JP3911614B2 - Biomass resin composition, method for producing the same, and molding material comprising the biomass resin composition - Google Patents

Description

  The present invention relates to a biomass resin composition and a method for producing the same. Moreover, this invention relates to the biomass origin curable resin composition which consists of this biomass resin composition, a thermosetting biomass resin molding material, and a thermosetting biomass resin molding. The biomass-derived curable resin composition of the present invention has a low melting point and good moldability, and is excellent in terms of flexibility, impact strength, water resistance, and the like of the obtained molded product. It is suitable as an organic or inorganic base material binder (binder), impregnating varnish, molding resin.

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

  The phenol resin is usually produced by heating and reacting phenols and formaldehydes in the presence of an acidic or alkaline catalyst. Usually, in the case of the novolak type, hexamethylenetetramine is used together for curing, and an insoluble and 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 using a curing agent. It is known that a resin that can be cured with hexamethylenetetramine or the like can be obtained by reacting wood flour with phenols instead of formaldehydes, similarly to the novolac type phenol resin. In the production of this resin, abundant wood waste is used, it is not necessary to use formaldehyde, and the amount of phenol used can be greatly reduced. 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 because the thermal decomposition of wood easily occurs during the reaction, the resin yield of the product is low, and the reactivity as a resin raw material is also low. . On the other hand, in the acid catalyst method, the solvolysis of wood by the action of the catalyst and the reaction between the wood component and phenols mainly occur, and the resin product having high reactivity can be obtained by introducing the phenol nucleus. Therefore, much research has been done on the acid catalyst method.

  However, the resin composition obtained by the chemical reaction between wood and phenols (wood phenolization) usually has a high melting point of 120 to 150 ° C. after removing unreacted excess phenols, In terms of moldability, it was significantly inferior to conventional novolac resins (melting point: 60 to 110 ° C.). In addition, the wood resin having a melting point of 120 ° C. or higher in this way has a melting point close to the crosslinking reaction temperature with a normal curing agent (hexamethylenetetramine), so that a crosslinking reaction starts to occur before the resin sufficiently flows during the molding process. Therefore, the curing reaction becomes non-uniform, and defects such as cavities and bubbles are present inside the molded product. As a result, the obtained molded product was inferior to a commercially available novolak resin in terms of mechanical strength, acetone resistance and the like. Furthermore, since the melting point of the wood resin is high, even in the production of the resin, there are difficulties in processes such as purification, transfer, discharge, and equipment maintenance.

Further, due to the hydrophilicity inherent in biomass such as wood, the obtained wood resin and its cured product have high water absorption, and the water resistance of products such as molding materials is poor.
Further, compared to conventional synthetic phenol / formaldehyde resins, products such as molded products produced from phenol / wood resins are more brittle and less flexible and impact strength.

  In order to lower the melting point of the 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 (see, for example, Patent Document 6). . By this method, the softening point is lowered and the performance as a resin for molding material is improved to some extent, but the gel time is fast due to the influence of unreacted phenol, and the improvement effect on moldability is limited. Further, the presence of unreacted phenol present in large amounts in the resin is not preferable from the viewpoint of adverse effects on the health and environment of workers.

  Further, Patent Document 7 discloses a method for lowering the melting point of wood resin by causing a large excess of phenol 50 times that of wood to exist 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 of phenol is used in the reaction, the yield of the wood resin that is a product with respect to the total amount of the reactant is increased. Low, reaction equipment efficiency is poor. Moreover, since a great amount of time and energy are required to remove a large amount of unreacted phenol after the reaction, the wood resin is expensive and is not practical. Moreover, although the above method has a certain effect in lowering the melting point of the resin, the water resistance and flexibility of the wood resin cannot be improved.

  Therefore, 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 Japanese Patent Laid-Open No. 3-59035 Japanese Patent Laid-Open No. 3-126728 Japanese Patent Publication No. 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 that can freely control the melting point, is excellent in fluidity, workability, and physical properties after curing reaction, and has a simple production method, and a production method thereof. . The present invention also provides a curable biomass resin composition comprising a biomass resin composition, a binder, a thermosetting biomass resin molding material, and a molded body comprising a binder or thermosetting biomass resin molding material. Objective.

  In order to solve the above-mentioned problems, the characteristics of the chemical structure of a reaction product of a biomass material such as wood and phenol were examined and compared with the chemical structure of a conventional phenol / formaldehyde resin. As a result, it was found that the conventional novolac-type phenol / formaldehyde resin has a linear molecular structure, whereas the phenol / biomass resin has a branched molecular structure. This is because the biomass material is highly reactive with phenol and has many reaction sides. Therefore, after the biomass material is solvolyzed with phenol during the reaction, it further reacts with phenol or another biomass material component to branch off. This is because it has a structure. In particular, as the amount of phenol bound to the biomass material increases, such a branched structure becomes more complex, the thermal fluidity of the phenol / biomass resin further decreases, and the molecular structure lacks flexibility. In addition, conventional phenol / formaldehyde resins contain a large amount of components having low molecular weight and low melting point such as dinuclear and trinuclear, whereas phenol / biomass resin has such low molecular weight. The component was hardly contained (refer FIG. 1). Moreover, the carbohydrate which is a constituent component of the biomass substance is a highly hydrophilic substance containing many hydroxyl groups, and the biomass resin obtained by the influence of the carbohydrate 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 compared to conventional phenol / formaldehyde resins (see Table 1). ) And physical properties are inferior to conventional phenol resins. As described above, as a result of earnest research on the chemical structure and composition of phenol / biomass resin, reactive materials having a melting point other than phenol of 100 ° C. or less, particularly oils that can impart flexibility and hydrophobic properties to phenol / biomass resin. The present invention achieves the object by adding these substances and coexisting these reactive substances or reactive substance precursors in the phenol / biomass resin manufacturing process for phenolizing biomass substances. It is.

That is, the present invention is a biomass composition for a biomass resin composition, which includes a phenolized biomass material and a reactive material other than phenol having a melting point of 100 ° C. or less , and the amount of the reactive material is a biomass resin. 3-50% by weight based on the total composition, and the reactive substance is butylphenol, octylphenol, nonylphenol, benzylphenol, benzylphenyl ether, an oil containing an aliphatic chain having an unsaturated bond or a dry oil on biomass set Narubutsu.

The biomass set Narubutsu includes a biomass material, and phenol, and a reactive material other than melting point of 100 ° C. or less phenol preferably contains a product obtained by reacting in the presence of an acid catalyst.

  Furthermore, the drying oil is preferably one or more substances selected from the group consisting of paulownia oil, linseed oil, and cashew oil because the effect of improving water resistance is greater.

  The biomass material is preferably a lignocellulosic material because it is inexpensive and excellent in physical properties of the obtained resin composition.

Further, the present invention is the presence of an acid catalyst, a biomass material, in a process for producing phenol biomass material by phenolization with phenol, wherein the biomass set adding a reactive product quality in the reaction system The present invention relates to a method for producing a composition.

Further, the present invention provides a method for producing a biomass composition in which benzyl alcohol is added to a reaction system in a step of producing a phenolized biomass material by phenolizing the biomass material with phenols in the presence of an acid catalyst. Also related .

  Moreover, in the said manufacturing method, after making a biomass substance, a reactive substance, and phenols react in presence of an acid catalyst, it can be made to react with an aldehyde or an aldehyde derivative.

The present invention, hexamethylenetetramine, an epoxy resin, a phenolic resole resin, a urea resin, a melamine resin, one or more materials selected from the group consisting of polyamic acids and polyvalent isocyanate, and the biomass of sets formed of It relates to a curable biomass set Narubutsu.

The present invention relates to a binding agent comprising the curable biomass pair formed of.

The present invention also relates to thermosetting biomass resin molding material made of the curable biomass pair formed of.

  Furthermore, this invention relates to the molded object which consists of said binder or a thermosetting biomass resin molding material.

  The biomass resin composition of the present invention has a low melting point, good fluidity and molding processability, and is excellent in various physical properties such as strength properties, flexibility and water resistance of the obtained molding material or molded body, and is cured. It can be used as a molding resin and a thermosetting resin molding material. Moreover, according to the manufacturing method of this invention, a biomass resin composition can be manufactured simply.

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

  In the present invention, the phenolized biomass material is a product obtained by chemically reacting a biomass material and phenols, such as a decomposition product of the biomass material itself or a conjugate of a biomass material-derived component and phenols. Including.

  The biomass material that can be used in the present invention is not particularly limited, but examples thereof include lignocellulosic materials such as trees, bamboo, kenaf, bagasse, rice straw, and wood fibers, wood chips derived therefrom, Paper such as veneer waste, pulp, waste paper, etc .; cereals such as rice, wheat and corn; potatoes such as potato and sweet potato; starch as processed products thereof; saccharides such as sucrose and glucose. Among these, lignocellulosic materials mainly composed of wood are more preferable from the viewpoints of abundance of raw materials, stability of raw material quality, and physical properties of the produced resin. The shape of the biomass material is not particularly limited, but is preferably pulverized as appropriate 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. Among these, phenol is preferable in terms of cost and reactivity.

  In the phenolization reaction of a biomass material, intramolecular bonds such as carbohydrates and lignin, which are main components of the biomass material, are cleaved in various degrees, and phenols are further introduced into the product. The resulting product is thermoplastic and highly reactive. The phenolization reaction of the biomass material proceeds by simply heating the biomass material and phenols without using a catalyst, but in this case, a considerably high temperature of 200 to 250 ° C. is required. Further, under such high temperature conditions, the pyrolysis of the biomass material also occurs violently with the phenolization reaction, so the yield of the phenolized biomass material is low and the reactivity of the product is also low. In order to cause the phenolization reaction of biomass materials more easily and selectively, mineral acids such as sulfuric acid, hydrochloric acid and phosphoric acid, organic acids such as toluenesulfonic acid and phenolsulfonic acid, aluminum chloride, zinc chloride, trifluoride The reaction is preferably carried out in the presence of an acid such as a Lewis acid such as boron fluoride. The phenolization reaction in the presence of an acid is preferably performed at a temperature of 100 to 180 ° C. Below 100 ° C., the phenolization reaction takes a long time and is not practical. When the temperature exceeds 180 ° C., the high-temperature pyrolysis reaction of the biomass material becomes violent, the reactivity of the reaction product decreases, and the yield tends to decrease.

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

  When the phenolization reaction of the biomass material is performed 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, with respect to 100 parts by weight of the biomass material. More preferably, 0.5 to 5 parts by weight are used. When the amount of the acid catalyst is less than 0.1 parts 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 phenolization reaction of the biomass material is not particularly limited, but is within a range of 10 to 300 minutes depending on the required reaction rate of the biomass material, fluidity and reactivity of the phenolized biomass material. Just do it.

  In the phenolization reaction of the biomass material, it is not always necessary to react the biomass material 100%, and 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 the insoluble matter 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 increase the fluidity of the biomass resin composition, the phenolization reaction is preferably performed with an unreacted residue amount in the biomass resin composition of preferably 20% or less. Is carried out until 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, or phenol during the process of producing the biomass resin composition or during the curing reaction of the biomass resin composition. It reacts with the curing agent added to cure the components in the product or 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 lower. If the melting point exceeds 100 ° C., the biomass resin composition has a high melting point, the moldability becomes insufficient, and the physical properties tend to be lowered. Moreover, when phenol is used as the reactive substance, when the biomass resin composition is cured using hexamethylenetetramine, the acidic phenol accelerates the decomposition reaction of the curing agent hexamethylenetetramine, and the entire biomass resin composition. Therefore, the moldability of the biomass resin composition is lowered. Furthermore, the use of phenol is not preferable because a large amount of phenol in the resin adversely affects the working environment. A reactive substance other than phenol having a melting point of 100 ° C. or less and having a reactive ability is not particularly limited, but a compound having a phenolic hydroxyl group in consideration of a production method and a curing method of a biomass resin composition 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-tert-butylphenol, 2,6-di-tert-butylphenol, 3,5-di-tert-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 formaldehydes A condensate having a melting point of 100 ° C. or lower obtained by a reaction under acidic or alkaline conditions with; a compound having one or more epoxy groups and a melting point of 100 ° C. or lower; tung oil, linseed oil, cashew, soybean oil Natural oil such as rapeseed oil and dehydrated castor oil Dry oils; and synthetic oils containing aliphatic unsaturated bonds. Among these, butylphenol, octylphenol, nonylphenol, benzylphenol or benzylphenyl ether is preferable in that 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, and cashew oil have a large 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. This is particularly preferable. One type of reactive substance may be used, or two or more types may be used in combination.

  A method of obtaining a biomass resin composition by mixing or reacting a phenolized biomass substance and a reactive substance is not particularly limited, but may be appropriately selected according to the action mode 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 diphenylether; acidic or alkaline conditions of phenols and formaldehydes A condensate having a melting point of 100 ° C. or lower obtained by the reaction in the above; a compound having one or more epoxy groups and a melting point of 100 ° C. or lower has a certain effect even if it does not react with a biomass substance. Therefore, a reactive substance may be added to the reaction system before, during or after the phenolization reaction of the biomass substance, and after the phenolization reaction, the phenolized biomass substance and the reactive substance are mixed. You may let them. Usually, since it is preferable to melt-mix the phenolized biomass material and the reactive material, the reactivity can be achieved before, during, or after the reaction of the phenolization reaction of the biomass material because the melt-mixing can be easily performed. It is preferable to add the substance into the reaction system. In addition, the reactive mixture is added to the reaction system before, during or after the phenolization reaction of the biomass material because the resulting molten mixture has a low melting point and facilitates handling such as discharge. It is preferable to do. Furthermore, the viscosity of the reaction system decreases due to the dilution action of the reactive substance to be added, the phenolization 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 makes the molecular structure more linear, thereby further reducing the melting point of the phenolized biomass material before the reaction. 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, so the addition of the biomass substance after the phenolization reaction has no 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 the reforming effect with the drying oil, it is necessary to chemically react the drying oil with biomass and / or phenolized biomass. Therefore, it is preferable to add the drying oil before or during the reaction. Moreover, it is preferable to perform reaction with drying oil, biomass, and / or phenolized biomass at 60-180 degreeC on acidic conditions, and 80-160 degreeC is more preferable. 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 carried out in the presence of a strong acid such as sulfuric acid or phenolsulfonic acid at a temperature of 100 ° C. or higher, so that drying oil modification is performed directly in parallel with the phenolization of biomass under the same conditions. be able to. Moreover, after making dry oil and phenol react first, you may add biomass and continue phenolization.

  The reactive substance can also be produced by direct phenolization reaction of a reactive substance precursor and phenols in a biomass substance phenolization reaction system. When the reactive substance precursor is added to the reaction system when producing the phenolized biomass material, 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, or the reactive substance precursor and the reactive substance can be used in combination. Since the reactive substance precursor is cheaper than the reactive substance and the amount added may be small, it is preferable to add the reactive substance precursor from the viewpoint of manufacturing cost. Moreover, since the process of manufacturing a reactive substance separately can be skipped, it is preferable also in terms of convenience of work. As the reactive substance precursor, a substance that can react with phenols and that has a melting point of 100 ° C. or less 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 such as p-hydroxybenzyl alcohol, p-methylbenzyl alcohol, m-nitrobenzyl alcohol or derivatives thereof. Of these, benzyl alcohol, which is inexpensive and easily available industrially, is particularly suitable. For example, when benzyl alcohol is used as a reactive material precursor, benzyl alcohol is less reactive than biomass material than phenol, so it reacts less directly with biomass material, but exists in the system under an acidic catalyst. It reacts rapidly with phenol to convert to 2-benzylphenol (melting point 54 ° C.), 4-benzylphenol (melting point 83 ° C.), and benzyl phenyl 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 phenolization reaction of the biomass substance. If the reactive substance precursor can be reacted with phenol in the reaction system, an effect can be obtained. However, in order to obtain a further softening point reduction effect, it is preferably added before the reaction of the phenolization reaction of the biomass material. By adding it before the reaction, the solvent increasing effect and the viscosity reducing effect by the reactive substance precursor can be obtained. This improves the reaction uniformity of the biomass material and further reduces the amount of binding between the biomass material and phenol due to the action of the reactive material precursor, resulting in a good phenolization product having a lower melting point. .

  The compounding amount of the reactive substance is preferably in the range of 3 to 50% by weight and more preferably in the range of 5 to 40% with respect to the total weight of the biomass resin composition. When the blending amount is less than 3%, the amount of the reactive substance is small and a sufficient reforming effect cannot be obtained. When 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 by using methods such as washing with water, solvent extraction, steam distillation, vacuum distillation, etc., 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 distillation under reduced pressure is not particularly limited, but is preferably 5% or less, and more preferably 2% or less.

  In the present invention, after the reaction of biomass material, reactive material and phenol, unreacted free phenol is not removed, but aldehyde or 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, reactive substance and phenols, an aldehyde or an aldehyde derivative is added to the resulting 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, and 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 in a molar ratio of 1 or less with respect to the amount of phenols in the reaction system under acidic reaction conditions. When the molar ratio exceeds 1, the reactant tends to rapidly polymerize or gel. Moreover, it is preferable to add 1.0-4.0 by molar ratio on alkaline conditions. If the molar ratio is less than 1.0, the methylol group tends to be insufficient and the curing reactivity tends to be insufficient. When the molar ratio exceeds 4.0, a large amount of aldehyde tends to remain in the reaction product. The biomass resin composition methylolized by this method is usually in a liquid state and can be used for adhesives, impregnating varnishes, and the like. The reaction temperature when the aldehyde or aldehyde derivative is added and the reaction is continued is not particularly limited. Although the range of 60-150 degreeC is preferable, when a rapid exothermic reaction can occur, it is more preferable to set reaction temperature to 60-100 degreeC. The reaction time is not particularly limited, and can usually be performed for 0 to 180 minutes.

  The melting point of the biomass resin composition of the present invention obtained by the above production method (other than those subjected to methylolation) is controlled in the range of 60 to 120 ° C. by adjusting the species or / and the amount of the reactive substance. can do. The biomass resin composition of the present invention is excellent in fluidity, moldability, and physical properties such as strength of cured resin, heat resistance, and solvent resistance. Furthermore, by using dry oil as the 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 aldehydes are added and methylolated under alkaline conditions, but by adding a cross-linking agent (or cross-linked resin) that becomes a curing agent. It can be used as a curable biomass resin composition. As a hardening | curing agent, the 1 type (s) or 2 or more types selected from the group which consists of a hexamethylenetetramine, an epoxy resin, a phenol resole resin, a urea resin, a melamine resin, a polyamic acid, and a polyvalent isocyanate can be used. Among these, hexamethylenetetramine is preferable from the viewpoints of high-speed reactivity, low cost, and small addition amount. The addition amount of the curing agent varies depending on the type of the curing agent, but may be a normal dose in each curing system. For example, when using hexamethylenetetramine as a curing agent, it is preferable to add 5 to 25 parts by weight with respect to 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 exceeds 25 parts by weight, a large amount of gas is generated during the curing reaction, resulting in defects in the cured product. In some cases, good physical properties may not be obtained. In the case of crosslinking with an epoxy resin or a polyvalent isocyanate, it is preferable to add 0.5 to 2.0 equivalents with respect to 1 equivalent of the hydroxyl group of the biomass resin composition. When the amount is less than 0.5 equivalent and exceeds 2.0 equivalent with respect to 1 equivalent of the hydroxyl group, curing may be incomplete and good cured properties may not be obtained. Moreover, when using phenol resole resin, urea resin, melamine resin, and polyamic acid as a hardening | curing agent, it is preferable to add 30-300 weight part with respect to 100 weight part of biomass resin compositions. When the amount is less than 30 parts by weight or more than 300 parts by weight, curing may be incomplete and good cured 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 the curable biomass resin composition / hexamethylenetetramine system, addition of an oxide or hydroxide of earth metal such as calcium oxide, magnesium oxide or calcium hydroxide, phenol such as resorcinol and hexamethylenetetramine Products, sodium tetraborate, dicarboxylic acid, various amine compounds, and the like can be used. In the curable biomass resin composition / epoxy resin system, diazabicycloalkene and derivatives thereof; tertiary amines such as triethylenediamine; imidazoles such as 2-methylimidazole; and 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. unless a polyvalent polyisocyanate is used. In the case of a polyvalent isocyanate, a temperature range from room temperature to 120 ° C. is preferable.

  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 organic and inorganic materials such as shell molds, grindstones, refractories, friction materials, etc. It is useful as a binder (binder) and as a resin for molding materials for machine, automobile, electrical / electronic, and communication equipment parts.

  The curable biomass resin composition of the present invention can be used as a binder for all base materials and auxiliary materials conventionally used in various industries depending on applications. A curable biomass resin composition blend obtained by blending a base material / submaterial with a curable biomass resin composition is used in various industries as a molded article after molding.

  As base materials / sub-materials, for example, casting sand such as silica sand for shell molds; various abrasive grains, fillers, cloths, etc. for abrasives; rock wool, Kevlar fiber, glass for friction materials Fibers, inorganic fillers, etc .; refractories such as fused alumina, electrofused magnesia, fired products such as fired magnesia, various metal oxides, carbides, graphite, etc .; various molded products such as building materials and interior materials Examples thereof include rock wool, glass fiber, inorganic filler, inorganic lightweight aggregate, wood chip, pulp, and organic fiber. You may add a hardening accelerator, a mold release agent, a coloring agent, etc. to a curable biomass resin composition formulation as needed. Thus, when using as a binder, curable biomass resin composition is 1-30 weight part normally with respect to 100 weight part of base materials and auxiliary materials, Preferably 2-20 weight part is mix | blended.

  The mixing order and mixing method of the base material / submaterial and the curable biomass resin composition are not particularly limited, and conventionally known methods for each application can be used. For example, a method of mixing with a mixer at room temperature, a method of heating and mixing, a method of coating, spraying or applying a solution in which a biomass resin composition is dissolved in a solvent to a base material / sub-material, and a method of applying the base material / sub-material to the solution The method of impregnation etc. is mention | raise | lifted.

  The molding method of the curable biomass resin composition blend 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, in addition to the biomass resin composition and the curing agent, if necessary, a curing accelerator, an inorganic filler, or an organic filler is added. You may make it contain. By adding a filler, the strength, dimensional stability, and the like of the obtained molded body can be further improved. As the filler, various organic fillers 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 Examples thereof include carbonates; metal borates such as magnesium borate; inorganic fillers such as silica, carbon black, mica, and fused silica. Although the compounding quantity of a filler is not specifically limited, For example, 20-2000 weight part normally with respect to 100 weight part of resin components (curable resin composition) which added the hardening | curing agent to the biomass resin composition, Preferably it is 30-. 1000 parts by weight, more preferably 50 to 500 parts by weight. Moreover, the thermosetting biomass resin molding material can further contain an additive as necessary. Examples of the additives include internal mold release agents such as silicone 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 a curing accelerator, a filler, and various additives as necessary, and is applied to the production of a molded body. In the present invention, the mixing order of the biomass resin composition and an optional component such as a curing agent is not particularly limited. For example, after the biomass resin composition and the curing agent are mixed well, a filler and others may be added as necessary. These additives 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, after the biomass resin composition and hexamethylenetetramine are pulverized and mixed at room temperature using a mixer or the like, additives such as a curing accelerator and a release agent are added and mixed to the mixture, and a filler is added. And mix. After that, the mixture can be heated and kneaded with a hot roll machine or a biaxial 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 and the curing agent. Alternatively, a method of mixing only at room temperature without heating and kneading, or a method of wet-mixing each component using 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 cast molding. More specifically, when a molded body is produced by transfer molding using the biomass resin molding material of the present invention, a molding temperature of 120 to 200 ° C., an injection pressure of 5 to 300 kgf / cm ² (0.49 to 29.29). 4 MPa)
, Preferably 20 to 300 kgf / cm ² (1.96 to 29.4 MPa), mold clamping pressure 50 to 250 kgf / cm ² (4.9 to 24.5 MPa), and molding conditions under molding conditions of 1 to 10 minutes. Can be manufactured.

  The molded body obtained from the thermosetting biomass resin molding material of the present invention is used for parts such as machines, automobiles, electric / electronics, communication equipment, building materials such as various organic / inorganic boards, and miscellaneous goods such as synthetic lacquer ware. .

  Examples are shown below to explain the present invention in detail, but they are not intended to limit the present invention.

Example 1
A separable flask equipped with a stirrer, a thermometer, a reflux condenser and a charging port is first charged with 100 parts by weight of dried rice pine wood flour, and then 300 parts by weight of phenol containing 1% by weight of sulfuric acid is added. 20 parts by weight of benzyl alcohol was added. After completion of the addition, the mixture was reacted at 145 to 150 ° C. under reflux for 2 hours while continuing to stir. Next, it was neutralized with magnesium oxide, and unreacted phenol was distilled off at a maximum temperature of 160 ° C. under reduced pressure. As a result, 0.2 parts of free phenol and 220 parts by weight of a wood flour 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 amount of phenol containing 1 wt% sulfuric acid was 250 parts by weight and the amount of benzyl alcohol added was 25 parts by weight with respect to 100 parts by weight of dried rice pine wood flour. Thus, 215 parts by weight of a wood powder resin composition was obtained. The analysis results of the wood powder resin composition are shown in Table 2.

Example 3
Implemented after adding 100 parts by weight of dried office paper (pulverized with Schretter) instead of wood powder as biomass material, adding 300 parts by weight of phenol containing 2% by weight sulfuric acid and 20 parts by weight of benzyl alcohol Under the same conditions as in Example 1, 240 parts by weight of the used paper resin composition was obtained. Table 2 shows the analysis results of the used paper resin composition.

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

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

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

Example 7
A separable flask equipped with a stirrer, a thermometer, a reflux condenser and a charging port was charged with 100 parts by weight of dried rice pine wood flour, and then 300 parts by weight of phenol containing 1% by weight of sulfuric acid was added. After completion of the addition, the mixture was reacted for 1 hour under reflux at 145 to 150 ° C. while stirring, and then 100 parts by weight of Tung Oil (Nacalai Tesque) was added and reacted at the same temperature for another 60 minutes. Next, after neutralizing with magnesium oxide, the unreacted phenol was distilled off to a maximum temperature of 160 ° C. under reduced pressure, whereby 336 parts by weight of a woody resin composition was obtained. The analysis results of the wood powder resin composition are shown in Table 2.

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

Examples 9-11
Linseed oil (Nacalai Tesque Co., Ltd.), cashew oil (Kyowa Oil Industry Co., Ltd.) and soybean oil (Nacalai Tesque Co., Ltd.) was used in place of paulownia oil under the same conditions as in Example 8. Oil-modified wood resin, cashew oil-modified wood resin, and soybean oil-modified wood resin were prepared. Table 2 shows the analysis results of each wood flour resin composition.

Example 12
A separable flask equipped with a stirrer, a thermometer, a reflux condenser and a charging port is first charged with 100 parts by weight of dried rice pine wood flour, and then 300 parts by weight of phenol containing 1% by weight of sulfuric acid is added. 20 parts by weight of benzyl alcohol was added. After completion of the addition, the mixture was reacted at 145 to 150 ° C. under reflux for 1 hour while continuing to stir, and then 100 parts by weight of tung oil was added and 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, whereby 331 parts by weight of a woody resin composition was obtained. Table 2 shows the analysis results of the obtained wood powder resin composition.

Example 13
A separable flask equipped with a stirrer, a thermometer, a reflux condenser and a charging port is first charged with 100 parts by weight of dried rice pine wood flour, and then 300 parts by weight of phenol containing 1% by weight of sulfuric acid is added. 20 parts by weight of benzyl alcohol was added. After completion of the addition, the mixture was reacted at 145 to 150 ° C. under reflux for 2 hours while continuing to stir. 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) was added dropwise over 20 minutes. Then, after reacting at 90 ° C. for another 30 minutes, neutralized with magnesium oxide and reduced pressure to remove unreacted phenol at a maximum temperature of 160 ° C., 300 parts by weight of a wood flour resin composition was obtained. It was. Table 2 shows the analysis results of the obtained wood powder resin composition.

Example 14
A separable flask equipped with a stirrer, a thermometer, a reflux condenser and a charging port is first charged with 100 parts by weight of dried rice pine wood flour, and then 200 parts by weight of phenol containing 1% by weight of sulfuric acid is added. 100 parts by weight of tung oil was added. After completion of the addition, the mixture was reacted at 145 to 150 ° C. under reflux for 2 hours while continuing to stir. After that, 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 were added to the reaction product, and 162 parts by weight of 35% formalin (2.0 moles relative to free phenol) was added over 20 minutes while refluxing at 60 ° C. And dripped. Thereafter, the mixture was further reacted 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 for 1 month at room temperature.

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

Comparative Example 2
The same conditions as in Comparative Example 1 were used after using 100 parts by weight of dried office paper (pulverized with a Schletter) instead of wood flour as a biomass material, and adding 300 parts by weight of phenol containing 2% by weight sulfuric acid. Thus, 220 parts by weight of a used paper resin composition having 2.1% free phenol and a softening point of 132.4 ° C. was obtained. The amount of the unliquefied residue was 7.1% (including the filler component in the waste paper).

Examples 15-27
15 parts by weight of hexamethylenetetramine is added to 100 parts by weight of the biomass resin obtained in Examples 1 to 13, and 10 minutes at room temperature using a vibration ball mill (manufactured by Chuo Kako Co., Ltd., MB-3). 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 JISK6910-1999. Further, 4 parts by weight of calcium hydroxide as a hardening accelerator and 2 parts by weight of zinc stearate as a lubricant were further 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 Co., Ltd.) were added and mixed. The obtained 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 molded compound (molding). Material). Table 3 shows the results of measuring the moldability (disk type flow) of the obtained molding material based on JISK6911-1995. Further, the obtained compound was subjected to bending test molding (test piece, 4 mm × 10 mm × 100 mm) according to JISK6911-1995 standard using a compression molding die and a hot press at 175 ° C., 300 kgf / cm. ² (29.4 MPa) for 5 minutes. Table 3 shows the results of measuring the bending strength, bending elastic modulus, bending breaking strain, and 24-hour immersion water absorption of the test piece based on JISK6911-1995, and the appearance of the molded article evaluated according to the following evaluation criteria.

Appearance evaluation of molded product ○: The surface is uniform and glossy.
(Triangle | delta): The surface has a color spot or a lusterless part.
X: There is no gloss in the whole or there is a crack.

Comparative Examples 3-4
A curable biomass resin mixture, as in Examples 15 to 27, except that the biomass resin compositions obtained in Comparative Examples 1 and 2 were used instead of the biomass resins obtained in Examples 1 to 13. A compound and a molded body were obtained. The results of measuring the fluidity of the obtained curable biomass resin composition are shown in Table 2, and the results of evaluating the moldability of the compound, the appearance of the molded body, the bending strength and the bending elastic modulus of the molded body are shown in Table 3.

Examples 28-29
Using the curable resin composition obtained in Example 15 as a binder, each component was mixed by a mixer at a blending ratio shown in Table 4, and then hot-press molded at 180 ° C. for 15 minutes under a pressure of 10 MPa, and a thickness of 15 mm. A molded body was prepared. 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.

  From Table 2, the softening point of the obtained resin composition was 100 degrees C or less in Examples 1-3 which added the benzyl alcohol which is a reactive substance precursor. In particular, in Example 2 in which the amount of benzyl alcohol added was 25 parts by weight, a resin composition having a softening point of 85 ° C. was obtained. The measurement result about the flow of the resin composition obtained in Examples 1 to 43 was 43 mm, 55 mm, and 32 mm at 125 ° C., respectively.

  In Example 4, benzyl alcohol was added after the end of phenolization. The softening point of the resin composition was 104.8 ° C., which was 10 ° C. higher than the softening point of the resin composition obtained in Example 1 added in the initial stage of the phenolization reaction of the biomass material.

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

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

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

  Example 12 is an example of the combined use of benzyl alcohol and tung oil. By the combined use, the softening point of the resin composition was lowered to 83 ° C. and the fluidity was excellent.

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

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

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

  From Table 3, the biomass molding compound consisting of the resin composition obtained in Examples 1 to 13 and the molding consisting of the compound are compared with the biomass molding compound consisting of the resin composition obtained in Comparative Examples 1 and 2 and its molding. Thus, it was found that the moldability was good, and the appearance, strength characteristics and water resistance of the molded body were excellent. Particularly in Examples 21 to 26 using a dry oil-modified resin, the elastic modulus of the molded product was further reduced as compared with the use of other additives, and the bending fracture strain was greatly improved. The water absorption was about 1/3 of the comparative example, 50% lower than Examples 15-20. That is, the use of 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 and low strength properties, and the surfaces such as the corners of the molded article were matte. Table 4 also shows that the biomass resin composition of the present invention has 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 (11)

A biomass composition for a biomass resin composition, comprising a phenolized biomass material and a reactive material other than phenol having a melting point of 100 ° C. or less , wherein the amount of the reactive material is based on the whole biomass resin composition A biomass composition comprising 3 to 50% by weight, and wherein the reactive substance is butylphenol, octylphenol, nonylphenol, benzylphenol, benzylphenyl ether, an oil containing an aliphatic chain having an unsaturated bond, or a dry oil . And biomass materials, phenol and, biomass sets composition as claimed in claim 1, including a melting point and a reactive material other than 100 ° C. or less phenol, the product obtained by reacting in the presence of an acid catalyst. Drying oil, tung oil, linseed oil, biomass sets composition as claimed in claim 1 wherein the one or more materials selected from the group consisting of cashew oil. Biomass material, biomass sets composition as claimed in claim 1, 2 or 3, wherein the lignocellulosic material. The presence of an acid catalyst, a biomass material, in a process for producing phenol biomass material by phenolization with phenols, according to claim 1, wherein the addition of a reactive Substance in the reaction system of biomass sets Narubutsu Production method. The presence of an acid catalyst, a biomass material, in a process for producing phenol biomass material by phenolization in phenols, the production of biomass sets formed of claim 1, wherein you added benzyl alcohol in the reaction system Method. The presence of an acid catalyst, biomass materials, reactive substances and phenols mixture was reacted method according to claim 5 or 6 biomass pairs formed product according reacted with an aldehyde or aldehyde derivative. Hexamethylenetetramine, epoxy resins, phenolic resole resins, urea resins, melamine resins, one or more materials selected from the group consisting of polyamic acid and a polyvalent isocyanate, as well as claim 1, 2, 3 or 4 according curable biomass set Narubutsu made from biomass assembly formed products. Binder consisting claim 8 curable biomass sets forming composition according. Thermosetting biomass resin molding material composed of claims 8 curable biomass sets forming composition according. The molded object which consists of the binder of Claim 9 , or the thermosetting biomass resin molding material of Claim 10 .

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