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WO2016063779A1 - Résine époxy et durcisseur pour résine époxy - Google Patents

Résine époxy et durcisseur pour résine époxy Download PDF

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Publication number
WO2016063779A1
WO2016063779A1 PCT/JP2015/079079 JP2015079079W WO2016063779A1 WO 2016063779 A1 WO2016063779 A1 WO 2016063779A1 JP 2015079079 W JP2015079079 W JP 2015079079W WO 2016063779 A1 WO2016063779 A1 WO 2016063779A1
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Prior art keywords
epoxy resin
lignin
carboxylic acid
modified
mass
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.)
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PCT/JP2015/079079
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English (en)
Japanese (ja)
Inventor
康典 大橋
霖 周
麻衣子 山本
高橋　昭雄
俊幸 大山
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Harima Chemicals Inc
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Harima Chemicals Inc
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Publication of WO2016063779A1 publication Critical patent/WO2016063779A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols

Definitions

  • the present invention relates to an epoxy resin and an epoxy resin curing agent.
  • the cured epoxy resin is usually produced by blending an epoxy resin and an epoxy resin curing agent and curing the mixture, for example, an electrical / electronic component such as a semiconductor sealing material, for example, a paint or an adhesive. It is widely used in various industrial fields.
  • an epoxy resin obtained by reacting a gramineous plant lignin recovered from a pulp waste liquor by an alkali digestion method with epichlorohydrin has been proposed.
  • the use of plant lignin as an epoxy resin curing agent has also been proposed (see Patent Document 2).
  • an epoxy resin it can be obtained by further reacting epichlorohydrin with a lignin phenol resin obtained by reacting a grass lignin recovered from pulp waste liquor by an alkali digestion method and a phenol under an acid catalyst.
  • An epoxy resin has been proposed, and the use of the above lignin phenol resin as an epoxy resin curing agent has also been proposed (see Patent Document 3).
  • the epoxy resin composition described in Patent Document 1 has a disadvantage that the fluidity is relatively low and the handling property is inferior because the molecular weight of lignophenol as a raw material component is relatively large.
  • the resulting epoxy resin cured product may not have sufficient heat resistance.
  • an object of the present invention is to provide an epoxy resin and an epoxy resin curing agent capable of obtaining an epoxy resin cured product having excellent handleability and heat resistance.
  • the epoxy resin of the present invention is characterized in that it is obtained by reacting at least lignin modified with carboxylic acid and epichlorohydrin.
  • the lignin modified with the carboxylic acid is phenol-modified.
  • the lignin modified with the carboxylic acid is extracted with an organic solvent.
  • the epoxy resin curing agent of the present invention is characterized by containing lignin modified with carboxylic acid.
  • the lignin modified with the carboxylic acid is phenol-modified.
  • the lignin modified with the carboxylic acid is extracted with an organic solvent.
  • the epoxy resin and the epoxy resin curing agent of the present invention are obtained using lignin modified with carboxylic acid, the handling property is excellent and the heat resistance of the cured epoxy resin product can be improved.
  • Epoxy resin of the present invention can be obtained by reacting lignin modified with carboxylic acid (hereinafter sometimes referred to as carboxylic acid-modified lignin) and epichlorohydrin.
  • 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 9% by mass or more, more preferably 14% by mass or more.
  • 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.
  • 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.
  • 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 a carboxylic acid as described above is a polar organic solvent (for example, acetone, methanol, phenol, tetrahydrofuran, acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, Dimethyl sulfoxide, hexamethylphosphonilamide, etc.) are relatively high in solubility, and the melting temperature is relatively low (about 100 to 200 ° C.), so that the handling property is excellent.
  • a polar organic solvent for example, acetone, methanol, phenol, tetrahydrofuran, acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, Dimethyl sulfoxide, hexamethylphosphonilamide, etc.
  • the carboxylic acid-modified lignin is preferably extracted from the product (crude product) obtained by the above-described method with an organic solvent.
  • organic solvent examples include the polar organic solvents described above, and preferably acetone.
  • the carboxylic acid-modified lignin By extracting the carboxylic acid-modified lignin with an organic solvent, the carboxylic acid-modified lignin can be purified, and the heat resistance of the cured epoxy resin (described later) can be improved.
  • the extraction method is not particularly limited, and a known method is employed.
  • the extraction rate of the carboxylic acid-modified lignin is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, for example, 90% by mass or less, preferably 80% by mass or less. is there.
  • the carboxylic acid-modified lignin is preferably phenol-modified.
  • carboxylic acid-modified lignin for example, carboxylic acid-modified lignin (carboxylic acid-modified lignin that has not been phenol-modified) and phenols are reacted in the presence of an acid catalyst.
  • phenols examples include phenol, cresol (o-cresol, m-cresol, p-cresol, etc.), resorcinol and the like.
  • phenols can be used alone or in combination of two or more.
  • the phenols are preferably cresol, more preferably p-cresol, from the viewpoint of performance improvement.
  • the blending ratio of the phenols is, for example, 100 parts by mass or more, preferably 300 parts by mass or more, for example, 5000 parts by mass or less, preferably 100 parts by mass or less, based on 100 parts by mass of the carboxylic acid-modified lignin not modified with phenol. It is 3000 parts by mass or less.
  • the acid catalyst is not particularly limited, and may be a known acid catalyst. Specific examples include strong inorganic acids such as sulfuric acid, nitric acid, and hydrochloric acid.
  • These acid catalysts can be used alone or in combination of two or more.
  • the acid catalyst is preferably sulfuric acid from the viewpoint of low cost and improved performance.
  • the mixing ratio of the acid catalyst is, for example, 1 part by mass or more, preferably 5 parts by mass or more, for example, 20 parts by mass or less, preferably 100 parts by mass with respect to 100 parts by mass of the carboxylic acid-modified lignin not modified with phenol. 15 parts by mass or less.
  • formaldehyde can be used in combination in the reaction of carboxylic acid-modified lignin and phenols.
  • formaldehyde When formaldehyde is used, formaldehyde is copolymerized with carboxylic acid-modified lignin and phenols, and formaldehyde becomes a methylene group by dehydration condensation, so that phenol-modified carboxylic acid-modified lignin (carboxylic acid-modified lignin-phenol resin) In this method, a phenol group is bonded through a methylene group.
  • the blending ratio is 2 mol or less, preferably 1 mol or less with respect to 1 mol of phenols.
  • a solvent may be added if necessary.
  • the solvent include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphonamide, and preferably N, N-dimethylformamide.
  • the blending amount is, for example, 25 parts by mass or more, preferably 40 parts by mass or more, for example, 100 parts by mass or less, preferably 60 parts by mass with respect to 100 parts by mass of the carboxylic acid-modified lignin. It is below mass parts.
  • each component may be blended in the above ratio and heated.
  • the reaction temperature is, for example, 100 ° C. or more, preferably 110 ° C. or more, for example, 200 ° C. or less, preferably 150 ° C. or less.
  • the reaction time is, for example, 30 minutes or longer, for example, 3 hours or shorter.
  • phenol-modified carboxylic acid-modified lignin phenol-modified carboxylic acid-modified lignin, carboxylic acid-modified lignin-phenol resin
  • carboxylic acid-modified lignin-phenol resin phenol-modified carboxylic acid-modified lignin, carboxylic acid-modified lignin-phenol resin
  • the acid catalyst can be neutralized by adding an alkali if necessary.
  • unreacted components can be removed and recovered by a known method such as filtration or distillation.
  • distillation conditions in particular in the case of distilling are not restrict
  • the recovered unreacted components can be directly used for the next production.
  • a phenol-modified carboxylic acid-modified lignin is obtained as a solution (for example, when an alkaline aqueous solution is added), the solution is dropped into an organic solvent such as hexane to add phenol.
  • Carboxylic acid-modified lignin can be recovered as a precipitate.
  • the phenol-modified carboxylic acid-modified lignin recovered as a precipitate can be dissolved in an organic solvent or the like and recovered as a precipitate again to purify the phenol-modified carboxylic acid-modified lignin.
  • the phenol-modified carboxylic acid-modified lignin (carboxylic acid-modified lignin-phenol resin) can be washed.
  • the washing method is not particularly limited, and for example, water may be added to phenol-modified carboxylic acid-modified lignin (carboxylic acid-modified lignin-phenol resin) and stirred. By such washing, impurities and salts generated by the neutralization can be removed.
  • the mixing ratio of carboxylic acid-modified lignin and epichlorohydrin is an excess amount of epichlorohydrin with respect to 100 parts by mass of carboxylic acid-modified lignin. Specifically, for example, 150 parts by mass or more, preferably 250 parts by mass or more, for example, 2000 parts by mass or less, preferably 1000 parts by mass or less.
  • the reaction temperature is, for example, 80 ° C. or higher, preferably 90 ° C. or higher, for example, 120 ° C. or lower, preferably 110 ° C. or lower.
  • the reaction time is, for example, 2 hours or more, preferably 2.5 hours or more, for example, 4 hours or less, preferably 3.5 hours or less.
  • a glycidyl ether group can be bonded to the carboxylic acid-modified lignin to obtain an epoxy resin.
  • epichlorohydrin is added to the carboxylic acid-modified lignin in the above ratio in the presence of a known phase transfer catalyst (for example, a quaternary ammonium salt such as tetramethylammonium (TBAC)).
  • a known phase transfer catalyst for example, a quaternary ammonium salt such as tetramethylammonium (TBAC)
  • TBAC tetramethylammonium
  • an epoxy resin can be obtained by combining carboxylic acid-modified lignin and epichlorohydrin by a two-step reaction in which an alkaline solution (such as an aqueous sodium hydroxide solution) is dropped to close the ring.
  • the reaction temperature in the first stage reaction is, for example, 60 ° C. or higher, preferably 75 ° C. or higher, for example, 90 ° C. or lower, preferably 85 ° C. or lower.
  • the reaction time is, for example, 6 hours or more, preferably 7 hours or more, for example, 10 hours or less, preferably 9 hours or less.
  • the reaction temperature in the second stage reaction is, for example, 20 ° C. or more, preferably 35 ° C. or more, for example, 50 ° C. or less, preferably 45 ° C. or less.
  • the reaction time is, for example, 10 hours or more, preferably 14 hours or more, for example, 20 hours or less, preferably 16 hours or less.
  • the binding ratio of carboxylic acid-modified lignin and epichlorohydrin is usually 20 to 35 parts by mass of epichlorohydrin with respect to 100 parts by mass of carboxylic acid-modified lignin. is there.
  • the content of the carboxylic acid-modified lignin in the epoxy resin thus obtained is, for example, 70 parts by mass or more, preferably 75 parts by mass or more, with respect to 100 parts by mass of the total amount of the epoxy resin. 85 parts by mass or less.
  • Epoxy resin curing agent contains a carboxylic acid-modified lignin.
  • Examples of the carboxylic acid-modified lignin include the above-described carboxylic acid-modified lignin.
  • carboxylic acid-modified lignin is preferably extracted with an organic solvent.
  • the carboxylic acid-modified lignin By extracting the carboxylic acid-modified lignin with an organic solvent, the carboxylic acid-modified lignin can be purified, and the heat resistance of the cured epoxy resin (described later) can be improved.
  • the carboxylic acid-modified lignin is preferably used after being phenol-modified.
  • the heat resistance of the cured epoxy resin (described later) can be further improved.
  • Epoxy resin composition contains a main agent composed of an epoxy resin and an epoxy resin curing agent.
  • Examples of the epoxy resin include the above-described epoxy resin of the present invention, and examples of the epoxy resin curing agent include the above-described epoxy resin curing agent of the present invention.
  • epoxy resin curing agents include, for example, aliphatic amines, aromatic amines, polyphenol compounds, novolak resins, acid anhydrides, and the like.
  • An epoxy resin curing agent can be used.
  • epoxy resin curing agent of the present invention When the above-described epoxy resin curing agent of the present invention is used as the epoxy resin curing agent, a known epoxy resin such as a bisphenol type epoxy resin or a novolac type epoxy resin can be used as the epoxy resin. .
  • epoxy resin the above-described epoxy resin of the present invention and a known epoxy resin can be used in an appropriate ratio
  • epoxy resin curing agent the above-described epoxy resin curing agent of the present invention
  • curing agent can also be used together in a suitable ratio.
  • the above-described epoxy resin of the present invention is used as the epoxy resin
  • the above-described epoxy resin curing agent of the present invention is used as the epoxy resin curing agent
  • the amine equivalent and / or phenolic hydroxyl group equivalent of the epoxy resin curing agent and the epoxy equivalent of the main agent are approximately equivalent to ⁇ 20% equivalent. It mix
  • the blending method is not particularly limited.
  • the main agent (epoxy resin) and the epoxy resin curing agent are dissolved in a common solvent (for example, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, acetonitrile, etc.), and if necessary.
  • a common solvent for example, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, acetonitrile, etc.
  • curing agent it can heat as needed.
  • the heating temperature is, for example, 40 ° C. or higher, preferably 50 ° C. or higher, for example, 70 ° C. or lower, preferably 60 ° C. or lower.
  • a curing accelerator can be added to the epoxy resin composition at an appropriate timing.
  • curing accelerator examples include 2-ethyl-4-methylimidazole and derivatives thereof, 1-cyanoethyl-2-ethyl-4-methylimidazole and derivatives thereof, and tertiary amines such as benzyldimethylamine, triphenyl Examples include phosphine (TPP) derivatives (such as caribol salt) and known curing accelerators.
  • TPP phosphine
  • the blending ratio is, for example, 0.1 parts by mass or more, preferably 0.2 parts by mass or more with respect to 100 parts by mass of the total amount of the epoxy resin and the epoxy resin curing agent. For example, 3 parts by mass or less, preferably 2 parts by mass or less.
  • an epoxy resin composition uses lignin modified with a carboxylic acid in an epoxy resin and / or an epoxy resin curing agent, it is excellent in handleability and improves the heat resistance of a cured epoxy resin. Can be achieved. 4).
  • Cured epoxy resin The cured epoxy resin can be obtained by curing the epoxy resin composition.
  • Examples of the method of curing the epoxy resin composition include a method of injecting the epoxy resin composition into a known mold and heating, a method of vacuum hot press molding, and the like.
  • the epoxy resin may be heated in one step, or may be heated in two or more steps. Preferably, the epoxy resin is heated in two stages.
  • the heating temperature at the first stage is, for example, 140 ° C. or higher, preferably 145 ° C. or higher, for example, 160 ° C. or lower, preferably 155 ° C. or lower.
  • the first stage heating time is, for example, 1.5 hours or more, preferably 2 hours or more, for example, 3 hours or less, preferably 2.5 hours or less.
  • the heating temperature in the second stage is, for example, 170 ° C. or higher, preferably 175 ° C. or higher, for example, 190 ° C. or lower, preferably 185 ° C. or lower.
  • the heating time of the second stage is, for example, 2.5 hours or more, preferably 3 hours or more, for example, 4 hours or less, preferably 3.5 hours or less.
  • such a cured epoxy resin is excellent in mechanical properties and electrical properties, and is obtained by using lignin modified with carboxylic acid, so it is compatible with carbon neutral and has an environmental impact. Can be reduced.
  • a cured epoxy resin is widely used in various industrial fields as an adhesive, a molding material, a structural material, a semiconductor encapsulant, an electronic material, and the like.
  • Production Example 2 (without extraction / with phenol modification) In the same manner as in Production Example 1, acetic acid-modified lignin was obtained as a solid content.
  • the mixture was cooled to a temperature of 100 ° C. or lower and neutralized by adding 45.3 parts by mass of a 20% aqueous sodium hydroxide solution. Subsequently, the insoluble part was removed by filtration, and then the obtained solution (filtrate) was dropped into 20 times volume of hexane to obtain a precipitate.
  • the obtained precipitate was collected by suction filtration and dissolved in the necessary minimum (about 100 parts by mass) of tetrahydrofuran (THF). Next, the obtained solution was added dropwise to 20 times volume of hexane in tetrahydrofuran to obtain a precipitate again.
  • THF tetrahydrofuran
  • the obtained precipitate was dried under the conditions of 60 ° C. and 40 mmHg for 15 hours to obtain a phenol-modified product of lignin acetate.
  • Production Example 3 (with extraction / no phenol modification) In the same manner as in Production Example 1, acetic acid-modified lignin was obtained as a solid content.
  • acetic acid-modified lignin was dissolved in an organic solvent (acetone), and insoluble matters were removed by filtration. Thereafter, an organic solvent solution of acetic acid-modified lignin was dried to obtain acetic acid-modified lignin (an extract with an organic solvent).
  • Production Example 4 (with extraction / with phenol modification) The acetic acid-modified lignin was phenol-modified in the same manner as in Production Example 2 except that the acetic acid-modified lignin obtained in Production Example 3 (extract with an organic solvent) was used. As a result, a phenol-modified product of lignin acetate (extract with an organic solvent) was obtained.
  • Comparative production example 1 (no extraction / no phenol modification) After neutralizing the straw straw alkaline digested pulp waste liquor (black liquor), it was filtered to obtain unmodified lignin as a solid content.
  • the unmodified lignin was phenol-modified in the same manner as in Production Example 2. As a result, a phenol-modified product of unmodified lignin (lignin not modified with carboxylic acid) was obtained.
  • Comparative Production Example 3 (with extraction / no phenol modification) In the same manner as in Comparative Production Example 1, unmodified lignin was obtained as a solid content.
  • the obtained unmodified lignin was dissolved in an organic solvent (methanol), and insoluble matters were removed by filtration. Thereafter, an organic solvent solution of native lignin was dried to obtain native lignin (an extract with an organic solvent).
  • Comparative Production Example 4 (with extraction / with phenol modification) The unmodified lignin was phenol-modified in the same manner as in Production Example 2, except that the unmodified lignin obtained in Comparative Production Example 3 (extract with an organic solvent) was used. As a result, a phenol-modified product of unmodified lignin (extract with an organic solvent) was obtained.
  • the obtained solution was transferred to a separatory funnel and washed five times with 100 mL of ion exchange water, and then anhydrous magnesium sulfate was added to remove moisture.
  • the epoxy equivalent (EEW) of the obtained epoxy resin was 280.
  • the epoxy equivalent (EEW) was measured by the following method.
  • the obtained epoxy resin (epoxidized lignin) was dissolved in deuterated chloroform, 1,1 ′, 2,2′-tetrachloroethane (TCE) as a reference material was added, and then 1 H-NMR The spectrum was measured, and the epoxy equivalent was calculated from the integrated intensity ratio of each peak according to the following formula (hereinafter the same).
  • TCE Integral intensity of 1,1 ′, 2,2′-tetrachloroethane
  • I epoxy Integral intensity of epoxy group
  • W epoxy resin Mass of epoxy resin (epoxidized lignin)
  • W TCE 1,1 ′, Mass of 2,2′-tetrachloroethane (TCE)
  • M TCE Molecular weight of 1,1 ′, 2,2′-tetrachloroethane (TCE) Comparative Example 1
  • An epoxy resin was obtained in the same manner as in Example 1 except that the unmodified lignin (extract with an organic solvent) obtained in Comparative Production Example 3 was used. The epoxy equivalent of the obtained epoxy resin was 290.
  • Evaluation 1 In order to examine the performance of each epoxy resin, an epoxy resin and an epoxy resin curing agent were blended and cured.
  • the epoxy resin curing agent a commercially available novolak resin (Phenolite TD-2131, manufactured by DIC Corporation) was used.
  • an epoxy resin and an epoxy resin curing agent are prepared so that the epoxy equivalent of the epoxy resin and the amine equivalent and / or phenolic hydroxyl group equivalent of the epoxy resin curing agent are approximately equal. Then, they are dissolved in tetrahydrofuran, and then a curing accelerator (1-cyanoethyl-2-ethyl-4-methylimidazole) is added in an amount of 0.5 parts by mass with respect to 100 parts by mass of the total amount of the epoxy resin and the epoxy resin curing agent. The varnish was obtained by adding so that it might become. Subsequently, the obtained varnish was cast on a film, dried at 60 ° C. for 2 hours, and tetrahydrofuran was removed to obtain an epoxy resin composition.
  • a curing accelerator (1-cyanoethyl-2-ethyl-4-methylimidazole
  • the product was filled in a Teflon (registered trademark) mold, heated in a vacuum press at 150 ° C. for 2 hours, and then heated at 180 ° C. for 3 hours to be cured.
  • the epoxy resin composition was cured after being melted and exhibited fluidity, and then cured.
  • the obtained cured epoxy resin was evaluated by the following method. The results are shown in Table 1.
  • DVA dynamic viscoelasticity analysis
  • the size of the test piece was 10 mm ⁇ 40 mm ⁇ 2 mm.
  • the measurement mode was a three-point bending mode.
  • the measurement conditions were an air condition, a temperature range of ⁇ 100 ° C. to 300 ° C., a temperature increase rate of 5 ° C./min, and a frequency of 1 Hz.
  • the ⁇ relaxation peak temperature of the tan ⁇ curve thus obtained was defined as the glass transition temperature (Tg).
  • Example 3 The phenol-modified product of acetic acid-modified lignin (extracted with an organic solvent) obtained in Production Example 4 was used as an epoxy resin curing agent.
  • Comparative Example 2 The phenol-modified product of unmodified lignin obtained in Comparative Production Example 2 was used as an epoxy resin curing agent.
  • Comparative Example 3 The phenol-modified product of unmodified lignin (extracted with an organic solvent) obtained in Comparative Production Example 4 was used as an epoxy resin curing agent.
  • Evaluation 2 In order to examine the performance of each epoxy resin curing agent, an epoxy resin and an epoxy resin curing agent were blended and cured.
  • the epoxy resin a commercially available bisphenol A type epoxy resin (trade name JER 828, manufactured by Mitsubishi Chemical Corporation) was used.
  • an epoxy resin and an epoxy resin curing agent are prepared so that the epoxy equivalent of the epoxy resin and the amine equivalent and / or phenolic hydroxyl group equivalent of the epoxy resin curing agent are approximately equal. Then, they are dissolved in tetrahydrofuran, and then a curing accelerator (1-cyanoethyl-2-ethyl-4-methylimidazole) is added in an amount of 0.5 parts by mass with respect to 100 parts by mass of the total amount of the epoxy resin and the epoxy resin curing agent. The varnish was obtained by adding so that it might become. Subsequently, the obtained varnish was cast on a film, dried at 60 ° C. for 2 hours, and tetrahydrofuran was removed to obtain an epoxy resin composition.
  • a curing accelerator (1-cyanoethyl-2-ethyl-4-methylimidazole
  • the product was filled in a Teflon (registered trademark) mold, heated in a vacuum press at 150 ° C. for 2 hours, and then heated at 180 ° C. for 3 hours to be cured.
  • the epoxy resin composition was cured after being melted and exhibited fluidity, and then cured.
  • the epoxy resin and the epoxy resin curing agent obtained using lignin modified with acetic acid have a relatively high glass transition temperature and excellent heat resistance. It was confirmed that a cured epoxy resin was obtained.
  • thermogravimetric analysis TGA-50 manufactured by Shimadzu Corporation was used. More specifically, a sample made into a powder form with a gold file is weighed into a platinum cell so that the weight is 3 to 4 mg, and the temperature range is from room temperature to 800 ° C., the heating rate is 10 ° C./min, and the nitrogen stream ( 20 mL / min). Based on the weight at 40 ° C., the temperature when the weight decreased by 5% was defined as the 5% weight decrease temperature (T d5 ), and the temperature when decreased by 10% was defined as the 10% weight decrease temperature (T d10 ).
  • the epoxy resin obtained by using lignin modified with acetic acid has a relatively high 5% weight reduction temperature and 10% weight reduction temperature, and is excellent in heat resistance. It was confirmed that a cured product was obtained.
  • the epoxy resin cured product obtained by using the epoxy resin and the epoxy resin curing agent of the present invention is widely used in various electronic fields such as electrical and electronic parts such as semiconductor sealing materials, and paints and adhesives.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Une résine époxy et un durcisseur pour résines époxy, la résine époxy étant caractérisée par étant obtenue par au moins la réaction d'épichlorhydrine avec la lignine modifiée avec un acide carboxylique.
PCT/JP2015/079079 2014-10-20 2015-10-14 Résine époxy et durcisseur pour résine époxy Ceased WO2016063779A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106243324A (zh) * 2016-08-02 2016-12-21 黄山市徽州天马化工有限公司 一种阻燃型环氧树脂及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006111600A (ja) * 2004-10-18 2006-04-27 Kansai Paint Co Ltd 防蟻剤
JP2009084320A (ja) * 2007-09-27 2009-04-23 Sumitomo Bakelite Co Ltd リグニン誘導体及びその二次誘導体
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
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 (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006111600A (ja) * 2004-10-18 2006-04-27 Kansai Paint Co Ltd 防蟻剤
JP2009084320A (ja) * 2007-09-27 2009-04-23 Sumitomo Bakelite Co Ltd リグニン誘導体及びその二次誘導体
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
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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106243324A (zh) * 2016-08-02 2016-12-21 黄山市徽州天马化工有限公司 一种阻燃型环氧树脂及其制备方法

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TW201623356A (zh) 2016-07-01

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