Lignin compositions and use thereof

Abstract

A lignin composition containing two or more compounds represented by the following formula (1) in a total content of 0.06% by mass or more. (In the formula, R a is a hydrogen atom, a methyl group, an ethyl group, a furanyl group, a hydroxymethyl furanyl group, a hydroxyphenyl group, a hydroxymethoxyphenol group, or a hydroxydimethoxyphenol group. R c1 , R c2 each independently represents a hydroxyl group, an alkoxy group, an amino group, or a thiol group. R 11 ~R 20 each independently represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 15 carbon atoms, a hydrocarbon ether group having 1 to 15 carbon atoms, or a group containing a carbonyl group.

Description

TECHNICAL FIELD

[0001] The present application relates to a lignin composition and use thereof. BACKGROUND

[0002] Attempts have been made to improve the mechanical properties such as the bending strength of the resulting molded product by mixing lignin to a resin or reacting with a resin. However, it is known that in the case where lignin is added to a thermosetting resin before molding, the flowability is generally reduced.

[0003] In view of the above problem, a method of modifying lignin with phenol or the like to prevent the reduction in flowability at the time of resin addition has been proposed in the past.

[0004] For example, Patent Literature 1 discloses that a molding material obtained by adding lignin to a novolak type phenol-aldehyde resin is poor in resin flow and cannot be molded due to clogging, but the moldability of a molding material added with a lignin-modified novolak type phenol resin obtained by reacting a novolak type phenol-aldehyde resin with lignin, phenol or a phenol derivative, and an aldehyde in the presence of an organic acid is improved. However, Patent Literature 1 has problems that the bending strength is slightly reduced compared to a general novolak type phenol-aldehyde resin, or the possibility of secondary treatment of lignin with a volatile organic base or the like is high, and the use of highly toxic formaldehyde is a problem.

[0005] Further, Patent Literature 2 discloses that the hot flowability at the time of molding of a friction material is good and the friction properties are improved by reacting lignin, phenol-based compounds, and aldehydes in the presence of an acid catalyst. However, Patent Literature 2 has problems that a pretreatment of refining lignin with methanol, ethanol, acetone, and tetrahydrofuran or the like is essentially required, and the use of highly toxic formaldehyde is a problem.

[0006] PRIOR ART DOCUMENTS

[0007] PATENT LITERATURE

[0008] Patent Literature 1: Japanese Patent Application Publication No. 2008-156601

[0009] Patent Literature 2: Japanese Patent Application Publication No. 2013-199561 SUMMARY

[0010] A thermosetting resin to which lignin is added and the flowability of which is reduced is sometimes difficult to uniformly fill into a mold or the like at the time of molding, and molding defects such as underfilling occur.

[0011] Thus, an object of the present application is to provide a lignin composition capable of imparting a flowability in conformity with molding when added to a thermosetting resin or the like.

[0012] According to the present application, it is possible to provide the following lignin composition or the like.

[0013] 1. A lignin composition comprising two or more compounds represented by the following formula (1), the total content of the compounds being 0.06% by mass or more.

[0014] [Chem. 1]

[0015]

[0016] (In the formula, R a is a hydrogen atom, a methyl group, an ethyl group, a furanyl group, a hydroxymethylfuranyl group, a hydroxyphenyl group, a hydroxymethoxyphenol group, or a hydroxydimethoxyphenol group. R c1 , R c2 each independently represent a hydroxyl group, an alkoxy group, an amino group, or a thiol group. R 11 to R 20 each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 15 carbon atoms, a hydrocarbon ether group having 1 to 15 carbon atoms, or a group containing a carbonyl group. R 11 to R 20 are each optionally the same or different from each other. Among them, at least one of R 11 to R 15 is a hydrogen atom, and at least one of R 16 to R 20 is a hydrogen atom.

[0017] 2. The lignin composition according to 1, having a weight average molecular weight (Mw) of 1,000 to 3,000.

[0018] 3. The lignin composition according to 1 or 2, having a molecular weight distribution (Mw / Mn) of 2.2 to 3.5.

[0019] 4. The lignin composition according to any one of 1 to 3, wherein the total content of the compounds represented by the formula (1) is 5% by mass or less.

[0020] 5. The lignin composition according to any one of 1 to 4, wherein the content of the following compound (2) is 0.1% by mass or less.

[0021] [Chem. 2]

[0022]

[0023] 6. The lignin composition according to any one of 1 to 5, wherein the content of free phenolic monomers is 0.02 mass% or more and 5.0 mass% or less.

[0024] 7. The lignin composition according to any one of 1 to 6, wherein the softening point is 100°C or more and less than 250°C.

[0025] 8. The lignin composition, wherein the maximum value of the differential distribution value (dw / dLogM) of the molecular weight LogM of the lignin composition existing in the peak of 2.4 to 2.6 is 50 or more and 150 or less, or the difference of the integral distribution value (%) of the molecular weight LogM of 2.4 to 2.55 is 5 or more and 15 or less, as measured by gel permeation chromatography (GPC).

[0026] 9. A thermosetting resin composition comprising the lignin composition according to any one of 1 to 8 and a thermosetting resin.

[0027] 10. Use of the lignin composition according to any one of 1 to 8 for promoting a crosslinking reaction in a thermosetting resin molding material comprising a thermosetting resin.

[0028] 11. The use of the lignin composition according to 10, wherein the aforementioned thermosetting resin is any one or more selected from the group consisting of phenol resin, urethane resin, epoxy resin, urea (urethane) resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, alkyd resin, and polyimide.

[0029] 12. A method for promoting a crosslinking reaction in a thermosetting resin molding material comprising a thermosetting resin using the lignin composition according to any one of 1 to 8.

[0030] 13. A modifier or crosslinking reaction promoter for a thermosetting resin, comprising the lignin composition according to any one of 1 to 8.

[0031] 14. A rubber composition comprising the lignin composition according to any one of 1 to 8 and a rubber material.

[0032] 15. A molded body obtained by curing the thermosetting resin composition according to 9 or the rubber composition according to 14.

[0033] 16. A method for producing the lignin composition according to any one of 1 to 8, comprising an extraction step of extracting a lignin composition comprising an extract derived from lignin from a material containing lignin using a solvent comprising an organic solvent.

[0034] By using the lignin composition of the present application, it is possible to produce a resin composition (molding material) having a fluidity in conformity with molding. In addition, it is possible to obtain a resin molded body having improved mechanical strength and the like. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 is a spectrum of differential distribution values of molecular weight calculated by GPC for the sample of Example 1.

[0036] Figure 2 is a spectrum of integral distribution values of molecular weight calculated by GPC for the sample of Example 1.

[0037] Figure 3 is a DSC curve of the lignin composition of Example 2 and the lignin of Comparative Example 1. DETAILED DESCRIPTION

[0038] Hereinafter in the present specification, "x ~ y" indicates a numerical range of "x or more and y or less". When there are a plurality of lower limit values such as "x or more" and a plurality of upper limit values such as "y or less" with respect to one technical matter, any of the upper limit values and the lower limit values can be arbitrarily selected and combined.

[0039] [Lignin composition]

[0040] The lignin composition according to one embodiment of the present application contains two or more compounds represented by the following formula (1) in a total content of 0.06% by mass or more.

[0041] [Chemical 3]

[0042]

[0043] (In the formula, R a is a hydrogen atom, a methyl group, an ethyl group, a furanyl group, a hydroxymethylfuranyl group, a hydroxyphenyl group, a hydroxymethoxyphenol group, or a hydroxydimethoxyphenol group. R c1 , R c2 each independently represents a hydroxyl group, an alkoxy group, an amino group, or a thiol group. R 11 ~ R 20 each independently represents a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 15 carbon atoms, a hydrocarbon ether group having 1 to 15 carbon atoms, or a group containing a carbonyl group. R 11 ~ R 20 are optionally the same as or different from each other.

[0044] wherein at least one of R 11 ~ R 15 is a hydrogen atom, and at least one of R 16 ~ R 20 is a hydrogen atom.)

[0045] The hydrocarbon group having 1 to 15 carbon atoms can be linear or branched, and can be saturated or unsaturated. The hydrocarbon group having 1 to 15 carbon atoms is preferably a linear or branched hydrocarbon group having 1 to 10 carbon atoms, more preferably a linear or branched hydrocarbon group having 1 to 5 carbon atoms, and further preferably a linear hydrocarbon group having 1 to 3 carbon atoms.

[0046] Each of these suitable hydrocarbon groups can be saturated or unsaturated.

[0047] The hydrocarbon ether group having 1 to 15 carbon atoms can be linear or branched, and the hydrocarbon can be saturated or unsaturated.

[0048] The hydrocarbon ether group having 1 to 15 carbon atoms is preferably a linear or branched hydrocarbon ether group having 1 to 10 carbon atoms, more preferably a linear or branched hydrocarbon ether group having 1 to 5 carbon atoms, and further preferably a linear hydrocarbon ether group having 1 to 3 carbon atoms.

[0049] Each of these suitable hydrocarbon groups can be saturated or unsaturated.

[0050] Note that the hydrocarbon ether group can be represented by, for example, -(CH2) a -O-(CH2) b - (a and b are each an integer of 0 or more. In this case, a + b is 1 or more.) In this case, the hydrocarbon ether group is linear and represented by -(CH2) a - and -(CH2) b - are linear, and the hydrocarbon ether group is branched and represented by -(CH2) a - or -(CH2) b - is branched.

[0051] In addition, the hydrocarbon of the hydrocarbon ether group is saturated and represented by -(CH2) a - and -(CH2) b - are saturated hydrocarbons, and the hydrocarbon of the hydrocarbon ether group is unsaturated and represented by -(CH2) a - or -(CH2) b - is an unsaturated hydrocarbon.

[0052] In addition, the hydrocarbon ether group is represented by -(CH2) a -O-(CH2) b -, the number of carbon atoms of the hydrocarbon ether group is the number represented by (a + b).

[0053] As the group containing a carbonyl group, there are, for example, an aldehyde group (-CHO), a carboxyl group (-COOH), a carbonyl group (-COR), an ester group (-COOR), and an amide group (-CONRR').

[0054] R c1 , R c2 may be any of a hydroxyl group, an alkoxy group, an amino group, or a mercaptan group, preferably a hydroxyl group or an alkoxy group, and more preferably a hydroxyl group.

[0055] The amount of lignin contained in the lignin composition can be confirmed by determining the amount of methoxyl group contained in the lignin composition according to the methoxyl group determination method based on the Viebock and Schwappach method (refer to "Lignin Chemistry Research Method", P336 to 340, published by Yuji Shuppan in 1994), and using the determined value of the amount of methoxyl group as the amount of lignin, in the form of a value thus calculated.

[0056] By causing the lignin composition to contain two or more kinds of compounds represented by formula (1) (hereinafter sometimes referred to as phenolic dimers) in a prescribed amount or more, it is possible to maintain the flowability at the time of compounding into a thermosetting resin.

[0057] The kinds and the amounts of the phenolic dimers contained in the lignin composition are confirmed by liquid chromatography / mass spectrometry (LC / MS).

[0058] When the lignin composition is measured by liquid chromatography / mass spectrometry (LC / MS), the amount of the phenolic dimers in the entire lignin composition can be calculated.

[0059] In addition, when the lignin composition is measured by liquid chromatography / mass spectrometry (LC / MS), the amount of the phenolic dimers in the entire thermosetting resin composition described later can be calculated depending on the containing ratio of the lignin composition and other components such as phenol-formaldehyde resins.

[0060] In LC / MS, it is assumed that the following compounds (a) to (h) are contained in the lignin composition as the compounds represented by formula (1). In the case where the detection limit is below, that is, the content of the object compound is less than 0.001 mass%, it is judged that the lignin composition does not contain the object compound. Details of the measurement are described in the examples.

[0061] Note that, in the content of each of the compounds (a) to (h) determined by the aforementioned LC / MS, the content of isomers having the same molecular weight but different bonding positions compared to each compound is also included.

[0062] [Chemical Formula 4]

[0063]

[0064] In the present embodiment, for example, the lignin composition contains two or more kinds of compounds selected from the aforementioned compounds (a) to (h).

[0065] The total content of the compound represented by formula (1) is 0.06% by mass or more relative to the entire lignin composition. Thus, the flowability of the resin composition can be maintained when compounded into a thermosetting resin. The above total content can be 0.07% by mass or more, and can be 0.1% by mass or more.

[0066] In addition, the above total content can be 5% by mass or less, can be 3% by mass or less, can be 2% by mass or less, and can be 1% by mass or less. The above total content can be appropriately adjusted depending on the thermosetting resin used, the molding conditions, and the like.

[0067] In one embodiment, the weight average molecular weight (Mw) of the lignin composition is 1,000 to 3,000. Thus, the flowability when compounded into a thermosetting resin can be easily maintained. In addition, a molded body having good mechanical properties can be easily obtained. The Mw can be 1,300 or more, and can be 1,500 or more. In addition, the Mw can be 2,900 or less, and can be 2,700 or less.

[0068] In one embodiment, the molecular weight distribution (Mw / Mn) of the lignin composition is 2.2 to 3.5. The Mw / Mn can be 2.3 or more, can be 2.4 or more, can be 2.5 or more, and can be 2.6 or more. In addition, the Mw / Mn can be 3.3 or less, can be 3.0 or less, and can be 2.7 or less.

[0069] The respective molecular weights of the lignin composition were measured by GPC as described in the Examples below.

[0070] In one embodiment, the content of the following compound (2) is 0.1% by mass or less, and can be 0.05% by mass or less, relative to the entire lignin composition.

[0071] [Chemical 5]

[0072]

[0073] By having the content of the compound (2) in the above range, it can be said that the loss of the solvent components due to the reaction of the solvent components with each other in the extraction process of the lignin described below is suppressed, and a composition obtained by having the solvent appropriately intervene in the generation of lignin in the extraction process of the lignin.

[0074] The content of the compound (2) was measured by the method described in the Examples below.

[0075] In one embodiment, the content of free phenol monomers is 0.02% by mass or more and 5.0% by mass or less relative to the entire lignin composition. The free phenol monomers contained in the lignin composition are mainly monomers that remain without being removed from a part of the phenol used at the time of manufacturing the lignin composition. The content of phenol can be 0.1% by mass or more, can be 0.5% by mass or more, can be 1.0% by mass or more, can be 2.0% by mass or more, or can be 3.0% by mass or more.

[0076] The content of phenol is measured using the method described in the Examples below.

[0077] In one embodiment, the softening point of the lignin composition is 100°C or more and less than 250°C. The softening point can be 110°C or more, can be 120°C or more, or can be 130°C or more. In addition, the softening point can be 200°C or less, can be 180°C or less, or can be 160°C or less.

[0078] The softening point is measured using the method described in the Examples below.

[0079] In another embodiment of the present application, the maximum value of the differential distribution value (dw / dLogM) of the molecular weight LogM of the lignin composition measured by GPC at the peak where the molecular weight LogM exists in the range of 2.4 to 2.6 is 50 or more and 150 or less, or the difference in the integrated distribution value (%) of the molecular weight LogM in the range of 2.4 to 2.55 is 5 or more and 15 or less.

[0080] By making the maximum value of the differential distribution value (dw / dLogM) of the molecular weight LogM of the lignin composition measured by GPC at the peak where the molecular weight LogM exists in the range of 2.4 to 2.6 be 50 or more and 150 or less, the flowability at the time of compounding into a thermosetting resin can be maintained. The above maximum value can be 130 or less, or can be 110 or less.

[0081] Similarly, by making the difference in the integrated distribution value (%) of the molecular weight LogM in the range of 2.4 to 2.55 be 5 or more and 15 or less, the flowability at the time of compounding into a thermosetting resin can be maintained. The above integrated distribution value can be 7 or more, or can be 8 or more. In addition, the above integrated distribution value can be 13 or less, or can be 12 or less.

[0082] The lignin composition of the present application is obtained by, for example, extraction and purification from a lignin-containing material using a solvent containing an organic solvent. The solvent containing an organic solvent typically contains at least a compound represented by the following formula (I).

[0083] [Chemical Formula 6]

[0084]

[0085] In the above formula (I), R 31 ~R 35 each independently represents a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 15 carbon atoms, a hydrocarbon ether group having 1 to 15 carbon atoms, or a group containing a carbonyl group, R 31 ~R 35 are optionally the same or different. Among them, R 31 ~R 35 is a hydrogen atom.

[0086] As R 31 ~R 35 is a hydrocarbon group having 1 to 15 carbon atoms, the hydrocarbon group is the same as R 11 ~R 20 in the above formula (1). In addition, as R 31 ~R 35 is a hydrocarbon ether group having 1 to 15 carbon atoms, the hydrocarbon ether group is the same as R 11 ~R 20 in the above formula (1). In addition, as R 31 ~R 35 is a group containing a carbonyl group, the group containing a carbonyl group is the same as R 11 ~R 20 in the above formula (1).

[0087] R c represents a hydroxyl group, an alkoxy group, an amino group, or a thiol group.

[0088] R c may be any of a hydroxyl group, an alkoxy group, an amino group, or a thiol group, and from the viewpoint of affinity with the basic skeleton of lignin, it is preferably a hydroxyl group or an alkoxy group, and more preferably a hydroxyl group.

[0089] The solvent can contain a substance other than the compound represented by the above formula (I). As the solvent component other than the compound represented by the above formula (I), from the viewpoints of solubility of lignin in the raw material and economy, any one or more of an alcohol, a ketone, an ether, an ester, an aromatic compound other than the compound represented by formula (I), and water can be cited.

[0090] In the present specification, "lignin" means a high molecular compound obtained by polymerizing three kinds of lignin monomers of p-hydroxycinnamyl alcohol, and has a basic skeleton represented by the following formula (A).

[0091] [Chemical Formula 7]

[0092]

[0093] In the above formula (A), R 3 and R 4represents a hydrogen atom or a methoxy group. R 3 and R 4 both of which are hydrogen atoms is referred to as a p-hydroxyphenyl nucleus (H-type skeleton), R 3 and R 4 either of which is a hydrogen atom is referred to as a guaiacyl nucleus (G-type skeleton), R 3 and R 4 neither of which is a hydrogen atom is referred to as a syringyl nucleus (S-type skeleton).

[0094] Note that X in the above formula (A) represents a bond to a carbon atom, and Y represents a bond to a hydrogen atom or a carbon atom.

[0095] (lignin-containing material)

[0096] The lignin-containing material is not particularly limited as long as it is a lignin-containing material.

[0097] In one embodiment, the lignin-containing material is one or more selected from the group consisting of biomass and biomass residue.

[0098] As the biomass residue, there can be mentioned, for example, biomass residue derived from plant-based biomass such as woody biomass and herbaceous biomass.

[0099] For example, as the biomass residue, there can be mentioned saccharification residue and fermentation residue of plant-based biomass (second-generation ethanol saccharification residue, second-generation ethanol fermentation residue, etc.), black liquor (sulfide lignin, kraft lignin, alkali lignin, organic solvent lignin, etc.), and the like, and one or more of these can be used. Among these, from the viewpoints of ease of acquisition, quality of the lignin composition, and economy, as the lignin-containing material, it is preferable to use one or more of the saccharification residue and fermentation residue of plant-based biomass.

[0100] The woody biomass and the herbaceous biomass can be non-edible plant biomass, and can be lignocellulose-based biomass.

[0101] As the woody biomass, there can be mentioned, for example, coniferous trees such as fir, Japanese cypress, Japanese arborvitae, cherry tree, eucalyptus, beech, and bamboo, and broad-leaved trees.

[0102] As the herbaceous biomass, there can be mentioned, for example, oil palm trunk · empty fruit bunch, fiber and seed of oil palm fruit, bagasse (press residue of sugarcane and high-biomass sugarcane), cane tops (tops and leaves of sugarcane), energy cane, rice straw, wheat straw, ear · stem · residue of corn (corn cob, corn stalk, corn husk), sorghum (including sweet sorghum) residue, skin and shell of Jatropha curcas, cashew nut shell, switchgrass, miscanthus, high-biomass yield crops, energy crops, and the like.

[0103] Among these, biomass of the herbaceous system is preferable, and biomass of the oil palm empty fruit bunches, fiber and seeds of the oil palm fruit, wheat straw, corn cob·stalk·residue (corn cob, corn cob, corn husk), bagasse, sorghum (including sweet sorghum) residue, cane tops, energy cane, and residue after extracting these useful components is more preferable. Biomass of the oil palm empty fruit bunches, corn cob·stalk·residue (corn cob, corn cob, corn husk), bagasse, sorghum (including sweet sorghum) residue, cane tops, energy cane, and residue after extracting these useful components is more preferable. Note that the useful components include, for example, hemicellulose, sugar, mineral, water, and the like.

[0104] Bagasse contains about 5 to 30 mass% of lignin. In addition, the lignin in the bagasse contains all of H core, G core, and S core as a basic skeleton.

[0105] The plant-based biomass can also be in the form of a powder. In addition, it can be in the form of a piece, a small piece, a powder, or a water-containing substance containing water.

[0106] The oil palm empty fruit bunches, bagasse, corn cob, and the like are subjected to an organic solvent method, a pressurized hot water method, a steam explosion method, an ammonia treatment method, an ammonia explosion method, an acid treatment method, a dilute sulfuric acid explosion method, an alkali treatment method, an oxidative decomposition method, a thermal decomposition method, a microwave heating method, and the like, and preferably subjected to an acid treatment, a dilute sulfuric acid explosion, a steam explosion, and the like. After hemicellulose is separated to the solution side, cellulose is made into glucose by an enzyme, and separated to the solution side, or directly saccharified together with the cellulose without separating the hemicellulose, and separated to the solution side. The remaining solid is a saccharification residue of the plant-based biomass. Alternatively, without separating the saccharides, ethanol is separated to the solution side by fermentation, and the remaining solid is a fermentation residue of the plant-based biomass.

[0107] The saccharification residue of the plant-based biomass contains lignin as a main component, and contains decomposition organic matter, a catalyst, an enzyme, ash, cellulose, and the like. In addition, the fermentation residue of the plant-based biomass contains lignin as a main component, and contains decomposition organic matter, a catalyst, an enzyme, yeast, ash, cellulose, and the like.

[0108] The method for producing a lignin composition is, for example, as follows.

[0109] One or more of the saccharification residue and the fermentation residue of the plant-based biomass is used as a raw material, and a solvent containing a compound having one or more selected from, for example, a hydroxyl group and an ether bond (hereinafter also referred to as "organic solvent A") is added. The solvent containing the organic solvent A typically contains at least the compound represented by the aforementioned formula (I). The organic solvent A is described in detail in the item "Solvent" described later.

[0110] After continuing heating for about 2 to 4 hours, since the heating liquid contains insoluble matter, filtration is performed using No. 2 filter paper. The filtered solid is the unextracted component and inorganic inclusions. The filtrate is subjected to distillation under reduced pressure to remove the solvent. The solvent that has not been removed by distillation is removed by vacuum drying. The separated solid is the lignin composition.

[0111] In addition, as the lignin-containing material used as the raw material, lignin isolated from non-edible plant biomass by treatment such as organic solvent method, pressurized hot water method, steam explosion method, ammonia treatment method, ammonia explosion method, acid treatment method, dilute sulfuric acid explosion method, alkali treatment method, oxidative decomposition method, thermal decomposition, and microwave heating method can also be used. Specifically, lignin obtained by, for example, subjecting non-edible plant biomass to treatment using an organic solvent or a solvent containing an organic solvent and water to dissolve lignin contained in the non-edible plant biomass into the solvent, and then removing cellulose and the like by filtering the lignin-containing solution, and then concentrating and drying the solution can also be used. Note that by using a solvent containing organic solvent A as the above-mentioned organic solvent, it is also possible to directly extract a lignin composition from non-edible plant biomass.

[0112] (Solvent)

[0113] The solvent used in the extraction contains an organic solvent. The solvent containing an organic solvent typically contains the above-mentioned compound represented by formula (I) as described above. Examples of the organic solvent other than the compound represented by formula (I) include alcohols such as methanol, ethanol, isopropanol, ethylene glycol, and polyethylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and 1,4-dioxane; esters such as ethyl acetate; and aromatic compounds other than the compound represented by formula (I) such as toluene.

[0114] In one embodiment, a solvent containing organic solvent A is used. By using organic solvent A as the organic solvent for extracting lignin, it is expected that the extract derived from the lignin is suitably prevented from being modified to be hydrophilic. Note that the extracted lignin composition can react with the organic solvent containing organic solvent A. By using organic solvent A, the extract derived from lignin can be suitably extracted.

[0115] In the case where the organic solvent A has a hydroxyl group, the number of hydroxyl groups possessed by the organic solvent A is not particularly limited, and can be, for example, 1 or more, and can be 10 or less, 5 or less, 4 or less, 3 or less, or 2 or less. The number of hydroxyl groups possessed by the organic solvent A can be 1, 2, 3, 4, or 5, can be 1, 2, or 3, can be 1 or 2, or can be 1.

[0116] As the organic solvent A having 2 hydroxyl groups, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, and the like can be exemplified. In addition, as the organic solvent A having 3 hydroxyl groups, for example, glycerol, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,3-heptanetriol, 1,2,4-heptanetriol, 1,2,5-heptanetriol, 2,3,4-heptanetriol, and the like can be exemplified. As the organic solvent A having 4 hydroxyl groups, for example, pentaerythritol, erythritol, and the like can be exemplified. As the organic solvent A having 5 hydroxyl groups, for example, xylitol, and the like can be exemplified. As the organic solvent A having 6 hydroxyl groups, for example, sorbitol, and the like can be exemplified.

[0117] As the organic solvent A having 2 or more hydroxyl groups (the organic solvent A having a plurality of hydroxyl groups), from the viewpoint of improving the extraction efficiency of lignin, economy, it is preferable that 1 or more selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, and glycerol, more preferable that 1 or more selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, polypropylene glycol, and glycerol, further preferable that 1 or more selected from the group consisting of ethylene glycol, polyethylene glycol, and glycerol, further preferable ethylene glycol and polyethylene glycol.

[0118] The organic solvent A is preferably a compound represented by the following formula (II).

[0119] R-OH (II)

[0120] (In formula (II), R is an alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenyl group.)

[0121] When R is an alkyl group having 1 to 10 carbon atoms, the number of carbon atoms of the alkyl group can be 1 or more, 2 or more, 3 or more, or 4 or more, and can be 10 or less, 8 or less, or 6 or less. The alkyl group can be linear, or branched.

[0122] In particular, by setting the number of carbon atoms of the alkyl group to 2 or more, it is expected that the extract derived from lignin is more significantly prevented from being modified to be hydrophilic. In addition, the larger the number of carbon atoms is, the more significantly it is expected to exert such an effect.

[0123] As the compound represented by formula (II) in which R is an alkyl group having 1 to 10 carbon atoms, for example, one or more selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-methyl-1-butanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethylhexanol, and the like, preferably one or more selected from the group consisting of methanol, ethanol, 1-propanol, and 2-propanol, more preferably one or more selected from the group consisting of methanol, ethanol, and 2-propanol, further preferably ethanol.

[0124] The aforementioned compound represented by formula (I) corresponds to the case where R in the above formula (II) is a substituted or unsubstituted phenyl group, and the hydroxyl group ("OH" group in formula (II)) is the aforementioned R c .

[0125] The aforementioned compound represented by formula (I) is preferably at least one of R 31 , R 33 , and R 35 is a hydrogen atom, more preferably R 31 , R 33 , and R 35 are all hydrogen atoms.

[0126] As the compound represented by formula (I), for example, one or more selected from the group consisting of phenol, o-dihydroxybenzene, m-dihydroxybenzene, hydroquinone, m-trihydroxybenzene, o-cresol, m-cresol, p-cresol, 2-ethylphenol, 2-propylphenol, and the like 2-alkylphenols; 3-ethylphenol, 3-propylphenol, and cashew phenol, and the like 3-alkylphenols; 4-ethylphenol, 4-propylphenol, 4-octylphenol, 4-nonylphenol, and the like 4-alkylphenols; 5-methyl-m-dihydroxybenzene, 5-ethyl-m-dihydroxybenzene, and 5-propyl-m-dihydroxybenzene, and the like 5-alkyl-m-dihydroxybenzenes; 3,5-dimethylphenol, 3-methyl-5-ethyl-phenol, and 3,5-diethylphenol, and the like 3,5-dialkylphenols; anisole, aniline, thio-phenol, and the like,

[0127] are all hydrogen atoms. As the compound represented by formula (I), for example, one or more selected from the group consisting of phenol, o-dihydroxybenzene, m-dihydroxybenzene, hydroquinone, o-cresol, m-cresol, p-cresol, cashew phenol, 4-octylphenol, 4-nonylphenol, anisole, and the like, more preferably one or more selected from the group consisting of phenol, o-dihydroxybenzene, m-dihydroxybenzene, hydroquinone, o-cresol, m-cresol, p-cresol, anisole, and the like, further preferably one or more selected from the group consisting of phenol, o-cresol, m-cresol, p-cresol, anisole, and the like, further preferably one or more selected from the group consisting of phenol, anisole, and the like, further preferably phenol.

[0128] As the organic solvent, when a compound represented by formula (I) such as phenol is used, by allowing the lignin composition to react with the compound represented by formula (I), it is expected that the skeleton of the H-type and G-type will increase.

[0129] When a compound represented by formula (I) is used as the organic solvent, by allowing the lignin to react with the compound represented by formula (I), it is expected that the substituent R in the basic skeleton of the lignin represented by formula (A) in the lignin will be replaced 3 and R 4 to a substituent derived from the structure of the compound represented by formula (I).

[0130] The organic solvent A can be used alone or in combination with two or more kinds.

[0131] As the organic solvent A, for example, one or two or more kinds selected from the group consisting of compounds represented by formula (II) in which R is an alkyl group having 1 to 10 carbon atoms and one or two or more kinds selected from the group consisting of compounds represented by formula (II) in which R is a substituted or unsubstituted phenyl group (i.e., a compound represented by formula (I)) can be used in combination. If specific examples are listed, ethanol and phenol can be used in combination.

[0132] The organic solvent can include other organic solvents in addition to the organic solvent A.

[0133] The other organic solvents are not particularly limited, and examples include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and aromatic compounds other than the compound represented by formula (I) such as toluene. The other organic solvents can be used alone or in combination with two or more kinds.

[0134] In one embodiment, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, or 99% by mass or more of the organic solvent is the organic solvent A.

[0135] The solvent used in the extraction can include water in addition to the organic solvent.

[0136] Regarding the ratio of water to the organic solvent in the solvent used in the extraction, for example, relative to 100 parts by mass of the organic solvent, it can be 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, or 70 parts by mass or more, and in addition, it can be 900 parts by mass or less, 700 parts by mass or less, 400 parts by mass or less, 300 parts by mass or less, or 100 parts by mass or less.

[0137] In the extraction of the lignin composition from the material containing lignin using a solvent, the solvent can or can not undergo phase separation. In the case where the solvent undergoes phase separation, the "solvent used in the extraction" refers to the solvent constituting the phase containing the lignin composition at the highest concentration.

[0138] (Extraction)

[0139] The extraction in the present application means extraction of a lignin composition containing a lignin-derived extract from a lignin-containing material containing components other than lignin.

[0140] The "extraction" in one embodiment means extraction of a lignin composition from a lignin-containing solid, in the case where the lignin-containing material is a lignin-containing solid, and does not mean an operation of adding an organic solvent to a solution in which all lignin has been dissolved (for example, an aqueous solution containing an alkaline compound). In this embodiment, the lignin-containing material before extraction (the lignin-containing material before addition of an organic solvent) contains:

[0141] a lignin-containing solid and lignin that has been dissolved in a solvent; or

[0142] a lignin-containing solid, but does not contain lignin that has been dissolved in a solvent.

[0143] The amount of the solvent added to the lignin-containing material at the time of extraction is not particularly limited.

[0144] The mass ratio of the solvent to lignin in the lignin-containing material [solvent / lignin] may, for example, be 0.1 or greater, and in addition, can be 15 or less, 10 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, 0.7 or less, or 0.5 or less.

[0145] (Acid catalyst)

[0146] The above extraction can be performed in the absence of a catalyst or in the presence of a catalyst. As the catalyst, for example, an acid catalyst or the like can be exemplified. As the acid catalyst, inorganic acids such as phosphoric acid, phosphoric acid ester, hydrochloric acid, sulfuric acid, and sulfuric acid ester; organic acids such as acetic acid, formic acid, oxalic acid, and p-toluenesulfonic acid; and the like can be exemplified. The acid catalyst can be used alone or in combination with two or more kinds.

[0147] When the total amount of lignin and solvent is set to 100 parts by mass, the acid catalyst may, for example, be more than 0 mass%, 0.1 mass% or more, or 0.2 mass% or more, and in addition, can be 5.0 mass% or less, 3.0 mass% or less, or 2.6 mass% or less.

[0148] When the extraction is performed in the absence of a catalyst, for example, the post-treatment (refining process) after the extraction process can be omitted.

[0149] The extraction temperature is not particularly limited as long as the lignin composition can be extracted from the lignin-containing material, and for example, can be 100°C or higher, 140°C or higher, more than 140°C, 150°C or higher, or 180°C or higher, and can be 350°C or lower, 300°C or lower, 270°C or lower, 250°C or lower, or 230°C or lower. If more than 140°C, the solubility of the lignin (lignin composition) can be increased to promote extraction, and if 300°C or lower, the progress of re-bonding of the lignin can be suitably prevented.

[0150] The extraction time can be appropriately set, and for example, can be 0.1 hour or more, 0.5 hour or more, 1 hour or more, or 2 hours or more, and can be 15 hours or less, 10 hours or less, or 8 hours or less.

[0151] The extraction pressure can be appropriately set, and for example, can be 0.1 MPa or more, 0.5 MPa or more, or 1.0 MPa or more, and can be 10 MPa or less, 5 MPa or less, 4 MPa or less, or 3 MPa or less.

[0152] (Purification)

[0153] The lignin composition is produced by the above extraction, and can be purified as needed after the extraction. Hereinafter, one example of the purification will be described.

[0154] As the purification (purification step), first, the lignin composition after the extraction can be subjected to a solid-liquid separation step. The lignin composition after the extraction is dissolved in the solvent, but the unextracted components and inorganic inclusions exist in the liquid in the form of solids. They are preferably removed by filtration (while hot). For example, the extraction liquid is poured into a pressurized (while hot) filter equipped with a filter paper of No. 5C or No. 2 or the like, and pressure filtration is performed at 20 to 100°C or so, 20 to 70°C or so, usually at 20 to 50°C or so, and 0.1 to 0.99 MPa or so, usually at 0.1 to 0.4 MPa or so. The filtration solid can be diluted and / or washed with an appropriate solvent, and subjected to filtration. In this filtration, the lignin composition is contained in the filtrate. In addition, for example, the extraction liquid can be diluted and / or washed with one or more kinds of low-boiling general solvents such as water, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, and isopropyl alcohol, and ethers such as tetrahydrofuran, and subjected to solid-liquid separation. In this solid-liquid separation, the lignin composition is contained in the solution.

[0155] The method of the solid-liquid separation is not particularly limited, and filtration, filter pressurization, centrifugal separation, dehydration, and the like can be exemplified.

[0156] As the solid-liquid separation device used in the solid-liquid separation, there is no particular limitation, and a filtration device using a filter or the like, a vacuum filter, a centrifugal separator, a screw decanter, a belt press dewatering machine, a screw press dewatering machine, a filter press dewatering machine, a vibrating screen, or the like can be used. As the centrifugal separator, a decanter type, a disc type, or the like can be exemplified. These solid-liquid separation devices can be used alone, or two or more devices can be used in combination.

[0157] By performing the solid-liquid separation using the aforementioned solid-liquid separation device, the solid components such as unextracted components and inorganic inclusions contained in the lignin composition can be efficiently and effectively removed. Therefore, even if the lignin composition obtained by the subsequent distillation and pressure reduction drying is not subjected to reprecipitation, a lignin composition in which the content of components other than lignin contained in a material containing lignin can be effectively reduced can be obtained.

[0158] In addition, the solution of the lignin-containing composition obtained through the aforementioned extraction step and the optional solid-liquid separation step can be subjected to distillation. The distillation can be performed by performing pressure reduction distillation at a temperature of about 40 to 200°C, usually about 50 to 150°C, and under a reduced pressure of about 3 to 20 kPa, usually about 5 to 10 kPa, to remove the solvent. In this distillation, the lignin composition can be obtained in the form of a solid or a viscous solid. In addition, when another dilution solvent is used, for example, pressure reduction distillation can be performed at an appropriate temperature taking into account the boiling point of the solvent to remove the low-boiling-point general-purpose solvent, and thereafter, the solvent used in the extraction can be removed using the same method as described above. In this distillation, the lignin composition is obtained in the form of a solid or a viscous solid.

[0159] Either one or both of the solid-liquid separation step and the distillation step can be performed as necessary after the aforementioned extraction step or the solid-liquid separation step, and the lignin composition obtained thereby can be subjected to a drying step in which the solvent (for example, the organic solvent A) remaining in the lignin composition is removed and refined.

[0160] The drying step can be performed by, for example, heating to about 50 to 250°C, usually about 100 to 180°C, under a reduced pressure of about 0.1 to 10 kPa, usually about 1.0 to 5.0 kPa, and performing vacuum drying or the like under a solid or molten state. In addition, the drying step can be performed by directly performing the same vacuum drying or the like under a reduced pressure on the lignin composition in a flow state after the distillation by heating.

[0161] In addition, the drying step is not limited to the aforementioned pressure reduction drying, and can be performed by, for example, blowing air to the lignin composition under normal pressure and under a non-reactive atmosphere (for example, under a nitrogen atmosphere) to remove the solvent remaining in the lignin composition. In addition, the drying step is not limited to the aforementioned pressure reduction drying, and can be performed by, for example, blowing air to the lignin composition under normal pressure and under a non-reactive atmosphere (for example, under a nitrogen atmosphere) to remove the solvent remaining in the lignin composition.

[0162] As the drying device used in the drying, a thin film dryer such as a tray dryer, a drum dryer, a paddle dryer, a stirring dryer, a devolatilization extruder, a twin-screw continuous kneader, and the like can be exemplified. These drying devices can be used alone or two or more devices can be used in combination.

[0163] By using the aforementioned drying device for drying, the solvent remaining in the lignin composition can be efficiently and effectively removed. Therefore, even if the lignin composition obtained by the drying step is not reprecipitated, a lignin composition in which the residual amount of the solvent component such as the organic solvent used in the extraction step can be effectively reduced can be obtained.

[0164] The lignin composition obtained by distillation or reduced pressure drying is preferably not reprecipitated. Thereby, the lignin composition containing the compound represented by the aforementioned formula (1) in the aforementioned content range can be easily obtained.

[0165] In addition, in the purification step, the aforementioned filtration, distillation, and reduced pressure drying can be performed singly or two or more in combination.

[0166] The organic solvent remaining in the lignin composition is not particularly limited, and is generally less than 30% by mass, preferably less than 10% by mass, more preferably less than 5% by mass, and further preferably less than 1% by mass, relative to the total amount thereof.

[0167] By the production method of the lignin composition of the present application, of the content of the lignin contained in the saccharified residue of the plant-derived biomass and the fermented residue of the plant-derived biomass, preferably 50% by mass or more is taken out in the form of the lignin composition, more preferably 60% by mass or more, further preferably 70% by mass or more, more further preferably 80% by mass or more, and more further preferably 90% by mass or more.

[0168] The lignin composition of the present application can be used as a molding material for various resins or rubbers. For example, it can be used as a modifier for thermosetting resins, a crosslinking reaction promoter, a rubber reinforcing material.

[0169] [Thermosetting resin composition]

[0170] The thermosetting resin composition (molding material) according to one embodiment of the present application contains the aforementioned lignin composition of the present application and a thermosetting resin. Note that the use of the lignin composition is also included in the production process of the thermosetting resin.

[0171] As the thermosetting resin, for example, phenol resin, urethane resin, epoxy resin, urea (urea) resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, alkyd resin, polyimide can be exemplified.

[0172] Among these, from the aspect that it can react with the lignin composition and also can be used as a diluent, phenol resin, urethane resin, epoxy resin are preferable, phenol resin, urethane resin are more preferable, and phenol resin is further preferable. Among the phenol resins, novolak-based phenol resin and resol-based phenol resin are more preferable, and novolak-based phenol resin is further preferable.

[0173] These thermosetting resins can be used singly or in combination of two or more.

[0174] As an example of the epoxy resin, glycidyl ether-based epoxy resins synthesized from a compound having two or more hydroxyl groups in the molecule such as 2,2-bis(4'-hydroxyphenyl)propane (referred to as bisphenol A), bis(2-hydroxyphenyl)methane (referred to as bisphenol F), 4,4'-dihydroxydiphenyl sulfone (referred to as bisphenol S), 4,4'-dihydroxydiphenyl, resorcinol, saligenin, trihydroxydiphenyl dimethylmethane, tetrahydroxyphenyl ethane, halogen-substituted and alkyl-substituted derivatives thereof, butanediol, ethylene glycol, sugar alcohol, novolak, glycerol, polyoxyalkane, and the like, and an epoxy chloropropane or the like; glycidyl ester-based epoxy resins synthesized from the compound having two or more hydroxyl groups in the molecule and a glycidyl phthalate or the like; glycidyl amine-based epoxy resins synthesized from a primary or secondary amine such as aniline, diamino diphenyl methane, m-xylylenediamine, 1,3-bisaminomethylcyclohexane, and the like, and epichlorohydrin or the like; epoxy resins containing a glycidyl group such as glycidyl amine-based epoxy resins; epoxy soybean oil, epoxy polyolefin, vinylcyclohexene dioxide, dicyclopentadiene dioxide, and the like, which do not contain a glycidyl group, can be exemplified.

[0175] Among these, phenol novolak type epoxy resins and phenol novolak type epoxy resins, which are compatible well due to the chemical structure similar to lignin, are preferable.

[0176] The content of the lignin composition in the thermosetting resin composition can be determined as desired, and from the viewpoint of obtaining good physical properties and moldability, 5 to 300 parts by mass, more preferably 10 to 100 parts by mass, and further preferably 20 to 100 parts by mass, relative to 100 parts by mass of the thermosetting resin, are preferable.

[0177] (Filler)

[0178] In one embodiment, the thermosetting resin composition can further contain a filler material. The filler material can be an inorganic filler material or an organic filler material.

[0179] As the inorganic filler, there can be mentioned, for example, spherical or crushed fused silica, crystalline silica, and the like; alumina powder, glass powder, glass fiber, glass flake, mica, talc, calcium carbonate, alumina, hydrated alumina, boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, magnesium oxide, and the like.

[0180] Further, as the organic filler, there can be mentioned, for example, carbon fiber, aramid fiber, paper powder, wood powder, cellulose fiber, cellulose powder, rice husk powder, fruit shell and nut powder, chitin powder, starch, and the like.

[0181] The inorganic filler and the organic filler can be used singly or in combination of two or more, and the content thereof is determined depending on the purpose. In the case where the inorganic filler and / or the organic filler is contained, it is desirable that the content of the inorganic filler and / or the organic filler be appropriate in order to obtain good physical properties and moldability. From this viewpoint, the content of the inorganic filler and / or the organic filler is preferably 50 to 200 parts by mass, and more preferably 80 to 150 parts by mass, relative to 100 parts by mass of the total of the thermosetting resin and the lignin composition.

[0182] (Curing agent)

[0183] The thermosetting resin composition can further contain a curing agent.

[0184] In the case where the thermosetting resin is a phenol resin, as the curing agent, there can be mentioned hexamethylenetetramine (hexamine), hexamethylene triperoxide, paraformaldehyde, and the like. They can be used singly or in combination of two or more.

[0185] In the case where the thermosetting resin is a urethane resin, as the curing agent, as the polyisocyanate, there can be mentioned toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), polymeric MDI (MDI-CR), carbodiimide-modified MDI (liquid MDI), and the like aromatic polyisocyanates, and norbornane diisocyanate (NBDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4'-methylenebis(cyclohexyl isocyanate) (hydrogenated MDI), xylylene diisocyanate (XDI), and the like aliphatic polyisocyanates, blocked isocyanate, and the like. They can be used singly or in combination of two or more.

[0186] In the case where the thermosetting resin is an epoxy resin, the lignin composition is used as the curing agent, and in this case, the epoxy resin and the novolak-based phenol resin can be used in combination.

[0187] On the basis of the use of the curing agent, in order to further increase the curing speed and the degree of curing, inorganic bases such as calcium hydroxide, sodium hydroxide, potassium hydroxide, calcium oxide, and magnesium oxide; Lewis acids such as zinc chloride and zinc acetate; catalysts such as triethylamine; organometallic catalysts such as zirconium and aluminum; dibutyltin laurate, phenoxide of DBU, octoate, amines, imidazoles, ammonium salts, phosphines, and phosphonium salts can be used. One or two or more of them can be used in combination.

[0188] (Other additives)

[0189] In the thermosetting resin composition described in the present embodiment, various additives can be added within a range that does not impair the properties of the molded body obtained from the thermosetting resin composition. In addition, a compatibilizer, a surfactant, or the like can be further added according to the purpose.

[0190] As the compatibilizer, a resin having a polar group introduced by adding maleic anhydride, epoxy, or the like to a thermoplastic resin, for example, a maleic anhydride-modified polyethylene resin, a maleic anhydride-modified polypropylene resin, and various commercially available compatibilizers can be used in combination.

[0191] In addition, as the surfactant, straight-chain aliphatic acids such as stearic acid, palmitic acid, and oleic acid; or branched and cyclic aliphatic acids formed with rosin, and the like can be exemplified, but are not particularly limited thereto.

[0192] Further, as the additive that can be compounded in addition to the above, a flexible agent, a heat stabilizer, an ultraviolet absorber, a flame retardant, an antistatic agent, an antifoaming agent, a thixotropy-imparting agent, a release agent, an antioxidant, a plasticizer, a low-stress agent, a coupling agent, a dye, a light scattering agent, a small amount of a thermoplastic resin, and the like can be exemplified. One or two or more of them can be used in combination.

[0193] (Mixing and molding)

[0194] The compounding and mixing of each component used in the thermosetting resin composition can be performed by pre-mixing using commonly used machines such as a ribbon blender, a drum, and the like, and using a method of a Henschel mixer, a Banbury mixer, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, a roll mixer, a co-kneader, and the like. The heating temperature at the time of mixing is usually appropriately selected within a range of 100 to 300°C.

[0195] As the method of molding the thermosetting resin composition, there is no particular limitation. For example, a press molding method, an injection molding method, a transfer molding method, a mold-in-mold method, an FRP molding method, and the like can be exemplified.

[0196] As examples of the molded body and the like obtained using the thermosetting resin composition, there can be mentioned thermal insulation materials (for housing, thermal insulation machines such as refrigerators, and for ships and vehicles), electronic parts, resin for fracturing sand, resin for coated sand, resin for impregnation, resin for lamination, prepreg, decorative board, bonding material, friction material, resin for FRP molding, adhesive, adhesive agent, paint, ink, sealing material, sliding material, carbon material, automobile parts, reinforcing material for automobile tires, OA machines, machines, information communication machines, industrial materials, and the like.

[0197] [Rubber composition]

[0198] The rubber composition according to one embodiment of the present application contains the above-described lignin composition of the present application and a rubber material.

[0199] As the rubber material, there can be mentioned, for example, various natural rubbers, various synthetic rubbers, and the like. Specifically, there can be mentioned natural rubber (NR), modified natural rubber, styrene butadiene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), butyl rubber (IIR), ethylene propylene diene rubber (EPDM), acrylonitrile butadiene rubber (NBR), chlorobutadiene rubber (CR). One of them can be used, and two or more of them can also be used in combination.

[0200] The amount of the rubber material to be added is not particularly limited, and is preferably 100 to 10,000 parts by mass relative to 100 parts by mass of the lignin composition. Thereby, the reinforcing effect of the rubber composition can be sufficiently ensured, and the hardness of the rubber composition can be inhibited from becoming excessively high and the elongation can be inhibited from becoming small.

[0201] In the rubber composition according to the present embodiment, in addition to the above-described components, a filler can be contained. As the filler, a filler generally used in rubber compositions, such as carbon black, silicon dioxide, aluminum oxide, cellulose fiber, and the like, can be used.

[0202] The content of the filler is preferably 10 to 150 parts by mass relative to 100 parts by mass of the rubber material.

[0203] In addition, in one embodiment, the rubber composition can contain a crosslinking agent.

[0204] As the crosslinking agent, there is no particular limitation as long as it can be crosslinked with either or both of the rubber material and the lignin composition.

[0205] Further, the rubber composition can contain, for example, a softening agent, a thickening agent, an antioxidant, an anti-ozone deterioration agent, an age resistor, sulfur or other vulcanizing agent, a vulcanization accelerator, a vulcanization aid, a peroxide, zinc oxide, stearic acid.

[0206] The rubber composition can be manufactured by, for example, mixing the rubber material, the lignin composition, and other raw materials. Note that, if necessary, the raw materials can be premixed and then mixed. The order in which the raw materials are mixed is not particularly limited, and all of the raw materials can be mixed at the same time, or the raw materials can be mixed sequentially in any order.

[0207] The cured product (molded body) of the rubber composition can be obtained by molding the rubber composition and curing it. The molding method varies depending on the use, and thus is not particularly limited. In the case of molding using a mold, the rubber composition is molded using a mold provided with an oil pressure press. Thus, a cured product of the rubber composition molded into a target shape is obtained.

[0208] The molded body obtained by curing the rubber composition of the present embodiment can be used in tires and the like.

[0209] Example

[0210] [Production of Lignin Composition]

[0211] Example 1

[0212] (1) Extraction Step

[0213] 100 parts by mass (68 parts by mass in terms of lignin) of the saccharified residue of non-edible plant biomass (lignin content: 68% by mass) and 272 parts by mass of phenol were charged into a stirrable pressure-resistant container, heated and stirred at 0.8 MPa and 220°C for 4 hours.

[0214] (2) Refining Step

[0215] (2-1) Filtration

[0216] After dilution with acetone, the extract obtained by the above extraction step was charged into a pressure filter equipped with No. 2 filter paper, pressurized to 0.1 to 0.4 MPa with compressed air or nitrogen, and filtered.

[0217] (2-2) Distillation

[0218] The filtrate obtained in the above (2-1) was heated (40 to 60°C) under reduced pressure (5 to 10 kPa) using an evaporator to perform reduced pressure distillation to remove acetone. In addition, the evaporator was used to perform reduced pressure distillation by heating (100 to 140°C) under reduced pressure to remove phenol.

[0219] (2-3) Reduced Pressure Drying

[0220] To remove the phenol remaining in the above (2-2), vacuum drying was performed under reduced pressure (1.0 to 5.0 kPa) with heating (120 to 150°C) to remove the phenol, and a lignin composition was obtained.

[0221] Example 2

[0222] A lignin composition was obtained in the same manner as in Example 1, except that the phenol was set to 245 parts by mass, the water was set to 27 parts by mass, the extraction pressure was set to 1.7 MPa, and the extraction time was set to 2 hours.

[0223] Example 3

[0224] A lignin composition was obtained in the same manner as in Example 1, except that the phenol was set to 55 parts by mass, the water was set to 27 parts by mass, the ethanol was set to 190 parts by mass, the extraction pressure was set to 2.8 MPa, and the extraction time was set to 2 hours.

[0225] Comparative Example 1

[0226] Bagasse (a material obtained by drying the juice-pressing residue of sugar cane) 500 g was heat-treated in the presence of 1-butanol 2100 mL and water 3300 mL at 200°C for 2 hours. Filtration (No. 2 filter paper) was performed, and a solid containing cellulose was removed. The water layer was separated from the filtrate, and the 1-butanol layer was taken out. The taken-out 1-butanol layer was concentrated and dried, and thus a lignin was obtained.

[0227] Comparative Example 2

[0228] Evaluation was performed on kraft lignin (Lignin, alkali manufactured by SIGMA-ALDRICH, product number 370959).

[0229] [Analysis of the lignin composition]

[0230] Evaluation was performed on the lignin compositions of Examples 1 to 3 and Comparative Examples 1 and 2, and the like, on the following matters.

[0231] (1) Average molecular weight

[0232] The number average molecular weight Mn, the weight average molecular weight Mw, the Z average molecular weight Mz, and the molecular weight distribution (Mw / Mn) were measured using gel permeation chromatography (GPC). Specifically, a measurement sample was prepared by dissolving a sample in tetrahydrofuran. To a GPC system "HLC-8220 GPC (manufactured by Tosoh Corporation)" or "HLC-8420 GPC (manufactured by Tosoh Corporation)" in which two organic general-purpose columns "TSKgel GMHXL (manufactured by Tosoh Corporation) added with a styrene-based polymer filler" and "G2000HXL (manufactured by Tosoh Corporation)" were connected in series, 100 μL of the measurement sample was injected, tetrahydrofuran as an eluent was developed at 40°C at a rate of 1.0 mL / min, and the retention time was measured using a differential refractive index (RI).

[0233] Each average molecular weight of the sample was calculated from a standard curve representing the relationship between the retention time and the molecular weight of a standard polystyrene prepared separately.

[0234] As the standard polystyrene used for preparing the standard curve, the following substances were used.

[0235] Standard curve: standard polystyrene, manufactured by Tosoh Corporation, "TSKgel" (weight average molecular weight: 590 (type: A-500), 1,010 (type: A-1000), 2,630 (type: A-2500), 5,970 (type: A-5000), 10,200 (type: F-1), 18,100 (type: F-2), 37,900 (type: F-4), 96,400 (type: F-10), 190,000 (type: F-20), 427,000 (type: F-40), 706,000 (type: F-80), 1,090,000 (type: F-128), 4,480,000 (type: F-450))

[0236] Note that the kraft lignin of Comparative Example 2 produced a part of insoluble components in tetrahydrofuran, and therefore, the soluble components were used as the analysis target.

[0237] From the spectrum of the molecular weight of the sample calculated using GPC, the following items (a) to (d) were calculated.

[0238] (a) The molecular weight LogM of the peak maximum value when the molecular weight LogM is 2.4 to 2.6

[0239] (the peak when the molecular weight LogM is 2.4 to 2.6)

[0240] The value of the molecular weight LogM at which the peak maximum value of the differential distribution value (dw / dLogM) appears in the spectrum of the molecular weight of the sample calculated using GPC (spectrum plotted with the y-axis as dw / dLogM and the x-axis as LogM) is set as "peak at molecular weight LogM 2.4-2.6".

[0241] (b) maximum value of the differential distribution value (dw / dLogM)

[0242] In the spectrum of the differential distribution value of the molecular weight calculated using GPC (spectrum plotted with the y-axis as dw / dLogM and the x-axis as LogM) for the sample of Example 1, the maximum value of the differential distribution value (dw / dLogM) at which the peak appears at a molecular weight LogM of 2.4-2.6 is set as "maximum value of the differential distribution value (dw / dLogM)".

[0243] Figure 1 The spectrum of the differential distribution value of the molecular weight calculated using GPC (spectrum plotted with the y-axis as dw / dLogM and the x-axis as LogM) for the sample of Example 1 is shown in FIG. 1.

[0244] Figure 1 In the spectrum of the differential distribution value of the molecular weight calculated using GPC (spectrum plotted with the y-axis as dw / dLogM and the x-axis as LogM) for the sample of Example 1, the peak of the differential distribution value (dw / dLogM) appears at LogM = 2.5 at a molecular weight LogM of 2.4-2.6, and this differential distribution value (dw / dLogM) is set as "maximum value of the differential distribution value (dw / dLogM)".

[0245] (c) integral distribution value (%) at a molecular weight LogM of 2.4 and integral distribution value (%) at a molecular weight LogM of 2.55

[0246] In the spectrum of the molecular weight of the sample calculated using GPC (spectrum plotted with the y-axis as the integral distribution value (%) and the x-axis as LogM), the integral distribution value (%) at a molecular weight LogM of 2.4 and the integral distribution value (%) at a molecular weight LogM of 2.55 are set as "integral distribution value at a molecular weight LogM of 2.4" and "integral distribution value at a molecular weight LogM of 2.55", respectively.

[0247] (d) integral distribution value (%) 2.55-2.4

[0248] The value of the difference obtained by subtracting the integral distribution value (%) at a molecular weight LogM of 2.4 from the integral distribution value (%) at a molecular weight LogM of 2.55 is set as "integral distribution value (%) 2.55-2.4".

[0249] Figure 2A graph (y axis: integral distribution value (%), x axis: Log M) showing the integral distribution value of the molecular weight calculated using GPC for the sample of Example 1 is shown in FIG. 1.

[0250] Figure 2 In FIG. 1, the integral distribution value at a molecular weight Log M of 2.4 is 4.8 (%), the integral distribution value at a molecular weight Log M of 2.55 is 16.8 (%), and the difference between these (integral distribution value (%) at a molecular weight Log M of 2.55 - integral distribution value (%) at a molecular weight Log M of 2.4) is set as "integral distribution value (%) 2.55-2.4".

[0251] (2) Phenol content

[0252] The phenol content was measured using high-performance liquid chromatography (HPLC). Specifically, a sample such as the lignin composition, 50 mg, was dissolved in tetrahydrofuran, 0.5 mL, and a mixed solvent of water / acetonitrile at 4 / 1 (volume ratio), 4.5 mL, was added, and the mixture was stirred for 30 minutes, and the supernatant was filtered to prepare a measurement sample. The measurement sample, 1 μL, was injected into "ACQUITY UPLC H-CLASS" connected to a BEH C18 (1.7 μm x 2.1 mm x 50 mm) column. The column temperature was set to 40°C, and a mixed solvent of 2 mM aqueous ammonium acetate (A) and acetonitrile (B) was used as the mobile phase, and the flow rate ratio (A:B) was gradually changed from 80:20 to 10:90 using a gradient method, and the measurement was performed using a UV-visible spectrometer (UV) detector at 280 nm. The phenol content in the sample was calculated from a standard curve prepared using a standard phenol solution.

[0253] (3) Phenol dimer (compounds represented by formulae (1) and (2))

[0254] The phenol dimer content was measured using liquid chromatography-mass spectrometry (LC / MS). Specifically, a sample such as the lignin composition, 50 mg, was dissolved in tetrahydrofuran, 0.5 mL, and a mixed solvent of water / acetonitrile at 4 / 1 (volume ratio), 4.5 mL, was added, and the mixture was stirred for 30 minutes, and the supernatant was filtered to prepare a measurement sample. The measurement sample, 1 μL, was injected into an LC-MS system of "ACQUITY UPLC H-CLASS" connected to a BEH C18 (1.7 μm x 2.1 mm x 50 mm) column and "Xevo G2-XS QTof" mounted in the detection section. The column temperature was set to 40°C, and a mixed solvent of 2 mM aqueous ammonium acetate (A) and acetonitrile (B) was used as the mobile phase, and the dimer component was separated using a gradient method in which the flow rate ratio (A:B) was gradually changed from 80:20 to 10:90.

[0255] The resulting dimer components were ionized using an electrospray ionizer, and the mass-to-charge ratio in the range of 50 to 1000 was measured using a negative mode quadrupole-time-of-flight mass spectrometer.

[0256] Assuming that all the compounds were detected as deprotonated bodies, the structures of the dimer contained in the sample were determined as the following compounds (a) to (h) and compound (2) based on the mass-to-charge ratio.

[0257] The chromatogram was extracted based on the mass-to-charge ratio corresponding to the structure of each compound, and the peak area was calculated.

[0258] The content of the phenol dimer components in the sample was calculated based on a standard curve of a standard 2,2'-dihydroxydiphenylmethane solution prepared separately.

[0259] [Chemical 8]

[0260]

[0261] (4) Softening point

[0262] The sample such as the lignin composition was crushed with a mortar, and 10 to 20 mg of the crushed sample was put into an aluminum cup (circular upper portion lower portion ). The aluminum cup containing the sample was placed on a hot plate (IKA C-MAG HP7), and was capped with an aluminum foil. After heating to 100°C, the temperature was increased at 10°C intervals, and visual observation was performed. The temperature at which dissolution occurred was used as the softening point.

[0263] (5) Differential scanning calorimetry (DSC) measurement

[0264] A vial was prepared by mixing 100 parts by weight of lignin or phenol-aldehyde resin and 15 parts by weight of hexamethylenetetramine (reagent special grade), and adding 500 parts by weight of methanol and acetone, respectively, and shaking for 5 minutes. Thereafter, the vial was heated at 40°C, and 100 parts by weight of methanol was further added and shaken to completely dissolve the solid components. The resulting solution was air-dried overnight, and the solvent was completely removed using a vacuum drier at 40°C. The resulting lignin / hexamethylenetetramine mixture was crushed with a mortar to obtain a measurement sample.

[0265] In the differential scanning calorimetry measurement (DSC), a GCA-0017 manufactured by Hitachi High-Technologies Corporation was used. 10 mg of the measurement sample prepared by the above method was sealed in an Al-sealed container (15 μL), and measurement was performed under the conditions of a measurement range: 30 to 240°C, and a measurement atmosphere: nitrogen (100 mL / min). As a reference, Al2O3 (10 mg) was used. Based on the results, the curing exothermic peak temperature and the heat of exotherm were calculated.

[0266] For reference, the peak temperature of DSC of the phenol resin (manufactured by Sumitomo Bakelite Co., Ltd., product name: PR-53195) was 143°C, and the peak area was 117 J / g.

[0267] The evaluation results are shown in Table 1.

[0268] [Table 1]

[0269]

[0270] The DSC curve of the lignin composition of Example 2 and the lignin of Comparative Example 1 is shown in Figure 3 . According to Figure 3 It was confirmed that the peak temperature of the lignin composition of Example 2 shifted to the low temperature side compared to the lignin of Comparative Example 1. This is because the lignin composition of Example 2 started the curing reaction at a lower temperature, showing higher reactivity closer to that of the phenol resin, and thus, it was expected that the uniformity of the molded body of the resin composition containing the lignin composition and the phenol resin would be improved.

[0271] In addition, the peak area of the lignin composition of Example 2 was wide (i.e., the heat of reaction was large) compared to the lignin of Comparative Example 1. This indicates that the reactivity was high. Thus, in the case where the lignin composition of Example 2 was used for a thermosetting resin molding material, it was expected that the crosslinking reaction would be promoted.

[0272] [Resin composition and molded body]

[0273] Example 4

[0274] (1) Preparation of resin composition

[0275] A separable flask equipped with a stirrer was charged with a phenol resin (manufactured by Sumitomo Bakelite Co., Ltd., product name: PR-53195, softening point: 115°C) and the lignin composition produced in Example 1 in such a manner that the mass ratio (phenol resin: lignin composition) became 7:3. The temperature was raised to 130°C, and the mixture was stirred in a molten state for 30 minutes. The treated product was taken out from the flask in a molten state, and a mixture of the lignin composition and the phenol resin was obtained.

[0276] To 50 parts by mass of the obtained mixture at normal temperature, 7 parts by mass of hexamethylenetetramine (curing agent: manufactured by Kanto Chemical Co., Inc.) was added, and mixed using a kneader for 5 minutes.

[0277] Thereafter, 50 parts by mass of glass fiber (glass milled fiber, manufactured by Nitto Boseki Co., Ltd., PF80E-401) as a filler material and 1 part by mass of magnesium stearate (lubricant: manufactured by ADEKA Co., Ltd.) and 1 part by mass of magnesium oxide (promoter: manufactured by Seiko Chemical Co., Ltd.) as an additive were compounded, and mixed using a kneader for about 5 minutes.

[0278] The obtained mixture was kneaded with a heated roll at 120°C for 7 minutes, and after cooling, pulverized to obtain a resin composition (molding material). The composition of the resin composition is shown in Table 2.

[0279] (2) Evaluation of flowability of the resin composition (spiral flow)

[0280] The obtained resin composition was compressed at room temperature at 15 tf to make a flat plate. After preheating (preheating) at 90°C for 10 minutes in a hot air circulation oven, it was put into a transfer molding machine (MF-O15: manufactured by Maruichi).

[0281] The length of flow of the resin composition was measured by performing molding at 165°C, 40 MPa, and 5 minutes with respect to a spiral flow mold. The evaluation results are shown in Table 2.

[0282] (3) Molding of the resin composition

[0283] The resin composition prepared in the above (1) was compressed at room temperature at 15 tf to make a flat plate. After preheating the flat plate at 90°C for 10 minutes in a hot air circulation oven, it was put into a transfer molding machine (MF-O15: manufactured by Maruichi).

[0284] Transfer molding was performed at 165°C, 40 MPa, and 3 minutes with respect to a test piece mold (10 mm x 80 mm x thickness 4 mm). Thereafter, heat treatment was performed at 180°C for 8 hours, whereby a molded body (cured product of a phenol-modified lignin resin composition) was obtained.

[0285] (4) Evaluation of physical properties of the molded body

[0286] With respect to the molded body (test piece) obtained in the above (3), the bending elastic modulus, the bending strength, and the bending deformation were measured in accordance with JIS K 7171 "Calculation method of bending properties of plastics". Specifically, a three-point bending test was performed using a universal material testing machine (Model 5966, manufactured by Instron Corporation) under conditions of a speed of 2 mm / minute and a distance between supports of 64 mm.

[0287] In addition, with respect to the moldability, evaluation was performed in accordance with the following criteria.

[0288] A: Good

[0289] B: Slight overflow from the mold, but the quality was not a problem

[0290] C: Partial lack of material

[0291] D: Complete lack of material

[0292] E: Overflow from the mold, quality in an unacceptable range

[0293] Further, the inside of the molded body was visually evaluated for the voids by X-ray CT. The case where the voids were uniformly present in the inside of the molded body was set as "Y", and the case where there were no voids or the voids were present only in a part of the molded body was set as "X".

[0294] The evaluation results are shown in Table 2.

[0295] [Table 2]

[0296]

[0297] Examples 5, 6 and Comparative Examples 3, 4

[0298] In the preparation of the resin composition, instead of the lignin composition produced in Example 1, the lignin composition or lignin of Examples 2, 3, Comparative Examples 1 and 2 was used, and otherwise, the same operation as in Example 4 was performed to produce the resin composition and the molded body, and evaluation was performed.

[0299] The above, several embodiments and / or examples of the present application are described in detail, but those skilled in the art can easily apply various modifications to the embodiments and / or examples as their examples within the scope of the present application without departing from the spirit of the present application. Therefore, these various modifications are included in the scope of the present application.

[0300] The entire contents of the documents described in this specification and the application based on the priority of the Paris Convention which is the basis of this application are incorporated by reference.

Claims

1. A lignin composition comprising two or more compounds selected from compounds (a) to (h) below, The total content of the compound is 0.06% by mass or more. The weight-average molecular weight (Mw) of the composition is 1000–3000. The molecular weight LogM of the lignin composition, as determined by gel permeation chromatography (GPC), is such that the peak value of the differential distribution dw / dLogM in the range of 2.4–2.6 is greater than 50 and less than 150, or the difference in the percentage of the integral distribution values ​​when the molecular weight LogM is between 2.4 and 2.55 is greater than 5 and less than 15. [Chemistry 10] 2. The lignin composition according to claim 1, wherein the molecular weight distribution Mw / Mn is 2.2 to 3.

5.

3. The lignin composition according to claim 1, wherein the molecular weight distribution Mw / Mn is 2.5 to 3.

0.

4. The lignin composition according to claim 1 or 2, wherein, The total content of compounds (a) to (h) is 0.1% by mass or more.

5. The lignin composition according to claim 1 or 2, wherein, The total content of compounds (a) to (h) is less than 5% by mass.

6. The lignin composition according to claim 1 or 2, wherein, The total content of compounds (a) to (h) is less than 2% by mass.

7. The lignin composition according to claim 1 or 2, wherein, The content of the following compound (2) is less than 0.1% by mass. [Chemistry 11] 。 8. The lignin composition according to claim 1 or 2, wherein, The content of free phenol monomer is 0.02% by mass or more and 5.0% by mass or less.

9. The lignin composition according to claim 1 or 2, wherein the softening point is above 100°C and below 250°C.

10. A thermosetting resin composition comprising the lignin composition and thermosetting resin as described in any one of claims 1 to 9.

11. The thermosetting resin composition according to claim 10, wherein, The thermosetting resin is selected from one or more of phenolic resin, urethane resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, alkyd resin and polyimide.

12. The thermosetting resin composition according to claim 10 or 11, wherein, The content of the lignin composition is 5 to 300 parts by weight relative to 100 parts by weight of the thermosetting resin.

13. The thermosetting resin composition according to claim 10 or 11, further comprising a filler material.

14. The thermosetting resin composition according to claim 13, wherein, The filler material is an inorganic filler material selected from any one or more of the following: spherical or broken fused silica, crystalline silica, alumina powder, glass powder, glass fiber, glass flakes, mica, talc, calcium carbonate, alumina, hydrated alumina, boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, and magnesium oxide.

15. The thermosetting resin composition according to claim 13, wherein, The filler material is an organic filler material selected from any one or more of the following: aramid fiber, paper powder, wood powder, cellulose fiber, cellulose powder, rice husk powder, fruit shell, nut powder, chitin powder, and starch.

16. The thermosetting resin composition according to claim 13, wherein, The filling material is carbon fiber.

17. The thermosetting resin composition according to claim 13, wherein, The content of the filler material is 50 to 200 parts by weight relative to the total of 100 parts by weight of the thermosetting resin and the lignin composition.

18. The thermosetting resin composition according to claim 10 or 11, further comprising a curing agent.

19. The thermosetting resin composition according to claim 10 or 11, comprising the lignin composition, phenolic resin, and a curing agent, wherein the curing agent is selected from one or more of hexamethylenetetramine, hexaformaldehyde, and paraformaldehyde.

20. The thermosetting resin composition according to claim 10 or 11, comprising the lignin composition, a urethane resin, and a curing agent, wherein the curing agent is selected from one or more of toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, polymeric 4,4'-diphenylmethane diisocyanate, carbodiimide-modified 4,4'-diphenylmethane diisocyanate, norbornene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), phenyldimethyl diisocyanate, and capped isocyanates.

21. The thermosetting resin composition of claim 18, comprising the lignin composition and an epoxy resin, wherein the lignin composition is used as the curing agent.

22. Use of the lignin composition according to any one of claims 1 to 9, for promoting a crosslinking reaction in a thermosetting resin molding material comprising a thermosetting resin.

23. Use of the lignin composition according to claim 22, wherein, The thermosetting resin is selected from one or more of phenolic resin, urethane resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, alkyd resin and polyimide.

24. Methods, in which, The lignin composition of any one of claims 1 to 9 is used to promote the crosslinking reaction in thermosetting resin molding materials containing thermosetting resins.

25. A thermosetting resin modifier or crosslinking reaction accelerator comprising the lignin composition according to any one of claims 1 to 9.

26. A rubber composition comprising the lignin composition and rubber material as described in any one of claims 1 to 9.

27. The rubber composition according to claim 26, wherein, The rubber material is selected from one or more of the following: natural rubber, modified natural rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, butyl rubber, ethylene propylene diene rubber, acrylonitrile butadiene rubber, and chloroprene rubber.

28. The rubber composition according to claim 26 or 27, wherein, The amount of rubber material added is 100 to 10,000 parts by weight relative to 100 parts by weight of the lignin composition.

29. A molded article obtained by curing the thermosetting resin composition of any one of claims 10 to 21 or the rubber composition of any one of claims 26 to 28.

30. A method for manufacturing the lignin composition according to any one of claims 1 to 9, comprising: an extraction step of extracting a lignin composition comprising an extract derived from lignin from a lignin-containing material using a solvent comprising an organic solvent of formula (I) below. Furthermore, no further sedimentation occurs during the refining process. [Chemistry 12] In the formula, R 31 ~R 35 Each of the following groups independently represents a hydrogen atom, a hydroxyl group, a hydrocarbon group with 1 to 15 carbon atoms, a hydrocarbon ether group with 1 to 15 carbon atoms, or a group containing a carbonyl group; R 31 ~R 35 Choose either the same or different, R c It is a hydroxyl or alkoxy group, wherein, R 31 ~R 35 At least one of them is a hydrogen atom. And R 31 ~R 35 At least one of them is a hydroxyl group, or R c It is a hydroxyl group.

31. The method for manufacturing the lignin composition according to claim 30, wherein, As the compound represented by formula (I), one or more compounds selected from phenol, catechol, resorcinol, hydroquinone, phloroglucinol, o-cresol, m-cresol, p-cresol, 2-ethylphenol, 2-propylphenol, 3-ethylphenol, 3-propylphenol, cashew nut shell powder, 4-ethylphenol, 4-propylphenol, 4-octylphenol, 4-nonylphenol, 5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol, 3,5-dimethylphenol, 3-methyl-5-ethylphenol, and 3,5-diethylphenol are used.

32. The method for manufacturing the lignin composition according to claim 30 or 31, wherein, The extraction temperature is above 140℃ and below 300℃.

33. The method for manufacturing the lignin composition according to claim 30 or 31 further comprises a refining step of performing one or more steps selected from solid-liquid separation, distillation and drying.

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