JPH0457714B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) There is currently a great desire to develop more effective methods of using forest resources, which are renewable resources. In addition, in industries that use wood as raw materials, such as the pulp industry and the wood industry, there is an urgent need to establish methods for effectively utilizing wood waste. In the present invention, wood that has been chemically modified to have plastic properties can easily undergo solvolysis of lignin with phenols and alcohols into aliphatic or aromatic polyhydric alcohols or bisphenols using the presence of a catalyst. , the fact that it dissolves in a high concentration, the fact that the wood component that is made plastic through chemical modification and is present as one of the main components after resinization contributes to increasing the adhesive performance of the adhesive, and furthermore, the above-mentioned dissolving solution The invention was completed based on the discovery that by combining with an α-olefin/maleic anhydride copolymer resin, it can be made into a resin and become an adhesive with excellent properties. The present invention relates to chemically modified lignocellulosic materials such as wood (hereinafter often simply referred to as wood), preferably in the presence of a suitable catalyst.
By processing at a temperature up to 270℃, preferably at a medium temperature of about 80 to 100℃, a high concentration range of 50% by weight or more is increased, and it is dissolved in aromatic or aliphatic polyhydric alcohols or bisphenols, and the necessary The first component obtained by neutralization according to the conditions and glycidyl etherification in the presence of epichlorohydrin and a suitable condensation catalyst, and the second component mainly consisting of an α-olefin/maleic anhydride copolymer resin. The present invention relates to a two-component plasticized lignocellulose/α-olefin/maleic anhydride resin adhesive characterized in that it consists of a combination. In this case, even more desirable results can be obtained when, if necessary, one or more compounds selected from metal hydroxides and metal oxides and styrene-butadiene var latex are present. Therefore, the present invention has a major feature in providing a non-formalin adhesive using wood, and when plasticized wood is heated to 270°C,
It can be easily dissolved in aromatic or aliphatic polyhydric alcohols or bisphenols, and the presence of an acid such as hydrochloric acid or Lewis acid or an alkali such as caustic soda or potash during the dissolution. If appropriate conditions are adopted, solvolysis of lignin, one of the main components in wood, can be partially induced to various degrees, and it is easy to obtain a solution under relatively mild conditions. One of its features is that it can provide such adhesives. At this time, polyhydric alcohols or bisphenols 100
10 to 1000 parts of plasticized wood. In addition, in order to dissolve plasticized wood in aromatic or aliphatic polyhydric alcohols or bisphenols at a high concentration, a mixed solvent of a low boiling point solvent such as methanol or acetone and a polyhydric alcohol or bisphenols is used. By distilling off the former after solvolysis, the concentration dissolved in the polyhydric alcohol or bisphenols can be increased. Another feature of the present invention is that the adhesive action of the adhesive of the present invention is due to the dissolved plasticized wood component. (Prior art) A simple chemical reaction such as esterification or etherification imparts plastic properties to wood, thereby allowing wood and other wood-based raw materials to be used in more advanced and new ways. The attempt to
Already proposed. For example, JP-A-57-103804 and JP-A-56-103804
No. 135552 states that by esterification or etherification,
A technique for introducing organic groups into some or all of the hydroxyl groups of wood has been disclosed, and the plasticized wood obtained in this way can be used as a molding raw material as it is or by mixing it with various synthetic polymer compounds. Are listed. Also, JP-A-57-2360
The issue discloses a technique for preparing a solution consisting of introducing a substituent into some of the hydroxyl groups by esterification or etherification and dissolving the resulting plasticized wood in an organic solvent. The solution can be formed into a film either alone or in the co-dissolution of various synthetic polymer substances;
Furthermore, it is described that it is also possible to fractionate derivatized wood components. In addition, there is a technology in which plasticized wood is dissolved in phenols and the solution is made into a phenol/formaldehyde adhesive, and a phenol/formaldehyde resin adhesive with excellent solution properties that causes phenolysis during the dissolution. Techniques to make adhesives, fibers, and even
We are currently applying for patents regarding the technology for dissolving plasticized wood in aromatic and aliphatic polyhydric alcohols, and the technology for preparing foamed resin products from the resulting solution. (Problem to be solved by the invention) However, conventionally, plasticized lignocellulose/α-olefin/maleic anhydride resin adhesives have lignocellulose such as wood as one of the main components and have excellent solution properties and adhesive performance. has not been proposed so far. Until now, there have been several studies on producing adhesives from lignin, which is one of the wood components, but most of them are related to the production of phenol-homaldehyde resin adhesives, and epoxy resin adhesives. There are only a few examples of its production, and those are from thiolignin, and its performance and
There were many problems with its nature. Proposals regarding epoxidation are based on the production of synthetic epoxy intermediates,
Even in cases where studies have been carried out not only from the perspective of an extender for urea resins, but also to the development of adhesives, the final products have poor solubility and problems with adhesive workability. The object of the present invention is to develop a new two-component plasticized lignocellulose material that has excellent solution properties, workability, and adhesive properties, and which falls within the category of high-grade adhesives.
An object of the present invention is to provide an α-olefin-maleic anhydride resin adhesive. (Means for Solving the Problems) The present invention is achieved by introducing at least one substituent into part or all of the hydroxyl groups to 100 parts of aliphatic or aromatic polyhydric alcohols or bisphenols. 10 to 1000 parts of lignocellulosic material, such as plasticized wood, are added and dissolved using solvolysis, generally at 270°C in the presence of a catalyst such as an acid or alkali that promotes the solvolysis of the lignin. Thereafter, the main components are solvolysed by heating preferably to a medium temperature of about 80 to 100°C, and if necessary, the acid used in the catalyst is neutralized, and then the hydroxyl groups in the obtained plasticized lignocellulose solution are , glycidyl etherification of epichlorohydrin in the presence or absence of a suitable condensation catalyst, such as caustic soda, a quaternary ammonium salt, or a Lewis acid such as _BF3 , and the first component thus obtained; This invention relates to a two-component plasticized lignocellulose/α-olefin-maleic anhydride resin adhesive in combination with a second component mainly consisting of α-offrein amines such as isobutylene and a maleic anhydride copolymer. . The plasticization modification reaction for introducing substituents into wood raw materials is a reaction in which substituents are introduced into at least some of the hydroxyl groups of cellulose, helselurol, or lignin present in the wood raw materials. The type of substituent to be introduced and the reaction for introduction are as follows:
Needless to say, the choice should be made depending on the type and characteristics of the intended lignocellulose resin adhesive. The esterification or etherification reaction of hydroxyl groups is a reaction that can be relatively easily employed to modify lignocellulosic materials such as wood into plastics. For esterification, various acids such as acid halides, acid anhydrides, dibasic acid anhydrides, and fatty acids are used. For etherification, methyl chloride, ethyl chloride,
Halides such as allyl chloride, benzyl chloride, and ethylene chlorohydrin; α-halogen acids such as sodium monochloroacetate and monochloroacetic acid; dialkyl sulfates such as dimethyl sulfate and diethyl sulfate; epoxy compounds such as ethylene oxide and propylene oxide; activated with negative groups such as acronitrile diazomethane; aldehydes such as formaldehyde; and organometallic compounds such as titanium alkylate are used as modifiers. In these reactions, sulfuric acid, perchloric acid, pyridine, zinc chloride, etc. can be used as a catalyst in the former, and an alkali such as caustic soda can be used in the latter. The organic groups to be introduced include fatty acid acyl groups such as acetyl, propionyl, butyryl, and valeroyl groups; dibasic acid monoester groups such as carboxypropenoyl; benzoyl and other aromatic acyl groups; methyl and ethyl groups. lower alkyl groups such as allyl groups; carboxymethyl groups; hydroxyalkyl groups such as hydroxyethyl groups; polyoxyalkylene glycol groups such as polyoxymethylene groups and polyokylethylene glycol groups; benzyl groups, bentyl groups, octyl groups, etc. Preferred are long-chain alkyl groups; cyanoethyl groups; methylene ether groups; and analogous groups. Furthermore, it is also possible to introduce two or more of these organic groups, for example, an acetyl group and a butyryl group. Furthermore, in addition to organic groups, inorganic groups such as nitro groups and organic groups containing atoms other than carbon, hydrogen, oxygen, and nitrogen, such as organometallic groups, may be introduced. The number of substituents to be introduced is not necessarily limited to one type. The exact degree of substitution varies depending on the type of substituent to be introduced, the type of the intended lignocellulose resin adhesive, and the intended adhesive properties. This plastic modification treatment of wood can be carried out according to known methods. Usually, fibrous or powdered wood is treated with a modifier in the presence of a solvent or swelling agent at room temperature or under heated conditions. Wash modified wood thoroughly. For example, it is poured into water or methanol, collected, washed with water or methanol, and then dried if necessary. In producing the lignocellulose resin adhesive of the present invention, in some cases, after washing with methanol, draining the liquid and adding polyhydric alcohol, or washing with methanol and then washing with the polyhydric alcohol. It is also possible to omit the drying process of the modified wood and directly enter the solution process, such as by mixing it with the necessary amount of polyhydric alcohol. According to the research of the present inventor, the plasticized wood obtained by such a reaction is imparted with thermoplasticity to a greater or lesser degree depending on the type and degree of substitution of substituents introduced, and in most cases ,
If at least an appropriate external plasticizer is also used, it will exhibit thermofluidity. In addition, they can improve their solubility and affinity in water, various aqueous solutions, organic solvents, or mixed solvents thereof, and can be improved by selecting a solvent by using severe dissolution conditions such as high temperatures and long periods of time. It can show a state of complete dissolution or close to complete dissolution. In general, substituents with a large molecular volume and a relatively high degree of substitution exhibit greater plasticity. Among the various methods mentioned above, the practical methods for making wood into plastics include acetylation, monoesterification with maleic acid or phthalic acid, ethylation,
These include methylation, carboxymethylation, hydroxyethylation, and allylation. These fall into the category of those in which the substituents introduced are relatively small. In the case of etherification, the degree of substitution is also relatively low, with only 1/3 of the hydroxyl groups in the wood being etherified. In these cases, thermal fluidity is generally quite low and solubility is limited as is. The present invention overcomes this fact and dissolves the above-mentioned practical plasticized wood in polyhydric alcohols or bisphenols and finally converts it into a homogeneous solution with resin as needed. It is used to make adhesives such as oxidation. In preparing the first component of the adhesive of the present invention, a plasticized lignocellulosic material, such as plasticized wood, is first dissolved in an aromatic or aliphatic polyhydric alcohol or bisphenols. By causing solvolysis to occur at least partially on the intramolecular bonds of the main component of plasticized wood, particularly the plasticized lignin segment, and by attempting to cleave various degrees of lignin intramolecular bonds, mild conditions, i.e., It enables easy dissolution at a relatively low dissolution temperature and short dissolution time, easily produces a polyhydric alcohol solution or phenol solution of plasticized wood, improves its solubility, and can be used as an adhesive subsequently. As a result, the solution properties of the adhesive finally obtained are to be better. During its dissolution, polyhydric alcohols or bisphenols are partially introduced into the main component of the plasticized wood, particularly at the alpha position of the lignin side chain, through chemical bonding, which improves the adhesive properties and other properties of the adhesive. work like that. In this description of the present invention, the general term solvolysis or solvolysis is used, and the term alcoholysis or phenolysis is not used later, but this is intended to encompass the effects of polyhydric alcohols or bisphenols. The other reason is that a mixed system of hexanediol or bisphenol A and a certain low-boiling point medium together with a polyhydric alcohol or bisphenol, such as an acetone system, is used. In the present invention, methylated wood, ethylated wood, carboxymethylated wood, hydroxyethylated wood,
When reacting hydroxypropylated wood, allylated wood, acetylated wood, acetylbutylated wood, carboxypropenoylated wood, etc. with polyhydric alcohols or bisphenols, acids such as hydrochloric acid, etc. When carried out under the catalyst of
The intramolecular bonds of lignin, including lignin-carbohydrate bonds, especially benzyl ether bonds, are cleaved, and lignin is partially derivatized, promoting dissolution, and these prosthetic woods are dissolved in polyhydric alcohol or bisphenol solutions. can be obtained. Therefore, it becomes possible to form a resin in a homogeneous phase including the plasticized wood component, making it suitable for producing a lignocellulose-based resinized adhesive. The polyhydric alcohols used in the present invention include ethylene glycol, propylene glycol, and trimethylene glycol as dihydric alcohols;
1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 2,4-hexanediol, 1,
7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, binacol, cyclopentane 1,2-diol, cyclohexane-1,2-diol, cycloxane 1,4-diol , polyoxypropylene glycol, polyoxypropylene-polyoxyethylene glycol, etc., trihydric alcohols such as glycerin, bisphenols such as bisphenol A, bisphenol F, halogenated bisphenol A, etc. Can be done. These polyhydric alcohols or bisphenols may be a mixture of two or more types, or may be a mixture with a suitable vehicle mainly having a low boiling point, such as a monohydric lower alcohol such as methanol or acetone. good. In producing the lignocellulose epoxy resin component in the present invention, dissolution using solvolysis is carried out using a medium, for example, at 80°C.
When carrying out the process at medium temperature, it can be carried out in a container equipped with a cooler. In this case, it can be carried out at a temperature from room temperature to the boiling point of each polyhydric alcohol solution, and the dissolution time depends on other conditions,
Generally, it takes about 15 to several hours. For example, when a catalyst is not used and the dissolution is carried out using solvolysis at a temperature above the boiling point of the polyhydric alcohol or bisphenol solution or about 270°C, it is usually best to carry out the dissolution in a pressure-resistant container. As a result, the dissolution concentration of plasticized wood can range from less than a few percent to 95 percent on a weight basis. In order to cause solvolysis, catalysts that promote solvolysis of lignin, such as mineral acids such as hydrochloric acid, sulfuric acid, trifluoroacetic acid, aluminum chloride, zinc chloride, and Lewis acids such as boron trifluoride, are used. It is particularly suitable to carry out the heat treatment in the presence of the above. It can also be dissolved in the presence of an alkali such as caustic soda. Methylated wood, ethylated wood, allylated wood,
In the case of carboxymethylated wood, hydroxyethylated wood, acetylated wood, etc., when dissolving it in polyhydric alcohol or bisphenols to the above concentration range at about 80℃, dissolve it in polyhydric alcohol or bisphenol. On the other hand, the coexistence of 0.5 to 20% hydrochloric acid is required. 3 to 10% gives particularly good results. Solvolysis occurs in a few minutes to a few hours, and a complete solution is obtained. In the past, it was generally thought that solvolysis of wood required high temperatures, but it is noteworthy that medium temperatures of around 80°C are possible when producing the adhesive of the present invention. . It is particularly suitable to use a reactor such as a kneader as the dissolving device, which is capable of sufficient stirring during dissolution and can also apply torque during the stirring, since it can promote dissolution and ease the solvolysis and dissolution conditions. It is. Also, during dissolution,
It is also possible to mix and dissolve more uniformly by adding an organic solvent such as water or acetone from the beginning or during the process. On the other hand, when a catalyst such as hydrochloric acid is not used, a pressure-resistant container is usually used as a reactor, and the reaction is carried out at a temperature up to about 270°C, preferably with stirring, for about 15 minutes to several hours to dissolve it. For solvolysis, 10 to 1000 parts of lignocellulose material is added to 100 parts of polyhydric alcohol or bisphenol. A low concentration solution can be easily prepared, but as an adhesive using wood components, it is meaningless unless the concentration is around 10%, so the lower limit was set at 10%. The upper limit was set at 1000 parts as a range to obtain an adhesive that is sufficiently meaningful in terms of performance. After the above dissolution operation, the catalyst used during solvolysis is neutralized, if necessary. If caustic soda or amines are used as a catalyst in the next resin formation step, these caustic sodas may be used for neutralization. Furthermore, it is possible to use an acid such as hydrochloric acid as a catalyst for subsequent resin formation, or to recover a catalyst such as hydrochloric acid or trifluoroacetic acid, in which case there is no need for neutralization. The step of converting the first component into a resin is a process in which a polyhydric alcohol or bisphenol solution of the obtained plasticized wood is converted into glycidyl ether. The hydroxyl groups of each component in the plasticized lignocellulose-polyhydric alcohol or bisphenol solution are condensed by adding epichlorohydrin in the presence of an appropriate catalyst if necessary to convert them into glycidyl ethers, thereby producing an epoxy resin. . This process can be carried out according to the conditions for conventional glycidyl etherification of bisphaere A and the like. That is, the necessary catalyst is mainly caustic soda, which is added as an aqueous solution in an amount of about 1.4 mol per mol of hydroxyl group to be glycidyl etherified. Boron trifluoride tetrabenzyl ammonium chloride and the like can also be used. After adding the catalyst, heat it to 45℃ and react to the hydroxyl group.
Immediately add 1.2 molar equivalents of epichlorohydrin with vigorous stirring, warm to 95°C, and
React under stirring for ~100 min. When the product is put into hot water, it separates into two layers, so the aqueous layer containing sodium chloride and alkali is removed with a siphon, and the candy-like product is repeatedly washed with hot water until it becomes neutral. The mixture is heated at ℃ for 3 hours to dehydrate to obtain a plasticized lignocellulose epoxy resin. The plasticized lignocellulose/epoxy resin adhesive component thus obtained is used in combination with an α-olefin maleic anhydride copolymer resin component such as isobutylene when used as an adhesive. The alpha-olefin maleic anhydride resin component to be used in combination with the plasticized lignocellulose epoxy resin component is based on an aqueous suspension of a 1:1 copolymer of alpha-olefin and maleic anhydride. Isobutylene is also preferred as the α-olefin. In this case, one or more metal hydroxides or metal oxides such as calcium hydroxide or calcium oxide may be present as necessary. Furthermore, when styrene-butadiene rubber latex was included, even more suitable results could be obtained. In this case, when mixed with the first component for use, this adhesive will contain the above α-olefin (isobutylene)/maleic anhydride copolymer, metal hydroxide, metal oxide, styrene/butadiene. There are four components: rubber latex and epoxy resin, and the α-olefin/maleic anhydride copolymer swells in water and is bonded to the carboxyl group in the polymer molecule by an alkali such as caustic soda. It dissolves as the sodium salt of the polymer. Then, the Na group is again substituted with another metal by the metal hydroxide or metal oxide suspended in the aqueous polymer solution, and the polymer aggregates as a water-insoluble polymer. In addition, a bonding effect occurs between the polymer and the metal salt through ionic bonding. Then, the epoxy compound having two or more epoxy groups in the epoxy resin component reacts with the carboxyl group of the polymer, causing a cross-linking reaction between the polymers, and water in the suspension is selectively absorbed by the adherend. It is thought that curing and adhesion occur due to several combined effects described below, such as evaporation, which rapidly breaks the suspension and causes aggregation. However, the above description is not intended to limit the scope of the invention. In addition, one or more of secondary amines, polyamide resins, boron trifluoride amine complexes, acid anhydrides, etc. can be further present as required, thereby curing and forming a three-dimensional resin. can help. Suitable examples include diethylenetriamine, triethylenetetramine, N
-Aminoethylpiperazine, diethylaminopropylamine, polyamide resin, imidazole, diaminodiphenylmethane, diaminodiphenyl sulfone, dicyandiamide, _BF3 -monoethylamine, phthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, chlorendican Examples include hydrite, hexamethylene diisocyanate, diphenylmethane diisocyanate, etc. If necessary, when used in combination with a tertiary amine such as triethylamine, epoxy groups can react with each other or accelerate the curing reaction as a whole. You can also do that. When using the adhesive of the present invention, both the first and second components described above are mixed and used in a neutral or alkaline state. In order to further improve the performance of the adhesive of the present invention, various additives can be added before use. For example, reducing the cost of adhesives, reducing thermal swelling, etc.
It is desirable to add a filler to reduce curing shrinkage, suppress heat generation during curing, and improve adhesion. Suitable examples of fillers include inorganic fillers such as crushed stone, sand, silica, talc, fillers such as calcium carbonate, reinforcing fillers such as mica, asbestos, and glass chips, and other fillers depending on the purpose. Quartz powder, graphite, ceramic powder, alumina, silica gel (particularly to impart thixotropic properties), aluminum, aluminum oxide, iron,
Substances that contribute to thermal expansion coefficient, thermal conductivity, and adhesion, such as iron oxide and copper, or substances that provide combustibility, such as antimony oxide, and weight-saving fillers, such as fine plastic powders (phenolic resin, urea resin, etc.) You can add things that have functions as . Additionally, to improve adhesive performance, prepolymer solution adhesives may be supplemented with natural and synthetic polymers, oligomers, low molecular weight plasticizers, and other known additives such as heat and weathering agents, lubricants, etc. , fibrous reinforcing agents, etc.). Examples of polymeric additives used in the adhesive of the present invention include polyamide resins, polysulfide resins, triphenyl phosphite, and in some cases, coal tar. As oligomers, formalin resins such as phenol-formalin initial condensates, low condensation degree alkyd resins, and glycol esters such as polyethylene glycol esters can be suitably used. Examples of low molecular weight plasticizers include phthalic acid diesters such as dimethyl phthalate, aliphatic dibasic acid esters such as adipic acid (2-ethylhexyl), dibutyltin laurate, and rosins. The adhesive of the present invention is used by mixing both components immediately before use and applying the solution or paste to the surface to be adhered. Adhesion conditions such as adhesion temperature, adhesion time, and adhesion pressure can be set according to conditions used in conventional α-olefin/maleic anhydride resin adhesives. That is, depending on the composition, it is possible to heat bond at room temperature or as a composite, and the bonding time varies from several minutes to several hours or even several days, depending on the type of curing agent and the bonding temperature. This adhesive can provide excellent adhesion under low adhesive pressure. Adhesion using the adhesive of the present invention can be suitably carried out by pressing at room temperature, heating with a hot press, or by hot pressure using high-frequency heating, microwave heating, or low-voltage heating. The adhesive of the present invention can be used for wooden building materials, general woodworking,
In addition to being able to be used for bonding wood and other materials,
It can be used to bond various materials including metals, plastics, etc. (Example) Examples will be given below for further explanation. Example 1 (1) Production of methylated wood flour 50 g of dried Macamba wood flour (20 to 60 meshes) was weighed into a reaction flask of a 1-volume simple reaction device, and 500 ml of toluene was added. Next, 40 g of caustic soda was added as a 40% aqueous solution and stirred at room temperature for 1 hour to effect mercerization. Thereafter, 50 ml of methyl iodide is added, the container is sealed, the temperature is raised to 80°C, and the reaction is allowed to proceed for 6 hours. At the end of the reaction,
When the stirring is stopped, the reaction system separates into two layers, so remove the supernatant toluene with a slant, add a mixture of acetic acid and acetone/methanol (3:7 volume), stir, and neutralize and wash. , remove the supernatant. Subsequently, excess acetone is added in the same manner,
Stir and wash twice, collect, air dry, and then
Dry for one day in a blow dryer at 60°C, and finally vacuum dry at 50°C to obtain a sample. The obtained methylated wood flour is in the form of an orange-yellow powder whose appearance has not changed much. The apparent weight increase rate is 8%. (2) Production of epoxy resin adhesive from methylated wood flour 5g of methylated wood flour in a 50ml separable flask
Weigh out 5g of glycerin and stir while stirring.
Add 0.62 ml of a 35% aqueous hydrochloric acid solution (5% of the amount of glycerin if hydrochloric acid is added). Thereafter, the temperature was raised to 80°C, and the mixture was reacted for 2 hours with stirring to form a solution.
Then, attach a cooling tube to the flask and adjust the temperature.
Lower the temperature to 60°C and add 15 ml of epichlorohydrin (3.57 mole of glycerin). While stirring, 0.5 ml of BF ₃ -ether complex salt was added dropwise over 30 minutes, and the mixture was allowed to react for 2 hours. Then, 15 ml of a 30% caustic soda aqueous solution was added dropwise over a period of 10 minutes, and the mixture was allowed to react for 1 hour. The obtained glycidylated compound has a brown viscosity and is liquid at room temperature, with NaCl (sodium chloride) precipitated at the bottom. Therefore, this product was poured into excess distilled water, the top light was removed by tilting it repeatedly, the pH was washed to 7, and the dependent water was removed in a blow dryer at 60°C (overnight). . (3) Adhesion test and adhesion results Epoxy resin adhesive manufactured in (2) and commercially available isobutylene (α-olefin)-maleic anhydride resin adhesive (Kurataku No. 110 Oshika Shinko Co., Ltd.)
), methylated wood, epoxy,
An adhesion test was conducted as an α-olefin/maleic anhydride resin adhesive to examine the adhesive performance. The relationship between the amounts of the two added is that 20 parts of methylated wood flour and epoxy resin are added to 100 parts of α-olefin/maleic anhydride resin, and after blending and mixing thoroughly, veneer (birch wood)
A sample was cut out according to JIS standards to make a 3-ply plywood, and the tensile shear adhesive strength was measured. Adhesion was carried out under two conditions. That is,
Two conditions were used: heat-pressing and curing at 120° C. and 5 kgf/cm ² for 30 minutes, and bonding and curing at room temperature for 6 hours under a pressure of 5 kgf/cm ² . The results are shown in the table below.

[Table] Example 2 (1) Production of methylated wood flour Produced in the same manner as in Example 1 (1). (2) Production of bisphenol A type epoxy resin from methylated wood flour Weigh 8 g of Bisphenol-A, 5 ml of ethanol, and 1 ml of 35% hydrochloric acid aqueous solution into a 50 ml separable flask, mix well, and then add 6 g of methylated wood flour. Add. After being left at 80°C for 1 hour and then stirred for 1 hour, the methylated wood flour was completely dissolved, forming a viscous solution with black strings. A 30% caustic soda solution containing 8 g of caustic soda is slowly added dropwise to the solution to make it alkaline to about PH12. In addition, epichlorohydrin 13
After adding ml, raise the temperature to 95℃ and incubate for 1.5 hours.
Allow to react under stirring. When the resulting yellow-brown reaction solution is poured into excess hot water, it separates into two phases: an aqueous phase containing inorganic salts and alkalis, and a resin phase with a unique luster (metallic luster). The operation of removing the aqueous phase by decanting and pouring it into hot water again is repeated to wash the resin phase until it becomes neutral. Then, heat at 105°C for 3 hours to proceed with dehydration. At this stage, the resin still retains some moisture but is pasty. (3) Adhesion test and adhesion results 100 parts of the epoxy resin adhesive prepared in section (2),
Main ingredient of commercially available isobutylene (α-olefin)-maleic anhydride resin adhesive (Kurataku No. 110
20 parts (manufactured by Ohshika Shinko Co., Ltd.) and 10 parts of Polymeric MDI as a three-dimensional curing accelerator for the adhesive.
Immediately before adhesion, the materials were mixed and adhered in substantially the same manner as in Example 1, and the tensile shear adhesive strength was measured. However, the bonding conditions used were heat pressing at 120° C. and 5 kgf/cm ² for 20 minutes. As a result, the average normal adhesive strength was 25.3 Kgf/cm ² and the adhesive strength after repeated boiling was 12.6 Kgf/cm ² , which was found to meet the standards for JAS Class 1 plywood.

[Claims]

1. To 100 parts of phenols, add 10 to 1000 parts of plasticized lignocellulose material such as wood that has been made into plastic by introducing at least one substituent to some or all of the hydroxyl groups,
After dissolving using solvolysis, formalin containing about 0.7 to 1 mole of formaldehyde is added to 1 mole of the phenol used, and the mixture is reacted under an acid catalyst to produce a novolak resin in the system. A method for producing a plasticized lignocellulose novolac epoxy resin adhesive, which comprises adding epichlorohydrin, condensing the adhesive in the presence of a condensation catalyst, and converting the adhesive into glycidyl ether. 2. The method for producing a plasticized lignocellulose novolac epoxy resin adhesive according to claim 1, wherein the solvolysis with phenols is carried out in the presence of a catalyst that promotes the solvolysis of lignin. 3. The method for producing a plasticized lignocellulose/novolac epoxy resin adhesive according to claim 2, wherein the catalyst that promotes solvolysis by phenols is an acid including a mineral acid or a Lewis acid. 4 Solvolysis with phenols at 270℃

Claims (1)

Sticky lignocellulose/α-olefin
Maleic anhydride resin adhesive. 4. Claim 1, wherein the first component is solvolysis using aliphatic or aromatic polyhydric alcohols or bisphenols in the presence of a catalyst that promotes solvolysis of lignin.
The two-component plasticized lignocellulose/α-olefin-maleic anhydride resin adhesive described in 2.