JP2014136741A - Resin composition and resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which contains a plant-derived component as a main material and has excellent resistance against distortion and excellent moldability without impairing solvent resistance, and to provide a resin molding.SOLUTION: A resin composition comprises a lignin derivative (A), at least one crosslinking agent (B) having no aromatic ring selected from epoxy compounds and isocyanate compounds, and a crosslinking agent (C) whose crosslinking point and kind are different from those of the crosslinking agent (B). The crosslinking agent (C) preferably contains at least one selected from quinuclidine, pydine, and hexamethylenetetramine. A material obtained by subjecting biomass to a subcritical treatment is preferably used as the lignin derivative (A).

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, a resin composition containing lignin as a resin raw material sometimes has insufficient crosslinking in the case of a molding material that requires higher solvent resistance.
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 protection effect may be impaired.

  Furthermore, an epoxy compound having an aromatic group has a rigid structure and thus has a low flexibility and a resistance to distortion may be insufficient. Moreover, since the epoxy compound which has an aromatic has low fluidity | liquidity, there existed a possibility that a moldability might be impaired.

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 resistance to distortion and moldability without impairing solvent resistance, and a resin molded body.

Such an object is achieved by the present inventions (1) to (11) below.
(1) The lignin derivative (A), at least one crosslinking agent (B) selected from an epoxy compound having no aromatic and an isocyanate compound having no aromatic, and the crosslinking agent (B) are crosslinking points. And a different type of crosslinking agent (C).
(2) The resin composition according to (1), wherein the crosslinking agent (C) contains at least one of quinuclidine, pyridine, hexamethylenetetramine and 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. ]
(3) The said crosslinking agent (C) is a resin composition as described in (2) which contains what is represented by either of following formula (2)-(5) at least 1 sort (s).
[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. ]
(4) The resin composition according to (2), wherein the crosslinking agent (C) contains a compound represented by the following formula (6) or (7).
[In Formula (6), n represents the integer of 1-3. ]
[In formula (7), n represents the integer of 1-3. ]
(5) The at least one crosslinking agent (B) selected from the epoxy compound having no aromatic and the isocyanate compound having no aromatic contains a functional group equivalent of 400 or less. The resin composition according to any one of (1) to (4).
(6) The lignin derivative (A) contains those having a polystyrene-equivalent number average molecular weight of 200 to 2000 as measured by gel permeation chromatography (GPC) analysis. The resin composition in any one.
(7) The resin composition according to any one of (1) to (6), wherein the lignin derivative (A) contains a product obtained by subjecting biomass to subcritical treatment.
(8) With respect to 100 parts by weight of the lignin derivative (A), at least one crosslinking agent (B) selected from the epoxy compound having no aromatic and the isocyanate compound having no aromatic and the crosslinking agent ( The resin composition according to any one of (1) to (7), wherein the total content of C) is 5 to 100 parts by weight.
(9) The content of at least one crosslinking agent (B) selected from the epoxy compound having no aromatic and the isocyanate compound having no aromatic is divided by the content of the crosslinking agent (C). The resin composition according to any one of (1) to (8), wherein the ratio [(B) / (C)] is 1 to 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 article obtained by molding the resin composition according to any one of (1) to (10).

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition excellent in the moldability and the tolerance with respect to distortion is obtained, without using a plant-derived component as a main material and impairing solvent resistance.

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

<Resin composition>
The resin composition of the present invention comprises a lignin derivative (A), at least one crosslinking agent (B) selected from an epoxy compound having no aromatic and an isocyanate compound having no aromatic, and a crosslinking agent (B ) Includes different crosslinking points and different types of crosslinking agents (C).

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

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.

  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 an epoxy compound having no aromatic group and an isocyanate compound having no aromatic group)
Next, at least one crosslinking agent (B) (hereinafter also referred to as crosslinking agent (B)) selected from an epoxy compound having no aromatic and an isocyanate compound having no aromatic 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), the resistance to strain can be improved without impairing the solvent resistance.

  The epoxy compound of the cross-linking agent (B) refers to monomers, oligomers and polymers that do not have aromaticity and have an epoxy group in one molecule.

  The number of epoxy groups contained in the epoxy compound of the crosslinking agent (B) is not particularly limited as long as it has at least one, but the viewpoint of improving the solvent resistance of the resin composition or the resin molded body. Therefore, it is preferable to have two or more.

  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 an alcoholic hydroxyl group or a method of oxidizing a compound having an unsaturated bond is preferred.

  A method for epoxidizing the compound having an alcoholic hydroxyl group will be described. It can be obtained by glycidyl etherification of an alcoholic hydroxyl group 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 alcoholic 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 etherifying the alcoholic hydroxyl group, for example, the alcoholic hydroxyl group is dissolved and mixed with an excess of epihalohydrin such as epichlorohydrin, epibromohydrin, sodium hydroxide, hydroxide, etc. A method of adding an alkali metal hydroxide such as potassium or reacting at 20 to 120 ° C. for 1 to 10 hours while adding can be employed.

  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.

  Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like is added to the dissolved mixture of the compound having an alcoholic hydroxyl group and epihalohydrin as a catalyst, and 1 to 5 at 50 to 150 ° C. A method in which a halohydrin etherified product is obtained by reacting for a period of time, and then a solid or aqueous solution of an alkali metal hydroxide is added and reacted at 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure). Can also be adopted. The amount of the quaternary ammonium salt used in this case is usually 1 to 10 g, preferably 2 to 8 g, based on 1 mol of the hydroxyl group of the compound having an alcoholic hydroxyl group.

  Usually, the amount of epihalohydrin used in these reactions is usually 1 to 20 mol, preferably 2 to 10 mol, relative to 1 equivalent of the hydroxyl group of the compound having an alcoholic hydroxyl group. The usage-amount of an alkali metal hydroxide is 0.8-1.5 mol normally with respect to 1 equivalent of hydroxyl groups of the compound which has an alcoholic hydroxyl group, 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 alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 1 to 0.1 mol of the hydroxyl group of the compound having an alcoholic hydroxyl group in the present invention used for glycidyl etherification. Is 0.05 to 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.

  Next, a method for epoxidizing the compound having an unsaturated bond will be described. Examples of the method of epoxidizing the compound having an unsaturated bond include a method of oxidizing the unsaturated bond of the compound having the unsaturated bond using a predetermined compound. The predetermined compound is not particularly limited as long as it is a compound that can epoxidize the unsaturated bond, and examples thereof include oxidizing agents such as peracetic acid and hydrogen peroxide. Furthermore, as a method of epoxidizing the compound having an unsaturated bond, a method of epoxidizing by generating peracetic acid or the like in the reaction system can be used.

  The compound having an unsaturated bond is not particularly limited, and a compound having an unsaturated bond can be used. Examples of the compound having an unsaturated bond include vegetable oils such as soybean oil, cottonseed oil, linseed oil, and rice bran oil.

  An example of reaction conditions for the method of epoxidizing the compound having an unsaturated bond will be described. As the reaction conditions, for example, an unsaturated bond of a compound having an unsaturated bond, acetic acid, and 50% hydrogen peroxide are dissolved in toluene, and then reacted at 50 ° C. for 6 hours to obtain an oil phase. It can be obtained by washing with water and distilling off or fractionating the solvent.

  The reaction solvent in the epoxidation method is not particularly limited, and various solvents can be used as long as they do not impair the epoxidation reaction. Examples of the reaction solvent include aromatic hydrocarbons such as toluene and benzene, and chlorinated hydrocarbons such as dichloromethane. Moreover, it is also possible to carry out the epoxidation reaction without using the reaction solvent.

  Further, from the viewpoint of increasing the efficiency of the epoxidation reaction, a salt may be added during the reaction. When adding a salt, the salt may be, for example, inorganic acids such as sulfuric acid, carbonic acid, nitric acid, hydrochloric acid, acidic compounds such as acetic acid and propylene acid, inorganic basic compounds such as sodium, potassium, and ammonium, amines, pyridine, etc. And organic base compounds.

Specifically, as the epoxy compound of the crosslinking agent (B), for example, polyethylene glycol type epoxy resin, polypropylene glycol type epoxy resin, hexanediol type epoxy resin, trimethylolpropane type epoxy resin, pentaerythritol type epoxy resin, Examples thereof include epoxy compounds having no aromaticity, such as glycerol type epoxy resins, polyglycerol type epoxy resins, sorbitol type epoxy resins, soybean oil-derived epoxy resins, linseed oil-derived epoxy resins, epoxy resin derived from rice bran oil. One or a mixture of two or more of these may be used. Among these, trimethylolpropane type epoxy resin, pentaerythritol type epoxy resin, glycerol type epoxy resin, polyglycerol type epoxy resin, sorbitol type epoxy resin, and linseed oil-derived epoxy resin are preferable in terms of excellent solvent resistance.
Moreover, the compound obtained by epoxidizing the non-petroleum origin compound can also be used as an epoxy compound of the said crosslinking agent (B). When such a compound is used as the epoxy compound of the cross-linking agent (B), it has a high degree of natural origin, which is preferable from the viewpoint of excellent environmental compatibility.

  The isocyanate compound of the crosslinking agent (B) refers to monomers, oligomers, and polymers in general that have no aromatic group and have an isocyanate group in one molecule.

  The number of isocyanate groups contained in the isocyanate compound of the crosslinking agent (B) is not particularly limited as long as it has at least one, but the viewpoint of improving the solvent resistance of the resin composition or the resin molded body Therefore, it is preferable to have two or more.

  Specific examples include hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4-4'-diisocyanate, dichlorohexylmethane-2-4'-diisocyanate, and norbornene methane diisocyanate. One or a mixture of two or more of these may be used.

  Among the specific examples of the isocyanate compound, norbornene methane diisocyanate and dicyclohexylmethane-4-4'-diisocyanate are preferable from the viewpoint of moldability, and hexamethylene diisocyanate is more preferable from the viewpoint of ensuring solvent resistance.

  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 different crosslinking points and different types from 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 have any structure different from that of 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 not only the compound represented by the above formula (1) contained in the crosslinking agent (C) has a multifunctional crosslinking point, but also the crosslinking agent (B) forms a crosslinking point. This is thought to be due to having a plurality of different cross-linked structures. Furthermore, a plurality of different cross-linked structures improve the resistance to strain and durability (boiling resistance, etc.) of the cured product, and also suppress 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, the blending ratio can be optimized from the viewpoint of achieving both the moldability of the resin composition and the resistance to distortion of the cured product, and a resin molded article excellent in dimensional accuracy and resistance to distortion can be 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. 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” contained in at least one “—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 plurality of different cross-linked structures are formed, and a cured product having excellent resistance to strain, durability and appearance can be obtained.

[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. ]

  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 excellent resistance to distortion, durability and appearance can be obtained.

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

[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 cross-linking agent (C) contains at least one compound of quinuclidine, pyridine and hexamethylenetetramine instead of or together with the compound represented by the formula (1). Also good. The cured product containing such a crosslinking agent (C) has excellent mechanical strength and high durability and appearance. This is because quinuclidine, pyridine and hexamethylenetetramine cross-link the lignin derivative (A) with high density and uniformity to form a homogeneous and rigid skeleton.
In addition, when a proton from the lignin derivative (A) is added to quinuclidine, pyridine and hexamethylenetetramine, 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 cross-linking agent (B) and the cross-linking agent (C) is not particularly limited, but is preferably 1 to 50 and more preferably 3 to 40 by weight ratio. 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.

  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, 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 having high dimensional accuracy and excellent resistance to strain can be produced. . Moreover, since the said resin composition has the high impregnation property with respect to a core material, and is excellent in a cure rate, it can manufacture the laminated board excellent in durability and an external appearance.

  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.

  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)
The resin composition of the present invention may contain a catalyst. Various catalysts can be used as long as they can promote crosslinking and curing of the resin composition.

  When the crosslinking agent (B) group is an epoxy compound, examples of the catalyst include 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, tertiary amines such as tris (dimethylaminomethyl) phenol, benzyldimethylamine, triphenylphosphine, tetra-n -General catalysts for epoxy resins such as butylphosphonium tetraphenylborate are listed.

  When the crosslinking agent (B) group is a diisocyanate compound, examples of the catalyst include an organotin compound, a carboxylic acid tin salt, a carboxylic acid lead salt, and a carboxylic acid bismuth salt.

  When the catalyst is added, the catalyst is added in an amount of 0.01 to 5. with respect to 100 parts by weight of the total content (J) of the resin (A), the crosslinking agent (B), and the crosslinking agent (C). 0 parts by weight is preferable, and 0.1 to 2.5 parts by weight is more preferable.

  Further, when a reactive functional group is introduced into the lignin derivative (A) as will be described later, 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, examples of the catalyst include 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 Common catalysts for epoxy resins such as -n-butylphosphonium tetraphenylborate are listed.

  In addition, when the reactive functional group is an isocyanate group, examples of the curing agent include general isocyanate resin catalysts such as polyvinyl alcohol and polyamine compounds, and one or more of these may be used. A mixture 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 0.05-3.0 with respect to 100 weight part of total content (J) of resin (A), a crosslinking agent (B), and a crosslinking agent (C). Part by weight is preferable, and 0.2 to 2.5 parts by weight is more preferable.

(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, it is possible to fill the cavity with the molding material without gaps, and to obtain a resin molded body that is homogeneous and excellent in strain resistance, durability, and appearance.

  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 solvent resistance after curing can be achieved at a high level.

(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.

  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 metal salts thereof, mold release agents such as paraffin, pigments such as carbon black, dyes such as Sudan Black B, silicone oil, silicone Low stress components such as antimony, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, flame retardants such as phosphazene, inorganic ion exchangers such as bismuth oxide hydrate, internal separation A mold agent etc. are mentioned, What combined 1 type, or 2 or more types of these 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.

  Next, an example of 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. Depending on the processing conditions, an aqueous layer and an organic layer are obtained, and the resin composition is obtained by separating and distilling the organic layer. Hereinafter, an example of each process will be sequentially described.

[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 a solvent at the time of 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 produced by curing when or after the resin composition of the present invention is molded.

  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), but the condensation reaction or addition accompanying the dealcoholization reaction or dehydration reaction. It is considered that the crosslinking agent (B), the crosslinking agent (C) and the crosslinking reaction point of the lignin derivative (A) are crosslinked by reaction or the like.

  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. Condensate.

  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 lignin derivative (A) was obtained by drying the solution and collecting the solute.

(2) Preparation of resin composition Next, 100 parts by mass of the obtained lignin derivative (A), 30 parts by weight of a sorbitol glycidyl ether compound (functional group equivalent 191) as a crosslinking agent (B), and 2-methylimidazole 0 0.5 parts by weight, 400 parts by mass of silica powder (manufactured by Denki Kagaku Co., Ltd., average particle size 15 μm) and 10 parts by mass of hexamethylenetetramine as a crosslinking agent (C) were kneaded at 80 ° C. with a hot roll, By kneading for 5 minutes, a sheet-like kneaded product was obtained.
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 by transfer shaping | molding for 5 minutes on the shaping | molding conditions of 175 degreeC and 6.9 Mpa, 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.

(4) Evaluation of number average molecular weight of lignin derivative The obtained lignin derivative (A) 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 a 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 Table 1.

(5) Evaluation of presence or absence of carboxyl group of lignin derivative The obtained lignin derivative (A) 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 Table 1.

(6) Evaluation of degree of curing of temporary molded body The obtained resin composition 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
In addition, the evaluation criteria of the hardening degree of a temporary molded object are as follows.
◎: Curing degree is 80% or more ○: Curing degree is 70% or more and less than 80% △: Curing degree is 60% or more and less than 70% X: Curing degree is less than 60% Measurement result The results are shown in Table 1.

(7) Evaluation of degree of cure of resin molded body The obtained resin composition was treated under the conditions of 175 ° C. for 10 minutes and then treated at 180 ° C. for 6 hours to obtain a resin molded body by heat molding. . 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
In addition, the evaluation criteria of the hardening degree of a resin molding are as follows.
◎: Curing degree is 95% or more ○: Curing degree is 90% or more and less than 95% △: Curing degree is 85% or more and less than 90% ×: Curing degree is less than 85% Measurement result The results are shown in Table 1.

(8) Evaluation of gel time The resin composition which does not add a silica powder was produced, and the gel time (gel time) in 175 degreeC was measured based on the method prescribed | regulated to JISK6910.
The measurement results are shown in Table 1.

(9) Evaluation of strain at bending fracture of resin molded body The obtained lignin resin molded body was subjected to a bending test until it broke according to the method defined in JIS-C6481. And the ratio (elongation at the time of bending fracture) of the change of the dimension after a test to the dimension before a test was evaluated.
In addition, the evaluation criteria of the strain at the time of bending fracture are as follows.
○: Bending fracture is 0.5% or more ×: Bending fracture is less than 0.5% The measurement results are shown in Table 1.

(10) Evaluation of external appearance of resin molding The external appearance of the obtained resin molding was confirmed and evaluated.
The appearance evaluation criteria are as follows.
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. The measurement results with 6 or more spots are shown in Table 1.

(Example 2)
The same procedure as in Example 1 was carried out except that the crosslinking agent (B) was changed to 30 parts by weight of a glycerol type glycidyl ether compound (functional group equivalent 144).

(Example 3)
The procedure was the same as Example 1 except that the crosslinking agent (B) was changed to 30 parts by weight of epoxidized linseed oil (functional group equivalent 112).

(Example 4)
The same treatment as in Example 1 was performed except that the biomass decomposition temperature was changed to 290 ° C. and the biomass treatment pressure was changed to 9 MPa.

(Example 5)
The same procedure as in Example 1 was performed except that the biomass decomposition treatment temperature was changed to 250 ° C. and the biomass treatment pressure was changed to 4 MPa.

(Example 6)
The same procedure as in Example 1 was conducted except that the biomass decomposition treatment time was changed to 180 minutes and the crosslinking agent (B) was changed to 30 parts by weight of the glycerol type glycidyl ether compound (functional group equivalent 144).

(Example 7)
The same procedure as in Example 1 except that the crosslinking agent (B) was changed to 30 parts by weight of a glycerol type glycidyl ether compound (functional group equivalent 144) and the crosslinking agent (C) was changed to 7.5 parts by weight of hexamethylenetetramine. did.

(Example 8)
The biomass is changed to Miso bamboo, the biomass decomposition temperature is changed to 270 ° C., the biomass decomposition pressure is changed to 7 MPa, and the crosslinking agent (B) is 20 parts by weight of a sorbitol glycidyl ether compound (functional group equivalent 191). The procedure was the same as Example 1 except that the glycerol type glycidyl ether compound (functional group equivalent 144) was changed to 10 parts by weight and the crosslinking agent (C) was changed to 8 parts by weight of hexamethylenetetramine.

Example 9
The same procedure as in Example 1 was conducted except that the crosslinking agent (C) was changed to 6 parts by weight of hexamethylenetetramine, 2 parts by weight of quinuclidine, and 2 parts by weight of pyridine.

(Example 10)
The crosslinking agent (C) was prepared by adding 7 parts by weight of hexamethoxymethylmelamine, 1 part by weight of Nicalak MX-290 (manufactured by Sanwa Chemical Co., Ltd.), 1 part by weight of Nicarak MX-280 (manufactured by Sanwa Chemical Co., Ltd.) and Nicarak MX-270 (three The product was the same as Example 1 except that the amount was changed to 1 part by weight.

(Example 11)
The same procedure as in Example 1 except that the crosslinking agent (B) was changed to 45 parts by weight of the glycerol type glycidyl ether compound (functional group equivalent 144) and the crosslinking agent (C) was changed to 0.5 parts by weight of hexamethylenetetramine. did.

(Example 12)
The same procedure as in Example 1 was conducted except that the crosslinking agent (B) was changed to 75 parts by weight of a sorbitol-type glycidyl ether compound (functional group equivalent 191) and the crosslinking agent (C) was changed to 1 part by weight of hexamethylenetetramine.

(Example 13)
The same procedure as in Example 1 was conducted except that the crosslinking agent (B) was changed to 30 parts by weight of hexamethylene diisocyanate (functional group equivalent 84).

(Comparative Example 1)
Example 1 was repeated except that the resin was changed to a novolac type phenol resin.

(Comparative Example 2)
Example 1 was repeated except that the crosslinking agent (B) was not added.

(Comparative Example 3)
Example 1 was repeated except that the crosslinking agent (C) was not added.

  As is clear from Table 1, the lignin derivative (A) obtained in each example contains such a lignin derivative (A) because the gel time value is preferably 30 to 90 seconds from the viewpoint of moldability. The resin composition has excellent moldability.

  Further, as is apparent from Table 1, 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, excellent resistance to distortion, and excellent appearance. It becomes.

  From the above, according to the present invention, a resin composition excellent in moldability and resistance to strain and a resin molded body can be obtained without impairing solvent resistance.

Claims (11)

  The lignin derivative (A), at least one crosslinking agent (B) selected from an epoxy compound having no aromatic and an isocyanate compound having no aromatic, and the crosslinking agent (B) have different crosslinking points and A resin composition comprising different types of crosslinking agents (C). The resin composition according to claim 1, wherein the crosslinking agent (C) contains at least one of quinuclidine, pyridine, hexamethylenetetramine, and 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. ] The resin composition according to claim 2, wherein the crosslinking agent (C) contains at least one of those represented by any one of the following formulas (2) to (5).
[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. ] The resin composition according to claim 2, wherein the crosslinking agent (C) contains a compound represented by the following formula (6) or (7).
[In Formula (6), n represents the integer of 1-3. ]
[In formula (7), n represents the integer of 1-3. ]   2. The at least one crosslinking agent (B) selected from the epoxy compound having no aromatic and the isocyanate compound having no aromatic contains one having a functional group equivalent of 400 or less. The resin composition in any one of thru | or 4.   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. Resin composition.   The resin composition according to any one of claims 1 to 6, wherein the lignin derivative (A) contains a product obtained by subjecting biomass to subcritical processing.   Of 100 parts by weight of the lignin derivative (A), at least one crosslinking agent (B) selected from the epoxy compound having no aromatic and the isocyanate compound having no aromatic and the crosslinking agent (C) The resin composition according to any one of claims 1 to 7, wherein the total content is 5 to 100 parts by weight.   Ratio obtained by dividing the content of at least one crosslinking agent (B) selected from the epoxy compound having no aromatic and the isocyanate compound having no aromatic by the content of the crosslinking agent (C) [( The resin composition according to any one of claims 1 to 8, wherein B) / (C)] is 1 to 50.   The resin composition according to any one of claims 1 to 9, wherein the lignin derivative (A) contains a carboxyl group.   A resin molded article obtained by molding the resin composition according to claim 1.