BINDER COMPOSITION COMPRISING POLYAMINE(S) AS WELL AS 1,3 -DIHYDROXYACETONE, GLYCOLALDEHYDE AND/OR GLYCERALDEHYDE FOR COMPOSITE ARTICLES

Abstract

The present invention relates to a binder composition comprising a) component A comprising polymer(s) A1 having primary and/or secondary amino groups, wherein polymer(s) A1 has(have) a primary and secondary amine group nitrogen content of at least 1 wt.-% and b) component B comprising component B1 which is 1,3-dihydroxyacetone, glycolaldehyde, glyceraldehyde or any mixture thereof, wherein the polymer(s) A1 has(have) a total weight average molecular weight M.sub.w,total of at least 800 g/mol.

Claims

1.-31. (canceled)

32. A binder composition comprising a) component A comprising polymer(s) A1 having primary and/or secondary amino groups wherein polymer(s) A1 has(have) a NC.sub.ps of at least 1 wt.-%, wherein the polymer(s) A1 comprise(s) polymerization product(s) of i) amino acids, and/or ii) amines comprising at least two amino groups, wherein the amines are no amino acids, and amino acids, and/or iii) amines comprising at least two amino groups, wherein the amines are no amino acids, and di and/or tricarboxylic acids, and optionally amino acids and/or iv) at least two compounds defined in i) to iii), and b) component B comprising component B1 which is 1,3-dihydroxyacetone, glycolaldehyde, glyceraldehyde or any mixture thereof, wherein polymer(s) A1 has(have) a total weight average molecular weight M.sub.w,total of at least 800 g/mol.

33. A binder composition according to claim 32, wherein polymer(s) A1 has(have) a total weight average molecular weight M.sub.w,total of at least 1000 g/mol and at most 20,000 g/mol.

34. A binder composition according to claim 32, wherein component B1 is a mixture of 1,3-dihydroxyacetone, glycolaldehyde and glyceraldehyde.

35. A binder composition according to claim 32, wherein component B1 is a mixture consisting of 1 to 30 wt.-% 1,3-dihydroxyacetone, 10 to 50 wt.-% glycolaldehyde and 20 to 80 wt.-% glyceraldehyde, based on the total weight of component B1, wherein the weight amounts of 1,3-dihydroxyacetone, glycolaldehyde, and glyceraldehyde in total are selected such that the total weight of the sum of dihydroxyacetone, glycolaldehyde, and glyceraldehyde is 100 wt. %.

36. A binder composition according to claim 32, wherein the number ratio of the sum of the numbers of primary and secondary amine groups of Component A1 to sum of the numbers of aldehyde and keto groups of component B1 is from 10:1 to 0.3:1.

37. A binder composition according to claim 32 comprising at least 10 wt.-% to 95 wt.-% polymer(s) A1 based on the total weight of the sum of polymer(s) A1 and component B1.

38. A binder composition according to claim 32, wherein polymer(s) A1 comprise(s) or consist(s) of branched polymer(s).

39. A binder composition according to claim 38, wherein polymer(s) A1 comprise(s) or consist(s) of branched polymer(s) having a degree of branching of at least 0.05.

40. A binder composition according to claim 32, wherein (i) the polymer(s) A1 comprise(s) at least one polymer selected from the group consisting of polyalkyleneimines, (ii) polyamides, (iii) block copolymers comprising polyalkleneimine segments and polyamide segments, (iv) graft copolymers comprising polyalkyleneimine segments and polyamide segments and (v) mixtures of at least two of (i), (ii), (iii) and/or (iv).

41. A binder composition according to claim 32, wherein polymer(s) A1 comprises a polymerization product of amino acids, wherein optionally at least 50 wt.-% amino acids are used as monomers for the polymerization reaction based on total amount of monomers.

42. A binder composition according to claim 41, wherein for the polymerization of 100 g polymer(s) A1 at least 15 g diamino carboxylic acid(s) are used.

43. A binder composition according to claim 32, wherein the polymer(s) A1 comprise(s) or consist(s) of poly(amino acids).

44. A binder composition according to claim 32 wherein the binder composition comprises 50 to 90 wt.-%, of polymer(s) A1, and 10 to 50 wt.-%, of component B1, based on the total weight of the sum of polymer(s) A1 and component B1, wherein the weight amounts of the polymer(s) A1 and component B1 are selected such that the total weight of the sum of polymer(s) A1 and component B1 is 100 wt.-%.

45. A binder composition according to claim 32, wherein the polymer(s) A1 comprise(s) or consist(s) of polylysine(s).

46. A binder composition according to claim 32, wherein the polymer(s) A1 comprise(s) or consist(s) of at least one a polymerization product of: i) 1,2-ethylenediamine, 1,3-propylenediamine, bis-(3-aminopropyl)amine, N-(2-aminoethyl)-1,3-propylenediamine, bis-(2-aminoethyl)amine, bis-N-(2-aminoethyl)-1,3-propylenediamine, N,N-bis-(3-aminopropyl)-1,2-ethylenediamine, N,N-bis-(3-aminopropyl)-1,2-ethylenediamine, or mixtures thereof and ii) adipic acid, succinic acid or mixtures thereof.

47. A reacted binder composition Obtained by reacting the binder components A and B according to claim 32.

48. A plastic material comprising the reaction product of component A and B according to claim 32.

49. A composition kit comprising the binder composition according to claim 32, wherein component A and component B are stored separately.

50. A lignocellulosic composite article comprising a plurality of lignocellulosic pieces, and a binder composition according to claim 32 or a reacted binder composition obtained by reading the binder components A and according to claim 32.

51. The lignocellulosic composite article according to claim 50, wherein the article is plywood, an oriented strand board, a chip board and/or a fiber board.

52. A multi-layer particle board comprising at least one core layer and at least one surface layer, wherein the surface layer comprises a binder composition according to claim 32 and the core layer comprises a binder selected form the group consisting of urea/formaldehyde binder, phenol/formaldehyde binder, melamine/urea/formaldehyde binder, PMDI binder and mixtures thereof.

53. A lignocellulosic composite article comprising a plurality of lignocellulosic pieces, and a binder composition according to claim 32 or a reacted binder composition obtainable or obtained by reacting the binder components A and B according to claim 32 or a multi-layer particle board comprising at least one core layer and at least one surface layer, wherein the surface layer comprises a binder composition according to claim 32 and the core layer comprises a binder selected form the group consisting of urea/formaldehyde binder, phenol/formaldehyde binder, melamine/urea/formaldehyde binder, PMDI binder and mixtures thereof, wherein 3 to 15 wt.-% polymer(s) A1 and component B1 in total based on the total oven-dry weight of the lignocellulosic pieces are used for the preparation of the lignocellulosic composite article.

54. The multi-layer particle board according to claim 52, wherein the formaldehyde emission measured according to EN 717-2 is lower than 2.0 mg/m.sup.2 h.

55. A process for the batchwise or continuous production of lignocellulosic composite articles which are single-layered lignocellulose-based boards or of multi-layered lignocellulose-based boards with a core and with at least one upper and one lower surface layer, comprising the following steps: a) mixing the lignocellulosic particles with a binder composition for each layer, wherein the mixture for at least one layer comprises the binder composition according to claim 32, b) layer-by-layer scattering of the mixtures of the individual layers to form a mat, c) pressing the mat to a board at a temperature of 80 to 300 C. and at a pressure of 1 to 100 bar or c) pressing the mat to a board at a temperature of 80 to 200 C. and at a pressure of 0.1 to 100 bar, wherein a high-frequency electrical field is applied during pressing until 80 to 200 C. is reached in the center of the mat.

56. A process according to claim 55 with a core and with at least one upper and one lower surface layer, wherein the surface layer comprises a binder composition comprising: a) component A comprising polymer(s) A1 having primary and/or secondary amino groups wherein polymer(s) A1 has(have) a NC.sub.ps of at least 1 wt.-%, wherein the polymer(s) A1 comprise(s) polymerization product(s) of v) amino acids, and/or vi) amines comprising at least two amino groups, wherein the amines are no amino acids, and amino acids, and/or vii) amines comprising at least two amino groups, wherein the amines are no amino acids, and di and/or tricarboxylic acids, and optionally amino acids and/or viii) at least two compounds defined in i) to iii), and b) component B comprising component B1 which is 1,3-dihydroxyacetone, glycolaldehyde, glyceraldehyde or any mixture thereof, wherein polymer(s) A1 has(have) a total weight average molecular weight M.sub.w,total of at least 800 g/mol; and the core layer comprises a binder selected form the group consisting of urea/formaldehyde binder, phenol/formaldehyde binder, melamine/urea/formaldehyde binder, PMDI binder and mixtures thereof.

57. A process for the batchwise or continuous production of lignocellulose-based composite articles which are glulam, plywood, cross laminated timber, blockboards or solid wood boards, comprising the following steps a) applying the binder components as defined in claim 32 onto at least one surface of one or more lignocellulosic pieces b) joining the one or more lignocellulosic pieces having the binder composition thereon with one or more lignocellulosic pieces and c) pressing the lignocellulosic pieces at a temperature of 20 to 200 C. and at a pressure of 1 to 100 bar together, wherein the lignocellulosic pieces are beams, lamellas, blanks and/or veneers.

58. The process according to claim 55, wherein in step c) or c) the press time factor is at most 12 s/mm.

59. The process according to claim 55, wherein 3 to 15 wt.-% polymer(s) A1 and hydroxyacetone in total, based on the total oven-dry weight of the lignocellulosic pieces are used for the preparation of the lignocellulose-based composite article.

60. The process according to claim 55, wherein both components A and B of the binder composition are added to the lignocellulosic pieces in step a) either a1) separately from one another or a2) as a mixture.

61. The process according to claim 55, wherein the lignocellulosic pieces are prepared from wood.

62. The process according to claim 55, wherein the component B of the binder composition comprises a mixture obtained by a formose reaction from formaldehyde.

Description

EXAMPLES

Example 1

Synthesis of Polylysines 1-6 and 11

[0466] 2200 g of L-lysine solution (50% in water, ADM) was heated under stirring in an oil bath (external temperature 140 C.). Water was distilled off and the oil bath temperature was increased by 10 C. per hour until a temperature of 180 C. is reached. The reaction mixture was stirred for an additional hour at 180 C. (oil bath temperature) and then pressure was slowly reduced to 200 mbar. After reaching the target pressure, distillation was continued for another period of time t (as specified in the following Table 1). The product was hotly poured out of the reaction vessel, crushed after cooling and dissolved in water to give a 50 wt. % solution.

[0467] Residual lysine monomer content, NC.sub.ps and M.sub.w were determined from this solution without any further purification. The residual lysine monomer is included in the calculation of M.sub.w

TABLE-US-00002 TABLE 1 L-Lysine t M.sub.w NC.sub.ps monomer content ratio Polylysine [min] [g/mol] [wt.-%] [wt.-%]* / Polylysine-1 90 1510 11.0 10.3 1.9 Polylysine-2 120 2010 10.5 5.9 2.1 Polylysine-3 150 2240 10.2 4.2 2.2 Polylysine-4 180 2740 9.80 2.5 2.3 Polylysine-5 210 3360 9.50 2.0 2.3 Polylysine-6 240 3690 9.15 1.3 2.2 Polylysine-11 325 11080 5.56 0.3 2.3 *The residual lysine monomer content is given as wt.-% based on the total weight of polylysine including lysine monomer.

Example 2

Synthesis of Polylysine-7 (Derivative)

[0468] 2200 g of L-Lysine solution (50% in water, ADM) was heated under stirring in an oil bath (external temperature 140 C.). Water was distilled off and the oil bath temperature was increased by 10 C. per hour until a temperature of 180 C. is reached. The reaction mixture was stirred for an additional hour at 180 C. (oil bath temperature) and then pressure was slowly reduced to 200 mbar. After reaching the target pressure, distillation was continued for further two hours. The apparatus was ventilated, and 11.0 g of stearic acid was slowly added. The mixture was stirred for 15 min at 180 C. (oil bath temperature). The product was hotly poured out of the reaction vessel, crushed after cooling and dissolved in water to give a 50 wt.-% solution.

[0469] M.sub.w and NC.sub.ps were measured analogous to Example 1 and are reported in Table 5 a and b.

Example 3

Synthesis of Polylysine-8 (Derivative)

[0470] 2200 g of L-Lysine solution (50% in water, ADM) was heated under stirring in an oil bath (external temperature 140 C.). Water was distilled off and the oil bath temperature was increased by 10 C. per hour until a temperature of 180 C. is reached. The reaction mixture was stirred for an additional hour at 180 C. (oil bath temperature) and then pressure was slowly reduced to 200 mbar. After reaching the target pressure, distillation was continued for further two hours. The apparatus was ventilated, and 11.0 g of oleyl alcohol was slowly added. The mixture was stirred for 15 min at 180 C. (oil bath temperature). The product was hotly poured out of the reaction vessel, crushed after cooling and dissolved in water to give a 50 wt.-% solution.

[0471] M.sub.w and NC.sub.ps were measured analogous to Example 1 and are reported in Table 5 a and b.

Example 4

Synthesis of Polyamide-9

[0472] 85.0 g of 1,2-ethylenediamine, 365 g of N-(2-aminoethyl)-1,3-propylenediamine and 500 g of N,N-Bis-(3-aminopropyl)-1,2-ethylenediamine were mixed at room temperature and heated to 80 C. 1040 g of adipic acid was added under nitrogen atmosphere. The reaction mixture was stirred under nitrogen atmosphere for 30 min at 80 C. Temperature was increased to 190 C. within 60 min and was kept at 190 C. for 3 h, while water was distilled off. After cooling, water was added to give a 65 wt.-% solution.

[0473] M.sub.w and NC.sub.ps were measured analogous to Example 1 and are reported in Table 5 a and b.

Example 5

Synthesis of Polyamide-10

[0474] 514 g of a 65 wt.-% solution of Polyamide-9 in water, 268 g water and 5.75 g sulfuric acid were mixed and heated to 90 C. Under nitrogen atmosphere a cooled solution (0 C.) of 338 g ethylene imine in 225 water was slowly added to this mixture within 2 h. Subsequently, the reaction mixture was stirred for 4 h at 90 C. until there is no ethylene imine monomer detectable by the Preussmann test (spectrophotometric determination after reaction with 4-(4-nitro-benzyl)-pyridinium perchlorate, Preussmann et al, Justus Liebigs Annalen der Chemie, 1965, 684, 57-61). After cooling, water was added to give a 50 wt.-% solution. M.sub.w and NC.sub.ps were measured analogous to Example 1 and are reported in Table 5 a and b.

Example 6

[0475] Synthesis of Formose Mixtures FM-1 to FM-4

Example 6.1

Synthesis of the NHC catalyst (1,3,4-Triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene)

[0476] 1086 g of thionyl chloride was added to a suspension of 600 g of benzanilide in 4200 mL of toluene within 15 min at room temperature. The reaction mixture was refluxed for 5 hours. The volatiles were removed under vacuum at 80 C. Upon complete removal of volatiles, 2100 mL of toluene was added and completely removed under vacuum at 80 C. The residue was dissolved in 4200 mL THF. The resulting solution was cooled to 25 C. followed by addition of 270 g of triethyl amine and 192 g of phenyl hydrazine. The reaction mixture was stirred for 12 hours at 25 C. The reaction mixture was dried in vacuum and 4000 mL of acetic acid solution (2 wt.-% in water) were added to the residue and warmed to 60 C. The resulting precipitate was cooled to 25 C. and filtered, washed with water to give 683 g of N-anilino-N-phenyl-benzamidine.

[0477] 78.5 g ammonium chloride were added to a suspension of 422 g of N-anilino-N-phenyl-benzamidine in 652 g of triethyl orthoformate. The reaction mixture was refluxed for 4 hours with stirring. The reaction mixture was cooled to room temperature and 800 mL of methanol were added, followed by addition of 635 mL of 25 wt. % solution sodium methoxide in methanol. The mixture was stirred for 30 mins at room temperature. The reaction mixture was filtered. The crude solid obtained was washed with 2 L of water, dried and finally washed with 250 mL methanol to yield 250 g 1,3,4-triphenyl-5-methoxy-1,2,4-triazoline (N-heterocyclic carbene (NHC) compound, nonactivated).

[0478] For the activation of the NHC compound, it was recrystallized from methanol in a first step: 50 g of 1,3,4-triphenyl-5-methoxy-1,2,4-triazoline was dissolved in 50 mL of methanol and heated to 62 C. under nitrogen while stirring. After reaching the boiling point, 380 g of methanol was added in portions until the solid was nearly completely dissolved. After stirring for 45 min at 62 C., the mixture was cooled down to room temperature, followed by filtration and washing with methanol. The solid was dried with air, yielding 41.8 g of recrystallized 1,3,4-triphenyl-5-methoxy-1,2,4-triazoline (83.6%). In a second step, 23.9 g of this recrystallized solid was filled into a Schlenk tube, evacuated and purged with argon five times. The tube was heated to 90 C. for 22 h under vacuum (<1 mbar). After cooling down to room temperature, the activated NHC catalyst was stored under argon until use.

Example 6.2

[0479] Oligomerization of Formaldehyde

[0480] The oligomerization of formaldehyde to C2 and C3 compounds was performed in a glass vessel (250 mL 4-neck round bottom flask or 6 L double walled vessel). The vessel is equipped with a nitrogen or argon stream, a stirrer and condenser.

[0481] FM-1

[0482] 2.00 kg of diisobutyl carbinol was placed in a 6 L double wall vessel and purged with argon. After heating up to 60 C., 541 g of 37 wt.-% aqueous formaldehyde solution was added and the mixture was heated to 90 C. while stirring. 1.99 g of activated NHC catalyst was added rapidly in one portion.

[0483] After stirring for 4 h at 95 C., the mixture was cooled down to 80 C. and 200 g of distilled water was added. After stirring for further 30 min, the reaction mixture was cooled down to 22 C. and the phases were separated.

[0484] The aqueous phase is used as formose mixture FM-1 for the preparation of the chipboards without any further purification. The water content of FM-1 was determined by coulometric Karl-Fischer titration. The composition of FM-1 was determined by GC measurements as described above. The composition is reported in Table 2.

[0485] FM-2

[0486] 2.00 kg of diisobutyl carbinol and 540 g of 37 wt.-% aqueous formaldehyde solution were placed in a 6 L double wall vessel and purged with argon. The mixture was heated up while stirring and after reaching 80 C., 1.96 of activated NHC catalyst was added rapidly in one portion.

[0487] The temperature was increased in 2 h to 105 C. The mixture was cooled down to 80 C. and 200 g of distilled water was added. After stirring for further 30 min, the reaction mixture was cooled down to 22 C. and the phases were separated.

[0488] The aqueous phase is used as formose mixture FM-2 for the preparation of the chipboards without any further purification. The water content of FM-2 was determined by coulometric Karl-Fischer titration. The composition of FM-2 was determined by GC measurements as described above. The composition is reported in Table 2.

[0489] FM-3

[0490] 2.00 kg of 2-ethyl-1-hexanol (1998.7 g) and 540 g of 37 wt.-% aqueous formaldehyde solution were placed in a 6 L double wall vessel and purged with argon. The mixture was heated up while stirring and after reaching 88 C., 1.96 of activated NHC catalyst was added rapidly in one portion.

[0491] The temperature was increased in 1 h to 105 C. The mixture was cooled down to 80 C. and 200 g distilled water was added. After stirring for further 30 min, the reaction mixture was cooled down to 22 C. and the phases were separated.

[0492] The aqueous phase is used as formose mixture FM-3 for the preparation of the chipboards without any further purification. The water content of FM-3 was determined by coulometric Karl-Fischer titration. The composition of FM-3 was determined by GC measurements as described above. The composition is reported in Table 2.

[0493] FM-4

[0494] 4.00 kg of diisobutyl carbinol and 1.08 kg of 37 wt.-% aqueous formaldehyde solution were placed in a 6 L double wall vessel and purged with argon. The mixture was heated up while stirring and after reaching 90 C., 4.06 g of the activated NHC catalyst was added rapidly in one portion.

[0495] The temperature was increased in 1.5 h to 105 C. The mixture was cooled down to 80 C. and 400 g of distilled water was added. After stirring for further 30 min, the reaction mixture was cooled down to 22 C. and the phases were separated.

[0496] The aqueous phase is used as formose mixture FM-4 for the preparation of the chipboards without any further purification. The water content of FM-4 was determined by coulometric Karl-Fischer titration. The composition of FM-4 was determined by GC measurements as described above. The composition is reported in Table 2.

TABLE-US-00003 TABLE 2 water content and composition of FM-1 to FM-4 B1 weight ratio of (GA + GLA + compounds in C4/C5/ GA GLA DHA DHA) component B1 C6 * others water Sample [wt. %] [wt. %] [wt. %] [wt. %] GA:GLA:DHA [wt. %] [wt. %] [wt. %] FM-1 7.3 7.3 4.6 19.2 38:38:24 23.8 <0.1 57.0 FM-2 14.2 15.2 1.0 30.4 47:50:3 8.9 0.7 60.0 FM-3 5.0 13.7 1.5 20.2 25:68:7 23.8 0.1 55.9 FM-4 11.3 15.8 1.5 28.6 40:55:5 14.2 0.1 57.1 * this value corresponds to the sum of all signals of the condensation products of formaldehyde with four, five and six carbons (C4/C5/C6)

Comparative Example 7*

[0497] Comparative Binder Composition-1

[0498] 161 g glucose monohydrate, 146 g fructose and 161 g L-lysine were mixed with 35 g water and slowly heated (110 C. oil bath temperature). At 94 C. the mixture foamed and turned black. The reaction was stopped. The resulting reaction mixture contained a solid and was not completely soluble in water.

Comparative Example 8*

[0499] Comparative Binder Composition-2

[0500] 286 g glucose monohydrate, 260 g fructose and 286 g L-lysine were mixed with 174 g water and slowly heated (100 C. oil bath temperature). At 90 C. the mixture foamed and turned dark brown. The oil bath was removed for 10 minutes. The reaction was heated up again for 10 min to 100 C. until gas formation stopped. After cooling down to RT the mixture was filled in bottles and stored at 60 C. for 48 h.

Comparative Example 9*

[0501] Comparative Binder Composition-3

[0502] 235 g hexamethylene diamine is dissolved in 730 g water. 791 g fructose and 853 g glucose monohydrate were slowly added and stirred at room temperature for one hour.

[0503] Comparative Binder Composition-4

[0504] 22.5 g of carboxymethylcellulose sodium salt (NaCMC, M.sub.w ca. 250,000) was dissolved in 600 g of water. 67.5 g of hexamethylene diamine and 360 g of glucose monohydrate were slowly added and stirred at room temperature for 24 h.

Example 10

[0505] Single-Layered Chipboards with Polylysine-2 and DHA in Comparison with State-of-the-Art Binders

Example 10-1

[0506] In a mixer, 499 g of Polylysine-2 solution (50 wt.-% in water) was sprayed onto 5.56 kg (5.40 kg dry weight plus 160 g water (from residual particle moisture content) of spruce core layer chips (moisture content 3.0%) while mixing. Immediately, 149 g of a 1,3-dihydroxyacetone solution (50 wt.-% DHA in water) was sprayed onto the mixture while mixing. Finally, 90 g of water was sprayed onto the mixture while mixing to adjust the final moisture of the resinated chips. After addition of the water mixing was continued for 3 min.

[0507] The term resinated chips is used for the mixture of the chips with the binder composition and additionally added water.

[0508] Calculation of the Binder Amount (Polymer(s) A1 and DHA):

(499 g0.5+149 g0.5): 5400 g=6.0%

[0509] Calculation of the Ratio of Polymer(s) A1 and DHA:

(499 g0.5):(149 g0.5)=77:23

[0510] Calculation of the Moisture Content of the Chips/Binder Mixture:

Total weight of water=499 g0.5 (from polylysine solution)+149 g0.5 (from DHA solution)+90 g (from additional water)+160 g (from chips moisture)=574 g

Total weight of solids=499 g0.5 (from polylysine solution)+149 g0.5 (from DHA solution)+5400 g (dry chips)=5724 g

Resulting moisture content=574 g/5724 g=10.0%

[0511] This water content was confirmed by the method analogous to EN 322:1993 as described above resulting in a water content of 10%.

Comparative Example 10-2*

[0512] Binder composition-1 was inhomogeneous. Spraying of Binder composition-1 onto the chips wasn't possible. Attempts to mix Binder composition-1 with the chips by pouring the binder composition onto the chips and stirring also failed to give an even mixture, which can be used for the pressing of a chipboard.

Comparative Example 10-3*

[0513] In a mixer, a mixture of 404 g of Binder composition-2 and 244 g of water was sprayed onto 5.56 kg (5.40 kg dry weight plus 160 g water from residual particle moisture content) of spruce core layer chips (moisture content 3.0%) while mixing. 90 g of water was sprayed onto the mixture while mixing to adjust the final moisture of the resinated chips. After addition of the water mixing was continued for 3 min.

Comparative Example 10-4*

[0514] In a mixer, a mixture of 469 g of Binder composition-3 and 179 g of water was sprayed onto 5.56 kg (5.40 kg dry weight plus 160 g water from residual particle moisture content) of spruce core layer chips (moisture content 3.0 wt.-%) while mixing. 90 g of water was sprayed onto the mixture while mixing to adjust the final moisture of the resinated chips. After addition of the water mixing was continued for 3 min.

Comparative Example 10-5*

[0515] In a mixer, 816 g of Binder composition-4 was sprayed onto 5.49 kg (5.40 kg dry weight plus 90 g water (from residual particle moisture content) of spruce core layer chips (moisture content 1.7%) while mixing. 90 g of water was sprayed onto the mixture while mixing to adjust the final moisture of the resinated chips. After addition of the water mixing was continued for 3 min.

Comparative Example 10-6*

[0516] In a mixer, 499 g of Polylysine-2 solution (50 wt.-% in water) was sprayed onto 5.47 kg (5.40 kg dry weight plus 70 g water from residual particle moisture content) of spruce core layer chips (moisture content 1.3%) while mixing. Immediately, a solution of 164 g of glucose monohydrate (corresponding to 149 g of glucose) in 320 g of water was sprayed onto the mixture while mixing. After addition of the water mixing was continued for 3 min.

[0517] In the comparative examples 10-2* to 10-6* the amount of the comparative binder composition is 6.0% solids referred to dry wood. The solids of the comparative binder compositions (binder composition-2, binder composition-3 and binder composition-4) was calculated from the starting materials as shown in the following example.

[0518] Comparative Binder Composition-2: [0519] 286 g of glucose monohydrate (260 g glucose+26 g water) [0520] 260 g of fructose [0521] 286 g of L-lysine [0522] 174 g of water

Solid content=(260 g+260 g+286 g)/(260 g+260 g+286 g+26 g+174 g)=80.1%

[0523] 404 g of binder composition-2 contains 324 g (80.1% of 404 g) of solids. The amount of the comparative binder composition-2 is 6.0% solids referred to dry weight of the wood chips (5.40 kg).

[0524] In the comparative examples 10-5* the amount of the comparative binder composition is also 6.0 wt.-% solids referred to dry wood.

[0525] Pressing the resinated chips to chipboards (Example 10-1 and comparative examples 10-3* to 10-61 Immediately after resination, 720 g of the chips/binder mixture were scattered into a 3030 cm mold and pre-pressed under ambient conditions (0.4 N/mm.sup.2). Subsequently, the pre-pressed chip mat thus obtained was removed from the mold, transferred into a hot press and pressed to a thickness of 10 mm to give a chipboard (temperature of the press plates 210 C., max pressure 4 N/mm.sup.2, pressing time 180 sec, 120 sec or 100 sec).

TABLE-US-00004 TABLE 3 single-layered chipboards, 10 mm, with different binder compositions according to the invention and comparative examples, binder amount 6 wt.-% (solids/dry wood). B Component B1 or A comparative Ratio.sup.1) of Press Internal Polymer binder polymer A1 time bond 24 h A1 or CB component and factor Density strength swelling Example component glucose B1/glucose [sec/mm] [kg/m.sup.3] [N/mm.sup.2] [%] 10-1 Polylysine-2 DHA 77:23 18 712 0.70 40 12 701 0.62 42 10 700 0.53 45 10-2* CB-1 (Glucose/ n.p. fructose/lysine) 10-3* CB-2(Glucose/ 18 681 0.47 n.q. fructose/lysine) 12 no board 10-4* CB-3 (Glucose/ 18 720 0.14 n.q. fructose/HMDA) 12 no board 10-5* CB composition-4 18 661 0.30 n.q. (Glucose/ 12 657 0.19 n.q. HMDA/NaCMC) 10 No board 10-6* Polylysine-2 Glucose 77:23 18 713 0.56 61 12 699 0.40 62 10 No board *Comparative Example, CB = Comparative Binder .sup.1)ratio by weight n.p. = production of a chip board was not possible, since Comparative Binder-1 is inhomogeneous and cannot be evenly distributed on the chips n.q. = not quantifiable since test sample fell to pieces within 24 h no board means that the resulting material after pressing was not a sound chipboard and showed fractures, blows and/or bursts.

[0526] Table 2 shows that the binder composition according to the present invention allows the production of boards having an improved Internal bond strength compared boards prepared with binder composition known from prior art. Furthermore, the binder composition according to the present invention allows the production of boards at lower press time factors.

Example 11

[0527] Single-Layered Chipboards with Polylysine-2 and Glycolaldehyde Dimer (GA-D), Glyceraldehyde (GLA) or 1,3-Dihydroxyacetone (DHA) and Different Ways of Application

[0528] Separate application of the binder composition to the wood particles (Example 11-1 to 11-8 and comparative examples 11-16* and 11-17*)

[0529] In a mixer, an amount x of a solution of A1 (50 wt.-% in water) was sprayed onto 5.56 kg (5.40 kg dry weight) of spruce core layer chips (moisture content 3.0 wt.-%) while mixing. Subsequently, an amount y of a solution of component B1 (50 wt.-% in water) was sprayed onto the mixture while mixing. Finally, an amount z of additional water was sprayed onto the mixture while mixing to adjust the final moisture of the resinated chips. After addition of the water mixing was continued for 3 min. x, y and z are given in Table 4a.

[0530] Separate application of the binder composition to the wood particles (Example 11-9) In a mixer, 499 g of Polylysine-2 solution (50 wt.-% in water) was sprayed onto 5.56 kg (5.40 kg dry weight) of spruce core layer chips (moisture content 3.0 wt.-%) while mixing. Subsequently, 149 g of a solution of 1,3-dihydroxyacetone (50 wt.-% in water) was sprayed onto the mixture while mixing. Finally, 90 g of additional water was sprayed onto the mixture while mixing to adjust the final moisture of the resinated chips. After addition of the water mixing was continued for 3 min.

[0531] Mixed application of the binder composition to the wood particles (Examples 11-10 to 11-15) 2.20 kg of Polylysine-2 solution (50 wt.-% in water) and 657 g of a 1,3-dihydroxyacetone solution (50 wt. % in water) were mixed by stirring for 1 min at 22 C. After a waiting time of z min (time between end of stirring and start of spraying, during which the mixture was stored at 22 C. as given in Table 4b, 648 g of this mixture was sprayed to 5.56 kg (5.40 kg dry weight) of spruce core layer chips (moisture content 3.0 wt.-%) while mixing. Subsequently, 90 g of water was sprayed onto the mix while mixing to adjust the final moisture of the resinated chips. After addition of the water mixing was continued for 3 min.

TABLE-US-00005 TABLE 4a Amounts of A1, B1 and water Amount of Amount of A1 solution B1 solution Amount of (50 wt.-% (50 wt.-% additional in water) in water) water Example A1 x [g] B1 y [g] z [g] 11-1 PL-2 590 GLA 58.5 90 11-2 PL-2 499 GLA 149 90 11-3 PL-2 480 GA-D 168 90 11-4 PL-2 499 GA-D 149 90 11-5 PL-2 499 DHA 149 90 11-6 PL-2 499 DHA 149 90 11-7 PL-2 832 DHA 248 0 11-8 PL-2 832 DHA 248 0 11-16* L-Lysine 499 DHA 149 90 11-17* L-Lysine 499 DHA 149 90 *Comparative Example, PL-2 = Polylysine-2 Pressing the resinated chips to chipboards (Examples 11-1 to 11-15 and Comparative Examples 11-16* and 11-17*).

[0532] Immediately after resignation, 1.03 kg of the chips/binder composition mixture were spreaded into a 3030 cm mold and pre-pressed under ambient conditions (0.4 N/mm.sup.2). Subsequently, the pre-pressed chip mat thus obtained was removed from the mold, transferred into a hot press and pressed to a thickness of 16 mm to give a chipboard (temperature of the press plates 210 C., max pressure 4 N/mm.sup.2, pressing time 96 sec).

TABLE-US-00006 TABLE 4b single-layered chipboards, 16 mm, no further components A2, B2, C included Waiting Press Weight Amount time time Internal Ratio A1 + B1 z factor Density bond Example A1 B1 A1:B1 [wt.-%].sup.1) Application [min] [s/mm] [kg/m.sup.3] [N/mm.sup.2] 11-1 PL-2 GLA 91:9 6 sep. 6 643 0.56 11-2 PL-2 GLA 77:23 6 sep. 6 654 0.58 11-3 PL-2 GA-D 74:26 6 sep. 6 640 0.53 11-4 PL-2 GA-D 77:23 6 sep. 6 648 0.52 11-5 PL-2 DHA 77:23 6 sep. 6 656 0.44 11-6 PL-2 DHA 77:23 6 sep. 12 646 0.48 11-7 PL-2 DHA 77:23 10 sep. 6 655 0.88 11-8 PL-2 DHA 77:23 10 sep. 12 657 0.98 11-9 PL-2 DHA 77:23 6 sep.** 6 660 0.45 11-10 PL-2 DHA 77:23 6 mix 1 6 656 0.43 11-11 PL-2 DHA 77:23 6 mix 30 6 657 0.41 11-12 PL-2 DHA 77:23 6 mix 60 6 660 0.39 11-13 PL-2 DHA 77:23 6 mix 90 6 654 0.36 11-14 PL-2 DHA 77:23 6 mix 120 6 649 0.30 11-15 PL-2 DHA 77:23 6 mix 150 6 638 <0.1 11-16* L-Lysine DHA 77:23 6 sep. 18 656 <0.1 11-17* L-Lysine DHA 77:23 6 sep. 12 No board *Comparative Example PL-2 = Polylysine-2 Waiting time = time between end of mixing of Polylysine-2 and DHA and start of spraying the binder composition mixture onto the chips sep. = separate application (first A1, second B1) sep.** = separate application (first B1, second A1) mix = application of a mixture of A1 and B1 .sup.1)amount is given in wt.-% solids per dry wood

[0533] Table 4b shows that the binder composition according to the present invention, which is polylysine in combination with glyceraldehyde, glycolaldehyde or 1,3-dihydroxyacetone, allows the production of boards having an improved Internal bond strength at shorter press times compared to binder compositions using lysine instead of polylysine.

Example 12

[0534] Single-Layered Chipboards with Different Polymers A1 and 1,3-Dihydroxyacetone (DHA)

[0535] Preparation of the resinated chips (Examples 12-1* to 12-12 and 12-14) In a mixer, 499 g of L-lysine solution (Comparative Example 12-11 or Polymer(s) A1 solution (50 wt.-% in water) (Example 12-2 to 12-12 and 12-14) was sprayed onto 5.56 kg (5.40 kg dry weight) of spruce core layer chips (moisture content 3.0%) while mixing. Subsequently, 149 g of a 1,3-dihydroxyacetone solution (50 wt.-% DHA in water) was sprayed onto the mixture while mixing. Finally, 90 g of water was sprayed onto the mixture while mixing to adjust the final moisture of the resinated chips. After addition of the water mixing was continued for 3 min.

Preparation of the Resinated Chips (Example 12-13)

[0536] In a mixer, 648 g of Lupasol G100 (50 wt.-% of polyetheyleneimine in water) was sprayed onto 5.56 kg (5.40 kg dry weight) of spruce core layer chips (moisture content 3.0%) while mixing. Subsequently, 90 g of water was sprayed onto the mixture while mixing to adjust the final moisture of the resinated chips. After addition of the water mixing was continued for 3 min.

Pressing the Resinated Chips to Chipboards (Examples 12-1* to 12-14)

[0537] Immediately after resination, 1.10 kg of the chips/binder mixture were scattered into a 3030 cm mold and pre-pressed under ambient conditions (0.4 N/mm.sup.2). Subsequently, the pre-pressed chip mat thus obtained was removed from the mold, transferred into a hot press and pressed to a thickness of 16 mm to give a chipboard (temperature of the press plates 210 C., max pressure 4 N/mm.sup.2). The pressing time was 96 sec (Table 5a) or 160 sec (Table 5b).

TABLE-US-00007 TABLE 5a single-layered chipboards, 16 mm, binder amount (polymer A1 + component B1 or lysine + component B1):6 wt.-% (solids/dry wood), separate application, press time factor 6 sec/mm, no further components B2, A2 and C included. M.sub.w of A1 or Polymer(s) NC.sub.ps of molecular weight A1 or polymer of comparative Weight Internal comparative A1 component.sup.1) ratio Density bond Example component [wt.-%] [g/mol] B1 A1:B1 [kg/m.sup.3] [N/mm.sup.2] 12-1a* L-Lysine 19.2 146 DHA 77:23 No board 12-2a Polylysine-1 11.0 1510 DHA 77:23 658 0.35 12-3a Polylysine-2 10.5 2010 DHA 77:23 669 0.46 12-4a Polylysine-3 10.2 2240 DHA 77:23 671 0.44 12-5a Polylysine-4 9.80 2740 DHA 77:23 668 0.48 12-6a Polylysine-5 9.50 3360 DHA 77:23 676 0.44 12-7a Polylysine-6 9.15 3690 DHA 77:23 683 0.51 12-8a Polylysine-7 9.68 2180 DHA 77:23 674 0.42 12-9a Polylysine-8 9.88 2380 DHA 77:23 678 0.44 12-10a Polyamide-9 6.48 10600 DHA 77:23 680 0.72 12-11a Polyamide-10 10.4 17600 DHA 77:23 699 0.71 12-12a Polyethyleneimine 15.4 4730 DHA 77:23 692 0.59 (Lupasol G100) 12-13a* Polyethyleneimine 15.4 4730 No board (Lupasol G100) 12-14a Polylysine-11 5.56 11080 DHA 77:23 675 0.25 *Comparative Examples .sup.1)M.sub.w of the polymers A1 are measured by size exclusion chromatography.

TABLE-US-00008 TABLE 5b single-layered chipboards, 16 mm, binder amount (polymer A1 + component B1 or lysine + component B1):6 wt.-% (solids/dry wood), separate application, press time factor 10 sec/mm, no further components A2, B2, C included. M.sub.w of A1 or molecular Polymer(s) NC.sub.ps of weight of A1 or polymer comparative Weight Internal comparative A1 component.sup.1) ratio Density bond Example component [wt.-%] [g/mol] B1 A1:B1 [kg/m.sup.3] [N/mm.sup.2] 12-1b* L-Lysine 19.2 146 DHA 77:23 No board.sup.2) 12-2b Polylysine-1 11.0 1510 DHA 77:23 695 0.41 12-3b Polylysine-2 10.5 2010 DHA 77:23 700 0.53 12-4b Polylysine-3 10.2 2240 DHA 77:23 696 0.56 12-5b Polylysine-4 9.80 2740 DHA 77:23 693 0.58 12-6b Polylysine-5 9.50 3360 DHA 77:23 674 0.43 12-7b Polylysine-6 9.15 3690 DHA 77:23 700 0.45 12-8b Polylysine-7 9.68 2180 DHA 77:23 685 0.52 12-9b Polylysine-8 9.88 2380 DHA 77:23 693 0.51 12-10b Polyamide-9 6.48 10600 DHA 77:23 679 0.82 12-11b Polyamide-10 10.4 17600 DHA 77:23 711 0.75 12-12b Polyethyleneimine** 15.4 4730 DHA 77:23 701 0.65 12-13b* Polyethyleneimine** 15.4 4730 No board 12-14b Polylysine-11 5.56 11080 DHA 77:23 684 0.28 *Comparative Examples **Lupasol G100 .sup.1)M.sub.w of the polymers A1 are measured by size exclusion chromatography. .sup.2)No board was obtained also when a higher binder amount of binder was used (10% of L-Lysine and DHA (77:23) instead of 6% of L-lysine and DHA (77:23).

Example 13

[0538] Single-Layered Chipboards with Polylysine-2 and DHA and Paraffin Emulsion

[0539] Mixed application of the binder composition to the wood chips (Examples 13-1 to 13-3) 2.20 kg of Polylysine-2 solution (50 wt.-% in water) and 657 g of a 1,3-dihydroxyacetone solution (50 wt. % DHA in water) were mixed by stirring for 1 min at 22 C. In a mixer 648 g of this mixture was sprayed either immediately after mixing or after a waiting time (stored in a closed box at 22 C.) as given in the Table 3, to 5.56 kg (5.40 kg dry weight) of spruce core layer chips (moisture content 3.0%) while mixing. Subsequently, a mixture of 45.0 g HydroWax 138 (60 wt.-% paraffin in water) and 72.0 g of water was sprayed onto the mix while mixing. After addition mixing was continued for 3 min.

[0540] Pressing the resinated chips to chipboards (Examples 13-1 to 13-3) Immediately after resination, 1.11 kg of the chips/binder mixture were scattered into a 3030 cm mold and pre-pressed under ambient conditions (0.4 N/mm.sup.2). Subsequently, the pre-pressed chip mat thus obtained was removed from the mold, transferred into a hot press and pressed to a thickness of 16 mm to give a chipboard (temperature of the press plates 210 C., max pressure 4 N/mm.sup.2, pressing time 96 sec).

TABLE-US-00009 TABLE 6 single-layered chipboards, 16 mm, binder amount (polymer A1 + component B1):6 wt.-% (solids/dry wood), C1 = paraffin, press time factor = 6 sec/mm, no further components A2, B2 included. Weight Weight Amount Waiting Internal 24 h Polymer ratio ratio of C1 time Density bond swelling Example A1 B1 A1:B1 A1:B1:C1 [wt.-%]* [min] [kg/m.sup.3] [N/mm.sup.2] [%] 13-1 PL-2 DHA 77:23 71:21:8 0.5 1 657 0.44 38 13-2 PL-2 DHA 77:23 71:21:8 0.5 30 656 0.40 39 13-3 PL-2 DHA 77:23 71:21:8 0.5 60 654 0.40 42 11-10 PL-2 DHA 77:23 77:23:0 0 1 656 0.43 41 11-11 PL-2 DHA 77:23 77:23:0 0 30 657 0.41 43 11-12 PL-2 DHA 77:23 77:23:0 0 60 660 0.39 44 *amount is given in wt.-% solids per dry wood Waiting time = time between end of mixing of Polylysine-2 and DHA and start of spraying the binder composition mixture onto the chips PL-2 = Polylysine-2

[0541] Table 6 shows that the addition of paraffine improves swelling properties.

Example 14

[0542] Single-Layered Chipboards with Polylysine-2 and Different Amounts of 1,3-Dihydroxyacetone

[0543] In a mixer, an amount x of Polylysine-2 solution (50 wt.-% in water) as given in Table 7 was sprayed onto 5.56 kg (5.40 kg dry weight) of spruce core layer chips (moisture content 3.0%) while mixing.

[0544] Subsequently, an amount y of a 1,3-dihydroxyacetone solution (50 wt.-% DHA in water) as given in Table 7 was sprayed onto to the mixture while mixing. Finally, 90 g of water was sprayed onto the mixture while mixing to adjust the final moisture of the resinated chips. After addition of the water mixing was continued for 3 min.

TABLE-US-00010 TABLE 7 Amount of Amount of Polylysine-2 solution DHA solution (50 wt.-% in water) (50 wt.-% in water) Example x [g] y [g] 14-1 64.8 583 14-2 214 434 14-3 259 389 14-4 324 324 14-5 421 227 14-6 486 162 14-7 518 130

[0545] Immediately after resination, 1.10 kg of the chips/binder mixture were scattered into a 3030 cm mold and pre-pressed under ambient conditions (0.4 N/mm.sup.2). Subsequently, the pre-pressed chip mat thus obtained was removed from the mold, transferred into a hot press and pressed to a thickness of 16 mm to give a chipboard (temperature of the press plates 210 C., max pressure 4 N/mm.sup.2, pressing time 96 sec)

TABLE-US-00011 TABLE 8 single-layered chipboards, 16 mm, binder amount (polymer A1 + component B1):6 wt.-% (solids/dry wood), separate application, press time factor 6 sec/mm, no further components A2, B2, C included. Weight Number Internal ratio ratio Density bond Example A1 B1 A1:B1 X [kg/m.sup.3] [N/mm.sup.2] 14-1 Polylysine-2 DHA 10:90 0.07:1 No board 14-2 Polylysine-2 DHA 33:67 0.34:1 640 0.24 14-3 Polylysine-2 DHA 40:60 0.45:1 641 0.30 14-4 Polylysine-2 DHA 50:50 0.67:1 634 0.37 14-5 Polylysine-2 DHA 65:35 1.25:1 652 0.49 14-6 Polylysine-2 DHA 75:25 2.01:1 650 0.59 14-7 Polylysine-2 DHA 80:20 2.68:1 648 0.57 Number ratio X = number ratio of the amine groups of polylysine-2 and the keto functions of 1,3-dihydroxyacetone

[0546] Table 8 clearly shows that the number ratio of the sum of the numbers of primary and secondary amine groups of polymer A1 to the sum of the numbers of aldehyde and keto groups of component B1 should be at least 0.3:1. Preferably the number ratio of the sum of the numbers of primary and secondary amine groups of polymer A1 to sum of the numbers of aldehyde and keto groups of component B1 should be larger than 1.

Example 15

[0547] Single-Layered Chipboards with Polylysine-2 (PL-2) and Formose Mixtures FM-1 to FM-4

[0548] In a mixer, 5.56 kg (5.40 dry weight) of spruce particles (core layer particles; moisture content 3.0 wt.-%) were mixed with 499 g of a solution of Polylysine-2 (50 wt.-% in water). Subsequently an amount y of Component B as defined in Table 9 was added into the mixer while mixing. Finally, an amount z of additional water was sprayed onto the mix while mixing to adjust the final moisture of the resinated particles. After addition of the water mixing was continued for 3 min.

TABLE-US-00012 TABLE 9 Concen- Amount of Amount tration additional of B of B1 in B water Example B y [g] [wt.-%] z [g] 13-1 FM-1 174 19.2 113 13-2 FM-2 187 30.4 97 13-3 FM-3 168 20.2 115 13-4 FM-4 173 28.6 110 13-5 DHA (50 wt. % in water) 113 50.0 96 13-6 GLA (50 wt. % in water) 113 50.0 96

TABLE-US-00013 TABLE 10 single-layered chipboards, 16 mm, separate application, press time factor 6 s/mm no further components A2, B2, C included. Amount Amount weight ratio of A1 B1 weight compounds in Internal [%/dry [%/dry ratio component B1 Density bond Example A1 wood] B wood] A1:B1 GA:GLA:DHA [kg/m.sup.3] [N/mm.sup.2] 13-1 PL-2 4.62 FM-1 0.62 88:22 38:38:24 673 0.78 13-2 PL-2 4.62 FM-2 1.05 81:19 47:50:3 664 0.63 13-3 PL-2 4.62 FM-3 0.63 88:22 25:68:7 659 0.57 13-4 PL-2 4.62 FM-4 0.92 83:17 40:55:5 664 0.57 13-5 PL-2 4.62 DHA 1.05 81:19 658 0.44 13-6 PL-2 4.62 GLA 1.05 81:19 661 0.42 PL-2 = Polylysine-2

[0549] Table 10 shows that boards prepared with a binder composition comprising a mixture of glyceraldehyde, glycolaldehyde and 1,3-dihydroxyacetone as component B1 provide a higher internal bond strength than boards prepared with pure glyceraldehyde or pure 1,3-dihydroxyacetone as component B-1.

Example 16

[0550] Plastic Material

[0551] 50 g of Polylysine-2 (50 wt.-% in water) and 7.5 g of 1,3-dihydroxyacetone (weight ratio A1 to B1=77:23) were mixed in a speed mixer for 1 min at 2000 rpm. Straight after that the mixture was poured in a metal form for rods. The form is placed in an oven at 120 C. for 90 min and for further 90 min at 180 C. After cooling down to RT the form was removed and dark brown to black rods were obtained.

Example 17

[0552] Three-layered chipboards with Polylysine-2 solution and HA-1 in the surface layer and standard urea formaldehyde resin in the core layer

Preparation of Resinated Core Layer Chips (for Comparative Examples 17-1*,17-2* and 17-10* and Examples 17-3 to 17-9)

[0553] In a mixer, a mixture of 748 g of Kaurit glue 350 (65% solid content) and 22.4 g of ammonium sulfate was sprayed onto 5.58 kg (5.40 kg dry weight) of spruce core layer chips (moisture content 3.4%) while mixing. Subsequently, 95.0 g of water was sprayed onto the mixture to adjust the final moisture of the resinated chips while mixing. Thereafter, mixing was continued for 3 min.

Preparation of the Resinated Surface Layer Chips (Comparative Example 17-11

[0554] In a mixer, a solution of 42.3 g of HMDA, 154 g of glucose monohydrate and 142 g of fructose in 312 g of water was sprayed onto 5.67 kg (5.40 kg dry weight) of spruce surface layer chips (moisture content 5.0%) while mixing. Thereafter, mixing was continued for 3 min.

Preparation of the Resinated Surface Layer Chips (Comparative Example 17-21

[0555] In a mixer, 84.6 g of Polylysine-2 solution (50 wt.-% in water) was sprayed onto 5.67 kg (5.40 kg dry weight) of spruce surface layer chips (moisture content 5.0%) while mixing. Subsequently, a solution of 154 g of glucose monohydrate and 142 g of fructose in 270 g of water was sprayed onto the mixture while mixing. Thereafter, mixing was continued for 3 min.

Preparation of the Resinated Surface Layer Chips (Example 17-3)

[0556] In a mixer, 486 g of Polylysine-2 solution (50 wt.-% in water) was sprayed onto 5.67 kg (5.40 kg dry weight) of spruce surface layer chips (moisture content 5.0%) while mixing. Subsequently, 162 g of a 1,3-dihydroxyacetone solution (50 wt.-% DHA in water) was sprayed onto the mixture while mixing. Thereafter, mixing was continued for 3 min.

Preparation of the Resinated Surface Layer Chips (Example 17-4)

[0557] In a mixer, a mixture of 486 g of Polylysine-2 solution (50 wt.-% in water) and 162 g of urea was sprayed onto 5.67 kg (5.40 kg dry weight) of spruce surface layer chips (moisture content 5.0%) while mixing. Subsequently, 162 g of a 1,3-dihydroxyacetone solution (50 wt.-% DHA in water) was sprayed onto the mixture while mixing. Thereafter, mixing was continued for 3 min.

Preparation of the Resinated Surface Layer Chips (Example 17-5)

[0558] In a mixer, a mixture of 486 g of Polylysine-2 solution (50 wt.-% in water) and 81 g of urea was sprayed onto 5.67 kg (5.40 kg dry weight) of spruce surface layer chips (moisture content 5.0%) while mixing. Subsequently, 162 g of a 1,3-dihydroxyacetone solution (50 wt.-% DHA in water) was sprayed onto the mixture while mixing. Thereafter, mixing was continued for 3 min.

Preparation of the Resinated Surface Layer Chips (Example 17-6)

[0559] In a mixer, a mixture of 564 g of Polylysine-2 solution (50 wt.-% in water) and 162 g of urea was sprayed onto 5.67 kg (5.40 kg dry weight) of spruce surface layer chips (moisture content 5.0%) while mixing. Subsequently, 84.2 g of a 1,3-dihydroxyacetone solution (50 wt.-% DHA in water) was sprayed onto the mixture while mixing. Thereafter, mixing was continued for 3 min.

Preparation of the Resinated Surface Layer Chips (Example 17-7)

[0560] In a mixer, a mixture of 564 g of Polylysine-2 solution (50 wt.-% in water) and 81 g of urea was sprayed onto 5.67 g (5.40 kg dry weight) of spruce surface layer chips (moisture content 5.0%) while mixing. Subsequently, 84.2 g of a 1,3-dihydroxyacetone solution (50 wt.-% DHA in water) was sprayed onto the mixture while mixing. Thereafter, mixing was continued for 3 min.

Preparation of the Resinated Surface Layer Chips (Example 17-8)

[0561] In a mixer, a mixture of 356 g of Polylysine-2 solution (50 wt.-% in water) and 162 g of urea was sprayed onto 5.67 kg (5.40 kg dry weight) of spruce surface layer chips (moisture content 5.0%) while mixing. Subsequently, 292 g of a 1,3-dihydroxyacetone solution (50 wt.-% DHA in water) was sprayed onto the mixture while mixing. Thereafter, mixing was continued for 3 min.

Preparation of the Resinated Surface Layer Chips (Example 17-9)

[0562] In a mixer, a mixture of 356 g of Polylysine-2 solution (50 wt.-% in water) and 81 g of urea was sprayed onto 5.67 g (5.40 kg dry weight) of spruce surface layer chips (moisture content 5.0%) while mixing. Subsequently, 292 g of a 1,3-dihydroxyacetone solution (50 wt.-% DHA in water) was sprayed onto the mixture while mixing. Thereafter, mixing was continued for 3 min.

Preparation of the Resinated Surface Layer Chips (Comparative Example 17-101

[0563] In a mixer, a mixture of 748 g of Kaurit glue 350 (65% solid content), 14.6 g of ammonium sulfate and 80.0 g of water was sprayed onto 5.67 kg (5.40 kg dry weight) of spruce surface layer chips (moisture content 5.0%) while mixing. Thereafter, mixing was continued for 3 min.

Pressing the Resinated Chips to Chipboards (Comparative Examples 17-1*,17-2* and 17-10* and Examples 17-3 to 17-9)

[0564] Immediately after resination, 452 g of resinated surface layer chips, followed by 1807 g of resinated core layer chips, followed by 452 g of resinated surface layer chips, were scattered into a 56,544 cm mold and pre-pressed under ambient conditions (0.4 N/cm 2). Subsequently, the pre-pressed chip mat thus obtained was removed from the mold, transferred into a hot press and pressed to a thickness of 16 mm to give a chipboard (temperature of the press plates 210 C., max pressure 4 N/mm.sup.2, 96 s or 128 s corresponding to a press time factor of 6 s/mm or 8 s/mm (board thickness was adjusted by two steel spacing strips which were inserted in the press).

TABLE-US-00014 TABLE 11 3-layered chipboards, 16 mm, binder in core layer:Kaurit glue 350 9 wt.-% (solid/dry wood), binder in surface layer as given, binder amount in surface layer (components A1 + B1 + B2):6 wt.-%, binder in surface layer Polymer(s) Weight press A1 or Weight ratio time Internal Formaldehyde comparative DHA ratio A2:(A1 + factor Density bond emission Example component A2 (B1) B2 A1:B1:B2 B1 + B2) [s/mm] [kg/m.sup.3] [N/mm.sup.2] [mg/m.sup.2h] 17-1* HMDA Fru/ 13:0:87 6 655 0.34 4.2 Glu.sup.1) 8 658 0.34 4.4 17-2* Polylysine-2 Fru/ 13:0:87 6 652 0.42 4.3 Glu.sup.1) 8 656 0.43 4.3 17-3 Polylysine-2 DHA 75:25:0 6 665 0.79 1.7 8 666 0.80 1.6 17-4 Polylysine-2 Urea DHA 75:25:0 50:100.sup.2) 6 667 0.85 1.3 8 672 0.90 1.3 17-5 Polylysine-2 Urea DHA 75:25:0 25:100.sup.3) 6 669 0.90 1.5 8 678 0.91 1.4 17-6 Polylysine-2 Urea DHA 87:13:0 50:100.sup.4) 6 663 0.84 1.1 8 665 0.84 1.0 17-7 Polylysine-2 Urea DHA 87:13:0 25:100.sup.5) 6 661 0.80 1.2 8 670 0.81 1.2 17- Polylysine-2 Urea DHA 55:45:0 50: 6 663 0.73 1.6 8 662 0.75 1.5 17-9 Polylysine-2 Urea DHA 55:45:0 25:100.sup.7) 6 664 0.69 1.7 8 664 0.71 1.6 17-10* UF resin (Kaurit glue 350) 8 690 0.87 2.7 9.0 wt.-% (solid/dry wood) *Comparative Examples .sup.1)weight ratio Fructose (Fru):Glucose (Glu) = 50:50 .sup.2)weight ratio of Urea to Polylysine-2 = 40:60 .sup.3)weight ratio of Urea to Polylysine-2 = 25:75 .sup.4)weight ratio of Urea to Polylysine-2 = 36:64 .sup.5)weight ratio of Urea to Polylysine-2 = 22:78 .sup.6) weight ratio of Urea to Polylysine-2 = 48:52 .sup.7)weight ratio of Urea to Polylysine-2 = 31:69 3-layered chipboards with UF-resin in core layer and a binder according to the present invention in the surface layer have a reduced formaldehyde emission. The addition of urea as component A2 further reduces formaldehyde emission. indicates data missing or illegible when filed

Example 18

11 mm Single-Layer Chipboards by Pressing in a High-Frequency Press

Preparation of the resinated chips (Examples 18-1 to 18-71

[0565] In a mixer, an amount x1 of Polylysine-2 solution (50 wt.-% in water) or an amount x2 of a solution of L-Lysine (50 wt.-% in water) as given in Table 12 was sprayed onto 5.56 kg (5.40 kg dry weight) of spruce core layer chips (moisture content 3.0%) while mixing. Subsequently, an amount y of a 1,3-dihydroxyacetone solution (50 wt.-% DHA in water) as given in Table 7 was sprayed onto to the mixture while mixing. Finally, 90 g of water was sprayed onto the mixture while mixing to adjust the final moisture of the resinated chips. After addition of the water mixing was continued for 3 min.

TABLE-US-00015 TABLE 12 Amount of Amount of Amount of Polylysine-2 L-Lysine DHA solution solution solution (50 wt.-% (50 wt.-% (50 wt.-% in water) in water) in water) Example x1 [g] x2 [g] y [g] 18-1 583 64.8 18-2 518 130 18-3 499 149 18-4 454 194 18-5 389 259 18-6 259 389 18-7* 499 149

Preparation of the Resinated Chips (Comparative Example 18-81

[0566] In a mixer, 499 g of a solution of L-Lysine (50 wt.-% in water) was sprayed onto 5.56 kg (5.40 kg dry weight) of spruce core layer chips (moisture content 3.0%) while mixing. Subsequently, an solution of 81.9 g of glucose monohydrate in 157 g of water was sprayed onto to the mixture while mixing. The mixing was continued for 3 min.

Pressing the Resinated Chips to Chipboards in a High-Frequency Press (Examples 18-1 to 18-81

[0567] Immediately after resination, 640 g of the resinated chips were scattered into a 3030 cm mold and pre-pressed under ambient conditions (0.4 N/mm.sup.2). Subsequently, the pre-pressed chip mat thus obtained was removed from the mold. For monitoring a temperature sensor (GaAs chip) was introduced into the center of said pre-pressed chip mat. Nonwoven separators were then provided to the upper and lower side of the pre-pressed chip mat. The pre-pressed chip mat was inserted in a HLOP 170 press from Hoefer Presstechnik GmbH, whereby a birch plywood (thickness 6 mm) was placed between the nonwoven separator and the press plate on each side of the mat. The pre-pressed chip mat was then compacted to 11 mm thickness in the press within a period of 2 s, and then heated by applying a high-frequency electrical field (27.12 MHz, anode current 2.5 A) while the press was remaining closed. When the target temperature 130 C. (HF temperature) was reached in the center of the pressed mat, the press was opened.

TABLE-US-00016 TABLE 13 single-layered chipboards (high frequency press), 11 mm, binder amount (components A1 + B1):6 wt.-% (solids/dry wood), no further components A2, B2, C included Polymer A1 or Weight comparative DHA ratio HF HF Internal 24 h binder (B1) or A1:B1 or temperature time Density bond swelling Example component Glu A1:Glu [ C.] [sec] [kg/m.sup.3] [N/mm.sup.2] [%] 18-1 PL-2 DHA 90:10 130 68 613 0.75 52 18-2 PL-2 DHA 80:20 130 68 616 0.83 42 18-3 PL-2 DHA 77:23 130 69 630 0.94 42 18-4 PL-2 DHA 70:30 130 69 617 0.72 43 18-5 PL-2 DHA 60:40 130 72 614 0.56 47 18-6 PL-2 DHA 40:60 130 73 610 0.19 89 18-7* L-Lysine DHA 77:23.sup.1) 130 82 no board 18-8* L-Lysine Glu 77:23.sup.2) 130 59 no board .sup.1)ratio L-Lysine:B1 is given instead of A1:B1 .sup.2)ratio L-Lysine:Glucose is given instead of A1:B1 *comparative example Glu = Glucose

[0568] Table 13 clearly shows that the internal bond strength as well as 24 h swelling properties improves in case Polymer(s) A1 is used in excess.