JP2004352978A - Biomass resin composition, method for producing the same, and molding material comprising the biomass resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a biomass resin composition freely controllable of its melting point and excellent in physical characteristics, such as fluidity, processability, water resistance, and impact resistance, and to provide a method for producing the composition, capable of simply producing the composition. <P>SOLUTION: This biomass resin composition contains a phenolated biomass substance and a reactive substance having a melting point of ≤ 100°C other than a phenol. The composition is produced by adding the reactive substance, such as a phenol derivative or a drying oil, to a reaction system of a process in which the phenolated biomass substance is produced by subjecting a biomass substance to phenolation reaction with phenols in the presence of an acid catalyst. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a biomass resin composition and a method for producing the same. Further, the present invention relates to a biomass-derived curable resin composition, a thermosetting biomass resin molding material, and a thermosetting biomass resin molded article comprising the biomass resin composition. The biomass-derived curable resin composition of the present invention has a low melting point, good moldability, flexibility of the obtained molded article, excellent impact strength and water resistance, and particularly, various types of It is suitable as a binder (binder) for organic or inorganic substrates, a varnish for impregnation, and a resin for molding materials.

  Phenolic resins are inexpensive and have excellent properties such as moldability, mechanical properties, heat resistance, electrical insulation, chemical resistance, etc., so that various molding materials, electric parts, machine parts, laminated materials, paints, It is used in a wide range of industrial fields as a resin for abrasives and friction materials.

  A phenol resin is usually produced by reacting a phenol with formaldehyde by heating in the presence of an acidic or alkaline catalyst. In the case of the novolak type, hexamethylenetetramine is usually used for curing, and an insoluble or infusible cured resin is obtained by heating. In the case of the resol type, since it is self-curing, it is usually cured by heating without a curing agent. It is known that, by reacting wood powder with phenols instead of formaldehydes, a resin that can be cured with hexamethylenetetramine or the like can be obtained in the same manner as a novolak-type phenol resin. The production of this resin uses abundant wood waste material, does not require the use of formaldehyde, and greatly reduces the amount of phenol used. is there. As the reaction method, a non-catalytic high temperature method (for example, see Patent Document 1, Patent Document 2, and Patent Document 3) and an acid catalyst method (for example, see Patent Document 4 and Patent Document 5) have been reported.

  The non-catalytic high-temperature method is disadvantageous in terms of equipment such as the use of a pressure-resistant reactor, and the thermal decomposition of wood is apt to occur during the reaction, resulting in a low resin yield of the product and low reactivity as a resin raw material. . On the other hand, in the acid catalyzed method, solvolysis of wood and reaction of woody components with phenols mainly occur by the action of a catalyst, and a resin product having high reactivity is obtained by introducing a phenol nucleus. Therefore, much research has been done on the acid catalysis method.

  However, the resin composition obtained by a chemical reaction between wood and phenols (phenolification of wood) has a high melting point of usually 120 to 150 ° C. after removing unreacted excess phenols, and has high usability, In terms of moldability, it was significantly inferior to conventional novolak resins (melting point: 60 to 110 ° C.). Moreover, since the melting point of the wood resin having a melting point of 120 ° C. or higher is close to the crosslinking reaction temperature of a normal curing agent (hexamethylenetetramine), a crosslinking reaction starts to occur before the resin flows sufficiently during molding. Therefore, the curing reaction becomes non-uniform, and defects such as voids and bubbles are present inside the molded product. As a result, the mechanical strength and acetone resistance of the obtained molded product were inferior to those of commercially available novolak resins. Further, since the melting point of the wood resin is high, in the production of the resin, it is difficult to perform processes such as purification, transfer, discharge, and maintenance of facilities.

Further, under the influence of the inherent hydrophilicity of biomass such as wood, the obtained wood resin and its cured product have high water absorption, and the products such as molding materials have poor water resistance.
In addition, products such as molded products made from phenol / wood resin are more brittle than conventional synthetic phenol / formaldehyde resins, and have lower flexibility and impact strength.

  In order to lower the melting point of wood resin, a method has been proposed in which after the phenolization reaction of wood, unreacted phenol remaining in the reaction product is partially left in the resin as a plasticizer (for example, see Patent Document 6). . According to this method, the softening point is lowered, and the performance as a resin for molding materials is improved to some extent. However, the gel time is short due to the effect of unreacted phenol, and the effect of improving the moldability is limited. Furthermore, the presence of a large amount of unreacted phenol in the resin is not preferable from the viewpoint of adverse effects on worker health and the environment.

  Further, Patent Document 7 discloses a method for lowering the melting point of wood resin by causing a large excess of phenol, which is 50 times that of wood, in the reaction between wood and phenol. In this method, it is possible to lower the melting point of the wood resin to 100 ° C. or less. However, since a large excess amount of phenol is used in the reaction, the yield of the wood resin as a product relative to the total amount of the reactants is reduced. Low efficiency of the reaction equipment. Further, after the reaction, a great deal of time and energy are required to remove a large amount of unreacted phenol, so that the cost of the wood resin is high and its practicality is low. Although the above method has a certain effect in lowering the melting point of the resin, it has failed to improve the water resistance and flexibility of the wood resin.

  Therefore, the conventional wood resins are not practical because they are difficult to produce and have problems such as a high melting point or insufficient molding processability and physical properties.

JP-A-61-261358 JP-A-3-59035 JP-A-3-126728 JP-B-61-2697 Japanese Patent Application No. 2-175578 Japanese Patent Application No. 3-328078 JP-A-6-192357

  An object of the present invention is to provide a biomass resin composition in which the melting point can be freely controlled, excellent fluidity, processability and physical properties after a curing reaction, and a simple production method, and a production method thereof. . Further, the present invention provides a curable biomass resin composition comprising a biomass resin composition, a binder, a thermosetting biomass resin molding material, and a molded article comprising a binder or a thermosetting biomass resin molding material. Aim.

  In order to solve the above problem, the characteristics of the chemical structure of a reaction product of phenol and a biomass material such as wood were examined and compared with the chemical structure of a conventional phenol / formaldehyde resin. As a result, it was found that the conventional novolak type phenol / formaldehyde resin had a mainly linear molecular structure, whereas the phenol / biomass resin had a branched molecular structure. This is because biomass material is highly reactive with phenol and has many reaction sides, so during the reaction, the biomass material is solvolyzed by phenol, and then reacts with phenol or another biomass material component to branch off. This is because it has a structure. In particular, when the amount of phenol bound to the biomass material increases, such a branched structure becomes more complicated, the heat fluidity of the phenol / biomass resin further decreases, and the molecular structure lacks flexibility. Conventional phenol / formaldehyde resins contain a large amount of components having low molecular weight and low melting point, such as binuclear and trinuclear, whereas phenol / biomass resins contain such low molecular weight. Almost no components were contained (see FIG. 1). In addition, carbohydrates, which are constituents of biomass substances, contain a large amount of hydroxyl groups and are highly hydrophilic substances, and the biomass resin obtained under the influence of the carbohydrates easily absorbs water and has insufficient water resistance. Due to the composition and structural characteristics of such a phenol / biomass resin, the phenol / biomass resin has a significantly higher melting point despite having a lower average molecular weight than conventional phenol / formaldehyde resins (see Table 1). ) And physical properties are inferior to conventional phenolic resins. As described above, as a result of intensive studies on the chemical structure and composition of the phenol / biomass resin, a reactive substance having a melting point of 100 ° C. or less other than phenol, particularly an oil capable of imparting flexibility and hydrophobic properties to the phenol / biomass resin Achieved the present invention by attaining the object by adding a similar substance, and further coexisting these reactive substances or reactive substance precursors in a process of producing a phenol / biomass resin for phenolizing a biomass substance. It is.

  That is, the present invention relates to a biomass resin composition comprising a phenolated biomass substance and a reactive substance having a melting point of 100 ° C. or less.

  The biomass resin composition preferably contains a product obtained by reacting a biomass substance, phenol, and a reactive substance having a melting point of 100 ° C. or less in the presence of an acid catalyst.

  The reactive substance is preferably at least one compound selected from the group consisting of phenols, phenol derivatives, and condensates of phenols and aldehydes.

  The reactive substance is preferably butylphenol, octylphenol, nonylphenol, benzylphenol or benzylphenyl ether, because it is inexpensive and easily available.

  The reactive substance is preferably an oil containing an aliphatic chain having an unsaturated bond, since the effect of improving water resistance and flexibility is large.

  The reactive substance is preferably a drying oil because it is easily available.

  Further, it is preferable that the drying oil is at least one substance selected from the group consisting of tung oil, linseed oil, and cashew oil because the effect of improving water resistance is greater.

  It is preferable that the biomass material is a lignocellulosic material because it is inexpensive and has excellent physical properties of the obtained resin composition.

  The amount of the reactive substance is preferably 3 to 50% by weight based on the entire biomass resin composition.

  Further, in the present invention, in the step of producing a phenolized biomass substance by phenolizing a biomass substance with phenols in the presence of an acid catalyst, a reactive substance or a reactive substance precursor is added to the reaction system. The present invention relates to a method for producing the biomass resin composition.

  In the above production method, the reactive substance precursor is preferably benzyl alcohol.

  In the above-mentioned production method, the amount of the reactive substance is preferably 3 to 50% by weight based on the whole biomass resin composition.

  In the above-mentioned production method, the biomass substance, the reactive substance, and the phenol can be reacted in the presence of an acid catalyst and then reacted with an aldehyde or an aldehyde derivative.

  The present invention provides a composition comprising at least one substance selected from the group consisting of hexamethylenetetramine, epoxy resin, phenol resole resin, urea resin, melamine resin, polyamic acid and polyvalent isocyanate, and curing comprising the biomass resin composition. The present invention relates to a biomass resin composition.

  The present invention relates to a binder comprising the curable biomass resin composition.

  The present invention also relates to a thermosetting biomass resin molding material comprising the curable biomass resin composition.

  Furthermore, the present invention relates to a molded article comprising the binder or the thermosetting biomass resin molding material.

  The biomass resin composition of the present invention has a low melting point, good fluidity, good moldability, and excellent strength properties, flexibility, and various physical properties such as water resistance of the obtained molding material or molded article, and is cured. It can be used as a thermosetting resin and a thermosetting resin molding material. Further, according to the production method of the present invention, a biomass resin composition can be easily produced.

  The present invention relates to a biomass resin composition containing a phenolated biomass substance and a reactive substance, and a method for producing the same.

  In the present invention, a phenolated biomass substance is a product obtained by chemically reacting a biomass substance with phenols, and includes a decomposed product of the biomass substance itself, or a conjugate of a biomass substance-derived component and phenols. Including.

  Examples of the biomass substance that can be used in the present invention include, but are not limited to, trees, bamboo, kenaf, bagasse, lignocellulosic substances such as rice straw, and wood fibers and wood chips derived therefrom. Paper such as veneer waste, pulp and waste paper; cereals such as rice, wheat and corn; potatoes such as potatoes and sweet potatoes; starch as processed products thereof; and sugars such as sucrose and glucose. Among these, a lignocellulose substance mainly composed of wood is more preferable from the viewpoints of abundance of raw materials, stability of raw material quality, and physical properties of a produced resin. The shape of the biomass material is not particularly limited, but is preferably appropriately ground from the viewpoint of workability and processing speed.

  Examples of phenols that can be used in the present invention include compounds having a phenolic hydroxyl group, such as phenol, cresol, xylenol, bisphenol A, hydroquinone, resorcinol, and alkylresorcinol. These may be used alone or in combination of two or more. Of these, phenol is preferred in terms of cost and reactivity.

  In the phenolation reaction of a biomass substance, intramolecular bonds of carbohydrate and lignin, which are main components of the biomass substance, are cleaved at various degrees, and phenols are further introduced into the product. The resulting product has thermoplasticity and high reactivity. The phenolation reaction of the biomass material proceeds by simply heating the biomass material and the phenol without a catalyst. In this case, a considerably high temperature such as 200 to 250 ° C is required. In addition, under such high temperature conditions, thermal decomposition of the biomass material occurs intensely at the same time as the phenolization reaction, so that the yield of the phenolized biomass material is low and the reactivity of the product is low. To make the phenolation reaction of biomass substances easier and more selective, mineral acids such as sulfuric acid, hydrochloric acid and phosphoric acid, organic acids such as toluenesulfonic acid and phenolsulfonic acid, aluminum chloride, zinc chloride and trifluoride are used. The reaction is preferably performed in the presence of an acid such as a Lewis acid such as boron chloride. The phenolation reaction in the presence of an acid is preferably performed at a temperature of 100 to 180 ° C. If the temperature is lower than 100 ° C., the phenolation reaction requires a long time, which is not practical. When the temperature exceeds 180 ° C., the high-temperature pyrolysis reaction of the biomass material becomes intense, and the reactivity of the reaction product decreases, and the yield tends to decrease.

  In the phenolation reaction of the biomass substance, the phenol is used in a weight ratio of preferably 0.5 to 10 times, more preferably 1 to 5 times, and still more preferably 1.5 to 4 times the weight of the biomass material. If it is less than 0.5 times, the biomass substance cannot be sufficiently phenolized, and the thermoplasticity and reactivity tend to be insufficient. If the ratio exceeds 10 times, there is no problem in the reaction, but the yield of the phenolated biomass substance to be produced becomes low, which is not preferable in terms of working efficiency.

  When performing the phenolation reaction of the biomass material in the presence of an acid catalyst, the acid catalyst is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the biomass material. More preferably, 0.5 to 5 parts by weight is used. If the amount of the acid catalyst is less than 0.1 part by weight, a sufficient catalytic effect cannot be obtained, and the thermoplasticity and reactivity of the reaction product tend to be insufficient. When the amount exceeds 20 parts by weight, the biomass material is polymerized and a crosslinking reaction occurs, and the thermal fluidity tends to decrease.

  The reaction time of the phenolation reaction of the biomass material is not particularly limited, but is in the range of 10 to 300 minutes depending on the required reaction rate of the biomass material, the fluidity and the reactivity of the phenolated biomass material. Just do it.

  In the phenolation reaction of the biomass material, it is not always necessary to make the biomass material react 100%, and the unreacted biomass material may remain in the biomass resin composition as an unreacted residue. The amount of the unreacted residue is measured by dissolving the obtained biomass resin composition in methanol after the reaction, separating insoluble components by filtration, drying, and weighing. This unreacted residue usually does not need to be separated from the biomass resin composition, and may be used as a filler. However, in order to increase the resin ratio in the reaction product and to increase the fluidity of the biomass resin composition, the phenolation reaction is carried out in such a manner that the amount of the unreacted residue in the biomass resin composition is preferably 20% or less, more preferably Is performed until it becomes 10% or less, more preferably 5% or less.

  In the present invention, the reactive substance contained in the biomass resin composition is a resin composition such as a biomass substance, a phenolized biomass substance, and phenol during the production process of the biomass resin composition or during the curing reaction of the biomass resin composition. It reacts with components in the product or a curing agent added to cure the biomass resin composition, and is incorporated into the polymer network. The reactive substance is preferably a substance other than phenol having a melting point of 100 ° C. or less. If the melting point is higher than 100 ° C., the melting point of the biomass resin composition is high, the moldability is insufficient, and the physical properties tend to be reduced. Also, when phenol is used as a reactive substance, when the biomass resin composition is cured using hexamethylenetetramine, the acidic phenol promotes the decomposition reaction of hexamethylenetetramine as a curing agent, and the entire biomass resin composition , The moldability of the biomass resin composition decreases. Furthermore, the use of phenol is not preferred because the presence of a large amount of phenol in the resin adversely affects the working environment. The reactive substance having a melting point of 100 ° C. or less and having a reactive ability other than phenol is not particularly limited, but in consideration of a method for producing a biomass resin composition and a curing method, a compound having a phenolic hydroxyl group Alternatively, a derivative thereof, an oily substance having an aliphatic unsaturated bond, or the like can be used. For example, ot-butylphenol, pt-butylphenol, mt-butylphenol, 2,4-di-t-butylphenol, 2,6-di-t-butylphenol, 3,5-di-t-butylphenol, substituted phenols such as pt-octylphenol, p-nonylphenol, 2-benzylphenol, 4-benzylphenol, o-phenylphenol and 3-methoxyphenol; phenol derivatives such as benzylphenyl ether and diphenyl ether; phenols and formaldehyde Condensate having a melting point of 100 ° C. or less obtained by a reaction under acidic or alkaline conditions with water; a compound having one or more epoxy groups and a melting point of 100 ° C. or less; tung oil, linseed oil, cashew, soybean oil Natural such as rapeseed oil, dehydrated castor oil Drying oils; and synthetic oils containing aliphatic unsaturated bonds. Among them, butyl phenol, octyl phenol, nonyl phenol, benzyl phenol or benzyl phenyl ether is preferred because it has a large effect of lowering the melting point of the biomass resin composition and improving moldability. In addition, natural drying oils such as tung oil, linseed oil, cashew oil and the like have a great effect of lowering the melting point of the biomass resin, improving moldability, and improving the water resistance, flexibility, and impact strength of the biomass resin. In this respect, it is particularly preferable. One type of reactive substance may be used, or two or more types may be used in combination.

  The method of obtaining the biomass resin composition by mixing or reacting the phenolized biomass substance and the reactive substance is not particularly limited, but may be appropriately selected depending on the mode of action of the reactive substance. . For example, substituted phenols such as pt-butylphenol, mt-butylphenol, 2-benzylphenol, and 3-methoxyphenol; phenol derivatives such as benzylphenyl ether and diphenyl ether; and acidic or alkaline conditions between phenols and formaldehyde. Condensates having a melting point of 100 ° C. or lower obtained by the reaction in step 1; compounds having a melting point of 100 ° C. or lower having one or more epoxy groups have a certain effect even without reacting with biomass substances. Therefore, a reactive substance may be added to the reaction system before, during or after the phenolation reaction of the biomass substance, or after the phenolation reaction, the phenolated biomass substance and the reactive substance may be mixed. You may let it. Usually, it is preferable that the phenolated biomass material and the reactive material are melt-mixed, so that the melt-mixing can be easily performed. Preferably, the substance is added into the reaction system. In addition, the reactive substance is added to the reaction system before, during, or after the phenolation reaction of the biomass substance, because the resulting molten mixture has a low melting point, which facilitates handling such as discharge. Is preferred. Furthermore, the viscosity of the reaction system decreases due to the diluting action of the added reactive substance, the phenolation reaction of the biomass substance proceeds more easily, and a more uniform product can be obtained. Involvement in the reaction system reduces the degree of reactivity between the phenol and the biomass material, and the molecular structure becomes more linear, so that the melting point of the phenolated biomass material can be further reduced. More preferably, a reactive substance is added.

  Furthermore, when the reactive substance is a drying oil, the drying oil has low compatibility with the biomass component, and therefore, the addition after the phenolation reaction of the biomass substance does not cause a chemical reaction between the drying oil and the biomass or the phenolized biomass component. Since the drying oil and the phenolized biomass are phase-separated, it is difficult to obtain an effect of improving physical properties such as water resistance and flexibility. In order to obtain a reforming effect by the drying oil, it is necessary to chemically react the drying oil with the biomass and / or the phenolized biomass. Therefore, it is preferable to add the drying oil before or during the reaction. The reaction between the drying oil and the biomass and / or phenolized biomass is preferably performed at 60 to 180 ° C under acidic conditions, more preferably at 80 to 160 ° C. The reaction time is not particularly limited, and may be, for example, 30 to 180 minutes.

  The phenolization reaction of biomass such as wood is usually performed in the presence of a strong acid such as sulfuric acid or phenolsulfonic acid at a temperature of 100 ° C. or higher, so that the drying oil denaturation is performed directly in parallel with the phenolation of biomass under the same conditions. be able to. Alternatively, the drying oil and phenol may be reacted first, and then biomass may be added to continuously perform phenolation.

  The reactive substance can also be produced by directly phenolizing a reactive substance precursor and a phenol in a phenolation reaction system of a biomass substance. When the reactive substance precursor is added to the reaction system when producing the phenolized biomass substance, the reactive substance precursor reacts with the phenols present in the reaction system to generate a reactive substance. Therefore, when a reactive substance precursor is used, the reactive substance need not be added, and the reactive substance precursor and the reactive substance can be used in combination. The reactive substance precursor is cheaper than the reactive substance and can be added in a small amount. Therefore, it is preferable to add the reactive substance precursor from the viewpoint of manufacturing cost. In addition, a step of separately producing a reactive substance can be omitted, which is preferable in terms of work convenience. As the reactive substance precursor, a substance that can react with phenols and has a melting point of 100 ° C. or less of the generated reactive substance can be used. Although not particularly limited, for example, benzyl alcohol, 2,4-dimethoxybenzyl alcohol, 3,4-dimethoxybenzyl alcohol, 3,5-dimethoxybenzyl alcohol, 2,5-dimethoxybenzyl alcohol, m-hydroxybenzyl alcohol Benzyl alcohol and its derivatives such as p-hydroxybenzyl alcohol, p-methylbenzyl alcohol and m-nitrobenzyl alcohol. Among these, benzyl alcohol, which is inexpensive and easily available industrially, is particularly preferred. For example, when benzyl alcohol is used as a reactive substance precursor, benzyl alcohol is less reactive with biomass substances than phenol, and therefore reacts less directly with biomass substances, but is present in the system under an acidic catalyst. It reacts quickly with the phenol to be reacted and is converted into the reactive substances 2-benzylphenol (melting point 54 ° C), 4-benzylphenol (melting point 83 ° C) and benzylphenyl ether (melting point 39 ° C).

  The timing of addition of the reactive substance precursor is not particularly limited, and it may be added before, during or after the phenolation reaction of the biomass substance. An effect can be obtained if the reactive substance precursor can be reacted with phenol in the reaction system. However, in order to obtain a further softening point reducing effect, it is preferable to add the biomass substance before the phenolation reaction. By adding before the reaction, the effect of increasing the solvent and the effect of reducing the viscosity by the reactive substance precursor can be obtained. Thereby, the uniformity of the reaction of the biomass material is improved, and furthermore, the amount of the bond between the biomass material and phenol is reduced by the action of the reactive substance precursor, so that a good phenolation product having a lower melting point can be obtained. .

  The amount of the reactive substance is preferably in the range of 3 to 50% by weight, more preferably in the range of 5 to 40% by weight based on the total weight of the biomass resin composition. If the amount is less than 3%, the amount of the reactive substance is small, and a sufficient reforming effect cannot be obtained. If the amount of the reactive substance exceeds 50% by weight, the reactivity and physical properties of the resin tend to decrease.

In the present invention, after preparing the biomass resin composition, usually unreacted free phenols are present in the reaction system. In the presence of a large amount of free phenol, the moldability and physical properties of the resin deteriorate, so it is preferable to remove the free phenol. The method for removing free phenol is not particularly limited, and can be removed using a method such as washing with water, solvent extraction, steam distillation, and vacuum distillation, but vacuum distillation is preferable in terms of workability and cost. . The vacuum distillation can be carried out under the conditions of a normal temperature of 120 to 200 ° C. and a pressure of 20 to 100 mmHg (2.6 × 10 ^{−3 to} 1.3 × 10 ⁻² MPa). The amount of free phenol in the biomass resin composition after purification by vacuum distillation is not particularly limited, but is preferably 5% or less, more preferably 2% or less.

  In the present invention, after the reaction of the biomass substance, the reactive substance and the phenol, the unreacted free phenol is not removed, and an aldehyde or an aldehyde derivative is added to the reaction system and the reaction is continued under acidic or alkaline conditions. You can also. After the reaction of the biomass substance, the reactive substance, and the phenol, an aldehyde or an aldehyde derivative is added to the obtained reaction product to further add a phenol nucleus or add a methylol group (methylolation). be able to. The aldehyde or aldehyde derivative to be added is not particularly limited. Examples of the aldehyde include paraformaldehyde, formalin, and furfural, and examples of the aldehyde derivative include hexamethylenetetramine. The aldehyde or aldehyde derivative is preferably added at a molar ratio of 1 or less under the acidic reaction conditions to the amount of the phenols in the reaction system. If the molar ratio exceeds 1, the reactants tend to rapidly polymerize or gel. Further, under alkaline conditions, it is preferable to add 1.0 to 4.0 in a molar ratio. If the molar ratio is less than 1.0, there is a tendency that the curing reactivity becomes insufficient due to insufficient methylol groups. If the molar ratio exceeds 4.0, a large amount of aldehyde tends to remain in the reaction product. The biomass resin composition converted into methylol by this method is usually in a liquid state, and can be used for an adhesive, a varnish for impregnation, and the like. The reaction temperature when adding aldehyde or aldehyde derivative and continuing the reaction is not particularly limited. The temperature is preferably in the range of 60 to 150 ° C, but when a rapid exothermic reaction can occur, the reaction temperature is more preferably set to 60 to 100 ° C. The reaction time is not particularly limited, and the reaction can be usually performed for 0 to 180 minutes.

  The melting point of the biomass resin composition of the present invention obtained by the above-mentioned production method (other than those subjected to methylolation) is controlled in the range of 60 to 120 ° C by adjusting the species and / or the amount of the reactive substance. can do. The biomass resin composition of the present invention has excellent fluidity, moldability, and physical properties such as strength, heat resistance, and solvent resistance of the cured resin. Furthermore, by using a drying oil as a reactive substance, the water resistance and flexibility of the obtained biomass resin are simultaneously improved.

  The biomass resin composition of the present invention can be used as a curable biomass resin composition or a biomass molding material.

  The biomass resin composition of the present invention is thermoplastic, except that the above-mentioned aldehydes are added and methylolated under alkaline conditions, but by adding a cross-linking agent (or cross-linked resin) as a curing agent. And a curable biomass resin composition. As the curing agent, one or more selected from the group consisting of hexamethylenetetramine, epoxy resin, phenol resole resin, urea resin, melamine resin, polyamic acid and polyvalent isocyanate can be used. Among these, hexamethylenetetramine is preferred from the viewpoints of high-speed reactivity, low cost, and small addition amount. The amount of the curing agent to be added depends on the type of the curing agent, but may be a normal amount in each curing system. For example, when using hexamethylenetetramine as a curing agent, it is preferable to add 5 to 25 parts by weight based on 100 parts by weight of the biomass resin composition. If the amount is less than 5 parts by weight, curing may be incomplete and good physical properties may not be obtained. If the amount is more than 25 parts by weight, a large amount of gas is generated during the curing reaction, and defects are generated in the cured product. Good physical properties may not be obtained. When crosslinking with an epoxy resin or a polyvalent isocyanate, it is preferable to add 0.5 to 2.0 equivalents to 1 equivalent of the hydroxyl group of the biomass resin composition. If the amount is less than 0.5 equivalent or more than 2.0 equivalents to 1 equivalent of the hydroxyl group, curing may be incomplete in any case, and good cured physical properties may not be obtained. When a phenol resole resin, a urea resin, a melamine resin, or a polyamic acid is used as a curing agent, it is preferable to add 30 to 300 parts by weight based on 100 parts by weight of the biomass resin composition. If the amount is less than 30 parts by weight or more than 300 parts by weight, curing may be incomplete, and good cured physical properties may not be obtained.

  Various curing accelerators can be further added to the curable biomass resin composition. The curing accelerator is not particularly limited, and any of those usually used in each curing system can be used. For example, in a curable biomass resin composition / hexamethylenetetramine system, addition of hexamethylenetetramine with phenols such as earth metal oxides or hydroxides such as calcium oxide, magnesium oxide and calcium hydroxide, and resorcinol. , Sodium tetraborate, dicarboxylic acid, various amine compounds and the like can be used. In the curable biomass resin composition / epoxy resin system, diazabicycloalkene and its derivatives; tertiary amines such as triethylenediamine; imidazoles such as 2-methylimidazole; organic phosphines such as tributylphosphine are used. be able to. The curing temperature is not particularly limited, but is preferably in the range of 120 to 300 ° C. except when a polyvalent polyisocyanate is used. In the case of a polyvalent isocyanate, the temperature is preferably in the range of room temperature to 120 ° C.

  Since the curable biomass resin composition of the present invention becomes a three-dimensional cured product having excellent strength, heat resistance and solvent resistance by heating, various types of organic and inorganic substances such as shell molds, grindstones, refractories, and friction materials can be used. It is useful as a binder (binder) and as a resin for molding materials for parts of machines, automobiles, electric / electronic and communication equipment.

  The curable biomass resin composition of the present invention can be used as a binder for all conventionally used base materials and auxiliary materials in various industries depending on the application. The curable biomass resin composition composition in which the curable biomass resin composition is blended with the base material / sub-material is used as a molded article in various industries after molding.

  Examples of the base material and auxiliary materials include casting sand such as silica sand for shell molds; various abrasives, fillers, and cloths for abrasives; rock wool, Kevlar fiber, and glass for friction materials. Fibers, inorganic fillers, etc .; Refractories include fused products such as fused alumina and fused magnesia, burned products such as burned magnesia, various metal oxides, carbides, graphite, etc .; various molded products such as building materials and interior materials Examples include rock wool, glass fibers, inorganic fillers, inorganic lightweight aggregates, wood chips, pulp, and organic fibers. If necessary, a curing accelerator, a release agent, a coloring agent, and the like may be added to the curable biomass resin composition composition. When used as a binder as described above, the curable biomass resin composition is generally blended in an amount of 1 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the base material / sub-material.

  The mixing order and mixing method of the base material / sub-material and the curable biomass resin composition are not particularly limited, and a conventionally known method for each application can be used. For example, a method of mixing with a mixer at room temperature or a method of heating and mixing, a method in which a solution obtained by dissolving a biomass resin composition in a solvent is coated on a substrate / sub-material, a method of spraying or applying, or a method in which the substrate / sub-material is applied to the solution. And a method of impregnation.

  The method for molding the curable biomass resin composition composition is not particularly limited, and any conventionally known method can be used. For example, hot-press molding, firing molding, heat molding and the like can be mentioned. The molding temperature varies depending on the application, but is usually 120 to 300 ° C. When producing a refractory, it can be carbonized at 1200 ° C.

  When the curable biomass resin composition of the present invention is used for a thermosetting resin molding material, the biomass resin composition, in addition to the curing agent, if necessary, a curing accelerator, an inorganic filler or an organic filler. You may make it contain. By adding the filler, the strength, dimensional stability, and the like of the obtained molded body can be further improved. As the filler, various organic or inorganic fillers that can be used as a filler or a reinforcing material in a plastic material can be used. For example, reinforcing fibers such as wood flour, cellulose, wood pulp, glass fiber, carbon fiber, phosphor fiber, and boron fiber; hydrated metal oxides such as aluminum hydroxide and magnesium hydroxide; metals such as magnesium carbonate and calcium carbonate Carbonates; metal borates such as magnesium borate; and inorganic fillers such as silica, carbon black, mica, and fused silica. The amount of the filler is not particularly limited. For example, it is usually 20 to 2,000 parts by weight, preferably 30 to 2,000 parts by weight, based on 100 parts by weight of a resin component (curable resin composition) obtained by adding a curing agent to a biomass resin composition. It is 1000 parts by weight, more preferably 50 to 500 parts by weight. Further, the thermosetting biomass resin molding material may further contain an additive, if necessary. Examples of the additives include internal release agents such as silicones and waxes, coupling agents, flame retardants, light stabilizers, antioxidants, pigments, extenders, and the like.

  The thermosetting biomass resin molding material of the present invention is prepared by mixing a biomass resin composition, a curing agent, and if necessary, a curing accelerator, a filler, and various additives, and is applied to the production of a molded article. In the present invention, the mixing order of the biomass resin composition and the optional component such as a curing agent is not particularly limited, but, for example, after the biomass resin composition and the curing agent are mixed well, if necessary, filler and other components And the like can be added and mixed to obtain a powdery or granular molding material (compound).

  For example, specifically, the compound can be prepared by the following procedure. First, the biomass resin composition and hexamethylenetetramine are pulverized and mixed at room temperature using a mixer or the like, and then the mixture is added with additives such as a curing accelerator and a release agent, mixed, and further, a filler is added. Mix. Thereafter, the mixture is heated and kneaded with a hot roll machine or a twin-screw kneader adjusted to 80 to 100 ° C., returned to room temperature, and pulverized to obtain a compound. The filler and other additives can be added at any time, not after mixing the biomass resin composition with the curing agent. Alternatively, a method of mixing only at room temperature without heating and kneading, or a method of wet-mixing each component with a mixer or the like using a solvent such as methanol and drying after mixing may be used.

The thermosetting biomass resin molding material of the present invention can be formed into a molded body by various conventionally known resin molding means. Examples of such resin molding means include compression molding, injection molding, extrusion molding, transfer molding, and casting. More specifically, when a molded article is manufactured by transfer molding using the biomass resin molding material of the present invention, a molding temperature of 120 to 200 ° C and an injection pressure of 5 to 300 kgf / cm ² (0.49 to 29. 4MPa)
Preferably 20~300kgf / cm ² (1.96~29.4MPa), clamping pressure 50~250kgf / cm ² (4.9~24.5MPa) and moldings at molding conditions of the molding time to 10 minutes Can be manufactured.

  The molded product obtained from the thermosetting biomass resin molding material of the present invention is used for parts such as machinery, automobiles, electric / electronic, communication devices, building materials such as various organic / inorganic boards, and miscellaneous goods such as synthetic lacquerware. .

  Examples are shown below to explain the present invention in detail, but the present invention is not limited by these.

Example 1
First, 100 parts by weight of dried rice pine wood flour is charged into a separable flask equipped with a stirrer, a thermometer, a reflux condenser and a charging port, and then 300 parts by weight of phenol containing 1% by weight of sulfuric acid are added. 20 parts by weight of benzyl alcohol were added. After completion of the addition, the mixture was reacted at 145 to 150 ° C. under reflux for 2 hours while stirring was continued. Next, the mixture was neutralized with magnesium oxide, and unreacted phenol was distilled off at a reduced pressure at a maximum temperature of 160 ° C. to obtain 0.2% of free phenol and 220 parts by weight of a wood powder resin composition having a softening point of 94.6 ° C. Obtained. The amount of unliquefied wood flour residue was 1.2%.

Example 2
The same conditions as in Example 1 except that the addition amount of phenol containing 1% by weight of sulfuric acid was 250 parts by weight and the addition amount of benzyl alcohol was 25 parts by weight based on 100 parts by weight of dry rice pine wood flour. Thus, 215 parts by weight of the wood flour resin composition was obtained. Table 2 shows the analysis results of the wood powder resin composition.

Example 3
As a biomass substance, 100 parts by weight of dry office paper (crushed with a shredder) was used instead of wood flour, and 300 parts by weight of phenol containing 2% by weight of sulfuric acid and 20 parts by weight of benzyl alcohol were added. Under the same conditions as in Example 1, 240 parts by weight of a waste paper resin composition were obtained. Table 2 shows the analysis results of the waste paper resin composition.

Example 4
Under the same conditions as in Example 1 except that benzyl alcohol as a reactive substance precursor was not added to the phenolation of dried rice pine wood flour, the wood flour was subjected to phenolation reaction under reflux at 145 to 150 ° C. for 2 hours. Thereafter, 20 parts by weight of benzyl alcohol was added, and the mixture was further reacted at the same temperature for 20 minutes. Next, after neutralizing with magnesium oxide, unreacted phenol was distilled off to a temperature of up to 160 ° C. under reduced pressure to obtain 265 parts by weight of the woody resin composition. Table 2 shows the analysis results of the wood powder resin composition.

Example 5
First, 100 parts by weight of dried rice pine wood flour is charged into a separable flask equipped with a stirrer, a thermometer, a reflux condenser and a charging port, and then 300 parts by weight of phenol containing 1% by weight of sulfuric acid are added. 35 parts by weight of pt-butylphenol were added. After completion of the addition, the mixture was reacted at 145 to 150 ° C. under reflux for 2 hours while stirring was continued. Next, after neutralization with magnesium oxide, the pressure was reduced and the unreacted phenol was distilled off at a maximum temperature of 160 ° C., whereby 235 parts by weight of the wood flour resin composition was obtained. Table 2 shows the analysis results of the wood powder resin composition.

Example 6
First, 100 parts by weight of dried rice pine wood flour was charged into a separable flask equipped with a stirrer, a thermometer, a reflux condenser and a charging port, and then 300 parts by weight of phenol containing 1% by weight of sulfuric acid were added. After completion of the addition, the mixture was reacted at 145 to 150 ° C. under reflux for 2 hours while stirring was continued. Next, after neutralizing with magnesium oxide, 35 parts by weight of p-nonylphenol was added and dissolved with sufficient stirring. The unreacted phenol was distilled off at a maximum pressure of 160 ° C. under reduced pressure to obtain 260 parts by weight of the wood flour resin composition. Table 2 shows the analysis results of the wood powder resin composition.

Example 7
First, 100 parts by weight of dried rice pine wood flour was charged into a separable flask equipped with a stirrer, a thermometer, a reflux condenser and a charging port, and then 300 parts by weight of phenol containing 1% by weight of sulfuric acid were added. After completion of the addition, the mixture was reacted at 145 to 150 ° C. under reflux for 1 hour while stirring was continued. Then, 100 parts by weight of tung oil (Nacalai Tesque, Inc.) was added, and the mixture was further reacted at the same temperature for 60 minutes. Next, after neutralizing with magnesium oxide, unreacted phenol was distilled off to a maximum temperature of 160 ° C. under reduced pressure to obtain 336 parts by weight of the woody resin composition. Table 2 shows the analysis results of the wood powder resin composition.

Example 8
284 parts by weight of a tung oil-modified woody resin composition was obtained under the same conditions as in Example 7, except that the amount of tung oil was changed to 50 parts by weight. Table 2 shows the analysis results of the wood powder resin composition.

Examples 9 to 11
Except for using linseed oil (Nacalai Tesque Co., Ltd.), cashew oil (Kyowa Oil Industry Co., Ltd.), and soybean oil (Nacalai Tesque Co., Ltd.) instead of tung oil, linseed oil was used under the same conditions as in Example 8. An oil-modified wood resin, a cashew oil-modified wood resin, and a soybean oil-modified wood resin were prepared. Table 2 shows the analysis results of the respective wood powder resin compositions.

Example 12
First, 100 parts by weight of dried rice pine wood flour is charged into a separable flask equipped with a stirrer, a thermometer, a reflux condenser and a charging port, and then 300 parts by weight of phenol containing 1% by weight of sulfuric acid are added. 20 parts by weight of benzyl alcohol were added. After completion of the addition, the mixture was reacted at 145 to 150 ° C. under reflux for 1 hour while stirring was continued. Then, 100 parts by weight of tung oil was added, and the mixture was further reacted at the same temperature for 60 minutes. Next, after neutralization with magnesium oxide, unreacted phenol was distilled off to a maximum temperature of 160 ° C. under reduced pressure to obtain 331 parts by weight of the woody resin composition. Table 2 shows the analysis results of the obtained wood flour resin composition.

Example 13
First, 100 parts by weight of dried rice pine wood flour is charged into a separable flask equipped with a stirrer, a thermometer, a reflux condenser and a charging port, and then 300 parts by weight of phenol containing 1% by weight of sulfuric acid are added. 20 parts by weight of benzyl alcohol were added. After completion of the addition, the mixture was reacted at 145 to 150 ° C. under reflux for 2 hours while stirring was continued. Thereafter, the temperature of the reaction product was lowered to 90 ° C., and a small amount of the reaction product was sampled and measured by HPLC. As a result, 172 parts by weight of unreacted phenol was present. While refluxing, 89 parts by weight of formalin (0.6 mol based on phenol) were added dropwise over 20 minutes. Thereafter, the mixture was further reacted at 90 ° C. for 30 minutes, and then neutralized with magnesium oxide, and the unreacted phenol was distilled off at a reduced pressure of 160 ° C. to obtain 300 parts by weight of a wood flour resin composition. Was. Table 2 shows the analysis results of the obtained wood flour resin composition.

Example 14
First, 100 parts by weight of dried rice pine wood flour is charged into a separable flask equipped with a stirrer, a thermometer, a reflux condenser and a charging port, and then 200 parts by weight of phenol containing 1% by weight of sulfuric acid are added. 100 parts by weight tung oil were added. After completion of the addition, the mixture was reacted at 145 to 150 ° C. under reflux for 2 hours while stirring was continued. Thereafter, the temperature of the reaction product was lowered to 60 ° C., and a small amount of the reaction product was sampled and measured by HPLC. As a result, 89 parts by weight of unreacted phenol was present. 9.4 parts by weight of 50% sodium hydroxide and 100 parts of water are added to the above reaction product, and 162 parts by weight of 35% formalin (2.0 moles based on free phenol) are refluxed at 60 ° C. for 20 minutes. And dropped. Thereafter, the reaction was further performed at 60 ° C. for 180 minutes to obtain 670 parts by weight of a resol type wood resin solution. The obtained resin had a nonvolatile content of 63%, a viscosity at 25 ° C of 1900 CP, and a gel time at 150 ° C of 82 seconds. It was stable even after storage at room temperature for one month.

Comparative Example 1
First, 100 parts by weight of dried rice pine wood flour was charged into a separable flask equipped with a stirrer, a thermometer, a reflux condenser and a charging port, and then 300 parts by weight of phenol containing 1% by weight of sulfuric acid were added. After completion of the addition, the mixture was reacted at 145 to 150 ° C. under reflux for 2 hours while stirring was continued. Next, the mixture was neutralized with magnesium oxide, and the unreacted phenol was distilled off at a reduced pressure at a maximum temperature of 160 ° C. to obtain 3.2% of free phenol and 230 parts by weight of the wood powder resin composition having a softening point of 126.3 ° C. Obtained. The amount of unliquefied wood flour residue was 1.3%.

Comparative Example 2
As a biomass substance, 100 parts by weight of dry office paper (crushed with a shredder) was used instead of wood flour, and 300 parts by weight of phenol containing 2% by weight of sulfuric acid were added. Thus, 220 parts by weight of a waste paper resin composition having a free phenol of 2.1% and a softening point of 132.4 ° C. was obtained. The amount of unliquefied residue was 7.1% (including the filler component in waste paper).

Examples 15 to 27
15 parts by weight of hexamethylenetetramine was added to 100 parts by weight of the biomass resin obtained in Examples 1 to 13, and a vibration ball mill (MB-3, manufactured by Chuo Kakoki Co., Ltd.) was used for 10 minutes at room temperature. The mixture was pulverized and mixed to obtain a curable biomass resin composition. Table 2 shows the results of measuring the fluidity (flow) of the obtained curable biomass resin composition based on JIS K6910-1999. Further, 4 parts by weight of calcium hydroxide as a curing accelerator and 2 parts by weight of zinc stearate as a lubricant were added to and mixed with 100 parts by weight of the obtained mixture, and then wood flour (cellulosin No. 100; 100 parts by weight (manufactured by Casino Inc.) were added and mixed. The resulting mixture was kneaded at 100 ° C. and 60 rpm using a biaxial kneader (manufactured by Toshiba Machine Co., Ltd.) with L / D = 24, cooled to room temperature, pulverized with a power mill, and formed into a molding compound (molding). Material). Table 3 shows the results of measuring the moldability (disc flow) of the obtained molding material based on JIS K6911-1995. Further, using a compression molding die and a hot press, the obtained compound was molded at 175 ° C. and 300 kgf / cm into a bending test molded product (test piece, 4 mm × 10 mm × 100 mm) in accordance with JIS K6911-1995 standard. ² (29.4 MPa) for 5 minutes. Table 3 shows the results obtained by measuring the flexural strength, flexural modulus, flexural rupture strain, and 24-hour immersion water absorption of the test piece based on JIS K6911-1995, and the results of evaluating the appearance of the molded article according to the following evaluation criteria.

Appearance evaluation of molded article ：: The surface is uniform and glossy.
Δ: There are spots of color or dull parts on the surface.
×: There is no gloss or cracks on the whole.

Comparative Examples 3 and 4
Except for using the biomass resin compositions obtained in Comparative Examples 1 and 2 instead of the biomass resins obtained in Examples 1 to 13, in the same manner as in Examples 15 to 27, a curable biomass resin mixture, Compounds and compacts were obtained. Table 2 shows the results of measuring the fluidity of the obtained curable biomass resin composition, and Table 3 shows the results of evaluating the moldability of the compound, the appearance of the molded body, the bending strength and the flexural modulus of the molded body.

Examples 28 to 29
The curable resin composition obtained in Example 15 was used as a binder, and the components were mixed at a mixing ratio shown in Table 4 using a mixer. Then, the mixture was hot-pressed at 180 ° C. for 15 minutes under a pressure of 10 MPa to a thickness of 15 mm. Was formed. The molded body was cut out in a size of 20 mm × 100 mm, and the bending strength was measured by a three-point bending strength test method (fulcrum distance 80 mm). Table 4 shows the measurement results.

  As shown in Table 2, in Examples 1 to 3 in which benzyl alcohol as a reactive substance precursor was added, the softening point of the obtained resin composition was 100 ° C or less. In particular, in Example 2 in which the addition amount of benzyl alcohol was 25 parts by weight, a resin composition having a softening point of 85 ° C. was obtained. The measurement results of the flows of the resin compositions obtained in Examples 1 to 3 were 43 mm, 55 mm, and 32 mm at 125 ° C., respectively.

  In Example 4, benzyl alcohol was added after completion of phenolation. The softening point of the resin composition was 104.8 ° C., which was higher by 10 ° C. than the softening point of the resin composition obtained in Example 1 added at the beginning of the phenolation reaction of the biomass substance.

  Examples 5 and 6 are systems in which an alkylphenol is added as a reactive substance. In Example 5, the reactive substance was added before the phenolation reaction. In Example 6, the reactive substance was added after the phenolation reaction. Although the softening point reducing effect was somewhat lower than the systems of Examples 1 to 3 to which benzyl alcohol was added, practical results were obtained.

  Examples 7 and 8 are systems in which tung oil was added as a reactive substance. In Example 7, tung oil was added in the same amount as wood flour. In Example 8, 50% by weight of wood flour was added. In both cases, the softening points were 100 ° C. or less, and the fluidity was good.

  In Examples 9 to 11, linseed oil, cashew oil, and soybean oil were used instead of tung oil as the reactive substance, but in all cases, the softening point was 100 ° C or less, and the fluidity was good.

  Example 12 is an example in which benzyl alcohol and tung oil were used in combination. The combined use lowered the softening point of the resin composition to 83 ° C. and was excellent in fluidity.

  In Example 13, after the phenolation reaction in the presence of benzyl alcohol, formalin was subsequently added to partially incorporate the unreacted phenol into the biomass resin composition. As a result, the yield of the resin composition was increased by 80 parts by weight as compared with Example 1, and the softening point and fluidity were almost the same as those of Example 1.

  Example 14 is an example of the preparation of a liquid resole resin, but the resulting resole had good stability, reactivity and viscosity properties.

  On the other hand, in Comparative Examples 1 and 2, the biomass resin compositions obtained by the conventional method without the addition of a reactive substance had high softening points of 126.3 ° C. and 132.4 ° C., respectively, and a fluidity of 0. Was.

  From Table 3, the biomass molding compound comprising the resin composition obtained in Examples 1 to 13 and the molded product comprising the compound were compared with the biomass molding compound comprising the resin composition obtained in Comparative Examples 1 and 2, and the molded product thereof. As a result, it was found that the moldability was good and the appearance, strength properties and water resistance of the molded article were excellent. In particular, in Examples 21 to 26 using the drying oil-modified resin, the elastic modulus of the molded product was further reduced as compared with the use of other additives, and the bending rupture strain was greatly improved. The water absorption was about 1/3 of the comparative example, and was 50% lower than that of Examples 15 to 20. That is, the use of the drying oil significantly improved the water resistance and flexibility of the resin molded product.

  On the other hand, the molded articles of Comparative Examples 3 and 4 had poor moldability, not only low strength physical properties, but also had matte surfaces such as corners of the molded articles. From Table 4, it was found that the biomass resin composition of the present invention had excellent performance as a binder.

It is a figure which shows the comparison of the molecular weight distribution of the conventional phenol / formaldehyde resin and phenol / biomass resin.

Claims (17)

A biomass resin composition comprising a phenolated biomass substance and a reactive substance having a melting point of 100 ° C. or less. The biomass resin composition according to claim 1, comprising a product obtained by reacting a biomass substance, phenol, and a reactive substance having a melting point of 100 ° C or less in the presence of an acid catalyst. 3. The biomass resin composition according to claim 1, wherein the reactive substance is at least one compound selected from the group consisting of phenols, phenol derivatives, and condensates of phenols and aldehydes. The biomass resin composition according to claim 3, wherein the reactive substance is butylphenol, octylphenol, nonylphenol, benzylphenol or benzylphenylether. The biomass resin composition according to claim 1 or 2, wherein the reactive substance is an oil containing an aliphatic chain having an unsaturated bond. The biomass resin composition according to claim 1 or 2, wherein the reactive substance is a drying oil. The biomass resin composition according to claim 6, wherein the drying oil is at least one substance selected from the group consisting of tung oil, linseed oil, and cashew oil. The biomass resin composition according to claim 1, wherein the amount of the reactive substance is 3 to 50% by weight based on the entire biomass resin composition. The biomass resin composition according to claim 1, 2, 3, 4, 5, 6, 7, or 8, wherein the biomass material is a lignocellulose material. The biomass according to claim 1, wherein in the step of producing a phenolized biomass material by phenolizing the biomass material with phenols in the presence of an acid catalyst, a reactive substance or a reactive substance precursor is added into the reaction system. A method for producing a resin composition. The method for producing a biomass resin composition according to claim 10, wherein the reactive substance precursor is benzyl alcohol. The method for producing a biomass resin composition according to claim 10 or 11, wherein the amount of the reactive substance is 3 to 50% by weight based on the entire biomass resin composition. The method for producing a biomass resin composition according to claim 10, wherein the biomass substance, the reactive substance, and the phenol are reacted in the presence of an acid catalyst and then reacted with an aldehyde or an aldehyde derivative. 7. One or more substances selected from the group consisting of hexamethylenetetramine, epoxy resin, phenol resole resin, urea resin, melamine resin, polyamic acid and polyvalent isocyanate, and claim 1, 2, 3, 4, 5, 6, 10. A curable biomass resin composition comprising the biomass resin composition according to claim 7, 7, 8, or 9. A binder comprising the curable biomass resin composition according to claim 14. A thermosetting biomass resin molding material comprising the curable biomass resin composition according to claim 14. A molded article comprising the binder according to claim 15 or the thermosetting biomass resin molding material according to claim 16.

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