JP6217064B2 - Resin composition and resin molded body - Google Patents

Description

  The present invention relates to a resin composition and a resin molded body.

  Many wood-based waste materials (biomass) such as bark, thinned wood, and building waste have been disposed of so far. However, protection of the global environment is becoming an important issue, and from this point of view, the reuse and recycling of wood-based waste materials are being considered.

  Common woody main components are cellulose, hemicellulose and lignin. Among these, lignin contained at a ratio of about 30% has a structure containing abundant aromatic rings, phenolic hydroxyl groups, and alcoholic hydroxyl groups, and therefore, utilization as a resin raw material has been studied (for example, (See Patent Document 1).

  In Patent Document 1, lignin obtained through the Kraft method, acid / oxygen saccharification method, steaming / explosion method, solvent method, etc. is used as a curing agent, mixed with epoxidized linseed oil, and heat-treated. It is disclosed that the obtained composition is used as an insulating polymer material.

  However, in general, lignin often has substituents at the ortho-position and para-position of the phenol nucleus contained in the lignin, and the hydrogen of the phenolic hydroxyl group is protected by an alkyl group or the like. In many cases, the number of reaction points is small, the reaction with the crosslinking agent does not easily proceed, and the crosslinking density tends to be low. Therefore, the low molecular component of lignin may remain uncrosslinked, and in the case of a molding material that requires higher solvent resistance, crosslinking may be insufficient. In addition, it is conceivable to increase the amount of the epoxy compound added in order to achieve sufficient crosslinking, but in this case, the proportion of lignin in the resin composition decreases, so that the degree of plant origin decreases and the global environment decreases. The protective effect tends to be impaired, and the heat resistance such as the glass transition temperature may be lowered.

JP 2008-138061 A

  An object of the present invention is to provide a resin composition having a plant-derived component as a main material and excellent in heat resistance such as moldability and glass transition temperature without impairing solvent resistance, and a resin molded body. .

Such an object is achieved by the present inventions (1) to (11) below.
(1) a lignin derivative (A);
At least one crosslinking agent (B) selected from an epoxy compound and an isocyanate compound;
Containing at least one selected from quinuclidine, pyridine and hexamethylenetetramine, having a different crosslinking point from the crosslinking agent (B) and a different type of crosslinking agent (C);
A resin composition comprising:

(2) a lignin derivative (A),
At least one crosslinking agent (B) selected from an epoxy compound and an isocyanate compound;
Containing at least one of the compounds represented by the following formula (1), having a crosslinking point different from the crosslinking agent (B) and a different type of crosslinking agent (C);
A resin composition comprising:
_{Z- (CH 2 OR) m (} 1)
[Z in Formula (1) is any one of a melamine residue, a urea residue, a glycolyl residue, an imidazolidinone residue, and an aromatic ring residue. Moreover, m represents the integer of 2-14. R is independently an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. However, -CH 2 _OR, the nitrogen atom of the melamine residues, the nitrogen atom of the primary amino groups of the urea residues, the nitrogen atom of the secondary amino group of the glycolyl residues, the secondary amino group of the imidazolidinone residues It is directly bonded to either the nitrogen atom or the carbon atom of the aromatic ring residue. ]

［式（２）中、ＸはＣＨ_２ＯＲまたは水素原子であり、Ｒは独立して炭素数１〜４のアルキル基または水素原子である。また、ｎは１〜３の整数を表す。］

［式（３）中、Ｒは独立して炭素数１〜４のアルキル基または水素原子である。］

［式（４）中、Ｒは独立して炭素数１〜４のアルキル基または水素原子である。］

［式（５）中、Ｒは独立して炭素数１〜４のアルキル基または水素原子である。］ (3) a lignin derivative (A);
At least one crosslinking agent (B) selected from an epoxy compound and an isocyanate compound;
The following formulas (2) to (5) and at least one Tane含 chromatic those represented by any one of the crosslinking agent (B) and have different cross-linking points and different cross-linking agent (C), and
A resin composition comprising:

[In the formula (2), X is _CH 2 OR or a hydrogen atom, R is independently an alkyl group or a hydrogen atom having 1 to 4 carbon atoms. N represents an integer of 1 to 3. ]

[In Formula (3), R is a C1-C4 alkyl group or a hydrogen atom independently. ]

[In Formula (4), R is a C1-C4 alkyl group or a hydrogen atom independently. ]

[In Formula (5), R is a C1-C4 alkyl group or a hydrogen atom independently. ]

［式（６）中、ｎは１〜３の整数を表す。］

［式（７）中、ｎは１〜３の整数を表す。］ (4) lignin derivative (A),
At least one crosslinking agent (B) selected from an epoxy compound and an isocyanate compound;
A containing the formula (6) or (7), compounds represented by the cross-linking agent (B) and have different cross-linking points and different cross-linking agent (C), and
A resin composition comprising:

[In Formula (6), n represents the integer of 1-3. ]

[In formula (7), n represents the integer of 1-3. ]

(5) the epoxy compound and at least one crosslinking agent selected from isocyanate compound (B) to the above (1) those containing those obtained by epoxidizing a compound having an aromatic (4) The resin composition in any one.

(6) at least one crosslinking agent selected from the epoxy compound and the isocyanate compound (B) is in any of the above (1) those containing one functional group equivalent weight of 400 or less (5) The resin composition as described.

(7) The above (1) to (6), wherein the lignin derivative (A) contains one having a polystyrene-equivalent number average molecular weight of 200 to 2000 measured by gel permeation chromatography (GPC) analysis. The resin composition in any one of.

(8) The total content of at least one crosslinking agent (B) selected from the epoxy compound and isocyanate compound and the crosslinking agent (C) is 5 to 100 masses per 100 parts by mass of the lignin derivative (A). The resin composition according to any one of (1) to (7) , which is a part.

(9) The ratio [(B) / (C)] obtained by dividing the content of at least one crosslinking agent (B) selected from the epoxy compound and the isocyanate compound by the content of the crosslinking agent (C) is 1. The resin composition according to any one of the above (1) to (8) , which is ˜50.

(10) The resin composition according to any one of (1) to (9) , wherein the lignin derivative (A) contains a carboxyl group.

(11) A resin molded body, which is a molded body of the resin composition according to any one of (1) to (10) .

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition excellent in heat resistance, such as a moldability and a glass transition temperature, without using a plant-derived component as a main material and impairing solvent resistance, and a resin molding are obtained.

  Hereinafter, the resin composition and the resin molded body of the present invention will be described in detail based on preferred embodiments.

<Resin composition>
In the resin composition of the present invention, the lignin derivative (A), at least one crosslinking agent (B) selected from an epoxy compound and an isocyanate compound, and the crosslinking agent (B) have different crosslinking points and different types of crosslinking. And an agent (C).

  The resin composition of the present invention is used to obtain a resin molded body by being molded by various molding methods.

  Such a resin composition has high moldability because of its low melt viscosity, and is rich in moldability (shape transferability) when molded by, for example, various molding methods, and also has solvent resistance after curing by crosslinking. It will be excellent. For this reason, even when the shape of the mold is complicated, when the amount of filler added is large, or when a curing catalyst is added, a resin molded body with high dimensional accuracy and excellent heat resistance such as glass transition temperature is produced. can do. Moreover, since the resin composition has a high impregnation property with respect to the core material and can form a rigid structure after curing, a laminate having excellent durability and appearance can be produced.

  The solvent resistance means the resistance of the resin molding of the present invention to an organic solvent. The solvent resistance is obtained, for example, by immersing the resin molded body in an organic solvent for a certain period of time and then taking it out and drying it. Next, the weight of the resin molded body after drying is measured, and the weight reduction amount from the resin molded body before immersion is calculated. It can be evaluated that the smaller the weight loss, the higher the solvent resistance. The decrease in weight is considered to occur due to the elution of uncrosslinked components, low molecular components and the like in the resin molded body into the organic solvent.

Hereinafter, each component of the resin composition will be sequentially described.
(Lignin derivative (A))
First, the lignin derivative (A) will be described. Lignin, together with cellulose and hemicellulose, is a major component that forms the skeleton of plants and is one of the most abundant substances in nature. The lignin derivative (A) is a compound having a phenol derivative as a unit structure, and this unit structure has a chemically and biologically stable carbon-carbon bond or carbon-oxygen-carbon bond. Less susceptible to degradation and biological degradation. Therefore, the lignin derivative (A) is useful as a resin raw material.

  The lignin derivative (A) used in the present invention is obtained by decomposing biomass. Biomass is a plant or a processed product of a plant, and these are formed by capturing and fixing carbon dioxide in the atmosphere in the process of photosynthesis, and thus contribute to the suppression of the increase in carbon dioxide in the atmosphere. For this reason, it can contribute to suppression of global warming by utilizing biomass industrially.

  Examples of the treatment method for decomposing biomass used in the present invention to obtain a lignin derivative (A) include, for example, a method of treating a plant or a processed plant product with a chemical, a method of hydrolyzing, a steam explosion method, and a supercritical water treatment. Method, subcritical water treatment method, mechanical treatment method, cresol sulfate method, pulp production method, and the like. From the viewpoint of environmental load, a steam explosion method, a supercritical water treatment method, a subcritical water treatment method, and a mechanical treatment method are preferred. From the viewpoint of the purity of the obtained lignin derivative (A), the steam explosion method and the subcritical water treatment method are more preferable.

  Specific examples of the lignin derivative (A) include a guaiacylpropane structure represented by the following formula (8), a syringylpropane structure represented by the following formula (9), and 4-hydroxyphenylpropane represented by the following formula (10). Examples include the structure. From conifers, mainly guaiacylpropane structures, from broadleaf trees, mainly guaiacylpropane structures and syringylpropane structures, and from herbs, mainly guaiacylpropane structures, syringylpropane structures, and 4-hydroxy Each phenylpropane structure is extracted.

  Further, the lignin derivative (A) in the present invention is preferably one in which at least one of the ortho-position and para-position of the aromatic ring is unsubstituted with respect to the hydroxyl group. Such a lignin derivative (A) is excellent in reactivity because it contains many reaction sites where the curing agent acts by electrophilic substitution reaction to the aromatic ring, and steric hindrance can be reduced in the reaction with a hydroxyl group. It becomes.

  In addition to the above basic structure, the lignin derivative (A) may be a lignin derivative (A) having a functional group (lignin secondary derivative).

  The functional group possessed by the lignin secondary derivative is not particularly limited, but for example, those in which two or more of the same functional groups can react with each other or those capable of reacting with other functional groups are suitable. Specific examples include an epoxy group, a methylol group, a vinyl group having a carbon-carbon unsaturated bond, an ethynyl group, a maleimide group, a cyanate group, and an isocyanate group. Of these, the lignin derivative (A) having a methylol group introduced (methylolated) is preferably used. Such a lignin secondary derivative is self-cross-linked by a self-condensation reaction between methylol groups, and is more cross-linked to the alkoxymethyl group and hydroxyl group in the cross-linking agent (C). As a result, a cured product having a particularly homogeneous and rigid skeleton and excellent in solvent resistance can be obtained.

  Moreover, as for the lignin derivative (A) in this invention, the number average molecular weight of polystyrene conversion measured by gel permeation chromatography is preferable 200-2000, and what is 300-1800 is more preferable. Such a lignin derivative (A) having a number average molecular weight has a higher degree of compatibility between its reactivity (curability) and meltability or solubility. Therefore, a resin composition having a high degree of compatibility between solvent resistance and moldability after curing can be obtained.

  An example of a method for measuring the molecular weight by the gel permeation chromatography will be described.

  The lignin derivative (A) in the present invention is dissolved in a solvent to prepare a measurement sample. The solvent used at this time is not particularly limited as long as it can dissolve the lignin derivative (A), but for example, tetrahydrofuran is preferable from the viewpoint of measurement accuracy of gel permeation chromatography.

  Next, “TSKgelGMMHXL (manufactured by Tosoh)” and “G2000HXL (manufactured by Tosoh)”, which are organic general-purpose columns filled with a styrene polymer filler, are connected in series to the GPC system “HLC-8320GPC (manufactured by Tosoh)”. To do.

  200 μL of the above measurement sample is injected into this GPC system, and the eluent tetrahydrofuran is developed at 1.0 mL / min at 40 ° C., and is retained using differential refractive index (RI) and ultraviolet absorbance (UV). Measure time. The number average molecular weight of the lignin derivative (A) can be calculated from a calibration curve showing the relationship between the retention time and molecular weight of standard polystyrene prepared separately.

  The molecular weight of the standard polystyrene used for preparing the calibration curve is not particularly limited. For example, the number average molecular weight is 427,000, 190,000, 96,400, 37,900, 18,100. Standard polystyrene (manufactured by Tosoh) of 10,200, 5,970, 2,630, 1,050 and 500 can be used.

In addition, the lignin derivative (A) in the present invention, when subjected to ¹ H-NMR analysis, in the obtained chemical shift spectrum, the integrated value of the peak attributed to the aromatic proton is the peak attributed to the aliphatic proton. Is preferably about 15 to 50%, more preferably about 15 to 45%, still more preferably about 20 to 40%, and particularly preferably about 20 to 35%. . Thereby, the reactivity which contributes to the mechanical characteristic of the crosslinked resin of a lignin derivative (A) and the meltability which contributes to the moldability of a molding material, or the solubility to a solvent can be made compatible more highly. As a result, a resin molded body having high dimensional accuracy and excellent heat resistance such as glass transition temperature can be obtained.

  When the ratio is lower than the lower limit, the reaction site for causing the crosslinking reaction or the reaction site for introducing the reactive group is substituted with an aliphatic group and the number of crosslinking reaction points is reduced, so that the lignin derivative (A ) May be deteriorated in physical properties of the crosslinked product. On the other hand, when the ratio exceeds the upper limit, the meltability of the lignin derivative (A) or the solubility in a solvent is lowered, and the moldability of the molding material containing the lignin derivative (A) may be lowered.

In addition, since aromatic protons and aliphatic protons generate peaks at distant positions in the chemical shift spectrum of ¹ H-NMR analysis, peaks can be separated, and peak identification and integral calculation are performed. be able to.

  Specifically, when tetramethylsilane is used as a reference substance for analysis, generally, a peak attributed to an aromatic proton is located in the vicinity of 6 to 8 ppm. In addition, the peak attributed to the aliphatic proton is located in the vicinity of 0.5 to 5 ppm.

  Note that the integrated value of the peak attributed to the aromatic proton and the integrated value of the peak attributed to the aliphatic proton described above can be adjusted according to the biomass treatment conditions. For example, it is considered that the integrated value of the peak attributed to aromatic protons tends to increase by increasing the processing temperature and processing pressure of biomass or increasing the processing time.

  Furthermore, the lignin derivative (A) in the present invention preferably has a carboxyl group. In the case of having the carboxyl group, it acts as a catalyst for the crosslinking agent (C), so that the crosslinking reaction between the lignin derivative (A) and the crosslinking agent (C) can be promoted, so that the solvent resistance is excellent. .

In addition, when the lignin derivative (A) described above has a carboxyl group, the carboxyl group is confirmed by the presence or absence of absorption of a peak at 172 to 174 ppm when subjected to ¹³ C-NMR analysis belonging to the carboxyl group. can do.

  A part of the lignin derivative (A) of the resin composition of the present invention may be replaced with other resin components. Specific examples include an epoxy resin, a phenol resin, a furan resin, a urea resin, and a melamine resin. By including these resin components, the relative melt viscosity of the resin components is lowered, so that the moldability of the resin composition is improved. When these resin components are included, the content of the lignin derivative (A) is preferably adjusted to 50% by mass or more, more preferably 60% by mass or more before the crosslinking reaction.

(At least one crosslinking agent (B) selected from epoxy compounds and isocyanate compounds)
Next, at least one crosslinking agent (B) selected from an epoxy compound and an isocyanate compound (hereinafter also referred to as a crosslinking agent (B)) will be described.

  The crosslinking agent (B) can be crosslinked mainly by the reaction of the hydroxyl group of the lignin derivative (A) with an epoxy group or an isocyanate group. By crosslinking with the lignin derivative (A), heat resistance such as glass transition temperature can be improved without impairing solvent resistance.

  The epoxy compound of the crosslinking agent (B) refers to monomers, oligomers and polymers in general having two or more epoxy groups in one molecule.

  Various methods are mentioned about the preparation methods of the epoxy compound in this invention. From the viewpoint of versatility and cost, a method of epoxidizing a compound having a phenolic hydroxyl group is preferred.

  A method for epoxidizing the compound having a phenolic hydroxyl group will be described. It can be obtained by glycidyl etherification of a phenolic hydroxyl group of a phenolic resin using a predetermined compound. Although it will not specifically limit if it is a compound which can be glycidyl etherified, For example, epihalohydrins, such as epichlorohydrin, can be mentioned. Furthermore, the phenolic hydroxyl group can also be epoxidized by a method other than glycidyl etherification, that is, a method of epoxidation using another compound containing an epoxy group.

  In the present invention, as a method for glycidyl etherification of a phenolic resin, for example, a phenolic resin is dissolved and mixed with an excess of epihalohydrin such as epichlorohydrin or epibromohydrin, and sodium hydroxide or potassium hydroxide. The method of making it react at 20-120 degreeC for 1 to 10 hours, adding alkali metal hydroxides, such as, can be employ | adopted.

  At this time, as the alkali metal hydroxide, an aqueous solution thereof may be used. In that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and the solution is under reduced pressure or normal pressure. Then, water and epihalohydrin may be continuously distilled off, followed by liquid separation, water may be removed, and epihalohydrin may be continuously returned to the reaction system.

  In addition, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to a dissolved mixture of phenolic resin and epihalohydrin, and reacted at 50 to 150 ° C. for 1 to 5 hours. After obtaining a halohydrin etherified product, a method of adding a solid or aqueous solution of an alkali metal hydroxide and reacting at 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure) is adopted. You can also. In this case, the amount of the quaternary ammonium salt used is usually 1 to 10 g, preferably 2 to 8 g, with respect to 1 mol of the hydroxyl group of the phenolic resin.

  Usually, the amount of epihalohydrin used in these reactions is usually 1 to 20 mol, preferably 2 to 10 mol, per 1 equivalent of the hydroxyl group of the phenolic resin. The usage-amount of an alkali metal hydroxide is 0.8-1.5 mol normally with respect to 1 equivalent of hydroxyl groups of a phenol-type resin, Preferably it is 0.9-1.1 mol. Furthermore, in order to make the reaction proceed smoothly, it is preferable to carry out the reaction by adding an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide in addition to alcohols such as methanol and ethanol.

  When using alcohol, the amount of its use is 2-20 weight% normally with respect to the quantity of epihalohydrin, Preferably it is 4-15 weight%. Moreover, when using an aprotic polar solvent, it is 5 to 100 weight% normally with respect to the quantity of epihalohydrin, Preferably it is 10 to 90 weight%.

  After the reaction product of these glycidyl etherification reactions is washed with water or not, the epihalohydrin, the solvent, and the like are removed under heating and reduced pressure at 110 to 250 ° C. and a pressure of 10 mmHg or less. Furthermore, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is obtained. A further reaction can be carried out by adding an aqueous solution of to ensure ring closure. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.00, with respect to the hydroxyl group 1 equivalent ratio of the phenol-based condensate used in the present invention for glycidyl etherification. It is 05-0.2 mol. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After completion of the reaction, the generated salt is removed by filtration, washing with water, and the like, and further, a solvent such as toluene and isobutyl ketone is distilled off under heating and reduced pressure to obtain an epoxy resin constituting the epoxy resin material.

  Specifically, for example, biphenyl type epoxy resins, stilbene type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins and other bisphenol type epoxy resins, triphenolmethane type epoxy resins, alkyl-modified triphenolmethane type epoxy resins Epoxy having aromatic properties such as dicyclopentadiene modified phenolic epoxy resin, triazine nucleus-containing epoxy resin, phenol aralkyl epoxy resin, naphthol epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin Compound etc. are mentioned. One or a mixture of two or more of these may be used. Among these, bisphenol A type epoxy resins and cresol novolac type epoxy resins are preferred because of excellent heat resistance such as glass transition temperature.

  The isocyanate compound of the crosslinking agent (B) refers to monomers, oligomers and polymers in general having two or more isocyanate groups in one molecule.

  Specifically, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4-4′-diisocyanate, diphenylmethane-2 -4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4-4'-diisocyanate, and dicyclohexylmethane-2-4'-diisocyanate. One or a mixture of two or more of these may be used.

  Among the specific examples of the isocyanate compound, 2,4-tolylene diisocyanate, diphenylmethane-4-4′-diisocyanate, and hexamethylene diisocyanate are preferable from the viewpoint of moldability, and diphenylmethane diisocyanate is further preferable from the viewpoint of ensuring solvent resistance. preferable.

  The upper limit of the functional group equivalent of the crosslinking agent (B) is preferably 400 from the viewpoint of the action as a crosslinking agent, and more preferably 200 from the viewpoint of the crosslinking density. When the functional group equivalent exceeds the upper limit, the appearance may be impaired. Moreover, the lower limit value of the functional group equivalent of the crosslinking agent (B) is not particularly limited, but is preferably 50 or more practically.

(Crosslinking agent (C) having a different crosslinking point and different type from the crosslinking agent (B))
Next, the crosslinking agent (C) having a different crosslinking point and different type from the crosslinking agent (B) (hereinafter also referred to as crosslinking agent (C)) will be described. Here, the cross-linking agent (C) may be any one that is different in structure and type from the cross-linking agent (B).

  The crosslinking agent (C) contained in the resin composition of the present invention is capable of mainly crosslinking with the aromatic ring of the lignin derivative (A), and preferably contains a compound represented by the following formula (1). .

_{Z- (CH 2 OR) m (} 1)
[Z in Formula (1) is any one of a melamine residue, a urea residue, a glycolyl residue, an imidazolidinone residue, and an aromatic ring residue. Moreover, m represents the integer of 2-14. R is independently an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. However, -CH 2 _OR, the nitrogen atom of the melamine residues, the nitrogen atom of the primary amino groups of the urea residues, the nitrogen atom of the secondary amino group of the glycolyl residues, the secondary amino group of the imidazolidinone residues It is directly bonded to either the nitrogen atom or the carbon atom of the aromatic ring residue. ]

  A resin composition containing such a compound is excellent in mechanical properties after curing, and contributes to improvement in durability and appearance of the cured product. This is because the compound represented by the above formula (1) contained in the cross-linking agent (C) can form a polyfunctional cross-linking point, so that the lignin derivative (A) is cross-linked with high density and uniformity. This is because a homogeneous and rigid skeleton is formed. The rigid skeleton improves the heat resistance such as the glass transition temperature and the durability (boiling resistance, etc.) of the cured product, and suppresses the occurrence of blisters and cracks, thereby improving the appearance of the cured product.

  The crosslinking agent (C) has self-curing properties and can form a co-crosslinked structure with the lignin derivative (A). Therefore, a cured product obtained by molding and curing such a resin composition has good compatibility between the lignin derivative (A) and the cross-linking agent (C) and high homogeneity. Therefore, it is possible to optimize the blending ratio from the viewpoint of achieving both the moldability of the resin composition and the heat resistance such as the glass transition temperature of the cured product, and the resin has excellent heat resistance such as dimensional accuracy and glass transition temperature. A molded body is obtained.

  Further, since the volatile component is moderately generated during the crosslinking reaction, the crosslinking agent can suppress problems such as blisters and cracks that occur when the volatile component is released to the outside of the cured product. As a result, a resin molded body having an excellent appearance can be obtained.

  In addition, the said crosslinking agent (C) contributes to the improvement of the moldability of a resin composition. This is because the melting point of the cross-linking agent (C) is low, the viscosity of the molding material is lowered during heating, and the cross-linking agent (C) is relatively slow cross-linkable and gradually cross-links when heated. This is probably because the reaction proceeds.

In addition, as described above, —CH ₂ OR is a nitrogen atom of a melamine residue, a nitrogen atom of a primary amino group of a urea residue, a nitrogen atom of a secondary amino group of a glycolyl residue, or 2 of an imidazolidinone residue. It is directly bonded to either the nitrogen atom of the primary amino group or the carbon atom of the aromatic ring residue, but two or more “—CH ₂ OR” are bonded to the same nitrogen atom or carbon atom. In this case, it is preferable that “R” included in at least one of “—CH ₂ OR” is an alkyl group. Thereby, a lignin derivative (A) can be bridge | crosslinked reliably.

  In this specification, the melamine residue refers to a group having a melamine skeleton represented by the following formula (A).

  In this specification, the urea residue refers to a group having a urea skeleton represented by the following formula (B).

  In this specification, the glycolyl residue refers to a group having a glycolyl skeleton represented by the following formula (C).

  In the present specification, the imidazolidinone residue refers to a group having an imidazolidinone skeleton represented by the following formula (D).

  In this specification, an aromatic ring residue refers to a group having an aromatic ring (benzene ring).

  Moreover, especially as a compound represented by the said Formula (1), the compound represented by either of following formula (2)-(5) is used preferably. These react with the crosslinking reaction points on the aromatic ring contained in the phenol skeleton in the lignin derivative (A) to reliably crosslink the lignin derivative (A) and self-crosslink by self-condensation reaction between functional groups. Arise. As a result, a cured product having a particularly homogeneous and rigid skeleton and excellent in heat resistance such as glass transition temperature, durability and appearance can be obtained.

［式（２）中、ＸはＣＨ_２ＯＲまたは水素原子であり、Ｒは独立して炭素数１〜４のアルキル基または水素原子である。また、ｎは１〜３の整数を表す。］

[In the formula (2), X is _CH 2 OR or a hydrogen atom, R is independently an alkyl group or a hydrogen atom having 1 to 4 carbon atoms. N represents an integer of 1 to 3. ]

［式（３）中、Ｒは独立して炭素数１〜４のアルキル基または水素原子である。］

[In Formula (3), R is a C1-C4 alkyl group or a hydrogen atom independently. ]

［式（４）中、Ｒは独立して炭素数１〜４のアルキル基または水素原子である。］

[In Formula (4), R is a C1-C4 alkyl group or a hydrogen atom independently. ]

［式（５）中、Ｒは独立して炭素数１〜４のアルキル基または水素原子である。］

[In Formula (5), R is a C1-C4 alkyl group or a hydrogen atom independently. ]

  As the compound represented by the above formula (2), a compound represented by the following formula (6) or (7) is particularly preferably used. These react with a crosslinking reaction point on the aromatic ring contained in the phenol skeleton in the lignin derivative (A) to specifically crosslink the lignin derivative (A), and self-crosslink by self-condensation reaction between functional groups. Produce. As a result, a cured product having a particularly homogeneous and rigid skeleton and excellent in heat resistance such as glass transition temperature, durability and appearance can be obtained.

［式（６）中、ｎは１〜３の整数を表す。］

[In Formula (6), n represents the integer of 1-3. ]

［式（７）中、ｎは１〜３の整数を表す。］

[In formula (7), n represents the integer of 1-3. ]

  Specific examples of the compound represented by the above formula (1) include Sumikanol 507A (Taoka Chemical Industries), 2,4,6-tris [bis (methoxymethyl) amino] -1,3,5-triazine. (Manufactured by Tokyo Chemical Industry Co., Ltd.), Nikarak MW-30HM, Nikarak MW-390, Nikarak MW-100LM, Nikarak MX-750LM, Nikarak MX-290, Nikarak MX-280, Nikarak MX-270 (all manufactured by Sanwa Chemical), etc. Is mentioned.

  Among the compounds represented by the above formula (1), those in which Z is any one of a melamine residue, a urea residue, a glycolyl residue, and an imidazolidinone residue include, for example, JP-A-2005 And the compounds described in Chemical formula 16 and Chemical formula 18 of JP-A-43883.

  Among the compounds represented by the above formula (1), those in which Z is an aromatic ring residue include, for example, the compounds described in Chemical Formulas 21 to 26 of JP-A-2005-37925, And the compounds described in Chemical formula 17 of Kaikai 2005-43883.

On the other hand, the crosslinking agent (C) may contain at least one compound of quinuclidine and pyridine, instead of or together with the compound represented by the above formula (1). The cured product containing such a crosslinking agent (C) has excellent mechanical strength and high durability and appearance. This is because quinuclidine and pididine cross-link the lignin derivative (A) at high density and uniformly to form a homogeneous and rigid skeleton.
In addition, when a proton from the lignin derivative (A) is added to quinuclidine and pyridine, a carbocation is generated. This carbocation reacts with the lignin derivative (A) to form a methylene bond. In this way, the homogeneous and rigid skeleton described above is formed.

  The total content (J) of the crosslinking agent (B) and the crosslinking agent (C) in the resin composition is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the lignin derivative (A). Part by mass is more preferable. When the total content (J) is less than the lower limit, it may take a long time for crosslinking. When the total content (J) exceeds the upper limit, at least one of the crosslinking agent (B) and the crosslinking agent (C) that has not been crosslinked is present. Since it remains, there exists a possibility that the external appearance of a resin molding may be impaired.

  The weight ratio [(B) / (C)] of the crosslinking agent (B) and the crosslinking agent (C) is not particularly limited, but is preferably 1 to 50, more preferably 5 to 40, by weight. preferable. The amount of the crosslinking agent to the lignin derivative (A) is an amount of a ratio in accordance with the number of hydroxyl groups that the crosslinking agent (B) can crosslink and the number of aromatic carbons that the crosslinking agent (C) can crosslink. It is because it is preferable to add. When the weight ratio [(B) / (C)] is in the above range, each crosslinking agent can react with the lignin derivative (A) and crosslink without excess or deficiency. When the weight blending ratio [(B) / (C)] is less than the lower limit, the surface of the resin molded body may become rough, and when the upper limit is exceeded, it may take a long time to cure. is there.

  The resin composition of the present invention may contain a catalyst, a latent catalyst, a filler, and other additives in addition to the lignin derivative (A), the crosslinking agent (B), and the crosslinking agent (C).

(catalyst)
Further, as described later, when a reactive functional group is introduced into the lignin derivative (A), a catalyst corresponding to the type of the reactive functional group may be appropriately selected and used.

  Specifically, when the reactive functional group is an epoxy group, for example, a phenol resin such as a novolak type phenol resin, a lignin compound having a phenolic hydroxyl group, diethylenetriamine, m-xylylenediamine, N-aminoethylpiperazine For general epoxy resins such as amine compounds, acid anhydrides such as phthalic anhydride, succinic anhydride, maleic anhydride, dicyandiamide, guanidines, 2-methylimidazole, 2-ethyl-4-methylimidazole, etc. A catalyst is mentioned.

  When the reactive functional group is an isocyanate group, examples of the curing agent include general isocyanate resin catalysts such as phenol resins, lignin decomposition products, polyvinyl alcohol, and polyamine compounds. One kind or a mixture of two or more kinds is used.

  When the reactive functional group is a vinyl group, examples of the curing agent include anionic polymerization initiators such as butyl lithium and sodium ethoxide, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO). The polymerization initiator of a general vinyl group-containing compound such as a radical polymerization initiator such as) is used, and one or a mixture of two or more of these is used.

  Further, when the reactive functional group is an ethynyl group, examples of the curing agent include polymerization catalysts for general ethynyl group-containing compounds such as molybdenum pentachloride, tungsten pentachloride, norbornadiene rhodium chloride dimer, and the like. One of them or a mixture of two or more of them is used.

  When the reactive functional group is a maleimide group, examples of the curing agent include peroxides such as BPO and polymerization initiators of general maleimide group-containing compounds such as the anionic polymerization initiator described above. One or a mixture of two or more of these is used.

  Further, when the reactive functional group is a cyanate group, the curing includes, for example, a polymerization catalyst of a general cyanate group-containing compound such as a metal catalyst such as cobalt naphthenate, and one of these or A mixture of two or more is used.

  When adding a catalyst, the addition amount of the catalyst is preferably 0.1 to 3.0 parts by weight with respect to 100 parts by weight of the total content (J) of the crosslinking agent (B) and the crosslinking agent (C). More preferred is 0.3 to 2.5 parts by weight.

(Latent catalyst)
Further, in addition to the curing agent, a latent catalyst that varies the presence or absence of the crosslinking reaction of the crosslinking agent (C) or the speed of the crosslinking reaction according to the temperature may be included. By including such a latent catalyst, the resin composition of the present invention can initiate a crosslinking reaction of the crosslinking agent (C) when heated or increase the reaction rate of the crosslinking reaction. It will be possible. Thereby, when filling the cavity of the mold with the resin composition, the crosslinking reaction is not caused or the reaction rate is slowed, and when the molding is completed, the temperature is raised to cause the crosslinking reaction, or The reaction rate can be increased. As a result, a molding material can be filled in the cavity without gaps, and a resin molded body that is homogeneous and excellent in heat resistance such as glass transition temperature, durability, and appearance can be obtained.

  Examples of the latent catalyst include compounds that release an acidic substance by heating. This acidic substance acts to promote the crosslinking reaction by the crosslinking agent (C). Thereby, the curing rate when heated is increased, the appearance of the resin molded body is improved, and the production efficiency can be increased.

  Further, the compound that releases an acidic substance by heating is preferably a compound that releases an acidic substance having a dissociation constant pKa of 2 or less by heating. By including such a compound capable of releasing an acidic substance as a latent catalyst, the crosslinking reaction by the crosslinking agent (C) can be particularly promoted.

  Examples of the acidic substance having a dissociation constant pKa of 2 or less include oxalic acid (pKa = 1.3), p-toluenesulfonic acid (pKa = 1.7), and the like.

  Examples of compounds that release such acidic substances include cyclohexyl = 4-methylbenzenesulfonate, 2-methylcyclohexyl = 4-methylbenzenesulfonate, 3-methylcyclohexyl = 4-methylbenzenesulfonate, and 4-methylcyclohexyl. = 4-methylbenzenesulfonate, 4-butylcyclohexyl = 4-methylbenzenesulfonate, 4-cyclohexylcyclohexyl = 4-methylbenzenesulfonate, 2,6-dimethylcyclohexyl = 4-methylbenzenesulfonate, 2,4-dimethylcyclohexyl = 4 -Methylbenzenesulfonate, 3,4-dimethylcyclohexyl = 4-methylbenzenesulfonate, 3,5-dimethylcyclohexyl = 4-methylbenzenesulfonate, 2-I Propyl-5-methylcyclohexyl = 4-methylbenzenesulfonate, 2-hydroxycyclohexyl = 4-methylbenzenesulfonate, 4-hydroxycyclohexyl = 4-methylbenzenesulfonate, cyclohexyl = 4-biphenylsulfonate and 4,4′-bicyclohexyl = Benzylsulfonic acid cyclohexyls such as bis (4-methylbenzenesulfonate), various aromatic sulfonic acid cyclohexyls such as cyclohexyl = 1-naphthalenesulfonate and naphthalenesulfonic acid cyclohexyls such as cyclohexyl-2-naphthalenesulfonate. It is done. Such cyclohexyl sulfonates are useful as latent catalysts because they stably release acidic substances and hardly inhibit the crosslinking reaction by the crosslinking agent (B).

  Of these, hexyl benzenesulfonate is particularly preferably used, and cyclohexyl = 4-methylbenzenesulfonate, 3-methylcyclohexyl = 4-methylbenzenesulfonate, 3,5-dimethylcyclohexyl = 4-methylbenzenesulfonate. 4-butyl cyclohexyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl 4-methylbenzenesulfonate, 2-hydroxycyclohexyl 4-methylbenzenesulfonate, and 4-hydroxycyclohexyl 4-methylbenzenesulfonate At least one selected from the group is more preferably used, and cyclohexyl = 4-methylbenzenesulfonate is more preferably used. According to the hexyl benzenesulfonates, the effects brought about by the cyclohexyl aromatic sulfonates become more remarkable.

  Moreover, it is preferable that the heating temperature in which an acidic substance is discharge | released in the compound mentioned above is about 120-150 degreeC. Such a temperature range is very close to the treatment temperature for curing the resin composition containing the lignin derivative (A), the crosslinking agent (B) and the crosslinking agent (C). By molding the resin molded body and then raising the temperature to this temperature range, both excellent moldability and heat resistance such as a glass transition temperature after curing can be made highly compatible.

(Filler)
The resin composition of the present invention may contain a filler. Examples of fillers include talc, calcined clay, unfired clay, mica, silicates such as glass, oxides such as titanium oxide and alumina, fused silica (fused spherical silica, fused crushed silica), crystalline silica Silicon compounds like, carbonates like calcium carbonate, magnesium carbonate, hydrotalcite, hydroxides like aluminum hydroxide, magnesium hydroxide, calcium hydroxide, like barium sulfate, calcium sulfate, calcium sulfite Sulfate or sulfite, zinc borate, barium metaborate, aluminum borate, calcium borate, borate such as sodium borate, powder such as nitride such as aluminum nitride, boron nitride, silicon nitride, glass In addition to inorganic fillers such as fiber, carbon fiber, etc., wood powder, pulp pulverized powder, cloth砕粉, cured thermosetting resin powder, organic fillers, and the like, such as aramid fibers. Among these, as the filler, among metal oxide, metal hydroxide, metal nitride, silicon oxide, glass fiber, carbon fiber, aramid fiber, wood powder, pulp pulverized powder, and cloth pulverized powder, Those containing at least one kind are preferably used. These fillers can reduce the expansion coefficient of the resin molded body produced from the resin composition.

  In this case, the content of the filler is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the lignin derivative (A), and 100 to 400 parts by mass. More preferably. When the content rate of a filler is less than the said lower limit, there exists a possibility that the expansion coefficient of the resin molding manufactured from the resin composition cannot fully be reduced. On the other hand, when the content rate of the filler exceeds the upper limit, the moldability of the resin composition may be deteriorated because the ratio of the filler is too large.

  Moreover, it is preferable that the average particle diameter of a filler is about 0.1-500 micrometers, and it is more preferable that it is about 0.2-300 micrometers. When the average particle diameter of the filler is within the above range, the resin molded body produced from the resin composition is highly compatible with a low expansion coefficient and excellent moldability. The average particle size of the filler refers to the particle size of the powder distributed in 50% of the cumulative volume in the particle size distribution of the filler.

  In addition, examples of the shape of the filler include, but are not particularly limited to, flake shape, dendritic shape, spherical shape, and fibrous shape.

  In addition, when a filler is fibrous, it is preferable that it is a fiber diameter of 0.5-100 micrometers and fiber length about 1-50 mm.

(Other additives)
In addition to the above-mentioned components, the resin composition of the present invention may contain an alkali metal salt such as sodium methoxy, t-butoxy potassium, an alkaline earth metal salt such as calcium acetate, Na ₂ O, K ₂ , if necessary. A curing accelerator such as an alkali metal oxide such as O, or an alkaline earth metal oxide such as CaO or BaO may be included.

  In particular, when a lignin secondary derivative having an epoxy group as a reactive group is included, for example, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5, 4,0) undecene-7,1,5-diazabicyclo (4.3.0) nonane-5-ene, tris (dimethylaminomethyl) phenol, tertiary amines such as benzyldimethylamine, triphenylphosphine, tetra -N-butylphosphonium tetraphenylborate or the like may be contained.

Moreover, when the lignin secondary derivative which has a methylol group, a vinyl group, an ethynyl group, a maleimide group, a cyanate group etc. as a reactive group is included, the said polymerization catalyst may be included, for example.
Furthermore, various additives may be included as necessary.

  Examples of such various additives include silane coupling agents such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane, titanate coupling agent, aluminum coupling agent, and aluminum / zirconium coupling agent. Various coupling agents, colorants such as carbon black and bengara, polyethylene wax, higher fatty acid esters, fatty acid amides, ketones and amines, synthetic waxes such as hydrogenated oil, natural waxes such as paraffin wax and montan wax , Higher fatty acids such as stearic acid and zinc stearate and their metal salts, mold release agents such as paraffin, silicone oil, low stress components such as silicone rubber, antimony trioxide, aluminum hydroxide Flame retardants such as magnesium hydroxide, zinc borate, zinc molybdate, phosphazene, inorganic ion exchangers such as bismuth oxide hydrate, internal mold release agents, etc., one or two of these A combination of the above is used.

  Moreover, when a resin composition contains a mold release agent, it is preferable that content of a mold release agent is 0.01-10 mass parts with respect to 100 mass parts of lignin derivatives (A), 0.1-5 More preferred is part by mass. In addition, when the content of the release agent is less than the above, when the resin composition is filled in a mold and molded, there is a possibility that the release property may be insufficient, while the content of the release agent is When exceeding the said upper limit, there exists a possibility that the sclerosis | hardenability of a resin composition may fall.

  The resin composition of the present invention is preferably in the form of a lump from the viewpoint of improving workability, and more preferably in the form of a pellet or plate from the viewpoint of enhancing the molding stability of the resin composition.

<Method for producing resin composition>
Next, a method for producing the resin composition of the present invention will be described.

  The method for producing the resin composition of the present invention comprises: [1] placing biomass in the presence of a solvent and decomposing them under high temperature and high pressure; and [2] treating a solid component in the treated product with a polar solvent. A step of separating the insoluble matter from the polar solvent and the solution, [3] a step of drying the solution and recovering the solute (lignin derivative (A)), and [4] the recovered solute and crosslinking agent (B And a crosslinking agent (C) to obtain a resin composition. Hereinafter, each process will be described sequentially.

[1]
First, biomass is placed in the presence of a solvent and decomposed under high temperature and pressure. Biomass is a plant or a processed product of a plant as described above. Examples of this plant include broadleaf trees such as beech, birch and oak, conifers such as cedar, pine and cypress, bamboo, rice straw. Such grasses, coconut shells and the like.

  In the decomposition treatment, it is preferable to pulverize the biomass into blocks, chips, powders, or the like. In that case, the size after pulverization is preferably about 100 μm to 1 cm, and more preferably about 200 to 1000 μm. By using biomass of such a size, it is possible to improve the dispersibility of the biomass in the liquid and to efficiently perform the biomass decomposition treatment.

  Examples of the solvent used in this step include water, alcohols such as methanol and ethanol, phenols such as phenol and cresol, ketones such as acetone and methyl ethyl ketone, dimethyl ether, ethyl methyl ether, diethyl ether, Ethers such as tetrahydrofuran, nitriles such as acetonitrile, amides such as N, N-dimethylformamide, and the like, and one or two or more of them are used as a mixed solvent.

  As the solvent, water is particularly preferably used. As the water, for example, ultrapure water, pure water, distilled water, ion exchange water or the like is used. By using water, unintended denaturation of the lignin derivative (A) is suppressed, and the waste liquid generated by the decomposition treatment is aqueous, so that the environmental burden can be minimized. As a usage-amount of a solvent, it is so good that it is large with respect to biomass, However, Preferably it is about 1-20 mass times with respect to biomass, and it is more preferable that it is about 2-10 mass times.

  Next, the biomass in the presence of the solvent is decomposed under high temperature and pressure. Thereby, biomass is decomposed | disassembled into lignin, a cellulose, hemicellulose, those other decomposition products, reaction materials, etc.

  In the generation of a high temperature and high pressure environment, a pressure vessel such as an autoclave is used. Moreover, as this pressure vessel, what is equipped with a heating means and a stirring means is used preferably, and it is preferable to stir biomass under high temperature and pressure. Moreover, you may provide the means to pressurize independently from the factor which influences pressure, such as the temperature in a container, as needed. Examples of such means include means for introducing an inert gas such as argon gas into the container.

  As for the conditions in the decomposition treatment, the treatment temperature is preferably 150 to 400 ° C, more preferably 180 to 350 ° C, and further preferably 220 to 320 ° C. When the treatment temperature is within the above range, the molecular weight of the lignin derivative (A) obtained after decomposition can be optimized. Thereby, the moldability of the resin composition and the solvent resistance after curing can be made more compatible in hardness.

  Moreover, it is preferable that the processing time in a decomposition process is 480 minutes or less, and it is more preferable that it is 30 to 360 minutes. If the treatment time is within the above range, the ratio of the aromatic proton and the aliphatic proton of the lignin derivative (A) obtained after decomposition becomes an appropriate value, and the moldability of the resin composition and the mechanical properties after curing Can be made highly compatible.

  Furthermore, the pressure in the decomposition treatment is preferably 1 to 40 MPa, more preferably 1.5 to 25 MPa, and further preferably 3 to 20 MPa. When the pressure is within the above range, the biomass decomposition efficiency can be significantly increased, and the processing time can be shortened accordingly.

  In addition, it is preferable to perform the process which fully stirs biomass and the said solvent as a pre-process of a decomposition | disassembly process, and adjusts both. Thereby, the decomposition of biomass can be particularly optimized. The stirring temperature is preferably about 0 to 150 ° C, and more preferably about 10 to 130 ° C. Further, the stirring time is preferably about 1 to 120 minutes, more preferably about 5 to 60 minutes. Further, examples of the stirring method include various mills such as a ball mill and a bead mill, a method using a stirrer equipped with a stirring blade, a method using water flow stirring using a homogenizer, a jet pump, and the like.

  Moreover, you may make it add the catalyst and oxidizing agent which accelerate | stimulate a decomposition process as needed in a solvent. Examples of the catalyst include inorganic bases such as sodium carbonate, inorganic acids such as acetic acid and formic acid, and examples of the oxidizing agent include hydrogen peroxide. The amount of the catalyst and the oxidizing agent added is preferably about 0.1 to 10% by mass, more preferably about 0.5 to 5% by mass in terms of the concentration in the aqueous solvent.

  Further, as a pretreatment for the decomposition treatment, it is preferable to perform a step of sufficiently stirring the biomass and the aqueous solvent and allowing them to blend. Thereby, the decomposition of biomass can be particularly optimized.

  In addition, as stirring temperature, it is preferable that it is about 0-150 degreeC, and it is more preferable that it is about 10-130 degreeC.

  Moreover, as stirring time, it is preferable that it is about 1 to 120 minutes, and it is more preferable that it is about 5 to 60 minutes.

  Further, examples of the stirring method include various mills such as a ball mill and a bead mill, a method using a stirrer equipped with a stirring blade, a method using water flow stirring using a homogenizer, a jet pump, and the like.

The solvent used in the decomposition treatment is preferably used in a subcritical or supercritical state (condition). A solvent in a subcritical or supercritical state can accelerate the biomass decomposition treatment without a special additive component such as a catalyst. For this reason, it is possible to decompose biomass in a short time without using a complicated separation process, and it is possible to reduce the manufacturing cost of the lignin derivative (A) and simplify the manufacturing process.
As an example, the critical temperature of water is about 374 ° C., and the critical pressure is about 22.1 MPa.

[2]
Next, the processed product in the pressure vessel is filtered. Then, the filtrate is removed, and the solid component separated by filtration is recovered. And the collect | recovered solid component is immersed in the solvent in which lignin is soluble. The solid component immersed in a solvent capable of lignin is separated into a component soluble in the solvent (soluble component) and a component insoluble in the solvent (insoluble component).

  As the solvent in which lignin is soluble, various polar solvents are used, and particularly those containing lower alcohols such as methanol and ethanol, and ketones such as acetone and methyl ethyl ketone are preferably used. By using these polar solvents, the lignin derivative (A) dissolved in the polar solvent and the lignin derivative (A) insoluble in the polar solvent can be separated and extracted from the recovered solid component.

  The immersion time is not particularly limited, but is preferably about 1 to 48 hours, and more preferably about 2 to 30 hours. Moreover, it is also possible to heat at the boiling point or less of the solvent during immersion.

[3]
Next, the processed product obtained by the dipping process is filtered. Then, the solvent in which lignin is soluble is distilled off from the filtrate (dissolved solution), and the dried solute (lignin derivative (A)) is recovered.
On the other hand, insolubles are also recovered from the treated product by filtration.

  In addition, when obtaining the resin composition containing a lignin secondary derivative, a reactive functional group is reacted with the lignin derivative (A) by bringing a compound containing a reactive functional group into contact with the extracted lignin derivative (A). A group may be introduced.

  As a method for introducing a reactive functional group, for example, a method of mixing a lignin derivative (A) and a compound containing a reactive functional group is used, and after mixing, a catalyst or the like is added as necessary. Also good.

  Specifically, when an epoxy group is introduced, a lignin derivative (A), epichlorohydrin, and a solvent are mixed, and a base catalyst such as sodium hydroxide may be added thereto under reflux under reduced pressure.

  When a vinyl group is introduced, a lignin derivative (A), a halogen compound containing a vinyl group such as allyl halide or vinylbenzyl halide and a solvent are mixed, and a base such as sodium hydroxide is added to the mixture under heating and stirring. What is necessary is just to add a catalyst.

  In addition, when introducing an ethynyl group, a lignin derivative (A), a halogen compound containing an ethynyl group such as propargyl halide or phenylacetylene and a solvent are mixed, and a base such as sodium hydroxide is added to the mixture under heating and stirring. What is necessary is just to add a catalyst.

  Moreover, when introduce | transducing a cyanate group, a lignin derivative (A), halogenated cyanate, and a solvent are mixed, and a base catalyst, such as sodium hydroxide, may be added to this under heating and stirring.

  When introducing a maleimide group, the lignin derivative (A) and parachloronitrobenzene are mixed. As a result, a chloro group reacts with the phenolic hydroxyl group of the lignin derivative (A) to obtain a polynitrated lignin bonded via an ether bond. Subsequently, polynitrated lignin is reduced to be converted to polyaminated lignin, and further reacted with maleic anhydride to introduce a maleimide group.

  Moreover, when introduce | transducing an isocyanate group, the hydroxyl group in a lignin derivative (A) is converted into a carboxyl group by mixing a lignin derivative (A) and maleic anhydride. Thereafter, the isocyanate group is introduced by heating the mixture in the presence of diphenyl phosphate azide.

[4]
Next, the recovered solute (lignin derivative (A)), crosslinking agent (B), and crosslinking agent (C) are mixed in an arbitrary method and order. As needed, the catalyst, latent catalyst, filler, and various additives are mixed in any manner and order. Thereby, a resin molding is prepared.

  Moreover, when mixing, using a kneading machine such as a hot plate, a pressure kneader, a roll, a kneader, or a twin screw extruder, the mixture is heated and melt-kneaded at a temperature lower than the temperature at which the mixture is cured. Although the specific heating temperature at the time of heating is a little different depending on the composition to be selected, it is preferably about 50 to 130 ° C. A granular resin composition is obtained by pulverizing the cooled mixture.

  Moreover, when preparing a resin composition, you may make it add an organic solvent as needed. Examples of the organic solvent include, but are not limited to, methanol, ethanol, propanol, butanol, methyl cellosolve, acetone, methyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, quinoline, cyclopentanone, xylene, m-cresol, chloroform and the like can be mentioned, and one or a mixture of two or more of these can be used.

In addition, you may make it add a diluent as needed. Examples of the diluent include organic solvents having a relatively high boiling point such as butyl cellosolve, carbitol, butyl cellosolve acetate, carbitol acetate, ethylene glycol diethyl ether, and α-terpineol.
Furthermore, you may mix the other additive mentioned above.

<Resin molding>
Next, the resin molding manufactured from the resin composition of this invention is demonstrated. For example, the resin molded body is manufactured by molding when the resin composition of the present invention is molded or after.

  Specifically, the resin composition is manufactured by heating and pressing in a molding die and then curing.

  The temperature at the time of heat and pressure molding is preferably about 100 to 280 ° C, more preferably about 120 to 250 ° C. Further, the pressure is preferably about 0.5 to 20 MPa, more preferably about 1 to 10 MPa.

  The obtained resin molding is applied to uses such as semiconductor parts, aircraft parts, automobile parts, industrial machine parts, electronic parts, electric parts, mechanical parts, and the like.

  The molding method is not particularly limited, and the resin molded body of the present invention may be formed into a molded product using a known molding method, for example, an injection molding method, a compression molding method, an extrusion molding method, a cast molding method, or the like. it can. The form of the molded product thus obtained may be any form, for example, an intermediate molded product before the molding material is made into a final molded product or a final molded product. .

  The resin molded body is heated and cured by crosslinking the lignin derivative (A) with the crosslinking agent (B) and the crosslinking agent (C). It is considered that the crosslinking agent (B), the crosslinking agent (C) and the crosslinking reaction point of the lignin derivative (A) are crosslinked.

  Further, when the lignin derivative (A) is methylolated, a dehydration condensation reaction occurs, the crosslinking agent (C) and the methylol group are crosslinked, and the crosslinking agent (C) and the lignin derivative (A) are self-reacting. To condense.

  When the resin composition is cured by the reaction as described above, since the generation of volatile components accompanying the reaction is gentle, problems such as swelling and voids can be effectively suppressed.

  Although the present invention has been described above, the present invention is not limited to this. For example, an optional component may be added to the resin composition.

  Moreover, the resin plate excellent in mechanical characteristics, durability, and external appearance can be manufactured by impregnating core materials, such as paper and a fabric, with a resin composition. As the core material, for example, thin paper, craft paper, titanium paper, linter paper, paperboard, base paper for gypsum board, coated paper, art paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, Japanese paper and various other papers, glass Fiber, asbestos fiber, potassium titanate fiber, alumina fiber, silica fiber, carbon fiber, metal fiber, inorganic fiber such as mineral fiber, synthetic resin fiber such as aramid fiber, polyester fiber, acrylic fiber, vinylon fiber or natural fiber Non-woven fabrics or woven fabrics of various fibers such as these are used, and one or more of these composites are used.

Next, specific examples of the present invention will be described.
1. Production of resin composition and resin molded body

Example 1
(1) Extraction of lignin derivative (A) 100 g of cedar wood flour (60 mesh under) and 400 g of a solvent composed of pure water were mixed and introduced into a 1 L autoclave. Then, while stirring the contents at 300 rpm, as a pretreatment, the mixture was stirred for 15 minutes at room temperature. After sufficiently blending the cedar wood flour and the solvent, it was treated at 300 ° C. and 10 MPa for 60 minutes to obtain cedar wood flour. Disassembled.

Subsequently, the obtained decomposition product was filtered, and the solid component separated by filtration was recovered.
Subsequently, the obtained solid component was immersed in acetone which is a polar solvent, and separated into an insoluble component and a soluble component with respect to acetone. This was filtered, and the solution separated by filtration was recovered.
Next, the solution was dried to recover the solute (lignin derivative).

(2) Preparation of resin composition Next, 100 parts by mass of the obtained lignin derivative, 30 parts by mass of a bisphenol A type epoxy resin (functional group equivalent 189), 10 parts by mass of hexamethylenetetramine, and 0.2 methylimidazole. 5 parts by weight and 400 parts by mass of silica powder (manufactured by Denki Kagaku Co., Ltd., average particle size 15 μm) were blended and kneaded with a hot roll at 90 ° C. for 5 minutes to obtain a sheet-like kneaded product.

  Next, the sheet-like kneaded product was cooled and then pulverized to obtain a granular resin composition having an average particle diameter of 3 mm.

(3) Manufacture of resin molding Next, the obtained granular resin composition was supplied to the tablet machine, and it was set as the tablet of outer diameter 20mm.

  Subsequently, it shape | molded for 5 minutes by the shaping | molding conditions of 175 degreeC and 6.9 MPa by transfer shaping | molding, and obtained the plate-shaped temporary molded object of average thickness 1.6mm. Furthermore, the obtained temporary molded body was heated at 175 ° C. for 6 hours to obtain a resin molded body of the present invention.

(Examples 2 to 22)
A resin molded body was obtained in the same manner as in Example 1, except that the type of biomass, the extraction conditions of the lignin derivative, and the preparation conditions of the resin composition were changed as shown in Tables 1 to 3, respectively.

(Example 2)
A resin molded product was obtained in the same manner as in Example 1 except that the crosslinking agent (B) component was changed to o-cresol novolac type epoxy resin (functional group equivalent 199) (functional group equivalent 199).

(Example 3)
A resin molded body was obtained in the same manner as in Example 1 except that the crosslinking agent (B) component was changed to 20 parts by weight of diphenylmethane diisocyanate (functional group equivalent 125).

Example 4
A resin molded product was obtained in the same manner as in Example 1 except that the curing catalyst component 2-methylimidazole was not added.

(Example 5)
A resin molded body was obtained in the same manner as in Example 1 except that the crosslinking agent (C) component was changed to hexamethoxymethylmelamine (corresponding to the compound represented by the formula (7) where n is 1). Obtained.

(Example 6)
The curing catalyst component 2-methylimidazole was changed so as not to be added, and the cross-linking agent (C) component was changed to hexamethoxymethylmelamine (corresponding to n of the compound represented by the formula (7) set to 1). A resin molded body was obtained in the same manner as in Example 1 except for the change.

(Example 7)
The addition amount of the crosslinking agent (B) bisphenol A type epoxy resin (functional group equivalent 189) was changed to 40 parts by weight, and the addition amount of the crosslinking agent (C) component hexamethylenetetramine was changed to 12.5 parts by weight. In the same manner as in Example 1, a resin molded body was obtained.

(Example 8)
Resin molded bodies were obtained in the same manner as in Example 1 except that the biomass decomposition temperature was changed to 250 ° C. and the decomposition pressure was changed to 4 MPa.

Example 9
A resin molded product was obtained in the same manner as in Example 1, except that the biomass decomposition treatment time was changed to 180 minutes and the cross-linking agent (B) component was changed to o-cresol novolac type epoxy resin (functional group equivalent 199). Obtained.

(Example 10)
The biomass decomposition treatment temperature was changed to 330 ° C., the decomposition treatment pressure was changed to 13 MPa, the crosslinking agent (B) component was changed to 15 parts by weight of o-cresol novolac type epoxy resin (functional group equivalent 199), and a curing catalyst Resin molded bodies were obtained in the same manner as in Example 1 except that the amount was changed to 0.2 parts by weight of component 2-methylimidazole.

(Example 11)
Example 1 except that the crosslinking agent (B) component was changed to o-cresol novolac type epoxy resin (functional group equivalent 199) and changed to 7.5 parts by weight of the crosslinking agent (C) component hexamethylenetetramine. Thus, a resin molded body was obtained.

Example 12
Change biomass to beech, change biomass decomposition temperature to 280 ° C, change decomposition pressure to 8 MPa, change decomposition time to 25 minutes, crosslinker (B) component o-cresol novolac type epoxy Change to 40 parts by weight of resin (functional equivalent 199), change to 12.5 parts by weight of crosslinking agent (C) component hexamethylenetetramine, change to 1 part by weight of curing catalyst component 2-methylimidazole, filler component silica Resin molded bodies were obtained in the same manner as in Example 1 except that the amount of powder added was changed to 500 parts by weight.

(Example 13)
Biomass was changed to Munetake, biomass decomposition temperature was changed to 270 ° C., decomposition pressure was changed to 7 MPa, cross-linking agent (B) component bisphenol A type epoxy resin (functional group equivalent 189) 20 parts by weight and o -Change to 10 parts by weight of cresol novolac epoxy resin (functional group equivalent 199), change to 8 parts by weight of cross-linking agent (C) component hexamethylenetetramine, change to 1 part by weight of curing catalyst component 2-methylimidazole, and fill Resin molded bodies were obtained in the same manner as in Example 1 except that the additive amount of the agent component silica powder was changed to 300 parts by weight.

(Example 14)
The biomass decomposition treatment temperature was changed to 200 ° C., the decomposition treatment pressure was changed to 3 MPa, the crosslinking agent (B) component bisphenol A type epoxy resin (functional group equivalent 189) 20 parts by weight and o-cresol novolac type epoxy resin ( The resin molding was obtained in the same manner as in Example 1 except that the functional group equivalent 199) was changed to 20 parts by weight and the crosslinking agent (C) component was changed to 7.5 parts by weight of hexamethylenetetramine.

(Example 15)
The crosslinking agent (B) component diphenylmethane diisocyanate 20 parts by weight (functional group equivalent 125) was changed to 20 parts by weight, and the crosslinking agent (C) component hexamethoxymethylmelamine (n of the compound represented by the above formula (7) was set to 1. A resin molded body was obtained in the same manner as in Example 1 except that the amount was changed to 15 parts by weight.

(Example 16)
The crosslinking agent (B) component diphenylmethane diisocyanate 20 parts by weight (functional group equivalent 125) was changed to 20 parts by weight, and the crosslinking agent (C) component 2 parts by weight of hexamethylenetetramine and hexamethoxymethylmelamine (expressed by the above formula (7)) The resin molded product was obtained in the same manner as in Example 1 except that the compound was changed to 8 parts by weight and the addition of the curing catalyst was omitted.

(Example 17)
Resin moldings were obtained in the same manner as in Example 1 except that the crosslinking agent (C) component was changed to 6 parts by weight of hexamethylenetetramine, 2 parts by weight of quinuclidine, and 2 parts by weight of pyridine.

(Example 18)
The crosslinking agent (C) is 7 parts by weight of hexamethylenetetramine and Nicalac MX-290 (manufactured by Sanwa Chemical Co., Ltd. (corresponding to the compound represented by the above formula (3) in which R is CH ₃ ). Parts, 1 part by weight of Nicalac MX-280 (manufactured by Sanwa Chemical, equivalent to the compound represented by the above formula (4) where R is CH ₃ ), and Nicalac MX-270 (manufactured by Sanwa Chemical) (Equivalent to the compound represented by the above formula (5) in which R is CH ₃ ) Except for changing to 1 part by weight, resin molded bodies were obtained in the same manner as in Example 1, respectively.

(Example 19)
A resin molded body was obtained in the same manner as in Example 1 except that the crosslinking agent (C) component was changed to 0.5 parts by weight of hexamethylenetetramine.

(Example 20)
Resin in the same manner as in Example 1 except that the crosslinking agent (B) component bisphenol A type epoxy resin (functional group equivalent 189) was changed to 75 parts by weight and the crosslinking agent (C) component hexamethylenetetramine was changed to 1 part by weight. A molded body was obtained.

(Example 21)
Resin in the same manner as in Example 1 except that the crosslinking agent (B) component bisphenol A type epoxy resin (functional group equivalent 189) was changed to 3 parts by weight and the crosslinking agent (C) component hexamethylenetetramine was changed to 1 part by weight. A molded body was obtained.

(Example 22)
A resin molded product was obtained in the same manner as in Example 1 except that the crosslinking agent (B) component was changed to a bisphenol F type epoxy resin (functional group equivalent 850) and the crosslinking agent (C) component was changed to 1 part by weight of hexamethylenetetramine. Obtained.

(Comparative Examples 1-3)
A resin molded body was obtained in the same manner as in Example 1 except that the type of biomass, the extraction conditions of the lignin derivative (A), and the preparation conditions of the resin composition were changed as shown in Table 3.

(Comparative Example 1)
A resin molded body was obtained in the same manner as in Example 1 except that the resin component lignin derivative (A) was changed to a novolac type phenol resin.

(Comparative Example 2)
A resin molded body was obtained in the same manner as in Example 1 except that the crosslinking agent (B) component was changed so as not to be added.

(Comparative Example 3)
A resin molded body was obtained in the same manner as in Example 1 except that the crosslinking agent (C) component was changed so as not to be added.

2. 2. Evaluation of lignin derivative 2.1 Evaluation of number average molecular weight The lignin derivative (A) obtained in each Example and each Comparative Example was dissolved in tetrahydrofuran to prepare a measurement sample. Next, “TSKgelGMMHXL (manufactured by Tosoh)” and “G2000HXL (manufactured by Tosoh)”, which are organic general-purpose columns filled with styrene polymer filler, are connected in series to the GPC system “HLC-8320GPC (manufactured by Tosoh)”. did.

  200 μL of the measurement sample was injected into this GPC system, the eluent tetrahydrofuran was developed at 1.0 mL / min at 40 ° C., and the retention time was measured using the differential refractive index (RI) and ultraviolet absorbance (UV). Was measured. The number average molecular weight of the lignin derivative (A) was calculated from a calibration curve showing the relationship between the retention time and molecular weight of standard polystyrene prepared separately.

In addition, as the molecular weight of standard polystyrene used for preparing a calibration curve, the number average molecular weight is 427,000, 190,000, 96,400, 37,900, 18,100, 10,200, 5,970, Standard polystyrenes (manufactured by Tosoh) of 2,630, 1,050 and 500 were used.
The measurement results are shown in Tables 1-3.

2.2 Presence / absence of carboxyl group The lignin derivative (A) obtained in each Example and each Comparative Example was subjected to ¹³ C-NMR analysis and confirmed by the presence or absence of absorption at a peak of 172 to 180 ppm.
The measurement results are shown in Tables 1-3.

3. 3. Evaluation of Resin Molded Body 3.1 Evaluation of Hardness of Temporary Molded Body The resin composition obtained in each Example and each Comparative Example was thermoformed at 175 ° C. for 10 minutes to prepare a temporary molded body. The obtained temporary molded body was pulverized, and the temporary molded body placed in a cylindrical filter paper was immersed in boiling acetone solvent and boiled for 1 hour using a rapid solvent extraction device “Soctest SER148 / 6 (manufactured by Actac)”. . Next, the cylindrical filter paper was pulled up from the acetone solvent, and acetone cooled down and liquefied at the upper part of the apparatus was dropped onto the sample in the cylindrical filter paper, and rinsed for 1 hour. The obtained acetone extract was air-dried for 12 hours and further dried under reduced pressure at 50 ° C. for 2 hours. The weight of the extracted solid obtained by drying was defined as the weight of acetone eluted. Using the obtained acetone elution weight, the degree of cure was calculated by the following formula. The resin content in the cured product was calculated from the composition of the resin composition.
Curing degree (%) = (resin content in cured product−acetone elution weight) / resin content in cured product × 100
The measurement results are shown in Tables 1-3.

<Evaluation criteria for degree of curing of temporary molded body>
A: Curing degree is 80% or more B: Curing degree is 70% or more B: Curing degree is 60% or more X: Curing degree is less than 60%

3.2 Evaluation of degree of cure of resin molded body The resin compositions obtained in each Example and each Comparative Example were heated at 175 ° C for 10 minutes, and then heated at 175 ° C for 3 hours. The obtained resin molding was pulverized, and the temporary molding put in the cylindrical filter paper was immersed in boiling acetone solvent and boiled for 1 hour using a rapid solvent extraction device “Soctest SER148 / 6 (manufactured by Actac)”. . Next, the cylindrical filter paper was pulled up from the acetone solvent, and acetone cooled down and liquefied at the upper part of the apparatus was dropped onto the sample in the cylindrical filter paper, and rinsed for 1 hour. The obtained acetone extract was air-dried for 12 hours and further dried under reduced pressure at 50 ° C. for 2 hours. The weight of the extracted solid obtained by drying was defined as the weight of acetone eluted. Using the obtained acetone elution weight, the degree of cure was calculated by the following formula. The resin content in the cured product was calculated from the composition of the resin composition.
Curing degree (%) = (resin content in cured product−acetone elution weight) / resin content in cured product × 100
The measurement results are shown in Tables 1-3.

<Evaluation criteria for degree of cure of resin molded product>
◎: Curing degree is 95% or more ○: Curing degree is 90% or more △: Curing degree is 85% or more ×: Curing degree is less than 85%

3.3 Evaluation of Gel Time In each Example and each Comparative Example, a resin composition to which no silica powder was added was prepared, and the gel time (gelation time) at 175 ° C. was measured in accordance with the method specified in JIS K 6910. did. The measurement results are shown in Tables 1-3.

3.4 Evaluation of Glass Transition Temperature The resin molded bodies obtained in each Example and each Comparative Example were cut into a thickness of 2 mm and a width of 4 mm with a precision cutting machine to obtain a test sample. This test sample was measured using a dynamic viscoelasticity measuring apparatus (EXSTAR DMS6100, manufactured by SII Nano Technology) under a nitrogen atmosphere at a frequency of 1 Hz and a temperature rising condition of 5 ° C./min. The top value was taken as the glass transition point. The measurement results are shown in Tables 1-3.

3.5 Evaluation of Appearance For the resin molded bodies obtained in each Example and each Comparative Example, the appearance was visually confirmed and evaluated according to the following evaluation criteria. The measurement results are shown in Tables 1-3.

<Evaluation criteria for appearance>
A: The surface of the molded product is smooth and no distortion, wrinkles, or spots are observed. ○: The surface of the molded product has irregularities that cannot be seen with the naked eye, or there are 1 to 2 strains, wrinkles, or spots. : Concavities and convexities that can be recognized with the naked eye are observed on the surface of the molded product, or 3 to 5 strains, wrinkles, and spots are observed. There are 6 or more spots

  As is apparent from Tables 1 to 3, since the lignin derivatives obtained in each example have a gel time value of 25 to 70 seconds, which is preferable from the viewpoint of moldability, a resin molding composition containing such a lignin derivative. Is excellent in moldability.

  In addition, as is clear from Tables 1 to 3, the resin composition and the resin molded body obtained in each example have a high degree of curing that is a measure of solvent resistance, and a glass transition temperature that is a measure of heat resistance. High and excellent in appearance.

  From the above, according to the present invention, a resin composition excellent in solvent resistance and heat resistance, and a resin molded body can be obtained.

Claims (11)

A lignin derivative (A);
At least one crosslinking agent (B) selected from an epoxy compound and an isocyanate compound;
Containing at least one selected from quinuclidine, pyridine and hexamethylenetetramine, having a different crosslinking point from the crosslinking agent (B) and a different type of crosslinking agent (C);
A resin composition comprising: A lignin derivative (A);
At least one crosslinking agent (B) selected from an epoxy compound and an isocyanate compound;
Containing at least one of the compounds represented by the following formula (1), having a crosslinking point different from the crosslinking agent (B) and a different type of crosslinking agent (C);
A resin composition comprising:
_{Z- (CH 2 OR) m (} 1)
[Z in Formula (1) is any one of a melamine residue, a urea residue, a glycolyl residue, an imidazolidinone residue, and an aromatic ring residue. Moreover, m represents the integer of 2-14. R is independently an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. However, -CH 2 _OR, the nitrogen atom of the melamine residues, the nitrogen atom of the primary amino groups of the urea residues, the nitrogen atom of the secondary amino group of the glycolyl residues, the secondary amino group of the imidazolidinone residues It is directly bonded to either the nitrogen atom or the carbon atom of the aromatic ring residue. ] A lignin derivative (A);
At least one crosslinking agent (B) selected from an epoxy compound and an isocyanate compound;
Containing at least one compound represented by any one of the following formulas (2) to (5), having a crosslinking point different from the crosslinking agent (B) and a different type of crosslinking agent (C);
A resin composition comprising:

[In the formula (2), X is _CH 2 OR or a hydrogen atom, R is independently an alkyl group or a hydrogen atom having 1 to 4 carbon atoms. N represents an integer of 1 to 3. ]

[In Formula (3), R is a C1-C4 alkyl group or a hydrogen atom independently. ]

[In Formula (4), R is a C1-C4 alkyl group or a hydrogen atom independently. ]

[In Formula (5), R is a C1-C4 alkyl group or a hydrogen atom independently. ] A lignin derivative (A);
At least one crosslinking agent (B) selected from an epoxy compound and an isocyanate compound;
A compound represented by the following formula (6) or (7), a crosslinking agent (C) having a different crosslinking point from the crosslinking agent (B) and a different type,
A resin composition comprising:

[In Formula (6), n represents the integer of 1-3. ]

[In formula (7), n represents the integer of 1-3. ]   The at least one crosslinking agent (B) selected from the epoxy compound and the isocyanate compound contains a compound obtained by epoxidizing a compound having an aromatic group. Resin composition.   The resin composition according to any one of claims 1 to 5, wherein the at least one crosslinking agent (B) selected from the epoxy compound and the isocyanate compound contains a functional group equivalent of 400 or less. object.   The said lignin derivative (A) contains what has the number average molecular weight of polystyrene conversion 200-2000 measured by the gel permeation chromatography (GPC) analysis. The resin composition as described. The total content of at least one crosslinking agent (B) selected from the epoxy compound and isocyanate compound and the crosslinking agent (C) is 5 to 100 parts by mass with respect to 100 parts by mass of the lignin derivative (A). The resin composition according to any one of claims 1 to 7 . The ratio [(B) / (C)] obtained by dividing the content of at least one crosslinking agent (B) selected from the epoxy compound and the isocyanate compound by the content of the crosslinking agent (C) is 1 to 50 The resin composition according to any one of claims 1 to 8 . The resin composition according to any one of claims 1 to 9 , wherein the lignin derivative (A) contains a carboxyl group. A resin molded body, which is a molded body of the resin composition according to any one of claims 1 to 10 .