JP4402499B2 - Thermosetting biomass resin composition and molded product thereof - Google Patents

Description

  The present invention relates to a thermosetting resin composition obtained from biomass such as wood and having excellent moldability, strength properties, water resistance, and the like, and a molded product thereof.

  Phenol resins are inexpensive and have excellent properties such as moldability, mechanical properties, heat resistance, electrical insulation, and chemical resistance, so they are industrially used as resins for various molding materials, electrical parts, and machine parts. Used in a wide range of fields.

  A novolac type phenolic resin used for the production of a molded article is usually produced by heating and reacting phenols and formaldehyde in the presence of an acidic catalyst. A molded product can be obtained by blending the obtained resin with a curing agent, a filler, and the like, followed by heat curing.

  By the way, it is known that a resin that can be cured with hexamethylenetetramine or the like can be obtained by reacting wood powder with phenols instead of formaldehydes, like novolak type phenol resins. Since abundant wood waste materials are used in the production of this resin, it is not necessary to use formaldehyde and the amount of phenols used can be greatly reduced. It has great significance. As a method of reacting the wood waste material and phenols, 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). It has 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 phenolized biomass resin and its cured product obtained by chemical reaction between biomass such as wood and phenols (wood phenolization) have strong water absorption due to the hydrophilicity inherent in biomass, and physical properties due to water absorption. The appearance was greatly deteriorated.

  In addition, wood flour is generally used as a filler added at the time of curing the phenolized biomass resin from the viewpoints of moldability, cost, ease of processing at the time of disposal, and the like. However, phenolic biomass resin molded products using wood flour as a filler have problems such as a significant decrease in strength due to moisture absorption and water absorption, as well as the appearance of fillers on the molded product surface and the occurrence of small blisters. there were. In addition, such a phenolized biomass resin has a problem that its fluidity and moldability are insufficient as compared with conventional synthetic phenol / formaldehyde resins.

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

  An object of the present invention is to provide a biomass resin molded article that has low hygroscopicity and water absorption, and has little change in strength and appearance after water absorption. Moreover, an object of this invention is to provide the thermosetting biomass resin composition used for manufacture of such a molded article.

  In order to solve the above-mentioned problems, the causes of moisture absorption and water absorption of a biomass resin molded article using wood flour as a filler were examined. As a result, the cause of the decrease in water resistance of the molded product is that the wood powder as the filler absorbs the moisture that has penetrated into the molded product through the hydrophilic biomass resin, and the wood powder expands due to moisture absorption / water absorption. It was found that wood powder particles floated and blisters were generated on the outer surface of the molded product, and the strength properties of the molded product were reduced.

  Also, regarding the cause of insufficient fluidity of biomass resin using wood flour as a filler, since biomass resin is prepared from biomass materials such as wood flour, it has an affinity with wood flour as a filler. The amount of effective resin in the molding material that allows the biomass resin to easily penetrate into the wood flour and develop fluidity is reduced accordingly, leading to a decrease in the fluidity and moldability of the molding material. I also found.

  As a result of further research, when a pulverized paper base laminate containing a thermosetting resin is used as a filler, the water absorption of the molded product is greatly reduced, and changes in strength properties and changes in appearance after water absorption. Both were found to be significantly reduced. Moreover, it has also been found that by using such a pulverized product of a paper base laminate, the flowability and moldability of the biomass resin molding material are greatly improved, and the present invention has been achieved.

  That is, the present invention relates to a thermosetting biomass resin composition comprising a phenolized biomass resin, a curing agent, and a filler that is a pulverized product of a paper base laminate. The thermosetting biomass resin composition has good moldability, and by using the thermosetting biomass resin composition, it is possible to obtain a molded product having good water resistance and appearance after water absorption.

  The phenolized biomass resin is preferably a product obtained by phenolizing a biomass material with phenols in the presence of an acid catalyst.

  More preferably, the phenolized biomass resin contains a product obtained by phenolizing a biomass material with phenols in the presence of an acid catalyst and drying oil. With the drying oil, it is possible to obtain a biomass resin composition having excellent moldability and water resistance.

  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 further great.

  Further, it is preferable that the biomass material is lignocellulose because it is inexpensive and easily available and the performance of the obtained biomass resin is excellent.

  It is preferable that the content of the thermosetting resin in the paper base laminate is 25% by weight or more of the paper base laminate because the effect of improving water resistance is large.

  The particle size of the filler is preferably 150 μm or less because a molded product having excellent strength properties and an aesthetic appearance can be obtained.

  Furthermore, this invention relates to the molded article which consists of the said thermosetting biomass resin composition. The molded article is excellent in water resistance and has good physical properties and appearance after water absorption.

  By using the biomass resin composition of the present invention, it is possible to obtain a molded article that is excellent in moldability and strength properties, has reduced performance due to moisture absorption and water absorption, and has little appearance change. Since the molded article of the present invention has excellent strength properties and water resistance, it is particularly effective for applications such as daily miscellaneous goods such as machinery and automobile parts, lacquerware, and tableware, and household goods.

  The thermosetting biomass resin composition of the present invention is a thermosetting biomass resin composition comprising a phenolic biomass resin, a curing agent, and a filler that is a pulverized product of a paper base laminate.

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

  The biomass material used in the present invention is not particularly limited. For example, lignocellulosic materials such as trees, bamboo, kenaf, bagasse and rice straw, and wood fibers, wood chips, and veneer scraps derived therefrom. Paper such as pulp, waste paper; 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 water resistance of the produced resin. Of the lignocellulosic materials, wood is more preferred due to its availability and quality stability. 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 the phenols used in the present invention include compounds having a phenolic hydroxyl group such as phenol, cresol, xylenol, bisphenol A, hydroquinone, resorcinol, alkylresorcinol, and alkylphenol. These may be used alone or in combination of two or more. Among these, phenol is preferable in terms of cost and reactivity.

  Moreover, you may use together various additives and modifier | denaturants for reaction (phenolation reaction) of biomass substance and phenols. For example, solvents such as toluene and xylene for adjusting the viscosity of the reaction system, and reactive substances such as benzyl alcohol for reducing the melting point of the phenolized biomass resin can be used.

  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. Moreover, under such high temperature conditions, the pyrolysis of the biomass material occurs violently simultaneously with the phenolization reaction, so the yield of the phenolized biomass resin 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 of the reaction product tend to be insufficient. If it exceeds 10 times, there is no problem in the reaction, but the yield of the phenolic biomass resin 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 it ranges from 10 to 300 minutes depending on the required reaction rate of the biomass material, the fluidity and reactivity of the phenolized biomass resin. 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 as an unreacted residue. After the reaction, the amount of unreacted residue is measured by dissolving the resulting phenolized biomass resin in methanol, separating the insoluble matter by filtration, drying and weighing. This unreacted residue usually does not need to be separated from the biomass resin and may be used as a filler. However, in order to increase the resin ratio in the reaction product and increase the water resistance of the molded product, the phenolization reaction is preferably performed so that the amount of unreacted residue in the phenolized biomass resin is 20% or less, more preferably 10%. % Or less, more preferably 5% or less.

  In the present invention, in order to improve the water resistance of the phenolized biomass resin and improve the fluidity, it is preferable to perform the phenolization reaction of the biomass substance in the presence of dry oil. By the reaction of drying oil and phenols or drying oil and phenolized biomass resin, the effect of modification can be obtained.

  The drying oil that can be used is not particularly limited, and natural drying oils such as paulownia oil, linseed oil, soybean oil, rapeseed oil, dehydrated linseed oil, cashew oil, or synthetic drying oil having an aliphatic unsaturated bond, etc. can give. Among these, tung oil, linseed oil, and cashew oil are particularly preferable because they are inexpensive and easily available, and also have an excellent effect of improving water resistance.

  The blending amount of the drying oil is preferably 10 to 300 parts by weight and more preferably 20 to 200 parts by weight with respect to 100 parts by weight of the biomass substance. If the blending amount is less than 10 parts by weight, the effect of improving water resistance is insufficient, and if it exceeds 300 parts by weight, physical properties such as the reactivity and heat resistance of the biomass resin tend to decrease.

  The reaction between the drying oil and the phenols or the drying oil and the phenolized biomass resin is performed at 70 to 180 ° C, more preferably 80 to 160 ° C under acidic conditions. The reaction time is not particularly limited, and usually 30 to 180 minutes, since it is sufficient that the drying oil is reacted with the phenolized biomass resin without being separated from the phenolic biomass resin.

  The timing of adding the drying oil to the reaction system of the phenols and the biomass material is not particularly limited, and may be any before, during or after the reaction between the phenols and the biomass material. Phenolization reaction of biomass materials such as wood is usually carried out at a temperature of 100 ° C or higher in the presence of strong acids such as sulfuric acid and phenolsulfonic acid. It can be performed in parallel with the reaction. Moreover, after making dry oil and phenols react previously, biomass material may be added and a phenolization reaction may be continued. Furthermore, drying oil can be added after the phenolization reaction of the biomass material, and the reaction can be performed under milder conditions. The reaction of the drying oil needs to be performed under acidic conditions. Therefore, when a strong acid such as sulfuric acid or phenolsulfonic acid is used for phenolization of biomass material (biomass liquefaction), it is sufficient to add no acid for the reaction of drying oil. In some cases, an acid such as sulfuric acid or toluenesulfonic acid may be further added to react with the drying oil.

In the present invention, after preparing the phenolized biomass resin, generally 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 phenolized biomass resin are lowered, so it is preferable to remove the free phenol. The method for removing free phenol is not particularly limited, and it can be removed by using methods such as water washing, solvent extraction, steam distillation, and vacuum distillation. However, vacuum distillation is advantageous in terms of workability and cost. preferable. The vacuum distillation can be carried out under 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 after purification by vacuum distillation is not particularly limited, but is preferably 5% or less, and more preferably 2% or less.

  The softening point of the resulting phenolized biomass resin is preferably 80 to 120 ° C, and more preferably 85 to 110 ° C. If the softening point is less than 80 ° C, the flowability tends to be too high and molding tends to be difficult, and if it exceeds 120 ° C, the flowability tends to be insufficient and molding tends to be poor.

  Examples of the curing agent used in the thermosetting biomass resin composition of the present invention include hexamethylenetetramine and epoxy resin, and hexamethylenetetramine is more preferable because it is excellent in reactivity and inexpensive. For example, when hexamethylenetetramine is used as the curing agent, the amount of hexamethylenetetramine is preferably 12 to 25 parts by weight with respect to 100 parts by weight of the phenolized biomass resin. When the blending amount of hexamethylenetetramine is less than 12 parts by weight, the curing time of the biomass resin composition becomes long and the productivity is lowered, and the physical properties of the molded product tend to be lowered. On the other hand, if the amount of hexamethylenetetramine exceeds 25 parts by weight, a large amount of gas is generated during the curing reaction, resulting in defects in the cured product, and the physical properties of the molded product may not be good. In addition, the reaction rate is too high, and there is a tendency for molding defects.

  The filler used in the biomass resin composition of the present invention is a pulverized product of a paper base laminate. Examples of the paper base laminate include a decorative board, a printed wiring board used for an electric device and an electronic device, and a coating plate used for punching a wiring board. A paper base laminate is made by impregnating a paper base material with a thermosetting resin composition mainly composed of phenol resin, melamine resin, epoxy resin, etc. to produce a prepreg, and heat and press this prepreg to cure the resin. It is a laminated board obtained by making it. Examples of the paper substrate include kraft paper, linter paper, and mixed papers thereof. The type of laminate that can be used is not particularly limited, but the main component of the thermosetting resin composition is a phenol resin or a melamine resin, and 25% or more of the weight of the paper substrate laminate, preferably 30. It is preferable that the weight percent or more is the resin component from the viewpoint that the pulverizability of the paper base laminate and the water resistance of the pulverized product are good.

  The particle size of the pulverized material of the paper base laminate is preferably 150 μm or less. When the particle size exceeds 150 μm, a molded product obtained by molding the biomass resin composition is rough, and the appearance appearance and the strength physical properties tend to decrease.

  The blending amount of the pulverized material of the paper base laminate in the biomass resin composition is preferably 60 to 150 parts by weight with respect to 100 parts by weight of the phenolized biomass resin. If the pulverized product is less than 60 parts by weight, the physical properties of the molded product tend to decrease, and if the pulverized product exceeds 150 parts by weight, the fluidity during molding tends to decrease.

  In addition to the phenolized biomass resin, the curing agent, and the filler, an inorganic filler, a curing accelerator, a release agent, a colorant, and the like can be added to the biomass resin composition of the present invention as necessary. Examples of inorganic fillers include calcium carbonate and talc, examples of curing accelerators include calcium hydroxide and magnesium oxide, and examples of mold release agents include aliphatic stearates and metal salts of stearic acid. Examples of the colorant include pigments, diazo compounds, and carbon black. These blending amounts are not particularly limited, and may be blended within the range used for ordinary phenol resin molding materials.

  The thermosetting biomass resin composition of the present invention can be obtained as a molding compound by mixing a phenolized biomass resin, a curing agent, a filler, and necessary additives. For example, after phenolized biomass resin, curing agent, filler and necessary additives are uniformly mixed with a mixer, blender, etc., heated with a hot roll machine adjusted to 80 to 100 ° C. or a twin-screw kneader A compound for molding can be obtained by kneading, returning to room temperature and grinding. Even if a method of mixing only at room temperature without heating and kneading, or a method of using a solvent such as methanol to wet-mix each component using a mixer and drying after mixing, it is possible for molding. A compound can be obtained.

By molding a molding compound obtained from the thermosetting biomass resin composition of the present invention, the molded product of the present invention can be produced. The molding method is not particularly limited, and can be molded by various conventionally known resin molding means. Examples of the resin molding means include compression molding, injection molding, transfer molding, and the like. The molding conditions include a molding temperature of 160 to 190 ° C., a molding pressure of 50 to 250 kgf / cm ² (4.9 to 24.5 MPa), and a molding time of 1 to 10 minutes, depending on the shape and thickness of the molded product. Can be selected as appropriate.

  The molded article of the present invention is used for applications such as machinery, automobiles, parts such as electric / electronic and communication equipment, and miscellaneous goods such as synthetic lacquerware.

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

Production 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 stirring. 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, 220 parts by weight of biomass resin (1) having a free phenol of 0.2% and a softening point of 94.6 ° C. was gotten. The amount of unliquefied wood flour residue was 1.2%.

Production Example 2
In a separable flask equipped with a stirrer, a thermometer, a reflux condenser and a charging port, 100 parts by weight of dried rice pine wood flour was charged first, 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 1 hour while continuing to stir, and then 100 parts by weight of Tung oil (provided by 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. As a result, 336 of biomass resin (2) having a free phenol of 0.8% and a softening point of 96.6 ° C. was obtained. Part by weight was obtained. The amount of unliquefied wood flour residue was 1.7%.

Example 1
For 100 parts by weight of biomass resin (1), 15 parts by weight of hexamethylenetetramine (Mitsubishi Chemical Co., Ltd.) as a curing agent, 4 parts by weight of calcium hydroxide as a curing accelerator, 2 parts of zinc stearate as a release agent After mixing with MixMuller (manufactured by Shinto Kogyo Co., Ltd.), the decorative plate pulverized product having a particle size of 150 μm or less (made by Sanshu Frit Co., Ltd., made of phenol resin and melamine resin) 120 parts by weight) was added and mixed. The obtained mixture was kneaded at 100 ° C. and 60 rpm using a biaxial kneader (Toshiba Machine Co., Ltd.) with L / D = 24, cooled to room temperature, pulverized with a power mill, and molded biomass resin composition I got a thing.

Example 2
A biomass resin composition was obtained in the same manner as in Example 1 except that the biomass resin (2) was used instead of the biomass resin (1).

Example 3
A biomass resin composition was obtained in the same manner as in Example 2 except that the blending amount of the decorative board pulverized product as the filler was 100 parts by weight.

Example 4
A biomass resin composition was obtained in the same manner as in Example 2 except that the blending amount of the decorative board pulverized product as the filler was 140 parts by weight.

Example 5
The same procedure as in Example 1 was performed except that a decorative board pulverized product having a maximum particle size of 250 μm (manufactured by Sanshu Frit Co., Ltd., the total content of phenolic resin and melamine resin was 35% by weight) was used as the filler. Thus, a biomass resin composition was obtained.

Comparative Example 1
A biomass resin composition was obtained in the same manner as in Example 1 except that wood powder (Cellulosin No. 100, manufactured by Casino Co., Ltd.) was used instead of the crushed decorative plate as the filler.

Comparative Example 2
A biomass resin composition was obtained in the same manner as in Comparative Example 1 except that the biomass resin (2) was used instead of the biomass resin (1).

  The moldability of the biomass resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 2 was evaluated by measuring the disk flow. Moreover, the water resistance of the molded article produced from the obtained biomass resin composition, boiling resistance, bending strength, bending elastic modulus, and fracture | rupture distortion were evaluated. The evaluation method is as follows, and the evaluation results are shown in Table 1.

<Preparation of test piece>
A test piece (4 mm × 10 mm × 100 mm) conforming to the JISK6911-1995 standard was formed by heating and pressing at 175 ° C. and 300 kgf / cm ² (29.4 MPa) for 5 minutes using a compression mold and hot press. ).

<Disc flow>
The disk flow of the biomass resin composition is measured according to JISK6911-1995.

<Water resistance>
The test piece is immersed in water at 23 ° C. for 72 hours, and the weight change rate before and after immersion and the appearance after immersion are evaluated. The appearance is evaluated according to the following evaluation criteria.
○: Glossy and no blistering.
Δ: Gloss is lost or the filler is lifted up.
×: Small blisters are generated.

<Boil resistance>
The test piece is boiled for 1 hour, the weight change rate before boiling and after boiling is measured, and the bending strength retention rate after drying the boiled test piece with a 70 ° C. blower dryer is measured. The appearance of the test piece after boiling is also observed and evaluated. The appearance is evaluated according to the following evaluation criteria.
○: Glossy and no blistering.
Δ: Gloss is lost or the filler is lifted up.
×: Small blisters are generated.

<Bending strength, bending elastic modulus, bending breaking strain>
This is performed according to JISK6911-1995.

  As shown in Table 1, when the biomass composition obtained in any of the examples was used, the physical properties of the molded article were good, and the water resistance and boiling resistance were also good. In particular, the molded article using the biomass resin (2) modified with tung oil had higher water resistance, bending strength and breaking strain. The disc flowability was as good as 100 mm or more except for those containing a large amount of the filler of Example 4. Also about what was obtained in Example 4, since the disk flowability was 93 mm, the moldability was sufficient.

  In Example 5, a decorative plate pulverized product having a large particle size was used as the filler. The obtained molded article lacked aesthetics such as filler particles seen from the surface. In addition, a decreasing tendency was observed in terms of strength properties. Regarding the immersion water absorption and boiling water absorption, values similar to those in Examples 1 to 4 were shown, but the strength retention after boiling was as low as 83.6%. This is considered to be due to the large shape of the filler.

  On the other hand, the molded article of Comparative Example 1 using wood powder as the filler has a water absorption rate of 2.86% after 72 hours of water immersion, and 4 of Examples 1 to 4 using a decorative plate crushed material as the filler. It was more than twice. After immersion in water for 72 hours, wood powder, which is a filler, emerged on the surface of the molded product. The water absorption after boiling for 1 hour was as high as 2.29%, and the bending strength was greatly reduced to 75.2% before boiling. Moreover, the disk flow of the biomass resin composition obtained in Comparative Example 1 was 85 mm, and compression molding was not particularly problematic, but was inferior to Examples 1-5.

  In Comparative Example 2, biomass resin 2 with improved water resistance was used. Compared with Comparative Example 1, all the characteristics such as disk flow, bending strength, and water resistance were improved. However, compared with Example 2 in which a decorative board pulverized product was used as a filler, the water absorption rate was high and 1 hour. The strength retention after boiling is 82.4%, which is quite inferior. As for the appearance after boiling, it can be seen that the wood powder as the filler is emerging on the surface of the molded product.

  From the above results, the moldability of the thermosetting biomass resin composition, the molding obtained from the thermosetting biomass resin composition, by using the pulverized material of the paper base laminate as a filler of the phenolized biomass resin It was found that the physical properties and water resistance of the product were greatly improved.

Claims (6)

Phenolic biomass resin, curing agent, and Ri Do from the filler is a pulverized paper base laminates,
The phenolized biomass resin is a product obtained by phenolizing a biomass material with phenols in the presence of an acid catalyst;
The biomass material is a lignocellulosic material;
The curing agent is hexamethylenetetramine, and the amount of hexamethylenetetramine is 12 to 25 parts by weight with respect to 100 parts by weight of the phenolized biomass resin,
The compounding quantity of the ground material of the said paper base material laminated board is a thermosetting biomass resin composition which is 60-150 weight part with respect to 100 weight part of phenolization biomass resin. The thermosetting biomass resin composition according to claim 1, wherein the phenolized biomass resin contains a product obtained by phenolizing a biomass substance with phenols in the presence of an acid catalyst and a drying oil. The thermosetting biomass resin composition according to claim 2 , wherein the drying oil is one or more substances selected from the group consisting of tung oil, linseed oil and cashew oil. The thermosetting biomass resin composition according to claim 1, 2 or 3 , wherein the paper substrate laminate contains 25% by weight or more of the thermosetting resin of the paper substrate laminate. It claims 1 to 4 thermosetting biomass resin composition according the particle size of the filler is 150μm or less. A molded article comprising the thermosetting biomass resin composition according to claim 1, 2, 3, 4 or 5 .