JPWO2013190777A1 - Bagasse molded body - Google Patents

Abstract

The present invention relates to a bagasse molded body obtained by molding bagasse, which is a pomace of sugarcane. This bagasse is bonded by an adhesive component generated by modifying the components contained in the bagasse during the heat and pressure molding. Bagasse is bonded in the presence of a polyvalent carboxylic acid and an organic sulfonic acid. By using the polyvalent carboxylic acid and the organic sulfonic acid in combination, it is possible to obtain a molded article having high adhesiveness and water resistance, and formaldehyde is hardly diffused, and generation of mold is suppressed.

Description

  The present invention relates to a bagasse molded body obtained by using bagasse as a plant piece as a raw material and bonding bagasse using a modified substance of the component contained in bagasse as an adhesive component.

  Particle board and fiberboard wood-based board can be manufactured using particles and fine fibers obtained from waste materials and construction waste materials during lumber production. Wood-based boards are cheaper than plywood, so their production volume is increasing worldwide. In addition, a board using plant pieces is also known as a wooden board. In addition to wood, herbaceous plants such as bamboo, kenaf and flax, rice straw, wheat straw, oil palm fiber, bagasse, beet pulp and the like are used as plant pieces. Oil palm fiber is the fiber after extracting the oil, bagasse is the extract after sugarcane sugar is extracted, and beet pulp is the extract after extracting sugar beet sugar. It is possible to produce a wooden board using particles and fine fibers obtained from these agricultural wastes as raw materials.

  Particle boards and fiberboards are generally manufactured by mixing particles and fine fibers with a synthetic resin adhesive such as urea resin, melamine resin, and phenol resin, and molding the mixture. Therefore, there are cases where it contains components harmful to the human body, such as formaldehyde, which is a raw material for synthetic resin adhesives. Therefore, when such a board such as a particle board or a fiberboard is used as an interior material for a house, harmful components such as formaldehyde may volatilize from the board and adversely affect the health of the resident. When the board is recycled, the board is crushed to prepare particles and the like again, mixed with a synthetic resin adhesive, and then molded into particles. However, cured synthetic resin adheres to particles obtained by recycling from the board, and this causes adhesion inhibition. Therefore, there is a problem in performance such as board strength, and there is also a problem that recycling is difficult. Furthermore, in the case of incineration, there is also a problem that harmful gases are generated due to combustion of the synthetic resin adhesive. From these viewpoints, it is strongly desired to develop a board that does not use a synthetic resin adhesive and uses the components of particles and fine fibers themselves as adhesive components.

Japanese Unexamined Patent Publication No. 60-30309 Japanese Patent No. 3034956 JP 2002-361611 A WO2010 / 001988

  As a board that adheres with the ingredients of the plant piece itself, it is obtained by heat-pressing plant pieces such as particles and fine fibers and bonding the plant pieces together with the adhesive components contained in the plant pieces. Is known. For example, a method of producing a binderless board by heat-pressing at a temperature of about 180 ° C. to 230 ° C. using plant materials such as bagasse, corn stalk, sunflower stalk, flax stalk, etc. as a raw material is disclosed. (See Patent Document 1). Further, a method for producing a binderless board by using mallow bast fiber plant as a raw material as a lignocellulosic material and subjecting it to heat-pressure molding at a temperature of about 180 to 250 ° C. has been disclosed (patent document). 2).

  As described above, by applying a high temperature to the plant strip, the components contained in the plant are modified into an adhesive component, and the board is produced without a binder, so the adhesive component contains many components that are easily denatured. Herbaceous plants are being considered as raw materials for binderless boards.

  However, when the modification is insufficient, the adhesive strength is lowered. Therefore, the binderless board is not practically used regardless of whether the raw material is a herbaceous plant or a woody plant. Further, since heating and pressurization is performed in the presence of water vapor, there is a problem that a special press device such as a vapor injection type is required or a long time is required for pressing. In addition, when the presence of water vapor is unnecessary, there is a problem that heating at a high temperature exceeding 200 degrees is required, or that the plant piece is required to be processed into a fine powder.

  Under these circumstances, adding hydrochloric acid, sulfuric acid, nitric acid, acetic acid, nitrate and the like to adhere plant pieces has been studied (see Patent Document 3).

  However, in the method of Patent Document 3, it is necessary to add a large amount of water for modification, and as a result, there is a problem that a long time is required for pressing. In particular, in the case of a board with a large thickness, due to the low heat conduction from the press and the influence of latent heat due to residual water, the temperature rise is slow and a long time is required for the press. There was a problem of deterioration due to the pieces being exposed to heat for a long time.

  Also, in recent years, a composition for molding a powdered or fragmented plant-derived material and a polyvalent carboxylic acid, or a powdered or fragmented plant-derived material, a polyvalent carboxylic acid and a saccharide as essential components is used. It has been studied to make a composition for bonding materials or wood (see Patent Document 4).

  However, the molding composition of Patent Document 4 has a problem that the physical properties are low if no saccharide is added. Further, in addition to the problem that a long time is required for pressing, there is a problem of deterioration due to the plant pieces on the surface portion being exposed to heat for a long time.

  At present, particle boards and fiberboards made from herbaceous plants other than woody plants and using ordinary adhesives are not widespread. This is because herbaceous plants contain more low-molecular components than woody plants, and this component causes mold. Moreover, since the low molecular component causes inhibition of adhesion and a decrease in water resistance, the physical properties of the board are inferior to those of particle boards and fiber boards made from woody plants. In particular, bagasse, which is a squeezed rice cake after sugarcane sugar is collected, is a saccharide that has not been fully squeezed out of its low-molecular components. It will be directly connected. And when bagasse is used as a raw material, even if a board is produced by the methods of Patent Documents 3 and 4, it takes a long time for molding, and it is difficult to avoid mold generation and it is difficult to put it into practical use. there were. Since bagasse is an agricultural waste and an unused resource, its effective use is desired.

  The present invention has been made in view of the circumstances as described above, and provides a molded article using bagasse that has high adhesion and water resistance, is less likely to diffuse formaldehyde, and suppresses the generation of mold. The challenge is to do.

The bagasse molded article according to the present invention is a bagasse molded article obtained by molding bagasse which is a pomace of sugarcane,
The bagasse is bonded by an adhesive component that is generated by modifying the components contained in the bagasse during the heat and pressure molding,
The bagasse is bonded in the presence of a polyvalent carboxylic acid and an organic sulfonic acid.

The bagasse molded body preferably has one or more features selected from the following.
-As for the said bagasse, the soluble component ratio by 90 degreeC hot water extraction for 3 hours is 3 mass% or more in a dry part.
-The bagasse has a sucrose ratio of 3% by mass or more in the dry matter extracted by hot water at 90 ° C. for 3 hours, and the bagasse molded product has a sucrose ratio of 1% in the dry matter by extraction at 90 ° C. for 3 hours in hot water. %.
-The said polyvalent carboxylic acid contains 1 or more types chosen from a citric acid, itaconic acid, and malic acid.
-The said organic sulfonic acid contains 1 or more types chosen from p-toluenesulfonic acid and benzenesulfonic acid.
-The bagasse is bonded in the presence of sugars.
-As for the said bagasse, when the dry mass of the said bagasse is 100 mass parts, solid content mass of the said polyhydric carboxylic acid is 0.1 mass part-20 mass parts, and solid content mass of the said organic sulfonic acid is Bonding is performed under the condition of 0.1 to 20 parts by mass.
-The bagasse molded object is a board.
-The said bagasse molded object becomes 0 (no growth) by visual three-stage evaluation by the mold resistance test of JIS Z 2911.

  According to the bagasse molded article of the present invention, since bagasse is bonded in the presence of polyvalent carboxylic acid and organic sulfonic acid, it has high adhesion and water resistance, and formaldehyde is not easily diffused, and mold is hardly generated. can do.

  Hereinafter, modes for carrying out the present invention will be described.

  This invention is invention of the bagasse molded object which shape | molded the bagasse which is a pomace of sugarcane. This bagasse is bonded by an adhesive component generated by modifying the components contained in the bagasse during the heat and pressure molding. This bagasse is bonded in the presence of a polyvalent carboxylic acid and an organic sulfonic acid.

  In general, as a plant piece raw material of wood-based boards, woody plants such as conifers and broad-leaved trees, annual or biennial herbaceous plants, or agricultural waste after collecting cereals, vegetable oil, vegetable sugar, etc. Is mentioned. Specific examples of agricultural waste include herbs such as kenaf, rice, bamboo, and flax, bagasse, beet pulp, rice straw, wheat straw, and oil palm fiber. However, they are not widely used as plant piece raw materials for wooden boards. These generally contain more hot water-soluble components such as sugars than woody plants. When ordinary adhesives are used, the hot water-soluble components of plants cause mold generation, adhesion inhibition, and water resistance. It is because it will cause sex decline. The physical properties of the board are better when plant pieces with less hot water soluble components are used. For this reason, practical use of boards using annual or biennial herbaceous plants, agricultural wastes, etc. has not progressed.

  In particular, bagasse, which is squeezed after sugarcane sugar is collected, and beet pulp, which is squeezed after sugarcane sugar is collected, contain sucrose (sucrose) in which most of the low-molecular components contained cannot be squeezed. ). Therefore, even if it is formed into a board using a normal adhesive, it is difficult to put it into practical use because it directly leads to the generation of mold using sucrose as a nutrient source and a decrease in water resistance caused by sucrose.

  In the present invention, bagasse, which is a squeezed rice cake after sugarcane sugar is collected, is used as a plant material. Bagasse is an agricultural waste, which can be used effectively for resources. The bagasse molded body can be formed as a kind of wood-based board. Strictly speaking, the bagasse shaped body is not made of wood, but it can be shaped like a board (plate material) formed of wood particles and fibers.

  The bagasse used as a raw material of a molded object may contain at least one of a small piece and a fiber. Bagasse pieces can be obtained by grinding bagasse. The bagasse pieces may be chip-shaped bagasse chips. The bagasse fiber may be a defatted bagasse. Further, the bagasse powder may be used by breaking the bagasse into powder. In view of availability of raw materials, it is preferable to use bagasse pieces.

  Bagasse can be processed into granular particles having a diameter of several hundred μm to several cm by pulverization. Bagasse is processed into fine fibers having a diameter (fiber diameter) of about 50 μm to 2 mm and a length (fiber length) of about 100 μm to 20 mm by defibrating the bast and stem core. Can do. Using these particles and fine fibers as plant pieces (fine pieces), a bagasse molded body can be produced.

  The main components of bagasse are cellulose, hemicellulose, and lignin, as in the case of woody plants such as conifers and broadleaf trees, but there are sugars that could not be squeezed out of bagasse. In bagasse, residual sugar is denatured under heat and pressure, and can function as an adhesive component. When bagasse is used as described above, the residual sugar can be used, the physical properties can be improved, and the adverse effects of the residual sugar can be suppressed.

  Bagasse has a high content of low-molecular components such as hemicellulose components and hot water-soluble components compared to woody plants, and is characterized by being rich in components that denature into adhesive components under heat and pressure. Suitable as Specific examples of the hemicellulose component include arabinoglucuronoxylan, glucomannan, and glucuronoxylan. Arabinoglucuronoxylan and glucomannan are components that are mainly contained in conifers. Glucuronoxylan and glucomannan are components that are mainly contained in hardwoods. Bagasse may contain these components or components similar thereto.

  Specific examples of the hot water-soluble component in bagasse include low-molecular sugars such as monosaccharides and oligosaccharides, polysaccharides such as pectin, tannins and lignans. In bagasse, low temperature saccharides such as monosaccharides and oligosaccharides, polysaccharides such as pectin, tannins, lignans and the like, which are main hot water soluble components, contribute to adhesion. These hot water-soluble components serve to polymerize the organic sulfonic acid and carboxylic acid as a catalyst, and promote the reaction between the modified products and the reaction between the modified product and the polyvalent carboxylic acid.

  Low molecular components such as hemicellulose components and hot water soluble components contained in the bagasse plant pieces are modified into adhesive components under heat and pressure, but the reaction is promoted by the coexistence of polyvalent carboxylic acid and organic sulfonic acid, It becomes a strong adhesive component. Further, if low molecular components such as hemicellulose components and hot water soluble components remain in the molded product after molding, this component may cause mold generation, adhesion inhibition, and water resistance reduction. However, since the reaction is promoted by the coexistence of organic sulfonic acid and polyvalent carboxylic acid, the residue of low molecular components such as hemicellulose component and hot water soluble component can be reduced, generation of mold, adhesion inhibition, water resistance Deterioration can be suppressed.

  Hemicellulose components and sugars are hydrolyzed due to the presence of polyvalent carboxylic acids and organic sulfonic acids, temporarily reduced in molecular weight, then modified to low molecular compounds having a furan ring, and organic sulfonic acids serve as catalysts. The reaction between furan ring compounds is promoted. For this reason, a furan ring compound is polymerized and contributes to adhesion. Polyvalent carboxylic acids contribute to the modification of hemicellulose components and sugars, and reduce the number of hydroxyl groups that deteriorate water absorption and hygroscopicity by ester bonding with hydroxyl groups in cellulose, hemicellulose, lignin and hot water soluble components contained in bagasse. Let For this reason, the water resistance, hot water resistance, and moisture resistance of the molded body are improved. Therefore, in order to form a molded article having high physical properties and suppressing the occurrence of mold in a short time, the polyvalent carboxylic acid and the organic sulfonic acid are allowed to coexist. If the addition of polyvalent carboxylic acid is lacking, ester bonds with hydroxyl groups are not formed, resulting in a significant decrease in physical properties and the occurrence of mold. If the addition of the organic sulfonic acid is lacking, the reaction between the low molecular compounds having a furan ring in which the sugar is modified is slowed down, the physical properties are greatly lowered, and mold is easily generated.

  In addition, polyvalent carboxylic acids and organic sulfonic acids are less reactive with metals than inorganic acids, and thus are less likely to be adversely affected by metal equipment during molding. Further, the reaction system does not contain an organic solvent or formaldehyde, and does not contain a tertiary amine or the like that generates formaldehyde by decomposition. Therefore, it becomes easy to suppress the emission of the organic solvent and formaldehyde derived from the molded product.

  In addition, the polyvalent carboxylic acid acts as a reaction catalyst, and a plurality of carboxyl groups of the polyvalent carboxylic acid are ester-bonded with hydroxyl groups such as hemicellulose components and sugars to reduce hydroxyl groups that deteriorate water absorption and hygroscopicity. Crosslink. Therefore, in addition to water resistance, hot water resistance, and moisture resistance, the adhesiveness of a molded object improves.

  Here, as the carboxylic acid, not a monovalent carboxylic acid but a polyvalent carboxylic acid is used. The above action is not sufficiently exhibited only by monovalent carboxylic acid. This is because the polyvalent carboxylic acid has two or more carboxylic acids in the molecule and thus has high reactivity. Therefore, polyvalent carboxylic acid is used for bagasse molding. Of course, in addition to the polyvalent carboxylic acid, a monovalent carboxylic acid may be further added. Examples of the monovalent carboxylic acid include formic acid, acetic acid, benzoic acid and the like.

  As the organic sulfonic acid, for example, alkyl sulfonic acid, aromatic sulfonic acid and the like can be used. Examples of the organic sulfonic acid include p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid and the like. Of these, aromatic sulfonic acids are preferable, and sulfonic acids having a benzene ring are more preferable. Among these, p-toluenesulfonic acid is particularly effective as a material for a molded article because it has a high effect and a reaction between low-molecular modified products proceeds to polymerize and contribute to adhesion. Benzenesulfonic acid is also suitable as a material for a molded article because it is highly effective and the reaction between low-molecular modified products proceeds to polymerize and contribute to adhesion. Therefore, it is preferable to include one or more selected from p-toluenesulfonic acid and benzenesulfonic acid. The organic sulfonic acid may have a molecular weight of 500 or less, preferably 300 or less. When the molecular weight is small, the catalyst efficiency can be increased.

  The polyvalent carboxylic acid is preferably an organic carboxylic acid having a plurality of carboxyl groups (COOH) in one molecule. As the polyvalent carboxylic acid, a divalent carboxylic acid, a trivalent carboxylic acid, a tetravalent carboxylic acid, a pentavalent or higher carboxylic acid, or the like can be used. Of these, divalent to tetravalent carboxylic acids are preferable because they are easy to use. The polyvalent carboxylic acid may have a hydroxyl group. In that case, adhesiveness can be improved. The polyvalent carboxylic acid may have a molecular weight of 500 or less, preferably 300 or less. When the molecular weight is small, the catalyst efficiency can be increased. An anhydride may be used as the polyvalent carboxylic acid.

  Examples of the polyvalent carboxylic acid include citric acid, itaconic acid, malic acid, tartaric acid, succinic acid, oxalic acid, adipic acid, malonic acid, phthalic acid, sebacic acid, maleic acid, fumaric acid, pentanedioic acid glutarate, Examples include gluconic acid, glutaconic acid, pentenedioic acid, and the like. Among these, the polyvalent carboxylic acid preferably contains one or more selected from citric acid, itaconic acid and malic acid. When one or more selected from citric acid, itaconic acid and malic acid are used, these can be produced from plants. In this case, since the use of fossil resources can be suppressed, the burden on the environment is reduced, which is preferable.

  The addition rate of the organic sulfonic acid and the polyvalent carboxylic acid is not particularly limited, and can be appropriately adjusted depending on the amount of low molecular components such as hemicellulose component and hot water soluble component contained in the bagasse. The preferable example of the addition rate of organic sulfonic acid and polyhydric carboxylic acid is shown.

  The addition rate of the organic sulfonic acid is preferably a condition where the solid content mass of the organic sulfonic acid is 0.1 parts by mass to 20 parts by mass when the dry mass of bagasse is 100 parts by mass. When the solid content of the organic sulfonic acid is 0.1 parts by mass or more, the effect as a reaction catalyst is easily obtained. In addition, when the solid content mass of the organic sulfonic acid is 20 parts by mass or less, hydrolysis reaction of hemicellulose components, sugars and the like is hardly promoted, and polymerization is hardly inhibited. In addition, the acid hardly remains to make it difficult to reduce the strength of the molded body, and further, the metal corrosion is difficult to proceed at the time of contact with a press machine or the like during pressurization. More preferably, the solid content mass of the organic sulfonic acid is 0.15 to 10 parts by mass. More preferably, the solid content mass of the organic sulfonic acid is 0.2 parts by mass to 5 parts by mass.

  The addition rate of the polyvalent carboxylic acid is preferably a condition where the solid content mass of the polyvalent carboxylic acid is 0.1 to 20 parts by mass when the dry mass of bagasse is 100 parts by mass. When the solid content mass of the polyvalent carboxylic acid is 0.1 parts by mass or more, it is easy to obtain a reaction catalytic effect, and the effect of reducing hydroxyl groups that deteriorate water absorption and hygroscopicity by ester bonds with hydroxyl groups is obtained. It becomes easy. When the solid content mass of the polyvalent carboxylic acid is 20 parts by mass or less, hydrolysis reaction of hemicellulose components, sugars and the like is hardly promoted, and polymerization is hardly inhibited. Moreover, it becomes difficult for the acid to remain and the strength of the molded body to be lowered, and the volatilization at the time of heating is small and the working environment is hardly deteriorated. More preferably, the solid content mass of the polyvalent carboxylic acid is 1 to 15 parts by mass. More preferably, the solid content of the polyvalent carboxylic acid is 2 to 10 parts by mass.

  In the adhesion of bagasse, the solid content mass of the polyvalent carboxylic acid is 0.1 mass parts to 20 mass parts when the dry mass of the bagasse is 100 mass parts, and the solid mass mass of the organic sulfonic acid. Is preferably bonded under the condition of 0.1 to 20 parts by mass. When bonding is performed under such conditions, the above-described action is further easily obtained.

  The bagasse preferably has a soluble component ratio of 3% by mass or more in the dry matter by extraction with hot water at 90 ° C. for 3 hours. Thereby, excellent adhesiveness can be obtained. When the soluble component ratio by extraction with hot water at 90 ° C. for 3 hours is less than 3% by mass, there is little generation of an adhesive component due to organic sulfonic acid and polyvalent carboxylic acid, and the physical properties as a molded article may be reduced. The upper limit of the soluble component ratio by extraction with hot water at 90 ° C. for 3 hours is not particularly limited, but is preferably 10% by mass or less. When it exceeds 10% by mass, it takes time for all the hot water-soluble components to react, and components such as cellulose are relatively reduced, and the physical properties as a molded article may be lowered. The soluble component ratio of bagasse extracted by hot water at 90 ° C. for 3 hours is more preferably 5% by mass or more and 10% by mass or less in the dry matter.

  The bagasse preferably has a sucrose ratio of 3% by mass or more in the dry matter by extraction with hot water at 90 ° C. for 3 hours. Thereby, adhesiveness can be improved. Saccharose abundantly contained in bagasse, particularly sucrose occupying most, functions as an adhesive component of bagasse. Therefore, the sucrose component is preferably 3% by mass or more. When the sucrose ratio of the bagasse is less than 3% by mass, there is little production of adhesive components due to the organic sulfonic acid and carboxylic acid, and the physical properties as a molded article may be reduced. The upper limit of the sucrose ratio in the bagasse is not particularly limited, but is preferably 10% by mass or less. When it exceeds 10% by mass, it takes time for all sucrose to react, and components such as cellulose are relatively decreased, and the physical properties as a molded article may be lowered. Moreover, when there is much sucrose amount, there exists a possibility that sucrose may remain in a molded object and there exists a possibility of causing generation | occurrence | production of mold.

  As the measurement of the amount of sucrose in bagasse, sucrose can be quantified by analyzing the pulverized extract of bagasse by high performance liquid chromatography (HPLC). In the measurement, it is preferable to use a dried bagasse. An example of HPLC measurement conditions will be described in the examples described later.

  The bagasse as a raw material usually contains sucrose, but it is better that the molded bagasse formed body does not contain sucrose as much as possible. Therefore, the bagasse molded body preferably has a sucrose ratio of less than 1% by mass in the dry matter by extraction with hot water at 90 ° C. for 3 hours. Thereby, while being able to improve water resistance, generation | occurrence | production of mold | fungi can be suppressed. When the sucrose ratio in the molded product is 1% by mass or more after molding, a large amount of unreacted sucrose remains in the molded product, and mold using sucrose as a nutrient source may easily occur. Moreover, when much sucrose remains, there exists a possibility that the water resistance of a molded object may fall because of it. The smaller the sucrose ratio in the bagasse molded body, the better, and there is no particular lower limit. The sucrose ratio is more preferably 0.2% by mass or less. The sucrose ratio is more preferably less than the measurement limit or 0% by mass.

  In order for the bagasse molded body to have a sucrose ratio of less than 1% by mass, it is performed by appropriately adjusting the molding conditions for molding. Although it does not specifically limit as shaping | molding conditions, About the shaping | molding temperature, the ratio of the sucrose after shaping | molding can be less than 1 mass% by setting shaping | molding time suitably at 160 degreeC or more and 220 degrees C or less, for example. As molding time, 5 minutes or more are preferable and 7 minutes or more are more preferable. If the molding time is too long, the production efficiency may deteriorate. Therefore, the molding time is preferably 30 minutes or less, and more preferably 20 minutes or less.

  As the measurement of the amount of sucrose in the bagasse molded article, sucrose can be quantified by analyzing the pulverized extract of the bagasse molded article by high performance liquid chromatography (HPLC). The measurement method of HPLC may be the same as the measurement of bagasse as a raw material.

  Bagasse has a sucrose ratio of 3% by mass or more in a dry matter after extraction with hot water at 90 ° C. for 3 hours, and bagasse molded product has a sucrose ratio of 1% by mass in the dry matter after extraction at 90 ° C. for 3 hours with hot water. More preferably, it is less. A large amount of sucrose is contained before molding, and the sucrose is reduced after molding, so that adhesion and water resistance can be improved, generation of mold can be suppressed, and a better molded product can be obtained.

  Note that the soluble component ratio and sucrose ratio obtained by extracting bagasse at 90 ° C. with hot water for 3 hours can vary depending on the growth period and the collection time. Furthermore, the soluble component ratio and the sucrose ratio can also vary depending on the process of obtaining bagasse from sugarcane and the processing conditions such as heat treatment and pulverization when processing bagasse as a raw material. Considering these conditions, bagasse having a desired soluble component ratio and sucrose ratio can be selected. Moreover, you may make it adjust the quantity of a soluble component and sucrose by mixing (blending) several types of bagasse.

  Bagasse is preferably bonded in the presence of sugars. Thereby, adhesiveness can be improved. Even when bagasse is used, there are cases where a component that is denatured into an adhesive component is scarce. As described above, since bagasse is an agricultural product, the content of components such as sucrose is likely to fluctuate. Therefore, when saccharides are added, the adhesiveness can be improved even when there are few components that denature into the adhesive component. Here, since the saccharide is usually contained in the bacus, the presence of the saccharide means the presence of the saccharide added separately from the saccharide contained in the bacas.

  The saccharide may be any one or more of monosaccharides, oligosaccharides, and polysaccharides. Examples of monosaccharides include glucose, fructose, ribose, arabinose, rhamnose, xylulose, deoxyribose and the like. Examples of the oligosaccharide include disaccharides such as sucrose, maltose, trehalose, and tulanose, and fructooligosaccharides, galactooligosaccharides, mannan oligosaccharides, stachyose, and the like. The oligosaccharide may be, for example, a saccharide in which 10 or less sugar chains are linked. Examples of the polysaccharide include starch, agarose, alginic acid, glucomannan, inulin, chitin, chitosan, hyaluronic acid, glycogen, and cellulose. As the saccharide, one or a combination of the above compounds can be used. As the saccharide, an oligosaccharide can be preferably used. Furthermore, disaccharides can be preferably used. Furthermore, sucrose and maltose can be used more preferably.

  The addition rate of the saccharide is not particularly limited, and can be appropriately adjusted depending on the amount of low molecular components such as hemicellulose component, sugar, and hot water soluble component contained in the bagasse. For example, when the dry mass of bagasse is 100 parts by mass, the saccharide content is preferably 0.1 parts by mass to 20 parts by mass. Adhesiveness can be improved as content of saccharides is 0.1 mass part or more. When the saccharide content is 20 parts by mass or less, it is possible to easily suppress the occurrence of mold due to the saccharide remaining in the molded body. Moreover, water resistance can be improved and adhesion inhibition can be suppressed. More preferably, the saccharide content is 1 to 15 parts by mass. More preferably, the saccharide content is 2 to 10 parts by mass.

  Bagasse may be bonded in the presence of a petroleum-based thermosetting resin adhesive. Thereby, the adhesiveness and water resistance of a molded object can be improved. Generally, wood based boards such as particle boards and fiber boards mainly use amino resins such as phenol resins and urea / melamine resins and isocyanate resin based adhesives. Also in a bagasse molded object, as long as bagasse is adhere | attached with the adhesive component derived from the component contained in a bagasse, a petroleum thermosetting resin adhesive agent can be added for the further improvement of a physical property.

  As the petroleum-based thermosetting resin adhesive, a phenol resin adhesive, a urea / melamine resin adhesive, an isocyanate adhesive, and the like are suitable, but are not particularly limited. It is preferable to select the type and amount of the adhesive depending on the usage of the molded body. When strength is required, the amount added can be increased. When water resistance is required, an adhesive having high water resistance such as a phenol resin adhesive or an isocyanate resin adhesive is suitable.

  The petroleum thermosetting resin adhesive is preferably blended so that the solid content is 3 parts by mass or more and 30 parts by mass or less when the dry mass of bagasse is 100 parts by mass. In that case, the strength of the bagasse molded body can be increased. More preferably, the blending amount of the adhesive is 5 parts by mass or more and 25 parts by mass or less with respect to the dry mass of bagasse. However, when a petroleum-based thermosetting resin adhesive is contained, formaldehyde is likely to be generated. Therefore, from the viewpoint of formaldehyde suppression, it is preferable not to contain a petroleum-based thermosetting resin adhesive. Moreover, even if it is a case where a petroleum thermosetting resin adhesive is mix | blended, the one where the quantity is smaller is preferable. For example, the solid content of the petroleum-based thermosetting resin adhesive is more preferably 20 parts by mass or less, more preferably 15 parts by mass or less, when the dry mass of bagasse is 100 parts by mass. Even more preferably, it is 10 parts by mass or less. In the bagasse molded product, even when a petroleum thermosetting resin adhesive is used, the amount thereof can be reduced, so that the generation of formaldehyde can be suppressed. In addition, petroleum-based thermosetting resin adhesives may cause harmful gas generation during combustion at the time of disposal, but this adhesive may not be used or the amount of adhesive used may be reduced. By doing so, generation of harmful gases can be suppressed.

  The bagasse molded body can be produced by adding polyvalent carboxylic acid and organic sulfonic acid and other components as required to bagasse, which is a pomace of sugarcane, and then heating and pressing the mixture thereof. The bagasse used as a raw material may be a dry raw material. Thereby, handling becomes easy. Moreover, the ground material which grind | pulverized the bagasse molded object can also be used as bagasse. In that case, the bagasse can be reused. In molding, heat and pressure molding can be efficiently performed by using a polyvalent carboxylic acid and an organic sulfonic acid in combination. For this reason, heating and pressing can be performed in a shorter time.

  The bagasse molded article is preferably obtained by attaching a polyvalent carboxylic acid and an organic sulfonic acid to the bagasse shown above, and heat-pressing the bagasse to which the deposit is attached. At this time, for example, it is preferable to obtain a bagasse by attaching an aqueous solution in which polyvalent carboxylic acid and organic sulfonic acid are dissolved in water, and then heating and pressing the mixture. By using water, polyvalent carboxylic acid and organic sulfonic acid can be efficiently attached to the surface of bagasse. Of course, an organic solvent may be used instead of the aqueous solution, but the aqueous solution is more advantageous from the viewpoint of manufacturability. One or both of the saccharide and the petroleum-based thermosetting resin adhesive described above may be added to the aqueous solution as necessary.

  Bagasse is bonded by an adhesive component generated by modifying the components contained in the bagasse itself by heat and pressure molding. At this time, the bagasse is firmly bonded by bonding in the presence of the polyvalent carboxylic acid and the organic sulfonic acid. Moreover, the amount of sucrose falls.

  As a method for attaching the organic sulfonic acid and the polyvalent carboxylic acid to the bagasse, an appropriate attachment method can be used. For example, it can be made to adhere by spraying aqueous solution toward bagasse by spray etc. Moreover, it can be made to adhere by immersing bagasse in aqueous solution. Moreover, it can be made to adhere by apply | coating with a roll, a brush, etc. Moreover, it can be made to adhere by using organic sulfonic acid and polyhydric carboxylic acid as powder as it is instead of aqueous solution, and spraying this powder directly on bagasse. In addition, if the petroleum thermosetting resin adhesive is dissolved in water as a raw material, the moisture may be used.

  The conditions for heat and pressure molding, for example, the molding pressure, molding temperature, molding time, and the like can be appropriately set depending on the type and shape of bagasse, the surface state, the thickness of the molded body, and the like. The molding temperature is preferably 160 ° C. or higher and 220 ° C. or lower. When the molding temperature is 220 ° C. or lower, the deterioration of the components hardly proceeds, so that the physical properties as a molded body are not easily lowered. In addition, when the molding temperature is 160 ° C. or higher, the reaction rate is unlikely to decrease and curing is likely to be sufficient.

  The molding pressure is appropriately set depending on the thickness and specific gravity of the molded body, but is preferably 0.5 MPa or more and 4 MPa or less. When the molding pressure is 0.5 MPa or more, it is possible to sufficiently press-bond and easily improve the strength of the molded body. If the molding pressure is 4 MPa or less, the molding pressure is not too high, and the molded body is hardly broken.

  Regarding the molding time, for example, it can be in the range of 1 minute to 60 minutes, preferably 3 minutes to 45 minutes, more preferably 5 minutes to 30 minutes, and even more preferably 7 minutes to 20 minutes. It is also preferable to set the molding time to 10 minutes or longer. Thereby, water resistance can be improved.

  The bagasse molded body is preferably a board. Thereby, it can be easily used for various uses such as architecture. In this case, the bagasse molded body is a so-called bagasse molded board. The bagasse molded body may have a three-dimensional shape other than the board. For example, a molded body that is partially raised or a molded body that is bent in the middle. In this case, it becomes a bagasse solid molded object. In the case of a three-dimensional shape, a shape that matches the purpose of use can be obtained. However, the board is preferable because the usability is enhanced and the board can be applied to various applications.

  It is preferable that the bagasse molded product has a visual three-stage evaluation of 0 (no growth) according to the fungus resistance test of JIS Z 2911. Thereby, the molded object which suppressed generation | occurrence | production of mold | fungi can be obtained. Such mold resistance can be obtained by the material of the molded body and the method for manufacturing the molded body described above.

  The mold resistance test (JIS Z 2911) can be performed by a test detailed in the following examples. The outline is a method in which a mold spore solution is dropped onto a specimen (bagasse shaped body), and after culturing at 26 ° C./99% RH for 28 days, the growth of mold on the specimen is observed. In this test, evaluation is made in three stages: “0: no growth”, “1: growth less than 1/3 of the test area”, and “2: growth of 1/3 or more of the test area”. In the case of “0: no growth”, it can be said that the occurrence of mold is sufficiently suppressed.

  In the bagasse molded product, since the bagasse as the raw material is bonded in the presence of polyvalent carboxylic acid and organic sulfonic acid, after molding, traces of polyvalent carboxylic acid and organic sulfonic acid were confirmed during molding Can be done. When polyvalent carboxylic acid remains after molding, the bagasse molded article may contain polyvalent carboxylic acid. Moreover, when organic sulfonic acid remains after shaping | molding, the organic sulfonic acid may be contained in the bagasse molded object. Or the bagasse molded object does not need to contain one or both of polyvalent carboxylic acid and organic sulfonic acid. In this case, the polyvalent carboxylic acid and the organic sulfonic acid are modified by the reaction, and the modified products are included in the bagasse molded article. For example, a molecular skeleton derived from a polyvalent carboxylic acid or a molecular skeleton derived from an organic sulfonic acid can be confirmed in the bagasse molded article. The presence of these molecular skeletons makes it possible to confirm that bagasse is adhered in the presence of a polyvalent carboxylic acid and an organic sulfonic acid. Detection of polyvalent carboxylic acid and organic sulfonic acid or their modified products can be performed by chemical analysis. For example, it may be performed by high performance liquid chromatography (HPLC), gas chromatography (GPC) or the like. From the viewpoints of adhesion and water resistance, it is preferable that the low-molecular compound is not contained in the bagasse molded article. Therefore, it is a preferred embodiment that the bagasse molded body does not contain any polyvalent carboxylic acid or organic sulfonic acid.

  The bagasse molded body may be provided with a surface material on one surface or both surfaces thereof. The surface material constitutes an adherend. By providing the surface material, the strength of the molded body can be increased. The surface material may be a board shape, a sheet shape, or the like. In this case, the bagasse molded body becomes a part of the composite molded body composed of the composite material. In the case of a board, it becomes a composite board containing a bagasse molded body. The surface material may be provided by being bonded to the bagasse molded body after the bagasse molding, or may be provided by being bonded by an adhesive component generated from the bagasse by being overlapped when the bagasse molded body is molded. As the surface material, a board-like material such as wood, particle board or fiberboard, a veneer obtained by thinly slicing wood, a decorative sheet made of plastic or paper, a sheet-like material such as a moisture-proof sheet, etc. The appropriate one described in the above can be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all. In addition, "part" shows a mass part.

[Examples 1 to 9, Comparative Examples 1 to 10]
A bagasse chip board (thickness 12 mm) was produced.

<Example 1>
Bagasse chips obtained by squeezing sugar of sugarcane, which is a herbaceous plant, were cut into lengths of about 5 cm and pulverized using a pulverizer (hammer mill) to obtain bagasse chips. The dimensions of this chip were an average length of 15 mm, an average width of 5 mm, and an average thickness of 2 mm. The soluble component ratio of the bagasse chips extracted by hot water at 90 ° C. for 3 hours was 8.2% by mass in the dry bagasse chips.

  The hot water extract of this bagasse chip was subjected to high performance liquid chromatography analysis (HPLC) under the following conditions, and the sucrose ratio in the dry portion of the bagasse chip obtained by extracting the bagasse chip with hot water at 90 ° C. for 3 hours (based on the total amount) The ratio of the sucrose component was determined.

HPLC conditions Column: CAPCELL PAK NH2 UG80
(4.6 mm Id × 250 mm, particle size 5 μm: manufactured by Shiseido)
Eluent: acetonitrile / water = 85/15
Flow rate: 2.0 mL / min
Temperature: 40 ° C
Injection volume: 10 μL
Detector: RI detector A calibration curve was appropriately created using a standard sample (sucrose).

  From the HPLC measurement, the sucrose ratio obtained by extracting the bagasse chips with hot water at 90 ° C. for 3 hours was 5.1% by mass in the dried bagasse chips.

  As the organic sulfonic acid, p-toluenesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter the same) was used. Citric acid (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter the same) was used as the polyvalent carboxylic acid. These were mixed with water to prepare a p-toluenesulfonic acid / citric acid mixed aqueous solution (hereinafter referred to as “PTSA-CA aqueous solution”). The mixing ratio of this PTSA-CA aqueous solution was p-toluenesulfonic acid: citric acid: water = 9: 1: 10 by mass ratio.

  This PTSA-CA aqueous solution was sprayed on 100 parts of the bagasse chip by spraying so that the solid content addition rate was 10 parts. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed at a surface pressure of 2 MPa for 15 minutes while being heated to 200 ° C. with a heating press apparatus to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  Next, this bagasse chip board was pulverized, and this pulverized product was extracted with hot water under the conditions of extraction at 90 ° C. for 3 hours. This hot water extract is subjected to high performance liquid chromatography analysis (HPLC) under the above-mentioned HPLC conditions, and the sucrose ratio in the dry bagasse chipboard is obtained by extracting the bagasse chipboard with hot water at 90 ° C. for 3 hours by quantifying the sucrose peak. It was.

  From the HPLC measurement, no sucrose ratio was detected by extraction of bagasse chipboard with 90 ° C. hot water for 3 hours. D. It was (below the measurement limit) and was 0% by mass in the dry matter of the molded article.

<Example 2>
P-Toluenesulfonic acid was used as the organic sulfonic acid. Itaconic acid (manufactured by Iwata Chemical Industry Co., Ltd., hereinafter the same) was used as the polyvalent carboxylic acid. These were mixed with water to prepare a mixed aqueous solution of p-toluenesulfonic acid / itaconic acid (hereinafter referred to as “PTSA-IA aqueous solution”). The mixing ratio of this PTSA-IA aqueous solution was p-toluenesulfonic acid: itaconic acid: water = 2: 8: 10 by mass ratio.

  With respect to 100 parts of bagasse chips used in Example 1, this PTSA-IA aqueous solution was sprayed by spraying so that the solid content addition rate was 10 parts. Thereafter, a bagasse chip board was obtained in the same manner as in Example 1.

  From the HPLC measurement, no sucrose ratio was detected by extraction of bagasse chipboard with 90 ° C. hot water for 3 hours. D. It was (below the measurement limit) and was 0% by mass in the dry matter of the molded article.

<Example 3>
Bagasse harvested at a different time from Example 1 was pulverized to obtain bagasse chips having an average length of 15 mm, an average width of 5 mm, and an average thickness of 2 mm. The soluble component ratio of the bagasse chips extracted by hot water at 90 ° C. for 3 hours was 3.8% in the dry bagasse chips. Moreover, the sucrose ratio by the 90 degreeC hot water 3 hour extraction of a bagasse chip | tip was 3.1 mass% in a bagasse chip | tip dry matter from HPLC measurement.

  Benzenesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter the same) was used as the organic sulfonic acid. Itaconic acid was used as the polyvalent carboxylic acid. These were mixed with water to prepare a mixed aqueous solution of benzenesulfonic acid and itaconic acid (hereinafter referred to as “BSA-IA aqueous solution”). The mixing ratio of this BSA-IA aqueous solution was benzenesulfonic acid: itaconic acid: water = 18: 2: 20 by mass ratio.

  The BSA-IA aqueous solution was sprayed on 100 parts of the bagasse chip by spraying so that the solid content addition rate was 20 parts. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed for 7.5 minutes at a surface pressure of 2 MPa while being heated to 200 ° C. with a heating press device to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  From the HPLC measurement, no sucrose ratio was detected by extraction of bagasse chipboard with 90 ° C. hot water for 3 hours. D. It was (below the measurement limit) and was 0% by mass in the dry matter of the molded article.

<Example 4>
A p-toluenesulfonic acid / citric acid mixed aqueous solution (PTSA-CA aqueous solution) having a mass ratio of p-toluenesulfonic acid: citric acid: water = 2: 18: 20 was prepared.

  With respect to 100 parts of bagasse chips used in Example 1, this PTSA-CA aqueous solution was sprayed by spraying so that the solid content addition rate was 20 parts. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed for 7.5 minutes at a surface pressure of 2 MPa while being heated to 200 ° C. with a heating press device to form a molded body.

  From the HPLC measurement, no sucrose ratio was detected by extraction of bagasse chipboard with 90 ° C. hot water for 3 hours. D. It was (below the measurement limit) and was 0% by mass in the dry matter of the molded article.

<Example 5>
P-Toluenesulfonic acid was used as the organic sulfonic acid. Citric acid was used as the polyvalent carboxylic acid. Sucrose (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter the same) was used as the saccharide. These were mixed with water to prepare a mixed aqueous solution of p-toluenesulfonic acid / citric acid / sucrose (hereinafter referred to as “PTSA-CA-SR aqueous solution”). The mixing ratio of this PTSA-CA-SR aqueous solution was p-toluenesulfonic acid: citric acid: sucrose: water = 0.2: 9.9: 9.9: 20 by mass ratio.

  With respect to 100 parts of bagasse chips used in Example 3, this PTSA-CA-SR aqueous solution was sprayed by spraying so that the solid content addition rate was 20 parts. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed for 7.5 minutes at a surface pressure of 2 MPa while being heated to 200 ° C. with a heating press device to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  From the HPLC measurement, no sucrose ratio was detected by extraction of bagasse chipboard with 90 ° C. hot water for 3 hours. D. It was (below the measurement limit) and was 0% by mass in the dry matter of the molded article.

<Example 6>
P-Toluenesulfonic acid / citric acid / sucrose mixed aqueous solution (PTSA-CA-SR) having a weight ratio of p-toluenesulfonic acid: citric acid: sucrose: water = 0.2: 9.9: 9.9: 20 Aqueous solution) was prepared.

  With respect to 100 parts of bagasse chips used in Example 3, this PTSA-CA-SR aqueous solution was sprayed by spraying so that the solid content addition rate was 20 parts. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed at a surface pressure of 2 MPa for 15 minutes while being heated to 200 ° C. with a heating press apparatus to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  From the HPLC measurement, no sucrose ratio was detected by extraction of bagasse chipboard with 90 ° C. hot water for 3 hours. D. It was (below the measurement limit) and was 0% by mass in the dry matter of the molded article.

<Example 7>
Benzenesulfonic acid was used as the organic sulfonic acid. Citric acid was used as the polyvalent carboxylic acid. Maltose (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the saccharide. A phenol resin adhesive (“Aika PX-431” manufactured by Aika Industry Co., Ltd.) was used as a petroleum thermosetting resin adhesive. This phenolic resin adhesive is commercially available in aqueous solution. These were mixed with water to prepare a phenol resin-containing benzenesulfonic acid / citric acid / maltose mixed aqueous solution (hereinafter referred to as “phenol resin-containing BSA-CA-MT aqueous solution”). The mixing ratio of the phenol resin-containing BSA-CA-MT aqueous solution was benzenesulfonic acid: citric acid: maltose: phenol resin adhesive: water = 0.4: 7.6: 2: 10: 20 in a substantial mass ratio. It was.

  The phenol resin-containing BSA-CA-MT aqueous solution was sprayed on 100 parts of the bagasse chip used in Example 3 so that the solid content addition rate was 20 parts. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed at a surface pressure of 2 MPa for 15 minutes while being heated to 200 ° C. with a heating press apparatus to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  From the HPLC measurement, no sucrose ratio was detected by extraction of bagasse chipboard with 90 ° C. hot water for 3 hours. D. It was (below the measurement limit) and was 0% by mass in the dry matter of the molded article.

<Example 8>
P-Toluenesulfonic acid was used as the organic sulfonic acid. Malic acid was used as the polyvalent carboxylic acid. As a petroleum-based thermosetting resin adhesive, a urea-melamine resin adhesive (“Oshika Resin MC32” manufactured by Oshika Co., Ltd. (containing a curing agent)) was used. This urea-melamine resin adhesive is commercially available as an aqueous solution. These were mixed with water to prepare a melamine resin-containing p-toluenesulfonic acid / malic acid mixed aqueous solution (hereinafter referred to as “melamine resin-containing PTSA-MA aqueous solution”). The mixing ratio of this melamine resin-containing PTSA-MA aqueous solution was p-toluenesulfonic acid: malic acid: melamine resin adhesive: water = 1: 9: 10: 20 in a substantial mass ratio.

  The melamine resin-containing PTSA-MA aqueous solution was sprayed on the bagasse chip 100 parts used in Example 1 by spraying so that the solid content addition rate was 20 parts. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed at a surface pressure of 2 MPa for 15 minutes while being heated to 200 ° C. with a heating press apparatus to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  From the HPLC measurement, the sucrose ratio obtained by extracting the bagasse chipboard with hot water at 90 ° C. for 3 hours was 0.2% by mass in the dry matter of the molded body.

<Example 9>
Benzenesulfonic acid was used as the organic sulfonic acid. Malic acid was used as the polyvalent carboxylic acid. As a petroleum-based thermosetting resin adhesive, a urea-melamine resin adhesive (“Oshika Resin MC32” manufactured by Oshika Co., Ltd. (containing a curing agent)) was used. This urea-melamine resin adhesive is commercially available as an aqueous solution. These were mixed with water to prepare a melamine resin-containing benzenesulfonic acid / malic acid mixed aqueous solution (hereinafter referred to as “melamine resin-containing BSA-MA aqueous solution”). The mixing ratio of this melamine resin-containing BSA-MA aqueous solution was benzenesulfonic acid: malic acid: urea melamine resin adhesive: water = 0.5: 5: 10: 20 in a substantial mass ratio.

  With respect to 100 parts of bagasse chips used in Example 1, this melamine resin-containing BSA-MA aqueous solution was sprayed with a spray so that the solid content addition rate was 20 parts. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed for 7.5 minutes at a surface pressure of 2 MPa while being heated to 200 ° C. with a heating press device to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  From the HPLC measurement, the sucrose ratio obtained by extracting the bagasse chipboard with hot water at 90 ° C. for 3 hours was 0.2% by mass in the dry matter of the molded body.

<Comparative Example 1>
20 parts of water was sprayed on the 100 parts of bagasse chip used in Example 3. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed at a surface pressure of 2 MPa for 15 minutes while being heated to 200 ° C. with a heating press apparatus to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  From the HPLC measurement, the sucrose ratio obtained by extracting the bagasse chipboard with hot water at 90 ° C. for 3 hours was 2.0% by mass in the dry matter of the molded body.

<Comparative Example 2>
20 parts of water was sprayed on 100 parts of bagasse chip used in Example 1. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed at a surface pressure of 2 MPa for 20 minutes while being heated to 250 ° C. with a heating press apparatus to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  From the HPLC measurement, the sucrose ratio obtained by extracting the bagasse chipboard with hot water at 90 ° C. for 3 hours was 1.5% by mass in the dry matter of the molded body.

<Comparative Example 3>
Benzenesulfonic acid was used as the organic sulfonic acid. No polyvalent carboxylic acid was used. A benzenesulfonic acid aqueous solution was prepared by mixing benzenesulfonic acid and water. The content of benzenesulfonic acid was benzenesulfonic acid: water = 2: 3 by mass ratio.

  With respect to 100 parts of bagasse chips used in Example 3, this aqueous benzenesulfonic acid solution was sprayed so that the solid content addition rate was 2 parts. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed at a surface pressure of 2 MPa for 15 minutes while being heated to 200 ° C. with a heating press apparatus to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  From the HPLC measurement, the sucrose ratio obtained by extracting the bagasse chipboard with hot water at 90 ° C. for 3 hours was 0.4% by mass in the dry matter of the molded body.

<Comparative Example 4>
P-Toluenesulfonic acid was used as the organic sulfonic acid. No polyvalent carboxylic acid was used. p-Toluenesulfonic acid and water were mixed to prepare a p-toluenesulfonic acid aqueous solution. The content of p-toluenesulfonic acid was p-toluenesulfonic acid: water = 10: 15 by mass ratio.

  With respect to 100 parts of bagasse chips used in Example 1, this p-toluenesulfonic acid aqueous solution was sprayed with a spray so that the solid content addition rate was 10 parts. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed at a surface pressure of 2 MPa for 15 minutes while being heated to 200 ° C. with a heating press apparatus to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  From the HPLC measurement, the sucrose ratio obtained by extracting the bagasse chipboard with hot water at 90 ° C. for 3 hours was 0.3% by mass in the dry matter of the molded body.

<Comparative Example 5>
No organic sulfonic acid was used. Itaconic acid was used as the polyvalent carboxylic acid. Itaconic acid and water were mixed to prepare an itaconic acid aqueous solution. The content of itaconic acid was itaconic acid: water = 10: 10 by mass ratio.

  This itaconic acid aqueous solution was sprayed on the bagasse chip 100 parts used in Example 1 by spraying so that the solid content addition rate was 10 parts. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed at a surface pressure of 2 MPa for 15 minutes while being heated to 200 ° C. with a heating press apparatus to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  From the HPLC measurement, the sucrose ratio obtained by extracting the bagasse chipboard with hot water at 90 ° C. for 3 hours was 0.1% by mass in the dry matter of the molded body.

<Comparative Example 6>
Benzenesulfonic acid was used as the organic sulfonic acid. No polyvalent carboxylic acid was used. A benzenesulfonic acid aqueous solution was prepared by mixing benzenesulfonic acid and water. The content of benzenesulfonic acid was benzenesulfonic acid: water = 20: 30 by mass ratio.

  With respect to 100 parts of bagasse chips used in Example 3, this aqueous benzenesulfonic acid solution was sprayed so that the solid content addition rate was 20 parts. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed for 7.5 minutes at a surface pressure of 2 MPa while being heated to 200 ° C. with a heating press device to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  From the HPLC measurement, the sucrose ratio obtained by extracting the bagasse chipboard with hot water at 90 ° C. for 3 hours was 0.3% by mass in the dry matter of the molded body.

<Comparative Example 7>
No organic sulfonic acid was used. Citric acid was used as the polyvalent carboxylic acid. Citric acid and water were mixed to prepare an aqueous citric acid solution. The content of citric acid was citric acid: water = 20: 20 by mass ratio.

  With respect to 100 parts of bagasse chips used in Example 1, this citric acid aqueous solution was sprayed by spraying so that the solid content addition rate was 20 parts. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed for 7.5 minutes at a surface pressure of 2 MPa while being heated to 200 ° C. with a heating press device to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  From the HPLC measurement, the sucrose ratio obtained by extracting the bagasse chipboard with hot water at 90 ° C. for 3 hours was 0.2% by mass in the dry matter of the molded body.

<Comparative Example 8>
No organic sulfonic acid was used. Citric acid was used as the polyvalent carboxylic acid. Sucrose was used as a saccharide. Citric acid, sucrose, and water were mixed to prepare a citric acid / sucrose mixed aqueous solution. The contents of citric acid and sucrose were citric acid: sucrose: water = 10: 10: 20 by mass ratio.

  The citric acid / sucrose mixed aqueous solution was sprayed on 100 parts of the bagasse chip used in Example 3 by spraying so that the solid content addition rate was 20 parts. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed for 7.5 minutes at a surface pressure of 2 MPa while being heated to 200 ° C. with a heating press device to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  From the HPLC measurement, the sucrose ratio obtained by extracting the bagasse chipboard with hot water at 90 ° C. for 3 hours was 0.2% by mass in the dry matter of the molded body.

<Comparative Example 9>
Organic sulfonic acids and polycarboxylic acids were not used. A phenol resin adhesive (“Aika PX-431” manufactured by Aika Industry Co., Ltd.) was used as a petroleum thermosetting resin adhesive. Phenol resin adhesive and water were mixed to prepare phenol resin adhesive diluted water. The content of the phenol resin adhesive in the phenol resin adhesive dilution water was phenol resin adhesive solids: water = 1: 1 in a substantial mass ratio.

  With respect to 100 parts of bagasse chips used in Example 1, this phenol resin adhesive diluted water was sprayed so that the solid content addition rate was 20 parts. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed at a surface pressure of 2 MPa for 15 minutes while being heated to 200 ° C. with a heating press apparatus to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  From the HPLC measurement, the sucrose ratio obtained by extracting the bagasse chipboard with hot water at 90 ° C. for 3 hours was 4.3% by mass in the dry matter of the molded body.

<Comparative Example 10>
Organic sulfonic acids and polycarboxylic acids were not used. As a petroleum-based thermosetting resin adhesive, a urea-melamine resin adhesive (“Oshika Resin MC32” manufactured by Oshika Co., Ltd. (containing a curing agent)) was used. A urea-melamine resin adhesive and water were mixed to prepare a urea-melamine resin adhesive diluted water. The content of the urea / melamine resin adhesive in the urea / melamine resin adhesive dilution water was a substantial mass ratio of urea / melamine resin adhesive solids: water = 1: 1.

  The urea / melamine resin adhesive diluted water was sprayed on 100 parts of bagasse chip used in Example 1 so that the solid content addition rate was 20 parts. Thereafter, bagasse chips were laminated to form a laminated mat, and this laminated mat was pressed at a surface pressure of 2 MPa for 15 minutes while being heated to 200 ° C. with a heating press apparatus to form a molded body.

As a result, a bagasse chip board having a thickness of 12 mm and an air-drying density of 0.6 g / cm ³ was obtained.

  From the HPLC measurement, the sucrose ratio obtained by extracting the bagasse chipboard with hot water at 90 ° C. for 3 hours was 4.2% by mass in the dry matter of the molded body.

<Evaluation>
For the molded bodies (boards) obtained in the above examples and comparative examples, a peel test (strength test) and a water absorption test (water resistance test) are conducted according to JIS A 5905, and the peel strength and the water absorption thickness expansion coefficient are determined. It was measured.

  In addition, as a hot water resistance test, a hot water absorption thickness expansion coefficient was measured when a 200 mm square sample was immersed in warm water at 80 ° C. for 5 minutes.

  Further, the formaldehyde emission amount was measured according to JIS A 5905. In terms of formaldehyde emissions, “+” indicates that the amount of formaldehyde emitted from the same amount of bagasse chips is “+”, and “−” indicates that the amount of formaldehyde emitted from the same amount of bagasse chips is equal to or less than that. . “+” Is a sample having formaldehyde emission in addition to the bagasse chip. "-" Is a sample with no formaldehyde emission other than from bagasse chips.

  Further, as a simple mold generation test, a wet cloth was placed on the board, left in a plastic bag at 40 ° C./90% RH for 2 weeks, and the presence or absence of mold generation on the board surface was visually observed. The case where mold was observed was “+” (positive) as “mold occurred”, and the case where mold was not observed was “−” (negative) as “no mold occurred”.

  Moreover, the mold resistance test of JIS Z 2911 was tested and evaluated by the following procedure.

Mold resistance test (JIS Z 2911)
(1) Five kinds of molds (Aspergillus, Penicillium, Rhizopus, Cladosporium, Chaetomium) designated by JIS Z 2911 are pre-cultured (PDA / 25 ° C./10 days).
(2) 20 mL of DW (distilled water) is added to each cultured medium, and the spores are suspended with a spreader. Each is filtered with gauze to remove the mycelium.
(3) Collect 5 ml of each spore suspension, mix, and make up to 150 ml.
(4) About 1.4 ml of the spore solution is dropped on the surface of the compact sample placed in the petri dish, and then cultured at 26 ° C./99% RH for 28 days.
(5) Perform visual three-stage evaluation according to JIS Z 2911. The three criteria are:
0: No growth 1: Growth of less than 1/3 of the test area 2: Growth of 1/3 or more of the test area

  Table 1 shows the board configuration, bonding conditions, board molding conditions, and evaluation results.

  In Comparative Example 1, only a board with low physical properties was obtained. In addition, mold occurred.

  In Comparative Example 2, molding was performed at a higher temperature and longer time than Comparative Example 1, but water resistance and hot water resistance were low, and mold was generated. In Comparative Examples 1 and 2, since the modification of the components in the bagasse has not progressed sufficiently, it is considered that the physical properties were lowered and mold was generated.

  In Comparative Examples 3 and 4, it was possible to produce a board by adding organic sulfonic acid, but water resistance and hot water resistance were low, and mold was generated in the JIS test.

  In Comparative Example 5, it was possible to produce a board by adding a polyvalent carboxylic acid and no mold was generated, but the board had low water resistance and hot water resistance.

  In Comparative Examples 6 to 8, the board could be produced by adding organic sulfonic acid or carboxylic acid, but the physical properties were greatly reduced. It is thought that it is also influenced by shortening the molding time. Since either of these organic sulfonic acids and polyvalent carboxylic acids is not added, it takes time to modify the sugar contained in the bagasse chip or the added sugar, and it is considered that the physical properties are lowered. Moreover, sugar remained on the board, and mold was generated in the JIS mold test.

  In Comparative Examples 9 to 10, by adding the petroleum-based thermosetting resin adhesive, it was possible to produce a board with high physical properties except for mold, but the sucrose in the board remained. For this reason, very many molds were generated.

  On the other hand, in Examples 1 to 10, it was possible to produce a board having high physical properties and less fungi by adding organic sulfonic acid and polyvalent carboxylic acid to bagasse. In the boards of Examples 1 to 10, the water absorption thickness expansion coefficient of normal temperature water and the water absorption thickness expansion coefficient of hot water are less than 20%, and it is considered that the boards can withstand the use of interior building materials.

  In Examples 1 and 2, the physical properties are higher than those of Comparative Examples 1 and 2 without addition, Comparative Examples 3 and 4 with only organic sulfonic acid added, and Comparative Example 5 with only polyvalent carboxylic acid added. Moreover, mold did not occur.

  In Examples 3 and 4, even when the molding time was shortened, the physical properties exceeded that of Comparative Example 6 in which only the organic sulfonic acid was added and Comparative Example 7 in which only the polycarboxylic acid was added, and no mold was generated. In particular, in Example 4, the water absorption thickness expansion coefficient of normal temperature water and the water absorption thickness expansion coefficient of hot water were 15% or less.

  In Examples 5 and 6, by adding organic sulfonic acid, polyvalent carboxylic acid, and saccharide, the physical properties greatly exceeded that of Comparative Example 8 in which no organic sulfonic acid was added. In particular, in Example 5, even when the molding time was shortened, the water absorption thickness expansion coefficient of normal temperature water and the water absorption thickness expansion coefficient of hot water were less than 20%. Furthermore, in Example 6, the water absorption thickness expansion coefficient of normal temperature water and the water absorption thickness expansion coefficient of hot water were less than 10%, and a high-performance board was obtained.

  In Examples 7 and 8, a petroleum-based thermosetting resin adhesive is added, but the physical properties are higher than those of Comparative Examples 9 and 10 in which a petroleum-based thermosetting resin adhesive is similarly added, and generation of mold is also caused. There wasn't. This is probably because the amount of petroleum thermosetting resin adhesive added was halved, and organic sulfonic acid and polyvalent carboxylic acid were added instead. The water absorption thickness expansion coefficient of normal temperature water and the water absorption thickness expansion coefficient of hot water were less than 10%. There was no mold. However, the emission of formaldehyde other than that derived from bagasse was confirmed.

  In Example 9, petroleum-based thermosetting resin adhesive was added in half the amount of Comparative Example 10, and the pressing time was shortened to 7.5 minutes. Although the physical properties tended to decrease slightly due to the shortening of the press time, the water absorption thickness expansion coefficient of room temperature water and the water absorption thickness expansion coefficient of hot water were 15% or less. There was no mold. However, the emission of formaldehyde other than that derived from bagasse was confirmed.

  From the results of the above examples, using bagasse which is a sugarcane pomace that is an unused resource as a plant piece, it is a very simple process by adding both organic sulfonic acid and polyvalent carboxylic acid, high performance It was found that a bagasse molded body of the above was obtained. This bagasse molded article has high adhesiveness and water resistance, and formaldehyde is hardly diffused, and has the performance of suppressing the generation of mold.

Claims (9)

A bagasse molded body obtained by molding bagasse which is a pomace of sugarcane,
The bagasse is bonded by an adhesive component that is generated by modifying the components contained in the bagasse during the heat and pressure molding,
The bagasse molded article is characterized in that the bagasse is bonded in the presence of a polyvalent carboxylic acid and an organic sulfonic acid.   2. The bagasse molded body according to claim 1, wherein the bagasse has a soluble component ratio of 3% by mass or more in dry matter by extraction with hot water at 90 ° C. for 3 hours. The bagasse has a sucrose ratio of 3% by mass or more based on extraction at 90 ° C. in hot water for 3 hours,
The said bagasse molded object is a bagasse molded object of Claim 1 or 2 whose sucrose ratio by extraction at 90 degreeC hot water for 3 hours is less than 1 mass% in a dry part.   The bagasse molded body according to any one of claims 1 to 3, wherein the polyvalent carboxylic acid includes one or more selected from citric acid, itaconic acid, and malic acid.   The bagasse molded body according to any one of claims 1 to 4, wherein the organic sulfonic acid includes one or more selected from p-toluenesulfonic acid and benzenesulfonic acid.   The bagasse molded body according to any one of claims 1 to 5, wherein the bagasse is bonded in the presence of sugars.   As for the said bagasse, when the dry mass of the said bagasse is 100 mass parts, the solid content mass of the said polyhydric carboxylic acid is 0.1 mass part-20 mass parts, and the solid content mass of the said organic sulfonic acid is 0 The bagasse molded body according to any one of claims 1 to 6, wherein the bagasse molded body is bonded under a condition of 1 to 20 parts by mass.   The said bagasse molded object is a board, The bagasse molded object of any one of Claims 1-7 characterized by the above-mentioned.   The bagasse molded article according to any one of claims 1 to 8, wherein the bagasse molded article has a visual three-stage evaluation by a JIS Z 2911 mold resistance test of 0 (no growth).