JP2009046646A - Plant-derived composition and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plant-derived composition which has high reactivity and from which a cured product having high heat resistance and mechanical properties can be formed, and to provide the cured product. <P>SOLUTION: The plant-derived composition comprises: an extracted component of a plant, obtained by treating the plant with pressurized hot water of 160-400°C and 0.8-30 MPa and containing a phenolic component having at least one phenol nucleus; and an epoxy compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

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 plastics 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 has not been widely used because of its low heat resistance and mechanical properties compared to general-purpose petroleum-derived thermoplastic resins (PE, PP, ABS, etc.). 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 next to cellulose 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. Further, 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 effectively use lignin, a phenolic hydroxyl group of lignin and a polyisocyanate are reacted to form a urethane resin (see Non-patent Document 1), and the phenolic hydroxyl group of lignin is epoxidized to produce another epoxy resin. (See Non-Patent Document 2), adding a rosin-based component and the like and a component that reacts with it to lignin (see Patent Document 1), and the like.
JP 2003-277615 A “New Wood Handbook”, Gihodo Publishing, p. 685 "New epoxy resin made from plant-derived lignophenol" Network polymer, 27 (2), 118 (2006)

  However, these conventional technologies use many petroleum-derived components, so 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, which has been widely put into practical use. There is no 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, can form a cured product having high heat resistance and mechanical properties, and has a high reactivity and a plant-derived composition 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.

  1stly, the plant origin composition of this invention contains the phenolic component which has at least 1 phenol nucleus, The extract component of the plant processed with 160 to 400 degreeC and the pressurized hot water of 0.8 to 30 MPa, And an epoxy compound.

  Second, in the first plant-derived composition, the epoxy compound is an epoxy compound of vegetable oil.

  Third, the first or second plant-derived composition is characterized by containing paratoluenesulfonic acid hydrate as a curing accelerator.

  Fourth, in the third plant-derived composition, the content of paratoluenesulfonic acid hydrate is 0.2 to 4 parts by mass with respect to 100 parts by mass of the total amount of the plant extract component and the epoxy compound. It is a range.

  5thly, the hardened | cured material of this invention hardens | cures the said plant origin composition in any one of the said 1st thru | or 4th, It is characterized by the above-mentioned.

  According to the said 1st invention, the phenolic component with high reactivity with an epoxy compound is taken out from a plant as an extract by processing and extracting a plant with the pressurized hot water of specific conditions. Unlike the lignophenol extracted using the kraft lignin, the lignin sulfonic acid, and the sulfuric acid which are by-produced at the time of pulp manufacture, the extraction component containing the said phenolic component has high reactivity with an epoxy compound. Furthermore, a cured product having high heat resistance and mechanical properties can be formed, and can be used as a molding material or an adhesive.

  According to the said 2nd invention, since the epoxy compound of vegetable oil is used as an epoxy compound, in addition to the effect of the said 1st invention, raising the ratio of the plant-derived component in a plant-derived composition and hardened | cured material Carbon neutral characteristics can be further enhanced.

  According to the third invention, by using paratoluenesulfonic acid hydrate as a curing accelerator, in addition to the effect of the first invention, the reaction between the phenolic component and the epoxy resin is promoted, The reactivity can be improved.

  According to the fourth invention, since a specific amount of paratoluenesulfonic acid hydrate is used, in addition to the effect of the third invention, the reaction between the phenolic component and the epoxy resin is particularly promoted, The reactivity can be greatly improved.

  According to said 5th invention, it is set as the hardened | cured material by making the plant origin composition of the said 1st thru | or 4th invention react, The said composition is heating, light irradiation, similarly to the conventional curable resin, Since it reacts by the addition of a curing accelerator or the like to form 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 the raw material of the extract component is not particularly limited, but specific examples thereof include tree plants (conifers, broadleaf trees) and herbaceous plant trunks, stems, branches, bark, leaves, etc. Examples include those containing polyphenols called tannins. 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 plant is pulverized into a plant material, treated with pressurized hot water, and a phenolic component having high reactivity with the epoxy compound is extracted as an extraction component by extraction.

  The treatment with pressurized hot water is performed under the conditions of 160 to 400 ° C. and 0.8 to 30 MPa. The treatment 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-mentioned conditions, high-reactivity phenolic compounds such as lignin and tannin, which are high molecular weight molecules, are dissolved by the action of dissolving organic substances and hot hydrolysis with pressurized hot water. Become an ingredient.

  When the treatment with pressurized hot water is performed under conditions of less than 160 ° C. or less than 0.8 MPa, the solubility of organic substances such as lignin and tannin contained in the pulverized plant material in water is reduced, and the ability to further hydrolyze Decreases. Therefore, the molecular weight reduction becomes insufficient, and the reactivity of the extracted phenolic component decreases.

  If the treatment with pressurized hot water exceeds 400 ° C or exceeds 30 MPa, 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. In addition, since a condensation reaction occurs simultaneously, a highly reactive phenolic component cannot be obtained.

  The extraction conditions of the product by the pressurized hot water treatment 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. are also set appropriately. Is done. An extraction component containing a highly reactive phenolic component is obtained by the extraction operation.

  The extraction component containing the phenolic component having at least one phenol nucleus extracted from the plant as described above is not clear in its factor, but craft lignin, lignin sulfonic acid, sulfuric acid by-produced during pulp production Unlike lignophenol and the like extracted using, the reactivity with the epoxy compound is increased. The “phenolic component having at least one phenol nucleus” includes a compound comprising an aromatic ring having at least one phenolic hydroxyl group, particularly a benzene ring, and a compound having at least one aromatic ring in the structure. included. The aromatic ring may have a substituent other than the phenolic hydroxyl group.

  The epoxy compound contained in the plant-derived composition of the present invention is not particularly limited as long as it has an epoxy group. In particular, the plant-derived composition and its cured product can be obtained by using an epoxy compound of vegetable oil. The ratio of the plant-derived component in the inside can be increased, and the carbon neutral characteristics can be further enhanced. As such an epoxy compound for vegetable oils and fats, for example, commercially available epoxy compounds for vegetable oils and fats such as soybean, flax, paulownia, sesame and palm seeds can be used.

  In addition, in the plant-derived composition of the present invention, those other than the epoxy compound of vegetable oils and fats, for example, those derived from petroleum may be used as the epoxy compound. Specific examples of such an epoxy compound include a bisphenol type epoxy resin, a biphenyl type epoxy resin, a cresol novolac type epoxy resin, and a polyfunctional type epoxy resin. These may be used alone or in combination of two or more.

  The plant-derived composition of the present invention can be prepared by mixing an extraction component containing the phenolic component and an epoxy compound. The mixing ratio of the extraction component and the epoxy compound is appropriately set in consideration of the reactivity of the phenolic component in the extraction component, the hydroxyl equivalent, and the like.

  The plant-derived composition of the present invention may contain other additive components in addition to the extraction component and the epoxy compound. Specific examples of such additive components include curing accelerators, fillers, and extenders commonly used in curable resins such as paratoluenesulfonic acid hydrate, triphenylphosphine, imidazole, and diazabicycloundecene. Etc. Moreover, the plant-derived composition of the present invention may be diluted with a solvent.

  When paratoluenesulfonic acid hydrate is added as a curing accelerator to the plant-derived composition of the present invention, the reaction between the phenolic component and the epoxy compound is particularly accelerated, and the reactivity can be greatly improved. . The content of paratoluenesulfonic acid hydrate is preferably in the range of 0.2 to 4 parts by mass with respect to 100 parts by mass of the total amount of the extraction component and the epoxy compound. When the content is less than 0.2 parts by mass, the effect of promoting the reaction is small. When the content exceeds 4 parts by mass, the paratoluenesulfonic acid hydrate, which is a strong acid, becomes excessive, so that the cured product is decomposed. In addition, the physical properties of the cured product may deteriorate.

  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, glass fiber, or the like, or applied to a single plate and suitably used as a laminated plate, and can also be suitably used as an adhesive.

  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, a reaction between a phenolic hydroxyl group and an epoxy group proceeds as a main reaction, and a reaction between epoxy groups proceeds as a side reaction, resulting in a cured product having a three-dimensional network structure. It is considered a thing. 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.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all.
<Example 1>
300 g of birch wood flour (average particle size 0.7 mm) and 5 L of water were placed in a pressure vessel and treated with pressurized hot water at 220 ° C., 4 MPa for 10 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.

  When the obtained extract component was analyzed by GC-MS, the extract component was a mixture composed of many kinds of compounds and contained a phenolic component having at least one phenol nucleus such as 2-methoxyphenol and vanillin. It was confirmed.

  A plant-derived composition obtained by mixing this extracted component, an epoxy compound made from petroleum (epoxy resin “EP4100” Adeka Co., Ltd.) and a curing accelerator benzimidazole (Nacalai Tesque Co., Ltd.) in methyl ethyl ketone as a solvent. It was a thing. The mixing ratio was extraction component: epoxy compound: curing accelerator: solvent = 75: 25: 5: 200.

About this plant origin composition, the gelation time in 150 degreeC was measured based on the gelation time B method of JISK6910. The results are shown in Table 1.
<Example 2>
300 g of cedar wood flour (average particle size 0.7 mm) and 5 L of water were placed in a pressure vessel and treated with hot pressurized water at 180 ° C., 1 MPa for 10 minutes. After the treatment residue was dried, it was extracted with methyl ethyl ketone (Nacalai Tesque Co., Ltd.) at room temperature and normal pressure for 2 hours, and the soluble part was concentrated under reduced pressure to obtain a plant extract component.

  When the obtained extract component was analyzed by GC-MS, the extract component was a mixture composed of many kinds of compounds and contained a phenolic component having at least one phenol nucleus such as 2-methoxyphenol and vanillin. It was confirmed.

  A plant-derived composition obtained by mixing this extracted component, an epoxy compound made from petroleum (epoxy resin “EP4100” Adeka Co., Ltd.) and a curing accelerator benzimidazole (Nacalai Tesque Co., Ltd.) in methyl ethyl ketone as a solvent. It was a thing. The mixing ratio was extraction component: epoxy compound: curing accelerator: solvent = 75: 25: 5: 200.

About this plant origin composition, the gelation time in 150 degreeC was measured based on the gelation time B method of JISK6910. The results are shown in Table 1.
<Example 3>
Plant-derived components obtained in the same manner as in Example 1, a plant-derived epoxy compound (epoxidized linseed oil “Daimac L-500”, Daicel Chemical Industries, Ltd.), and a curing accelerator, paratoluenesulfonic acid hydrate The product (Nacalai Tesque Co., Ltd.) was mixed in methyl ethyl ketone as a solvent to obtain a plant-derived composition. The mixing ratio was extraction component: epoxy compound: curing accelerator: solvent = 95: 5: 2: 200.

About this plant origin composition, the gelation time in 150 degreeC was measured based on the gelation time B method of JISK6910. The results are shown in Table 1.
<Comparative Example 1>
Lignin sulfonate (“Vanilex N” Nippon Paper Chemicals Co., Ltd.), which is a plant extract component, and a plant-derived epoxy compound (epoxidized linseed oil “Dymak L-500”, Daicel Chemical Industries, Ltd.) and curing Accelerator p-toluenesulfonic acid hydrate (Nacalai Tesque Co., Ltd.) was mixed in a solvent methyl ethyl ketone to obtain a plant-derived composition. The mixing ratio was extraction component: epoxy compound: curing accelerator: solvent = 95: 5: 2: 200.

About this plant origin composition, the gelation time in 150 degreeC was measured based on the gelation time B method of JISK6910. The results are shown in Table 1.
<Comparative example 2>
300 g of birch wood flour (average particle size 0.7 mm) and 5 L of water were placed in a pressure vessel and treated with pressurized hot water at 130 ° C., 0.4 MPa for 10 minutes. The treatment residue was dried and extracted in the same manner as in Example 1, and then concentrated to obtain a plant extract component.

  A plant-derived composition obtained by mixing this extracted component, an epoxy compound made from petroleum (epoxy resin “EP4100” Adeka) and a curing accelerator benzimidazole (Nacalai Tesque) in methyl ethyl ketone as a solvent. It was a thing. The mixing ratio was extraction component: epoxy compound: curing accelerator: solvent = 75: 25: 5: 200.

  About this plant origin composition, the gelation time in 150 degreeC was measured based on the gelation time B method of JISK6910. The results are shown in Table 1.

  As shown in Table 1, the plant-derived compositions of Examples 1 and 2 in which an extract component of a plant treated with pressurized hot water under specific conditions and an epoxy compound were mixed reacted and gelled.

  In Example 3 using epoxidized linseed oil, which is a plant-derived epoxy compound, a plant-derived composition obtained by mixing a plant extract component treated with pressurized hot water under specific conditions and a plant-derived epoxy compound. Reacted and gelled by heating.

  On the other hand, the plant-derived composition of Comparative Example 1 using lignin sulfonate as the plant extract component did not gel even when heated. This is thought to be due to the fact that lignin sulfonate is not treated with pressurized hot water and has low reactivity with epoxy groups.

In addition, the plant-derived composition of Comparative Example 2, which used the extracted component of the plant treated with pressurized hot water but had a low treatment temperature and treatment pressure, did not gel even when heated. This is considered to be due to the low reactivity of the extraction component to the epoxy group because the molecular weight reduction by the pressurized hot water treatment is insufficient.
<Example 4>
The plant-derived composition obtained in Example 3 was impregnated into impregnated paper for laminates (Nippon Paper Industries Co., Ltd.) and then dried at 130 ° C. 20 sheets of these were stacked and pressed under conditions of 150 ° C., 120 minutes, and 4 MPa pressure.

The thickness of the obtained laminate was 2.0 mm, the specific gravity was 1.2, and the weight ratio of paper and cured product was 40:60. This laminate was cut out and measured for bending strength and deflection temperature under load (load 1.8 MPa) in accordance with JIS K6911. The results are shown in Table 2.
<Comparative Example 3>
Lignin sulfonate (“Vanilex N” Nippon Paper Chemicals Co., Ltd.) as a plant extract component, petroleum phenol resin (“Resitop PL-2211”, Gunei Chemical Industry Co., Ltd.) and sodium carbonate ( Tokuyama Co., Ltd.) was mixed in a solvent methyl ethyl ketone to obtain a plant-derived composition. The mixing ratio was: extraction component: phenol resin 150 ° C. non-volatile content: curing accelerator: solvent = 95: 5: 2: 200.

  The plant-derived composition was impregnated into the impregnated paper for laminates and then dried at 130 ° C. Twenty sheets were stacked and pressed under the conditions of 150 ° C., 120 minutes, and 4 MPa pressure, but could not be molded properly. Therefore, the mixing ratio was 50: 50: 2: 200, the ratio of petroleum-based phenol resin was increased, and after impregnation and drying, pressing was performed.

The thickness of the obtained laminate was 2.0 mm, the specific gravity was 1.2, and the weight ratio of paper and cured product was 40:60. This laminate was cut out and measured for bending strength and deflection temperature under load (load 1.8 MPa) in accordance with JIS K6911. The results are shown in Table 2.
<Example 5>
Plant-derived components obtained in the same manner as in Example 1, a plant-derived epoxy compound (epoxidized linseed oil “Daimac L-500”, Daicel Chemical Industries, Ltd.), and a curing accelerator, paratoluenesulfonic acid hydrate The product (Nacalai Tesque Co., Ltd.) was mixed in methyl ethyl ketone as a solvent to obtain a plant-derived composition. The mixing ratio was extraction component: epoxy compound: curing accelerator: solvent = 95: 5: 5: 200.

  The plant-derived composition was impregnated into a laminated board impregnated paper (Nippon Paper Industries Co., Ltd.) and then dried at 130 ° C. 20 sheets were stacked and pressed under the conditions of 150 ° C., 120 minutes, and 4 MPa pressure.

The thickness of the obtained laminate was 1.8 mm, the specific gravity was 1.2, and the weight ratio of paper to cured product was 60:40. This laminate was cut out and measured for bending strength and deflection temperature under load (load 1.8 MPa) in accordance with JIS K6911. The results are shown in Table 2.
<Example 6>
Plant-derived components obtained in the same manner as in Example 1, a plant-derived epoxy compound (epoxidized linseed oil “Daimac L-500”, Daicel Chemical Industries, Ltd.), and a curing accelerator, paratoluenesulfonic acid hydrate The product (Nacalai Tesque Co., Ltd.) was mixed in methyl ethyl ketone as a solvent to obtain a plant-derived composition. The mixing ratio was extraction component: epoxy compound: curing accelerator: solvent = 95: 5: 0.1: 200.

  The plant-derived composition was impregnated into a laminated board impregnated paper (Nippon Paper Industries Co., Ltd.) and then dried at 130 ° C. 20 sheets were stacked and pressed under the conditions of 150 ° C., 120 minutes, and 4 MPa pressure.

  The thickness of the obtained laminate was 2.0 mm, the specific gravity was 1.2, and the weight ratio of paper and cured product was 50:50. This laminate was cut out and measured for bending strength and deflection temperature under load (load 1.8 MPa) in accordance with JIS K6911. The results are shown in Table 2.

  In Examples 4-6, the laminated board was able to be shape | molded by making the plant-derived composition containing the extract component of the plant processed with the pressurized hot water of the specific conditions, and an epoxy compound react.

  Further, as shown in Table 2, the laminate of Example 4 exceeded the laminate of Comparative Example 3 in physical properties and had high mechanical strength and heat resistance. Furthermore, in the laminated board of Example 4, the plant-derived component ratio in the cured product excluding paper could be as high as 98%, and the carbon neutral characteristics could be improved.

  When Example 4 was compared with Examples 5 and 6, the addition rate of paratoluenesulfonic acid hydrate, which is a curing accelerator, was different, but this caused a large difference in the strength and heat resistance of the laminate. The laminated board of Example 5 was thinner than the laminated board of Example 4 after pressing, and a large amount of resin oozed out from the impregnated paper, and was very brittle. This is thought to be due to the decrease in viscosity of the resin due to the decomposition of the strong acid with paratoluenesulfonic acid hydrate, resulting in increased oozing and reduced physical properties.

  Also in the laminated board of Example 6, the resin oozed out from the impregnated paper, and the physical properties were greatly reduced as compared with Example 4. This is considered to be due to the slow curing reaction resulting in a large amount of oozing and consequently a decrease in physical properties.

  On the other hand, in the laminated board of Example 4, since an appropriate amount of para-toluenesulfonic acid hydrate that does not cause decomposition of the cured product was used as a curing accelerator, the curing reaction could proceed, It is considered that a laminate having excellent physical properties could be obtained.

Claims (5)

  A plant characterized by containing an extract component of a plant treated with pressurized hot water at 160 ° C. to 400 ° C. and 0.8 to 30 MPa, which contains a phenolic component having at least one phenol nucleus, and an epoxy compound Origin composition.   The plant-derived composition according to claim 1, wherein the epoxy compound is an epoxy compound of vegetable oil.   The plant-derived composition according to claim 1, comprising paratoluenesulfonic acid hydrate as a curing accelerator.   The content of paratoluenesulfonic acid hydrate is in the range of 0.2 to 4 parts by mass with respect to 100 parts by mass of the total amount of the plant extract component and the epoxy compound. Plant-derived composition.   Hardened | cured material formed by hardening | curing the plant origin composition as described in any one of Claims 1 thru | or 4.