TW200900477A - Method of producing a wood based product - Google Patents

Abstract

The present invention relates to a method of producing a wood based product comprising applying a water-based adhesive composition comprising non-gelatinised starch, the composition further comprises from about 0. 1 to about 50 weight % of one or more polymers (P) containing an amine group or an amide group, onto one or more pieces of a wood-based material and joining the one or more pieces with one or more further pieces of a wood based material.

Description

200900477 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method of manufacturing a wood-based product. [Prior Art] Formaldehyde-based resins such as phenol·formaldehyde resins, melamine-formaldehyde resins, and urea-formaldehyde resins are widely used as binders in the manufacture of wood-based products. Examples of such wood-based products include composite products in which multiple layers are glued together, such as plywood, laminate flooring products, and gluing products for use in, for example, furniture. Other examples are sheet products such as pellet board, chipboard and fiberboard, in which the chips and/or fibers and the binder are pressed into a sheet. After the formaldehyde-based resin is cured, the formaldehyde is released during the manufacture of the wood-based product during and after the product is used. Over the years, due to health factors, the spread of formaldehyde into indoor air has received attention. There is a growing demand for formaldehyde-free wood adhesives that provide adequate bond strength and overall end product quality, making them suitable as alternatives to prior art formaldehyde-based resin adhesives. Water resistance and bond strength are often important properties that reflect the quality of wood-based products. There are specific quality parameters required to meet the criteria established for a particular end product. For example, granular panels must meet certain criteria, such as internal bonding, thickness swell, and water absorption. Laminated 2-sheet products must meet certain criteria, such as delamination and fiber tear. As an alternative, a formaldehyde-based tree can be used as a base material for a polymer dispersion such as a polyvinyl acetate adhesive. However, when the extruded product is obtained by gluing the thin plate and pressing the structure into a certain shape, it is important to minimize the so-called, spring back of the gluing structure when it is released from the mold. ),,. The rebound results of adhesives based on polyvinyl acetate vinegar are generally poor. It is also important that the extruded molded product substantially maintains its shape during use, i.e., when a load is applied. This property can be measured by a fatigue test as described in a household product, in which an extrusion molded product is subjected to multiple load cycles. It has been proposed to use a starch-based adhesive as a wood adhesive. A substitute for a resin based on A. ham et al. "Wood Adhesives derived from the poly (vinyl alcohol) of the father's joint and partially gelatinized starch: clothing and I. From Crosslinked Poly(vinyi alcohol) and Partially Gelatinized Starch : Preparation and

A mouth-to-mouth starch-based adhesive.

Accordingly, the present invention provides a method of providing a wood-based material for use as a substrate and providing an excellent combination: a combination method, and a composition of the composition. Quality Sticky 200900477 SUMMARY OF THE INVENTION The present invention provides a method of making a wood-based product comprising applying a water-based adhesive composition comprising ungelatinized starch, the composition further comprising, about (M i about 5G% by weight of _ or a plurality of amine or amgan group-containing polymers (P), which are applied to one or more wood-based village materials and make this - or multiple pieces with - or more Other wood-based materials are combined. As used herein, ungelatinized; temple powder means that the temperature at the aqueous temperature is below 5 〇t, suitably below about 45 Torr and thus is not deuterated. Preferably, it is less than about 4 〇r ' The weight ratio of the powder of the temple to the polymer (p) in the adhesive composition used in the method is suitably from about 1:2 to about 25: preferably about 1. Preferably, the adhesive composition used in the method suitably comprises from about 〇 〇 to about 重量 % %, preferably from about 15 to about 4 4 % by weight. More preferably from about 25 to about 35% by weight... about the dot composition used in this method suitably comprises about one or more reset % of one or more The polymer (P) is preferably from about 1.5 to about 0 / most preferably from about 2 to about 15 % by weight based on 7 parts. 5 虞 虞 / 勒 丨丨 丨丨 amp amp amp amp 此 此 此 此 此 此 此 此Solid content

20 to about 70% by weight, more preferably from about 35 to about 60% by weight of the εW field, to about 50% ❶/〇. Take a good 4 υ here, the so-called "cake + Β adhesive composition in this method, 圊 / / V amount"

Refers to the non-aqueous part of the adhesive composition. Yi solid containing I 200900477

Chitin-acid modified starch, oxidized starch, hydroxypropylated starch, cationic starch, amylopectin, potato starch, natural artichoke starch, day, high amylose acetylated starch, wood natural corn Starch, natural wheat starch, natural rice starch and natural pea flour. One or more of the polymers (p) in the adhesive composition used in the method suitably comprise monomer units containing an amine group or a guanamine functional group. Suitably, from about 5 to about 1% of the monomer units of the one or more polymers (P) contain an amine group or an acid amine group, preferably from about 25 to about 1%, more preferably from about 50 to about 1 00 〇 / 〇, and more preferably about 90 to about 1 〇 0%. Most preferably, all of the monomeric elements in the one or more polymers (p) contain an amine group or a guanamine group. The one or more polymers (P) suitably contain a primary amine group or a guanamine group. Preferably, the one or more polymers (P) comprise polyvinylamine 'poly(vinyl alcohol_co-vinylamine), poly(vinyl alcohol·co-vinylamine), polyallylamine, polyethylene One or more of an amine, a polyamine amine, and a polyvinylformamide. More preferably, the one or more polymers (P) comprise one or more of polyvinylamine and poly(vinyl alcohol-co-vinylamine). Most preferably, the polymer (P) is a polyvinylamine. In one embodiment, the one or more polymers (P) suitably belong to the group of vinyl polymers. In this case, preferably, the one or more polymers (P) comprise polyvinylamine, poly(vinyl alcohol-co-vinylamine), poly(vinyl alcohol-co-vinylcarboxamide), polyallylamine And one or more of polyvinyl decylamine. Preferably, the one or more vinyl polymers (P) contain a primary amine group. Best 200900477 Ground, the vinyl polymer (P) is a polyvinylamine. In one embodiment, the one or more polymers (P) suitably contain a primary amine group or a pendant guanamine group. Preferably, the one or more polymers (p) comprise polyvinylamine, poly(vinyl alcohol-co-vinylamine), poly(vinyl alcohol-co-vinylamine), polyallylamine, polyethylene One or more of an amine and a polyvinylformamide.

Polyvinylamine is usually prepared by hydrolyzing polyvinylformamide to a certain extent. The term "polyvinylamine" as used herein refers to a polyvinylamine having a molar ratio of an amine group to a formammine group in the range of 5.95 to 100:0. If the amine group is a molar group with a carbenamine group The ratio is lower & 5: 95, the polymer is defined as polyvinylformamide. The amine group in the polyvinylamine is preferably about 10.90 to about 1 与: 〇'约约5〇: 5〇 to about 1〇〇: 〇, preferably about 80: 20 to about 100: 〇. Poly(vinyl alcohol·co-vinylamine) usually by making vinyl acetate with vinyl Hydrolysis of the amine after copolymerization gives a copolymer having vinyl alcohol and vinylamine units. There may also be residual mercaptoamine groups and residual acetic acid acetate groups in the copolymer. Poly(vinyl alcohol_co-ethylene amine) The molar ratio of the amine group to the amine formate is 5: 95 i 100 1. If the molar ratio of the amine group to the carbenamine group is less than 5:95, the polymer is defined as poly(vinyl alcohol- The molar ratio of the hydroxyl group to the acetate group in the poly(vinyl alcohol-co-vinylamine) or poly(vinyl alcohol-co-vinylformamide) is suitably from about 25 : 75 to 0 ° poly(vinyl alcohol-co-vinylamine) amine and guanamine group and hydroxy 3: 97 to about 1 () 〇: 〇, more than 100: 0, preferably about 75: 25 to 100: The molar ratio of the decylamine or poly(vinyl alcohol-co-vinyl fluorenyl group to the acetate group is suitably from about 9 200900477 to about 10:90 to about 100: 〇, preferably about 25:75 to about 100: 0. The one or more polymers (Ρ) suitably have a weight average molecular weight of from about 1, 〇〇〇 to about 1,000,000 g/mole, preferably from about 1 Torr, to about 8 Torr. , 〇〇〇克/莫耳' is preferably from about 20,000 to about 6 inches, gram/mole, preferably from about 50,000 to about 500,000 grams per mole. The viscosity of the adhesive (Brookfield, 12 rpm, Mandrel 4, at 20 ° C)

Suitably below 10 〇, 〇〇〇mpa*s, preferably from about L000 to about 5 〇, 〇〇〇 mPa*s ' is preferably from about 5,000 to about 2 〇 pa mpa*s. The adhesive composition used in this method can also be combined with another % agent shortly before use. Suitable crosslinkers are reactive with amine groups and/or hydroxyl groups! Examples of parent binders are: isocyanates, monomers or polymers containing adipic acid, melamine formaldehyde resins, urea formaldehyde resins, melamine salts, aldehydes such as valeraldehyde, glyoxal, and polymerizations such as, for example, dialdehyde starch. Type aldehyde 4 and a miscending agent such as #盐. It can be added to the two groups of the viscous n composition. If used, the amount of the crosslinking agent in the component of the adhesive composition is suitably up to about 30% by weight, or from about 01 to about 30% by weight. . The adhesive composition used in this application suitably comprises one or more polymers of the p-methoxy group (P1). The content of the Iethoxycarbonyl group in the one or more polymers (P) is suitably from about 〇 to about 15 mol%, preferably from about 1 to about 10 Torr. / ^ 7 _ ,. . Preferably, the side or polymers (P1) are polyvinyl alcohol (AAPVA) containing acetonitrile. Or the plurality of polymers (P1) suitably have a weight average molecular weight from ',,, _ to about 5, _g/mole, more than (iv) lQ, _ to about 10 200900477 2,000,000 g / mol. One or more components of the adhesive composition used in the method comprise human starch, a polymer (P) and a polymer (ρι), which may further comprise additives such as a viscosity modifier and a filler, such as kaolin, Wheat meal, soy meal, walnut meal or other formula known to be suitable for wood adhesives. The adhesive composition used in the method may also contain an inorganic or organic salt which may be derived from a solution of the starch-based adhesive composition or a plurality of polymers (P) or (P1). The or the +-portions of the plurality of polymers (p) and / or (P1) may carry an ionic charge, preferably a cation charge. The amount of negative relative ions of the salt in the adhesive composition may range from 纟0 to about 10% by weight, or from about 0.1 to about 5% by weight, or from about 〇·2 to about 5% by weight. The adhesive composition used in this method may also comprise a polymer or copolymer (Ρ2) of - or more ethylenically unsaturated monomers different from one or more of the agglomerates (Ρ). The polymer or copolymer (Ρ2) suitably does not contain any ethyl acetoxy group. The content of the polymer or copolymer (ρ2) in the adhesive composition is suitably from about 1 to about 5 % by weight, preferably from about 3 to about 40% by weight, more preferably from about 5 to about 30% by weight. In addition to the formation of the adhesive composition in the starch and/or the plurality of polymers (p), the polymer or copolymer (10) dispersion can also be used as a separate component in combination with the adhesive composition to form an adhesive according to the present invention. A combination of a composition of the agent and a dispersion of the polymer or copolymer (4) of cerium or a plurality of unsaturated monomers. Rand will swear you n) privately use this combination in the method of the present invention. In this combination 'based on the total weight of the combination, the amount of the adhesive composition 200900477 is suitably from about 25 to about 99% by weight 'preferably from about 4 to about 9% by weight, most preferably from about 50 to About 85% by weight. The amount of the dispersion of the polymer or copolymer (P2) is suitably from about 1 to about 75% by weight, preferably from about 1 to about 60, based on the total weight of the combined. /. , the best is about 2 〇 to about 5 〇. The content of the t compound or copolymer (p2) in the dispersion thereof is suitably from about 10 to about 90% by weight, preferably from about 2 5 to about 75 weight 0 / Torr. Examples of suitable polymers or copolymers f of one or more ethylenically unsaturated monomers are copolymerization of vinyl ester homopolymers such as polyvinyl acetate, vinyl esters such as ethylene-vinyl acetate copolymer (EVa). a copolymer of vinyl acetate vinegar with one or more propylene glycol monomers such as methyl methacrylate or butyl acrylate, styrene-butadiene rubber (SBR) and polyacrylate. Typically, the polymer or copolymer of one or more of the foregoing types of ethylenically unsaturated monomers is included in the starch-based adhesive composition used in the process, or in combination with a starch-based adhesive composition. It is possible to improve the bonding properties of the fiber tearing properties such as a glued product or a laminated product. In one embodiment, the method suitably comprises applying the adhesive composition to a sheet of wood-based material such that the surface having the applied adhesive composition is in contact with the surface of another wood-based sheet of material, This 'bonds the sheet by forming an adhesive joint between the sheets. In a specific example of this method, the adhesive composition is dried after application and thereafter activated by the addition of an aqueous composition. In one embodiment, when the laminate product is manufactured, the method suitably comprises applying the adhesive composition to the surface such that the bonding will comprise the amount originally applied, from about 0.1 to about 500 grams per square meter. The amount applied depends on 12 200900477: manufactured product · used to squeeze the factory to form a thin sheet, preferably about 5 〇 to about 克 / + square meter, when used for laminating floor materials, preferably about ι〇 It is about (9) g/m2, and when used for laminating beams, it is preferably about 18 to about 5 (eight) g/m2. The appropriate upper limit also depends on the type of wood-based material to which the solution has been applied. This adhesive composition can be applied to the - or both sides of the table 2 to be joined. If both sides are applied, the sum of the amounts applied to each surface is comparable to the preferred amount for a particular integral gluing. In the manufacture of extruded molding sheets, the method suitably comprises joining of more than two wood-based materials, preferably 2 to 丨5. The term "wood-based material" as used herein, in addition to solid wood, also includes wood materials such as fiberboard, chipboard and pelletized board materials. The surfaces to be joined may be the same or different types of wood-based materials. The wood-based material can be any type and form of wood-based material, such as wood chips, fibers, flakes, sheets, veneers, blocks, etc. - a specific real money, this method includes Glued wood-based pieces of material, and wood-based pieces of material are pieces of wood chips, which are referred to herein as "chips", shavings (sha), flakes, (four) fragments and Any similar small wood-based material. Here, the wood-based product is a composite product such as crushed wood, granular or fiberboard or oriented granules. Suitably from about 0 to about 20% by weight, preferably from about 1 to about 9% by weight, more preferably from about 5 to about 5% by weight. 13 200900477 Used chips and adhesives used in this method The weight ratio of the product (by dry weight: from about 100:1 to about 1:1, preferably about 5:1 to about 2:1), preferably about 3:1 to about 2.5:1' Preferably, the moisture content of the chip mixture and the adhesive composition used in the method is suitably from about 3 to about 25 weight %, preferably about the beginning of the pressurization. 5 to 2, 20% by weight, more preferably from about 6 to about 18% by weight, most preferably from about 7 to about 5% by weight. Preferably, the ink is applied after the application of the adhesive composition. (4) Properly carried out at the temperature of the south. The squeezing temperature depends on the wood-based product to be manufactured, but may suitably be from about Q to about 25 generations, and more than (four) 200 〇 C. Used; layered or glued product 'no crosslinker added to the adhesive In the composition of the agent, the temperature of the squeezing is suitably from about 〇t to about 约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约Sometimes, depending on the cross-linking agent, the extrusion temperature is effectively reduced. For the granular plastic board, chipboard or fiberboard product, the extrusion temperature is preferably from about 100 to about 225t, and the optimum core is from about 5 to about . to The combined product 'such as a splint, laminated floor product or glued floor product, preferably has a extrusion temperature of from about 70 to about 17 generations, preferably from about 90 to about 16 rc. The extrusion time is related to the extrusion temperature. The extrusion temperature usually requires a longer extrusion zone. The wood-based product to be produced also determines the appropriate squeezing temperature and duration. Suitably, the squeezing time is at least about W seconds, about seconds to about. 60 minutes is also appropriate, preferably at least about % seconds 14 200900477 hours, preferably about 30 seconds to about 3 minutes, preferably at least about eight and preferably about 1 to about 15 minutes. The 'wood-based material sheet is the board. Here the wood-based product is suitably laminated, thin-glued flooring, glued furniture, wall panels, ceiling panels, plywood or laminate Combined beam. \ 、 纟 纟 纟 纟 木材 木材 木材 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当 适当For panels, laminates or complexes, such as granular panels, fiberboard, chipboard or oriented pellets. Preferably, it is a splint, glued furniture material, glued flooring material, laminated flooring material or a granular plastic panel. The invention is further illustrated by the following non-limiting examples. Parts and percentages are by weight and by weight, respectively, unless otherwise stated. [Examples] Example 6 mixed with 65.5 g of an aqueous solution of about 7.5% by weight of polyvinylamine (LuPamin® 9095 from BASF), 5.7 g of water and 32 4 g of corn starch (C*) at room temperature (251) Gnm NC 03432, available from Cerestar, with a moisture content of 10%), is made with an adhesive based on the powder. The numerical ratio of the amine group to the formamidine group in the polyamine is more than 90:10. The weight average molecular weight of the polyvinylamine is 340,000 g/mole. The composition had a viscosity of 12, 〇〇〇 mPa*s (Brookfield > 12 rpm, mandrel 4) measured at 20 °C. - Example 2: 7 5 parts by weight of the adhesive composition according to Example 1 and 25 parts by weight of an acrylate/pvAc dispersion 15 200900477 having a polymer content of 50% by weight were mixed to obtain a starch-based adhesive. Example 3: Face Λ <古,丨,,_ _ v The top of the beech top is glued on one side of the 15x15 granules, and the politicians are erected by the 曰w I仵 glued products. Apply 3.7 grams according to the application of 1 and 2 eve: & fishing, /,,,, * 2 of the adhesive composition and the sheet is directly on the plate at 90 and 130 C for 1 minute. Test fiber Tearing (drilling disc).

. Repeat this money, but the time (4) is 9G. (10) minutes and 130 C 5 minutes instead. The results are shown in Table 2. Table 1. (Fj_^ when squeezing) Today, ‘·V goods!吋 I 〇 minute) Extrusion temperature extrusion time fiber tear Γ%, Example 1 Example 2 Temperature and cold temperature 90 ° C — — 10 minutes 10 10 80-90 1 Λ Π 13〇t 5 minutes 90-100 100 90-100 1 UU 100 ^ ^ ^ ^ ^ 5 The buckets were respectively combined with 12 (TC extrusion molding for 8 minutes to make two 13 layers of crepe 4 sheets glued together. This is the rebound of the product. The rebound of the product is very low. The 864 g of wood chips with a moisture content of 1.7 wt% and the 216 g of the adhesive composition of 16 200900477 are prepared to prepare a granulated plastic sheet. The adhesive composition is mixed at room temperature. 131 g of about 7.5 wt% of an aqueous solution of polyvinylamine (Lupamin@9〇95, available from BASF), 75 g of corn powder (c*Gum NC 03432, obtained from Cerestar '10% moisture content) and 10 g of water The mixture was prepared at room temperature (22 C) for 5 minutes. The chip mixture was made into a 3 〇χ 3 〇 plate and extruded at 189 ° C for three minutes to form a 16 mm thick plate. The extrusion procedure was 150 kg/cm 2 for 30 seconds, 40 kg/cm 2 for 2 minutes and 2 kg/cm 2 for at least 3 seconds. By placing 5 χ 5 cm The sheet was glued to the two metal blocks and torn them to determine the tensile strength (internal bond 'ΙΒ). Thickness swelling (TSw) and water absorption (ABS) were also measured. Thickness swelling was achieved by making 5 x The 5 cm piece was immersed in water (20 ° C, 24 hours), and the degree of swelling was measured. The water absorption was measured by measuring 5 χ 5 cm of the sheet into the water (2〇c»c, After 24 hours), the measured weight was measured and measured. The IB value was 690 kPa ' TSW 53% and ABS (24 hours) was 121%. [Simplified illustration] No [Main component symbol description]

Claims (1)

200900477 X. Patent Application Range: 1_ A method of manufacturing a wood-based product comprising applying an adhesive composition comprising ungelatinized starch in an aqueous phase, the composition additionally comprising from about 0.1 to about 5 G weight percent The polymer or polymers containing the amine or acid amine group (P)' are applied to one or more wood-based materials and the one or more sheets are combined with one or more other materials. 2. The method of claim 1, wherein the amount of starch in the adhesive composition is from about i 5 to about 4% by weight. 3. The method according to any one of the preceding claims, wherein the amount of the polymer (p) in the adhesive composition is from about 2 to about 9% by weight. The method according to any one of claims 1 to 2, wherein the one or more polymers (P) belong to a polyamine, a poly(vinyl alcohol-co-ethyleneamine), a polyallylamine, a group of polyethyleneimine and polyvinylformamide. 5. According to the scope of the patent application, the polymer (P) is polyacetamide. The method according to any one of the items (1), wherein the method of any one of the items (1) or (2) The method of any one of the preceding claims, wherein the adhesive composition further comprises one or more ethylenically unsaturated monomers different from the one or more polymers (P). Polymer or copolymer (P2). S 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 18 200900477 According to the method of claim 7, wherein the polymer (10) is a copolymer of vinyl acetate and/or a plurality of propylene monomers. 〇 〇 According to the scope of claim 1 or 2, _ contains a wood-based material ‘, the sheet is a sheet or a sheet. A method of any of the items of the present invention, wherein the wood-based material is a wood chip. The material sheet according to claim 1 or the wood-based material sheet is a wood chip. 12. The method of any one of clauses 1 or 2 of the patent application, wherein the wood-based product is a laminate flooring material, a glued flooring material, a triumphant furniture material, a wall panel, a ceiling, a splint or Laminated. I. The method according to any one of the preceding claims, wherein the wood-based product is a slab, a slab or a slab. Flying 疋 XI, schema: benefit 4 19