[go: up one dir, main page]

WO2015178103A1 - Composition de résine et son procédé de fabrication - Google Patents

Composition de résine et son procédé de fabrication Download PDF

Info

Publication number
WO2015178103A1
WO2015178103A1 PCT/JP2015/060086 JP2015060086W WO2015178103A1 WO 2015178103 A1 WO2015178103 A1 WO 2015178103A1 JP 2015060086 W JP2015060086 W JP 2015060086W WO 2015178103 A1 WO2015178103 A1 WO 2015178103A1
Authority
WO
WIPO (PCT)
Prior art keywords
lignin
mass
carboxylic acid
resin composition
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/060086
Other languages
English (en)
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
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harima Chemicals Inc
Osaka Municipal Technical Research Institute
Original Assignee
Harima Chemicals Inc
Osaka Municipal Technical Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harima Chemicals Inc, Osaka Municipal Technical Research Institute filed Critical Harima Chemicals Inc
Publication of WO2015178103A1 publication Critical patent/WO2015178103A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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 and a method for producing the same, and more particularly to a resin composition containing a thermosetting resin and a method for producing the same.
  • 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).
  • Such a lignin-added thermosetting resin can ensure excellent mechanical properties, heat resistance and electrical insulation.
  • thermosetting resin may require water resistance depending on its use.
  • an object of the present invention is to provide a resin composition that can obtain a molded product that is excellent in mechanical properties, heat resistance and electrical insulation properties, and also has excellent water resistance, and a method for producing the same.
  • the resin composition of the present invention is characterized by containing a thermosetting resin and lignin modified with carboxylic acid.
  • the carboxylic acid is acetic acid.
  • the lignin is a herbaceous plant-derived lignin.
  • thermosetting resin is a phenol resin.
  • the method for producing the resin composition of the present invention is characterized by kneading a thermosetting resin and a lignin modified with a carboxylic acid at 80 ° C. or higher and 180 ° C. or lower.
  • the resin composition of the present invention contains a thermosetting resin and a lignin modified with a carboxylic acid, it is excellent in mechanical properties, heat resistance and electrical insulation, and further has a molded product excellent in water resistance. Obtainable. Moreover, since the lignin modified with carboxylic acid is excellent in handleability, the resin composition of the present invention can be obtained easily and with good operability.
  • the resin composition of the present invention can be produced easily.
  • the resin composition of the present invention contains a thermosetting resin and lignin modified with carboxylic acid (hereinafter sometimes referred to as carboxylic acid-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.
  • 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 is relatively high in solubility in polar solvents such as methylphosphoric acid
  • 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 carboxylic acid-modified lignin is preferably a crude carboxylic acid-modified lignin and a soluble component.
  • the average particle size of the carboxylic acid-modified lignin used in the production of the resin composition is, for example, 0.1 ⁇ m or more, preferably 5 ⁇ m or more, for example, 2 cm or less, preferably 1 cm or less.
  • thermosetting resin is excellent in solubility, the carboxylic acid-modified lignin can be well dispersed in the thermosetting resin, and the resin composition has excellent mechanical properties and heat resistance. , Electrical insulation and water resistance can be ensured.
  • 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 preferable, and wood powder and glass fiber are more preferable.
  • glass fiber is more preferable. Further, from the viewpoint of improving heat resistance and electrical insulation, wood powder is more preferable.
  • a combination of wood flour and glass fiber is more preferable.
  • wood powder and glass fiber are used in combination, their blending ratio is not particularly limited, and glass fiber is, for example, 20 parts by mass or more, preferably 50 parts by mass or more with respect to 100 parts by mass of wood powder. Yes, for example, 300 parts by mass or less, preferably 200 parts by mass or less.
  • 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.
  • the additive may be added in advance to the thermosetting resin and / or carboxylic acid-modified lignin, or may be added at the same time when the thermosetting resin and the carboxylic acid-modified lignin are blended. And a mixture of carboxylic acid-modified lignin.
  • thermosetting resin and a carboxylic acid-modified lignin may be blended and kneaded.
  • the blending ratio of the thermosetting resin and carboxylic acid-modified lignin (solid content when dissolved in a solvent) is such that the carboxylic acid-modified lignin is, for example, 10 parts by mass or more with respect to 100 parts by mass of the thermosetting resin.
  • the amount is preferably 20 parts by mass or more, for example, 300 parts by mass or less, and preferably 200 parts by mass or less.
  • thermosetting resin and the carboxylic acid-modified lignin are within the above range, it is possible to suppress an increase in viscosity and ensure excellent moldability, and further, mechanical properties and heat resistance of the obtained molded body. , Electrical insulation and water resistance can be improved.
  • the carboxylic acid-modified lignin is more preferably 10 parts by mass or more, more preferably 20 parts by mass or more, particularly preferably 100 parts by mass of the thermosetting resin.
  • the amount is preferably 30 parts by mass or more, more preferably 100 parts by mass or less, still more preferably 80 parts by mass or less, and particularly preferably 75 parts by mass or less.
  • the carboxylic acid-modified lignin is 50 parts by mass or more, more preferably 60 parts by mass or more, particularly preferably 100 parts by mass of the thermosetting resin. 70 parts by mass or more, more preferably 200 parts by mass or less, still more preferably 150 parts by mass or less, and particularly preferably 110 parts by mass 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 a lignin modified with a carboxylic acid, it has excellent mechanical properties, heat resistance and electrical insulation properties, and also has excellent water resistance. A molded product can be obtained. Moreover, since the lignin modified with carboxylic acid is excellent in handleability, the above resin composition can be obtained easily and with good operability.
  • the above resin composition can be easily produced.
  • the above resin composition is molded by a known thermosetting resin molding method such as transfer molding or compression molding. Thereby, it is possible to obtain a molded article having excellent mechanical properties, heat resistance, and electrical insulation properties and excellent water resistance.
  • 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 2 Acetic acid-modified lignin was obtained in the same manner as in Production Example 1, except that 100 parts by mass of bamboo was used instead of 100 parts by mass of corn stover.
  • Production Example 3 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
  • Production Example 4 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.
  • Example 1 After neutralizing the straw straw alkaline digested pulp waste liquor (black liquor), it was filtered to obtain unmodified lignin as a solid content.
  • Example 2 A resin composition was obtained in the same manner as in Example 1 except that the kneading temperature was changed to 150 ° C.
  • Example 3 A resin composition was obtained in the same manner as in Example 1 except that 150 g of glass fiber (average length: 3 mm, aspect ratio: 250, manufactured by Nittobo Co., Ltd.) was blended instead of 150 g of wood powder.
  • 150 g of glass fiber average length: 3 mm, aspect ratio: 250, manufactured by Nittobo Co., Ltd.
  • Example 4 A resin composition was obtained in the same manner as in Example 1 except that 150 g of acetic acid-modified lignin obtained in Production Example 2 was blended in place of 150 g of acetic acid-modified lignin obtained in Production Example 1.
  • Example 5 A resin composition was obtained in the same manner as in Example 1 except that the blending amount of the novolac type phenol resin was 225 g and the blending amount of the acetic acid-modified lignin was 225 g.
  • Example 6 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 acetic acid-modified lignin was 270 g.
  • Example 7 A resin composition was obtained in the same manner as in Example 1 except that 150 g of the soluble acetic acid-modified lignin obtained in Production Example 3 was blended in place of 150 g of the acetic acid-modified lignin obtained in Production Example 1.
  • Example 8 A resin composition was obtained in the same manner as in Example 5 except that 225 g of the soluble acetic acid-modified lignin obtained in Production Example 3 was blended in place of 225 g of the acetic acid-modified lignin obtained in Production Example 1.
  • Example 9 A resin composition was obtained in the same manner as in Example 1 except that 150 g of insoluble acetic acid-modified lignin obtained in Production Example 4 was blended in place of 150 g of acetic acid-modified lignin obtained in Production Example 1.
  • Example 10 A resin composition was obtained in the same manner as in Example 5 except that 225 g of insoluble acetic acid-modified lignin obtained in Production Example 4 was blended in place of 225 g of acetic acid-modified lignin obtained in Production Example 1.
  • Example 11 A resin composition was obtained in the same manner as in Example 10 except that the amount of the novolac-type phenol resin was 200 g and the amount of the insoluble acetic acid-modified lignin obtained in Production Example 4 was 250 g.
  • Example 12 A resin composition was obtained in the same manner as in Example 1, except that 100 g of wood powder and 50 g of glass fiber (average length 3 mm, aspect ratio 250, manufactured by Nittobo Co., Ltd.) were blended in place of 150 g of wood powder.
  • Example 13 A resin composition was obtained in the same manner as in Example 1 except that 75 g of wood powder and 75 g of glass fiber (average length: 3 mm, aspect ratio: 250, manufactured by Nittobo Co., Ltd.) were blended instead of 150 g of wood powder.
  • Example 14 A resin composition was obtained in the same manner as in Example 1 except that 50 g of wood powder and 100 g of glass fiber (average length 3 mm, aspect ratio 250, manufactured by Nittobo Co., Ltd.) were blended in place of 150 g of wood powder.
  • Comparative Example 1 300 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 3 g of zinc stearate (manufactured by Wako Pure Chemical Industries, Ltd.) was blended and kneaded with two hot rolls at 100 ° C. for 10 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 3 g of zinc stearate manufactured by Wako Pure Chemical Industries, Ltd.
  • Comparative Example 2 A resin composition was obtained in the same manner as in Example 1 except that 150 g of unmodified lignin obtained in Production Comparative Example 1 was blended in place of 150 g of acetic acid-modified lignin obtained in Production Example 1. ⁇ 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.
  • volume resistivity (electrical insulation) According to JIS K6911 (1995 edition), volume resistivity ( ⁇ ⁇ cm) was measured using HP4339A (manufactured by Agilent Technologies). (6) Dielectric constant Using an impedance analyzer E4991A (manufactured by Agilent Technologies), the dielectric constant at a frequency of 1 GHz was measured by the capacitance method. (7) 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.
  • the molded product obtained using the resin composition of each example was the same as that of the molded product obtained using the resin composition of Comparative Example 1, while having excellent water resistance. It is clear that it has physical properties, heat resistance and electrical insulation.
  • the molded product obtained using the resin composition of each example is the same as the molded product obtained using the resin composition of Comparative Example 2, mechanical properties, heat resistance, electrical insulation, etc. It is clear that the water resistance is equivalent or better and has excellent water resistance.
  • Example 1 Example 7 and Example 9 are compared, by using the acetic acid-modified lignin obtained in Production Example 1 (crude acetic acid-modified lignin) and the soluble acetic acid-modified lignin obtained in Production Example 3, It is apparent that superior water resistance can be obtained as compared with the case where the insoluble acetic acid-modified lignin obtained in Production Example 4 is used.
  • Example 1 when comparing Example 1, Example 3 and Examples 12 to 14 in Table 1 and Table 3, the use of wood flour as the filler makes it possible to achieve superior heat resistance compared to the case where glass fiber is used as the filler. Is clearly obtained. Moreover, it is clear that the use of glass fiber as the filler is superior in mechanical properties and water resistance as compared with the case of using wood flour as the filler. Moreover, it is clear that they can be improved in a balanced manner by using wood flour and glass fiber in combination.
  • the resin composition of the present invention and the production method thereof are widely used, for example, as molded products in various industrial fields such as electric parts, automobile parts, building materials, and daily necessities.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette composition de résine contient une résine thermodurcissable et une lignine qui est modifiée par un acide carboxylique.
PCT/JP2015/060086 2014-05-23 2015-03-31 Composition de résine et son procédé de fabrication Ceased WO2015178103A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014106660A JP2017125077A (ja) 2014-05-23 2014-05-23 樹脂組成物およびその製造方法
JP2014-106660 2014-05-23

Publications (1)

Publication Number Publication Date
WO2015178103A1 true WO2015178103A1 (fr) 2015-11-26

Family

ID=54553779

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/060086 Ceased WO2015178103A1 (fr) 2014-05-23 2015-03-31 Composition de résine et son procédé de fabrication

Country Status (3)

Country Link
JP (1) JP2017125077A (fr)
TW (1) TW201546162A (fr)
WO (1) WO2015178103A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016080469A1 (fr) * 2014-11-20 2016-05-26 住友ベークライト株式会社 Composition de résine à base de lignine, objet durci et objet moulé
WO2016098666A1 (fr) * 2014-12-16 2016-06-23 ハリマ化成株式会社 Feuille imprégnée, feuille stratifiée et composition de résine
WO2016098667A1 (fr) * 2014-12-16 2016-06-23 ハリマ化成株式会社 Feuille imprégnée, feuille stratifiée et composition de résine
WO2016104634A1 (fr) * 2014-12-25 2016-06-30 出光ライオンコンポジット株式会社 Composition de résine thermoplastique et article moulé comprenant celle-ci
WO2016194600A1 (fr) * 2015-06-02 2016-12-08 ハリマ化成株式会社 Composition de résine, procédé de production d'une composition de résine, et objet moulé correspondant
JP2017179260A (ja) * 2016-03-31 2017-10-05 ハリマ化成株式会社 摩擦材

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06256665A (ja) * 1992-12-10 1994-09-13 Ruetgerswerke Ag バインダー混合物
JP2009227890A (ja) * 2008-03-25 2009-10-08 Sumitomo Bakelite Co Ltd リグニン樹脂組成物及び成形材料
JP2010163497A (ja) * 2009-01-13 2010-07-29 Toshiba Corp 高分子組成材料およびその製造方法
WO2010144969A1 (fr) * 2009-06-19 2010-12-23 Eze Board Australia Pty Ltd Production de perlite et carton pour panneaux composite à base de fibres
JP2011246630A (ja) * 2010-05-28 2011-12-08 National Institute Of Advanced Industrial Science & Technology 部分アシル化リグニン、およびそれを用いたエポキシ樹脂組成物及びその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06256665A (ja) * 1992-12-10 1994-09-13 Ruetgerswerke Ag バインダー混合物
JP2009227890A (ja) * 2008-03-25 2009-10-08 Sumitomo Bakelite Co Ltd リグニン樹脂組成物及び成形材料
JP2010163497A (ja) * 2009-01-13 2010-07-29 Toshiba Corp 高分子組成材料およびその製造方法
WO2010144969A1 (fr) * 2009-06-19 2010-12-23 Eze Board Australia Pty Ltd Production de perlite et carton pour panneaux composite à base de fibres
JP2011246630A (ja) * 2010-05-28 2011-12-08 National Institute Of Advanced Industrial Science & Technology 部分アシル化リグニン、およびそれを用いたエポキシ樹脂組成物及びその製造方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016080469A1 (fr) * 2014-11-20 2016-05-26 住友ベークライト株式会社 Composition de résine à base de lignine, objet durci et objet moulé
JPWO2016080469A1 (ja) * 2014-11-20 2017-08-31 住友ベークライト株式会社 リグニン樹脂組成物、硬化物および成形物
US10059793B2 (en) 2014-11-20 2018-08-28 Sumitomo Bakelite Co., Ltd. Lignin resin composition, cured product, and molded product
WO2016098666A1 (fr) * 2014-12-16 2016-06-23 ハリマ化成株式会社 Feuille imprégnée, feuille stratifiée et composition de résine
WO2016098667A1 (fr) * 2014-12-16 2016-06-23 ハリマ化成株式会社 Feuille imprégnée, feuille stratifiée et composition de résine
WO2016104634A1 (fr) * 2014-12-25 2016-06-30 出光ライオンコンポジット株式会社 Composition de résine thermoplastique et article moulé comprenant celle-ci
WO2016194600A1 (fr) * 2015-06-02 2016-12-08 ハリマ化成株式会社 Composition de résine, procédé de production d'une composition de résine, et objet moulé correspondant
JP2017179260A (ja) * 2016-03-31 2017-10-05 ハリマ化成株式会社 摩擦材

Also Published As

Publication number Publication date
TW201546162A (zh) 2015-12-16
JP2017125077A (ja) 2017-07-20

Similar Documents

Publication Publication Date Title
WO2015178103A1 (fr) Composition de résine et son procédé de fabrication
JP2023024831A (ja) 改質リグニンの製造方法及び改質リグニン、並びに改質リグニン含有樹脂組成材料
JP5879027B2 (ja) リグニン添加熱硬化性樹脂
JP5256813B2 (ja) リグニン樹脂組成物及び成形材料
JP7630786B2 (ja) 樹脂組成物
JP7545462B2 (ja) 改質リグニン及び改質ポリフェノールの製造方法、並びに改質リグニンを用いた樹脂組成材料
JP5348113B2 (ja) リグニン樹脂組成物の製造方法
TW201726769A (zh) 純化木質素之製造方法、純化木質素、樹脂組成物及成形體
JP7749182B2 (ja) ノボラック型フェノール樹脂および樹脂組成物
WO2015056758A1 (fr) Composition de résine et composition de caoutchouc
WO2016043218A1 (fr) Composition de résine thermodurcissable
JP5703203B2 (ja) 水不溶性リグニンおよびそれを含有する熱硬化性樹脂成形材料
JP6645440B2 (ja) リグニン樹脂組成物、硬化物および成形物
WO2018139074A1 (fr) Résine phénolique de type novolaque, composition de résine et procédé de production de résine phénolique de type novolaque
JP2014196416A (ja) エポキシ化リグニン、その製造方法、その樹脂組成物およびその成形材料
WO2016098667A1 (fr) Feuille imprégnée, feuille stratifiée et composition de résine
JP2013227470A (ja) リグニン樹脂組成物およびリグニン樹脂成形材料
WO2016194600A1 (fr) Composition de résine, procédé de production d'une composition de résine, et objet moulé correspondant
WO2016063779A1 (fr) Résine époxy et durcisseur pour résine époxy
JP2015193860A (ja) リグニン添加熱硬化性樹脂
JP2015048359A (ja) リグニン樹脂組成物、樹脂成形体および成形材料
JP2014193977A (ja) 樹脂組成物、樹脂組成物を含むプリプレグ、積層板、および成形材料
Anter et al. Dual-functionalized lignin as a sustainable modifier for high-performance phenol-formaldehyde adhesives in plywood production
JP2015048360A (ja) リグニン樹脂組成物、樹脂成形体および成形材料
WO2016098666A1 (fr) Feuille imprégnée, feuille stratifiée et composition de résine

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15795733

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15795733

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP