 3 Protein (SPI) Amount (g) AAPVA Amount (g) (kPa) • 1 127 0.2 1 222 0.5 1 359 2 1 480 5 1 322 5 - 176 19 200815556

[Simple diagram description] None [Main component symbol description] None 20

Claims (1)

200815556 X. Patent application scope: 1. An adhesive system comprising a protein and a polymer (p) of an oxiraneoxy group. Or a plurality of adhesive systems including B2: Please patent the scope of the item, wherein the weight ratio of the protein fish or the polymer (p) is from about 1: 2 to about 1 : i, as claimed in the patent range 帛 1 -2 The adhesion system of any of the items in the J-page, the weight ratio of the complex protein to the one or more polymers (p) is from about ^ · /, 20 : 1 . · 1 to about 4. A binder composition is included as described in the patent application. The adhesive system of any of items 1-3, wherein the adhesive agent composition of the adhesive system of claim 4 contains from about 5 to about 30% by weight of protein &amp; The adhesive system of any of item 5, wherein the binder composition comprises from about 3 to about 15% by weight of one or more compounds (P). people The adhesive system according to any one of claims 1-3, which comprises a protein and one or more polymers (P) as individual components. The adhesive system according to any one of claims 1 to 7, wherein the one or more polymers (P) comprise an ethylene glycol-based polyethylene glycol. The adhesive system according to any one of claims 1 to 8, which comprises one or more polymers (P1) comprising an amine group or a guanamine group. The adhesive system according to any one of claims 1 to 9, wherein the one or more polymers (P1) comprise polyvinylamine. 11. A method of making a wood-based product, comprising providing 21 200815556 an adhesive system to one or more pieces or a plurality of further materials, such as the scope of claim 1 to 10 of the item On the basis of the material and the combination of the sheet and the piece. Μ 12. For example, the method of applying for the patent festival 围 围 , , , , , , , , , , , , , , , , , , , , , 该 该 该 该 该 该 该 该13. The method of claim 12, wherein the binder composition is dried after coating and then added by water or comprises one or more The aqueous biochemical composition of the mash (Ρ) or an aqueous composition comprising one or more polymers comprising an amine group or a guanamine group (Ρ1) is activated. 14. The method of claim 5, wherein the adhesive system provides individual components to a wood-based material sheet i, one of the components comprising the protein and the other component comprising the one or more polymers (p) . The method of claim 14, wherein the first coating knife 匕S A white shell/trough solution or dispersion and the second coating component comprise a solution or dispersion of one or more polymers (P). 16. The method of claim 14, wherein the first coating component comprises a solution or dispersion of one or more polymers (P) and the second component comprises, as a solution or dispersion, or as The protein of the dry material. 17. The method of any one of claims 15-16, wherein the &quot;Xuandi coating component is dried after coating and prior to coating the second component. The method of any one of claims 11 or 14-17, wherein the lacing system comprises one or more polymers (P1) comprising an amine group or a guanamine group as individual components. The method of claim 13 or claim 8, wherein the one or more polymers (Ρ1) comprise polyvinylamine. The method of any one of the preceding claims, wherein the sheet is one or more of a sheet, a sheet, and a veneer. 21. The method of claim 20, wherein the wood-based product is a composite flooring material, an inlaid floor, an iron furniture material, a plywood, a siding, a roofing panel or a laminated beam. The method of claim </ RTI> wherein the sheet is wood chips or wood granules. - 23. The method of claim 22, wherein the wood-based product is chipboard, plywood or fiberboard or oriented flowerboard. A wood-based product obtainable by the method of any one of claims 11-22. 25. Use of an adhesive system as claimed in any of the claims </ RTI> to produce a wood based product from a wood based material U. Η^一,图: No 23