JPS60206883A - Production of adhesive - Google Patents

Abstract

PURPOSE:To produce an adhesive having excellent bond strength and water resistance after application, by adding a lignocellulose material to a phenol to effect phenolysis, adding a specified compd. thereto and heating the mixture to resinify it. CONSTITUTION:10-100pts. lignocellulose material (e.g. wood lignocellulose material obtd. by introducing at least one substituent into at least part of OH groups of cellulose, hemicellulose and lignin in wood to convert it into a plastic) is added to 100pts. phenol (e.g. p-cresol). The mixture is heated in the presence of an acid catalyst at 250 deg.C or below to effect phenolysis. A compd. selected from among formalin, paraformaldehyde and hexamethylenetetramine is added to the phenolysis product, and the mixture is heated at 60-100 deg.C to resinify it.

Description

[Detailed Description of the Invention] (Background and Summary of the Invention) There is currently a strong desire to develop a more effective method of utilizing forest resources, which are renewable resources. Also,
In industries that use wood as raw material, such as the pulp industry and the wood industry,
There is an urgent need to establish ways to effectively utilize wood waste.

This was based on the discovery that phenols dissolve easily and in high concentrations, and that this solution is an excellent adhesive with sufficient adhesive strength and water resistance after bonding. It was completed by discovering that it has certain properties.

The present invention preferably comprises chemically modified lignocellulosic materials such as wood (hereinafter simply referred to as wood) in the presence of a suitable catalyst at temperatures up to 2501:
By processing at a medium temperature of about 0°C, it is dissolved in two phenols, including a high concentration range of 50% by weight or more, and generally after neutralizing this, formalin or hexamethylenetetramine is added to this solution. The present invention relates to a method for producing a gnocellulose phenolic resin adhesive for making into plastic, which is characterized by adding a catalyst for polyaddition and condensation as necessary and heating to advance the resin formation.

The present invention relates to a method for producing adhesives using wood, and in particular, when dissolving plasticized wood in phenols, an appropriate catalyst such as hydrochloric acid is used as necessary to dissolve the main component in the wood. It is characterized by partially inducing lignin phenolysis, which is one type, to various degrees, and obtaining a solution under relatively mild conditions. At this time, 100 parts of phenol can be mixed with plasticized wood in a wide range of 10 to 1000 times the amount.

Moreover, these adhesives can be made into adhesives that are particularly endowed with adhesive water resistance by adding suitable crosslinking agents and catalysts immediately before use.

(Prior art) Attempts to impart plastic properties to wood through simple chemical reactions such as esterification or etherification, thereby attempting to utilize wood-based raw materials including wood in new and more sophisticated ways. Attempts have already been proposed.

For example, JP-A-57-103804 and JP-A-56-1
No. 35552 discloses a technique for introducing organic groups into some or all of the hydroxyl groups of wood by esterification or etherification, and the plasticized wood obtained in this way can be used as is or with various synthetic polymers. It is described that it can be mixed with a molecular substance and used as a molding raw material.

In addition, in JP-A-57-2360, some of the hydroxyl groups,
A technique for preparing a solution consisting of introducing a substituent by esterification or etherification and dissolving the obtained plasticized wood in an organic solvent is disclosed, and the prepared solution can be used alone or with various synthetic polymers. It is described that it is possible to form into a film while co-dissolving molecular substances.

In addition, we are currently applying for patents for a technology that involves dissolving plasticized wood in phenols and using the solution as an adhesive, as well as a technology for turning it into fibers.

However, in these methods, when plasticized wood is dissolved in phenols at a high concentration,
For example, in the case of phenol, 50 to 60
After mixing at a temperature of about 5 to 1 hour, transfer to a reactor equipped with a reflux device or a pressure vessel, and stir at a high temperature of 200 to 250 degrees Celsius for several hours, or alternatively, mix it in a pressure vessel from the beginning.
High temperature (for phenol, e.g. 23 (1-270
°C) Requires stirring for several hours under heating. However, in the case of adhesives, it is not necessary to completely dissolve them in the phenolics used for plasticized wood;
Although kneading for 5 to 2 hours at a medium temperature of about 120° C. may be sufficient, the viscosity and solubility of the final adhesive liquid may not necessarily be sufficiently suitable as an adhesive.

(Object of the invention) The object of the present invention is to produce plasticized IJ with excellent solution properties.
How to obtain gutsu cellulose phenolic resin adhesive,
Another object of the present invention is to provide a method for imparting strong adhesive water resistance to the adhesive.

(Structure of the Invention) The present invention involves adding 10 to 1000 parts of lignocellulose material such as wood, which has been made into a plastic by introducing at least one substituent to some or all of the hydroxyl groups, to 100 parts of phenols. In this case, in the presence of a catalyst such as an acid that basically promotes the phenolysis of lignin, the main component is phenolysed by heating to a medium temperature of 250 degrees or less, preferably around 80 degrees Celsius, and if necessary, the above-mentioned catalyst is heated. After neutralizing the acids used, formalin, paraformaldehyde, or hexamethylenetetramines are added, and if necessary, a polymerization catalyst is added.
The present invention relates to a method for producing a gnocellulose phenolic resin adhesive that is made into a plastic, which is characterized by proceeding with the process of making the resin through a heating reaction.

In the process of dissolving plasticized lignocellulose materials such as plasticized wood into phenols in the first step, phenolysis of the intramolecular bonds of the main component of plasticized wood, especially glassy lignin, occurs simultaneously, and the lignin molecules By measuring various degrees of cleavage of internal bonds and performing dissolution under mild conditions, that is, relatively low dissolution temperature and short dissolution time, a phenolic solution of plasticized wood can be easily prepared and finally obtained. To improve the solubility of an adhesive liquid and to make its workability appropriate.

Before use, the adhesive produced according to the present invention can be added with a crosslinking agent and a catalyst for accelerating the crosslinking reaction to improve the water resistance and weather resistance of the adhesive.

Glue cellulose materials as starting materials for the production process according to the invention are typically wood chips, wood flour, blasted pulp or mechanical pulp. There are no restrictions on the type of wood, and it can be applied to any type of wood.

The plastic 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, hemicellulose, or lignin present in the wood raw materials.

Types of substituents to be introduced and reactions for introduction.

Needless to say, the choice should be made depending on the desired characteristics of the adhesive. Esterification or etherification of hydroxyl groups is a reaction that can be easily adopted.

For ester ratios, various vinegars such as acids, halides, acid anhydrides, and fatty acids are used; for etherification, halides such as methyl chloride, ethyl chloride, benzyl chloride, and ethylene chlorohydrin; sodium monochloroacetate; monochloroacetic acid, etc. α-Norogenic acid; Dimethyl sulfate, diethyl sulfate, and other dialkyl sulfates Epoxy compounds such as ethylene oxide and propylene oxide; Vinyl compounds activated with negative groups such as acrylonitrile; Diazomethane; Aldehydes such as formaldehyde; Organometallic compounds such as titanium alkylate etc. are used as modifiers.

In addition, in these reactions, sulfuric acid, perchloric acid, pyridine, zinc chloride, etc. can be used as alkaline catalysts in the former, and hydrogenated soda can be used in the latter.

Suitable examples of organic groups to be introduced include aliphatic acyl groups such as acetyl, glopionyl, butyryl, and valeroyl groups; benzoyl and other aromatic acyl groups; and lower alkyl groups such as methyl and ethyl groups; Methyl group; Hydroxyalkyl group such as hydroxymethyl group and hydroxyethyl group; Polyoxyalkylene glycol group such as polyoxymethylene group and polyoxyethylene glycol group; Benzyl group; Long chain alkyl group such as pentyl group, octyl group, and dodecyl group ; a cyanoethyl group; a methylene ether group; and analogous groups. Furthermore, it is also possible to introduce two or more of these organic groups, such as an acetyl group and a butyryl group.

In addition to organic groups, inorganic groups such as nitro groups,
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 appropriate degree of substitution varies depending on the type of substituent to be introduced and the desired properties of the adhesive.

This plasticization modification treatment of wood can be carried out according to known techniques. Usually in the presence of a solvent or swelling agent,
Fibrous or powdered wood is treated with a modifier 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.

According to the research of the present inventor, the plasticized wood obtained by such a reaction is given thermoplasticity depending on the type and degree of substituent introduced, and in many cases, thermoplasticity is dependent on the type and degree of substituent introduced. At the same time, the solubility and affinity for water, various aqueous solutions, organic solvents, or mixed solvents thereof have been improved, and if severe dissolution conditions such as high temperatures and long periods of time are adopted, solvents can be dissolved. Depending on the selection, it is possible to exhibit a completely dissolved state or a state of near-complete dissolution.

To explain in more detail, wood has main components (cellulose,
Hemicellulose, lignin) all have reactive hydroxyl groups. therefore.

When converting wood into plastic, all types of hydroxyl group reactions can be considered, resulting in an enormous number of reactions. However, if a relatively large substituent is introduced at that time, the wood will even flow due to heat and pressure, and will be molded into a transparent film. Considering the scope of fatty acid esterification, wood exhibits thermal fluidity with fatty acid acylation that is greater than butyrylation.

Etherification, such as benzylation, results in very good thermal fluidity and can be formed into transparent films. Those with good thermal fluidity also have good solubility in solvents.

However, practical plasticization methods include acetylation,
This is the case when the molecular volume of the substituent is relatively small, such as carboxymethylation or hydroxyethylation. In the case of etherification, the degree of substitution is also relatively low, to the extent that + of the hydroxyl groups in the wood are etherified. In this case, their thermohydrolytic decomposition properties will be low.

The present invention overcomes this fact by causing phenolysis of mainly the lignin segment of plasticized wood during the dissolution process of plasticized wood into phenols, thereby significantly promoting dissolution. Dissolution,
This was completed based on the inventor's new knowledge that it can be easily carried out at a lower temperature and in a shorter time.

Phenols are a type of solvolysis, and the present invention utilizes phenolysis of the lignin fraction in plasticized wood. Acetylated wood, acetyl-butylated wood, carboxymethylated wood, hydroxyethylated wood, hydroxyethylated wood, etc. are examples of phenols and their aqueous solutions.

When reacted in the presence of a catalyst such as an acid such as hydrochloric acid.

Lignin and lignin intramolecular ether bonds, especially benzyl ether bonds, including carbohydrate bonds; are cleaved and lignin is eluted as a phenol derivative. Therefore, by phenolysis of carboxymethylated wood flour, etc., the ether bonds within the lignin molecule can be partially severed and its solubility in phenols can be improved, so it can be used in the production of solution-type reactive adhesives. be able to. As a result, the adhesive finally obtained has poor melting properties.

The degree of progress of phenolysis varies depending on the type of phenol used, the method of preparing plasticized wood, the type of substituent group introduced into the wood, the degree of substitution, etc.
The solubility will also be different, and the solution physical properties of the final adhesive will be different, resulting in adhesives exhibiting various solution physical properties.

Also, depending on the type of plasticized wood, organic solvent-soluble adhesives and water-soluble adhesives can be prepared respectively.

Phenols as used in the present invention is a general term for compounds in which hydrogen atoms bonded to benzene rings, naphthalene rings, and other aromatic rings are substituted with hydroxyl groups, including phenol as a -valent phenol, 0-cresol, Examples include m-cresol, p-cresol, 3.5-xylenol, 2,3-xylenol, α-naphthol, etc., divalent phenols such as catechol and resorcinol, and trivalent phenols such as phloroglucin.

A mixture of these phenols may also be used.

The phenolysis in the production method of the present invention can be sufficiently carried out in a container equipped with a cooler. The appropriate melting temperature range is from room temperature to 250°C, and the melting time is from about 15 minutes to several hours, although it largely depends on other conditions.

As a result, the dissolved concentration of plasticized wood can range from less than a few inches to 95% on a weight basis.

The conditions for causing phenolysis include heat treatment in the presence of a catalyst that promotes lignin phenolysis, such as mineral acids such as hydrochloric acid, sulfuric acid, and trifluoroacetic acid, and acids such as Lewis acids such as aluminum chloride and zinc chloride. It is to give. Depending on the type of phenol or plastic processing, a catalyst may not be necessary.

In the case of acetylated wood, carboxymethylated wood, hydroxyethylated wood, etc., when dissolving it in phenol to the above concentration range at about 80°C, it is necessary to coexist with 0.5 to 20% hydrochloric acid based on the phenol. However, a complete solution can be obtained within minutes to hours with phenolysis.

When dissolving in resorcinol, 100-200℃
Therefore, a good solution can be obtained without particularly requiring an acid catalyst. - Using sulfuric acid as a catalyst, using an acetic anhydride-acetic acid system at 50°C or less,
Even if acetylated wood obtained by acetylation is thoroughly washed after the reaction, sulfuric acid tends to remain as sulfuric acid bound to cellulose in the wood, which acts as a catalyst for phenolysis during the dissolution process. . For example, acetylated wood obtained by acetylation and thorough washing using the same acetic anhydride-acetic acid as the acetylating agent and sulfuric acid or perchloric acid as the catalyst, respectively, is mixed with 1 equal weight of phenol. When heated to 250°C and left for about 30 minutes, acetylated wood using sulfuric acid as a catalyst becomes a viscous and complete solution, whereas wood acetylated using perchloric acid as a catalyst only swells. , which is far removed from the solution. The latter alcohol (including partially saponified products), vinyl polymers such as polymethyl methacrylate and polyvinyl chloride, copolymers such as ethylene vinyl acetate copolymer, polyamides such as nylon 6, and thermoplastic polyesters such as polyethylene terephthalate. , polycarbonates, polyethers, epoxy resins, etc., and mixtures thereof, among which, in particular,
Polyvinyl acetate, polymethyl methacrylate, ethylene-vinyl acetate copolymer, ethyl acrylate-methyl methacrylate copolymer, cellulose nitrate, etc. have good affinity and miscibility with plasticized wood, and can improve adhesion. It can be suitably used.

As oligomers, phenol-formalin initial m
Compound, resorcinol-formalin? Formalin resins such as 7J period condensates, low condensation degree alkyd resins, and glycol esters such as polyethylene glycol esters can be suitably used.

In these cases, the aqueous solution is mixed with the plasticized wood-phenolic formalin resin initial shrinkage solution.

Examples of low molecular weight plasticizers include phthalic acid diesters such as dimethyl phthalate, and di(2-ethylhexyl adipate).
These include aliphatic dibasic acid esters, phosphoric acid triesters, epoxy compounds such as epoxy fatty acid esters, and polyesters.

These crosslinking agents, catalysts, reaction promoters, etc. are usually added before the adhesive is used.

The adhesive obtained in the present invention is usually in the form of a solution or paste, and is used by applying it to the surface to be bonded. It is also possible to insert the adhesive into the adhesive surface and perform heat-pressure bonding.

Adhesion using this adhesive can be appropriately achieved by heating with a hot press, high frequency heating, microwave heating, or heat pressure using low voltage heating.

The adhesive produced according to the present invention can be used not only primarily for wooden building materials, but also for general woodworking, for adhesion between wood and other materials, and even for adhesion between other materials. Wooden building materials do not require neutralization with plywood or particulate materials.

In the second step of the present invention, a reagent that can react with phenols to form a polymer, such as formalin, paraformaldehyde, hexamethylenetetramine, etc., is added to the phenol solution of the obtained plasticized wood, and if necessary, a catalyst is added. In addition, it is a process in which a resin formation reaction is carried out at a temperature of, for example, 60 to 100° C. or higher for a predetermined period of time to obtain a prepolymer having physical properties suitable for use as an adhesive.

This second step can be carried out according to the conventional conditions for obtaining a phenolic resin initial condensate, and the same conditions vary depending on the type of phenol, the substance to be reacted with it, and the like. For example, when making an aqueous solution phenol formaldehyde resin initial condensate, an alkali such as sodium hydroxide must be used, when making a phenol hexamethylenetetramine resin, no catalyst or an acid catalyst must be used, and when making a resorcinol/formalin resin, no catalyst must be used. is also possible.

In order to improve the performance of the adhesive obtained according to the invention, various additives can be added before use.

In particular, by adding a crosslinking agent, the adhesive can be given desired adhesive water resistance and weather resistance. However, in the case where this crosslinking agent is not added, it is not impossible to obtain an adhesive having water resistance and weather resistance. If the amount of formalin is appropriately selected, a water-resistant and weather-resistant bond can be obtained.

Examples of crosslinking agents that can be used include polyvalent isocyanate compounds such as diisocyanate compounds, polyvalent glycidyl compounds such as diglycidyl compounds, and polyvalent epoxy compounds such as general jepoxy compounds. During this process, an appropriate amount of a catalyst or reaction accelerator is added, if necessary.

Additionally, to improve adhesive performance, prepolymer solution adhesives may be supplemented with natural and synthetic polymers, oligomers, low molecular weight plasticizers, and other conventionally known additives such as heat and weathering agents. , lubricant, fibrous reinforcing agent, filler,
(shading agent) etc. can be added.

Examples of polymer additives include natural polymers such as cellulose acetate, polyvinyl acetate, polyvinyl alcohol (including partially saponified products), vinyl polymers such as polymethyl methacrylate and polyvinyl chloride, and ethylene-vinyl acetate copolymers. Copolymers, polyamides such as nylon 6,
Examples include thermoplastic polyesters such as polyethylene terephthalate, polycarbonates, polyethers, epoxy resins, etc., and mixtures thereof, but especially polyvinyl acetate, polymethyl methacrylate, ethylene-vinyl acetate, etc. Polymers such as ethyl acrylate-methyl methacrylate copolymer and cellulose nitrate have good affinity and miscibility with plasticized wood, and are preferably used to improve adhesion.

As oligomers, formalin resins such as phenol-formalin initial condensates and resorcinol-formalin initial condensates, low condensation degree alkyd resins, and glycol esters such as polyethylene glycol esters can be suitably used.

In these cases, the aqueous solution is mixed with a solution of a plasticized wood-phenolic formalin resin initial condensate.

Examples of low molecular weight plasticizers include phthalic acid diesters such as dimethyl phthalate, and di(2-ethylhexyl adipate).
These include aliphatic dibasic acid esters, phosphoric acid triesters, epoxy compounds such as epoxy fatty acid esters, and rotas.

These crosslinking agents, catalysts, reaction promoters, etc. are usually added before the adhesive is used.

The adhesive obtained in the present invention is usually in the form of a solution or paste, and is used by applying it to the surface to be bonded. It is also possible to insert the adhesive into the adhesive surface and perform heat-pressure bonding.

Bonding using this adhesive can be suitably carried out by heating with a hot press, high frequency heating, microwave heating, or heat pressure using low voltage heating.

The adhesive produced according to the present invention can be used not only primarily for wooden building materials, but also for general woodworking, for adhesion between wood and other materials, and even for adhesion between other materials. Wooden building materials refer to wood building materials such as plywood, particle board, and fiberboard that are formed using adhesives, and are for general woodworking.

Refers to the bonding that takes place during the manufacture of furniture, cabinets, boxes, and the like.

Examples will be given below for further explanation.

Example 1 (1) Preparation of carboxymethylated wood flour Macamba wood flour (
, 20-60 mesh) as a raw material, and a conventionally known standard solvent method (Method) using isopropanol as a medium.
s in Carbohydratechemistr
y” VOl, 1.p, 322 AcademicP
Carboxymethylated wood flour was prepared using the following method (refer to Res. (1963)). At that time, the standard was that the weight ratio of wood flour and monochloroacetic acid was 5 = 6, and as described later, the amount of the latter was expressed as % or ρ, and carboxymethylated wood flour was prepared. I also did

(2) Weigh out phenolysed phenol 5yk of carboxymethylated wood flour into a 50 ml round bottom flask,
The temperature is raised to 50-60°C to melt it. Add 1.7111eY of 35% hydrochloric acid aqueous solution to this and mix uniformly. Next, carboxymethylated wood flour 5y was added and left at 80° C. for 1 hour, followed by stirring for 30 minutes. At the end of the process, the carboxymethylated wood is dissolved into a black viscous solution.

(3) Production of phenol/formalin resin adhesive solution from phenolyzed carboxymethylated wood flour. To the phenol solution of phenolyzed carboxymethylated wood flour as described above, a 50% aqueous solution of caustic soda was added to adjust the pH to 9. After that, 6.51 g of 35% formalin was added, and methylolation and partial cocondensation reactions were carried out at 80 to 90°C for 3 hours with stirring to obtain carboxymethylated wood.
An aqueous solution of a phenol-formaldehyde resin initial condensate was obtained. Here, 50% caustic soda aqueous solution was added to adjust the pH to 11, and the mixture was stored at room temperature.

The solution properties such as viscosity of the obtained adhesive liquid are very similar to those of commercially available phenolic resin adhesives. Therefore,
In order to achieve good adhesion, it is necessary to increase the viscosity, here during gluing.

10 parts of wheat flour was mixed with 100 parts of this adhesive.

(4) Adhesion test method and adhesion results Adherent material wood test piece Niha, 30B(L)X251B(R)
A birch straight-grained test piece of x10 (T) was used.
) x 25m (R) surface was used as the adhesive surface. The amount of application is 320
~370y/rI? , hot plate temperature 170℃, clamping force 15
klp/crl, and heat pressure time was 25 minutes. At that time,
The specimen thickness was 1crn, and the actual temperature of the adhesive layer became a problem.As a result of inserting a thermocouple into the adhesive layer and actually measuring it, it was found that when using the above hot plate temperature of 170℃, the temperature of this type of phenolic resin It was found that it takes 20 minutes for the adhesive layer to reach the temperature of 130°C required for curing! In that sense, the above conditions correspond to the conditions of heat pressure at 130° C. for 5 minutes in the case of adhesion of veneers. This point was also confirmed by actually measuring the temperature of the adhesive layer using a veneer.

After adhesion, the specimen temperature was lowered to room temperature by cold pressing (15 Kf/crl), and the adhesion test method was completed. Adhesion test is JIS-
Perform a compression shear test in accordance with LK-6'852,
Adhesive strength was measured.

As a result of the adhesion test, the normal adhesive strength of the above adhesive was 19
The adhesive strength reached as much as 3 Ky/c4, which was a value that fully exceeded the adhesive strength (100 Kp/c4) required by the JIS standard.

The wood damage rate reached 90%.

Example 2 (1) A comparison of carboxymethylated wood flour Carboxymethylated wood flour was prepared in the same manner as in Example 1 (1).

(2) Phenolisis of carboxymethylated wood flour The phenolysis of carboxymethylated wood flour was also carried out in the same manner as in Example 1 (2).

(3) Production of phenol/formalin resin adhesive liquid from phenolyzed carboxymethylated wood flour. Perform sufficient phenolysis to make 1.4% of phenol.
Add formalin containing twice the molar amount of formaldehyde,
Resinization was carried out at pH 9 at 80-90°C for 3 hours, and the pH was adjusted to 11 as described above, followed by a further 80-60 minutes.
By continuing to heat the product at 0°C and further promoting resinization,
A resin with a suitable viscosity as an adhesive was obtained. This resin was used as is as an adhesive.

(4) Adhesion test method and adhesion results The adhesion test method was based on (4) of Example 1, except that the hot plate temperature t was 150°C.

One example of the results is as follows.

In this adhesive example, the adhesive layer temperature was 105 after 25 minutes of hot pressing.
Even though it only reaches ℃.

The value sufficiently exceeds the J Engineering S standard value (too6/crI).

Example 3 (1) Preparation of carboxymethylated wood flour Carboxymethylated wood flour was prepared in the same manner as in Example 1 (1).

(2) Phenolisis of carboxydimethylated wood flour In order to further increase the viscosity of the final adhesive, the degree of phenolysis may be slightly weakened to reduce the degree of low-molecularization of the wood components, e.g. Possible options include reducing the amount of hydrochloric acid, shortening the phenolysis time, or lowering the phenolysis temperature. Therefore, in this example,
Reduced phenolysis time. In the same manner as in Example 1 (2), phenol, hydrochloric acid and carboxymethylated wood flour were weighed into a round bottom flask, left at 80C for 1 hour, and then stirred at the same temperature for 15 minutes. . .

(3) Production of phenol-polmarine resin adhesive solution from phenolyzed carboxymethylated wood flour As mentioned above, add 1.4 times the amount of formaldehyde to 7-handed alcohol to the phenolyzed carboxymethylated wood flour solution. By adding formalin containing . Subsequently, resin conversion was performed at 80 to 90°C for 3 hours,
When the pH is adjusted to 11, heating is immediately stopped and the mixture is cooled to room temperature, resulting in an adhesive with appropriate viscosity.

(4) Adhesion test method and adhesion results The adhesion test method was based on (4) of Example 1, except that the hot pressing time was changed from 15 to 25 minutes.

As a result of the adhesive test, the normal adhesive strength of the above adhesive was 15
Even in the case of heat pressure for 25 minutes, the adhesive strength is 120/c-, which exceeds the J Engineering S standard value, and when bonding is performed for 25 minutes, the normal adhesive strength increases to 190/c-. outside,
In the JIS repeated boiling water resistant adhesion test, it was found that it withstood two boiling cycles and showed considerable water resistant adhesion.

Example 4゜(1) Preparation of carboxymethylated wood flour The carboxymethylated wood flour was prepared here except that the standard amounts of the etherification reagent (monochloroacetic acid) and caustic soda were reduced to A. , in the same manner as in Example 1 (1).

This is done in consideration of the fact that the lower the degree of carboxymethylation of the wood flour, the higher the water resistance of the ultimately obtained adhesive will be, as will be described later.

(2) Phenolisis of carboxymethylated wood flour The phenolysis method of carboxymethylated wood flour was carried out in Example 3, except that the volume of the 35% hydrochloric acid aqueous solution was 1.9 ml, and the phenolysis time was increased to a maximum of twice as long. In accordance with (2).

(3) Preparation of phenol-formalin resin adhesive solution of phenolyzed carboxymethylated wood flour A product was prepared in the same manner as in Example 3 (3).

(4) Adhesion test method and test results The adhesion test method was based on Example 3 (4).

One example of the results is as follows.

Example 5 (1) Preparation of carboxymethylated wood flour Three types of carboxymethylated wood flour with different degrees of carboxymethylation were prepared in the same manner as in Example 1 and Example 4 (1). (2) Carboxymethylated wood flour Pheno1) cis of methylated main flour According to (2) of Example 4, add the required amount of hydrochloric acid.

Phenolyzed.

(3) Preparation of phenol-formalin resin adhesive II liquid from phenolyzed carboxymethyl-based wood flour. The adhesive was prepared in the same manner as in Example 3 (3), and then diisocyanate-based hard wood IIIH-3M
(For water-based vinyl urethane resin adhesive) 20 g was added to the adhesive liquid (main ingredient) and stirred thoroughly.

(4) Adhesion test method and test binding The adhesion test method was in accordance with (4) of Example 3. however,
Taking into consideration the pot life and changes in the adhesive liquid after addition of the curing agent, stirring was carried out quickly, coating was carried out, and hot pressing was carried out within 10 minutes after addition of the curing agent.

As an example of test results, the compression shear adhesive strength after repeated boiling tests is shown below.

* ”Methods in Carbohydrat
e Chemistry” VOI I, p, 32
2. See Academic Press (1963).

As is clear from this table, Adhesive Chi 1 manufactured from carboxymethylated wood with a low degree of etherification has greater water resistance, exceeding the JIS standard value of 60 Kp/CI.

Example 6 In this example, forma 1) addition of tv during adhesive production
It is shown that it is possible to produce an adhesive that can perform water-resistant adhesion by increasing the amount of water.

(1) Preparation of carboxymethylated wood flour Example 4 (1)
), carboxymethylated wood flour was prepared.

(2) Phenollysis of carboxymethylated main flour Phenolysis was carried out in the same manner as in (2) of Example 4.

(3) Phenol-formalin resin welding of phenolyzed carboxymethyl Ihi wood flour [Production of liquid 11 The adhesive was prepared according to (3) of Example 5, except that the amount of formalin added was 1.5 times. liquid was produced.

(4) Adhesion test method and test results The adhesion test method was based on Example 3 (4).

As a result of the adhesion test, the compressive shear adhesive strength after the repeated boiling test is shown below.

As is known from the table, the amount of formalin added was determined in Examples 1 to 5.
By increasing the adhesive strength by 15 times, even higher water-resistant adhesion that satisfies the JIS standard value can be achieved. The wood damage rate is over 80. This result appears to indicate that wood components, particularly the phenolyzed lignin fraction, react with formaldehyde and are incorporated into the resinization system.

Example 7゜(1) Preparation of hydroxyethylated wood flour Macamba wood flour (
The conventionally known standard solvent method ("Meth
ods in CarbohydrateChemis
try ” Vow Seal, p. 322 Academy
cPrθ5s (1963)) to prepare hydroxyethylated wood flour. At that time, the standard was that the weight ratio of wood flour to ethylene oxide was 1:1.

(2) Weigh out hydroxyethylated wood flour phenolysis phenol 5y into a 50 m/capacity round bottom flask and heat at 50°C.
After melting with 0.48 ml of 35% hydrochloric acid aqueous solution
(Add and mix uniformly. Next, add 5y of hydroxyethylated wood flour, leave to stand at 80°C for 1 hour, and continue to mix at 30°C.
Stir in that state for a minute.

At the end of the process, the hydroxyethylated wood flour is dissolved into a black viscous solution.

(3) Production of a phenol/formalin resin adhesive solution from phenolyzed hydroxyethylated wood flour. Add a 50% caustic soda aqueous solution to the phenol solution of hydroxyethylated wood flour that has been phenolyzed as described above to adjust the pH to 9. Thereafter, 651 portions of 35-thiformin were added, and methylolization and partial cocondensation reactions were carried out at 80 to 90° C. for 3 hours with stirring to obtain a hydroxyethylated wood-phenol-formaldehyde resin initial condensate aqueous solution. Here, a 50% aqueous solution of caustic soda was added to adjust the pH to 11 to obtain the desired adhesive.

(4) Adhesion test method and adhesion results An adhesion test was conducted using the adhesive sample 1 obtained above.

The adhesion test method was based on (4) of Example 1.

As a result of the adhesion test, the following values of normal adhesive strength were obtained, and all of them satisfied the JIS standards.

It is known that even with this adhesive liquid, by adding a cross-linking agent H-3M (diisocyanate-based cross-linking agent) and increasing the amount of formalin added, it is possible to achieve adhesion that satisfies the water-resistant adhesive properties of the JIS standard. Ta.

Patent applicant Oji Paper Co., Ltd. (1 other person)

Claims (7)

[Claims] (1) To 100 parts of phenols, add 10 to 1000 parts of lignocellulose material such as wood that has been made into plastic by introducing at least one type of t# substituent into part or all of the hydroxyl groups, and perform phenolysis; A method for producing a gnocellulose phenolic resin adhesive to be made into a plastic, which comprises then adding formalin, paraformaldehyde, or hexamethylenetetramine and heating to advance the resin formation. (2) The method for producing a gnocellulose phenolic resin adhesive for plasticization according to claim 1, wherein the phenolysis is carried out in the presence of a catalyst that promotes the phenolysis of lignin. (3) The method for producing a gnocellulose phenolic resin adhesive for plasticization according to claim 2, wherein the catalyst that promotes phenolysis is an acid. (4) A method for producing a gnocellulose phenolic resin adhesive for plasticization according to any one of claims 1 to 3, wherein phenolysis is carried out by heating to a temperature of up to 250°C. (5) A method for producing a gnocellulose phenolic resin adhesive for plasticization according to claim 3 or 4, wherein the acid used as a catalyst is neutralized after fluorolysis. (6) The plasticized gnocellulose phenolic resin adhesive according to any one of claims 1 to 5, in which a polymerization catalyst is added when formalin, paraformaldehyde, or hexamethylenetetramine is added. manufacturing method. (7) Production of a gnocellulose phenolic resin adhesive for plasticization according to any one of claims 1 to 6, which comprises adding a crosslinking agent and a catalyst after the resinization process and before use. Law.