JPS61215676A - Two-pack plasticized lignocellulose/urethane resin adhesive - Google Patents

Abstract

PURPOSE:To provide an adhesive having excellent adhesion, etc., consisting of a combination of a main component composed of a soln. obtd. by dissolving a plasticized lignocellulose material in a polyhydric alcohol and a hardener composed of a polyisocyanate compd. soln. CONSTITUTION:10-1,000pts. lignocellulose material such as wood plasticized by introducing a substituent such as acid anhydride or acetyl group into hydroxyl group and pref. a solvolysis accelerating catalyst (e.g. Lewis acid) are added to 100pts. arom. or aliph. polyhydric alcohol (e.g. propylene glycol) or bisphenol (e.g. bisphenol A) and dissolved therein to effect simultaneously solvolysis. A main component composed of the resulting soln. and a hardener composed of a soln. of a polyisocyanate compd. (e.g. hexamethylene diisocyanate) are used in combination to provide the desired two-pack plasticized lignocellulose/ urethane resin adhesive.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) There is currently a great 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 bulp industry and wood industry,
There is an urgent need to establish ways to effectively utilize wood waste. In the present invention, wood imparted with plastic properties is preferably subjected to solvolysis of lignin using phenols and alcohols. The fact that it dissolves easily and in high concentrations in aliphatic or aromatic polyhydric alcohols or bisphenols in the presence of promoting catalysts, and the plasticized wood component present as one of the main components after resinization, contributes to the adhesion It was completed based on the discovery of the fact that it contributes to an increase in performance, and furthermore, the above solution is reacted with a compound that reacts with hydroxyl groups.

In some cases, it can be made into a resin by combining with an appropriate curing agent, and has excellent properties. It was completed by discovering a new urethane resin adhesive with scales.

The present invention utilizes chemically modified lignocellulosic materials such as wood (hereinafter often simply referred to as wood)'! ',
Preferably, in the presence of a suitable catalyst, aromatic or aliphatic polyhydric alcohols, including in the high concentration range of 50 wt. Solution A obtained by dissolving in or bisphenols and neutralizing as necessary, and Solution B consisting of a polyvalent isocyanate compound? This invention relates to a two-component plasticized lignocellulose urethane resin adhesive. These A and B liquids are used by directly mixing them just before adhesion, making this a new two-component adhesive. This is what we provide.

The present invention relates to a high-grade adhesive that uses wood, and has a major feature in this point. Also.

If plasticized wood is heated to 270°C, scales will be dissolved in aromatic or aliphatic polyhydric alcohol or bisphenols, and if necessary, hydrochloric acid or caustic soda may be added during the dissolution. Appropriate conditions such as using it as a catalyst? If adopted, it is possible to partially induce solvolysis of lignin, which is one of the main components in wood, to various degrees, and one of the characteristics is that the solution can be scaled under relatively mild conditions. I can say that. At that time, plasticized wood for every 100 parts of polyhydric alcohol or bisphenol.
It can be mixed in a wide range of 10 to 1000 parts of a'. By the way, plasticized wood? In order to dissolve aromatic or aliphatic polyhydric alcohols or bisphenols at high concentrations, a mixed solvent of low boiling point solvents such as methanol or acetone and polyhydric alcohols or bisphenols should be used. Use the former after solvolysis? gjllf concentration to polyhydric alcohols or phenols by distillation? can be increased.

Another feature of the present invention is that when the adhesive of the present invention develops its adhesive ability, the dissolved plasticized wood component can contribute to improving the adhesiveness.

(Prior art) By simple chemical reactions such as esterification or etherification, plastic properties are imparted to wood, thereby making it possible to utilize wood-based raw materials including wood in new and advanced forms. Attempts to achieve this have already been proposed.

For example, JP-A-57-103804 and JP-A-57-103804
Publication No. 135552 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.

Alternatively, it is described that the material is mixed with various synthetic polymer compounds and used as a molding raw material. Also.

In JP-A No. 57-2360, some of the hydroxyl groups.

Plasticized wood obtained by introducing substituents by esterification or etherification? A solution consisting of dissolving in an organic solvent? A preparation technique is disclosed, and the prepared solution can be formed into a film by co-dissolution with various synthetic polymer substances, and further,
It is also stated that it is possible to separate the derivatized wood components.

Outside of this, plasticized wood? Dissolved in phenol and dissolved solution? Technology to create a phenol/formaldehyde adhesive, technology to induce phenolysis during dissolution to create a phenol/formaldehyde resin adhesive with excellent solution properties, and technology to form fibers.

Technology for dissolving plasticized wood in aromatic and aliphatic polyhydric alcohols, and foaming resin compounds from the solution obtained by dissolving them? A patent application is currently pending for the preparation technology.

(Problems to be Solved by the Invention) However, to date, no urethane resin adhesive has been proposed that uses lignocellulose such as wood as one of its main components and has excellent solution properties and adhesive performance.

An object of the present invention is to provide a plasticized lignocellulose urethane resin adhesive that has excellent solution properties, workability, and adhesive properties and falls within the category of high-grade adhesives.

(Problems? Means for Solving) The present invention is achieved by introducing at least some substituents to some or all of the hydroxyl groups to 100 parts of aliphatic or aromatic polyhydric alcohols or bisphenols. ,
Lignocellulosic materials such as plasticized wood?
, 10 to 100 C1, and is dissolved using solvolysis, generally at 270° C. or lower, preferably at 80° C., in the presence of a catalyst such as an acid that promotes the solvolysis of lignin.
The main component is heated to a medium temperature of ~100℃. This is a plasticized lignocellulose urethane resin adhesive consisting of a combination of liquid A obtained by solvolysis and, if necessary, neutralization of the acid used in the catalyst, and liquid B consisting of a polyvalent isocyanate compound.

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

The type of substituent to be introduced and the reaction for introduction will depend on the type of lignocellulose resin adhesive intended.

Needless to say, it should be selected depending on the characteristics and properties. 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.

Various acids such as acid halides, acid anhydrides, dibasic acid anhydrides, and fatty acids are used for esterification, and halogens such as methyl chloride, ethyl chloride, allyl chloride, benzyl chloride, and ethylene chlorohydrin are used for etherification. Chemical compounds: Sodium monochloroacetate, monochloroacetic acid, etc. α-Halogen acids: Dimethyl sulfate, diethyl sulfate, etc. Dialkyl sulfate Epoxy compounds such as ethylene oxide, propylene oxide; Vinyl compounds activated with negative groups such as acrylonitrile Nidiazomethane; Aldehydes such as formaldehyde; Titanium Organometallic compounds such as alkylates are used as modifiers. In these reactions, sulfuric acid, perchloric acid, pyridine, subchloride, etc. can be used as a catalyst in the former case, and an alkali such as sodium chloride can be used in the latter case.

The organic groups to be introduced include fatty acid acyl groups such as acetyl, propionyl, butyryl, and valeroyl groups;
Carboxypropenoyl group and dibasic acid monoester group; benzoyl group and other aromatic acyl groups: lower alkyl groups such as methyl and ethyl groups: allyl group; carboxymethyl group: hydroxyalkyl group such as hydroxyethyl group; Suitable examples include polyoxyalkylene glycol groups such as oxymethylene groups and polyoxyethylene glycol groups; benzyl groups: long-chain fulkyl groups such as bentyl groups and octyl groups; dianoethyl groups; methylene ether groups: and similar groups. . Furthermore, it is also possible to introduce two or more of these organic groups, for example, an acetyl group and a butyryl group.

In addition to organic groups, inorganic groups such as nitro groups,
Atoms other than carbon, hydrogen, oxygen, and nitrogen? Containing organic groups, 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, the type of intended lignocellulose resin adhesive, and the intended adhesive properties.

This plasticization modification treatment of wood can be carried out according to a known method. Usually in the presence of a solvent or swelling agent,
Fibrous or powdered wood at room temperature or under heated conditions?
Treat with modifier. Wash modified wood thoroughly. For example, it is poured into water or methanol, collected with P, 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? 5. Modified wood can be directly converted into a solution by omitting the drying step 2. You can also join the process.

According to the research of the present inventor, the plasticized wood obtained by such a reaction is imparted with more or less thermoplasticity depending on the type and degree of substituent introduced, and in most cases , at least a suitable external plasticizer? If used together, it will exhibit thermal fluidity. They also have improved solubility and affinity for water, various aqueous solutions, organic solvents, or mixed solvents, and can be used at high temperatures for long periods of time. Strict melting conditions such as shadowing? Adopting levers,
Depending on the selection of the solvent, it is possible to achieve complete dissolution or nearly solubility. In general, the larger the molecular volume of the substituent (and the relatively high degree of substitution), the greater the plasticity.

Among the various methods mentioned above, practical methods for converting wood into plastic include acetylation, monoesterification with maleic acid or phthalic acid, ethylation, 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 relatively low, to the extent that the hydroxyl groups in the wood are etherified. In these cases, thermal fluidity is generally quite low and solubility is limited.

Is the present invention based on such facts? However, it is possible to overcome this problem by dissolving the above-mentioned practical plasticized wood in polyhydric alcohols or bisphenols, and finally converting it into an adhesive such as a resin in the form of a homogeneous solution if necessary. be.

The production of these receptors begins with plasticized lignocellulosic materials such as plasticized wood? , by dissolving in aromatic or aliphatic polyhydric alcohols or bisphenols.

Regarding the intramolecular bonds of the main components of plasticized wood, especially the plasticized lignin section, sorbo rinsing may occur at least partially, resulting in various degrees of cleavage of the intramolecular bonds of lignin? By measuring, it is easy to dissolve under mild conditions, i.e., relatively low melting temperature and short melting time. Is it possible to easily produce a polyhydric alcohol solution or bisphenol solution of plasticized wood? to make it easier to carry out subsequent reactions. As a result, the solution properties of the adhesive finally obtained are better. During this dissolution, some of the polyhydric alcohols or bisphenols are introduced into the main component of the plasticized wood, particularly at the α-position of the lignin side chain, through chemical bonding.

This works to enhance properties 2 such as adhesive properties of the adhesive.

In this description of the invention, the generic term solvolysis is often used.

I didn't call it alcoholysis, but is this bisphenol? In addition to using hexanediol and acetone, mixed systems of polyalcohols and some kind of low-boiling solvent are also used.

In the present invention, methylated wood, ethylated wood.

Carboxymethylated wood, hydroxyethylated wood, hydroxypropylated wood, allylated wood.

When acetylated wood, acetyl-butyrylated wood, carboxypropenoylated wood, etc. are reacted with alcohols or bisphenols under a catalyst such as an acid such as hydrochloric acid, they contain lignin/carbohydrate bonds. The intramolecular bonds of lignin, especially the benzyl ether bonds, are broken.

Lignin is also partially derivatized, which facilitates dissolution.
Polyhydric alcohol or phenol solutions of these plasticized woods are obtained. For this reason.

This makes it possible to perform a resin-forming reaction in a homogeneous phase including the plasticized wood component, making it suitable for producing a lignocellulose-based resin-forming forging agent.

The polyhydric alcohols used in the present invention include ethylene glycol, propylene glycol, trimethylene glycol as dihydric alcohols: 1°4-7'tanediol, 1.5-bentanediol, 1.6-hexanediol, 2. 5-bexanediol, 2.4-hexanediol, 1.7-hebutanediol, 1.8-octanediol, 1.9-nonanediol, 1.10-decanediol glycerin, pinacol, cyclopentane 1.
2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, bisphenol A, polyoxypropylene glycol, polyoxypropylene-polyoxyethylene glycol, etc., as well as glycerin as a trihydric alcohol, and hisphenol. A,
Bisphenol F, halogenated bisphenol A, resorcinol, tetrahydroxyphenylmethane? can be mentioned. These polyhydric alcohols or bisphenols may be a mixture, and may be monohydric lower alcohols such as methanol or mainly low boiling point alcohols such as acetone.
It can also be used as a mixture with suitable solvents.

In order to obtain the Aik of the present invention, the dissolution using solvolysis may be performed using a catalyst, for example. If the reaction is to be carried out at a medium temperature of about 80° C., it can be carried out in a container equipped with a cooler. In this case, the temperature range can be from room temperature to the boiling point of each polyhydric alcohol or bisphenol solution, and the dissolution time is as follows.

Although it depends on other conditions, it generally takes about 15 minutes to several hours. When a catalyst is not used, the boiling point of the polyhydric alcohol or bisphenol solution or higher is 27
When melting is carried out in conjunction with solvolysis at a temperature of about 0° C., it is usually best to carry out the melting in a pressure-resistant container. As a result, the dissolution concentration of plasticized wood is 1 weight,
This is possible from a few inches or less to 95%.

In order to cause solvolysis, in the presence of a catalyst that promotes norpolysis of lignin, from mineral acids such as hydrochloric acid, sulfuric acid, trifluoroacetic acid, etc. to Lewis acids such as aluminum chloride, zinc chloride, boron trifluoride, etc. It is suitable for performing heat treatment 2.

It can also be dissolved in the presence of a neutral alkali.

Methylated wood, ethylated wood, allylated wood.

For carboxymethylated wood, hydroxyethylated wood, acetylated wood, etc., at about 80°C.

When dissolving in polyhydric alcohol or bisphenol to achieve the above concentration range, 0.
The coexistence of 5 to 20 units of hydrochloric acid is required. 3-10% gives particularly good results. Sorbo rinse in minutes to hours? A complete solution is obtained.

Conventionally, it was generally thought that solvolysis of wood required high temperatures, but it is noteworthy that the present invention allows medium temperatures of about 80°C.

As a dissolving device, do you have a reactor such as a kneader that can sufficiently stir the melting process and can also apply torque during the stirring process? When used, it promotes dissolution and prevents full lysis.
This is particularly suitable because the dissolution conditions can be relaxed. Also during dissolution.

Was it an organic solvent such as water or acetone from the beginning or somewhere along the way? It is also possible to add and coexist to mix and dissolve more uniformly.

On the other hand, if you do not use a catalyst such as hydrochloric acid, do you use a pressure-resistant container? It is used as a reactor and treated at a temperature of up to about 270°C, preferably with stirring, for about 15 minutes to several hours to dissolve it.

For full polylysis, 10 to 1000 parts of polyhydric alcohol is added to the lignocellulose material. A low concentration solution can be easily prepared, but as an adhesive using wood components, it is meaningless unless the concentration is about 10%, so the lower limit was set at v10%. Is the upper limit for adhesives sufficiently meaningful in terms of performance? The amount obtained was set at 1000 parts.

After the dissolution operation, the catalyst used in the full polylysis is neutralized, if necessary. In this case, in the second stage of the primary resinization, is it hard soda or amines? When used as a catalyst, one of these can be used for neutralization, such as strong soda.

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.

As for the polyvalent isocyanate compound used for Bi, what is the one used as a polyicanate attaching agent? ,
A suitable example thereof is triphenylmethane-triisocyanate (Desmodur®
-20% methylene chloride solution)%1, -5 Naphthylene・
Diisocyanate (Desmodur 15).

613'-dichloro-4,4'-diphenyl diisocyanate (CDI), 4,4'-diphenyl diisocyanate (Mondur M, XDI), 3.3
'-Dimethyl-414'-diphenyl diisocyanate (TODI), 3,5'-dimethoxy-4,4'-diphenyl, diisocyanate (DADI), 4,4'-dimethyl-3,3'-diisocyanate diphenyl.

Urea (Hylene TU), 4,4'-diphenylmethane.

Diisocyanate (Hylene M) Urethane triinocyanate (Desmodur TH),) A
/ x diisocyanate, diphenylmethane-4,4
7-Diisocyanate (MDI), hexamethylene diisocyanate, polyphenylinocyanate (PAPI), etc.? can be mentioned.

When bonding is performed using the adhesive of the present invention, a polyhydric alcohol or bisphenol solution (CA solution) of the plasticized wood obtained as described above and a polyvalent isocyanate solution (B solution) are used. Mix it, apply it to the adherend, and perform operations such as heat pressure. Add. At that time, the hydroxyl groups in the polyhydric alcohol or bisphenol solution (liquid A) of the plasticized wood, that is, the hydroxyl groups of the plasticized wood component and the hydroxyl groups of the polyhydric alcohol or bisphenol.

Are urethane bonds formed through a reaction with the isocyanate groups in the polyvalent isocyanate compound solution (solution B)? Arise.

The polymerization reaction to form a three-dimensional resin, that is, a three-dimensional molecular structure, progresses, and the adhesive hardens.

Performance of adhesive obtained by the present invention? Various additives before use for better improvement? Can be added. For example, reducing the cost of adhesives, reducing thermal swelling, reducing curing shrinkage, and suppressing heat generation during curing.

It is desirable to add a filler χ to improve adhesion. For example, alpestin, carbon black, titanium dioxide, chalk, clay, etc. are used.

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 resistant agents, weathering agents, lubricants, etc. , fibrous reinforcing agents, etc.).

Examples of polymeric additives used in the adhesive of the present invention include polyamide resins and polysulfide resins.

Triphenyl phoshyde and, in some cases, coal tar can be used to improve reactivity, affinity, and miscibility with plasticized lignocellulose epoxy and urethane resins, and can be suitably used to improve adhesion.

As oligomers, formalin resins such as phenol-formalin initial condensates, low condensation dust 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 obtained in the present invention is usually used by applying it to a surface to be bonded in the form of a solution or paste. Adhesion conditions such as adhesion temperature, adhesion time, adsorption pressure, etc. can be set according to conditions used in conventional urethane resin strip adhesives.

That is, it hardens in about 24 hours at room temperature, and
Maximum strength is reached in days. Increase the amount of catalyst and further increase the
Heating at ~900C accelerates hardening and hardens in a few minutes.

Does this adhesive have good adhesion under low adhesive pressure? It can be done.

Adhesive of the present invention? Adhesion can be appropriately performed by pressing at room temperature, heating by 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 not only for wooden building materials, for general woodworking, and for bonding wood with other materials, but also for bonding various materials including metals and plastics.Example 1゜(1) Production of methylated wood flour Dried Macamba wood flour (20-60 mesh) 50? ? , weighed into a glass autoclave with a stirrer (capacity: 1),
Add 500rnlv of toluene. Next, the mixture was added to 60 d' of aqueous solution of 40% sodium chloride and stirred at room temperature for 1 hour to form a mercer. conduct. After that, iodide metal '5! :50r
ttl plus container? Seal tightly and raise the temperature to 80'C, 6
Allow time to react. At the end of the reaction, when the reaction solution is cooled to room temperature and stirring is stopped, the reaction solution separates into two layers, so the supernatant toluene? Remove with a slant and add acetic acid, acidic acetone/methanol (6:7 volume) mixture? Add, stir, neutralize and wash, and remove supernatant. Subsequently, pressurize in the same way as when applying excess acetone.

Stir and wash twice, collect 5 m, air dry, further dry in a blow dryer at 60° C. for 1 day, and finally vacuum dry at 50° C. to obtain a sample. Is the obtained methylated wood flour orange in color? It has a tinged yellow color, has a powdery appearance, and has a weight increase rate of about 8 times, which is not much changed compared to untreated wood flour.

(2) Production of non-aqueous urethane resin adhesive main ingredient (liquid A) from methylated wood flour Methylated wood flour 5? , hexylene glycol 5? and 6
Weigh 0.611 Ll of 5-thihydrochloric acid aqueous solution (6% by weight based on hexylene glycol) into a 50 ml separable flask. Ethanol (5 rnlff) was added as a diluent, and the mixture was reacted at 80° C. for 5 hours to dissolve.

Thereafter, it was connected to an aspirator and heated for 2 hours while degassing at 120°C. Remove and cool to room temperature. Add 72 drops of triethylamine to pH
6, and then diluted with acetone to obtain an appropriate viscosity, which was used as the main ingredient (Am) of this adhesive. This will be used in the second adhesion experiment.

(3) Adhesion test and adhesion results As adherend: 125 aug (LAX 125
I used MXl x 2 TofTl cover veneer. Immediately before adhesion, 15 parts of 75% polymeric MDI) luene solution (liquid B) was added to 100 parts of methylated main powder/hexylene glycol-acetone g liquid adhesive (polyol adhesive).
Stir well to mix. However, the polymeric MDI is a low polymer of 4,4'-diphenylmethane diisocyanate, and is a polyvalent isocyanate compound having a primary chemical structure.

(However, n = 0.1.2 and 2 or more are appropriately included.) Using this adhesive, the coating amount is 200 to 3005'/m
.

Hot plate temperature 120℃: Clamping force 6 kg f 7cm2”
, bonding under the condition of compression time of 20 minutes? Go, 3-bray plywood? Created. From this plywood, JIS standard (K-68
02), test piece t with an area of 25m x 75Jul
Cut out 4 sheets and test area for tensile shear adhesive strength is 13m x 2
A tensile shear adhesion test was conducted after making cuts from the front and back sides of the test piece to the adhesive layer so as to have a length of 5 m (normal adhesion). Further, the sample was subjected to repeated boiling treatment in accordance with the JIS standard (K-6802), and the water-resistant adhesive strength was measured. In other words, a sample? Boil in hot water for 4 hours, then 60℃ for 20 hours.
The sample was dried in a blow dryer, boiled for 4 hours, cooled to room temperature, and then subjected to a tensile shear test while being rewarmed. The average values of the obtained adsorption test results are as follows.

Normal adsorption force 1ZOkgf/crr12 Water resistant adhesive force
11.1 kgf/'rn2 Both values are based on the JAS standard (JIS K) required for phenolic resin adhesives.
2SO3) value (normal adhesive strength: 12 kgf/crn2, water-resistant adsorption strength: 10 kgf/z2).

Example 2゜ 11) Production of methylated main flour Methylated wood flour was produced in the same manner as in Example 1 (1).

(2) Production of water-based urethane resin adhesive base (Ag) from methylated wood flour Methylated wood flour 5y-11,4-butanediol 5? and 0.6 d of 35-thihydrochloric acid aqueous solution (6% based on 1,4-butanediol) were weighed into a 5M separable flask. Add 5 rnl of ethanol as a diluent and 80°
The mixture was reacted and dissolved at C for 3 hours with stirring. Then 100
Ethanol was distilled off at °C.

After cooling to room temperature, triethylamine was added dropwise to adjust the pH to 6. It was diluted with a small amount of acetone and adjusted to an appropriate viscosity with deionized water to be used as the main ingredient (Am) of an adhesive.

This is used for the first adhesion experiment.

(3) Adhesion test and adhesion results The adhesion operation and adhesion test were conducted in exactly the same manner as in Example 1 (3).

The average value of the obtained adhesion test results is as follows.

Normal adhesive strength 20.5 kgf/cm2 Water resistant adhesive strength 11.5 kgf/i Shoulder 2 All values are J
What are the standard values required for phenolic resin adhesives in ISK6802? It's better than that.

Example 6゜+1) Method for producing allylated wood flour Dried Macamba wood flour C20-60 mesh) 60%'k,
The mixture was weighed into a reaction flask of a 1 L simple reaction apparatus (manufactured by Taishu Kagaku Kogyo ■), and a 655"K40% aqueous solution of caustic soda and 500 g of toluene were added thereto, the mixture was sealed, and mercerization was carried out at room temperature for 1 hour under stirring.

After that, 3.6y-allyl bromide per 1 unit of wood flour? The mixture was then sealed again and reacted at 80° C. for 5 hours with stirring. After the reaction is complete, acetic acid methanol? Neutralize and wash under pressure and stirring. Remove the supernatant i'v, pressurize methanol,
Stir well and wash. Is this methanol cleaning? Repeat several times to purify the sample. At that time, perform 2 washes until the odor of allyl bromide disappears from the washing solution. Next, allylized wood flour was collected in one batch, air-dried, air-dried at 60°C, and further dried for 50'
Dry by vacuum drying at C to obtain a sample.

The obtained allylized wood flour has a wood powder-like appearance with a yellowish 2 tinge. The apparent weight increase rate is 14 to 18 inches.

(2) Production of non-aqueous urethane resin adhesive (liquid A) from methylated wood flour 1. Weigh 6-hexanediol into a 10-25M round bottom flask, heat it to 80°C, and add it to the alcohol. On the other hand, a 35% aqueous hydrochloric acid solution containing 5 g of hydrochloric acid? Add. After mixing well, add 10 y of allylized wood flour, attach the cooling tube and stirring device, and leave it at 80°C for 60 minutes.
Stir for 1 minute and allylated wood-1,6 hexanediol solution? obtain. Next, TEA? The solution was added dropwise to adjust the pH to 7, and the water in the system was removed at 80 to 100° C. under reduced pressure to obtain the main ingredient (Liquid A) of this adhesive. This will be used in the next adhesion experiment.

(3) Adhesion Test and Adhesion Results The adhesion operation and adhesion test were carried out in accordance with (3) of Example 1. However, as a curing agent (liquid B).

Millionate MR, a polymeric MDI
200 (manufactured by Nippon Polyurethane ■) was added to the main agent (Am) at a volume ratio of 1, mixed quickly, and immediately applied to the adherend wood specimen.
Adhesion was performed at 5'l-o/c- for 5 minutes. The resulting 6-ply plywood was subjected to a tensile shear test in the same manner as above, and the average normal adhesive strength was 10.2 Kz f.
/cm2 value 2 It rained.

Claims (7)

[Claims] (1) For 100 parts of aromatic or aliphatic polyhydric alcohols or bisphenols, 10 parts of lignocellulose material such as wood made into plastic by introducing at least one type of substituent into some or all of the hydroxyl groups is added.
A two-component plastic consisting of a combination of a main agent (liquid A) consisting of a solution obtained by adding ~1000 parts and dissolving it using solvolysis, and a curing agent (liquid B) consisting of a polyvalent isocyanate compound solution. Lignocellulose/urethane resin adhesive. (2) Liquid A is obtained by performing solvolysis with aromatic or aliphatic alcohols, polyhydric alcohols, or bisphenols in the presence of a catalyst that promotes solvolysis of lignin. Claim 1 The two-component plasticized lignocellulose/urethane resin adhesive described above. (3) Liquid A is obtained by using an acid containing a mineral acid or a Lewis acid as a catalyst that promotes solvolysis by aromatic or aliphatic polyhydric alcohols or bisphenols. Claim 2 Plasticized lignocellulose/urethane resin adhesive described in Section 1. (4) The liquid A is obtained by using an alkali containing caustic soda as a catalyst for promoting solvolysis by aromatic or aliphatic polyhydric alcohols or bisphenols. Plasticized lignocellulose/urethane resin adhesive. (5) The liquid A is obtained by heating solvolysis with aromatic or aliphatic polyhydric alcohols or bisphenols to a temperature of up to 270°C. Plasticized lignocellulose/urethane resin adhesive. (6) The plastic according to claim 1, wherein liquid A is obtained by neutralizing the acid used as a catalyst after solvolysis with aromatic and aliphatic polyhydric alcohols or bisphenols. Lignocellulose/urethane resin adhesive. (7) Solution A is obtained by dissolving plasticized lignocellulose in combination with solvolysis using a mixed solvent of volatile solvents with low boiling points such as lower alcohols and polyhydric alcohols, and then removing the low boiling point solvent. removed by distillation,
The plasticized lignocellulose/urethane resin adhesive according to claim 1, which is obtained by obtaining a highly concentrated solution.