JPS609737A - Manufacture of laminated board - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Furthermore, the present invention relates to a method for manufacturing a wood-based board with excellent heat resistance, abrasion resistance, etc.

Small pieces of wood, especially wood powder, impregnated or sprayed with a hardening grease liquid are sprinkled on the surface of a plate-shaped base material, a decorative sheet is laminated on top of that, and then the surface is embossed with an uneven pattern. A known method was to apply a plate and heat-press it to create a concave-convex pattern on the surface of the plate-like base material, and then apply a synthetic resin paint to this surface to obtain a laminated decorative board. . This 1-layer decorative board was used for flooring, walling, and furniture. It was a particularly suitable material for applications where the tactility of the feet and three-dimensional decorative properties were desired. However, since wood flour is rigid, it has the disadvantage that the decorative sheet is susceptible to damage such as cracks when carving the uneven pattern. Recently, small pieces of wood such as wood powder have been chemically treated,
Research is being conducted to impart thermoplasticity to small pieces of wood.
The 11th use of wood chips esterified with fatty acids or etherified such as benzylated is considered.
For example, a small piece of wood is immersed in a solution consisting of acetic anhydride, glacial acetic acid, a catalyst, etc. for a certain period of time (R) to obtain acetylated wood piece in which acetic anhydride is added to the hydroxyl groups in the wood through an esterification reaction. Next, a method has been proposed in which the acetylated wood pieces are scattered on the surface of a plate-shaped substrate, and then heated and pressed to form the pieces into one piece to obtain a laminate.

On the other hand, the present inventors discovered esterified wood KTi, in which carboxyl groups were introduced into the wood by reacting polybasic acid anhydrides with small pieces of wood, and after extensive research, found that small pieces of esterified wood containing carboxyl groups, or A compound containing two or more epoxy groups in the molecule is added to a small piece of carboxyl group-containing esterified wood containing unreacted polybasic acid anhydride, and the resulting mixture is thoroughly mixed. It was discovered that a wood-based laminate having favorable properties can be obtained by dispersing it on the surface of a plate-shaped base material and then heating and pressurizing it to form an integral body, leading to the present invention.

That is, in the present invention V, by employing the above manufacturing method, the carboxyl groups in the esterified wood pieces undergo an addition esterification reaction with the epoxy groups in the epoxy compound, and the esterified wood pieces become epoxy. When the main reaction of crosslinking occurs through the compound, and unreacted polybasic acid anhydride is present, and a wood base material is used as the plate-like base material, the surface layer of the wood base material The hydroxyl groups in the wood undergo a ring-opening esterification reaction with the anhydride groups in the unreacted polybasic acid anhydride, and the epoxy groups in the epoxy compound cause an addition esterification reaction to the carboxyl groups in the side chains produced by this. hand,
The surface of the wood-based base material is cross-linked with the esterified wood chips via a polybasic acid anhydride and an epoxy compound, and the laminate obtained by the manufacturing method of the present invention has a tough and durable surface. It is dense and has poor heat resistance, abrasion resistance, etc. Furthermore, depending on the composition of the mixture,
Surprisingly, the laminate of the present invention has small wood pieces made into Φ, and has a dense surface and a shiny plastic-like appearance.

The carboxyl group-containing esterified wood chips used in the present invention are made by reacting wood chips with a polybasic acid anhydride to extract cellulose, hemicellulose contained in the wood tissue,
Carboxyl groups are chemically introduced into small pieces of wood by esterifying hydroxyl groups in chemical components such as lignin.

- Types of small pieces of wood include wood chips, wood fibers, finely ground wood powder, etc., and logs and tree species are particularly susceptible to PHti control.
For example, red pine, cedar, cypress, birch, lauan, etc. are used.

The polybasic acid anhydride used in the present invention is a polyvalent carboxylic acid anhydride, and specifically, maleic anhydride, co-phosphoric anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and tetrabromophthalic anhydride. .

Examples include hexahydrontalic anhydride, 3.6-dichloroheptallic anhydride, 4.5-dichlorophthalic anhydride, itaconic anhydride, hetacetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Particularly preferred are maleic anhydride, phosphoric anhydride, phthalic anhydride, etc., which are industrially advantageous and have low friction.

The esterification reaction between small pieces of wood and a polybasic acid anhydride proceeds satisfactorily even in the absence of a catalyst; however, in order to accelerate the reaction, carbonates, oxides, hydroxides, Carboxylic acid salt or dimethylbenzylamine.

An amine compound such as triethylamine, or a catalyst such as pyridine or dimethylaniline may be used (c).Also, the esterification reaction may be carried out in a solvent such as dimethylformamide or dimethyl sulfoxide; After the reaction, it is necessary to separate the esterified wood pieces from the solvent.The present inventors first added the polybasic acid anhydride directly to the wood pieces in the absence of a solvent, and heated and stirred the mixture at a reaction temperature of 60°C or higher. It has been found that by doing so, the esterification reaction by addition proceeds smoothly, and the polybasic acid anhydride is easily added to the wood pieces to obtain carboxyl group-containing esterified wood pieces having various degrees of esterification.

After the above-mentioned reaction, it is advantageous to use the reaction product as it is, without any washing treatment, as the esterified wood chips used in the present invention. In this case, unreacted polybasic acid anhydride is present in the carboxyl group-containing esterified wood chips. Still after the above reaction, the reaction product is washed,
Dried pieces may be used as the esterified wood pieces used in the present invention. The addition rate of polybasic acid anhydride to the esterified wood pieces is 5 to 120 based on the wood pieces.
The preferred range is 5 to 70% by weight. I cut it,
The amount of polybasic acid anhydride added to a small piece of wood is 5 to 200 kg by weight based on the small piece of wood, and the preferred range is 5 to 8 kg.
It is 0% by weight.

Examples of compounds containing two or more epoxy groups in the molecule used in the present invention include bisphenol-type epoxy compounds obtained from bisphenol A and epichlorohydrin, and novolac-type epoxy compounds obtained from phenolic resin and epichlorohydrin. compound, a halogenated epoxy compound obtained from halogenated bisphenol A and shrimp chlorohydrin, a polyalkylene ether type epoxy compound obtained from polyalkylene glycol and epichlorohydrin, and a polybutadiene double bond with peracetic acid, etc. Other examples include a jepoxidized polybutadiene type epoxy compound, an epoxy compound obtained from diisocyanate and grindol, and a copolymer of a vinyl compound with grindyl acrylate or methacrylate. Particularly preferred are bisphenol-type epoxy compounds that are industrially produced in large quantities and available at low cost.

The amount of these epoxy compounds used is 1 1 of the acid anhydride groups in the mixture.
03 to 2 equivalents of epoxy groups based on the amount of foil, preferably 08 to
It should be 1.2 equivalents.

Examples of plate-like substrates used in the present invention include wood-based substrates, plant fiber-based substrates other than wood-based, gypsum boards, calcium silicate boards, asbestos cement boards, synthetic resin boards, metal plates, etc. It will be done. Wood-based substrates such as veneer, plywood, particle board, fiberboard, etc. are suitable. Furthermore, those in the process of manufacturing these wood-based base materials, such as fiber mats obtained by forming wood fibers coated with an adhesive by spraying, can also be used.

Next, the manufacturing method of the present invention will be explained step by step. First, a preferred method for producing carboxyl group-containing esterified wood pieces obtained by reacting hydroxyl groups in wood with a polybasic acid anhydride will be described, but the present invention is not limited thereto. It is preferable to use the wood pieces by drying them using a vacuum dryer, hot air dryer, etc. to reduce the moisture content of the wood to 5 parts or less. A polybasic acid anhydride is then added to the wood chips, and the mixture is heated to a reaction temperature of 60°C with or without further addition of a catalyst.
Heat and stir at ℃ or below. The reaction proceeds gradually during heating and stirring, but if the reaction temperature is less than 60° C., the addition rate of polyhydrochloric anhydride to the wood chips is extremely small, or there is no addition at all, which is not preferable. Also, reaction temperature 6
In a reaction system in which a catalyst such as sodium carbonate is added at 0° C. or higher, esterified wood chips with a high addition rate of 100% by weight or more can be obtained based on the wood chips. The reaction time is usually 5 minutes to 10 hours, preferably 10 minutes to 7 hours. The degree of esterification can be adjusted by controlling the reaction temperature and reaction time, and the reaction is carried out until a wood piece having a desired degree of esterification is obtained. After the reaction, depending on the type of laminate to be manufactured, one reaction product is washed with acetone, water, etc., and dried. The esterified wood pieces obtained by drying undergo a ring-opening esterification reaction between the hydroxyl groups in the wood and the polybasic acid anhydride, and the polybasic acid anhydride is added to the wood pieces, and carboxyl groups are added to the side chains. It is clear from the analysis results of infrared absorption spectra that this has been introduced. These esterified wood pieces are used as carboxyl group-containing esterified wood pieces used in the present invention. Further, as mentioned above, it is generally advantageous to use the reaction product as it is as the esterified wood pieces used in the present invention without washing the product. In this case, unreacted polybasic acid anhydride is present in the carboxyl group-containing esterified wood chips.

Now, in the present invention, first, the carboxyl group-containing esterified wood pieces prepared as described above or the carboxyl group-containing esterified wood pieces containing unreacted polybasic acid anhydride are added to the carboxyl group-containing esterified wood pieces prepared as described above. Compounds containing two or more epoxy groups are mixed. As the epoxy compound, the above-mentioned bisphenol type epoxy compound is preferred.

As the molecular weight increases, the crosslinking density of the southern resin phase after curing decreases, so those having an average molecular weight of about 200 to 2,000 degrees are usually preferred, and liquid type ones are more preferable.

In some cases, a monoepoxy compound such as phenylglycidyl ether, styrene oxide, epichlorohydrin, etc. may be added as a diluent to lower the viscosity. The curing reaction in the hot press molding of the present invention proceeds with sufficient C without a catalyst, but in order to further stop the curing reaction, catalysts conventionally used in the curing of epoxy resins with polycarboxylic acids or acid anhydrides, such as , metal salts of carboxylic acids, tertiary amines, etc. may be added. In order to further improve the mechanical strength of the obtained laminate, glass fiber was added.
It is still necessary to impart flame resistance... Rogen-containing compound 1
For example, tetrabromobisphenol A1 tetrachlorbisphenol A1 hexachlorobenzene, etc.
Dyes, pigments, etc. may be added at the same time as coloring agents.

The mixture prepared as described above is further uniformly mixed using a mixer such as a vacuum cleaner, a kneader, or a mixing roll. As mentioned above, the esterified wood chips used in the present invention V have an active carboxyl group and have a good affinity for epoxy compounds. The compounds can be dispersed very effectively. Therefore, any desired mixing ratio can be selected for the mixing ratio of the esterified wood chips and the epoxy compound. After mixing, it is preferable to form the mixture into uniform particles. Thereafter, the mixture is sprinkled on the plate surface with or without pre-drying. The time period during which the mixture is spread varies depending on the material and thickness of the plate-like substrate, the appearance of the laminate to be manufactured, and other factors. When the surface of the laminate is flat and has a textured surface, it is sufficient to spread the mixture at a rate of Q3kg/m2 to 15kg/m2, and when carving an uneven pattern, 1.51: !r/m2 or more -1
It is preferable to spray a mixture of -. In addition, if warpage occurs in the laminate due to the curing and shrinkage stress of the mixture after heating and pressing (in this case, apply impregnated paper made by impregnating paper with a liquid of curing resin No. 11 for balance purposes) on the back side of the plate-shaped base material. ,
By integrating the laminated IJ using heating and pressure, it is possible to prevent the laminated board from sticking. In addition, a laminate can be obtained by applying a mixture of the present invention Q or a small piece of wood spray-coated with a curable resin liquid to the back side of a plate-shaped base material and laminating them together by heating and pressing. It can also prevent warping. Next, a smooth interface plate or an embossed plate having an uneven pattern is placed on top of the mixture sprinkled on the surface of the plate-shaped substrate, and heat and pressure are applied for the required time. Further, at this time, a decorative sheet may be laminated on the above mixture depending on the case. The heating and pressing conditions are appropriately set depending on the type of laminate, but are usually a temperature of 100 to 250°C and a pressure of 1.0 kg/crrr2. Perform with pressure above Id. As the temperature of the mixture increases, the aforementioned esterification reaction proceeds.

As mentioned above, the epoxy groups in the carboxyl-to-epoxy compound in the laminated &+d esterified wood pieces obtained by the production method of the present invention undergo an addition esterification reaction, and the esterified wood pieces are cross-linked to form A. In addition, if unreacted polybasic acid anhydride exists and a wood base material is used as the plate-like base material, the hydroxyl groups in the wood in the surface layer may A ring-opening esterification reaction occurs with the hydroxyl group, and the epoxy group in the epoxy compound causes an addition esterification reaction with the carboxyl group of the side chain, and the surface of the wood base material is formed between the polybasic anhydride and the epoxy group. It is cross-linked with esterified wood chips through a compound.

That is, the esterified wood pieces and the esterified wood pieces and the wood base material are chemically integrated with very strong bonding force.

Therefore, the laminate obtained by the manufacturing method of the present invention has a tough and hard surface, and is excellent in heat resistance, R wear resistance, etc.

In addition, when a wood base material is used as the plate-like base material,
In the production of laminated boards, there is no need to apply adhesive to the surface of the wood base material.

In addition, the product "ψa board" obtained by the manufacturing method of the present invention surprisingly has plasticized wood pieces depending on the composition of the mixture, has a dense surface, and has a glossy glass-like appearance. This material can be used as a decorative material.

Furthermore, since the laminate obtained by the manufacturing method of the present invention can use a large amount of wood chips as its raw material, it is inexpensive, lightweight, and has excellent workability.

Therefore, the laminate obtained by the production method of the present invention is suitable as architectural materials such as flooring materials and wall materials, and decorative materials for furniture.

Next, the present invention will be explained in more detail with reference to Examples and Reference Examples. The following refers to the dried product. In addition,
It goes without saying that the present invention is not limited to the examples.

Example 1 Thickness], 5FJII, size 6cm x 66rn, two veneers of red lauan wood were washed with water and further washed with acetone, then dried in a hot air dryer and weighed on their absolute dry weight.
Next, at the center 3L:rn square of these veneer surfaces,
One veneer was treated with 2.0% maleic anhydride, and the other veneer was treated with 2.0% succinic anhydride. After spraying OF, a mirror plate was applied to the front and back of each veneer, and the plate was inserted between the hot plates of a press machine to perform hot press forming.The hot press condition was a temperature of 170℃.
℃ and a pressure of 80 kg/cm" for 40 minutes. After hot-pressing, these two veneers were thoroughly washed with acetone, and then dried in a hot air dryer until completely dry. The weight was calculated.The addition rate of maleic anhydride and succinic anhydride, in which the hydroxyl groups and anhydride groups in each veneer were bonded by causing an ester reaction, was 14.5% for maleic anhydride, based on the dry veneer. Double negative relationship, succinic anhydride is 18
．． It was 8% by weight.

These esterified veneers are produced by a ring-opening esterification reaction between hydroxyl groups in the wood and dicarboxylic acid anhydride.

It was clear from the infrared absorption spectrum analysis results that dicarboxylic acid anhydride was added to the wood and carboxyl groups were introduced into the monocyclic chain.

Reference example 2 Dry main powder of red pine wood that passed through a 24-meter sieve 2 (30,
OF, succinic anhydride/I5. Oy, sodium carbonate 090y as a catalyst was added to a flask and allowed to react at 140°C for 6 hours with stirring. It is 173 [wt%] based on the standard.

After the reaction, the reaction product was taken out and used as the esterified wood pieces used in the present invention without washing.

The addition rate of co-phosphoric anhydride added to the wood flour in this esterified wood flour was 14.3% by weight based on immortality. In this esterified wood flour, the hydroxyl groups in the wood undergo a ring-opening esterification reaction with succinic anhydride, resulting in the addition of co-phosphoric anhydride to the wood flour and the introduction of carboxyl groups into the side chains. It was more obvious from the analysis results of infrared absorption spectrum.

-Hethylated wood flour 149Y obtained by reference example, EPOMIKR139 manufactured by Mitsui Petrochemical Epoxy Co., Ltd.
Diglycidyl ether of bisphenol A with an i of 1.80 to 190 per ethoxy C. Hereinafter, it will be referred to as diglycidyl ether of bisphenol A. ) 407F was added and mixed uniformly with a mixing roll. Thereafter, the mixture was mixed at 80%
After drying in a hot air dryer at ℃ for about 1 hour, it was evenly formed into a specified mold. Next, this mold was inserted between hot plates of a press machine and hot-press molding was performed. Hot press molding conditions are temperature 1.50℃ and pressure 51JE/m immediately after inserting the mold.
After heating and pressurizing for 10 minutes at a temperature of 190°C and a pressure of 15OJrV for 40 minutes under the conditions of theory 2.Deaeration was performed at the initial stage of hot pressing.After hot-pressing, molding was performed from the mold. The board was taken out to obtain a wood-based molded board with a thickness of 6 rm.This wood-based molded board had a wood powder content of 670, a weight-to-weight specific gravity of 1.34, and A, S, TM test 1. The bending strength was 706 kg/cm as a result of a physical property test according to the thrift method.
2. Tensile strength 306 kg/cm”, compressive strength, 1
It is strong at 558 kg/cm2 and has a Rockwell hardness (
M scale) is hard with 110, heat distortion temperature (load 18,
6 kf/lJ) It had excellent heat resistance at 109°C, water absorption rate L06%, thickness expansion rate 0.91%, and water resistance VC1f.

Example 1 Esterified wood flour 1193y obtained by Reference Example 2
Bisphenol A diglycidyl ether/107F
was added and mixed uniformly with a mixing roll. Thereafter, the mixture was dried in a hot air dryer at 80° C. for about 1 hour, and then the mixture was evenly formed onto the surface of a 367-thick lauan core veneer at a spraying amount of 13 kg 7 m 2 . In addition, a polypropylene film with a thickness of 20 microns is attached to the back side of the core veneer to a thickness of Q, 9 as an adhesive.
I applied ZIJ's lauan wood backing veneer in advance.

Next, mirror plates were applied to the front and back sides of the laminate, and the plates were inserted between the hot plates of a press to perform hot-press molding.

The heat and pressure conditions were: temperature 150℃ and pressure 5kg/c during insertion.
After heating and pressurizing for 10 minutes at a temperature of 170° C. and a pressure of 801 g/crn2, the sample was heated and pressurized for 70 minutes. Note that deaeration was performed at the initial stage of hot pressure.

After thermoforming, the obtained laminate of the present invention had a tough, hard, and dense surface, and had a shiny, plastic-like appearance.

Reference Example 4 Dry wood flour of red lauan wood passed through 24 mesh sieves], 1
5.0 y, maleic anhydride 15.1 y, and 2 y of sodium carbonate as a catalyst were added to a separate parapet flask and allowed to react at 1/lO<0>C for 6 hours with stirring. In this reaction system, the amount of maleic anhydride added to the wood flour is 11% by weight based on the wood flour. After the reaction, the reaction product was taken out and used as the esterified wood pieces used in the present invention without washing. The addition rate of maleic anhydride added to the wood flour in this esterified wood flour was 78-car weight based on the wood flour.

Example 2 Esterified wood flour 13 obtained by Reference 1fli 4
Glycerin diglycidyl ether (NOF (
Co., Ltd.) #Epiol a -1,00) 23.2 After adding y, it was mixed uniformly with an ε kissing roll. After drying the preliminary mixture in a hot air dryer at 80°C for about 30 minutes,
Spray the mixture on the surface of lauan plywood with a thickness of 4 mm at an amount L.
Foaming was performed evenly at 4 cg/m2.

Note that impregnated paper, which is made by impregnating melamine resin with kraft paper having a paper weight of 5577 m 2 , was applied to the back side of the plywood 7) in advance. Next, mirror plates were placed on the front and back sides of the laminate, and the laminate was inserted between the hot plates of a press to perform hot-press molding. The heat and pressure conditions were as follows: during insertion, after heating and pressurizing for 10 minutes at a temperature of 150°C and a pressure of 5 kν box, the temperature was further increased to 170°C and a pressure of 80 kg.
/cm2 for 50 minutes under heat and pressure. Note that deaeration was performed at the initial stage of hot pressure. After hot-press molding, the obtained laminate of the present invention had a tough, hard and dense surface, and had a shiny plastic-like appearance.

Reference Example 5 115.0y of dry radiata pine wood powder passed through a 24-mesh sieve, 2L of maleic anhydride and 2j! .

Three portions of sodium carbonate 042y as a catalyst were added to a separable flask and reacted at 140° C. for 6 hours with stirring. In this reaction system, the amount of maleic anhydride charged to wood flour was 184 m-1i- based on wood flour.
%. After the reaction, the reaction product was taken out and used as the esterified wood pieces used in the present invention without washing. The addition rate of maleic anhydride added to the wood flour in this esterified wood flour was 17 and 144 by weight based on the wood flour.

Example 3 Esterified main powder 1457PK obtained according to Reference Example 5
Diglycidyl ether of bisphenol A 42,7 F
was added and mixed uniformly with a mixing roll. After that, the mixture was dried in a hot air dryer at 80°C for about 30 minutes, and then the mixture was sprinkled on the surface of a 75cm particle board. It was evenly formed at t 2.8 kfm2. Next, an embossed plate having an uneven pattern was applied to the surface of the plate, and the plate was inserted between the hot plates of a press to perform hot-press molding. The heat and pressure conditions are 150℃ during insertion.
, after heating and pressurizing at a pressure of 5 kg/ryn2 for 10 minutes,
Next, the mixture was heated and pressurized for 70 minutes at a temperature of 70° C. and a pressure of 100 kg/cm 2 . Note that deaeration was performed at the initial stage of hot pressure.

After hot-press molding, the obtained laminate of the present invention had a tough, hard surface, denseness, and a three-dimensional decorative appearance.

Reference Example 6 Dry wood powder of red pine wood passed through 24 Menonyu sieve 190,0
y1 Succinic anhydride95. 4.00y of sodium carbonate as a medium was added to a separable flask and reacted at 120°C for 25 minutes with stirring.After the reaction, the reaction product was taken out and extracted using a Soxhlet extractor. - After washing with acetone and then washing with water, the pieces were dried in a hot air dryer and used as the esterified wood pieces used in the present invention. The addition rate of anhydrous phosphoric acid was 183 times the weight of wood flour.

Example 4 Esterified wood flour obtained according to Reference Example 6 152.97
Digrindyl ether of bisphenol A: 3
After adding 7 F and dimethylbenzylane 022y as a catalyst, they were uniformly mixed using a mixing roll-c. On the other hand, a solvent-based polyurethane adhesive was applied to the surface of an asbestos cement board having a thickness of 6.0 WJ at a coating amount of 25 y/m, and then the solvent was evaporated using a hot air dryer. Next, the above mixture was evenly formed on the surface of the asbestos cement board coated with the adhesive at a spray rate of 321ζv/m 2 .

Next, an embossed plate having an uneven pattern on its surface was inserted between the hot plates of a press machine to perform hot pressure coloring. The heat and pressure conditions were as follows: upon insertion, the tube was heated and pressurized for 10 minutes at a temperature of 150° C. and a pressure of 51 [v], and then heated and pressurized for 70 minutes at a temperature of 170° C. and a pressure of 100 for 70 minutes.

Note that deaeration was performed at the initial stage of hot pressure. After hot press molding,
The obtained laminate of the present invention had a tough, hard and dense surface, and had a three-dimensional effect and excellent hardening properties.

Reference fl17 2.1 Dry wood powder of red pine wood passed through mesh sieve 190,
OF, phthalic anhydride 285.0 P 1 4.00 y of sodium carbonate as a catalyst were added to a separable flask and reacted at 140° C. for 2 hours with stirring. After the reaction, the reaction product was taken out, washed with acetone using a Soxhlet extractor, and then washed with water. Thereafter, the slurry was dried in a hot air dryer and used as the esterified wood pieces used in the present invention. The addition rate of phthalic anhydride added to the wood flour in this esterified wood flour was 269% by weight based on the wood flour.

Example 5 Diglycidyl ether of bisphenol A 399y was added to the esterified wood flour 15061 obtained in Reference Example 7, and then mixed uniformly with a mixing roll. on the other hand,
Thickness 6. ．． A solvent-based polyurethane sealer was applied to the surface of the 2+173 fiberboard at a coating amount of 20 y/m2 to impregnate the surface layer of the fiberboard, and then the solvent was evaporated using a hot air dryer. Next, sprinkle the above mixture on the fiberboard surface coated with the sealer in an amount of 12
It was leveled at kg/m2. The heat and pressure conditions are temperature 15 during insertion.
After heating and pressurizing for 10 minutes at 0° C. and a pressure of 5 kvcrn2, heating and pressurizing was performed for 80 minutes under the conditions of a temperature of 170° C. and a pressure of 801 g/1yn2. Note that deaeration was performed at the initial stage of hot pressure. After hot-press molding, the obtained laminate of the present invention had a tough, hard surface, denseness, and a shiny plastic-like appearance.

Reference Example 8 Dried chips of red lauan wood used as a raw material for particle board 130. OF, phthalic anhydride 35, ],
7. 0.691 ml of sodium carbonate as a catalyst was added to a separate parapet flask ((() and reacted at 160°C for 6 hours with stirring. Into this reaction system, phthalic anhydride was charged to the chips. The amount is 270% by weight based on the chip.After the reaction, the reaction product is taken out,
The reaction product was used as the esterified wood chips used in the present invention without any washing treatment. The addition rate of phthalic anhydride added to the chips in this esterified chip was 1fi6 weight ratio based on the chips.

Example 6 Esterified chips 71, 7 obtained according to Reference Example 8
y, diglycidyl ether of bisphenol A 232
y was added to the mixture and mixed uniformly using a niegu. after that,
After rolling and operating the mixture in a hot air dryer at 90°C for about 1 hour, the mixture was applied to the surface of a 55 mm thick plywood board in an amount of L 3.
Forming was performed evenly at kp/m2. Next, a boundary plate was applied from the surface, and the material was inserted between the hot plates of a press 7 to perform hot-press molding.

The heat and pressure conditions were: temperature 1.50°C, pressure 5 kg during insertion,
/J for 10 minutes, and then further heated and pressurized for 80 minutes under the conditions of a temperature of 170°C and a pressure of 80 kg/cm 2 . Note that deaeration was performed at the initial stage of hot pressure.

After thermoforming, the obtained laminate of the present invention had a tough, hard, dense, and smooth surface.

Reference Example 9 According to the normal manufacturing method of dry fiberboard, cedar,
Insert the mixed material chip into the digester and increase the vapor pressure to 81 (
After steaming under the conditions of g, /crn2 and a steaming time of 1 minute, fibers in a humid temperature state were obtained by defibrating with a refiner. This fiber was dried in a hot air dryer at a temperature of 90° C. to a moisture content of 5% or less. Next, dry fibers of cedar and cypress mixed materials passed through a 13-mesh sieve 11.5.0
fl, carbonic acid as phthalic anhydride 194y1 catalyst)
l) Ram 0391! 2 were added to a rosette paraple flask and reacted at 160° C. for 6 hours with stirring. In this reaction system.

The amount of phthalic anhydride added to the fiber was 169% by weight based on the fiber.

After the reaction, the reaction product was taken out and used as the esterified wood pieces used in the present invention without washing. The addition ratio of phthalic anhydride added to the fiber in this esterified fiber was 1/1, which was 11.7 layers based on the t-fiber. , Example 7 Esterified fiber 120 obtained according to Reference Example 9
．． 0y, diglycidyl ether of bisphenol A 2
6.5 F was completely added and mixed uniformly with a mixing roll. Then, dry the mixture with hot air at 90°C and dry it in a mortar for about 1 hour.
After the leaves had turned over for a while, the mixture was evenly formed on the surface of a 55" thick plywood board at a spraying rate of 2.81ζg/m2. Next, an embossed plate having a concavo-convex pattern was placed on the surface of the plate, and the plate was inserted between the hot plates of a press to perform hot-press molding. The heat and pressure conditions during insertion were a temperature of 150°C and a pressure of 5 ky.
After heating and pressurizing for 10 minutes in Theory 2, heating and pressurizing was then performed for 80 minutes at a temperature of 170° C. and a pressure of 100 and 5 c/cm 2 .

Note that deaeration was performed at the initial stage of hot pressure. After hot press molding,
The obtained laminate of the present invention had a tough, hard surface, denseness, and excellent cosmetic properties with a three-dimensional effect.

Patent applicant: Okura Industries Co., Ltd. Agent: Mi Ogawa

Claims (2)

[Claims] (1) A carboxyl group-containing esterified wood piece obtained by reacting a polybasic acid anhydride with a hydroxyl group in wood, or a carboxyl group-containing esterified wood piece containing an unreacted polybasic acid anhydride, has molecules. A compound containing two or more epoxy groups is added thereto, and the resulting mixture is thoroughly mixed, and the resulting mixture is sprayed onto the surface of a plate-shaped base material, and then heated and pressurized to form an integral piece. The manufacturing method of the special board. (2) A method for manufacturing a laminate according to claim 1, wherein a wood base material is used as the plate-like base material.