WO2004091909A1

WO2004091909A1 - Wooden board laminate

Info

Publication number: WO2004091909A1
Application number: PCT/JP2004/003422
Authority: WO
Inventors: Hyoe Hatakeyama; Shigeo Hirose
Original assignee: Hyoe Hatakeyama; Shigeo Hirose
Priority date: 2003-03-13
Filing date: 2004-03-15
Publication date: 2004-10-28
Also published as: JP4021348B2; JP2006043885A

Abstract

A biodegradable wooden board laminate is disclosed which is excellent in safety and can be produced at low cost. A wooden board laminate composed of at least two wooden boards and a cured resin composition layer interposed between two adjacent wooden boards is characterized in that the cured resin composition is a cured reaction product of a mixture containing (i) a polyol, (ii) a polyisocyanate and (iii) a soluble biodegradable material which is soluble in the polyol and the proportion of the soluble biodegradable material to the cured resin composition is 10-50% by weight.

Description

Memorandum Book Wood Pole Laminate

Technical field

The present invention relates to a biodegradable wooden board laminate, a method for producing the same, and a paste-like adhesive. Background art

BACKGROUND ART A wooden pod laminate in which at least two wooden boards are laminated and bonded with an adhesive layer interposed between two adjacent pods is widely known as a plywood or the like. In such a wooden board laminate, a formaldehyde-containing resin such as a urea resin or a phenol resin is widely used as the adhesive in terms of its adhesive strength and price.

However, since such a resin contains a small amount of free formaldehyde as a raw material, there is a problem that a small amount of the formaldehyde is emitted from the board laminate.

Therefore, in the field of wood board laminates, there is a strong demand for the development of low-priced products that emit no harmful gases such as formaldehyde and have excellent safety.

It is also desirable that the wooden board laminate be biodegradable when it is buried in the soil and disposed of. Disclosure of the invention

The present invention provides a wooden board laminate having excellent safety and biodegradability, which is inexpensive to produce, a method for producing the same, and a paste adhesive used for producing the wooden board laminate. That is the subject.

The present inventors have conducted intensive studies to solve the above problems, and as a result, completed the present invention.

That is, according to the present invention, a wooden board laminate shown below, a method for producing the same, The present invention provides a sheet-like adhesive for producing a porous ply laminate.

(1) A laminate comprising at least two wooden boards and a cured resin composition layer interposed between the two adjacent wooden boards, wherein the cured resin composition comprises: (i) a polyol, ii) a polyisocyanate and (iii) a curing reaction product of a mixture containing a soluble biodegradable substance soluble in the polyol, wherein the proportion of the soluble biodegradable substance in the cured resin composition A wooden board laminate having a weight of 10 to 50 ° / ₀ .

(2) A laminate comprising at least two wooden boards and a cured resin composition layer interposed between the two adjacent wooden boards, wherein the cured resin composition comprises: (i) a polyol, ii) a polyisocyanate, (iii) a curing reaction product of a mixture containing a soluble biodegradable substance (A) soluble in the polyol and (iv) an insoluble biodegradable substance (B) insoluble in the polyol. The total amount of the soluble biodegradable substance (A) and the insoluble biodegradable substance (B) is 10 to 90% by weight in the cured resin composition, and the soluble biodegradable substance (A) Is 10 to 50% by weight in the cured resin composition. / _0. A wooden board laminate characterized by being / ₀ .

(3) The soluble biodegradable substance (A) is composed of at least one selected from the group consisting of ligninsulfonic acid, partially neutralized salt of ligninsulfonic acid, and sugar compounds. The wooden board laminate according to (1).

(4) The method according to (2) to (3), wherein the insoluble biodegradable substance (B) comprises at least one selected from an insoluble lignin-based substance, a plant powder, and a plant short fiber. The wooden board laminate according to any one of the above.

(5) The wood board laminate according to any one of (1) to (4), further comprising a biodegradable fibrous sheet on an upper surface and / or a lower surface of the cured resin composition layer.

(6) The method for producing a woody board laminate according to the above (1), wherein at least two woody boards are heat-treated by interposing a cured resin composition precursor between two adjacent boards. Compression-bonding, wherein the cured resin composition precursor is a mixture of (i) a polyol, (ii) a polyisocyanate, and (iii) a mixture containing a soluble biodegradable substance soluble in the polyol. A pre-cured reaction product, the soluble biodegradable material A method for producing a wood board laminate, wherein the proportion of the substance is 10 to 50% by weight in the precured reaction product.

(7) The method for producing a woody board laminate according to the above (2), wherein at least two woody pods are provided with a cured resin composition precursor between two adjacent pods. Wherein the cured resin composition precursor comprises: (i) a polyol, (ii) a polyisocyanate, and (iii) a soluble biodegradable substance (A) and ( iv) a pre-curing reaction product of a mixture containing the insoluble biodegradable substance (B) that is insoluble in the polyol, and the sum of the soluble biodegradable substance (A) and the insoluble biodegradable substance (B) The amount is 10 to 90% by weight in the precured reaction product, and the ratio of the soluble biodegradable substance (A) is 10 to 50% by weight in the precured reaction product. A method for producing a wooden board laminate.

(8) The soluble biodegradable substance (A) comprising at least one selected from the group consisting of ligninsulfonic acid, partially neutralized salt of ligninsulfonic acid, and a saccharide compound. The method for producing a woody board laminate according to the above.

(9) The insoluble biodegradable substance (B) なる comprising at least one selected from an insoluble lignin-based substance, a vegetable powder and a vegetable short fiber. The method for producing a wooden board laminate according to any one of the above.

(10) The woody material according to any of (6) to (9), wherein the cured resin composition precursor has a biodegradable fibrous sheet on an upper surface and / or a lower surface. Manufacturing method of board laminate.

(11) A paste adhesive used for producing a wooden board laminate, comprising (i) a polyol, (ii) a polyisocyanate, and (iii) a soluble biodegradable soluble in the polyol. A paste for producing a wood board laminate, comprising a pre-cured reaction product of a mixture containing a substance, wherein the ratio of the soluble biodegradable substance is 10 to 50% by weight in the pre-cured reaction product. Glue.

(1 2) A first adhesive which is used when producing a wood board laminate, (i) a polyol, (ii) a polyisocyanate, and (iii) a soluble resin which is soluble in the polyol. A precuring reaction product of a mixture containing a decomposable substance (A) and (iv) an insoluble biodegradable substance (B) that is insoluble in the polyol; The total amount of the decomposable substance (A) and the insoluble biodegradable substance (B) is 10 to 90% by weight in the precured reaction product, and the ratio of the soluble biodegradable substance (A) is A paste-like adhesive for producing a wooden board laminate, which is contained in an amount of 10 to 50% by weight in the precured reaction product.

(13) The method according to (1), wherein the soluble biodegradable substance (A) comprises at least one selected from lignin sulfonic acid, lignin sulfonic acid partially neutralized salt, and a sugar compound. 1) or paste form for the manufacture of a woody board laminate according to (1 2)

(14) The insoluble biodegradable substance (B) comprises at least one selected from an insoluble lignin-based substance, a plant powder, and a plant short fiber.

The paste adhesive for producing a wood board laminate according to any one of (12) to (13). BEST MODE FOR CARRYING OUT THE INVENTION

The woody board used in the present invention includes various conventionally known woody (cellulosic) plate-like bodies such as those made of wood and those made of wood flour. The thickness of the wood board used in the present invention is not particularly limited, but is usually 5 to 30 mm, preferably 9 to 15 mm.

The wooden board laminate of the present invention has a structure in which at least two wooden boards are laminated and bonded between two adjacent boards via a cured resin composition (adhesive) layer. The number of the wooden boards in the wooden board laminate is 2 to 5, preferably 2 to 3. The wooden board laminate of the present invention may be a laminate of two wooden boards, or a plywood obtained by laminating and bonding 3 to 5 veneers (thickness: 0.5 to 3 mm). be able to.

One embodiment of the cured resin composition layer (adhesive layer) interposed between the wooden boards in the present invention includes (i) a polyol, (ii) a polyisocyanate, and (iii) a soluble resin dissolved in the polyol. A curing reaction product of a mixture (X) containing a degradable substance, wherein the proportion of the soluble biodegradable substance is 10 to 50% by weight in the curing reaction product, preferably 10 to 30%. % By weight of the cured resin composition layer. 4 003422

Five

Other embodiments of the cured resin composition layer (adhesive layer) interposed between the wooden boards in the present invention include (i) a polyol, (ii) a polyisocyanate, and (iii) a soluble biodegradable soluble in the polyol. And (iv) a curing reaction product of a mixture (Y) containing an insoluble biodegradable substance (B) insoluble in the polyol, wherein the soluble biodegradable substance (A) and the insoluble The total amount of the biodegradable substance (B) and the curing reaction product is 10 to 90% by weight. /. Wherein the proportion of the soluble biodegradable substance (A) is 10 to 50% by weight, preferably 10 to 30% by weight in the cured reaction product.

Examples of the polyol include ethylene glycol, diethylene diol, triethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentinole glycolone, trimethylone glycolone, glycerin, Low molecular weight polyols such as triethanolamine and sorbitol: Polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and ethylene oxide / propylene oxide copolymers: Polycaprolactone, poly] 3-methyl-δ-butyrolact And polyesters derived from diols and dibasic acids. Other examples include hydroxy group-containing liquid polybutadiene, polypropionate diol, ataryl polyol, castor oil-modified products, and palm oil-modified products.

Examples of the polyisocyanate include aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and modified products thereof. Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate. Net. Examples of aromatic polyisocyanates include, for example, tolylenediocyanate, xylylenediisocyanate, diphenylmethanediisocyanate, polymeric diphenylmethanediisocyanate, triphenylmethanetriisocyanate, tris (isosocyanate). Phenyl) thiophosphate and the like. Examples of the modified polyisocyanate include urethane prepolymer, hexamethylene diisocynate buret, and hexamethylene diisocene. 3422

6

G, trimer, isophorone diisocyanate trimer and the like.

The preferred polyisocyanate used in the present invention is (i) diisocyanate or (ii) a mixture of diisocyanate and a tri- to hexa-valent, preferably tri- to tetra-valent poly-isocyanate. In this mixing, the proportion of the polyisocyanate is a molar amount in terms of diisocyanate, that is, 1 mol of n (n: 3 to 4) valent polyisocyanate is converted into n / 2 mol of diisocyanate (for example, One mole of trivalent polyisocyanate is converted to 1.5 mole of diisocyanate), and is 0.5 to 2 moles, preferably 0.7 to 1.5 moles.

As the soluble biodegradable substance (A) soluble in the polyol used in the present invention, various conventionally known substances can be used. Such compounds include soluble lignin-based substances (lignin sulfonic acid, partially neutralized salts of lignin sulfonic acid), sugar compounds, soluble natural polymers, lignin and polyfunctional prolactone derivatives of saccharide compounds. Included.

The lignin sulfonic acid partially neutralized salt means a lignin substance which has both a sulfonic acid group and a sulfonic acid group and is soluble in a polyol. Lignin sulfonate is a low-cost product that is conventionally produced as a by-product in the sulphite pulp manufacturing process.However, since it is insoluble in ordinary polyols, polyurethane using lignin sulfonate as a raw material is not known. . To date, polyurethanes have been known in which lignin sulfonate is hydroxymethylated to make it soluble in a polyol and incorporated into the molecule. Such polyurethanes are costly and do not make use of the characteristics of inexpensive ligninsulfonate.

When the lignin sulfonic acid salt is partially hydrolyzed with an acid to form a partially neutralized salt, the lignin sulfonic acid partially neutralized salt easily dissolves in the polyol, and the lignin sulfonic acid It has been found that a condensation reaction of a polyol solution containing a solute in a dissolved state with a polyisocyanate results in a biodegradable polyurethane having excellent physical properties containing a ligninsulfonic acid component in a polyurethane molecular chain.

The lignin sulfonic acid partially neutralized salt is obtained by partially hydrolyzing a lignin sulfonic acid salt with an acid or partially cation-exchanging by ionic exchange. And can be obtained by In this case, the lignin sulfonate includes sodium salt, potassium salt, ammonium salt, calcium salt, magnesium salt and the like. The degree of the partial hydrolysis is usually such that the pH of the 5% aqueous solution is 1 to 8, preferably 2.5 to 6, and more preferably 3 to 4 as long as it is soluble in the polyol. Good.

In the partially neutralized lignin sulfonic acid salt used in the present invention, the sulfonic acid group can be partially desulfonated. This desulfonation can be performed before partially hydrolyzing the lignin sulfonate. The desulfonation in this case can be carried out, for example, by subjecting the lignin sulfonate to an oxidation reaction under high pressure and high temperature under alkaline conditions. This partial sulfonation ratio is 5 to 90%, preferably about 10 to 50% of all sulfonic acid groups bound to the lignin substance. Examples of the soluble lignin include sorborsis lignin in addition to the above-mentioned soluble lignin.

The saccharide compounds include molasses, monosaccharides, oligosaccharides, polysaccharides, sugar alcohols, and the like, and any compounds can be used as long as they are soluble in polyol. Such sugar compounds include, for example, gnorecose, galactose, xylose, sucrose, mannose, talose, rhamnose, arabinose, gnorecosinoremannose, lyxose, allose, anoretroses, growth, eose, ribose. , Erythrose, Treose, Psicose, Fnolectose, Sonorebose, Tagatose, Pentzulose, Tetrose, Sucrose, Manolethose, Isomanoletose, Cellobiose, Ratatoose, Trenoloose, Koujibiose, Soholose, Nigerose , Isomaltose, gentiobiose, melibiose, branteobiose, llanoose, visiananose, agarobiose, sylabiose, rutinose, primemeprose, kishi Biose, oral dimenabiose, erythritol, mesoeri tritone, manoletitone, lactitone, D—tray one, D—arabinite one, ribitol, xylitol, sorbitol, galactitol, D—mannitol, aritol In addition to higher alditols and the like, starch, dextran, mannan, pectin, pectic acid, alginic acid, chitosan, (polycaprolactone derivatives of the above sugar compounds) and the like can be mentioned. As the molasses, molasses or molasses is used.

As the insoluble biodegradable substance (B) that does not dissolve in the polyol used in the present invention, various conventionally known substances can be used. Such materials include biodegradable resins (polyester, polylactic acid, etc.) in addition to plant powder containing hydroxy groups and short plant fibers containing hydroxyl groups.

Conventionally known hydroxyl group-containing plant powders include various natural polymer powders such as pulp powder, kraft lignin powder, bagasse powder, wood powder, tea husk powder, coffee bean powder, coffee bean powder, and the like. No. The average particle size of the vegetable polymer powder is from 0.01 to 3 mm, preferably from 0.1 to 2 mm. When the average particle size of the vegetable polymer powder is larger than the above range, the mixing becomes non-uniform, the reactivity with the polyisocyanate becomes poor, and when the average particle size is smaller than the above range, the compressive strength and elastic modulus of the obtained polyurethane complex are reduced. Decreases. Examples of the hydroxy group-containing short plant fiber used in the present invention include natural plant polymer fibers such as cotton fiber, hemp fiber, banana fiber, pulp, wood, and coconut shell fiber. The average thickness of the plant polymer fiber is 0.01 to 2 mm, preferably 0.02 to 1 mm. The length of the fiber is 5 mm or less, preferably 3 mm or less, and its lower limit is about 1 mm. If the size of the vegetable polymer short fiber is larger than the above, the mixing becomes non-uniform, the reactivity with the polyisocyanate becomes worse, and if it is smaller than the above range, the compressive strength and elasticity of the obtained polyurethane composite are reduced. The rate drops.

In the present invention, it is preferable to use a conventionally known urethanation reaction catalyst in order to cause a urethanization reaction between the polyol and the polyurethane. As the urethanation reaction catalyst, a metal-based amine-based catalyst is usually used.

In the present invention, the use of an amine catalyst is preferred. Examples of the amine catalyst include triethylenediamine, bis (dimethylaminoethyl) ether, tetramethylhexamethylenediamine, tetramethylpropane-1,3-diamine, pentamethylmethylenetriamine, and trimethylamino. Ethyl piperazine, 1-methylimidazole, 1-isoptyl-2-methylimidazole and the like. The metal-based urethanization catalyst includes a lead-based tin-based catalyst. Specific examples thereof include, for example, dibutyltin dilaurate and the like. The proportion of the urethanization reaction catalyst used is 0.1 to 5% by weight, preferably 0.1 to 20% by weight in the case of an amine catalyst in the reaction mixture X or the reaction mixture Y described above. In the case of a system catalyst, it is 0.1 to 5% by weight, preferably 0.1 to 2% by weight.

In order to produce the woody board laminate of the present invention, the liquid or paste-like mixture X or mixture Y or a paste-like precuring reaction product thereof (hereinafter referred to as a mixture or the like) is used as a coating adhesive. ) Is applied to one or both bonding surfaces of two wood pods to be laminated and bonded, and the two wood boards are laminated. In this state, the mixture or the like is subjected to a urethanization reaction (a curing reaction). ) In this case, the reaction temperature is 20 to 150 ° C, preferably 50 to 150 ° C, more preferably 60 to 130 ° C. As the reaction pressure, normal pressure or pressurization is adopted.

When the wooden board laminate is manufactured as described above, in order to increase the mechanical strength of the laminate, between one of the two wooden boards to be laminated and the mixture or the like used as an adhesive or It is preferable to interpose a biodegradable fibrous sheet between each of the two boards and the mixture or the like. In this case, a wood board laminate is obtained in which an adhesive layer having the biodegradable fibrous sheet is interposed on the upper surface and / or the lower surface.

The fibrous sheet includes a nonwoven fabric, a woven fabric, a knitted fabric, and the like formed from biodegradable resin fibers. In this sheet, its thickness is 0.05-3 mm, preferably 0:!-2 mm.

The biodegradable resin includes various conventionally known ones, for example, aliphatic polyester and polylactic acid.

In the urethanization reaction, a curing reaction (urethane reaction) between the polyol and the polyisocyanate occurs, and the biodegradable substance (A) or (B) is a substance having a hydroxyl group at the mouth. In addition, a urethanization reaction occurs between those hydroxyl groups and the polyisocyanate. By this curing reaction, a cured resin composition layer is formed between the two boards.

The ratio of the polyisocyanate used is 0.5 to 1.5 times the equivalent number of the isocyanate equivalent to the equivalent number of the reactive hydroxyl groups present in the mixture X or Y. It is preferably 0.7 to 1.3 equivalents. The polyisocyanate is usually present in the mixture X or Y in an amount of 1 to 30% by weight, preferably 5 to 25% by weight.

The mixtures X and Y used in the present invention can be used in a liquid or paste form.

The paste adhesive according to the present invention is preferably a pre-cured reaction product of the mixture X or the mixture Y. The viscosity of the paste-form precuring reaction product varies depending on the degree of the curing reaction. In the case of the present invention, the viscosity may be appropriately selected according to the application operation.

Although the number of boards in the woody-ported laminate of the present invention is two or more, a laminate having three or more boards can also be manufactured in the same manner as described above.

In the woody-pored laminate of the present invention, the cured resin composition layer (adhesive layer) existing between the boards may be a foam layer. In this case, water as a blowing agent may be added to the mixture X or Y in an appropriate amount. Example

Next, the present invention will be described in more detail by way of examples.

Example 1

Molasses polyol (MP) was prepared by dissolving 1 part of molasses in 2 parts of polyethylene glycol 200 (PEG 200). To this MP, coffee bean shell powder (CBP) (particle diameter: about 350 to 710 μπι) was mixed so as to have the CBP content (wt%) shown in Table 1. Further, 0.015 parts of dibutyltin dilate as a catalyst was added to the obtained mixture, and diphenylmethane diisocyanate (MDI) having a weight calculated in advance so that NCOZOH was 1.2 was added. And stirred at a temperature of 30 ° C for about 10 minutes. The mixture thus obtained was a paste-like polyurethane precursor (cured resin composition precursor) and had thermosetting properties.

Next, this polyurethane precursor was interposed as an 8 mm-thick paste-like film between two 1-mm-thick plywood sheets, and the two plywood sheets were placed in the vertical direction. It was hot pressed at a temperature of 120 ° C. for 2 hours under a compressive force of 100 kg gZcm ² .

In this way, a wood panel (wood board laminate) having a total thickness of 1 cm was produced. Table 1 shows the mechanical properties of this wood panel.

The CBP content (wt%) shown in Table 1 is represented by the following equation.

CPP content (wt%) = A / B X 100

A: C B P weight

B: Total weight of CBP weight and MP weight

Example 2

A wood panel was produced in the same manner as in Example 1, except that coffee extraction residue (CG) (particle diameter: about 350 to 70 μιη) was used instead of CBP. This wood panel was manufactured. Table 2 shows the mechanical properties of the obtained wood panel.

Table 2

Example 3

A wood panel was produced in the same manner as in Example 1, except that wood flour (WM, particle diameter of about 150 to 250 μτη) was used instead of CBP. Table 3 shows the mechanical properties of the obtained wood panel. Table 3

Example 4

Example 1 was repeated except that a polylactic acid nonwoven fabric (thickness: 0.5 mm) was interposed between one of the plywood and the polyurethane precursor sheet and between the other plywood and the polyurethane precursor sheet. To make wood panels. Table 4 shows the mechanical properties of this wood panel.

Table 4

Example 5

A wood panel was prepared in the same manner as in Example 4, except that CG was used instead of CBP. Table 5 shows the mechanical properties of the obtained wood panel.

Table 5

CG content (wt¾) 50 60 70 80 90

Density (p) g cm— ³ 0.787 0.793 0.758 0.697 0.586

Compressive strength (h) (MPa) 21.8 44.7 55.6 31.4 4.72

Compression ratio strength

27.8 56.3 73.4 50.0 8.05

, Σ / p) (MPa / g cm

Modulus (E) (GPa) 1.42 3.77 4.12 2.42

Specific modulus

1.80 4.75 5.44 3.47 0.225

(E / p) (GPa / g cm " ³ ) [0 0 4 3]

Example 6

A wood panel was prepared in the same manner as in Example 4, except that WM was used instead of CBP. Table 6 shows the mechanical properties of the obtained wood panel.

6

Industrial applicability

According to the present invention, a wooden board laminate having excellent mechanical properties can be manufactured at low cost. This wooden board laminate is not suitable as the outermost material because it causes deterioration in the performance of interior materials (floor materials, wall materials, etc.) and exterior materials (water infiltration. However, painting the outermost surface is OK. ) Can be widely used. And since this wooden board laminate has biodegradability, it can be buried in the soil after use.

Claims

The scope of the claims

1. A laminate comprising at least two wooden boards and a cured resin composition layer interposed between the two adjacent wooden boards, wherein the cured resin composition comprises: (i) a polyol; ) A polyisocyanate and (iii) a curing reaction product of a mixture containing a soluble biodegradable substance soluble in the polyol, wherein the ratio of the soluble biodegradable substance is 10% in the cured resin composition. A wood board laminate characterized by being about 50% by weight.

2. A laminate comprising at least two wood boards and a cured resin composition layer interposed between the two adjacent wood boards, wherein the cured resin composition comprises: (i) a polyol; ) A polyisocyanate, (iii) a curing reaction product of a mixture containing a soluble biodegradable substance (A) soluble in the polyol and (iv) an insoluble biodegradable substance (B) insoluble in the polyol. The total amount of the soluble biodegradable substance (A) and the insoluble biodegradable substance (B) is 10 to 90% by weight in the cured resin composition, and the soluble biodegradable substance (A ) Is 10 to 50% by weight in the cured resin composition.

3. The method according to claim 1, wherein the soluble biodegradable substance (A) comprises at least one selected from lignin sulfonic acid, a partially neutralized salt of lignin sulfonic acid and a saccharide compound. 2. The woody pode laminate according to item 2.

4. The insoluble biodegradable substance (B) is composed of at least one selected from the group consisting of insoluble lignin-based substances, plant powders, and plant material short fibers. 4. The wooden board laminate according to any one of the above items 3.

5. The woody pod according to any one of claims 1 to 4, wherein a biodegradable fibrous sheet is provided on the upper surface and z or the lower surface of the cured resin layer a.

6. The method for producing a wood board laminate according to claim 1, wherein at least two wood boards are heated by interposing a cured resin composition precursor between two adjacent boards. The cured resin composition precursor is soluble in (i) a polyol, (ii) a polyisocyanate and (iii) a soluble in the polyol. A wood board comprising a pre-cured reaction product of a mixture containing a biodegradable substance, wherein the ratio of the soluble biodegradable substance is 10 to 50% by weight in the pre-cured reaction product. A method for manufacturing a laminate. ·

7. A method for producing a woody board laminate according to claim 2, wherein at least two woody pods are interposed with a cured resin composition precursor between two adjacent pods. Wherein the precursor of the cured resin composition is (i) a polyol, (ii) a polyisocyanate, (iii) a soluble biodegradable substance soluble in the polyol (A) and (iv) It consists of a pre-cured reaction product of a mixture containing an insoluble biodegradable substance (B) that is insoluble in the voryl, and the total amount of the soluble biodegradable substance (A) and the insoluble biodegradable substance (B) is 10 to 90% by weight in the precured reaction product, and the proportion of the soluble biodegradable substance (A) is 10 to 50% by weight in the precured reaction product. A method for producing a wooden board laminate.

8. The soluble biodegradable substance (A), which comprises at least one selected from the group consisting of 1 ligninsulfonic acid, a partially neutralized salt of ligninsulfonic acid, and a saccharide compound. Item 7. The method for producing a wooden board laminate according to Item 7.

9. The insoluble biodegradable substance (II), comprising at least one selected from the group consisting of 1 insoluble lignin-based substance, plant powder, and plant material short fiber. Item 9. The method for producing a wooden board laminate according to any one of items 8.

10. The wood according to any one of claims 6 to 9, wherein the cured resin composition precursor has a biodegradable fibrous sheet on an upper surface and a lower surface or a lower surface. A method for manufacturing a board laminate.

1 1. A paste-like adhesive used when manufacturing a wooden board laminate,

a mixture of (i) a polyol, (ii) a polyisocyanate, and (iii) a pre-cured reaction product of a mixture containing a soluble biodegradable substance soluble in the polyol, and a ratio of the soluble biodegradable substance. Is from 10 to 50% by weight in the precured reaction product.

1 2. A paste adhesive used for manufacturing a wooden board laminate,

(i) a polyol, (ii) a polyisocyanate, (iii) a soluble biodegradable substance soluble in the polyol (A) and (iv) an insoluble biodegradable insoluble in the polyol A precuring reaction product of a mixture containing the substance (B), wherein the total amount of the soluble biodegradable substance (A) and the insoluble biodegradable substance (B) is 10% in the precuring reaction product. To 90% by weight, and the proportion of the soluble biodegradable substance (A) is 10 to 50% by weight in the precured reaction product. Strand adhesive.

13. The method according to claim 11, wherein said soluble biodegradable substance (A) comprises at least one selected from lignin sulfonic acid, partially neutralized salt of lignin sulfonic acid and sugar compounds. Or a paste adhesive for producing a wooden board laminate according to item 12;

14. The insoluble biodegradable substance (B), which comprises at least one selected from the group consisting of 1 insoluble lignin-based substance, vegetable powder and vegetable short fiber.

A paste for producing a woody board laminate according to any one of Items 2 to 13