Xylooligosaccharide-containing resin composition

Abstract

The present invention utilizes a hemicellulose to provide a resin composition having improved fluidity as simply as possible. More specifically, a resin composition as mentioned below is provided. The resin composition contains a resin and a xylooligosaccharide, the resin comprising at least one selected from the group consisting of polypropylene, polyethylene, polycarbonate, polyethylene terephthalate, and block copolymers thereof. With respect to the xylooligosaccharide, the content of uronic acids contained in the structure thereof is 2 mass% or less.

Description

Xylooligosaccharide-containing resin composition

[0001] This disclosure relates to xylooligosaccharide-containing resin compositions, etc. All documents mentioned herein (especially those listed in the Prior Art section) are incorporated herein by reference.

[0002] From the perspective of biomass utilization, the use of plant-derived components is being widely explored to improve resins. For example, the kneading of hemicellulose with resins has been extensively studied (see, for example, Patent Document 1).

[0003] However, it has been difficult to knead hemicellulose alone with resin. When hemicellulose is kneaded with resin, it has been reported that the volume and dimensions of the molded product of the resulting resin composition change over time (for example, Patent Document 2, Non-Patent Document 1). For this reason, it has been necessary to use derivatized hemicellulose, or to mix hemicellulose with other plant-derived components such as cellulose or lignin before kneading with each resin (for example, Patent Documents 3 and 4).

[0004] Japanese Patent Publication No. 2023-095312, Japanese Patent Publication No. 2020-132790, Japanese Patent Publication No. 2010-527384, Japanese Patent Publication No. 2011-042168, International Publication No. 2019 / 054344

[0005] CMC Publishing Co., Ltd., "Wood Chemicals Technology," First Edition published 2007, p. 108.

[0006] The present inventors conducted research with the aim of obtaining a resin composition with improved fluidity as simply as possible using hemicellulose.

[0007] The inventors of the present invention conducted various treatments of hemicellulose and, through diligent research, discovered the possibility of easily obtaining a resin composition with improved fluidity by kneading xylooligosaccharides (preferably neutral xylooligosaccharides) with the resin, and further investigations were conducted.

[0008] This disclosure includes, for example, the following subjects: 1. A resin composition comprising a resin and a xylooligosaccharide, wherein the resin is at least one selected from the group consisting of polypropylene, polyethylene, polycarbonate, polyethylene terephthalate, and block copolymers thereof, and the xylooligosaccharide is a xylooligosaccharide having a uronic acid content of 2% by mass or less in its structure. 2. The resin composition according to 1, wherein the resin is polypropylene. 3. The resin composition according to 1 or 2, wherein the xylooligosaccharide is a neutral xylooligosaccharide. 4. The resin composition according to any one of 1 to 3, wherein the weight-average molecular weight of the xylooligosaccharide is 300 to 2400. 5. The resin composition according to any one of 1 to 3, wherein the weight-average molecular weight of the xylooligosaccharide is 600 to 1800. 6. The resin composition according to any one of 1 to 5, wherein the average degree of polymerization of the xylooligosaccharide is 2 to 16. 7. A resin composition according to any one of claims 1 to 6, wherein the average degree of polymerization of the xylooligosaccharide is 4 to 12. Claim 8. A resin composition according to any one of claims 1 to 7, wherein the xylooligosaccharide is contained in an amount of 0.01 times or more by mass ratio relative to the resin. Claim 9. A resin composition according to any one of claims 1 to 8, wherein the content of the xylooligosaccharide is 5 to 50% by mass relative to the resin composition. Claim 10. A resin composition according to any one of claims 1 to 9, wherein the melt flow rate (g / 10min) is 12 to 45. Claim 11. A resin composition according to any one of claims 1 to 10, wherein the flexural strength (MPa) at 23°C is 40 to 70 MPa and / or the flexural modulus (MPa) at 23°C is 1500 to 4500 MPa. Claim 12. A resin composition according to any one of claims 1 to 11, further comprising a dispersant. Claim 13. A resin composition according to claim 12, wherein the dispersant is acid-modified polypropylene.

[0009] A resin composition containing a resin and a low-acidity xylooligosaccharide is provided. The resin composition has stable fluidity. Furthermore, when cured, the resin composition also possesses excellent rigidity (flexural strength, flexural modulus). Moreover, the xylooligosaccharide used in the resin composition can be said to have a high biomass content, and consequently, the resin composition itself can be said to be a resin composition with a high biomass content.

[0010] This makes it possible to provide an advantageous resin composition that offers good handling due to its high fluidity when applied to a mold (e.g., poured) during molding, and excellent rigidity after curing.

[0011] The embodiments included in this disclosure will be described in more detail below. This disclosure preferably includes, but is not limited to, resin compositions containing resin and xylooligosaccharides, as well as methods for producing the same and their uses, and this disclosure includes everything disclosed herein and recognizable to those skilled in the art.

[0012] The resin composition contained herein contains a resin and xylooligosaccharides as described above. The resin composition contained herein may be referred to as the resin composition of this disclosure. Furthermore, the xylooligosaccharide contained in the resin composition of this disclosure has a uronic acid content of 2% by mass or less in its structure. The xylooligosaccharide may be referred to as the xylooligosaccharide of this disclosure.

[0013] Examples of resins included in the resin composition of this disclosure include polypropylene, polyethylene, polycarbonate, polyethylene terephthalate, and block copolymers in which two or more of these are linked together. Among these, polypropylene is preferred. The resins can be used individually or in combination of two or more.

[0014] The xylooligosaccharides contained in the resin composition of this disclosure (xylooligosaccharides of this disclosure) are, as described above, xylooligosaccharides with low acidity, and more specifically, xylooligosaccharides with a uronic acid content of 2% by mass or less. The uronic acid content is measured as follows.

[0015] Prepare a solvent by dissolving 10 g of boric acid and 15 g of sodium chloride in 1 L of water. Weigh 40 mg of xylooligosaccharide to be measured, dissolve it in the above solvent, and adjust the volume to 50 mL. Take 4 mL of this solution, add more of the above solvent to adjust the volume to 20 mL. Take 0.5 mL from the resulting 20 mL solution into a test tube, add 5 mL of sulfuric acid while cooling in ice water, mix, and heat in a water bath for 10 minutes. Cool immediately in ice water, add 0.2 mL of 1,2-dimethylphenol test solution, mix, heat in a water bath for 15 minutes, then allow to cool to obtain the sample solution. Separately, prepare a D-glucuronic acid standard stock solution with a concentration of 10 to 100 μg / mL, perform the same operation to obtain the standard solution, and measure the absorbance at wavelengths of 400 nm and 450 nm. (Note that glucuronic acid is the main uronic acid in xylooligosaccharides.) A calibration curve is prepared from the absorbance of the standard solution, and the amount (g) of uronic acid in the xylooligosaccharide to be measured is obtained. Then, the uronic acid content (% by mass) is obtained by the following formula. When the quantitative value is negative, it is regarded as 0%.

[0016] Uronic acid content (% by mass) = M Ｓ / M Ｔ × (A Ｔ４５０ - A Ｔ４００ ) / (A Ｓ４５０ - A Ｓ４００ ) × 10 M Ｓ : Weighed amount of D-glucuronic acid (mg) M Ｔ : Weighed amount of xylooligosaccharide converted to dry product (mg) A Ｔｉ : Absorbance of the sample solution at each wavelength (i: 450 nm or 400 nm) A Ｓｉ : Absorbance of the standard solution at each wavelength (i: 450 nm or 400 nm) The xylooligosaccharide of the present disclosure preferably has a uronic acid content of 0 to 2% by mass. 0% by mass indicates that no uronic acid can be detected by the aforementioned uronic acid content measurement method (below the detection limit; the quantitative value is 0 or negative). This is also sometimes referred to as neutral xylooligosaccharide. The upper limit of the range (0 to 2% by mass) may be, for example, 1.5, 1, 0.5, 0.3, 0.2, 0.1% by mass. For example, the range may be 0 to 1.5% by mass.

[0017] Furthermore, the xylooligosaccharides of this disclosure are preferably those having a number-average molecular weight of 300 to 2400. The upper or lower limits of this range may be, for example, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, or 2300. The range is more preferably 500 to 2000, and even more preferably 600 to 1800.

[0018] Furthermore, the xylooligosaccharides of this disclosure are preferably those having a weight-average molecular weight of 300 to 2400. The upper or lower limits of this range may be, for example, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, or 2300. The range is more preferably 500 to 2000, and even more preferably 600 to 1800.

[0019] The weight-average molecular weight is a value obtained by GPC (gel permeation chromatography), and more specifically, a value obtained by GPC under the following conditions: GPC column: Two Ultrahydrogel 250 columns linked together from Waters Japan Eluent: A mixture of aqueous solutions of 0.3 M sodium nitrate and 0.01 M disodium hydrogen phosphate with methanol in a volume ratio of 4:1 Flow rate: 0.7 mL / min Measurement temperature: 40°C Detector: Differential refractive index detector Furthermore, the xylooligosaccharide of this disclosure preferably has an average degree of polymerization of 2 to 16. The upper or lower limit of this range may be, for example, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. The range is more preferably 2 to 14, even more preferably 4 to 12, and even more preferably 3 to 6.

[0020] The average degree of polymerization is calculated from the molecular weight (132) and number-average molecular weight of the repeating unit of the xylooligosaccharide. More specifically, the average degree of polymerization can be calculated using the formula {number-average molecular weight × (1 - uronic acid content)} / 132. For example, the average degree of polymerization for a uronic acid content of 2% by mass can be calculated using the formula {number-average molecular weight × (1 - 0.02)} / 132. Also, for example, the average degree of polymerization for a uronic acid content of 0% by mass can be calculated using the formula number-average molecular weight / 132.

[0021] Examples of xylooligosaccharide structural formulas are shown below. However, these examples are not limited to the xylooligosaccharides of this disclosure and are merely illustrative. Furthermore, the number of 4-o-methylglucuronic acid molecules described in these examples may be zero (in this case, it indicates a xylooligosaccharide with a uronic acid content of 0% by mass).

[0022]

[0023] The xylooligosaccharides of this disclosure can be obtained, for example, by depolymerizing plant-derived raw materials. This is described in detail below.

[0024] Examples of plant-derived raw materials include wood-derived raw materials, seed-derived raw materials, grain-derived raw materials, and fruit-derived raw materials. Additionally, plant-derived raw materials such as cotton linters and cotton lint, kenaf, hemp, ramie, and rice straw (herbaceous plants) can also be used. Combinations of the above-mentioned plant-derived raw materials are also permitted.

[0025] In particular, it is preferable to use wood-derived raw materials as plant-derived raw materials. Examples of wood-derived raw materials include coniferous trees and broad-leaved trees. It is preferable to use at least one type of wood-derived raw material selected from coniferous trees and broad-leaved trees, and it is more preferable to use broad-leaved trees. A mixture of coniferous trees and broad-leaved trees may also be used as wood-derived raw materials. In addition, tree bark may be used as wood-derived raw material.

[0026] Examples of broad-leaved trees include beech, eucalyptus globulus, eucalyptus grandis, eucalyptus eurograndis, eucalyptus pelita, eucalyptus brassiana, and acacia melanchii. Examples of coniferous trees include cedar, cypress, pine, hinoki cypress, and hemlock.

[0027] The volumetric density of wood-derived raw materials is 450 kg / m³. 3 More than 700kg / m 3 Preferably, it is 500 kg / m 3 More than 650kg / m 3 The following is more preferable: By keeping the bulk density of the wood-derived raw material within the above range, the production efficiency of xylooligosaccharides can be further increased.

[0028] The wood-derived raw material is preferably wood chips obtained by crushing the wood mentioned above. By using wood chips as the plant-derived raw material, the depolymerization of the plant-derived raw material can be efficiently carried out, and the production efficiency of xylooligosaccharides can be increased. (First step) <Depolymerization step> The first step includes a step of depolymerizing the plant-derived raw material. In the step of depolymerizing the plant-derived raw material, the plant-derived raw material can be chemically and / or physically decomposed to produce xylooligosaccharides. Examples of steps for chemical and / or physical decomposition include a heat treatment step, an alkali treatment step, an acid treatment step, an enzyme treatment step, an ionic liquid treatment step, a catalyst treatment step, etc. Among these, the depolymerization step is preferably a heat treatment step or an enzyme treatment step, and more preferably a heat treatment step. The heat treatment step may also be a heating and pressurizing step.

[0029] The depolymerization process is preferably carried out under non-alkaline conditions (pH 9 or lower, preferably pH 8 or lower).

[0030] The heat treatment step is a step of heating a plant-derived raw material in the presence of a solution. Since the plant-derived raw material is hydrolyzed in such a heat treatment step, the heat treatment step is sometimes referred to as a hydrolysis treatment step or a pre-hydrolysis treatment step. The solution used in the heat treatment step is preferably water, and the ratio of water to the plant-derived raw material (mass ratio) is preferably from 1:1 to 1:10. By setting the ratio of water to the plant-derived raw material within the above range, the hydrolysis reaction can proceed efficiently. Note that the water used in the heat treatment step may be moisture added separately from the plant-derived raw material, or part thereof may be moisture originally contained in the plant-derived raw material.

[0031] In the heat treatment step, other chemicals may be added in addition to the plant-derived raw material and water. Examples of such other chemicals include alkalis, acids, and chelating agents. Further, chemicals that directly or indirectly assist depolymerization of polysaccharides, such as scale inhibitors, pitch control agents, and ionic liquids, may also be added.

[0032] The heat treatment step is a step of heating a plant-derived raw material in the presence of water. The heating temperature (liquid temperature) at this time is preferably 30°C or higher, more preferably 50°C or higher, still more preferably 75°C or higher, even more preferably 90°C or higher, particularly preferably 100°C or higher, and most preferably 120°C or higher. Further, the heating temperature (liquid temperature) is preferably 300°C or lower, more preferably 250°C or lower, and still more preferably 200°C or lower.

[0033] The treatment time in the heat treatment step can be appropriately determined according to the treatment temperature. For example, the treatment time is preferably 5 minutes or longer, more preferably 10 minutes or longer, and still more preferably 20 minutes or longer. The P-factor represented by the formula below is the product of temperature and time during heat treatment, and it is preferable to adjust the P-factor within a preferred range.

[0034]

[0035] In the above formula, P represents the P-factor, T represents the absolute temperature (°C + 273.5), t represents the heat treatment time, and K H1(T) / K 100℃ This represents the relative rate of hydrolysis of glycosidic bonds.

[0036] In the heat treatment process, the P-factor is preferably 200 or higher, more preferably 250 or higher, and even more preferably 300 or higher. It is also preferable that the P-factor be 1000 or lower. By appropriately adjusting the P-factor during the heat treatment process, the average degree of polymerization and thus the molecular weight of the xylooligosaccharide can be brought within a desired range.

[0037] In the heat treatment process, the pH of the solution containing the plant-derived raw materials is preferably 9 or less, more preferably 8 or less, and even more preferably 7 or less. In other words, the heat treatment process is preferably carried out under non-alkaline conditions. Note that the above pH values ​​refer to the pH of the solution before the heat treatment.

[0038] During the heat treatment process, acids derived from the raw materials may dissociate, and acid hydrolysis may occur in at least part of the process. Examples of acids derived from plant materials include organic acids such as acetic acid and formic acid. In this case, the pH of the solution containing the plant-derived raw materials after acid hydrolysis will decrease further.

[0039] In the manufacturing method, it is preferable to include a heat treatment step as the first step. This can increase the production efficiency of xylooligosaccharides. By including a heat treatment step as the first step, the number of steps required to obtain xylooligosaccharides can be significantly reduced compared to conventional methods. Furthermore, by including a heat treatment step under non-alkaline conditions as the first step, hexenuronic acid does not substitute for xylooligosaccharides, and xylooligosaccharides with suppressed discoloration can be efficiently produced.

[0040] The depolymerization step is preferably a heat treatment step, but other steps can also be used. For example, if the depolymerization step is an enzyme treatment step, the depolymerization step includes a step of mixing the plant-derived raw material with the enzyme. As the enzyme, for example, hemicellulase can be used. Specifically, commercially available enzyme preparations such as Cellulosin HC100 (manufactured by HBI), Cellulosin TP25 (manufactured by HBI), Cellulosin HC (manufactured by HBI), Cartazyme (manufactured by Clariant), Ecopulp (manufactured by Rohm Enzyme Co., Ltd.), Sumizyme (manufactured by Shin Nippon Chemical Industries, Ltd.), Pulpzyme (manufactured by Novo Nordics), and Multifect 720 (manufactured by Genencore) can be used, as well as xylanases produced by microorganisms such as Trichoderma, Thermomyces, Oureobasidium, Streptomyces, Aspergillus, Clostridium, Bacillus, Thermotoga, Thermoasuchus, Cardocerum, and Thermomonospora.

[0041] In the enzyme treatment process, the enzyme is added to a solution obtained by mixing plant-derived raw materials and water. The temperature of the solution at this time is preferably between 10°C and 90°C, and more preferably between 30°C and 60°C. It is preferable that the temperature of the solution be close to the optimal temperature of the enzyme used. Furthermore, it is preferable to adjust the pH of the solution to a range that enhances the activity of the enzyme, for example, adjusting the pH to between 3 and 10 is preferable.

[0042] Furthermore, if the depolymerization step involves an alkali treatment step or an acid treatment step, it includes a step of mixing the plant-derived raw material with an alkaline solution or an acid solution. In the alkali treatment step, it is preferable to add sodium hydroxide or potassium hydroxide. In the acid treatment step, it is preferable to add hydrochloric acid, sulfuric acid, acetic acid, etc. In this case as well, heating or pressurization may be performed as appropriate.

[0043] If the depolymerization step is selected from at least one of the enzyme treatment step, alkali treatment step, and acid treatment step, then further steps such as pressing, extraction, heating, filtration, separation, purification, concentration, and desalting may be provided after the treatment step. In addition, it may be necessary to provide a low-molecular-weight step after the treatment step. Other steps include those described in Japanese Patent Application Publication No. 2003-183303, and the contents of these steps are incorporated herein by reference. <Filtration Step> The first step may further include a filtration step after the depolymerization step described above. In the filtration step, the plant-derived raw material is separated into solids and a solution excluding the solids. Specifically, by providing a filtration step after the depolymerization step, the material is separated into solids that will become pulp raw materials and a filtrate. The solids that will become pulp raw materials are then processed in a subsequent step such as a pulping step to become cellulose raw materials (dissolved pulp).

[0044] The recovered filtrate can be separated into a gas layer and a liquid layer. The gas layer contains a large amount of furfural compounds, and by recovering these, the furfural compounds can be isolated. On the other hand, the liquid layer contains a large amount of hemicellulose containing xylooligosaccharides. In the process described later, xylooligosaccharides with low acidity (in particular xylooligosaccharides with a uronic acid content of 2% by mass or less, preferably neutral xylooligosaccharides) contained in this liquid layer can be separated and purified. <Separation and Purification Process> The first process may further include a separation and purification process after the depolymerization process described above. If the first process includes the filtration process described above, it is preferable that the separation and purification process be provided after the filtration process.

[0045] It is preferable to provide a filtration step after the depolymerization step, and further to provide a separation and purification step after the filtration step. In the first step, the separation and purification step may be provided immediately after the depolymerization step, but it is preferable to provide a filtration step after the depolymerization step, and to provide a step to separate and purify low-acidity xylooligosaccharides from the obtained filtrate. The filtration step may be provided as part of the separation and purification step, or it may be provided as a separate step independent of the separation and purification step. The separation and purification step is a step to separate and purify low-acidity xylooligosaccharides. Since the filtrate obtained in the filtration step contains high-acidity xylooligosaccharides in addition to low-acidity xylooligosaccharides, the separation and purification step is also a step to remove these other sugars.

[0046] In the separation and purification process, it is preferable to employ methods such as ion exchange chromatography, affinity chromatography, gel filtration, ion exchange treatment, NF membrane treatment, UF membrane treatment, RO membrane treatment, and activated carbon treatment. It is also preferable to combine multiple of the above methods in the separation and purification process. In particular, by performing ion exchange chromatography in the separation and purification process, low-acidity xylooligosaccharides can be selectively separated and purified. In ion exchange chromatography, low-acidity xylooligosaccharides can be mainly extracted from the permeate by adsorbing high-acidity xylooligosaccharides. Specifically, the sugar solution is first treated with a strong cation exchange resin to remove metal ions from the sugar solution. Next, sulfate ions and other substances are removed from the sugar solution using a strong anion exchange resin. Then, it is treated with a weak anion exchange resin to adsorb high-acidity xylooligosaccharides onto the resin. <Concentration Step> The first step may further include a concentration step. The concentration step is preferably provided, for example, after the filtration step and before the separation and purification step. By providing such a concentration step, the separation and purification process can be carried out more efficiently.

[0047] Concentration processes include, for example, membrane treatment processes using NF membranes, ultrafiltration membranes, reverse osmosis membranes, etc., and concentration processes using evaporation, etc.

[0048] In the concentration step, it is preferable to concentrate the solution so that the content of low-acidity xylooligosaccharides is 10% to 80% of the total mass of the concentrate, and more preferably 20% to 60%. <Dehydration step> The low-acidity xylooligosaccharides obtained in the first step may be obtained as a low-acidity xylooligosaccharide solution, but by going through the dehydration step, they may be obtained as a low-acidity xylooligosaccharide concentrate or a low-acidity xylooligosaccharide powder. When producing low-acidity xylooligosaccharide powder, it is preferable to further provide a powdering step after the separation and purification step. In the present invention, by providing a dehydration step, the sulfation in the sulfation step described later can be carried out efficiently.

[0049] In the powdering process, the low-acidity xylooligosaccharide solution obtained in the separation and purification process can be treated with, for example, a spray dryer, freeze dryer, hot air dryer, or water-soluble organic solvent to obtain a low-acidity xylooligosaccharide powder.

[0050] In the resin composition of the present disclosure, the xylooligosaccharide of the present disclosure is preferably contained in a mass ratio of 0.01 times or more the amount of the resin, more preferably 0.02 times or more, even more preferably 0.05 times or more, and even more preferably 0.1 times or more. Furthermore, although not particularly limited, the xylooligosaccharide of the present disclosure is preferably contained in a mass ratio of 1.5 times or less the amount of the resin, and more preferably 1 time or less. The upper or lower limit of the mass ratio range of the xylooligosaccharide to the resin (0.01 to 1.5 times) may be, for example, 0.02, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, or 1.4 times. For example, the range may be 0.05 to 1.2 times or 0.1 to 1 time.

[0051] Furthermore, for example, the mass ratio of resin to xylooligosaccharide is preferably 95:5 to 35:65, more preferably 90:10 to 40:60, and even more preferably 90:10 to 45:55.

[0052] Furthermore, in the resin composition of this disclosure, the resin is preferably contained in an amount of 95 to 35% by mass. The upper or lower limit of this range may be, for example, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, or 40% by mass. For example, the range is more preferably 90 to 40% by mass, and even more preferably 90 to 45% by mass. Furthermore, in the resin composition of this disclosure, the xylooligosaccharide of this disclosure is preferably contained in an amount of 5 to 65% by mass. The upper or lower limit of this range may be, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60% by mass. For example, the range is more preferably 5 to 50% by mass, and even more preferably 10 to 50% by mass.

[0053] The resin composition of this disclosure may contain other components in addition to the resin and the xylooligosaccharide of this disclosure, as long as they do not impair the effects of the resin composition of this disclosure. Such other components may include known resin composition additives, and more specifically, examples include dispersants, antioxidants, lubricants, fillers, plasticizers, flame retardants, ultraviolet absorbers, colorants, antistatic agents, antibacterial agents, antifungal agents, modifiers, nucleating agents, etc. The content of these components can be appropriately adjusted within the range that the effects of the resin composition of this disclosure are achieved. Furthermore, these components can be used individually or in combination of two or more.

[0054] While not particularly limited, acid-modified polypropylene is a preferred dispersant. In particular, when polypropylene is used as the resin in the resin composition of this disclosure, acid-modified polypropylene is preferred as the dispersant. While not particularly limited, a preferred acid-modified polypropylene is, for example, polypropylene modified with maleic anhydride (MAH-modified polypropylene). Such acid-modified polypropylene that acts as a dispersant is commercially available as Yumex (Sanyo Chemical Industries, Ltd.), and can be purchased and used as is. While not particularly limited, an acid-modified polypropylene used as a dispersant is preferred to have a weight-average molecular weight of about 9,000 to 70,000 as measured by GPC method. The upper or lower limits of the range are, for example, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, 24000, 25000, 26000, 27000, 28000, 29000, 30000, 31000, 32000, 33000, 34000, 35000, 36000, 37000, 38000, 39 The range may be 000, 40000, 41000, 42000, 43000, 44000, 45000, 46000, 47000, 48000, 49000, 50000, 51000, 52000, 53000, 54000, 55000, 56000, 57000, 58000, 59000, 60000, 61000, 62000, 63000, 64000, 65000, 66000, 67000, 68000, or 69000. For example, the range is more preferably 10000 to 50000, and even more preferably 20000 to 45000. Furthermore, an acid value (mgKOH / g) of approximately 10 to 60 is preferred, a value of approximately 40 to 60 is more preferred, and a value of approximately 50 to 60 is even more preferred.

[0055] When a dispersant is used, its content can be set as appropriate, for example, 0.1 to 20% by mass relative to the resin composition of this disclosure. The upper or lower limit of this range may be, for example, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19% by mass. This range may be, for example, 0.2 to 10% by mass, or 0.5 to 5% by mass.

[0056] When a dispersant is used, its content can be set as appropriate, for example, 0.1 to 20% by mass relative to the resin composition of this disclosure. The upper or lower limit of this range may be, for example, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19% by mass. This range may be, for example, 0.2 to 10% by mass, or 0.5 to 5% by mass.

[0057] Furthermore, although not particularly limited, preferred antioxidants include phenolic antioxidants, phosphoric acid antioxidants, sulfuric acid antioxidants, and amine antioxidants, with phenolic antioxidants and phosphoric acid antioxidants being more preferred, and phenolic antioxidants being even more preferred. Examples of phenolic antioxidants include monophenolic antioxidants, bisphenolic antioxidants, and hindered phenolic antioxidants, with hindered phenolic antioxidants being preferred among them. Examples of hindered phenolic antioxidants include IRGANOX 1010, IRGANOX 1076, IRGANOX 1081, and IRGANOX 1300 (all from BASF). Although not particularly limited, hindered phenolic antioxidants with a molecular weight of 500 or more are preferred, and those with a molecular weight of 600 or more are more preferred. Furthermore, there is no particular upper limit to the molecular weight, but for example, those with a molecular weight of 1500 or less are preferred, and those with a molecular weight of 1300 or less or 1200 or less are more preferred. The upper or lower limit of the molecular weight range (500 to 1500) may be, for example, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, or 1450. The range may also be, for example, 550 to 1300 or 600 to 1200.

[0058] The resin compositions of this disclosure can be prepared by known methods or by methods readily conceivable from known methods. For example, they can be prepared by kneading (preferably by melt kneading) a resin and xylooligosaccharides, and other components as needed. For kneading, known suitable equipment such as a twin-screw extruder can be used.

[0059] The resin compositions of this disclosure preferably have a melt flow rate (MFR) (g / 10min) of 12 or more, and more preferably between 12 and 45. The upper or lower limit of this range may be, for example, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, or 44. For example, the range of 13 to 20 is more preferred.

[0060] The melt flow rate is measured according to Method A (mass measurement method) of ISO 1133-1:2011 (a similar provision exists in JIS K 7210-1:2014), under conditions of temperature: 230°C and load: 2.16 kgf.

[0061] Furthermore, when the resin composition of this disclosure is cured, it is preferable that the flexural strength (MPa) at 23°C is 40 or higher, more preferably 45 or higher, and even more preferably 50 or higher. The upper limit is not particularly limited, but is preferably 70 or lower. The upper or lower limit of this range (40 to 70 MPa) may be, for example, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, or 69 MPa. For example, the range is more preferably 45 to 68 MPa, and even more preferably 50 to 65 MPa.

[0062] Furthermore, when the resin composition of this disclosure is cured, the flexural modulus (MPa) at 23°C is preferably 1500 or higher, more preferably 1800 or higher, and even more preferably 1900 or higher. The upper limit is not particularly limited, but is preferably 4500 or lower. The upper or lower limit of this range (1500 to 4500 MPa) may be, for example, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, or 4400 MPa. For example, the range is more preferably 1800 to 4300 MPa, and even more preferably 1900 to 4000 MPa.

[0063] The bending strength and flexural modulus are determined as follows: An evaluation sample (dumbbell-shaped test piece) is prepared from the resin composition in accordance with ISO 20753:2008, and the bending strength (MPa) and flexural modulus (MPa) of the evaluation sample at 23°C are measured in accordance with ISO 178:2010. The test speed during measurement is 2 mm / min, and the distance between supports is 64 mm.

[0064] In this specification, the term "comprising" includes both "consisting essentially of" and "consisting of." Furthermore, this disclosure encompasses all combinations of the constituent elements described herein.

[0065] Furthermore, the various characteristics (properties, structure, function, etc.) described for each embodiment of this disclosure described above may be combined in any way to identify the subject matter covered by this disclosure. In other words, this disclosure covers all subject matter consisting of any combination of the combinable characteristics described herein.

[0066] The embodiments of this disclosure will be described in more detail below with examples, but the embodiments of this disclosure are not limited to the examples below.

[0067] Preparation of neutral xylooligosaccharide: 10 parts by mass of wood chips (hardwood) were mixed with 40 parts by mass of water and heat-treated at 160°C for 3 hours. Then, solid-liquid separation was performed using a screw press (Shinryo Seisakusho: 250 x 1000 SPH-EN), and the filtrate was recovered. The filtrate was filtered through a bag filter with a micron rate of 1 μm (ISP Filters), 5 parts by mass of activated carbon (Mikura Kasei Co., Ltd.: PM-SX) were added, and the mixture was treated at 50°C for 2 hours. Finally, the mixture, including the activated carbon, was filtered through a ceramic filter with a micron rate of 0.2 μm (Nippon Pall Co., Ltd.) to recover a clear filtrate. The clarified filtrate was concentrated 20-fold using a reverse osmosis membrane (Nitto Denko Corporation: NTR-7450) to obtain a concentrated sugar solution. This concentrated sugar solution was then passed through a four-bed, four-column ion exchange resin consisting of a strong cationic resin (Mitsubishi Chemical Corporation: PK-218), a weak anionic resin (Mitsubishi Chemical Corporation: WA30), a strong cationic resin (Mitsubishi Chemical Corporation: PK-218), and a weak anionic resin (Mitsubishi Chemical Corporation: WA30) at a space velocity (SV) of 1.5 to recover a neutral xylooligosaccharide solution. Sodium hydroxide was added to the obtained neutral xylooligosaccharide solution to adjust the pH to 13, and the mixture was stirred at room temperature for 3 hours to carry out deacetylation. Hydrochloric acid was added to the resulting solution to adjust the pH to less than 5, and the mixture was powdered using a spray dryer (Okawara Chemical Machinery Co., Ltd.).

[0068] To 10 parts by mass of acidic xylooligosaccharide wood chips (hardwood), 40 parts by mass of water were added and the mixture was heat-treated at 160°C for 3 hours. Then, solid-liquid separation was performed using a screw press (Shinryo Seisakusho: 250 x 1000 SPH-EN), and the filtrate was recovered. The filtrate was filtered through a bag filter with a micron rate of 1 μm (ISP Filters), 5 parts by mass of activated carbon (Mikura Kasei Co., Ltd.: PM-SX) were added, and the mixture was treated at 50°C for 2 hours. Finally, the mixture, including the activated carbon, was filtered through a ceramic filter with a micron rate of 0.2 μm (Nippon Pall Co., Ltd.) to recover a clear filtrate. The clarified filtrate was concentrated 20-fold using a reverse osmosis membrane (Nitto Denko Corporation: NTR-7450) to obtain a concentrated sugar solution. This concentrated sugar solution was then passed through a four-bed, four-column ion exchange resin consisting of a strong cationic resin (Mitsubishi Chemical Corporation: PK-218), a weak anionic resin (Mitsubishi Chemical Corporation: WA30), a strong cationic resin (Mitsubishi Chemical Corporation: PK-218), and a weak anionic resin (Mitsubishi Chemical Corporation: WA30) at a space velocity (SV) of 1.5. Acidic xylooligosaccharides were adsorbed onto the weak anionic resins in the second and fourth columns. Subsequently, a 50 mM sodium chloride aqueous solution was passed through the second and fourth columns at a space velocity (SV) of 1.5 to recover the acidic xylooligosaccharide solution. Sodium hydroxide was added to the obtained acidic xylooligosaccharide solution to a pH of 13, and the mixture was stirred at room temperature for 3 hours to perform deacetylation. Hydrochloric acid was added to the resulting liquid to a pH of less than 5, and the mixture was powdered using a spray dryer (manufactured by Okawara Kogyo Co., Ltd.).

[0069] Measurement of uronic acid content of xylooligosaccharides The uronic acid content of xylooligosaccharides was measured as follows.

[0070] A solvent was prepared by dissolving 10 g of boric acid and 15 g of sodium chloride in 1 L of water. 40 mg of neutral xylooligosaccharide or acidic xylooligosaccharide (or commercially available xylan (Biosynth)) was weighed out and dissolved in the solvent to make 50 mL. 4 mL of this solution was weighed out and the solvent was added to make 20 mL.

[0071] 0.5 mL of the obtained 20 mL of solution was taken into a test tube, 5 mL of sulfuric acid was added while cooling in ice water, and the mixture was heated in a water bath for 10 minutes. Immediately after, it was cooled in ice, 0.2 mL of 1,2-dimethylphenol reagent was added and mixed, and the mixture was heated in a water bath for 15 minutes, after which it was allowed to cool to obtain the sample solution. Separately, a D-glucuronic acid standard stock solution with a concentration of 10–100 μg / mL was prepared, and the same procedure was performed to obtain the standard solution, and the absorbance at wavelengths of 400 nm and 450 nm was measured. A calibration curve was created from the absorbance of the standard solutions, and the amount of uronic acid (g) of xylooligosaccharide was determined. The uronic acid content (mass%) was calculated using the following formula. If the quantitative value was negative, it was considered to be 0%.

[0072] Amount of uronic acid (mass %) = M Ｓ / M Ｔ × (A Ｔ４５０ -A Ｔ４００ ) / ( A Ｓ４５０ -A Ｓ４００ ) × 10 M Ｓ : Amount of D-glucuronic acid weighed (mg) M Ｔ : Amount of xylooligosaccharide weighed out (mg) on ​​a dry basis. Ｔｉ Absorbance of the sample solution at each wavelength (i: 450 nm or 400 nm) A Ｓｉ Absorbance measurements of the standard solutions at various wavelengths (i: 450 nm or 400 nm) revealed that the uronic acid content of the prepared neutral xylooligosaccharide was 0.0% by mass, while the uronic acid content of the acidic xylooligosaccharide was 15.8% by mass. Furthermore, the uronic acid content of commercially available xylan (Biosynth) was 9.7% by mass.

[0073] Molecular Weight Analysis of Xylooligosaccharides The number-average molecular weight and weight-average molecular weight of xylooligosaccharides were determined by GPC (gel permeation chromatography) under the following conditions: GPC column: Two linked Ultrahydrogel 250 columns manufactured by Waters Japan Eluent: A mixture of aqueous solutions of 0.3 M sodium nitrate and 0.01 M disodium hydrogen phosphate with methanol in a volume ratio of 4:1 Flow rate: 0.7 mL / min Measurement temperature: 40°C Detector: Differential refractive index detector The results showed that the number-average molecular weight of acidic xylooligosaccharides was 1376, and the number-average molecular weight of neutral xylooligosaccharides was 688. The average degree of polymerization of neutral xylooligosaccharides is calculated to be approximately 5.2 by dividing the number-average molecular weight by the molecular weight of the repeating unit of xylooligosaccharides (132) (688 ÷ 132). The average degree of polymerization of acidic xylooligosaccharides can be calculated using the formula {number-average molecular weight × (1 - uronic acid content)} / 132, specifically {1376 × (1 - 0.158)} / 132 ≈ 8.8. Furthermore, the weight-average molecular weight of acidic xylooligosaccharides was 1604, and the weight-average molecular weight of neutral xylooligosaccharides was 889.

[0074] Furthermore, the number-average molecular weight of commercially available xylan (Biosynth) was 6947, and the weight-average molecular weight was 15867. The average degree of polymerization of commercially available xylan can be calculated in the same way as for the acidic xylooligosaccharides mentioned above, specifically as {6947 × (1 - 0.097)} / 132 ≈ 47.5. The number-average molecular weight and weight-average molecular weight of commercially available xylan were determined under the following conditions: Column: Linked OHpak SB-G 6B and OHpak SB-806M HQ from Resonaq Eluent: 20 mM phosphoric acid and 20 mM LiBr solution (solvent: DMSO / DMF = 80 / 20 (volume ratio)) Flow rate: 0.6 mL / min Measurement temperature: 50°C Detector: Differential refractive index detector, light scattering detector (RALS, LALS), viscosity detector

[0075] Preparation of xylooligosaccharides with different uronic acid content: The acidic xylooligosaccharides and neutral xylooligosaccharides obtained were mixed as described below to prepare xylooligosaccharides with different uronic acid content.

[0076] [Preparation of xylooligosaccharide with 9.5% by mass uronic acid content] 240 g of acidic xylooligosaccharide powder and 160 g of neutral xylooligosaccharide powder were placed in a High Clean poly bag and shaken 100 times. Then, the mixture was sieved through an 850 μm sieve, collected in the High Clean poly bag, shaken 100 times again, and sieved through an 850 μm sieve. This yielded xylooligosaccharide with a uronic acid content of 9.5% by mass.

[0077] [Preparation of xylooligosaccharide with uronic acid content of 4.7% by mass] 280 g of acidic xylooligosaccharide powder and 120 g of neutral xylooligosaccharide powder were placed in a High Clean poly bag and shaken 100 times. Then, the mixture was sieved through an 850 μm sieve, collected in the High Clean poly bag, shaken 100 times again, and sieved through an 850 μm sieve. This yielded xylooligosaccharide with a uronic acid content of 4.7% by mass.

[0078] [Preparation of xylooligosaccharide with 2.3% by mass uronic acid content] 60 g of acidic xylooligosaccharide powder and 340 g of neutral xylooligosaccharide powder were placed in a High Clean poly bag and shaken 100 times. Then, the mixture was sieved through an 850 μm sieve, collected in the High Clean poly bag, shaken 100 times again, and sieved through an 850 μm sieve. This yielded xylooligosaccharide with a uronic acid content of 2.3% by mass.

[0079] Resin compounding process: Each component was placed in a twin-screw extruder (manufactured by Shibaura Machinery Co., Ltd., product name "TEM18SS", extrusion temperature: 190°C, φ: 18 mm) to produce the composition shown in each example in the table below, and the mixture was kneaded to produce a resin composition (compound resin). The values ​​for each component in the table below are in grams (g).

[0080] In each component listed in the table below, 105G (Prime PolyPro) from Prime Polymer Co., Ltd. was used as the polypropylene (PP). Since three different polypropylene products from different lots were used, these lots are denoted as A, B, and C. In the tables below, Lot A was used in each example in Table 1A, Lot B in each example in Table 1B, and Lot C in each example in Table 2C. To confirm that there was little difference between these lots, the physical properties of the polypropylene itself were also measured (Comparative Examples 1, 5, and 6).

[0081] In addition, Yumex 1010 from Sanyo Chemical Industries, Ltd. was used as a dispersant, and IRGANOX 1010 from BASF was used as an antioxidant.

[0082] Yumex 1010 is an acid-modified polypropylene, represented by the following formula. Its weight-average molecular weight (GPC method) is approximately 23,000, and its acid value is 52 mgKOH / g (JIS K 0070).

[0083]

[0084] Furthermore, IRGANOX1010 is a hindered phenol antioxidant and is represented by the following formula.

[0085]

[0086] Physical Property Measurement Method (Melt Flow Rate: MFR) For the resin composition, the melt flow rate (MFR (g / 10min)) was measured using "F-F01" manufactured by Toyo Seiki Seisakusho Co., Ltd., in accordance with Method A (mass measurement method) of ISO 1133-1:2011 (similar provisions exist in JIS K 7210-1:2014), and the fluidity was evaluated. The test conditions for the MFR test of the resin composition were temperature: 230°C and load: 2.16 kgf. (Bending Strength, Bending Modulus) An 80-ton injection molding machine (manufactured by Toyo Machinery & Metal Co., Ltd., product name "Sj-80IV", molding temperature: 190°C, mold temperature: 50°C) was used to prepare evaluation samples (dumbbell-shaped test pieces) from the resin composition in accordance with ISO 20753:2008. The bending strength (MPa) and flexural modulus (MPa) of the evaluation sample at 23°C were measured in accordance with ISO 178:2010. The test speed was 2 mm / min, and the distance between supports was 64 mm.

[0087] The measurement results are shown in the table below. In the table, "Measurement not possible" indicates that the fluidity of the target resin composition was too high under the measurement conditions to be measured, and "Measurement impossible" indicates that the target resin composition overflowed from the top of the device and could not be measured.

[0088]

[0089]

[0090]

Claims

1. A resin composition comprising a resin and a xylooligosaccharide, wherein the resin is at least one selected from the group consisting of polypropylene, polyethylene, polycarbonate, polyethylene terephthalate, and block copolymers thereof, and the xylooligosaccharide is a xylooligosaccharide having a uronic acid content of 2% by mass or less in its structure.

2. The resin composition according to claim 1, wherein the resin is polypropylene.

3. The resin composition according to claim 1, wherein the xylooligosaccharide is a neutral xylooligosaccharide.

4. The resin composition according to any one of claims 1 to 3, wherein the weight-average molecular weight of the xylooligosaccharide is 300 to 2400.

5. The resin composition according to any one of claims 1 to 3, wherein the weight-average molecular weight of the xylooligosaccharide is 600 to 1800.

6. The resin composition according to any one of claims 1 to 3, wherein the average degree of polymerization of the xylooligosaccharide is 2 to 16.

7. The resin composition according to any one of claims 1 to 3, wherein the average degree of polymerization of the xylooligosaccharide is 4 to 12.

8. The resin composition according to any one of claims 1 to 3, wherein the xylooligosaccharide is contained in an amount of 0.01 times or more by mass relative to the resin.

9. The resin composition according to any one of claims 1 to 3, wherein the xylooligosaccharide content is 5 to 50% by mass relative to the resin composition.

10. The resin composition according to any one of claims 1 to 3, wherein the melt flow rate (g / 10min) is 12 to 45.

11. The resin composition according to any one of claims 1 to 3, wherein the flexural strength (MPa) at 23°C is 40 to 70 MPa, and / or the flexural modulus (MPa) at 23°C is 1500 to 4500 MPa.

12. The resin composition according to any one of claims 1 to 3, further comprising a dispersant.

13. The resin composition according to claim 12, wherein the dispersant is acid-modified polypropylene.

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