JPH01158021A - Lignocellulose-phenolic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition, containing an addition.condensation reaction product of a mixture containing a phenolic compound and a lignocellulosic material with formaldehyde, having excellent curability, coating properties and adhesive strength and useful as an adhesive. CONSTITUTION:The aimed composition containing an addition.condensation reaction product of (A) a mixture containing 100 pts.wt. phenolic compound and 10-1000 pts.wt. lignocellulosic material with (B) 30-1500 pts.wt. formaldehyde in the presence of a basic catalyst. Furthermore, 1-50 pts.wt. at least one selected from resorcinol compounds and precondensates of resorcinol compounds-formaldehyde is preferably contained in 100 pts.wt. resultant composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a lignocellulose-phenol resin composition and an adhesive containing the same as a main component.

More specifically, the present invention provides a lignocellulose-phenolic resin composition containing a lignocellulose material, a phenol compound, and a formaldehyde addition/condensation reaction product, and having excellent curability, coating properties, and adhesive strength, and a lignocellulose-phenolic resin composition mainly comprising the same. This relates to the adhesive used as a component.

[Prior art and problems to be solved by the invention] Lignocellulosic materials such as wood are not necessarily fully utilized in terms of high-yield, high-value-added use, and therefore improvements are desired. There is. In other words, a considerable amount of these materials are discarded without being used or become waste materials (currently, they are used for low-grade uses or are discarded by incineration, etc.).

The present invention is one of the high value-added utilization methods of these lignocellulose materials, and in particular, is intended to utilize lignocellulose materials in water-soluble adhesive resin compositions.

Water-soluble phenolic resin compositions (resol resin compositions) are widely used as wood adhesives that are required to have high durability and water resistance.

One of the problems with this type of adhesive is that it must be heated at temperatures above 140°C to allow sufficient curing during bonding.
This requires a high bonding temperature of 70°C.

Therefore, unless the moisture content of the wood to be bonded is extremely reduced, heating during bonding will cause a fatal problem called "banking." This problem,
This places significant restrictions on the bonding operation, resulting in the need for extra operations. On the other hand, attempts have been made to develop adhesives from biomass such as lignin or lignocellulose materials, and some of the results have been put into practical use. The major problem in this case is that biomass-modified adhesives such as lignin-modified adhesives have inferior reactivity and curing properties compared to corresponding commercially available adhesives, and therefore require more severe bonding conditions. Such bonding conditions reduce the efficiency of industrial bonding operations and result in large amounts of energy consumption.

In addition, many attempts have already been made to prepare water-soluble phenolic resin adhesives using lignin materials, and many of these attempts have been reported to have performance as water-resistant adhesives, but the above-mentioned like,
These adhesives require harsher bonding conditions such as higher bonding temperatures and longer bonding times than normal water-soluble adhesives. For example, Sakai et al. (28th Lignin Chemistry Symposium (1983)') reported that Na-based high-yield sp.
A basic formaldehyde resin adhesive is prepared from a pretreated product obtained by using waste liquid as a sample and varying the amount of inorganic salts added and the phenol dissolution/treatment conditions. As a result of this study, PTT: 2.0, phenol blending ratio (
50 parts concentration of waste liquid): 0.33 to 0.50, temperature: 20
Phenol treatment of lignin material under the conditions of 0°C and time = 120 minutes, formaldehyde was blended with the dissolved product, and p
The water-soluble lignin/phenol resin adhesive obtained by resinizing under conditions of H: 9.5 to 11.5 and temperature: 80 to 90°C has useful performance as a water-resistant adhesive. , however, was known to require somewhat higher bonding temperatures than usual. Also, some copies (Monthly Report of the Forest Products Experiment Station, Vo
l, 15. tlk179.10 (1966)) uses caustic soda pretreatment (liquid ratio: 1/3, NaOH addition rate: 20
% to lignin, reaction conditions: 140°C, 3 hours), 40 parts of phenol and 42 parts of formaldehyde were blended with 60 parts of kraft lignin, and these were co-condensed (80°C, 60 minutes). We have prepared resins with relatively good fluidity and thermosetting properties. However, this preparation method requires high temperature and long alkali pretreatment, and in order to obtain plywood with excellent adhesive performance using the resulting resin, relatively high temperature and long time conditions are required. Problems have been pointed out, such as the need for heat-pressure bonding. It has also been pointed out that to improve the latter problem, it is effective to add a small amount of a curing accelerator (resorcinol).

In contrast to the use of lignin materials, the preparation of water-soluble phenolic resin adhesives using lignocellulose materials such as wood has been reported in the past 1-2 years by the present inventors and Ono et al. Abstracts of the Lignin Discussion Conference, p. 13
3 (1986)). The inventors discovered that this method dissolves lignocellulosic materials such as wood in phenol, formalin, or phenolic resin solution (Japanese Unexamined Patent Publication No. 61-26
This is probably because it was not known before (No. 1358).

The lignocellulose phenolic resin adhesives that the present inventors and Ono et al. have announced so far have a lower temperature and time required for curing than the corresponding commercially available water-soluble phenolic resin adhesives (alkaline resol type). , each had the problem of being expensive and long. In other words, the adhesive had some problems in its curability.

As mentioned above, conventional alkaline resol type phenolic resin adhesives require high temperature and long-term heat-pressure conditions for bonding, and have the disadvantage that the moisture content of the veneer must be kept low during use. have. Therefore, it can be bonded under the same conditions as urea resin and melamine resin, and J
There has been interest in phenolic resins that have adhesive properties that meet the AS standards. That is, the proposition of bonding a phenolic resin adhesive under the same conditions as a 7-mino resin adhesive has arisen, and various methods have been studied to solve this problem. One method is to use a highly condensed resin adhesive with improved reaction rate of phenolic resin, but this resin adhesive has drawbacks such as extremely low storage stability.

In addition, as another method, attempts have been made to obtain high-speed curing using acid-curable phenolic resin adhesives. In the case of the latter adhesive, it will harden even at room temperature, but the pH of the adhesive must be lower than 2, and
causes canning of the wood. After several trials and errors as described above, it has been discovered that a phenol-melamine cocondensation resin can achieve the above-mentioned objective in making a phenol resin harden faster. In other words, the phenol/melamine resin adhesive can be bonded under the same conditions as amino resin, and can be mixed with urea resin to meet the JAS standard.
It has characteristics such as being able to obtain adhesion performance that passes any standard from special class to class 2, and is able to achieve its intended purpose and has been put into practical use.

As mentioned above, the lignocellulose and
The properties of phenol resin and lignin/phenol resin have both advantages and disadvantages, and it has to be said that they are unsatisfactory overall. At the same time, the objective of lowering the heat-pressure curing temperature of water-soluble phenolic resin adhesives to the same level as that of amino resins has not been sufficiently achieved with conventional lignocellulose phenolic resin adhesives.

That is, the present invention addresses the following problems with conventional lignocellulose-phenolic resin compositions and adhesives: (a) The required adhesive curing temperature is higher than the desired temperature.

(b) The required adhesive curing time is longer than the desired time.

The purpose of the present invention is to provide a resin composition and an adhesive that can cure the problem at a relatively low temperature and at a high speed.

[Means to solve the problem]

The lignocellulose-phenolic resin composition of the present invention is
a mixture comprising 100 parts by weight of a phenolic compound and 10 to 100 parts by weight of lignocellulosic material;
It is characterized in that it contains an addition/condensation reaction product with 500 parts by weight of formaldehyde in the presence of a basic catalyst.

Further, another lignocellulose-phenolic resin composition of the present invention includes 100 parts by weight of a phenol compound and 10 to 1 part by weight of a phenol compound.
100 parts by weight of the addition/condensation reaction product of a mixture containing 1,000 parts by weight of lignocellulosic material with 30 to 1,500 parts by weight of formaldehyde in the presence of a basic catalyst.
parts by weight, and 1 to 50 parts by weight of at least one selected from a resorcinol compound and a resorcinol compound-formaldehyde initial condensate.

The present invention also includes an adhesive containing the lignocellulose-phenol resin composition as a main component.

In preparing the resin composition of the present invention, first, a mixture containing 100 parts by weight of a phenol compound, 10 to 1000 parts by weight of lignocellulose material, and 30 to 1500 parts by weight of formaldehyde are mixed in the presence of a basic catalyst. Lignocellulose-resol resin is prepared by addition/condensation reaction below.

The phenolic compounds used in the present invention include phenol,
It can be selected from cresol, xylenol, alkylphenol, phenylphenol and resorcinol.

Furthermore, the lignocellulose material used in the present invention can be selected from wood chips, wood fibers (pulp), waste paper bulbs, wood flour, rice straw, etc., and there are no particular restrictions on the tree species.

The basic catalyst for the addition/condensation reaction used in the present invention includes at least one selected from caustic soda, potassium hydroxide, ammonia, organic amines, and hydroxides of zinc, calcium, magnesium, and aluminum. can be used.

The addition/condensation reaction between the phenolic compound-lignocellulose material mixture and formaldehyde is carried out at 60°C to 1°C.
Preferably, the reaction is carried out at a temperature of 50°C, and the reaction time generally ranges from 30 to 360 minutes.

Lignocellulosic materials can be produced by phenolysing their constituent components, especially lignin, to achieve various degrees of cleavage of intramolecular bonds in lignin, cellulose, hemicellulose, etc. and various degrees of phenol introduction into the α-position of the lignin side chain. The scale can facilitate the dissolution of lignocellulosic material and improve the performance and properties of the solution. In addition, this increases the reactivity of lignocellulose constituents such as lignin, making it easier to carry out subsequent reactions. As a result, the physical properties and adhesive properties of the adhesive are improved.

In addition, polysaccharide components such as cellulose and hemicellulose are also partially hydrolyzed during the resin production reaction of the present invention, resulting in highly reactive reaction products including oxymethylfurfural, and the performance of the resulting adhesive. can be increased.

The phenolic compound-lignocellulosic material-containing mixture may include a phenolization reaction product of the lignocellulosic material with the phenolic compound. Phenolization of lignocellulosic materials, especially their lignin components, can also proceed by simply heating without a catalyst, but in this case, a fairly high temperature is required, reaching 140°C to 220°C. . To facilitate the phenolation of lignocellulosic materials, mineral acids such as hydrochloric, sulfuric, and nitric acids, formic acid, acetic acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, phenolsulfonic acid, and trifluorocarbon An acidic catalyst consisting of at least one selected from organic acids such as acetic acid, and Lewis acids such as aluminum chloride, zinc chloride, and boron trifluoride, or at least one selected from quaternary aluminum salts and caustic soda. 1 in the presence of an alkali catalyst of
It is particularly preferred to carry out the heat treatment at a temperature of 50''C or less.

If the lignocellulosic material is phenolated in the presence of an acid catalyst, the acid catalyst is optionally neutralized. However, in the subsequent addition/condensation reaction using formaldehyde, a basic catalyst preferably consisting of caustic soda is used, so it is convenient to use caustic soda for the above neutralization.

However, if the phenolization and dissolution proceed without a catalyst, this problem of neutralization will not occur, and in consideration of the formation of salts due to neutralization, non-catalytic phenolization is more suitable. In addition, when Lewis acids such as boron trifluoride or quaternary ammonium salts are used as catalysts in the phenolization reaction, they may be used as catalysts for subsequent resin formation, or catalysts such as hydrochloric acid or trifluoroacetic acid may be used as catalysts. In some cases, it can be recovered by distillation, etc., and in those cases there is no need to neutralize the catalyst.

In preparing the lignocellulose material-phenol compound-formaldehyde addition/condensation reaction product, 10 to 1000 parts by weight of the lignocellulose material is added to 100 parts by weight of the phenol compound. A low concentration solution can be easily prepared, but as an adhesive using lignocellulose materials, it is meaningless unless the content is 10 parts by weight or more, and the amount used may be 1000 parts by weight or more. , an adhesive having sufficient performance significance can be obtained with a usage amount of 1000 parts by weight or less. The lignocellulose material may be used in a large amount of 1000 parts by weight or more per 100 parts by weight of phenol, but in order to dissolve it at such a high concentration, a mixed solvent of phenol and a low boiling point solvent such as methanol or acetone is required. Alternatively, a method may be used in which the solvent is removed after solvolysis.

Further, in preparing the lignocellulose material-phenol compound-formaldehyde addition/condensation reaction product, the amount of formaldehyde used is 10 to 100 parts by weight per 100 parts by weight of the total amount of the lignocellulose material and the phenol material used. It is preferable. If the amount of formaldehyde used is less than 10 parts by weight, the curing properties of the resulting reaction product may be unsatisfactory, while if it is more than 100 parts by weight, the storage stability of the resulting reaction product may be insufficient for practical use. It may turn out to be unsatisfactory.

In the preparation of other resin compositions of the present invention, phenolic compound - cellulose material - formaldehyde addition/
100 parts by weight of the lignocellulose-phenol resin produced by the condensation reaction and 1 to 50 parts by weight of at least one selected from resorcinol compounds and resorcinol compound-formaldehyde initial condensates are mixed.

Both of the above components may be mixed and reacted.

The resorcinol compounds used in the present invention include resorcinol, alkylresorcinol (for example, methyl-,
dimethyl-, trimethyl-resorcinol and mixtures thereof), meta-cresol, meta-aminophenol,
and tannins.

The resorcinol compound-formaldehyde initial condensate used in the present invention is prepared by combining at least one of the above resorcinol compounds and formaldehyde with a suitable catalyst, such as caustic soda, potassium hydroxide, ammonia, organic amine, calcium hydroxide, and magnesium hydroxide. Basic catalysts such as hydrochloric acid, sulfuric acid, formic acid, acetic acid,
It can be produced by condensation in the presence of an acidic catalyst such as phenolsulfonic acid. At this time, the molar ratio of the resorcinol compound and formaldehyde may be the same as that used in ordinary resorcinol resins, but
In particular, it is preferable that the ratio is 1:0.5 to t:t, S.

If the amount of formaldehyde used is less than 0.5 mol,
The resulting resin composition may have unsatisfactory curability, and if the amount exceeds 1.5 mol, the resulting initial condensate and resin composition may have unsatisfactory storage stability. There is.

In the resin composition of the present invention, lignocellulose material-
1 to 50 parts by weight, preferably 5 to 50 parts by weight of a resorcinol compound component consisting of at least one selected from a resorcinol compound and a resorcinol compound-formaldehyde initial condensate, per 100 parts by weight of the phenol compound-formaldehyde addition/condensation product. It is used in an amount of 25 parts by weight.

The resorcinol compound-formaldehyde initial condensate used in the present invention contains copolymerized components of 10 moles or less per mole of the resorcinol compound, such as phenol,
It may also contain cresol or the like.

If the amount of the resorcinol compound or resorcinol compound-formaldehyde initial condensate is less than 1 part by weight, the desired effect of reinforcing resorcinol will be unsatisfactory, and if the amount is more than 50% by weight, the resulting composition or adhesive The effective storage time and pot life of
This results in the inconvenience of being economically disadvantaged.

The reaction (or copolymerization reaction) between the resorcinol compound or the resorcinol compound-formaldehyde initial condensate and the cellulose-resole resin is preferably carried out at a temperature of 100°C or lower, preferably between room temperature and 80°C, and the reaction time is , - generally from 1 minute to 20 hours.

In the resin composition of the present invention, lignocellulose material-
By adding a resorcinol compound and/or a resorcinol compound-formaldehyde initial condensate to the phenol compound-formaldehyde addition/condensation reaction product, not only the rapid curing properties and storage stability of the resin composition are improved, but also the , it is possible to improve the permeability and transferability to the surface to be adhered, and to prevent the occurrence of dry adhesive development.

The resin composition of the present invention is useful as a main component of an adhesive, and when used, a curing agent such as paraformaldehyde formalin or hexamethylenetetramine may be added to the resin composition as necessary. Furthermore, fillers, extenders, etc. may be added.

In the composition of the present invention, a lignocellulose material-phenol compound-formaldehyde addition/condensation product,
In the copolymerization reaction with a resorcinol compound and/or a resorcinol compound-formaldehyde initial condensate, as the amount of the resorcinol compound component and formaldehyde such as paraformaldehyde and formalin increases, the curing characteristics of the resulting resin composition and the water resistance of the adhesive increase. Although the pot life is increased, it is important to get the balance of these properties right. When a component such as formalin that contains formaldehyde and can be directly supplied to the reaction system is added later in an amount exceeding a certain limit, or when such a component is already present in a large amount in the reaction system, the resin It significantly increases the curability of the composition and significantly shortens its pot life. in this way,
For the purpose of shortening the curing time without shortening the pot life, the use of hexamethylenetetramine has given good results. In addition, when preparing the lignocellulose-resole resin, the amount of formaldehyde added is set at about 2.5 mol per 1 mol of the phenol compound, and if a chemical species that generates formaldehyde is not added afterwards, the resorcinol compound can be obtained. If it is added in an excessive amount of 10% or more based on the weight of the resin composition, the curability will conversely decrease as the amount added increases.

This is thought to be because the free resorcinol compound exhibits a melting effect due to the lack of formaldehyde in the reaction system. Following the post-addition of the resorcinol compound as described above, the reaction mixture is heated, e.g.
The reaction product may be left to stand for a minute to 20 hours, or the resulting resin composition may be usable at moderate temperatures, such as by leaving the reaction product for 30 minutes at 1 to 35°C. The reaction is carried out under appropriate conditions within a range that does not significantly shorten the reaction time. That is, at a temperature of 100°C or less, preferably room temperature to 80°C, for example, 1 minute to 20 minutes.
Generally, the reaction is carried out over a period of time.

The present invention uses a large amount of lignocellulose material, which is considerably cheaper than phenolic compounds, as one of the main components of the resin composition (50 to 60% of phenolic compounds).
Even if lignocellulose is used to replace lignocellulose, the performance of the resulting adhesive will not deteriorate), and a reduction in the cost of the resulting resin composition and adhesive can be expected. In this way, it is economically possible to use a toughening agent that is more expensive than phenol due to the reduction in raw material costs. In the present invention, sufficient effects have been observed even when alkylresorcinol is used within this range. Additionally, alkylresorcinols, such as methyl- and dimethyl-resorcinol,
The price of resorcinol is said to be four times that of phenol, but half that of resorcinol.

In order to further improve the performance of the resin composition adhesive of the present invention, various additives can be added before its use. For example, it is desirable to add an extender or filler to adjust the viscosity of the adhesive, reduce cost, reduce thermal expansion rate, reduce curing shrinkage rate, suppress heat generation during curing, and improve adhesive properties. . As fillers, grain flours such as wheat flour, barley flour, rice flour, corn flour, etc., as well as animal and vegetable protein powders such as defatted soybean flour, blood meal, casein powder, etc. are commonly used in phenolic adhesives. Bulking agents can be used. In addition, suitable examples of inorganic fillers include crushed stone, sand,
These include silica, talc, calcium carbonate clay, sodium carbonate, slaked lime, etc. In addition to reinforcing fillers such as mica, asbestos, and glass chips, depending on the purpose, quartz powder, graphite, ceramic powder, alumina, Silica gel (effective for imparting sixotropic properties), aluminum, aluminum oxide, iron, iron oxide, etc.
Examples include metals such as copper that contribute to thermal expansion coefficient, thermal conductivity, and adhesive properties, and inorganic materials that provide flame retardancy such as antimony oxide. Also,
Organic, quality fillers include wheat flour, kurji, coconut grain powder, wood flour, and rice hull powder, as well as fine plastic powders (phenolic resin, urea resin, etc.), glass fiber, rock wool, carbon fiber, etc. It is possible to use materials that have the function of a weight-reducing filler.

Furthermore, in order to improve the performance of adhesives, pre-oligomer solution adhesives should be combined with conventionally used amino resins such as urea resins and melamine resins, as well as natural and synthetic polymers, oligomers, and small molecules. Plasticizers and other known additives (heat resistant agents, weather resistant agents, lubricants, fibrous reinforcing agents, etc.) can be added.

The adhesive of 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, and adhesion pressure in the adhesion operation can be set according to conditions used for conventional water-soluble phenolic resin adhesives. and(ni,
In fact, the bonding temperature can be lower than that of conventional phenolic resin adhesives.

That is, bonding temperature: 120°C to 140°C, bonding time:
0.5~1 (min/fi thickness/plywood), adhesive pressure near~15
Excellent adhesion including water-resistant adhesion can be achieved under adhesion conditions such as kgf/cd.

The bonding operation using the adhesive of the present invention can be carried out as appropriate by pressing at room temperature, heating and pressing using a hot press, or by using a thermopressing method using high-frequency heating, microwave heating, or low-voltage heating.

The adhesive of the present invention can be used for wood building materials, ceramic building materials, general woodworking, and for bonding wood with other materials, as well as various types of adhesives including metal materials, plastic materials, fiber materials, etc. It can be used to bond materials. The composition of the present invention also includes matrix resin for composite materials,
Alternatively, it can also be used in applications where phenolic resins are normally used as resins for molding materials.

〔Example〕

The present invention will be further explained below with reference to Examples.

Weigh out 100 parts by weight of Macamba wood chips and 80 parts by weight of phenol into a stainless steel pressure-resistant reaction can, and
The wood chips were heated in an oil bath at 50° C. for 2 hours to dissolve them while also causing phenolization of the wood chips. After adding 40 parts by weight of dioxane to this solution, a 35% formaldehyde aqueous solution was weighed out so that formaldehyde was 2.5 moles per mole of phenol, and the above phenolized Macamba wood-phenol solution was prepared. In addition to
Furthermore, 40% aqueous caustic soda solution was added to adjust the pH of the solution.
was adjusted to 9. This reaction mixture was transferred to a 500 d two-necked flask equipped with a stirrer and condenser, and while stirring,
A reaction was carried out at 0° C. for 1 hour to produce a lignocellulose-resol resin. During this reaction, the po of the reaction mixture was measured approximately every 20 minutes, and 40% aqueous sodium hydroxide solution was added as necessary to maintain the pH at 9. After the reaction, 40 parts by weight of the fraction containing dioxane was distilled off, and 5 parts of coconut shell powder was added to the resulting lignocellulose-resol resin composition.
The composition was subjected to the following adhesion test.

As a test piece for the adhesive bonding, we used birch straight-grained veneer (11X
11 cm), one side of which was coated with adhesive, and the coating amount per adhesive surface was 120 g/rrr. On this occasion,
Place the adhesive specimen so that the wood grain directions are perpendicular to each other, and
Lay them together to form ply plywood, and add 13 pieces of this laminate.
Cold compaction was performed under a pressure of kgf/crJ for 30 minutes, and then heat compaction was performed at 120°C and 13 kgf/d for 6 hours.
It was applied for a minute. After adhesion, the laminate was left indoors overnight, and then specimens for tensile shear tests were cut out according to a conventional method. In this way, for each adhesive, four test pieces were prepared for measuring normal adhesive strength, and four test pieces were prepared for measuring water-resistant adhesive strength. The normal adhesive strength was measured according to the usual method at a tensile rate of 1.
At 0 mm/sin, Shimadzu Autograph DO3-R-5
This was done using 00.

Water-resistant adhesive ability was evaluated by repeated boiling test (4 hours boiling - 6
Dry at 0℃ for 20 hours - Boil for 4 hours - Pour into cold water, approx.
After standing for 5 minutes, the adhesive force was measured in a wet state), and the adhesive force was measured at a tensile speed of 1.0 m/m as above.
The test was carried out using a Shimadzu Autograph DC5-R-500. The adhesive strength characteristics of the obtained adhesive were as follows.

Average value of adhesive strength in normal state: 13.6 kg/cJ, wood breakage rate: 10%, average value of adhesive strength in wet state: 11.3kg/cJ, wood breakage rate: 33% 100 parts by weight of Emma birch wood chips in Example 1 and 80 parts by weight of phenol were weighed into a stainless steel pressure-resistant reaction vessel, and
The wood chips were heated in an oil bath at 50° C. for 2 hours to dissolve them while also causing phenolization of the wood chips. After adding 40 parts by weight of dioxane to this solution, a 35% formaldehyde aqueous solution was weighed out so that formaldehyde was 2.5 moles per mole of phenol, and the above phenolized Macamba wood-phenol solution was prepared. In addition to
Furthermore, 40% aqueous caustic soda solution was added to adjust the pH of the solution.
was adjusted to 9. The reaction mixture was transferred to a 500-capacity two-necked flask equipped with a stirrer and condenser, and heated for 90 mL while stirring.
The mixture was reacted at ℃ for 1 hour to produce lignocellulose-resol resin. During this reaction, the pH of the reaction mixture was measured approximately every 20 minutes, and 40% aqueous sodium hydroxide solution was added as necessary to maintain it at p119. After the reaction was completed, 40 parts by weight of the fraction containing dioxane was distilled off, and a 40% aqueous solution of caustic soda was added to the obtained resol resin liquid to adjust its pH to 11.

For 100 parts of the cellulose-resol resin solution obtained, alkyl resorcinol (
(manufactured by Nagoya Yuka Co., Ltd.) was added, and the reaction mixture was heated at 35°C for 3 hours.
The reaction was allowed to proceed with stirring for 0 minutes. After the reaction was completed, it was cooled to room temperature, and immediately paraformaldehyde, hexamethylenetetramine, and coconut shell powder were added in the amounts shown in Table 1, stirred, and the resulting resin adhesive was subjected to the same adhesion test as described in Example 1. Served. The results obtained are shown in Table 2.

The conventional JIS standard requirements for the adhesive strength of water-soluble phenolic resin (resol resin) adhesives determined by a tensile shear test are 12.0 kgf/cd for normal adhesive strength and 10.01 gf/a for water-resistant adhesive strength. . From this point of view, all the adhesives of the present invention, except for Example 3, meet the specifications. In other words, the excellent results shown in Table 2 were obtained even though the bonding operation was performed at 120°C for 6 minutes, which is much milder for a phenolic resin adhesive. This means that a water-soluble phenolic resin adhesive that can be bonded under the same bonding conditions as urea resins and melamine resins has been obtained, which is of great technical and industrial significance.

Implementation: Weigh out 100 parts by weight of Enigami Air Camba wood chips and 60 parts by weight of phenol into a stainless steel pressure-resistant reaction can.
This mixture was heated in an oil bath at 250° C. for 2 hours to dissolve the wood chips while also causing phenolization of the wood chips. The obtained Macamba wood/phenol solution was transferred to a 500 mff 1 volume 20 flask, and 4
55 parts by weight of 0% aqueous sodium hydroxide solution was added and stirred to dissolve.

Next, 100 parts by weight of 35% formaldehyde aqueous solution (
The molar ratio of formaldehyde to phenol is approximately 2.
1) Add and react at 90°C for 40 minutes under stirring and reflux,
After the completion of the 0 reaction in which the lignocellulose-resol resin was prepared, a 40% aqueous solution of caustic soda was added to the resulting resin liquid to adjust its pH to 11. To this lignocellulose-resole resin liquid, 10 to 25 parts by weight of alkylresorcinol was added to 100 parts by weight of raw material phenol (approximately 1.6 to 4 parts to the resin liquid), and the mixture was stirred at room temperature. (20°C) for 10 hours.

To 100 parts of this resin composition, 10 parts by weight of a mixture of coconut shell powder and wheat flour at a weight ratio of 2:1 was added as a filler, and the resulting adhesive was stirred and subjected to an adhesion experiment. The adhesion experiment was conducted in the same manner as in Example 1, and only the water-resistant adhesion was evaluated by the repeated boiling test. The results are shown in Table 3. As is clear from Table 3, even if the amount of alkylresorcinol added is reduced to about 2/25 to 4/15 of that in Examples 2 to 7, if the reaction is carried out at room temperature for about 10 hours after the addition, , 120° C. for 6 minutes, which is a much gentler bonding condition for a phenolic resin adhesive, and sufficient bonding results could be obtained.

Implementation ■Earthwork The same operation as in Example 2 was performed. However, the operation of adding alkylresorcinol and reacting at 35° C. for 30 minutes was not performed. Furthermore, 10 parts by weight of alkylresorcinol was mixed with 5 parts by weight of coconut shell powder and added to 100 parts by weight of the lignocellulose-resol resin liquid during the adhesion test. The results are shown in Tables 1 and 2.

For disaster relief purposes, the same operations as in Main Example 2 were performed. However, 15 parts by weight of tannin was used instead of alkylresorcinol.

This tannin was larch tannin. Results first
Shown in Table and Table 2.

Implementation group carried out the same operations as in Earthwork Example 2. However, 5 parts by weight of resorcinol was used instead of alkylresorcinol. The results are shown in Tables 1 and 2.

Table 1 Addition amount of alkyl resorcinol etc. (to Macamba wood/phenolic resin adhesive solution 100 parts) Table 2 Normal and wet adhesive strength measurement results Note Adhesive strength unit kg/cd Table 3 Small amount of alkyl resorcinol Alkylresorcinol-enriched Macamba wood is made by adding and reacting for a long time at room temperature.
Measurement results of W wet adhesive strength of phenolic resin adhesive (Note) Adhesive strength unit kg/cd In each of Examples 14 to 17, lignocellulose obtained by the same operation as described in Example 1.・To 100 parts by weight of the phenolic resin liquid, the amount of alkylresorcinol resin liquid (DFX-I manufactured by Nagoya Yuka KK) shown in Table 4 was added.
NS) and further added coconut flour and stirred to prepare a paste. Apply this glue to a thickness of about 2 cranes, 15 x 1
Apply 1 coat per adhesive surface on both sides of 5cs birch straight grain veneer.
It was applied at a rate of 50 g/cd.

Furthermore, birch straight-grain veneers of the same thickness and size are stacked on both sides so that the grain directions are perpendicular to each other, and 13
Temporary compression was carried out for 30 minutes at a pressure of kg/ai.

After that, 1 in a hot press maintained at a temperature of 120℃.
A pressure of 3 kg/cd was applied and hot pressure was applied for 3 minutes. The adhesion strength of the 3-ply sample plywood prepared in this way is J
Measured according to ASI:11 plywood test method. The results are summarized in Table 4.

Table 4 (Note) Adhesive strength unit: kg/cIi! , Wood breakage rate: % [Effect of the invention] The lignocellulose-phenolic resin composition and adhesive of the present invention contain a large amount of lignocellulose material as a raw material, and have a similar comparison with ordinary urea resin and melamine resin. Strong adhesive strength can be developed under moderate adhesive conditions (temperature, time).

Claims (1)

[Claims] 1,100 parts by weight of a phenol compound, and 10 to 100 parts by weight of a phenol compound;
0 parts by weight of lignocellulosic material;
A lignocellulose-phenolic resin composition comprising an addition/condensation reaction product with 0 to 1500 parts by weight of formaldehyde in the presence of a basic catalyst. 2. Claim 1, wherein the mixture containing the phenolic compound and the lignocellulosic material includes a reaction product of the phenolic compound and the lignocellulosic material.
The resin composition described in . 3. An adhesive containing the lignocellulose-phenol resin as described in claim 1 as a main component. 4, 100 parts by weight of a phenol compound, and 10 to 100 parts by weight
0 parts by weight of lignocellulosic material;
100 parts by weight of an addition/condensation reaction product with 0 to 1500 parts by weight of formaldehyde in the presence of a basic catalyst, and 1 to 50 parts by weight of at least one selected from resorcinol compounds and resorcinol compound-formaldehyde initial condensates. A lignocellulose-phenolic resin composition comprising parts by weight. 5. An adhesive containing the lignocellulose-phenol resin composition according to claim 4 as a main component.