Classifications

• • 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
  • C08G59/50—Amines
  • C08G59/52—Amino carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

• the present disclosure relates to a biomass epoxy resin composition.
• Epoxy resins are widely used as insulating materials for electrical equipment because they have excellent thermomechanical properties, electrical properties, moisture resistance, chemical resistance, dimensional stability, and the like.
• Epoxy resin is a type of thermosetting resin that, once cured, reacts in a three-dimensional network to form a strong cured product that becomes insoluble and infusible, making it difficult to reuse it after curing. .
• most used epoxy resins are disposed of by incineration, landfilling, etc., but when epoxy resins are incinerated, CO2 , which is a greenhouse gas, is generated.
• Patent Document 1 JP 2009-263549 A (Patent Document 1) and JP 2013-181040 A (Patent Document 2) disclose epoxy resin compositions comprising an epoxy resin and a curing agent derived from biomass that is solid at room temperature.
• Patent Document 1 proposes a method of using lignin having a phenol skeleton in the molecule as a curing agent, and discloses that a cured epoxy resin having a high glass transition temperature (Tg) of 200° C. or higher was obtained. ing.
• Patent Document 2 proposes a method using a relatively low molecular weight plant-derived polyphenol derivative as a curing agent from the viewpoint of moldability.
• Patent Document 3 discloses a multi-component synthetic resin adhesive containing at least one of a reactive diluent and a reactive resin (including an epoxy resin). .
• Patent Document 3 cites the challenges of increasing the proportion of biologically derived materials in synthetic resin adhesives and improving product characteristics related to environmental friendliness and sustainability, and uses biologically derived reactive diluents and A method has been proposed to solve the above problems by using a reactive resin.
• Patent Documents 1 and 2 both use a curing agent that is solid at room temperature, and there is a problem in that workability is inferior compared to resin compositions that use a liquid curing agent.
• Patent Document 1 when lignin with a large molecular weight is used as a curing agent, the viscosity of the resin composition increases and the workability decreases.
• Patent Document 2 when pyrogallol, which is a derivative of polyphenols, is used as a curing agent, it is expected that workability will be improved compared to lignin, but there is still room for improvement in heat resistance. There is.
• Patent Document 3 a reactive diluent derived from biomass is used as a constituent component, but there is no study on workability or heat resistance.
• heat resistance it is known that the structure of a cured product made of a multi-component synthetic resin has an effect, and control of the structure of the cured product is important.
• the present disclosure has been made to solve the above-mentioned problems, and aims to provide a biomass epoxy resin composition that is environmentally friendly and has both workability and heat resistance.
• the present inventors have found that by combining an epoxy resin, a biomass-derived curing agent, a biomass-derived monomer, and a polymerization initiator, the present inventors have achieved excellent environmental friendliness. It has also been found that the effect of achieving both workability and heat resistance can be obtained.
• the present disclosure relates to the following biomass epoxy resin composition.
• a biomass epoxy resin composition comprising an epoxy resin, a biomass-derived curing agent, a biomass-derived monomer, and a polymerization initiator, The gelation time of the polymer of the monomer at 100°C or less is within 20 minutes, A biomass epoxy resin composition, wherein a polymer of the monomer has a glass transition temperature of 60°C or higher.
• biomass epoxy resin composition that is not only environmentally friendly but also has workability and heat resistance.
• the biomass epoxy resin composition of this embodiment includes an epoxy resin (A), a biomass-derived curing agent (B), a biomass-derived monomer (C), and a polymerization initiator (D).
• the gelation time of the polymer of the biomass-derived monomer (C) at 100° C. or lower is within 20 minutes.
• the Tg of the polymer of the biomass-derived monomer (C) is 60°C or higher.
• the polymer of the biomass-derived monomer (C) is also simply referred to as a "polymer”.
• Epoxy resin (A) The epoxy resin (A) contained in the biomass epoxy resin composition of this embodiment is a compound having two or more oxirane rings (epoxy groups) per molecule.
• the shape of the epoxy resin (A) is not particularly limited, but from the viewpoint of dissolving the solid biomass-derived curing agent (B), the epoxy resin (A) is preferably liquid at room temperature.
• epoxy resins (A) examples include bisphenol A epoxy resins, bisphenol F epoxy resins, cresol novolac epoxy resins, alicyclic epoxy resins, glycidylamine epoxy resins, and the like.
• bisphenol A epoxy resins and bisphenol F epoxy resins are preferred from the viewpoint of workability and heat resistance. Furthermore, when high heat resistance is required, polyfunctional epoxy resins are preferred.
• the epoxy resin (A) may be derived from petroleum or biomass. Moreover, the epoxy resin (A) may be used alone or in combination of two or more types. When using two or more types in combination, the combination is not particularly limited.
• biomass epoxy resin composition of this embodiment includes a biomass-derived curing agent (B).
• a biomass-derived curing agent (B) By including the curing agent (B) derived from biomass, a biomass epoxy resin composition with excellent environmental properties can be obtained.
• the biomass-derived curing agent (B) is preferably a compound having an aromatic ring.
• aromatic compounds such as 4-aminobenzoic acid, 4-hydroxybenzoic acid, and protocatechuic acid, and lignin, which is a phenolic polymer compound, can be used in various ways. Examples include industrial lignin obtained by separation.
• 4-aminobenzoic acid, 4-hydroxybenzoic acid, and protocatechuic acid are preferred.
• 4-Aminobenzoic acid, 4-hydroxybenzoic acid, and protocatechuic acid have low molecular weights, and by using the low molecular weight biomass-derived curing agent (B), the mixing viscosity of the biomass epoxy resin composition can be kept low, making it easier to work with. This is because a biomass epoxy resin composition with excellent properties can be obtained.
• the biomass-derived curing agent (B) may be used alone or in combination of two or more. Moreover, the curing agent (B) derived from biomass may be completely derived from biomass or may be partially derived from biomass.
• the content of the biomass-derived curing agent (B) is based on the epoxy group in the molecule of the epoxy resin (A), the active hydrogen, hydroxyl group, carboxyl group, and acid of the amino group in the molecule of the biomass-derived curing agent (B).
• an epoxy group such as anhydride and a functional group capable of reacting react with a 1:1 chemical equivalent
• the epoxy group in the molecule of the biomass-derived curing agent (B) reacts with the epoxy group in the molecule of the epoxy resin (A).
• the equivalent ratio of the functional groups may be 0.3 to 3.0. If the relevant amount ratio is outside the above range, properties such as heat resistance may not be fully expressed.
• the content of the biomass-derived curing agent (B) is such that the number of active hydrogens between the epoxy groups in the epoxy resin (A) and the functional groups in the biomass-derived curing agent (B) is equivalent. It is preferable.
• a bisphenol A type epoxy resin with an epoxy equivalent of 190 g/eq as the epoxy resin (A) and 4-aminobenzoic acid as the biomass-derived curing agent (B)
• 100 parts by weight of the bisphenol A type epoxy resin is used.
• the amount of 4-aminobenzoic acid was 24.0 parts by weight.
• 4-hydroxybenzoic acid is added to 100 parts by weight of the bisphenol A type epoxy resin.
• the amount of benzoic acid is 36.4 parts by weight.
• biomass epoxy resin composition of this embodiment includes a biomass-derived monomer (C).
• a biomass epoxy resin composition with excellent environmental friendliness and workability can be obtained.
• biomass-derived monomer (C) examples include ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tetrabutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and isodecyl (meth)acrylate.
• the biomass-derived monomer (C) may be used alone or in combination of two or more. Moreover, the biomass-derived monomer (C) may be completely derived from biomass or may be partially derived from biomass. In addition, as long as it contains the monomer (C) derived from biomass, it may contain a monomer derived from petroleum.
• biomass-derived monomers (C) ethyl methacrylate, tetrabutyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl (meth)acrylate, etc. are preferred, and isobornyl (meth)acrylate is more preferred.
• isobornyl (meth)acrylate has a high Tg (Tg: 180°C)
• a biomass epoxy resin composition with excellent heat resistance can be obtained by dissolving isobornyl (meth)acrylate and the epoxy resin (A). be. Therefore, a biomass epoxy resin composition using isobornyl (meth)acrylate can be suitably used for applications requiring high heat resistance.
• the biomass epoxy resin composition of this embodiment has a polymer Tg of 60° C. or higher when it is made into a cured product.
• the above-mentioned biomass-derived monomers (C) include those with a Tg of less than 60°C; By combining two or more types of C), the Tg of the polymer may be adjusted to 60° C. or higher.
• the content of the biomass-derived monomer (C) is 10 to 70% by weight based on the epoxy resin (A), the biomass-derived curing agent (B), and the biomass-derived monomer (C).
• the content of the biomass-derived monomer (C) is less than 10% by weight, the effect of the biomass-derived monomer (C) may be reduced. If the content of the biomass-derived monomer (C) exceeds 70% by weight, the biomass epoxy resin composition may become brittle and moldability may be impaired.
• the biomass epoxy resin composition of this embodiment includes a polymerization initiator (D).
• the polymerization initiator (D) is a compound that can initiate the polymerization of the biomass-derived monomer (C), and can be a radical initiator that generates active radicals, acids, etc. by the action of light or heat, or a compound that utilizes a redox reaction. There are redox initiators that generate radicals.
• Examples of the polymerization initiator (D) include organic peroxides such as hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxycarbonates, peroxyketals, and ketone peroxides. Examples include combinations of these organic peroxides and reducing agents such as metal salts and amines. Among these polymerization initiators (D), combinations of hydroperoxides and metal salts and ketone peroxides and metal salts, which can efficiently generate radicals even at low temperatures, are preferred. Examples of hydroperoxides include tert-butyl hydroperoxide and cumene hydroperoxide.
• Examples of ketone peroxides include methyl ethyl ketone peroxide and cyclohexanone peroxide.
• Examples of the metal salt include cobalt salts such as cobalt naphthenate and cobalt octylate, and vanadium compounds such as vanadium pentoxide.
• the content of the polymerization initiator (D) depends on the type of biomass-derived monomer (C) used, but is 0.001 to 20 parts by weight per 100 parts by weight of the biomass-derived monomer (C). , preferably 0.005 to 10 parts by weight.
• the gelation time of the polymer described below can be adjusted to an appropriate range.
• the biomass epoxy resin composition of this embodiment may contain a curing accelerator in order to increase the curing speed of the epoxy resin (A).
• the curing accelerator is not particularly limited as long as it accelerates the curing of the epoxy resin (A), and examples thereof include tertiary amine accelerators such as benzyldimethylamine, and 2-ethyl-4-methylimidazole. Examples include imidazole promoters, phosphorus promoters such as triphenylphosphine, and organic metals such as zinc octylate.
• the curing accelerator may be used alone or in combination of two or more types.
• the content of the curing accelerator may be adjusted appropriately depending on the type of epoxy resin (A) and biomass-derived curing agent (B) used, and generally, the content of the curing accelerator is 0 to 100 parts by weight of the epoxy resin (A). .1 to 100 parts by weight.
• the gelation time of the polymer at 100° C. or lower is within 20 minutes. If the gelation time of the polymer at 100°C or lower exceeds 20 minutes, the volatilization of the biomass-derived monomer (C) progresses, and the reaction between the epoxy resin (A) and the biomass-derived curing agent (B) progresses. This is because the degree of polymerization of the biomass-derived monomer (C) is suppressed due to the increase in viscosity, making it difficult to obtain the effects of adding the biomass-derived monomer (C).
• the gelation time of the polymer at 100° C. or lower is preferably within 18 minutes. In addition, although the faster the gelation time, the better, from the viewpoint of moldability of the biomass epoxy resin composition, the gelation time is preferably 30 seconds or more.
• the gelation time can be measured, for example, by the following procedure.
• a gelling tester No. 153 Gel Time Tester manufactured by Yasuda Seiki Seisakusho Co., Ltd.
• a rotor is rotated in a test tube containing 1 ml of a polymer sample, and when the gelation of the sample progresses and a certain amount of torque is applied to the rotor, the rotor falls due to the magnetic coupling mechanism and the timer stops. This time is defined as gelation time.
• the biomass epoxy resin composition of this embodiment has a polymer Tg of 60° C. or higher when cured. When the Tg of the polymer is less than 60°C, heat resistance decreases.
• the Tg of the polymer is preferably 100°C or higher. Note that, although Tg is preferably higher, it may be, for example, 300° C. or lower.
• Tg can be measured, for example, by the following procedure.
• a dynamic mechanical analysis (DMA) device (DMS6100 manufactured by Hitachi High-Tech Science Co., Ltd.) is prepared.
• DMA dynamic mechanical analysis
• a test piece made of a polymer (40 mm long x 10 mm wide x 1 to 3 mm thick) was measured under the following test conditions, and the peak top temperature of loss tangent (tan ⁇ ) was defined as Tg.
• ⁇ Test conditions Deformation mode: Tensile mode Measurement temperature: 25-250°C Heating rate: 2°C/min Frequency: 0.2 ⁇ 5Hz
• phase structure (hereinafter simply referred to as "phase structure") of the cured product of the biomass epoxy resin composition affects physical properties such as heat resistance and mechanical strength.
• the phase structure is such that the epoxy resin cured product, which is a cured product of epoxy resin (A) and biomass-derived curing agent (B), exists in a separated state without being compatible with the polymer, that is, it is phase separated. Examples include a state in which the cured epoxy resin and the polymer are compatible with each other.
• the phase structure can be specified by the peak shape and peak temperature of tan ⁇ of the dynamic viscoelasticity of the cured product.
• Tg1 and Tg2 are different, and if they are completely phase separated from each other, the Tg of each will be two tan ⁇ . A peak appears.
• the cured epoxy resin and the polymer are compatible, one tan ⁇ peak will appear.
• the cured epoxy resin and the polymer have functional groups that can chemically bond to each other, and (2) the cured epoxy resin and the polymer each have a network structure.
• One of the cured epoxy resin and the polymer forms a network structure, and the other has a long chain structure that does not form a network structure. Examples include the state of being a polymer and having no functional groups that chemically bond to each other.
• the network structures or the network structure and the chain structure form one network structure through chemical bonds, there is one tan ⁇ peak.
• the peak of tan ⁇ may appear as two peaks or a shoulder peak at a value different from the Tg of the cured epoxy resin and the polymer, respectively.
• the cured epoxy resin and the polymer have functional groups that can chemically bond to each other, and (2) the mutual network structures of the cured epoxy resin and the polymer are uniformly physically entangled.
• a semi-IPN structure is formed in which one long-chain polymer is physically entangled with the other network structure.
• the compatibility between the cured epoxy resin and the polymer is improved by chemical bonding, but when there are few functional groups or when the molecular weight of the polymer is high, phase separation occurs partially or completely.
• Tg2 when Tg2 is lower than Tg1, it is preferable that the cured epoxy resin and the polymer in the biomass epoxy resin composition are phase-separated. In this case, since Tg1 exhibits a Tg equivalent to that of the epoxy resin (A) alone, a decrease in the Tg of the entire biomass epoxy resin composition can be prevented.
• Tg2 when Tg2 is higher than Tg1, it is preferable that the cured epoxy resin and the polymer in the biomass epoxy resin composition are completely or partially compatible. In this case, Tg1 can be improved more than the Tg of the epoxy resin (A) alone, and it can be suitably used for applications requiring higher heat resistance.
• the biomass epoxy resin composition of the present embodiment contains radioactive carbon (carbon-14, hereinafter referred to as "C14").
• C14 always exists in the atmosphere at a constant rate. During the growth process, plants take in CO2 from the atmosphere, so the amount of C14 contained in plants is the same as that in the atmosphere.
• fossil resources such as petroleum do not contain C14, and biomass-derived carbon can be distinguished from petroleum-derived carbon.
• the current concentration of C14 in the atmosphere is about 100 pMC (percent modern carbon), and if a certain biomass plastic was made from 100% biomass-derived material, the pMC of this sample would be around 100. . On the other hand, in the case of petroleum-derived substances, the pMC of this sample is approximately 0.
• the value will be around 50 pMC. Therefore, by determining the proportion of C14 in the biomass epoxy resin composition, it is possible to verify the environmental load of the biomass epoxy resin composition.
• the content of C14 based on the total carbon in the biomass epoxy resin composition of this embodiment is 20% or more.
• the content rate of C14 is calculated using the following formula (1).
• C14 content (%) in biomass epoxy resin composition 100 x C14 content in biomass epoxy resin composition/total carbon content in biomass epoxy resin composition... (1) If the content of C14 in the biomass epoxy resin composition is less than 20%, the effect as a carbon offset material will be poor.
• the mixed viscosity of the biomass epoxy resin composition is preferably 5000 mPa ⁇ s or less at 60°C, more preferably 1000 mPa ⁇ s or less, and even more preferably 300 mPa ⁇ s or less.
• the mixed viscosity of the biomass epoxy resin composition is measured using an E-type viscometer. Although it is preferable that the mixture viscosity is small, it may be, for example, 10 mPa ⁇ s or more.
• the use of the biomass epoxy resin composition of this embodiment is not particularly limited and can be used for various purposes.
• it may be used as a varnish for motors by dissolving it in an organic solvent, or it may be used as a molding resin for motors, power modules, etc. by adding a filler as in Embodiment 2, which will be described later.
• the method for producing the biomass epoxy resin composition of this embodiment is not particularly limited.
• an epoxy resin (A) and a biomass-derived curing agent (B) are mixed at room temperature or with heating to obtain a first mixture.
• the heating temperature is, for example, in the range of 40 to 180°C.
• a biomass-derived monomer (C) and a polymerization initiator (D) are mixed at room temperature to obtain a second mixture.
• a biomass epoxy resin composition is obtained by heating and mixing these first mixture and second mixture.
• the heating temperature and heating time may be appropriately set depending on the epoxy resin (A), biomass-derived curing agent (B), and biomass-derived monomer (C) to be used.
• the heating temperature is, for example, in the range of 40 to 180°C, but preferably in the range of 40 to 120°C from the viewpoint of suppressing volatilization of the biomass-derived monomer (C).
• the heating time is, for example, in the range of 1 to 180 minutes.
• the degree of polymerization of the biomass-derived monomer (C) changes depending on the heating temperature and heating time. For example, when heated at a high temperature for a short time and when heated at a low temperature for a long time, The degree of polymerization may be the same.
• a solvent may be used when mixing the epoxy resin (A) and the biomass-derived curing agent (B).
• the solvent is not particularly limited, and examples thereof include toluene, methyl ethyl ketone, and the like.
• the polymerization initiator (D) is added and the mixture is heated at room temperature or with heating.
• the heating temperature when the epoxy resin (A), the biomass-derived curing agent (B), and the biomass-derived monomer (C) are mixed is, for example, in the range of 40 to 180°C.
• the heating temperature after adding the polymerization initiator (D) is, for example, in the range of 40 to 180°C.
• the curing conditions for the biomass epoxy resin composition are not particularly limited, but for example, the heating temperature is in the range of 30 to 300°C, and the heating time is in the range of 1 minute to 100 hours.
• the biomass epoxy resin composition according to this embodiment further contains an inorganic filler (E).
• an inorganic filler (E) By including the inorganic filler (E) in the biomass epoxy resin composition, a biomass epoxy resin composition having desired mechanical strength and linear expansion coefficient can be obtained. Note that explanations other than points different from Embodiment 1 will be omitted.
• inorganic filler (E) examples include, but are not limited to, metal oxide particles such as aluminum oxide (alumina), zinc oxide, indium tin oxide (ITO), magnesium oxide, beryllium oxide, and titanium oxide, boron nitride, Examples include metal nitride particles such as silicon nitride and aluminum nitride, carbon compound particles such as silicon carbide, graphite, diamond, amorphous carbon, carbon black, and carbon fiber, and silica compound powders such as quartz and quartz glass. These may be used alone or in combination of two or more.
• metal oxide particles such as aluminum oxide (alumina), zinc oxide, indium tin oxide (ITO), magnesium oxide, beryllium oxide, and titanium oxide
• metal nitride particles such as silicon nitride and aluminum nitride
• carbon compound particles such as silicon carbide, graphite, diamond, amorphous carbon, carbon black, and carbon fiber
• silica compound powders such as quartz and quartz glass.
• aluminum oxide (alumina), zinc oxide, magnesium oxide, beryllium oxide, titanium oxide, boron nitride, silicon nitride, aluminum nitride, diamond, quartz, quartz glass, etc. are preferable.
• the average particle size of the inorganic filler (E) is preferably 1 nm to 100 ⁇ m, more preferably 1 nm to 80 ⁇ m.
• the average particle size of the inorganic filler (E) is less than 1 nm, the viscosity of the biomass epoxy resin composition becomes high, which may impair workability and moldability.
• the average particle size of the inorganic filler (E) exceeds 100 ⁇ m, the strength of the cured product of the biomass epoxy resin composition decreases and the inorganic filler (E) tends to settle during storage of the biomass epoxy resin composition.
• the content of the inorganic filler (E) is preferably 40 to 90% by weight, more preferably 70 to 85% by weight, based on the entire biomass epoxy resin composition.
• the content of the inorganic filler (E) is less than 40% by weight, there is a possibility that a cured product of the biomass epoxy resin composition having desired mechanical strength and thermal expansion coefficient cannot be obtained. If the content of the inorganic filler (E) exceeds 90% by weight, the viscosity of the biomass epoxy resin composition may increase, and workability and moldability may be impaired.
• the inorganic filler (E) may be subjected to a coupling treatment using a coupling agent.
• Examples of such coupling agents include ⁇ -glycidoxypropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltriethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, ⁇ - Examples include mercaptopropyltrimethoxysilane. These may be used alone or in combination of two or more.
• the content of the coupling agent may be appropriately set depending on the type of the epoxy resin (A) and the inorganic filler (E), but for example, 0.01 parts by weight per 100 parts by weight of the epoxy resin (A). ⁇ 5 parts by weight.
• the inorganic filler is A filler (E) may be mixed.
• the inorganic filler (E) may be mixed in the step of heating and mixing the first mixture and the second mixture.
• the inorganic filler (E) may be mixed in the step of mixing the epoxy resin (A), the biomass-derived curing agent (B), and the biomass-derived monomer (C) at room temperature or by heating.
• the coupling treatment of the inorganic filler (E) with a coupling agent may be carried out using a conventionally known method before mixing the inorganic filler (E).
• the biomass epoxy resin composition according to this embodiment further contains a compatible monomer (F).
• the biomass epoxy resin composition contains the compatible monomer (F)
• the epoxy resin cured product and the polymer partially form a chemical bond, and the compatibility between the epoxy resin cured product and the polymer is improved.
• a biomass epoxy resin composition with improved heat resistance can be obtained. Note that explanations other than points different from Embodiment 1 will be omitted.
• the compatible monomer (F) includes a first functional group that reacts with the epoxy resin (A) and the biomass-derived monomer (C), and a first functional group that reacts with the biomass-derived curing agent (B) and the biomass-derived monomer (C).
• the monomer preferably has at least one functional group selected from the group consisting of second functional groups.
• compatible monomers (F) having a first functional group examples include methacrylamide, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, 4-vinyl Phenol, acrylates and methacrylates such as ⁇ -carboxyethyl acrylate, styrenes such as p-acetoxystyrene, o-acetoxystyrene, m-acetoxystyrene, 3-methoxy-4-acetoxystyrene, p-hydroxyphenylstyrene, etc. Can be mentioned.
• Examples of the compatible monomer (F) having a second functional group include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, (meth)allyl glycidyl ether, (meth)allyl methylglycidyl ether, 3,4-epoxy Examples include cyclohexylmethyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, and the like.
• glycidyl methacrylate is preferred from the viewpoint of compatibility.
• the content of the compatible monomer (F) may be adjusted as appropriate depending on the types of the epoxy resin (A), biomass-derived curing agent (B), and biomass-derived monomer (C) used. Also, The content of the epoxy resin (A) or the biomass-derived curing agent (B) may be adjusted depending on the content of the compatible monomer (F).
• the content of the compatible monomer (F) is, for example, the epoxy group in the molecule of the epoxy resin (A), the active hydrogen of the amino group in the molecule of the compatible monomer (F), hydroxyl group, carboxyl group, acetoxy group,
• an epoxy group such as an acid anhydride and a reactive functional group react with a 1:1 chemical equivalent
• the epoxy group in the molecule of the epoxy resin (A) is compatible with the epoxy group in the molecule of the monomer (F).
• the equivalent ratio of the functional groups may be 0.3 to 3.0. If the relevant amount ratio is outside the above range, properties such as heat resistance may not be fully expressed.
• the content of the compatible monomer (F) is such that, for example, the content of the functional group that can react with the epoxy group in the molecule of the biomass-derived curing agent (B) and the epoxy group in the molecule of the compatible monomer (F),
• the equivalent ratio of the functional group in the molecule of the biomass-derived curing agent (B) to the epoxy group in the molecule of the compatible monomer (F) is 0.3 to 3.0. All you have to do is make it so that If the relevant amount ratio is outside the above range, properties such as heat resistance may not be fully expressed.
• the method of mixing the compatible monomer (F) is not particularly limited, but for example, the compatible monomer (F) is mixed in the step of mixing the biomass-derived monomer (C) and the polymerization initiator (D) at room temperature to obtain a second mixture. F) may be mixed.
• the compatible monomer (F) may be mixed in the step of heating and mixing the first mixture and the second mixture.
• the compatible monomer (F) may be mixed in the step of mixing the epoxy resin (A), the biomass-derived curing agent (B), and the biomass-derived monomer (C) at room temperature or by heating.
• Example 1 Components (A) to (D) in the amounts shown in Table 1 were prepared.
• Component (A-1) and component (B-1) were heated and mixed at 130° C. to obtain a first mixture.
• component (C-1) and (D-1) at room temperature component (D-2) was added and mixed uniformly to obtain a second mixture.
• the obtained first mixture and second mixture were mixed and heated at 100° C. for 15 minutes to obtain the biomass epoxy resin composition of Example 1. Further, the obtained biomass epoxy resin composition was heated at 80° C. for 2 hours, at 130° C. for 2 hours, and at 180° C. for 2 hours, respectively, to obtain a cured product of the biomass epoxy resin composition.
• Examples 2 to 4 A biomass epoxy resin composition and a cured product thereof were obtained in the same manner as in Example 1, except that the amounts of component (C) and component (D) were changed to those shown in Table 1.
• Example 5 Same as Example 1, except that the amount of the component (D) was changed to the amount shown in Table 1, and the heating time after mixing the first mixture and the second mixture was changed to 5 minutes. A biomass epoxy resin composition and its cured product were obtained by this method.
• Example 6 Component (B-1) was changed to component (B-2), component (C-1) was changed to component (C-2), and the blending amounts of each component (B) to (D) are shown in Table 1.
• a biomass epoxy resin composition and a cured product thereof were obtained in the same manner as in Example 1, except that the amounts were changed as shown.
• Example 7 Components (A) to (E) in the amounts shown in Table 1 were prepared. Component (A-1) and component (B-1) were heated and mixed at 130° C. to obtain a first mixture. Component (C-1) was heated to 100° C. and mixed into the obtained first mixture, and after returning to room temperature, component (E-1) was added and mixed. Component (D-2) was added to these mixtures, mixed uniformly, and heated at 100° C. for 15 minutes to obtain the biomass epoxy resin composition of Example 7. Furthermore, a cured product of the biomass epoxy resin composition was produced in the same manner as in Example 1.
• Example 8 Components (A) to (F) in the amounts shown in Table 1 were prepared. Component (A-1) and component (B-1) were heated and mixed at 130° C. to obtain a first mixture. After uniformly mixing component (C-1), component (F-1) and component (D-1) at room temperature, component (D-2) was added and mixed uniformly to obtain a second mixture. . The obtained first mixture and second mixture were mixed and heated at 100° C. for 15 minutes to obtain the biomass epoxy resin composition of Example 8. Furthermore, a cured product of the biomass epoxy resin composition was produced in the same manner as in Example 1.
• Comparative example 1 Component (A) and component (B') in the amounts shown in Table 1 were prepared.
• a biomass epoxy resin composition of Comparative Example 1 was obtained by heating component (A-1) and component (B'-1) at 100° C. for 15 minutes. Thereafter, the cured product was obtained in the same manner as in Example 1.
• Comparative example 2 Components (A) and (B) in the amounts shown in Table 1 were prepared.
• a biomass epoxy resin composition of Comparative Example 2 was obtained by heating component (A-1) and component (B-1) at 100° C. for 15 minutes. Thereafter, the cured product was obtained in the same manner as in Example 1.
• Comparative example 3 Components (A) and (B) in the amounts shown in Table 1 were prepared.
• a biomass epoxy resin composition of Comparative Example 3 was obtained by heating the components (A-1) and (B-2) at 100° C. for 15 minutes. Thereafter, the cured product was obtained in the same manner as in Example 1.
• Biomass was prepared in the same manner as in Example 1, except that the (C-1) component was changed to the (C'-1) component, and the blended amount of the (C') component was changed to the amount shown in Table 1. An epoxy resin composition and a cured product thereof were obtained.
• Component (A), component (B), and component (E) in the amounts shown in Table 1 were prepared.
• Component (A-1) and component (B-1) were heated and mixed at 130° C. to obtain a first mixture.
• component (E-1) was added, mixed uniformly, and heated at 100° C. for 15 minutes to obtain a biomass epoxy resin composition of Comparative Example 6.
• a cured product of the biomass epoxy resin composition was produced in the same manner as in Example 1.
• Each component shown in Table 1 (each component indicated by a symbol) is as follows.
• E component E component
• Fused silica FB74 manufactured by Denka Co., Ltd.
• average particle size 30 ⁇ m
• the samples used for the evaluation of (1) gelation time and (2) Tg are polymers obtained by polymerizing only component (C), and the samples used for the evaluation of (3) C14 are biomass epoxy resin compositions.
• the sample used for evaluating the tan ⁇ peak temperature is a cured product of the biomass epoxy resin composition.
• Tg A DMA device (DMS6100, manufactured by Hitachi High-Tech Science Co., Ltd.) was prepared. Using a test piece made of a polymer (40 mm long x 10 mm wide x 1 to 3 mm thick), measurements were made under the following test conditions. The peak top temperature of tan ⁇ in this measurement was defined as Tg. ⁇ Test conditions ⁇ Deformation mode: Tensile mode Measurement temperature: 25-250°C Heating rate: 2°C/min Frequency: 0.2 ⁇ 5Hz
• C14 The C14 content of each sample was calculated using the following formula (1).
• C14 content (%) in biomass epoxy resin composition 100 x C14 content in biomass epoxy resin composition/total carbon content in biomass epoxy resin composition...Formula (1)
• Tan ⁇ peak temperature The above-mentioned DMA device was prepared. The tan ⁇ peak temperature of each sample was measured. When two peaks were obtained, the higher tan ⁇ peak value (intensity) was taken as the tan ⁇ peak temperature.
• Table 1 shows the evaluation results of (1) to (5) above for the obtained evaluation samples.
• the biomass epoxy resin composition of the example uses a biomass-derived curing agent (B) and a biomass-derived monomer (C), and has a C14 content of 20% or more, so it has excellent environmental friendliness. Further, the biomass epoxy resin composition of the example has excellent workability since the gelation time of the polymer is within 20 minutes. Furthermore, the biomass epoxy resin composition of the example has excellent heat resistance since the Tg of the polymer is 60° C. or higher.
• Example 7 It was also confirmed that the mixture viscosity of Example 7 was significantly lower than that of Comparative Example 6 in which no biomass-derived monomer (C) component was added.
• Example 5 the tan ⁇ peak was broad, which confirmed that the cured epoxy resin and the polymer were partially compatible.
• Example 5 since two tan ⁇ peaks were obtained, it was confirmed that the epoxy resin cured product and the polymer were phase separated. As shown in Example 5, when the gelation time of the polymer is short, the cured epoxy resin and the polymer are not sufficiently compatible with each other, and the biomass epoxy resin composition is partially phase-separated. It is considered that a cured product is formed.
• the tan ⁇ peak temperature showed a value higher than the Tg of the polymer itself. It is presumed that this is because the molecular chains of the cured epoxy resin and the polymer are physically entangled and restrained, resulting in a higher Tg value than that of the polymer alone, resulting in improved heat resistance.
• Example 5 when the cured epoxy resin and the polymer undergo partial phase separation, the lower tan ⁇ peak temperature of the two tan ⁇ peaks is higher than that of the biomass epoxy that does not contain the biomass-derived monomer (C).
• the tan ⁇ peak temperature showed a value equivalent to that of Comparative Example 2, which is a resin composition.
• Example 6 Even when the Tg of the polymer is relatively low, as in Example 6, the mixing viscosity can be lowered compared to Comparative Example 3, which does not contain the biomass-derived monomer (C). It has been confirmed that it can improve sexual performance.
• Examples 1 and 8 have the same monomer component content.
• Example 1 only IBOMA, whose Tg as a single polymer is 180°C, is used, but in Example 8, the same amount of IBOMA and GM, whose Tg as a single polymer is 46°C, is used. ing.
• IBOMA and GM have a large difference in Tg as a single polymer, the tan ⁇ peak temperature of Example 7 is higher than the tan ⁇ peak temperature of Example 1. This is because the biomass epoxy resin composition contains a compatible monomer (F), and the cured epoxy resin and polymer form partial chemical bonds in addition to physical molecular chain entanglement. It is presumed that the compatibility between the cured epoxy resin and the polymer was improved, and the heat resistance was improved.
• F compatible monomer
• Comparative Example 1 does not contain the biomass-derived curing agent (B) and the biomass-derived monomer (C), so it is inferior in environmental friendliness.
• Comparative Examples 2 and 3 do not contain the biomass-derived monomer (C), so they are inferior in workability compared to Examples 1 to 6.
• Comparative Example 4 has poor heat resistance because the Tg of the polymer is less than 60°C.

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