JP2010121096A - Vegetable originated composition and cured product of the same - Google Patents

Abstract

The present invention provides a plant-derived composition capable of forming a cured product having high reactivity and high heat resistance and mechanical properties, and a cured product thereof.
An extract component of a plant having a weight average molecular weight of 500 to 10,000 treated with pressurized hot water of 160 to 400 ° C. and 0.8 to 30 MPa and an epoxy compound of a vegetable oil and fat are contained.
[Selection figure] None

Description

  The present invention relates to a plant-derived composition and a cured product thereof.

  In recent years, as interest in environmental issues such as global warming has increased, in the plastic field, attention has been focused on resins obtained by polymerizing low-emission, carbon-neutral plant-derived degradation products as an alternative to petroleum-derived materials. Are gathering.

  Among them, polylactic acid obtained by polymerizing lactic acid, which is a kind of plant-derived degradation product, has crystallinity and is one of the resins with higher physical properties compared to other plant-derived resins. The production cost is relatively low.

  However, polylactic acid is a thermoplastic resin, and since it has low heat resistance and mechanical properties compared to general-purpose petroleum-derived thermoplastic resins (PE, PP, ABS, etc.), it has not been widely used. In addition, polylactic acid does not have physical properties that can be replaced by engineering plastics or thermosetting resins with high heat resistance.

  On the other hand, lignin, which is a polyphenol contained in a large amount in wood and the like, is an abundance after plant as a plant-derived substance. Since lignin becomes waste during pulp production, attempts have been made for a long time to make effective use of it.

  For example, since lignin has a chemical structure similar to that of a phenol resin, it has been studied to use lignin as an adhesive by reacting it with formaldehyde and condensing it in the same manner as a phenol resin. In addition, tannin contained in bark and the like has been studied for use as an adhesive by reacting with formaldehyde and condensing in the same manner as lignin. Furthermore, in view of the reaction between the methylol group of the phenol resin and the phenolic hydroxyl group of lignin, studies have been made to add lignin to the phenol resin and incorporate the lignin into the polymer skeleton of the phenol resin.

  However, when lignin or the like is reacted with formaldehyde, there is a problem that residual formaldehyde or formaldehyde generated by hydrolysis is diffused. In addition, since the reactivity of lignin is lower than that of conventional phenol resins, physical properties and productivity are inferior, and the above technology is not widely put into practical use.

As other attempts to use lignin effectively, the phenolic hydroxyl group of lignin and polyisocyanate are reacted to form a urethane resin (see Non-Patent Document 1), the phenolic hydroxyl group of lignin is epoxidized, and other epoxy resins (See Non-Patent Document 2), adding a rosin-based component and a component that reacts with it to lignin (see Patent Document 1), and the like.
JP 2003-277615 A "New Wood Material Handbook", Gihodo Publishing, p. 685 "New epoxy resin made from plant-derived lignophenol" Network polymer, 27 (2), 118 (2006)

  However, since these oils use many petroleum-derived components, the ratio of plant-derived components cannot be increased, and there is a problem that physical properties and productivity are inferior due to low reactivity, and they are not widely put into practical use. is the current situation. Moreover, in patent document 1, the mixing | blending which mixed the lignin and the epoxy compound without adding a rosin-type component has low physical property. This is thought to be due to the low reactivity of lignin.

  The present invention has been made in view of the circumstances as described above, and has a high reactivity, a plant-derived composition capable of forming a cured product having high heat resistance and mechanical properties, and the cured product thereof It is an issue to provide.

  The present invention is characterized by the following in order to solve the above problems.

  First: derived from a plant, comprising an extract component of a plant having a weight average molecular weight of 500 to 10,000 treated with pressurized hot water of 160 to 400 ° C. and 0.8 to 30 MPa, and an epoxy compound of vegetable oil and fat Composition.

  Second: The plant-derived composition according to the first aspect, wherein the plant extract component contains a phenolic compound having at least one phenolic hydroxyl group and having two or more hydroxyl groups.

  Third: The first or second plant-derived composition described above, wherein the plant extract component is treated with pressurized hot water of 200 to 320 ° C. and 1.6 to 13 MPa.

  Fourth: A cured product obtained by curing any one of the first to third plant-derived compositions.

  According to the first aspect of the invention, the plant is treated with pressurized hot water at 160 to 400 ° C. and 0.8 to 30 MPa, and an extract component having a weight average molecular weight of 500 to 10,000 is taken out from the plant.

  The plant extraction component that satisfies the specific pressurized hydrothermal treatment conditions and the weight average molecular weight contains a phenolic compound having at least one phenolic hydroxyl group, but includes a plurality of aromatic rings. The proportion is the majority. This phenolic compound containing a plurality of aromatic rings has two or more hydroxyl groups in one molecule, and these two or more hydroxyl groups react with the epoxy group of the epoxy compound of the vegetable oil and fat, and the reaction product becomes 3D cross-linking.

  In other words, the phenolic compound can be treated with pressurized hot water compared to lignophenol extracted using kraft lignin, lignin sulfonic acid, sulfuric acid, etc., which are by-produced during pulp production, in a state where there is little modification of hydroxyl groups. Since it is extracted, it has two or more highly reactive hydroxyl groups and is highly reactive with the epoxy compound of vegetable oil.

  Then, the aromatic ring of the phenolic compound that improves the heat resistance is incorporated into the reaction product by the reaction with the epoxy compound of the vegetable oil and fat to form a three-dimensionally crosslinked cured product having high heat resistance and mechanical properties. Can do.

  According to the second aspect of the invention, the plant extract component has at least one phenolic hydroxyl group and contains a phenolic compound having two or more hydroxyl groups. The hydroxyl group of this reacts with the epoxy group of the epoxy compound of vegetable oil and fat, and the reaction product is three-dimensionally crosslinked.

  Then, the aromatic ring of the phenolic compound that improves the heat resistance is incorporated into the reaction product by the reaction with the epoxy compound of the vegetable oil and fat to form a three-dimensionally crosslinked cured product having high heat resistance and mechanical properties. Can do.

  According to the third aspect of the invention, the plant is treated with pressurized hot water at 200 to 320 ° C. and 1.6 to 13 MPa, and an extract component having a weight average molecular weight of 500 to 10,000 is taken out from the plant.

  In addition to the effects of the first and second inventions described above, the plant extract component satisfying the specific pressurized hydrothermal treatment conditions and the weight average molecular weight has a significant gelation time in the curing reaction of the vegetable oil with the epoxy compound. In particular, the reactivity of the vegetable oil with the epoxy compound can be particularly increased, and the heat resistance and mechanical properties of the cured product can be improved.

  Furthermore, by satisfying the specific pressurized hydrothermal treatment conditions and the weight average molecular weight, the yield of the extracted component of the plant having high reactivity with the epoxy compound of the vegetable oil and fat is greatly improved.

  According to the fourth invention, the plant-derived composition of the first to third inventions is cured by reaction, and the composition is heated and irradiated with light in the same manner as a conventional curable resin. In addition, since it reacts by the addition of a curing accelerator or the like to obtain a cured product having a three-dimensional network structure, higher heat resistance and mechanical strength can be obtained as compared with a thermoplastic resin or the like.

  Hereinafter, the present invention will be described in detail.

  In the present invention, the plant as a raw material for the extract component is not particularly limited. Specific examples thereof include woody plants (pine trees, cedars, cypresses, birchs, etc.) and herbaceous plant stems. , Stems, branches, bark, leaves, and the like containing polyphenols called lignin and tannin. The structure of the polyphenols contained varies depending on the plant type, site, etc., and studies are currently being conducted to identify these structures.

  The above-mentioned plant is pulverized into plant material, treated with pressurized hot water, and extracted components containing phenolic compounds are extracted by extraction.

  In this invention, the process by a pressurized hot water is performed on conditions of 160-400 degreeC and 0.8-30 MPa, and the extract component of a plant of the weight average molecular weights 500-10000 is obtained. In a particularly preferred embodiment, the treatment with pressurized hot water is performed under the conditions of 200 to 320 ° C. and 1.6 to 13 MPa, preferably 220 to 310 ° C. and 2.5 to 10 MPa, and the weight average molecular weight is 500 to 10,000, preferably Of 500 to 5000, more preferably 500 to 2000, and still more preferably 600 to 1600 plant extract components.

  Here, the treatment with pressurized hot water includes so-called steaming treatment, blasting treatment, subcritical treatment, and supercritical treatment. Here, “subcritical treatment” refers to treatment in subcritical water, and subcritical water is a temperature and pressure of water at a critical point (critical temperature 374.4 ° C., critical pressure 22.1 MPa). ) And water in a state where the temperature is 140 ° C. or higher and the pressure at that time is 0.36 MPa (saturated vapor pressure of 140 ° C.) or higher. “Supercritical treatment” means treatment in supercritical water, and supercritical water means water whose temperature and pressure exceed the critical point.

  By treating the pulverized plant material under the above conditions, the polymer lignin, tannin and the like are reduced in molecular weight by the action of dissolving the organic matter by the pressurized hot water and the strong hydrolysis action. It becomes a phenolic compound having high reactivity.

  The plant extraction component that satisfies the specific pressurized hydrothermal treatment conditions and the weight average molecular weight contains a phenolic compound having at least one phenolic hydroxyl group, but includes a plurality of aromatic rings. The proportion is the majority. This phenolic compound containing a plurality of aromatic rings has two or more hydroxyl groups in one molecule, and these two or more hydroxyl groups react with the epoxy group of the epoxy compound of the vegetable oil and fat, and the reaction product becomes 3D cross-linking.

  In other words, the phenolic compound can be treated with pressurized hot water compared to lignophenol extracted using kraft lignin, lignin sulfonic acid, sulfuric acid, etc., which are by-produced during pulp production, in a state where there is little modification of hydroxyl groups. Since it is extracted, it has two or more highly reactive hydroxyl groups and is highly reactive with the epoxy compound of vegetable oil.

  In the treatment with pressurized hot water, if the temperature is too low or the pressure is too low, the water solubility of organic substances such as lignin and tannin contained in the crushed plant material is reduced, and the ability to further hydrolyze Decreases. Therefore, the molecular weight reduction is insufficient and it is difficult to extract the phenolic compound.

  Further, in the treatment with pressurized hot water, when the temperature is too low or the pressure is too low, even if an extract component of the plant whose weight average molecular weight satisfies the above range is obtained, it is caused by the treatment conditions. The proportion of phenolic compounds containing a plurality of moderately low-molecular aromatic rings having two or more hydroxyl groups is reduced, and the reactivity of the extract with plant epoxy resin is significantly reduced. Tend to.

  In the treatment with pressurized hot water, if the temperature is too high or the pressure is too high, the hydrolyzing action on organic substances such as lignin and tannin contained in the pulverized plant material is too strong, resulting in excessively low molecular weight. The weight average molecular weight is less than the above range, and a phenolic compound having high reactivity with a plant epoxy resin cannot be obtained. That is, the plant extract component is excessively depolymerized and the proportion of the compound consisting of one aromatic ring increases. Most of the compounds having one aromatic ring have one hydroxyl group or no hydroxyl group, and such a compound does not react or reacts with an epoxy compound of vegetable oil. However, since there is only one hydroxyl group, three-dimensional crosslinking cannot be formed.

  In addition, when the weight average molecular weight of the plant extract component exceeds 10,000, the solubility in an appropriate solvent such as water or an organic solvent is greatly reduced, and it becomes difficult to take out the extract component as an extract component.

  In the treatment with pressurized hot water, when the temperature is high, the molecular weight of the plant extract component is reduced even in a short treatment time, but when the temperature is low, an extract component with a high molecular weight can be obtained by adjusting the treatment time. it can.

  In the present invention, in particular, the treatment with pressurized hot water is carried out under the conditions of 200 to 320 ° C. and 1.6 to 13 MPa, preferably 220 to 310 ° C. and 2.5 to 10 MPa, and the weight average molecular weight is 500 to 10,000, preferably Of 500 to 5000, more preferably 500 to 2000, and even more preferably 600 to 1600, the gelation time in the curing reaction of the vegetable oil with the epoxy compound is significantly shortened, The reactivity with the epoxy compound can be particularly increased, and the heat resistance and mechanical properties of the cured product can be improved. Furthermore, by satisfying the specific pressurized hydrothermal treatment conditions and the weight average molecular weight, the yield of the extracted component of the plant having high reactivity with the epoxy compound of the vegetable oil and fat is greatly improved.

  The product extraction conditions by the pressurized hot water treatment described above are not particularly limited, and an appropriate solvent such as water or an organic solvent is selected according to the solubility of the product, and the extraction temperature, pressure, time, etc. Is also set appropriately. By the extraction operation, a plant extract component containing a highly reactive phenolic compound is obtained.

  The epoxy compound for vegetable oils and fats blended in the plant-derived composition of the present invention is not particularly limited. For example, commercially available epoxy compounds for vegetable oils and fats such as soybean, flax, paulownia, sesame seeds, and palm seeds are used. Can be used. These are epoxidized products of glycerin esters of fatty acids, and the epoxy equivalents of the epoxy compounds of vegetable oils that are industrially produced and marketed are usually 100 to 400.

  And in this invention, the epoxy compound of the vegetable oil and fat which has an epoxy equivalent of 100-400 and has two or more epoxy groups is used, and two or more epoxy groups in 1 molecule contain in the extract component of a plant. It is possible to obtain a cured product having high heat resistance and mechanical properties by reacting with two or more hydroxyl groups in the phenolic compound containing a plurality of aromatic rings to be three-dimensionally crosslinked.

  The blending amount of the vegetable oil / fat epoxy compound in the plant-derived composition of the present invention is preferably 1 to 30% by mass with respect to the total amount of the plant extract component treated with pressurized hot water and the vegetable oil / fat epoxy compound. It is. By making content of the epoxy compound of vegetable oil and fat within the said range, the epoxy group in the epoxy compound of vegetable oil and fat easily reacts with the hydroxyl group of the phenolic compound in the extracted component of the plant treated with pressurized hot water. As a result, since the proportion of the aromatic ring of the phenolic compound that improves heat resistance is increased in the reaction product, a cured product having high heat resistance and mechanical properties can be obtained.

  The plant-derived composition of the present invention may contain other additive components in addition to the plant extract components treated with pressurized hot water and the vegetable fat / oil epoxy compounds. Specific examples of such additive components include curing accelerators, fillers, and weight gains commonly used in curable resins such as paratoluenesulfonic acid monohydrate, triphenylphosphine, imidazole, and diazabicycloundecene. Materials and the like. Moreover, the plant-derived composition of the present invention may be diluted with a solvent.

  When paratoluenesulfonic acid monohydrate is added as a curing accelerator to the plant-derived composition of the present invention, the reaction between the plant extract component treated with pressurized hot water and the epoxy compound of the vegetable oil and fat is particularly accelerated, This is preferable because the reactivity can be improved.

  The plant-derived composition of the present invention is cured by reacting under appropriate conditions. Although the reaction mechanism of the curing reaction is not clear, the reaction between the hydroxyl group of the phenolic compound in the extracted components of the plant treated with pressurized hot water and the epoxy group in the epoxy compound of the vegetable oil proceeds as a main reaction. It is considered that a cured product having a three-dimensional network structure is obtained by the reaction between epoxy groups in the epoxy compound of vegetable oil.

  The conditions for the curing reaction are not particularly limited, and conditions similar to those for conventional curable resins can be applied. Specifically, for example, the curing reaction can be advanced by heating, light irradiation, addition of a curing accelerator, or the like.

  Since the plant-derived composition of the present invention can form a cured product having high heat resistance and mechanical properties, it can be suitably used as a molding material. Further, it can be impregnated into paper or glass fiber, or applied to a single plate to be suitably used as a laminated plate, and can also be suitably used as an adhesive.

EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these Examples at all.
<Example 1>
140 g of red pine wood flour (average particle size 0.7 mm) and 1 L of water were placed in a pressure-resistant kettle and treated with hot hot water under the conditions of 210 ° C., 1.8 Mpa, 25 minutes. After the treatment residue was dried, it was extracted with methyl ethyl ketone (manufactured by Nacalai Tesque) at room temperature and normal pressure for 2 hours, and the soluble part was concentrated under reduced pressure to obtain a plant extract component.

The yield was determined by dividing the weight of the plant extract extracted with methyl ethyl ketone by the weight of the raw pine wood flour. Moreover, the weight average molecular weight of the extract component of the plant was measured by GPC (gel permeation chromatography). The measurement conditions of GPC are as follows.
GPC measurement conditions THF is added to the sample, and after ultrasonication (30 minutes), the soluble part is measured. Device: HLC-8120GPC manufactured by Tosoh Corporation
Column: G5000HXL + G3000HXL + G2000HXL + G1000HXL (each one connected)
Exclusion limit molecular weight: 4.0 × 106
Eluent: THF 1.0ml / min
Temperature: 40 ℃
Detector: Differential refractometer Molecular weight calculation: Table 1 shows the polystyrene conversion pressurized hot water treatment conditions, yield and weight average molecular weight.

  When the obtained plant extract component was analyzed by GC-MS, the plant extract component was a mixture of many kinds of compounds, and a phenolic compound having at least one phenolic aromatic ring, particularly a plurality of phenolic compounds. It was confirmed to contain a phenolic compound containing an aromatic ring. Moreover, when IR analysis was performed on the extracted component of this plant, a phenolic compound having two or more hydroxyl groups was confirmed.

  This plant extract component, an epoxy compound of vegetable oil (epoxidized linseed oil, Adeka Sizer O-180A, manufactured by Adeka Co., Ltd., epoxy equivalent 176, number of epoxy groups 6), and paratoluenesulfonic acid as a curing accelerator Monohydrate (manufactured by Nacalai Tesque Co., Ltd.) was mixed with methyl ethyl ketone as a solvent to obtain a plant-derived composition. The mixing ratio was as follows: plant extraction component: vegetable oil / epoxy compound: curing accelerator: solvent = 95: 5: 2: 200.

About this plant origin composition, the gelation time in 130 degreeC was measured based on the gelation time B method of JISK6910. The results are shown in Table 1.
<Example 2>
140 g of red pine wood flour (average particle size 0.7 mm) and 1 L of water were placed in a pressure vessel and treated with hot pressurized water at 230 ° C. and 3 MPa for 90 minutes. After the treatment residue was dried, it was extracted with methyl ethyl ketone (manufactured by Nacalai Tesque) at room temperature and normal pressure for 2 hours, and the soluble part was concentrated under reduced pressure to obtain a plant extract component. The yield and weight average molecular weight of the extracted components of this plant were measured in the same manner as in Example 1. Also, under the same conditions as in Example 1, this plant extract component, an epoxy compound of vegetable oil and fat, and paratoluenesulfonic acid monohydrate as a curing accelerator were mixed in methyl ethyl ketone as a solvent. A plant-derived composition having the same mixing ratio as 1 was obtained. And about this plant origin composition, the gelation time in 130 degreeC was measured like Example 1. FIG.

Table 1 shows the conditions for the pressurized hot water treatment, the yield of the extracted components of the plant, the weight average molecular weight, and the gelation time of the plant-derived composition.
<Example 3>
140 g of red pine wood flour (average particle size 0.7 mm) and 1 L of water were put in a pressure vessel and treated with hot pressurized water at 300 ° C., 8.8 MPa for 20 minutes. After the treatment residue was dried, it was extracted with methyl ethyl ketone (manufactured by Nacalai Tesque) at room temperature and normal pressure for 2 hours, and the soluble part was concentrated under reduced pressure to obtain a plant extract component. The yield and weight average molecular weight of the extracted components of this plant were measured in the same manner as in Example 1. Also, under the same conditions as in Example 1, this plant extract component, an epoxy compound of vegetable oil and fat, and paratoluenesulfonic acid monohydrate as a curing accelerator were mixed in methyl ethyl ketone as a solvent. A plant-derived composition having the same mixing ratio as 1 was obtained. And about this plant origin composition, the gelation time in 130 degreeC was measured like Example 1. FIG.

Table 1 shows the conditions for the pressurized hot water treatment, the yield of the extracted components of the plant, the weight average molecular weight, and the gelation time of the plant-derived composition.
<Example 4>
140 g of red pine wood flour (average particle size 0.7 mm) and 1 L of water were placed in a pressure-resistant kettle and treated with pressurized hot water at 180 ° C. and 1 MPa for 90 minutes. After the treatment residue was dried, it was extracted with methyl ethyl ketone (manufactured by Nacalai Tesque) at room temperature and normal pressure for 2 hours, and the soluble part was concentrated under reduced pressure to obtain a plant extract component. The yield and weight average molecular weight of the extracted components of this plant were measured in the same manner as in Example 1. Also, under the same conditions as in Example 1, this plant extract component, an epoxy compound of vegetable oil and fat, and paratoluenesulfonic acid monohydrate as a curing accelerator were mixed in methyl ethyl ketone as a solvent. A plant-derived composition having the same mixing ratio as 1 was obtained. And about this plant origin composition, the gelation time in 130 degreeC was measured like Example 1. FIG.

Table 1 shows the conditions for the pressurized hot water treatment, the yield of the extracted components of the plant, the weight average molecular weight, and the gelation time of the plant-derived composition.
<Comparative Example 1>
140 g of red pine wood flour (average particle size 0.7 mm) and 1 L of water were placed in a pressure vessel and treated with pressurized hot water at 340 ° C., 15 MPa for 20 minutes. After the treatment residue was dried, it was extracted with methyl ethyl ketone (manufactured by Nacalai Tesque) at room temperature and normal pressure for 2 hours, and the soluble part was concentrated under reduced pressure to obtain an extract component. The yield and weight average molecular weight of the extracted components of this plant were measured in the same manner as in Example 1. Also, under the same conditions as in Example 1, this plant extract component, an epoxy compound of vegetable oil and fat, and paratoluenesulfonic acid monohydrate as a curing accelerator were mixed in methyl ethyl ketone as a solvent. A plant-derived composition having the same mixing ratio as 1 was obtained. And about this plant origin composition, the gelation time in 130 degreeC was measured like Example 1. FIG.

Table 1 shows the conditions for the pressurized hot water treatment, the yield of the extracted components of the plant, the weight average molecular weight, and the gelation time of the plant-derived composition.
<Comparative example 2>
140 g of red pine wood flour (average particle size 0.7 mm) and 1 L of water were placed in a pressure vessel and treated with pressurized hot water at 150 ° C., 0.7 Mpa for 180 minutes. After the treatment residue was dried, it was extracted with methyl ethyl ketone (manufactured by Nacalai Tesque) at room temperature and normal pressure for 2 hours, and the soluble part was concentrated under reduced pressure to obtain a plant extract component. The yield and weight average molecular weight of the extracted components of this plant were measured in the same manner as in Example 1. Also, under the same conditions as in Example 1, this plant extract component, an epoxy compound of vegetable oil and fat, and paratoluenesulfonic acid monohydrate as a curing accelerator were mixed in methyl ethyl ketone as a solvent. A plant-derived composition having the same mixing ratio as 1 was obtained. And about this plant origin composition, the gelation time in 130 degreeC was measured like Example 1. FIG.

  Table 1 shows the conditions for the pressurized hot water treatment, the yield of the extracted components of the plant, the weight average molecular weight, and the gelation time of the plant-derived composition.

  From Table 1, the extract components of the plants of Examples 1 to 3 treated with pressurized hot water under specific conditions of temperature and pressure and having a weight average molecular weight of 500 or more reacted by heating and gelled in a short time. Furthermore, the yield of the plant extract component generally exceeded 10%, and the plant extract component highly reactive with the epoxy compound of the vegetable oil and fat could be extracted with high efficiency. Thus, the gelation time of a plant-derived composition is significantly shortened by treating with 200-320 ° C. and 1.6-13 MPa pressurized hot water to obtain an extract component with a weight average molecular weight of 500-10000. In addition, the yield of extracted components is greatly improved.

  The extracted component of the plant of Example 4 treated with pressurized hot water at 180 ° C. and 1 MPa and having a weight average molecular weight of 500 or more reacted and gelled by heating, but significantly longer than in Examples 1-3. Cost. This is because the processing temperature and the processing pressure are low, the proportion of phenolic compounds containing a plurality of appropriately reduced aromatic rings having two or more hydroxyl groups is reduced, and the epoxy compound of vegetable oils and fats This is thought to be due to the fact that the proportion of phenolic compounds having a high reactivity with the lower the ratio. Moreover, the yield of the extract component of the plant was low and the extraction efficiency was low. This is because the treatment temperature and the treatment pressure are low, so that the solubility of organic substances such as lignin and tannin contained in plant materials in water is lowered, and further the ability to hydrolyze is lowered. This is probably due to insufficient molecularization.

  The plant extract component of Comparative Example 1 treated with pressurized hot water at 340 ° C. and 15 MPa and having a weight average molecular weight of less than 500 gels within 60 minutes even when mixed with a vegetable oil epoxy compound and heated. There wasn't. This is because the hydrolysis of organic substances such as lignin and tannin contained in plant materials is too strong, the molecular weight is excessively reduced, and the reactivity of the extracted phenolic compounds with the epoxy compounds of vegetable oils and fats is reduced. It is thought to be due to.

  The plant extract component of Comparative Example 2 treated with pressurized hot water at 150 ° C. and 0.7 MPa and having a weight average molecular weight of 500 or more is mixed with an epoxy compound of vegetable oil within 60 minutes. Did not gel. This is because the processing temperature and the processing pressure are low, the proportion of phenolic compounds containing a plurality of appropriately reduced aromatic rings and having two or more hydroxyl groups is extremely low, and the epoxy of vegetable oils and fats. This is thought to be due to the fact that the proportion of phenolic compounds having high reactivity with the compounds has become extremely low. Moreover, the yield of the extract component of a plant was also very low, and the extraction efficiency was very low. This is because the treatment temperature and the treatment pressure are low, so that the solubility of organic substances such as lignin and tannin contained in plant materials in water is lowered, and further the ability to hydrolyze is lowered. This is probably due to insufficient molecularization.

  From the above, by treating with pressurized hot water at 160 to 400 ° C. and 0.8 to 30 MPa to obtain a plant extract component having a weight average molecular weight of 500 to 10,000, a cured product with an epoxy compound of vegetable oil is obtained. However, when the condition of the pressurized hot water treatment or the weight average molecular weight of the extracted component of the plant is out of the range, formation of a cured product of the vegetable oil with the epoxy compound becomes extremely difficult.

Claims (4)

  A plant-derived composition comprising an extract component of a plant having a weight average molecular weight of 500 to 10,000 treated with pressurized hot water of 160 to 400 ° C. and 0.8 to 30 MPa, and an epoxy compound of vegetable oil.   The plant-derived composition according to claim 1, wherein the plant extract component contains a phenolic compound having at least one phenolic hydroxyl group and having two or more hydroxyl groups.   The plant-derived composition according to claim 1 or 2, wherein the plant extract component is treated with pressurized hot water of 200 to 320 ° C and 1.6 to 13 MPa.   Hardened | cured material formed by hardening | curing the plant origin composition as described in any one of Claims 1 thru | or 3.