WO2016194600A1 - Resin composition, method for producing resin composition, and molded article - Google Patents

Resin composition, method for producing resin composition, and molded article Download PDF

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Publication number
WO2016194600A1
WO2016194600A1 PCT/JP2016/064575 JP2016064575W WO2016194600A1 WO 2016194600 A1 WO2016194600 A1 WO 2016194600A1 JP 2016064575 W JP2016064575 W JP 2016064575W WO 2016194600 A1 WO2016194600 A1 WO 2016194600A1
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WIPO (PCT)
Prior art keywords
lignin
mass
carboxylic acid
resin composition
phenol
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PCT/JP2016/064575
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French (fr)
Japanese (ja)
Inventor
康典 大橋
霖 周
麻衣子 山本
木村　肇
大塚　恵子
松本　明博
Original Assignee
ハリマ化成株式会社
地方独立行政法人 大阪市立工業研究所
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Application filed by ハリマ化成株式会社, 地方独立行政法人 大阪市立工業研究所 filed Critical ハリマ化成株式会社
Publication of WO2016194600A1 publication Critical patent/WO2016194600A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials

Definitions

  • the present invention relates to a resin composition, a method for producing a resin composition, and a molded article, and more specifically, a resin composition containing a thermosetting resin, a method for producing the resin composition, and molding the resin composition. It is related with the molded article obtained by doing.
  • thermosetting resins have been widely used in various industrial fields such as electric parts, automobile parts, building materials, and daily necessities.
  • thermosetting resins various physical properties such as mechanical properties (strength, etc.), heat resistance, electrical insulation, etc. of molded products are required depending on the application, and the required physical properties. In order to satisfy the above, it has been studied to add various additives to the thermosetting resin.
  • thermosetting resins As an additive to be added to the thermosetting resin, in recent years, effective use of plant-derived materials has been required from the viewpoint of environmental protection. Specifically, for example, thermosetting resins and herbaceous materials are used. A lignin-added thermosetting resin containing lignin has been proposed (see Patent Document 1).
  • thermosetting resin may not have sufficient heat resistance and electrical insulation.
  • an object of the present invention is to provide a resin composition capable of obtaining a molded article having excellent heat resistance and electrical insulation, a method for producing the resin composition, and a molded article obtained by molding the resin composition. There is to do.
  • the present invention [1] A resin composition comprising a thermosetting resin and lignin modified with carboxylic acid and phenols, [2] The resin composition according to [1], wherein the lignin modified with carboxylic acid and phenol is a reaction product of lignin modified with carboxylic acid and phenol. [3] In the reaction of the lignin modified with carboxylic acid and the phenols, the mixing ratio of the phenols is 30 parts by mass or more and 1000 parts by mass with respect to 100 parts by mass of the lignin modified with carboxylic acid.
  • the resin composition of the present invention contains a thermosetting resin and lignin modified with carboxylic acid and phenols, a molded product having excellent heat resistance and electrical insulation can be obtained. Moreover, since the lignin modified with carboxylic acid and phenols is excellent in handleability, the resin composition of the present invention can be obtained easily and with good workability.
  • the resin composition of the present invention can be produced easily.
  • the molded article of the present invention is obtained by molding the resin composition of the present invention, it is excellent in heat resistance and electrical insulation.
  • the resin composition of the present invention contains a thermosetting resin and lignin modified with carboxylic acid and phenols (hereinafter sometimes referred to as carboxylic acid-phenol modified lignin).
  • thermosetting resin is not particularly limited and may be a known thermosetting resin. Specifically, for example, phenol resins (such as novolac type phenol resins and resol type phenol resins), epoxy resins, melamine resins, urea resins, unsaturated polyester resins, urethane resins, benzoguanamine resins, and the like can be given.
  • phenol resins such as novolac type phenol resins and resol type phenol resins
  • epoxy resins such as novolac type phenol resins and resol type phenol resins
  • epoxy resins such as novolac type phenol resins and resol type phenol resins
  • epoxy resins such as novolac type phenol resins and resol type phenol resins
  • epoxy resins such as novolac type phenol resins and resol type phenol resins
  • epoxy resins such as novolac type phenol resins and resol type phenol resins
  • epoxy resins such as novolac type phenol resins and
  • thermosetting resins can be used alone or in combination of two or more.
  • thermosetting resin a phenol resin is preferable, and a novolac type phenol resin is preferable.
  • a curing agent can be blended in the resin composition according to the type of the thermosetting resin. More specifically, for example, when a phenol resin is used as the thermosetting resin, a phenol resin curing agent can be blended in the resin composition.
  • the phenol resin curing agent is not particularly limited, and a known curing agent can be used. Specific examples include hexamethylenetetramine, methylol melamine, and methylol urea.
  • phenolic resin curing agents can be used alone or in combination of two or more.
  • hexamethylenetetramine is preferable.
  • the blending ratio of the phenol resin curing agent is appropriately set according to the purpose and application.
  • Carboxylic acid-phenol-modified lignin can be obtained, for example, by reacting lignin modified with carboxylic acid (hereinafter sometimes referred to as carboxylic acid-modified lignin) with phenols.
  • examples of the carboxylic acid include a carboxylic acid having one carboxy group (hereinafter, sometimes referred to as a monofunctional carboxylic acid).
  • Functional carboxylic acid unsaturated aliphatic monofunctional carboxylic acid, aromatic monofunctional carboxylic acid and the like can be mentioned.
  • saturated aliphatic monofunctional carboxylic acid examples include acetic acid, propionic acid, butyric acid, lauric acid and the like.
  • Examples of the unsaturated aliphatic monofunctional carboxylic acid include acrylic acid, methacrylic acid, and linoleic acid.
  • aromatic monofunctional carboxylic acid examples include benzoic acid, 2-phenoxybenzoic acid, and 4-methylbenzoic acid.
  • carboxylic acids can be used alone or in combination of two or more.
  • the carboxylic acid is preferably a saturated aliphatic monofunctional carboxylic acid, and more preferably acetic acid. If the carboxylic acid is used, a carboxylic acid-modified lignin can be easily obtained, and the carboxylic acid-modified lignin obtained has a relatively high solubility in an organic solvent and has a melting temperature as described later. Since it is relatively low temperature (about 100 to 200 ° C.), it is excellent in handleability.
  • Lignin is a high molecular phenolic compound having a basic skeleton such as guaiacyl lignin (G-type), syringyl lignin (S-type), p-hydroxyphenyl lignin (H-type), and is included in all plants. .
  • G-type guaiacyl lignin
  • S-type syringyl lignin
  • H-type p-hydroxyphenyl lignin
  • Such natural lignin is industrially extracted, for example, soda lignin contained in waste liquid (black liquor) discharged when producing pulp from plant raw materials by soda method, sulfite method, kraft method, etc. , Sulfite lignin, craft lignin and the like are known.
  • lignin examples include woody plant-derived lignin and herbaceous plant-derived lignin.
  • woody plant-derived lignin examples include coniferous lignin contained in conifers (eg, cedar), for example, broadleaf lignin contained in broadleaf trees. Such woody plant-derived lignin does not contain lignin having H-type basic skeleton, for example, conifer lignin has G-type basic skeleton, and hardwood lignin has G-type and S-type basic skeleton. Yes.
  • herbaceous plant-derived lignin examples include rice-based lignin contained in grass family plants (wheat straw, rice straw, corn, bamboo, etc.). Such herbaceous plant-derived lignin has all of H-type, G-type and S-type as the basic skeleton.
  • lignins can be used alone or in combination of two or more.
  • the lignin is preferably a herbaceous plant-derived lignin, more preferably a herbaceous plant-derived lignin derived from corn stover (corn core, stem, leaf, etc.).
  • lignin from the viewpoint of reactivity, it is preferable to contain an H-type basic skeleton in a proportion of 3% by mass or more, more preferably 9% by mass or more, and still more preferably 14% by mass or more. It is done.
  • the production method of the carboxylic acid-modified lignin is not particularly limited, and can conform to a known method.
  • plant materials for example, conifers, hardwoods, gramineous plants, etc.
  • carboxylic acid preferably acetic acid
  • the cooking method is not particularly limited.
  • a plant material that is a raw material for lignin is mixed with a carboxylic acid and an inorganic acid (for example, hydrochloric acid, sulfuric acid, etc.) and reacted.
  • an inorganic acid for example, hydrochloric acid, sulfuric acid, etc.
  • the mixing ratio of the carboxylic acid is such that the carboxylic acid (100% conversion) is, for example, 500 parts by mass or more, preferably 900 parts by mass or more, for example, 30000 with respect to 100 parts by mass of the plant material that is the raw material for lignin. It is 1 part by mass or less, preferably 15000 parts by mass or less.
  • the blending ratio of the inorganic acid is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more with respect to 100 parts by mass of the plant material that is the raw material for lignin. For example, it is 10 parts by mass or less, preferably 5 parts by mass or less.
  • reaction temperature is, for example, 30 ° C. or higher, preferably 50 ° C. or higher, for example, 400 ° C. or lower, preferably 250 ° C. or lower.
  • reaction time is, for example, 0.5 hours or more, preferably 1 hour or more, for example, 20 hours or less, preferably 10 hours or less.
  • the pulp is separated by a known separation method such as filtration, and the filtrate (pulp waste liquid) is recovered.
  • the unreacted carboxylic acid is known using, for example, a rotary evaporator, vacuum distillation or the like. It is removed (distilled off) by the method. Thereafter, a large excess of water is added to precipitate the carboxylic acid-modified lignin, followed by filtration to recover the carboxylic acid-modified lignin as a solid content.
  • carboxylic acid-modified lignin is obtained by reacting lignin not modified with carboxylic acid (hereinafter, unmodified lignin) with carboxylic acid. You can also.
  • the native lignin is preferably powdered native lignin.
  • the average particle size of the powdered unmodified lignin is, for example, 0.1 ⁇ m or more, preferably 5 ⁇ m or more, for example, 1000 ⁇ m or less, preferably 500 ⁇ m or less.
  • the average particle diameter is in the above range, aggregation of the unmodified lignin can be suppressed and the unmodified lignin can be favorably dispersed in the carboxylic acid.
  • the powdered unmodified lignin can be obtained by drying and pulverizing the lump unmodified lignin by a known method, or a commercially available product can be used.
  • unmodified lignin and carboxylic acid for example, unmodified lignin, carboxylic acid and inorganic acid (for example, hydrochloric acid, sulfuric acid, etc.) are mixed and reacted.
  • unmodified lignin, carboxylic acid and inorganic acid for example, hydrochloric acid, sulfuric acid, etc.
  • the mixing ratio of the carboxylic acid is, for example, 300 parts by mass or more, preferably 500 parts by mass or more, for example, 15000 parts by mass or less, based on 100 parts by mass of the unmodified lignin. Preferably, it is 10000 parts by mass or less.
  • the blending ratio of the inorganic acid is such that the inorganic acid (100% conversion) is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more with respect to 100 parts by mass of the unmodified lignin. 10 parts by mass or less, preferably 5 parts by mass or less.
  • reaction temperature is, for example, 30 ° C. or higher, preferably 50 ° C. or higher, for example, 400 ° C. or lower, preferably 250 ° C. or lower.
  • reaction time is, for example, 0.5 hours or more, preferably 1 hour or more, for example, 20 hours or less, preferably 10 hours or less.
  • Such carboxylic acid-modified lignin is excellent in handleability.
  • lignin that has not been modified with carboxylic acid has relatively low solubility in organic solvents and does not melt, so that it may be inferior in handleability depending on the application.
  • lignin modified with carboxylic acid as described above is an organic solvent (for example, esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone).
  • esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
  • aliphatic alcohols such as methanol, for example, phenols such as phenol, cresol, bisphenol A, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, such as methyl cellosolve acetate, ethyl cellosolve acetate, methylcarbyl Tall acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybuty Glycol ether esters such as acetate and ethyl-3-ethoxypropionate, for example, nitriles such as acetonitrile, others, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexa Since it has a relatively high solubility in a polar solvent such as
  • the carboxylic acid-modified lignin can also be used as a solution of the above organic solvent.
  • the concentration of the carboxylic acid-modified lignin in the solution is, for example, 10% by mass or more, preferably 30% by mass or more, for example, less than 100% by mass, preferably 90% by mass or less, more preferably 80% by mass or less.
  • the carboxylic acid-modified lignin is obtained as a mixture of a component (soluble component) that can be dissolved by the organic solvent (preferably ethyl acetate) and a component that cannot be dissolved by the organic solvent (insoluble component).
  • soluble component preferably ethyl acetate
  • insoluble component a component that cannot be dissolved by the organic solvent
  • a mixture of a soluble component and an insoluble component (referred to as crude carboxylic acid-modified lignin) can be used as the carboxylic acid-modified lignin.
  • Extraction temperature is room temperature (for example, 25 degreeC), for example.
  • the average particle size of the carboxylic acid-modified lignin is, for example, 0.1 ⁇ m or more, preferably 5 ⁇ m or more, for example, 2 cm or less, preferably 1 cm or less.
  • the phenols are phenol and derivatives thereof, such as phenol, and further, for example, o-cresol, p-cresol, p-ter-butylphenol, p-phenylphenol, p- Bifunctional phenol derivatives such as cumylphenol, p-nonylphenol, 2,4- or 2,6-xylenol, for example, trifunctional phenol derivatives such as m-cresol, resorcinol, 3,5-xylenol, such as bisphenol A, tetrafunctional phenol derivatives such as dihydroxydiphenylmethane, and the like.
  • halogenated phenols substituted with halogen such as chlorine and bromine can be mentioned. These phenols can be used alone or in combination of two or more.
  • Phenols are preferably phenol.
  • the blending ratio of phenols is, for example, 30 parts by mass or more, preferably 50 parts by mass or more with respect to 100 parts by mass of carboxylic acid-modified lignin. It is 500 parts by mass or less, preferably 500 parts by mass or less.
  • Examples of the acid catalyst include organic acids and inorganic acids.
  • organic acid examples include sulfonic acid compounds such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, cumenesulfonic acid, dinonylnaphthalene monosulfonic acid, dinonylnaphthalenedisulfonic acid, for example, trimethyl phosphate, Examples thereof include phosphate esters having an alkyl group having 1 to 18 carbon atoms such as triethyl phosphate, monobutyl phosphate, dibutyl phosphate, tributyl phosphate, trioctyl phosphate, and the like, for example, formic acid, acetic acid, oxalic acid and the like.
  • sulfonic acid compounds such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, cumenesulfonic acid, dinonylna
  • inorganic acids examples include phosphoric acid, hydrochloric acid, sulfuric acid, and nitric acid.
  • These acid catalysts can be used alone or in combination of two or more.
  • the acid catalyst is preferably an inorganic acid, more preferably sulfuric acid.
  • the mixing ratio of the acid catalyst is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, for example, 10 parts by mass or less, preferably 5 parts by mass with respect to 100 parts by mass of the phenols. It is as follows.
  • the timing of addition of the acid catalyst is not particularly limited, and may be added in advance to at least one of the carboxylic acid-modified lignin and the phenols, or added at the same time when the carboxylic acid-modified lignin and the phenols are blended. Further, it may be added after blending carboxylic acid-modified lignin and phenols.
  • the reaction temperature is, for example, 60 ° C. or higher, preferably 80 ° C. or higher, for example, 250 ° C. or lower, preferably 200 ° C. or lower.
  • the reaction time is, for example, 0.5 hours or more, preferably 1 hour or more, for example, 10 hours or less, preferably 5 hours or less.
  • carboxylic acid-modified lignin is modified with phenols to obtain a carboxylic acid-phenol-modified lignin.
  • the method for obtaining the carboxylic acid-phenol-modified lignin is not limited to the above.
  • the carboxylic acid-modified lignin is produced (for example, when the unmodified lignin and the carboxylic acid are reacted), an appropriate proportion of phenols is obtained. Can also be added.
  • unmodified lignin is collectively modified with carboxylic acid and phenols to obtain a carboxylic acid-phenol modified lignin.
  • a phenol-modified lignin is produced by modifying an unmodified lignin with a phenol, and then the resulting phenol-modified lignin is modified with a carboxylic acid to obtain a carboxylic acid-phenol-modified lignin. You can also.
  • the carboxylic acid-phenol-modified lignin is preferably a reaction product of carboxylic acid-modified lignin and phenols from the viewpoint of production efficiency.
  • carboxylic acid-phenol-modified lignin is excellent in handleability because it can be dissolved in the above organic solvent.
  • the concentration of the carboxylic acid-phenol-modified lignin in the solution is, for example, 10% by mass or more, preferably 30% by mass or more, for example, 100% by mass. %, Preferably 90% by mass or less, more preferably 80% by mass or less.
  • the blending ratio of the thermosetting resin and the carboxylic acid-phenol-modified lignin will be described in detail later, but the carboxylic acid-phenol-modified lignin (dissolved in the solvent) is added to 100 parts by mass of the thermosetting resin.
  • the solid content (hereinafter the same) is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, for example, 300 parts by mass or less, preferably 200 parts by mass or less, more preferably 150 parts by mass. It is 125 parts by mass or less, more preferably 125 parts by mass or less.
  • the resin composition can further contain an additive.
  • additives include known additives added to thermosetting resin compositions, such as fillers (wood flour, pulp, glass fibers, etc.), colorants, plasticizers, stabilizers, release agents (stearic acid). Metal soap such as zinc).
  • additives can be used alone or in combination of two or more.
  • a filler is used, more preferably, wood powder and glass fiber are used, and still more preferably, wood powder is used.
  • the content of the additive is appropriately set according to the purpose and application within a range that does not impair the excellent effects of the present invention.
  • the blending ratio is, for example, 10 parts by mass or more, preferably 20 parts by mass or more with respect to 100 parts by mass of the thermosetting resin. 300 parts by mass or less, preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 125 parts by mass or less.
  • the additive may be added in advance to the thermosetting resin and / or the carboxylic acid-phenol modified lignin, or may be added simultaneously with the blending of the thermosetting resin and the carboxylic acid-phenol modified lignin. It may be added to a mixture of a thermosetting resin and a carboxylic acid-phenol modified lignin.
  • thermosetting resin and a carboxylic acid-phenol-modified lignin may be blended and kneaded.
  • the blending ratio of the thermosetting resin and the carboxylic acid-phenol modified lignin is such that the carboxylic acid-phenol modified lignin is, for example, 10 parts by mass or more, preferably 20 parts by mass or more with respect to 100 parts by mass of the thermosetting resin. For example, it is 300 parts by mass or less, preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 125 parts by mass or less.
  • thermosetting resin and the carboxylic acid-phenol-modified lignin are within the above range, it is possible to suppress an increase in viscosity, ensure excellent moldability, and further, heat resistance of the obtained molded product. In addition, electrical insulation can be improved.
  • the carboxylic acid-phenol-modified lignin is more preferably 70 parts by mass or more, more preferably 75 parts by mass or more, with respect to 100 parts by mass of the thermosetting resin. Particularly preferably, it is 80 parts by mass or more, more preferably 150 parts by mass or less, further preferably 125 parts by mass or less, and particularly preferably 110 parts by mass or less.
  • the carboxylic acid-phenol-modified lignin exceeds 100 parts by mass with respect to 100 parts by mass of the thermosetting resin, and more preferably 150 parts by mass. More preferably, it is 180 parts by mass or more, more preferably 300 parts by mass or less, still more preferably 250 parts by mass or less, and particularly preferably 220 parts by mass or less.
  • thermosetting resin by adjusting the blending ratio of the thermosetting resin and the carboxylic acid-phenol modified lignin, the mechanical strength and water resistance of the molded product can be further improved.
  • the carboxylic acid-phenol-modified lignin is preferably 30 parts by mass or more, more preferably 40 parts by mass or more with respect to 100 parts by mass of the thermosetting resin. Preferably, it is less than 100 mass parts, More preferably, it is 80 mass parts or less, More preferably, it is 70 mass parts or less.
  • the kneading method is not particularly limited, and for example, a known kneader such as a single screw extruder, a multi-screw extruder, a roll kneader, a kneader, a Henschel mixer, a Banbury mixer, etc. can be used.
  • a known kneader such as a single screw extruder, a multi-screw extruder, a roll kneader, a kneader, a Henschel mixer, a Banbury mixer, etc. can be used.
  • the kneading temperature is 80 ° C. or higher, preferably 90 ° C. or higher, more preferably 100 ° C. or higher, 180 ° C. or lower, preferably 170 ° C. or lower, more preferably 160 ° C. or lower.
  • the kneading time is, for example, 3 minutes or more, preferably 5 minutes or more, for example, 30 minutes or less, preferably 20 minutes or less.
  • the resin composition thus obtained contains a thermosetting resin and lignin modified with carboxylic acid and phenols, a molded product having excellent heat resistance and electrical insulation can be obtained. Moreover, since lignin modified with carboxylic acid and phenols is excellent in handleability, the above resin composition can be obtained easily and with good workability.
  • the above resin composition can be easily produced.
  • a molded product can be obtained by molding the above resin composition by a known thermosetting resin molding method such as transfer molding or compression molding.
  • the molded product obtained can be widely used in various industrial fields such as electric parts, automobile parts, building materials, and daily necessities.
  • Production Example 1 100 parts by mass of corn stover was mixed with 1000 parts by mass of 95% by mass acetic acid and 3 parts by mass of sulfuric acid, and reacted for 4 hours under reflux. After the reaction, the pulp was removed by filtration, and the pulp waste liquid was recovered. Next, after removing acetic acid in the pulp waste liquid using a rotary evaporator and concentrating until the volume becomes 1/10, 10 times the amount of the concentrated liquid (mass basis) is added and filtered, Acetic acid-modified lignin (crude acetic acid-modified lignin) was obtained as a solid content.
  • Production Example 2 The acetic acid-modified lignin (crude acetic acid-modified lignin) obtained in Production Example 1 was dissolved in ethyl acetate at room temperature (25 ° C.), and separated into a filtrate and a residue by filtration.
  • Acetic acid-modified lignin contained in the obtained filtrate was used as a soluble component (soluble acetic acid-modified lignin).
  • a soluble component soluble acetic acid-modified lignin
  • the obtained product was repeatedly washed with 1 kg of water until the pH became 6 to 7, and then subjected to suction filtration using a filter paper (Advantec No. 101), and a phenol-modified product of soluble acetic acid-modified lignin. (Soluble acetic acid-phenol modified lignin) was taken out.
  • Production Example 3 The acetic acid-modified lignin obtained in Production Example 1 was dissolved in ethyl acetate at room temperature (25 ° C.) and separated into a filtrate and a residue by filtration.
  • the obtained product was repeatedly washed with 1 kg of water until the pH became 6 to 7, and then filtered with suction using filter paper (Advantec No. 101) to obtain a phenol-modified product of insoluble acetic acid-modified lignin ( Insoluble acetic acid-phenol modified lignin) was taken out.
  • Production Example 4 After neutralizing the straw straw alkaline digested pulp waste liquor (black liquor), it was filtered to obtain unmodified lignin as a solid content.
  • Example 1 300 g of novolak type phenol resin (Asahi Organic Materials Co., Ltd.), 150 g of soluble acetic acid-phenol modified lignin obtained in Production Example 2, 150 g of wood flour (Asahi Organic Materials Co., Ltd.) as a filler, and curing 54 g of hexamethylenetetramine (manufactured by Lignite Co., Ltd.) as an agent and 4.5 g of zinc stearate (manufactured by Wako Pure Chemical Industries, Ltd.) as a mold release agent were sequentially blended, and 5 at 100 ° C. with two hot rolls. Kneading for a minute gave a resin composition.
  • Example 2 A resin composition was obtained in the same manner as in Example 1 except that the amount of the novolac-type phenol resin was 225 g and the amount of the soluble acetic acid-phenol-modified lignin was 225 g.
  • Example 3 A resin composition was obtained in the same manner as in Example 1 except that the amount of the novolac-type phenol resin was 180 g and the amount of the soluble acetic acid-phenol-modified lignin was 270 g.
  • Example 4 A resin composition was obtained in the same manner as in Example 1 except that the amount of the novolac-type phenol resin was 150 g and the amount of the soluble acetic acid-phenol-modified lignin was 300 g.
  • Example 5 A resin composition was obtained in the same manner as in Example 1 except that the amount of the novolak-type phenol resin was 112.5 g and the amount of the soluble acetic acid-phenol-modified lignin was 337.5 g.
  • Example 6 A resin composition was prepared in the same manner as in Example 1 except that 150 g of the insoluble acetic acid-phenol modified lignin obtained in Production Example 3 was added instead of 150 g of the soluble acetic acid-phenol modified lignin obtained in Production Example 2. Obtained.
  • Example 7 A resin composition was obtained in the same manner as in Example 6 except that the amount of the novolac-type phenol resin was 225 g and the amount of the insoluble acetic acid-phenol-modified lignin was 225 g.
  • Example 8 A resin composition was obtained in the same manner as in Example 6 except that the amount of the novolac-type phenol resin was 200 g and the amount of the insoluble acetic acid-phenol-modified lignin was 250 g.
  • Comparative Example 1 A resin composition was obtained in the same manner as in Example 1 except that 150 g of the unmodified lignin obtained in Production Example 4 was blended in place of 150 g of the soluble acetic acid-phenol-modified lignin obtained in Production Example 2.
  • Comparative Example 3 Instead of 150 g of insoluble acetic acid-phenol-modified lignin, 150 g of insoluble acetic acid-modified lignin (non-phenol-modified-insoluble acetic acid-modified lignin) before being modified with phenol in Production Example 3 was blended in the same manner as in Example 6. A resin composition was obtained.
  • Comparative Example 4 300 g of novolak type phenolic resin (manufactured by Asahi Organic Materials Co., Ltd.), 100 g of wood flour (manufactured by Asahi Organic Materials Co., Ltd.) as a filler, 54 g of hexamethylenetetramine (manufactured by Lignite) as a curing agent, and a release agent was mixed with 4.5 g of zinc stearate (manufactured by Wako Pure Chemical Industries, Ltd.) and kneaded with two hot rolls at 100 ° C. for 5 minutes to obtain a resin composition.
  • novolak type phenolic resin manufactured by Asahi Organic Materials Co., Ltd.
  • wood flour manufactured by Asahi Organic Materials Co., Ltd.
  • hexamethylenetetramine manufactured by Lignite
  • a release agent was mixed with 4.5 g of zinc stearate (manufactured by Wako Pure Chemical Industries, Ltd.) and kn
  • the resin composition of the present invention, the method for producing the resin composition, and the molded product are suitably used in various industrial fields such as electric parts, automobile parts, building materials, and daily necessities.

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Abstract

The resin composition contains a thermosetting resin and a lignin modified by a carboxylic acid and phenols.

Description

樹脂組成物、樹脂組成物の製造方法、および、成形品RESIN COMPOSITION, METHOD FOR PRODUCING RESIN COMPOSITION, AND MOLDED ARTICLE
　本発明は、樹脂組成物、樹脂組成物の製造方法、および、成形品に関し、詳しくは、熱硬化性樹脂を含有する樹脂組成物、その樹脂組成物の製造方法、および、樹脂組成物を成形して得られる成形品に関する。 The present invention relates to a resin composition, a method for producing a resin composition, and a molded article, and more specifically, a resin composition containing a thermosetting resin, a method for producing the resin composition, and molding the resin composition. It is related with the molded article obtained by doing.
　従来より、熱硬化性樹脂は、例えば、電気部品、自動車部品、建築材料、日用品などの各種産業分野において広く用いられている。 Conventionally, thermosetting resins have been widely used in various industrial fields such as electric parts, automobile parts, building materials, and daily necessities.
　このような熱硬化性樹脂としては、その用途に応じて、例えば、成形品の機械物性（強度など）、耐熱性、電気絶縁性など、各種物性の向上が要求されており、要求される物性を満足するため、各種添加剤を熱硬化性樹脂に添加することが検討されている。 For such thermosetting resins, various physical properties such as mechanical properties (strength, etc.), heat resistance, electrical insulation, etc. of molded products are required depending on the application, and the required physical properties. In order to satisfy the above, it has been studied to add various additives to the thermosetting resin.
　また、熱硬化性樹脂に添加される添加剤としては、近年、環境保全の観点から、植物由来の材料の有効利用が要求されており、具体的には、例えば、熱硬化性樹脂と草本系リグニンとを含有するリグニン添加熱硬化性樹脂が、提案されている（特許文献１参照）。 In addition, as an additive to be added to the thermosetting resin, in recent years, effective use of plant-derived materials has been required from the viewpoint of environmental protection. Specifically, for example, thermosetting resins and herbaceous materials are used. A lignin-added thermosetting resin containing lignin has been proposed (see Patent Document 1).
特開２０１２－０８２２５５号公報JP 2012-082255 A
　しかし、上記のリグニン添加熱硬化性樹脂では、耐熱性および電気絶縁性が十分ではない場合がある。 However, the above lignin-added thermosetting resin may not have sufficient heat resistance and electrical insulation.
　そこで、本発明の目的は、耐熱性および電気絶縁性に優れる成形品を得ることができる樹脂組成物、その樹脂組成物の製造方法、および、樹脂組成物を成形して得られる成形品を提供することにある。 Accordingly, an object of the present invention is to provide a resin composition capable of obtaining a molded article having excellent heat resistance and electrical insulation, a method for producing the resin composition, and a molded article obtained by molding the resin composition. There is to do.
　本発明は、
［１］　熱硬化性樹脂と、カルボン酸およびフェノール類により変性されたリグニンとを含有することを特徴とする、樹脂組成物、
［２］　カルボン酸およびフェノール類により変性された前記リグニンが、カルボン酸により変性されたリグニンと、フェノール類との反応生成物である、上記［１］に記載の樹脂組成物、
［３］　カルボン酸により変性された前記リグニンと、前記フェノール類との反応において、前記フェノール類の配合割合が、カルボン酸により変性された前記リグニン１００質量部に対して、３０質量部以上１０００質量部以下である、上記［２］に記載の樹脂組成物、
［４］　前記カルボン酸が、酢酸である、上記［１］～［３］のいずれか一項に記載の樹脂組成物、
［５］　前記リグニンが、草本系植物由来リグニンである、上記［１］～［４］のいずれか一項に記載の樹脂組成物、
［６］　前記熱硬化性樹脂が、フェノール樹脂である、上記［１］～［５］のいずれか一項に記載の樹脂組成物、
［７］　熱硬化性樹脂と、カルボン酸およびフェノール類により変性されたリグニンとを、８０℃以上１８０℃以下において混練することを特徴とする、樹脂組成物の製造方法、
［８］　上記［１］～［６］のいずれか一項に記載の樹脂組成物を成形して得られることを特徴とする、成形品
である。 The present invention
[1] A resin composition comprising a thermosetting resin and lignin modified with carboxylic acid and phenols,
[2] The resin composition according to [1], wherein the lignin modified with carboxylic acid and phenol is a reaction product of lignin modified with carboxylic acid and phenol.
[3] In the reaction of the lignin modified with carboxylic acid and the phenols, the mixing ratio of the phenols is 30 parts by mass or more and 1000 parts by mass with respect to 100 parts by mass of the lignin modified with carboxylic acid. Part or less of the resin composition according to the above [2],
[4] The resin composition according to any one of [1] to [3], wherein the carboxylic acid is acetic acid,
[5] The resin composition according to any one of [1] to [4], wherein the lignin is a herbaceous plant-derived lignin,
[6] The resin composition according to any one of [1] to [5], wherein the thermosetting resin is a phenol resin.
[7] A method for producing a resin composition, comprising kneading a thermosetting resin and lignin modified with a carboxylic acid and a phenol at 80 ° C. or higher and 180 ° C. or lower,
[8] A molded article obtained by molding the resin composition according to any one of [1] to [6].
　本発明の樹脂組成物は、熱硬化性樹脂と、カルボン酸およびフェノール類により変性されたリグニンとを含有しているため、耐熱性および電気絶縁性に優れる成形品を得ることができる。また、カルボン酸およびフェノール類により変性されたリグニンは、取扱性に優れるため、本発明の樹脂組成物は、簡易かつ作業性よく得ることができる。 Since the resin composition of the present invention contains a thermosetting resin and lignin modified with carboxylic acid and phenols, a molded product having excellent heat resistance and electrical insulation can be obtained. Moreover, since the lignin modified with carboxylic acid and phenols is excellent in handleability, the resin composition of the present invention can be obtained easily and with good workability.
　また、本発明の樹脂組成物の製造方法によれば、本発明の樹脂組成物を、簡易に製造することができる。 Moreover, according to the method for producing a resin composition of the present invention, the resin composition of the present invention can be produced easily.
　また、本発明の成形品は、本発明の樹脂組成物を成形して得られるため、耐熱性および電気絶縁性に優れる。 Moreover, since the molded article of the present invention is obtained by molding the resin composition of the present invention, it is excellent in heat resistance and electrical insulation.
　本発明の樹脂組成物は、熱硬化性樹脂と、カルボン酸およびフェノール類により変性されたリグニン（以下、カルボン酸－フェノール変性リグニンと称する場合がある。）とを含有している。 The resin composition of the present invention contains a thermosetting resin and lignin modified with carboxylic acid and phenols (hereinafter sometimes referred to as carboxylic acid-phenol modified lignin).
　熱硬化性樹脂としては、特に制限されず、公知の熱硬化性樹脂が挙げられる。具体的には、例えば、フェノール樹脂（ノボラック型フェノール樹脂、レゾール型フェノール樹脂など）、エポキシ樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル樹脂、ウレタン樹脂、ベンゾグアナミン樹脂などが挙げられる。 The thermosetting resin is not particularly limited and may be a known thermosetting resin. Specifically, for example, phenol resins (such as novolac type phenol resins and resol type phenol resins), epoxy resins, melamine resins, urea resins, unsaturated polyester resins, urethane resins, benzoguanamine resins, and the like can be given.
　これら熱硬化性樹脂は、単独使用または２種類以上併用することができる。 These thermosetting resins can be used alone or in combination of two or more.
　熱硬化性樹脂として、好ましくは、フェノール樹脂が挙げられ、好ましくは、ノボラック型フェノール樹脂が挙げられる。 As the thermosetting resin, a phenol resin is preferable, and a novolac type phenol resin is preferable.
　また、樹脂組成物には、熱硬化性樹脂の種類に応じて、硬化剤を配合することができる。より具体的には、例えば、熱硬化性樹脂としてフェノール樹脂が用いられる場合、樹脂組成物には、フェノール樹脂硬化剤を配合することができる。 Further, a curing agent can be blended in the resin composition according to the type of the thermosetting resin. More specifically, for example, when a phenol resin is used as the thermosetting resin, a phenol resin curing agent can be blended in the resin composition.
　フェノール樹脂硬化剤としては、特に制限されず、公知の硬化剤を用いることができる。具体的には、例えば、ヘキサメチレンテトラミン、メチロールメラミン、メチロール尿素などが挙げられる。 The phenol resin curing agent is not particularly limited, and a known curing agent can be used. Specific examples include hexamethylenetetramine, methylol melamine, and methylol urea.
　これらフェノール樹脂硬化剤は、単独使用または２種類以上併用することができる。 These phenolic resin curing agents can be used alone or in combination of two or more.
　フェノール樹脂硬化剤として、好ましくは、ヘキサメチレンテトラミンが挙げられる。 As the phenol resin curing agent, hexamethylenetetramine is preferable.
　フェノール樹脂硬化剤の配合割合は、目的および用途に応じて、適宜設定される。 The blending ratio of the phenol resin curing agent is appropriately set according to the purpose and application.
　カルボン酸－フェノール変性リグニンは、例えば、カルボン酸により変性されたリグニン（以下、カルボン酸変性リグニンと称する場合がある。）と、フェノール類との反応により、得ることができる。 Carboxylic acid-phenol-modified lignin can be obtained, for example, by reacting lignin modified with carboxylic acid (hereinafter sometimes referred to as carboxylic acid-modified lignin) with phenols.
　カルボン酸変性リグニンにおいて、カルボン酸としては、例えば、カルボキシ基を１つ有するカルボン酸（以下、単官能カルボン酸と称する場合がある。）が挙げられ、具体的には、例えば、飽和脂肪族単官能カルボン酸、不飽和脂肪族単官能カルボン酸、芳香族単官能カルボン酸などが挙げられる。 In the carboxylic acid-modified lignin, examples of the carboxylic acid include a carboxylic acid having one carboxy group (hereinafter, sometimes referred to as a monofunctional carboxylic acid). Functional carboxylic acid, unsaturated aliphatic monofunctional carboxylic acid, aromatic monofunctional carboxylic acid and the like can be mentioned.
　飽和脂肪族単官能カルボン酸としては、例えば、酢酸、プロピオン酸、酪酸、ラウリル酸などが挙げられる。 Examples of the saturated aliphatic monofunctional carboxylic acid include acetic acid, propionic acid, butyric acid, lauric acid and the like.
　不飽和脂肪族単官能カルボン酸としては、例えば、アクリル酸、メタクリル酸、リノール酸などが挙げられる。 Examples of the unsaturated aliphatic monofunctional carboxylic acid include acrylic acid, methacrylic acid, and linoleic acid.
　芳香族単官能カルボン酸としては、例えば、安息香酸、２－フェノキシ安息香酸、４－メチル安息香酸などが挙げられる。 Examples of the aromatic monofunctional carboxylic acid include benzoic acid, 2-phenoxybenzoic acid, and 4-methylbenzoic acid.
　これらカルボン酸は、単独使用または２種類以上併用することができる。 These carboxylic acids can be used alone or in combination of two or more.
　カルボン酸として、好ましくは、飽和脂肪族単官能カルボン酸、より好ましくは、酢酸が挙げられる。上記のカルボン酸を用いれば、カルボン酸変性リグニンを簡易に得ることができ、また、得られるカルボン酸変性リグニンは、後述するように、有機溶媒に対する溶解性が比較的高く、また、溶融温度が比較的低温（１００～２００℃程度）であるため、取扱性にも優れる。 The carboxylic acid is preferably a saturated aliphatic monofunctional carboxylic acid, and more preferably acetic acid. If the carboxylic acid is used, a carboxylic acid-modified lignin can be easily obtained, and the carboxylic acid-modified lignin obtained has a relatively high solubility in an organic solvent and has a melting temperature as described later. Since it is relatively low temperature (about 100 to 200 ° C.), it is excellent in handleability.
　リグニンは、グアイアシルリグニン（Ｇ型）、シリンギルリグニン（Ｓ型）、ｐ－ヒドロキシフェニルリグニン（Ｈ型）などの基本骨格からなる高分子フェノール性化合物であって、植物全般に含まれている。このような天然リグニンを工業的に取り出したものとしては、例えば、植物原料からパルプをソーダ法、亜硫酸法、クラフト法などによって製造する際、排出される廃液（黒液）中に含まれるソーダリグニン、サルファイトリグニン、クラフトリグニンなどが知られている。 Lignin is a high molecular phenolic compound having a basic skeleton such as guaiacyl lignin (G-type), syringyl lignin (S-type), p-hydroxyphenyl lignin (H-type), and is included in all plants. . Such natural lignin is industrially extracted, for example, soda lignin contained in waste liquid (black liquor) discharged when producing pulp from plant raw materials by soda method, sulfite method, kraft method, etc. , Sulfite lignin, craft lignin and the like are known.
　リグニンとして、具体的には、木本系植物由来リグニン、草本系植物由来リグニンが挙げられる。 Specific examples of lignin include woody plant-derived lignin and herbaceous plant-derived lignin.
　木本系植物由来リグニンとしては、例えば、針葉樹（例えば、スギなど）に含まれる針葉樹系リグニン、例えば、広葉樹に含まれる広葉樹系リグニンなどが挙げられる。このような木本系植物由来リグニンは、Ｈ型を基本骨格とするリグニンを含まず、例えば、針葉樹系リグニンはＧ型を基本骨格とし、広葉樹系リグニンは、Ｇ型およびＳ型を基本骨格としている。 Examples of woody plant-derived lignin include coniferous lignin contained in conifers (eg, cedar), for example, broadleaf lignin contained in broadleaf trees. Such woody plant-derived lignin does not contain lignin having H-type basic skeleton, for example, conifer lignin has G-type basic skeleton, and hardwood lignin has G-type and S-type basic skeleton. Yes.
　草本系植物由来リグニンとしては、例えば、イネ科植物（麦わら、稲わら、とうもろこし、タケなど）に含まれるイネ系リグニンなどが挙げられる。このような草本系植物由来リグニンは、Ｈ型、Ｇ型およびＳ型の全てを基本骨格としている。 Examples of herbaceous plant-derived lignin include rice-based lignin contained in grass family plants (wheat straw, rice straw, corn, bamboo, etc.). Such herbaceous plant-derived lignin has all of H-type, G-type and S-type as the basic skeleton.
　これらのリグニンは、単独使用または２種類以上併用することができる。 These lignins can be used alone or in combination of two or more.
　リグニンとして、好ましくは、草本系植物由来リグニン、より好ましくは、コーンストーバー（とうもろこしの芯、茎、葉など）に由来する草本系植物由来リグニンが挙げられる。 The lignin is preferably a herbaceous plant-derived lignin, more preferably a herbaceous plant-derived lignin derived from corn stover (corn core, stem, leaf, etc.).
　また、リグニンとして、好ましくは、反応性の観点から、Ｈ型の基本骨格を３質量％以上、より好ましくは、９質量％以上、さらに好ましくは、１４質量％以上の割合で含有することが挙げられる。 Further, as lignin, from the viewpoint of reactivity, it is preferable to contain an H-type basic skeleton in a proportion of 3% by mass or more, more preferably 9% by mass or more, and still more preferably 14% by mass or more. It is done.
　カルボン酸変性リグニンの製造方法は、特に制限されず、公知の方法に準拠することができる。 The production method of the carboxylic acid-modified lignin is not particularly limited, and can conform to a known method.
　具体的には、例えば、リグニンの原料となる植物材料（例えば、針葉樹、広葉樹、イネ科植物など）を、カルボン酸（好ましくは、酢酸）を用いて蒸解することによって、パルプ廃液としてカルボン酸変性リグニンを得ることができる。 Specifically, for example, plant materials (for example, conifers, hardwoods, gramineous plants, etc.), which are raw materials for lignin, are digested with carboxylic acid (preferably acetic acid), so that carboxylic acid modification is performed as pulp waste liquid. Lignin can be obtained.
　蒸解方法としては、特に制限されないが、例えば、リグニンの原料となる植物材料と、カルボン酸および無機酸（例えば、塩酸、硫酸など）とを混合し、反応させる。 The cooking method is not particularly limited. For example, a plant material that is a raw material for lignin is mixed with a carboxylic acid and an inorganic acid (for example, hydrochloric acid, sulfuric acid, etc.) and reacted.
　カルボン酸の配合割合は、リグニンの原料となる植物材料１００質量部に対して、カルボン酸（１００％換算）が、例えば、５００質量部以上、好ましくは、９００質量部以上であり、例えば、３００００質量部以下、好ましくは、１５０００質量部以下である。 The mixing ratio of the carboxylic acid is such that the carboxylic acid (100% conversion) is, for example, 500 parts by mass or more, preferably 900 parts by mass or more, for example, 30000 with respect to 100 parts by mass of the plant material that is the raw material for lignin. It is 1 part by mass or less, preferably 15000 parts by mass or less.
　また、無機酸の配合割合は、リグニンの原料となる植物材料１００質量部に対して、無機酸（１００％換算）が、例えば、０．０１質量部以上、好ましくは、０．０５質量部以上であり、例えば、１０質量部以下、好ましくは、５質量部以下である。 The blending ratio of the inorganic acid is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more with respect to 100 parts by mass of the plant material that is the raw material for lignin. For example, it is 10 parts by mass or less, preferably 5 parts by mass or less.
　また、反応条件としては、反応温度が、例えば、３０℃以上、好ましくは、５０℃以上であり、例えば、４００℃以下、好ましくは、２５０℃以下である。また、反応時間が、例えば、０．５時間以上、好ましくは、１時間以上であり、例えば、２０時間以下、好ましくは、１０時間以下である。 Moreover, as reaction conditions, the reaction temperature is, for example, 30 ° C. or higher, preferably 50 ° C. or higher, for example, 400 ° C. or lower, preferably 250 ° C. or lower. The reaction time is, for example, 0.5 hours or more, preferably 1 hour or more, for example, 20 hours or less, preferably 10 hours or less.
　このような蒸解によって、パルプが得られるとともに、パルプ廃液としてカルボン酸変性リグニンが得られる。 By such cooking, pulp is obtained and carboxylic acid-modified lignin is obtained as a pulp waste liquid.
　次いで、この方法では、濾過などの公知の分離方法によってパルプを分離し、濾液（パルプ廃液）を回収し、必要により、未反応のカルボン酸を、例えば、ロータリーエバポレーター、減圧蒸留などを用いた公知の方法により除去（留去）する。その後、大過剰の水を添加してカルボン酸変性リグニンを沈殿させ、濾過することによって、固形分としてカルボン酸変性リグニンを回収する。 Next, in this method, the pulp is separated by a known separation method such as filtration, and the filtrate (pulp waste liquid) is recovered. If necessary, the unreacted carboxylic acid is known using, for example, a rotary evaporator, vacuum distillation or the like. It is removed (distilled off) by the method. Thereafter, a large excess of water is added to precipitate the carboxylic acid-modified lignin, followed by filtration to recover the carboxylic acid-modified lignin as a solid content.
　また、カルボン酸変性リグニンを得る方法は、上記に限定されず、例えば、カルボン酸により変性されていないリグニン（以下、未変性リグニン）とカルボン酸とを反応させることにより、カルボン酸変性リグニンを得ることもできる。 The method for obtaining carboxylic acid-modified lignin is not limited to the above. For example, carboxylic acid-modified lignin is obtained by reacting lignin not modified with carboxylic acid (hereinafter, unmodified lignin) with carboxylic acid. You can also.
　このような方法では、未変性リグニンとして、好ましくは、粉末状の未変性リグニンが挙げられる。 In such a method, the native lignin is preferably powdered native lignin.
　粉末状の未変性リグニンの平均粒子径は、例えば、０．１μｍ以上、好ましくは、５μｍ以上であり、例えば、１０００μｍ以下、好ましくは、５００μｍ以下である。 The average particle size of the powdered unmodified lignin is, for example, 0.1 μm or more, preferably 5 μm or more, for example, 1000 μm or less, preferably 500 μm or less.
　平均粒子径が上記範囲であれば、未変性リグニンの凝集を抑制して、未変性リグニンをカルボン酸に対して良好に分散することができる。 If the average particle diameter is in the above range, aggregation of the unmodified lignin can be suppressed and the unmodified lignin can be favorably dispersed in the carboxylic acid.
　なお、粉末状の未変性リグニンは、塊状の未変性リグニンを公知の方法で乾燥および粉砕することにより得ることができ、また、市販品を用いることもできる。 The powdered unmodified lignin can be obtained by drying and pulverizing the lump unmodified lignin by a known method, or a commercially available product can be used.
　未変性リグニンとカルボン酸とを反応させる方法としては、例えば、未変性リグニンと、カルボン酸および無機酸（例えば、塩酸、硫酸など）とを混合し、反応させる。 As a method of reacting unmodified lignin and carboxylic acid, for example, unmodified lignin, carboxylic acid and inorganic acid (for example, hydrochloric acid, sulfuric acid, etc.) are mixed and reacted.
　カルボン酸の配合割合は、未変性リグニン１００質量部に対して、カルボン酸（１００％換算）が、例えば、３００質量部以上、好ましくは、５００質量部以上であり、例えば、１５０００質量部以下、好ましくは、１００００質量部以下である。 The mixing ratio of the carboxylic acid is, for example, 300 parts by mass or more, preferably 500 parts by mass or more, for example, 15000 parts by mass or less, based on 100 parts by mass of the unmodified lignin. Preferably, it is 10000 parts by mass or less.
　また、無機酸の配合割合は、未変性リグニン１００質量部に対して、無機酸（１００％換算）が、例えば、０．０１質量部以上、好ましくは、０．０５質量部以上であり、例えば、１０質量部以下、好ましくは、５質量部以下である。 The blending ratio of the inorganic acid is such that the inorganic acid (100% conversion) is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more with respect to 100 parts by mass of the unmodified lignin. 10 parts by mass or less, preferably 5 parts by mass or less.
　また、反応条件としては、反応温度が、例えば、３０℃以上、好ましくは、５０℃以上であり、例えば、４００℃以下、好ましくは、２５０℃以下である。また、反応時間が、例えば、０．５時間以上、好ましくは、１時間以上であり、例えば、２０時間以下、好ましくは、１０時間以下である。 Moreover, as reaction conditions, the reaction temperature is, for example, 30 ° C. or higher, preferably 50 ° C. or higher, for example, 400 ° C. or lower, preferably 250 ° C. or lower. The reaction time is, for example, 0.5 hours or more, preferably 1 hour or more, for example, 20 hours or less, preferably 10 hours or less.
　このようなカルボン酸変性リグニンは、取扱性に優れる。 Such carboxylic acid-modified lignin is excellent in handleability.
　すなわち、カルボン酸により変性されていないリグニンは、有機溶媒に対する溶解性が比較的低く、また、溶融しないため、用途によっては、取扱性に劣る場合がある。 That is, lignin that has not been modified with carboxylic acid has relatively low solubility in organic solvents and does not melt, so that it may be inferior in handleability depending on the application.
　一方、上記のようにカルボン酸により変性されたリグニンは、有機溶媒（例えば、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチルなどのエステル類、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン類、例えば、メタノールなどの脂肪族アルコール類、例えば、フェノール、クレゾール、ビスフェノールＡなどのフェノール類、例えば、ジエチルエーテル、テトラヒドロフラン、ジオキサンなどのエーテル類、例えば、メチルセロソルブアセテート、エチルセロソルブアセテート、メチルカルビトールアセテート、エチルカルビトールアセテート、エチレングリコールエチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート、３－メチル－３－メトキシブチルアセテート、エチル－３－エトキシプロピオネートなどのグリコールエーテルエステル類、例えば、アセトニトリルなどのニトリル類、その他、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、ジメチルスルホキシド、ヘキサメチルホスホニルアミドなどの極性溶媒など）に対する溶解性が比較的高く、溶融温度が比較的低温（１００～２００℃程度）であるため、取扱性に優れる。 On the other hand, lignin modified with carboxylic acid as described above is an organic solvent (for example, esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone). For example, aliphatic alcohols such as methanol, for example, phenols such as phenol, cresol, bisphenol A, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, such as methyl cellosolve acetate, ethyl cellosolve acetate, methylcarbyl Tall acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybuty Glycol ether esters such as acetate and ethyl-3-ethoxypropionate, for example, nitriles such as acetonitrile, others, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexa Since it has a relatively high solubility in a polar solvent such as methylphosphonilamide and the melting temperature is relatively low (about 100 to 200 ° C.), it is excellent in handleability.
　そのため、カルボン酸変性リグニンは、上記の有機溶媒の溶液として用いることもできる。そのような場合、溶液におけるカルボン酸変性リグニンの濃度は、例えば、１０質量％以上、好ましくは、３０質量％以上であり、例えば、１００質量％未満、好ましくは、９０質量％以下、より好ましくは、８０質量％以下である。 Therefore, the carboxylic acid-modified lignin can also be used as a solution of the above organic solvent. In such a case, the concentration of the carboxylic acid-modified lignin in the solution is, for example, 10% by mass or more, preferably 30% by mass or more, for example, less than 100% by mass, preferably 90% by mass or less, more preferably 80% by mass or less.
　また、カルボン酸変性リグニンは、上記の有機溶媒（好ましくは、酢酸エチル）により溶解可能な成分（可溶成分）と、上記の有機溶媒によって溶解不能な成分（不溶成分）との混合物として得られる場合がある。 The carboxylic acid-modified lignin is obtained as a mixture of a component (soluble component) that can be dissolved by the organic solvent (preferably ethyl acetate) and a component that cannot be dissolved by the organic solvent (insoluble component). There is a case.
　このような場合、カルボン酸変性リグニンとして、可溶成分と不溶成分との混合物（粗カルボン酸変性リグニンと称する。）を用いることができる。 In such a case, a mixture of a soluble component and an insoluble component (referred to as crude carboxylic acid-modified lignin) can be used as the carboxylic acid-modified lignin.
　また、可溶成分と不溶成分とを分離して、可溶成分のみを用いることもでき、また、不溶成分のみを用いることもできる。さらには、分離された可溶成分と不溶成分とを、混合して用いることもできる。 In addition, it is possible to separate the soluble component and the insoluble component and use only the soluble component, or it is possible to use only the insoluble component. Furthermore, the separated soluble component and insoluble component can be mixed and used.
　可溶成分と不溶成分とを分離する方法としては、例えば、上記した有機溶媒による抽出法などが採用される。 As a method for separating the soluble component and the insoluble component, for example, the above-described extraction method using an organic solvent is employed.
　なお、抽出条件としては、特に制限されないが、抽出温度が、例えば、室温（例えば、２５℃）である。 In addition, although it does not restrict | limit especially as extraction conditions, Extraction temperature is room temperature (for example, 25 degreeC), for example.
　また、カルボン酸変性リグニンの平均粒子径は、例えば、０．１μｍ以上、好ましくは、５μｍ以上であり、例えば、２ｃｍ以下、好ましくは、１ｃｍ以下である。 The average particle size of the carboxylic acid-modified lignin is, for example, 0.1 μm or more, preferably 5 μm or more, for example, 2 cm or less, preferably 1 cm or less.
　カルボン酸－フェノール変性リグニンにおいて、フェノール類は、フェノールおよびその誘導体であって、例えば、フェノール、さらには、例えば、ｏ－クレゾール、ｐ－クレゾール、ｐ－ｔｅｒ－ブチルフェノール、ｐ－フェニルフェノール、ｐ－クミルフェノール、ｐ－ノニルフェノール、２，４－または２，６－キシレノールなどの２官能性フェノール誘導体、例えば、ｍ－クレゾール、レゾルシノール、３，５－キシレノールなどの３官能性フェノール誘導体、例えば、ビスフェノールＡ、ジヒドロキシジフェニルメタンなどの４官能性フェノール誘導体などが挙げられる。また、例えば、塩素、臭素などのハロゲンにより置換されたハロゲン化フェノール類なども挙げられる。これらフェノール類は、単独使用または２種類以上併用することができる。 In the carboxylic acid-phenol modified lignin, the phenols are phenol and derivatives thereof, such as phenol, and further, for example, o-cresol, p-cresol, p-ter-butylphenol, p-phenylphenol, p- Bifunctional phenol derivatives such as cumylphenol, p-nonylphenol, 2,4- or 2,6-xylenol, for example, trifunctional phenol derivatives such as m-cresol, resorcinol, 3,5-xylenol, such as bisphenol A, tetrafunctional phenol derivatives such as dihydroxydiphenylmethane, and the like. Further, for example, halogenated phenols substituted with halogen such as chlorine and bromine can be mentioned. These phenols can be used alone or in combination of two or more.
　フェノール類として、好ましくは、フェノールが挙げられる。 Phenols are preferably phenol.
　カルボン酸変性リグニンとフェノール類との反応において、フェノール類の配合割合は、カルボン酸変性リグニン１００質量部に対して、例えば、３０質量部以上、好ましくは、５０質量部以上であり、例えば、１０００質量部以下、好ましくは、５００質量部以下である。 In the reaction of carboxylic acid-modified lignin and phenols, the blending ratio of phenols is, for example, 30 parts by mass or more, preferably 50 parts by mass or more with respect to 100 parts by mass of carboxylic acid-modified lignin. It is 500 parts by mass or less, preferably 500 parts by mass or less.
　また、この反応では、酸触媒が添加される。すなわち、上記の各成分は、酸触媒下において反応する。 In this reaction, an acid catalyst is added. That is, each of the above components reacts under an acid catalyst.
　酸触媒としては、例えば、有機酸、無機酸などが挙げられる。 Examples of the acid catalyst include organic acids and inorganic acids.
　有機酸としては、例えば、メタンスルホン酸、ｐ－トルエンスルホン酸、ドデシルベンゼンスルホン酸、キュメンスルホン酸、ジノニルナフタレンモノスルホン酸、ジノニルナフタレンジスルホン酸などのスルホン酸化合物、例えば、リン酸トリメチル、リン酸トリエチル、リン酸モノブチル、リン酸ジブチル、リン酸トリブチル、リン酸トリオクチルなどの炭素数１～１８のアルキル基を有するリン酸エステル類、例えば、ギ酸、酢酸、シュウ酸などが挙げられる。 Examples of the organic acid include sulfonic acid compounds such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, cumenesulfonic acid, dinonylnaphthalene monosulfonic acid, dinonylnaphthalenedisulfonic acid, for example, trimethyl phosphate, Examples thereof include phosphate esters having an alkyl group having 1 to 18 carbon atoms such as triethyl phosphate, monobutyl phosphate, dibutyl phosphate, tributyl phosphate, trioctyl phosphate, and the like, for example, formic acid, acetic acid, oxalic acid and the like.
　無機酸としては、例えば、リン酸、塩酸、硫酸、硝酸などが挙げられる。 Examples of inorganic acids include phosphoric acid, hydrochloric acid, sulfuric acid, and nitric acid.
　これら酸触媒は、単独使用または２種類以上併用することができる。 These acid catalysts can be used alone or in combination of two or more.
　酸触媒として、好ましくは、無機酸、より好ましくは、硫酸が挙げられる。 The acid catalyst is preferably an inorganic acid, more preferably sulfuric acid.
　酸触媒の配合割合は、フェノール類１００質量部に対して、例えば、０．１質量部以上、好ましくは、０．３質量部以上であり、例えば、１０質量部以下、好ましくは、５質量部以下である。 The mixing ratio of the acid catalyst is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, for example, 10 parts by mass or less, preferably 5 parts by mass with respect to 100 parts by mass of the phenols. It is as follows.
　なお、酸触媒の添加のタイミングは、特に制限されず、カルボン酸変性リグニンおよびフェノール類の少なくともいずれかに予め添加されていてもよく、また、カルボン酸変性リグニンおよびフェノール類の配合時に同時に添加されてもよく、さらに、カルボン酸変性リグニンおよびフェノール類の配合後に添加されてもよい。 The timing of addition of the acid catalyst is not particularly limited, and may be added in advance to at least one of the carboxylic acid-modified lignin and the phenols, or added at the same time when the carboxylic acid-modified lignin and the phenols are blended. Further, it may be added after blending carboxylic acid-modified lignin and phenols.
　反応条件としては、大気圧下、反応温度が、例えば、６０℃以上、好ましくは、８０℃以上であり、例えば、２５０℃以下、好ましくは、２００℃以下である。また、反応時間が、例えば、０．５時間以上、好ましくは、１時間以上であり、例えば、１０時間以下、好ましくは、５時間以下である。 As reaction conditions, under atmospheric pressure, the reaction temperature is, for example, 60 ° C. or higher, preferably 80 ° C. or higher, for example, 250 ° C. or lower, preferably 200 ° C. or lower. The reaction time is, for example, 0.5 hours or more, preferably 1 hour or more, for example, 10 hours or less, preferably 5 hours or less.
　これにより、カルボン酸変性リグニンがフェノール類により変性され、カルボン酸－フェノール変性リグニンが得られる。 Thereby, the carboxylic acid-modified lignin is modified with phenols to obtain a carboxylic acid-phenol-modified lignin.
　また、カルボン酸－フェノール変性リグニンを得る方法は、上記に限定されず、例えば、カルボン酸変性リグニンの製造時（例えば、未変性リグニンとカルボン酸との反応時）に、フェノール類を適宜の割合で添加することもできる。 Further, the method for obtaining the carboxylic acid-phenol-modified lignin is not limited to the above. For example, when the carboxylic acid-modified lignin is produced (for example, when the unmodified lignin and the carboxylic acid are reacted), an appropriate proportion of phenols is obtained. Can also be added.
　このような方法では、未変性リグニンが、カルボン酸およびフェノール類により一括変性され、カルボン酸－フェノール変性リグニンが得られる。 In such a method, unmodified lignin is collectively modified with carboxylic acid and phenols to obtain a carboxylic acid-phenol modified lignin.
　さらには、例えば、まず、未変性リグニンをフェノール類で変性することによりフェノール変性リグニンを製造し、その後、得られたフェノール変性リグニンをカルボン酸で変性することにより、カルボン酸－フェノール変性リグニンを得ることもできる。 Furthermore, for example, first, a phenol-modified lignin is produced by modifying an unmodified lignin with a phenol, and then the resulting phenol-modified lignin is modified with a carboxylic acid to obtain a carboxylic acid-phenol-modified lignin. You can also.
　カルボン酸－フェノール変性リグニンとして、製造効率の観点から、好ましくは、カルボン酸変性リグニンとフェノール類との反応生成物が挙げられる。 The carboxylic acid-phenol-modified lignin is preferably a reaction product of carboxylic acid-modified lignin and phenols from the viewpoint of production efficiency.
　また、カルボン酸－フェノール変性リグニンは、上記有機溶媒に溶解可能であるなど、取扱性に優れている。カルボン酸－フェノール変性リグニンが、有機溶媒の溶液として用いられる場合、溶液におけるカルボン酸－フェノール変性リグニンの濃度は、例えば、１０質量％以上、好ましくは、３０質量％以上であり、例えば、１００質量％未満、好ましくは、９０質量％以下、より好ましくは、８０質量％以下である。 In addition, carboxylic acid-phenol-modified lignin is excellent in handleability because it can be dissolved in the above organic solvent. When the carboxylic acid-phenol-modified lignin is used as an organic solvent solution, the concentration of the carboxylic acid-phenol-modified lignin in the solution is, for example, 10% by mass or more, preferably 30% by mass or more, for example, 100% by mass. %, Preferably 90% by mass or less, more preferably 80% by mass or less.
　樹脂組成物において、熱硬化性樹脂とカルボン酸－フェノール変性リグニンとの配合割合は、詳しくは後述するが、熱硬化性樹脂１００質量部に対して、カルボン酸－フェノール変性リグニン（溶媒に溶解される場合、その固形分（以下同様））が、例えば、１０質量部以上、好ましくは、２０質量部以上であり、例えば、３００質量部以下、好ましくは、２００質量部以下、より好ましくは、１５０質量部以下、さらに好ましくは、１２５質量部以下である。 In the resin composition, the blending ratio of the thermosetting resin and the carboxylic acid-phenol-modified lignin will be described in detail later, but the carboxylic acid-phenol-modified lignin (dissolved in the solvent) is added to 100 parts by mass of the thermosetting resin. The solid content (hereinafter the same) is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, for example, 300 parts by mass or less, preferably 200 parts by mass or less, more preferably 150 parts by mass. It is 125 parts by mass or less, more preferably 125 parts by mass or less.
　また、樹脂組成物は、さらに、添加剤を含有することができる。 The resin composition can further contain an additive.
　添加剤としては、熱硬化性樹脂組成物に添加される公知の添加剤、例えば、充填剤（木粉、パルプ、ガラス繊維など）、着色剤、可塑剤、安定剤、離型剤（ステアリン酸亜鉛などの金属石鹸など）などが挙げられる。 Examples of additives include known additives added to thermosetting resin compositions, such as fillers (wood flour, pulp, glass fibers, etc.), colorants, plasticizers, stabilizers, release agents (stearic acid). Metal soap such as zinc).
　これら添加剤は、単独使用または２種類以上併用することができる。 These additives can be used alone or in combination of two or more.
　添加剤として、好ましくは、充填剤が挙げられ、より好ましくは、木粉、ガラス繊維が挙げられ、さらに好ましくは、木粉が挙げられる。 As the additive, preferably, a filler is used, more preferably, wood powder and glass fiber are used, and still more preferably, wood powder is used.
　また、添加剤の含有量は、本発明の優れた効果を阻害しない範囲において、目的および用途に応じて、適宜設定される。 In addition, the content of the additive is appropriately set according to the purpose and application within a range that does not impair the excellent effects of the present invention.
　例えば、充填剤が添加される場合には、その配合割合は、熱硬化性樹脂１００質量部に対して、充填剤が、例えば、１０質量部以上、好ましくは、２０質量部以上であり、例えば、３００質量部以下、好ましくは、２００質量部以下、より好ましくは、１５０質量部以下、さらに好ましくは、１２５質量部以下である。 For example, when a filler is added, the blending ratio is, for example, 10 parts by mass or more, preferably 20 parts by mass or more with respect to 100 parts by mass of the thermosetting resin. 300 parts by mass or less, preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 125 parts by mass or less.
　また、添加剤は、熱硬化性樹脂および／またはカルボン酸－フェノール変性リグニンに予め添加されていてもよく、熱硬化性樹脂とカルボン酸－フェノール変性リグニンとの配合時に同時に添加されてもよく、熱硬化性樹脂とカルボン酸－フェノール変性リグニンとの混合物に添加されてもよい。 The additive may be added in advance to the thermosetting resin and / or the carboxylic acid-phenol modified lignin, or may be added simultaneously with the blending of the thermosetting resin and the carboxylic acid-phenol modified lignin. It may be added to a mixture of a thermosetting resin and a carboxylic acid-phenol modified lignin.
　そして、樹脂組成物を製造するには、例えば、熱硬化性樹脂およびカルボン酸－フェノール変性リグニン（さらに、必要により添加剤）を配合および混練すればよい。 In order to produce a resin composition, for example, a thermosetting resin and a carboxylic acid-phenol-modified lignin (and, if necessary, an additive) may be blended and kneaded.
　熱硬化性樹脂とカルボン酸－フェノール変性リグニンとの配合割合は、熱硬化性樹脂１００質量部に対して、カルボン酸－フェノール変性リグニンが、例えば、１０質量部以上、好ましくは、２０質量部以上であり、例えば、３００質量部以下、好ましくは、２００質量部以下、より好ましくは、１５０質量部以下、さらに好ましくは、１２５質量部以下である。 The blending ratio of the thermosetting resin and the carboxylic acid-phenol modified lignin is such that the carboxylic acid-phenol modified lignin is, for example, 10 parts by mass or more, preferably 20 parts by mass or more with respect to 100 parts by mass of the thermosetting resin. For example, it is 300 parts by mass or less, preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 125 parts by mass or less.
　熱硬化性樹脂とカルボン酸－フェノール変性リグニンとの配合割合が上記範囲であれば、粘度の上昇を抑制するとともに、優れた成形性を確保することができ、さらに、得られる成形品の耐熱性および電気絶縁性の向上を図ることができる。 If the blending ratio of the thermosetting resin and the carboxylic acid-phenol-modified lignin is within the above range, it is possible to suppress an increase in viscosity, ensure excellent moldability, and further, heat resistance of the obtained molded product. In addition, electrical insulation can be improved.
　とりわけ、成形品の耐熱性の向上を図る観点から、より好ましくは、熱硬化性樹脂１００質量部に対して、カルボン酸－フェノール変性リグニンが、７０質量部以上、さらに好ましくは、７５質量部以上、とりわけ好ましくは、８０質量部以上であり、より好ましくは、１５０質量部以下、さらに好ましくは、１２５質量部以下、とりわけ好ましくは、１１０質量部以下である。 In particular, from the viewpoint of improving the heat resistance of the molded product, the carboxylic acid-phenol-modified lignin is more preferably 70 parts by mass or more, more preferably 75 parts by mass or more, with respect to 100 parts by mass of the thermosetting resin. Particularly preferably, it is 80 parts by mass or more, more preferably 150 parts by mass or less, further preferably 125 parts by mass or less, and particularly preferably 110 parts by mass or less.
　また、成形品の電気絶縁性の向上を図る観点から、より好ましくは、熱硬化性樹脂１００質量部に対して、カルボン酸－フェノール変性リグニンが、１００質量部を超過し、さらに好ましくは、１５０質量部以上、とりわけ好ましくは、１８０質量部以上であり、より好ましくは、３００質量部以下、さらに好ましくは、２５０質量部以下、とりわけ好ましくは、２２０質量部以下である。 Further, from the viewpoint of improving the electrical insulation of the molded product, the carboxylic acid-phenol-modified lignin exceeds 100 parts by mass with respect to 100 parts by mass of the thermosetting resin, and more preferably 150 parts by mass. More preferably, it is 180 parts by mass or more, more preferably 300 parts by mass or less, still more preferably 250 parts by mass or less, and particularly preferably 220 parts by mass or less.
　また、熱硬化性樹脂とカルボン酸－フェノール変性リグニンとの配合割合を調整することにより、さらに、成形品の機械強度および耐水性の向上を図ることができる。 Further, by adjusting the blending ratio of the thermosetting resin and the carboxylic acid-phenol modified lignin, the mechanical strength and water resistance of the molded product can be further improved.
　成形品の機械強度および耐水性の向上を図る観点から、好ましくは、熱硬化性樹脂１００質量部に対して、カルボン酸－フェノール変性リグニンが、３０質量部以上、より好ましくは、４０質量部以上であり、好ましくは、１００質量部未満、より好ましくは、８０質量部以下、さらに好ましくは、７０質量部以下である。 From the viewpoint of improving the mechanical strength and water resistance of the molded article, the carboxylic acid-phenol-modified lignin is preferably 30 parts by mass or more, more preferably 40 parts by mass or more with respect to 100 parts by mass of the thermosetting resin. Preferably, it is less than 100 mass parts, More preferably, it is 80 mass parts or less, More preferably, it is 70 mass parts or less.
　また、混練方法としては、特に制限されず、例えば、単軸押出機、多軸押出機、ロール混練機、ニーダー、ヘンシエルミキサー、バンバリーミキサーなどの公知の混練機を用いることができる。 The kneading method is not particularly limited, and for example, a known kneader such as a single screw extruder, a multi-screw extruder, a roll kneader, a kneader, a Henschel mixer, a Banbury mixer, etc. can be used.
　混練条件としては、混練温度が、８０℃以上、好ましくは、９０℃以上、より好ましくは、１００℃以上であり、１８０℃以下、好ましくは、１７０℃以下、より好ましくは、１６０℃以下である。また、混練時間が、例えば、３分以上、好ましくは、５分以上であり、例えば、３０分以下、好ましくは、２０分以下である。 As the kneading conditions, the kneading temperature is 80 ° C. or higher, preferably 90 ° C. or higher, more preferably 100 ° C. or higher, 180 ° C. or lower, preferably 170 ° C. or lower, more preferably 160 ° C. or lower. . The kneading time is, for example, 3 minutes or more, preferably 5 minutes or more, for example, 30 minutes or less, preferably 20 minutes or less.
　このようにして得られる樹脂組成物は、熱硬化性樹脂と、カルボン酸およびフェノール類により変性されたリグニンとを含有しているため、耐熱性および電気絶縁性に優れる成形品を得ることができる。また、カルボン酸およびフェノール類により変性されたリグニンは、取扱性に優れるため、上記の樹脂組成物は、簡易かつ作業性よく得ることができる。 Since the resin composition thus obtained contains a thermosetting resin and lignin modified with carboxylic acid and phenols, a molded product having excellent heat resistance and electrical insulation can be obtained. . Moreover, since lignin modified with carboxylic acid and phenols is excellent in handleability, the above resin composition can be obtained easily and with good workability.
　また、上記の樹脂組成物の製造方法によれば、上記の樹脂組成物を簡易に製造することができる。 Further, according to the above method for producing a resin composition, the above resin composition can be easily produced.
　そして、このような樹脂組成物は、本発明の成形品の製造に用いられる。 And such a resin composition is used for manufacture of the molded article of the present invention.
　より具体的には、上記の樹脂組成物を、例えば、トランスファ成形、圧縮成形などの公知の熱硬化性樹脂の成形方法によって成形することにより、成形品を得ることができる。 More specifically, a molded product can be obtained by molding the above resin composition by a known thermosetting resin molding method such as transfer molding or compression molding.
　このような成形品は、上記の樹脂組成物を成形して得られるため、耐熱性および電気絶縁性に優れる。また、樹脂組成物に応じて、機械物性、耐水性にも優れる。 Since such a molded product is obtained by molding the above resin composition, it is excellent in heat resistance and electrical insulation. Further, depending on the resin composition, the mechanical properties and water resistance are also excellent.
　そのため、得られる成形品は、電気部品、自動車部品、建築材料、日用品などの各種産業分野において、広範に用いることができる。 Therefore, the molded product obtained can be widely used in various industrial fields such as electric parts, automobile parts, building materials, and daily necessities.
　次に、本発明を、実施例および比較例に基づいて説明するが、本発明は、下記の実施例によって限定されるものではない。なお、「部」および「％」は、特に言及がない限り、質量基準である。また、以下の記載において用いられる配合割合（含有割合）、物性値、パラメータなどの具体的数値は、上記の「発明を実施するための形態」において記載されている、それらに対応する配合割合（含有割合）、物性値、パラメータなど該当記載の上限値(「以下」、「未満」として定義されている数値）または下限値(「以上」、「超過」として定義されている数値）に代替することができる。 Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples. “Part” and “%” are based on mass unless otherwise specified. In addition, specific numerical values such as a blending ratio (content ratio), physical property values, and parameters used in the following description are described in the above-mentioned “Mode for Carrying Out the Invention”, and a blending ratio corresponding to them ( Substituting the upper limit value (numerical value defined as “less than” or “less than”) or the lower limit value (number defined as “greater than” or “exceeded”) such as content ratio), physical property values, parameters, etc. be able to.
　製造例１
　コーンストーバー１００質量部を、９５質量％の酢酸１０００質量部および硫酸３質量部と混合し、還流下において４時間反応させた。反応後、濾過してパルプを除去し、パルプ廃液を回収した。次いで、ロータリーエバポレーターを用いてパルプ廃液中の酢酸を除去し、体積が１／１０になるまで濃縮した後、その濃縮液の１０倍量（質量基準）の水を添加し、濾過することにより、固形分として酢酸変性リグニン（粗酢酸変性リグニン）を得た。 Production Example 1
100 parts by mass of corn stover was mixed with 1000 parts by mass of 95% by mass acetic acid and 3 parts by mass of sulfuric acid, and reacted for 4 hours under reflux. After the reaction, the pulp was removed by filtration, and the pulp waste liquid was recovered. Next, after removing acetic acid in the pulp waste liquid using a rotary evaporator and concentrating until the volume becomes 1/10, 10 times the amount of the concentrated liquid (mass basis) is added and filtered, Acetic acid-modified lignin (crude acetic acid-modified lignin) was obtained as a solid content.
　製造例２
　製造例１において得られた酢酸変性リグニン（粗酢酸変性リグニン）を、酢酸エチルに室温（２５℃）にて溶解させ、ろ過によりろ液と残渣に分別した。 Production Example 2
The acetic acid-modified lignin (crude acetic acid-modified lignin) obtained in Production Example 1 was dissolved in ethyl acetate at room temperature (25 ° C.), and separated into a filtrate and a residue by filtration.
　得られたろ液に含有される酢酸変性リグニンを、可溶成分（可溶酢酸変性リグニン）とした。ろ液を乾燥させることにより、固形分として、可溶成分（可溶酢酸変性リグニン）を得た。 Acetic acid-modified lignin contained in the obtained filtrate was used as a soluble component (soluble acetic acid-modified lignin). By drying the filtrate, a soluble component (soluble acetic acid-modified lignin) was obtained as a solid content.
　また、フェノール３２８．９ｇをフラスコに入れ、５０℃程度まで加熱してフェノールを液化させ、その後、上記の酢酸変性リグニンの可溶成分（可溶酢酸変性リグニン）１００ｇを添加した。 Also, 328.9 g of phenol was put in a flask and heated to about 50 ° C. to liquefy the phenol, and then 100 g of the soluble component of acetic acid-modified lignin (soluble acetic acid-modified lignin) was added.
　次いで、９８％濃硫酸（酸触媒）３ｇを添加し、その後、１３０℃、２．５時間反応させた。これにより、可溶酢酸変性リグニンをフェノールにより変性させた。 Next, 3 g of 98% concentrated sulfuric acid (acid catalyst) was added, and then reacted at 130 ° C. for 2.5 hours. Thereby, the soluble acetic acid-modified lignin was denatured with phenol.
　次いで、得られた生成物を、１ｋｇの水によってｐＨが６～７になるまで繰り返し洗浄し、その後、濾紙（Ａｄｖａｎｔｅｃ　Ｎｏ．１０１）を用いた吸引濾過によって、可溶酢酸変性リグニンのフェノール変性物（可溶酢酸－フェノール変性リグニン）を取り出した。 Subsequently, the obtained product was repeatedly washed with 1 kg of water until the pH became 6 to 7, and then subjected to suction filtration using a filter paper (Advantec No. 101), and a phenol-modified product of soluble acetic acid-modified lignin. (Soluble acetic acid-phenol modified lignin) was taken out.
　製造例３
　製造例１において得られた酢酸変性リグニンを、酢酸エチルに室温（２５℃）にて溶解させ、ろ過によりろ液と残渣に分別した。 Production Example 3
The acetic acid-modified lignin obtained in Production Example 1 was dissolved in ethyl acetate at room temperature (25 ° C.) and separated into a filtrate and a residue by filtration.
　得られた残渣を蒸留水で水洗し、再度ろ過して得られた残渣を、不溶成分（不溶酢酸変性リグニン）として得た。 The obtained residue was washed with distilled water and filtered again to obtain a residue obtained as an insoluble component (insoluble acetic acid-modified lignin).
　また、フェノール３２８．９ｇをフラスコに入れ、５０℃程度まで加熱してフェノールを液化させ、その後、上記の酢酸変性リグニンの不溶成分（不溶酢酸変性リグニン）１００ｇを添加した。 In addition, 328.9 g of phenol was put in a flask and heated to about 50 ° C. to liquefy the phenol, and then 100 g of the insoluble component of acetic acid-modified lignin (insoluble acetic acid-modified lignin) was added.
　次いで、９８％濃硫酸（酸触媒）３ｇを添加し、その後、１３０℃、２．５時間反応させた。これにより、不溶酢酸変性リグニンをフェノールにより変性させた。 Next, 3 g of 98% concentrated sulfuric acid (acid catalyst) was added, and then reacted at 130 ° C. for 2.5 hours. This modified the insoluble acetic acid-modified lignin with phenol.
　次いで、得られた生成物を、１ｋｇの水によってｐＨが６～７になるまで繰り返し洗浄し、その後、濾紙（Ａｄｖａｎｔｅｃ　Ｎｏ．１０１）を用いた吸引濾過によって、不溶酢酸変性リグニンのフェノール変性物（不溶酢酸－フェノール変性リグニン）を取り出した。 Subsequently, the obtained product was repeatedly washed with 1 kg of water until the pH became 6 to 7, and then filtered with suction using filter paper (Advantec No. 101) to obtain a phenol-modified product of insoluble acetic acid-modified lignin ( Insoluble acetic acid-phenol modified lignin) was taken out.
　製造例４
　麦わらのアルカリ蒸解パルプ廃液（黒液）を中和した後、濾過することにより、固形分として未変性リグニンを得た。 Production Example 4
After neutralizing the straw straw alkaline digested pulp waste liquor (black liquor), it was filtered to obtain unmodified lignin as a solid content.
　　＜樹脂組成物の製造＞
　　実施例１
　ノボラック型フェノール樹脂（旭有機材工業社製）３００ｇと、製造例２で得られた可溶酢酸－フェノール変性リグニン１５０ｇと、充填剤としての木粉（旭有機材工業社製）１５０ｇと、硬化剤としてのヘキサメチレンテトラミン（リグナイト社製）５４ｇと、離型剤としてのステアリン酸亜鉛（和光純薬工業社製）４．５ｇとを順次配合し、２本の熱ロールにて１００℃で５分間混練して、樹脂組成物を得た。 <Manufacture of resin composition>
Example 1
300 g of novolak type phenol resin (Asahi Organic Materials Co., Ltd.), 150 g of soluble acetic acid-phenol modified lignin obtained in Production Example 2, 150 g of wood flour (Asahi Organic Materials Co., Ltd.) as a filler, and curing 54 g of hexamethylenetetramine (manufactured by Lignite Co., Ltd.) as an agent and 4.5 g of zinc stearate (manufactured by Wako Pure Chemical Industries, Ltd.) as a mold release agent were sequentially blended, and 5 at 100 ° C. with two hot rolls. Kneading for a minute gave a resin composition.
　　実施例２
　ノボラック型フェノール樹脂の配合量を２２５ｇとし、また、可溶酢酸－フェノール変性リグニンの配合量を２２５ｇとした以外は、実施例１と同様にして樹脂組成物を得た。 Example 2
A resin composition was obtained in the same manner as in Example 1 except that the amount of the novolac-type phenol resin was 225 g and the amount of the soluble acetic acid-phenol-modified lignin was 225 g.
　　実施例３
　ノボラック型フェノール樹脂の配合量を１８０ｇとし、また、可溶酢酸－フェノール変性リグニンの配合量を２７０ｇとした以外は、実施例１と同様にして樹脂組成物を得た。 Example 3
A resin composition was obtained in the same manner as in Example 1 except that the amount of the novolac-type phenol resin was 180 g and the amount of the soluble acetic acid-phenol-modified lignin was 270 g.
　　実施例４
　ノボラック型フェノール樹脂の配合量を１５０ｇとし、また、可溶酢酸－フェノール変性リグニンの配合量を３００ｇとした以外は、実施例１と同様にして樹脂組成物を得た。 Example 4
A resin composition was obtained in the same manner as in Example 1 except that the amount of the novolac-type phenol resin was 150 g and the amount of the soluble acetic acid-phenol-modified lignin was 300 g.
　　実施例５
　ノボラック型フェノール樹脂の配合量を１１２．５ｇとし、また、可溶酢酸－フェノール変性リグニンの配合量を３３７．５ｇとした以外は、実施例１と同様にして樹脂組成物を得た。 Example 5
A resin composition was obtained in the same manner as in Example 1 except that the amount of the novolak-type phenol resin was 112.5 g and the amount of the soluble acetic acid-phenol-modified lignin was 337.5 g.
　　実施例６
　製造例２で得られた可溶酢酸－フェノール変性リグニン１５０ｇに代えて、製造例３で得られた不溶酢酸－フェノール変性リグニン１５０ｇを配合した以外は、実施例１と同様にして樹脂組成物を得た。 Example 6
A resin composition was prepared in the same manner as in Example 1 except that 150 g of the insoluble acetic acid-phenol modified lignin obtained in Production Example 3 was added instead of 150 g of the soluble acetic acid-phenol modified lignin obtained in Production Example 2. Obtained.
　　実施例７
　ノボラック型フェノール樹脂の配合量を２２５ｇとし、また、不溶酢酸－フェノール変性リグニンの配合量を２２５ｇとした以外は、実施例６と同様にして樹脂組成物を得た。 Example 7
A resin composition was obtained in the same manner as in Example 6 except that the amount of the novolac-type phenol resin was 225 g and the amount of the insoluble acetic acid-phenol-modified lignin was 225 g.
　　実施例８
　ノボラック型フェノール樹脂の配合量を２００ｇとし、また、不溶酢酸－フェノール変性リグニンの配合量を２５０ｇとした以外は、実施例６と同様にして樹脂組成物を得た。 Example 8
A resin composition was obtained in the same manner as in Example 6 except that the amount of the novolac-type phenol resin was 200 g and the amount of the insoluble acetic acid-phenol-modified lignin was 250 g.
　　比較例１
　製造例２で得られた可溶酢酸－フェノール変性リグニン１５０ｇに代えて、製造例４で得られた未変性リグニン１５０ｇを配合した以外は、実施例１と同様にして樹脂組成物を得た。 Comparative Example 1
A resin composition was obtained in the same manner as in Example 1 except that 150 g of the unmodified lignin obtained in Production Example 4 was blended in place of 150 g of the soluble acetic acid-phenol-modified lignin obtained in Production Example 2.
　　比較例２
　可溶酢酸－フェノール変性リグニン１５０ｇに代えて、製造例２においてフェノールによって変性される前の可溶酢酸変性リグニン（非フェノール変性－可溶酢酸変性リグニン）１５０ｇを配合した以外は、実施例１と同様にして樹脂組成物を得た。 Comparative Example 2
Example 1 except that 150 g of soluble acetic acid-modified lignin (non-phenol-modified-soluble acetic acid-modified lignin) before being modified with phenol in Preparation Example 2 was added instead of 150 g of soluble acetic acid-phenol-modified lignin. Similarly, a resin composition was obtained.
　　比較例３
　不溶酢酸－フェノール変性リグニン１５０ｇに代えて、製造例３においてフェノールによって変性される前の不溶酢酸変性リグニン（非フェノール変性－不溶酢酸変性リグニン）１５０ｇを配合した以外は、実施例６と同様にして樹脂組成物を得た。 Comparative Example 3
Instead of 150 g of insoluble acetic acid-phenol-modified lignin, 150 g of insoluble acetic acid-modified lignin (non-phenol-modified-insoluble acetic acid-modified lignin) before being modified with phenol in Production Example 3 was blended in the same manner as in Example 6. A resin composition was obtained.
　　比較例４
　ノボラック型フェノール樹脂（旭有機材工業社製）３００ｇと、充填剤としての木粉（旭有機材工業社製）１００ｇと、硬化剤としてのヘキサメチレンテトラミン（リグナイト社製）５４ｇと、離型剤としてのステアリン酸亜鉛（和光純薬工業社製）４．５ｇとを配合し、２本の熱ロールにて１００℃で５分間混練して、樹脂組成物を得た。
＜評価＞
　各実施例および各比較例において得られた樹脂組成物について、１７０℃において１５分間トランスファ成形し、成形品として、曲げ試験用の矩形試験片と、７５ｍｍφの円盤形試験片とを得た。 Comparative Example 4
300 g of novolak type phenolic resin (manufactured by Asahi Organic Materials Co., Ltd.), 100 g of wood flour (manufactured by Asahi Organic Materials Co., Ltd.) as a filler, 54 g of hexamethylenetetramine (manufactured by Lignite) as a curing agent, and a release agent Was mixed with 4.5 g of zinc stearate (manufactured by Wako Pure Chemical Industries, Ltd.) and kneaded with two hot rolls at 100 ° C. for 5 minutes to obtain a resin composition.
<Evaluation>
About the resin composition obtained in each Example and each comparative example, it transfer-molded for 15 minutes at 170 degreeC, and obtained the rectangular test piece for a bending test, and the disk-shaped test piece of 75 mmphi as a molded article.
　そして、得られた成形品を、下記の方法により評価した。その結果を、表１～２に示す。
（１）ガラス転移温度（Ｔｇ）
　Ｒｈｅｏｇｅｌ－Ｅ４０００（ユ－ビーエム社製）を用い、固体動的粘弾性を測定した（周波数１Ｈｚ、昇温速度２℃／分）。そして、得られるｔａｎδ曲線のピーク温度を、ガラス転移温度（Ｔｇ）として求めた。
（２）曲げ強度
　ＪＩＳ　Ｋ６９１１（１９９５年版）に準拠して、クロスヘッド速度３ｍｍ／分、スパン１００ｍｍにて曲げ強度を測定した。
（３）荷重たわみ温度
　ＡＳＴＭ　Ｄ６４８（２００４年版）に準拠して、ヒートディストーションテスター（マイズ試験機製）を用い、シリコーンオイル中において、昇温速度２℃／分、荷重１８．５ｋｇ/ｃｍ２の条件で、標準たわみ量（０．２５ｍｍ）に到達したときの温度を測定した。
（４）体積抵抗率（電気絶縁性）
　ＪＩＳ　Ｋ６９１１（１９９５年版）に従い、ＨＰ４３３９Ａ（アジレント・テクノロジー社製）を用いて、体積抵抗率（Ω・ｃｍ）を測定した。
（５）吸水率
　成形品の初期質量（乾燥質量）を測定し、次いで、成形品を沸騰水に２時間浸漬した後、その質量（吸水質量）および増加量を測定し、下記式により、吸水率を求めた。 And the obtained molded article was evaluated by the following method. The results are shown in Tables 1 and 2.
(1) Glass transition temperature (Tg)
The solid dynamic viscoelasticity was measured using Rhegel-E4000 (manufactured by UBM) (frequency 1 Hz, temperature rising rate 2 ° C./min). And the peak temperature of the obtained tan-delta curve was calculated | required as glass transition temperature (Tg).
(2) Bending strength The bending strength was measured at a crosshead speed of 3 mm / min and a span of 100 mm in accordance with JIS K6911 (1995 edition).
(3) Deflection temperature under load In accordance with ASTM D648 (2004 edition), a heat distortion tester (manufactured by Mize Tester) is used, and the temperature rise rate is 2 ° C./min and the load is 18.5 kg / cm 2 in silicone oil. Then, the temperature when the standard deflection amount (0.25 mm) was reached was measured.
(4) Volume resistivity (electrical insulation)
According to JIS K6911 (1995 edition), volume resistivity (Ω · cm) was measured using HP4339A (manufactured by Agilent Technologies).
(5) Water Absorption Rate After measuring the initial mass (dry mass) of the molded product and then immersing the molded product in boiling water for 2 hours, the mass (water absorption mass) and the amount of increase were measured. The rate was determined.
　吸水率（質量％）
　　　＝　１００　×　沸騰水の浸漬後における質量増加量　／　乾燥質量 Water absorption (mass%)
= 100 x mass increase after immersion in boiling water / dry mass
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
なお、上記発明は、本発明の例示の実施形態として提供したが、これは単なる例示に過ぎず、限定的に解釈してはならない。当該技術分野の当業者によって明らかな本発明の変形例は、後記請求の範囲に含まれる。 In addition, although the said invention was provided as exemplary embodiment of this invention, this is only a mere illustration and should not be interpreted limitedly. Variations of the present invention that are apparent to one of ordinary skill in the art are within the scope of the following claims.
　本発明の樹脂組成物、樹脂組成物の製造方法、および、成形品は、電気部品、自動車部品、建築材料、日用品などの各種産業分野において、好適に用いられる。 The resin composition of the present invention, the method for producing the resin composition, and the molded product are suitably used in various industrial fields such as electric parts, automobile parts, building materials, and daily necessities.

Claims (8)

  1. 　熱硬化性樹脂と、
    　カルボン酸およびフェノール類により変性されたリグニンと
    を含有することを特徴とする、樹脂組成物。     A thermosetting resin;
    A resin composition comprising a lignin modified with a carboxylic acid and a phenol.
  2. 　カルボン酸およびフェノール類により変性された前記リグニンが、
    　カルボン酸により変性されたリグニンと、フェノール類との反応生成物である、請求項１に記載の樹脂組成物。     The lignin modified with carboxylic acid and phenols is
    The resin composition according to claim 1, which is a reaction product of lignin modified with carboxylic acid and phenols.
  3. 　カルボン酸により変性された前記リグニンと、前記フェノール類との反応において、
    　前記フェノール類の配合割合が、カルボン酸により変性された前記リグニン１００質量部に対して、３０質量部以上１０００質量部以下である、請求項２に記載の樹脂組成物。     In the reaction of the lignin modified with carboxylic acid and the phenols,
    The resin composition according to claim 2, wherein a blending ratio of the phenols is 30 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the lignin modified with carboxylic acid.
  4. 　前記カルボン酸が、酢酸である、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the carboxylic acid is acetic acid.
  5. 　前記リグニンが、草本系植物由来リグニンである、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the lignin is a herbaceous plant-derived lignin.
  6. 　前記熱硬化性樹脂が、フェノール樹脂である、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the thermosetting resin is a phenol resin.
  7. 　熱硬化性樹脂と、
    　カルボン酸およびフェノール類により変性されたリグニンと
    を、８０℃以上１８０℃以下において混練することを特徴とする、樹脂組成物の製造方法。     A thermosetting resin;
    A method for producing a resin composition, comprising kneading a lignin modified with a carboxylic acid and a phenol at 80 ° C or higher and 180 ° C or lower.
  8. 　請求項１に記載の樹脂組成物を成形して得られることを特徴とする、成形品。 A molded product obtained by molding the resin composition according to claim 1.
PCT/JP2016/064575 2015-06-02 2016-05-17 Resin composition, method for producing resin composition, and molded article WO2016194600A1 (en)

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