Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
• • 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
  • C08G59/5033—Amines aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
  • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/06—Elements
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon

Definitions

• the present invention relates to an epoxy resin composition preferably used for a fiber-reinforced composite material for aerospace applications, general industrial applications, sports applications, etc., and a prepreg and a fiber-reinforced composite material using the epoxy resin composition. ..
• Fiber-reinforced composite materials that use carbon fiber or aramid fiber as reinforcing fibers utilize their high specific strength and specific elastic modulus to make structural materials such as aircraft and automobiles, tennis rackets, golf shafts, fishing rods, bicycles, etc. It is widely used for sports such as housings and general industrial applications.
• a thermosetting resin is mainly used from the viewpoint of heat resistance and productivity, and among them, an epoxy resin is preferable from the viewpoint of mechanical properties such as adhesiveness to the reinforcing fiber. Used.
• Patent Document 1 a method for improving elastic modulus and strength by combining an epoxy resin having a specific structure and a nanofiller has been studied. Further, a method for improving the resin strength by adding an additive in order to reduce that dicyandiamide used as a curing agent remains undissolved and becomes a defect has been studied (Patent Document 2). Further, a method of using a liquid curing agent which is unlikely to cause defects in a resin composition for an RTM molding method has been studied (Patent Document 3).
• an object of the present invention to provide an epoxy resin composition having excellent elastic modulus, strength, and pot life, which can be suitably used for prepreg and fiber reinforced composite material applications.
• the epoxy resin composition of the present invention is an epoxy resin composition containing the following components [A] to [C] and satisfying the following conditions (1) to (4).
• the present invention is a prepreg composed of the epoxy resin composition of the present invention and reinforcing fibers.
• the present invention is a fiber-reinforced composite material composed of a cured product of the epoxy resin composition of the present invention and reinforcing fibers.
• an epoxy resin composition having excellent elastic modulus, strength and pot life that can be suitably used for prepreg and fiber-reinforced composite material applications can be obtained.
• the resin composition of the present invention contains the constituent elements [A] to [C] as essential components.
• the "component” means a compound contained in the composition.
• the component [A] in the present invention is an epoxy resin.
• the epoxy resin of the component [A] one containing two or more epoxy groups in one molecule raises the glass transition temperature of the cured product obtained by heating and curing the resin composition and improves heat resistance. It is preferable because it can be used. Further, an epoxy resin containing one epoxy group in one molecule may be blended. These epoxy resins may be used alone or in combination as appropriate.
• Examples of the epoxy resin of the component [A] include diaminodiphenylmethane type, diaminodiphenylsulfone type, aminophenol type, bisphenol type, metaxylene diamine type, 1,3-bisaminomethylcyclohexane type, isocyanurate type, and hydantin type. , Phenol novolac type, orthocresol novolac type, trishydroxyphenylmethane type, tetraphenylol ethane type and other epoxy resins. Of these, diaminodiphenylmethane-type, aminophenol-type, and bisphenol-type epoxy resins are particularly preferably used because they have a good balance of physical properties.
• diaminodiphenylmethane type epoxy resin examples include ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), "Araldite (registered trademark)” MY720 (manufactured by Huntsman Advanced Materials Co., Ltd.), and "Araldite (registered trademark)” MY721.
• Examples of commercially available diaminodiphenyl sulfone type epoxy resins include TG3DAS (manufactured by Mitsui Kagaku Fine Co., Ltd.).
• aminophenol type epoxy resins include ELM120 (manufactured by Sumitomo Chemical Co., Ltd.), ELM100 (manufactured by Sumitomo Chemical Co., Ltd.), "jER (registered trademark)” 630 (manufactured by Mitsubishi Chemical Co., Ltd.), and "Araldite”.
• bisphenol A type epoxy resins include "EPON (registered trademark)” 825 (manufactured by Mitsubishi Chemical Corporation), “Epicron (registered trademark)” 850 (manufactured by DIC Corporation), and “Epototo (registered trademark)”. "YD-128 (manufactured by Toto Kasei Co., Ltd.), and DER-331 and DER-332 (manufactured by Dow Chemical Corporation) and the like can be mentioned.
• bisphenol F-type epoxy resins include "Araldite (registered trademark)” GY282 (manufactured by Huntsman Advanced Materials), “jER (registered trademark)” 806, “jER (registered trademark)” 807, and “jER”. (Registered trademark) “1750 (above, manufactured by Mitsubishi Chemical Corporation),” Epicron (registered trademark) “830 (manufactured by DIC Co., Ltd.) and” Epototo (registered trademark) "YD-170 (manufactured by Toto Kasei Co., Ltd.) ) And so on.
• an epoxy compound other than the above may be appropriately blended in the epoxy resin composition of the present invention.
• the component [B] in the present invention is an aromatic diamine.
• Polyamines containing aromatic diamines in the group have a plurality of amino groups capable of reacting with epoxy groups and function as a curing agent.
• aromatic polyamines, especially aromatic diamines are excellent as curing agents in that they can impart high mechanical properties and heat resistance to the cured epoxy resin.
• 2,2'-diethyldiaminodiphenylmethane 2,4-diethyl-6-methyl-m-phenylenediamine, 4,6-diethyl-2-methyl-m-phenylenediamine, 4 , Diethyltoluenediamine such as 6-diethyl-m-phenylenediamine, 4,4'-methylenebis (N-methylaniline), 4,4'-methylenebis (N-ethylaniline), 4,4'-methylenebis (N-) sec-butylaniline), N, N'-di-sec-butyl-p-phenylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3, 3'-diisopropyl-4,4'-diaminodiphenylmethane, 3,
• 3,3'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl sulfone are preferably used because the obtained cured product has excellent mechanical properties. Further, from the viewpoint that the increase in viscosity when the epoxy resin composition of the present invention is held at 70 ° C. can be suppressed and the pot life can be effectively improved, a solid aromatic diamine can be used. It is preferable to contain at least one of 3,3'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl sulfone.
• aromatic diamines include Seika Cure S (manufactured by Wakayama Seika Kogyo Co., Ltd.), MDA-220 (manufactured by Mitsui Chemicals Co., Ltd.), and "jER Cure (registered trademark)" WA (manufactured by Mitsubishi Chemicals Co., Ltd.).
• the ratio H / E of the number of moles E of the epoxy group of the component [A] to the number of moles H of the active hydrogen of the polyamine curing agent is 0.50 or more, 1. It is preferably 30 or less, more preferably 0.70 or more and 1.20 or less, and further preferably 0.80 or more and 1.10 or less.
• the total number of moles E of the epoxy group of the component [A] and at least one of 3,3'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl sulfone. ((Total number of moles of at least one of 3,3'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl sulfone) / E) is preferably 0.50 or more and 1.30 or less.
• the epoxy resin composition of the present invention can be adjusted to 70 ° C. It is possible to suppress the increase in viscosity when holding the pot with, and to effectively improve the pot life.
• the component [C] is a compound having a boiling point of 130 ° C. or higher and a molecular weight m of 50 or higher and 250 or lower, which does not have an epoxy group in the molecule and substantially has a curable ability of an epoxy resin. It is a compound that does not exist.
• compounds such as amines and phenols that can undergo an addition reaction with an epoxy resin, acid anhydrides that can copolymerize with an epoxy resin, imidazole that can be a self-polymerization reaction initiator of an epoxy resin, an aromatic urea compound, and a tertiary amine compound are used.
• It is a compound having an epoxy resin curable ability and does not correspond to a compound having no epoxy resin curable ability.
• the component [C] exists in the gap portion of the crosslinked structure without being incorporated into the crosslinked structure, and the state is maintained even after curing. As a result, the elastic modulus of the obtained cured epoxy resin product is increased. Further, surprisingly, the inventor has found that by blending the component [C], not only a high elastic modulus but also a high elongation and high strength epoxy resin cured product can be obtained. The reason for this is not clear, but the inventor thinks as follows. The component [C] does not have an epoxy group in the molecule and has substantially no curability of the epoxy resin, so that it does not react with the epoxy resin or the aromatic diamine forming the crosslinked structure.
• the component [C] is not constrained by the crosslinked structure formed by the reaction of the epoxy resin and the aromatic diamine and the covalent bond, and is appropriately retained in the voids of the crosslinked structure.
• the inventor believes that the voids in the cured product can be effectively filled and the elastic modulus of the cured product increases. Further, when the cured product is strained, the component [C] can move freely in the crosslinked structure, so that the strain energy leading to fracture can be relaxed, and the elongation and strength of the cured product are increased. The inventor thinks that.
• the component [C] is preferably a compound having at least one functional group selected from the group consisting of an amide group, a ketone group and a hydroxyl group in the molecule.
• the component [C] has the above-mentioned highly polar functional group in the molecule, the hydroxyl group in the crosslinked structure formed from the component [A] and the component [B] and the component [C] A strong intermolecular interaction acts between them, and the component [C] is easily held in the voids of the crosslinked structure, so that a particularly excellent effect of improving elongation and strength can be obtained.
• component [C] examples include amides such as N-methylpropionamide and N, N'-diphenylacetamide, and diols such as propanediol and hexanediol. These compounds may be used alone or in combination as appropriate.
• the boiling point of the component [C] is 130 ° C. or higher, preferably 180 ° C. or higher, volatilization of the component [C] when the epoxy resin composition is cured can be suppressed, and the cured resin product has excellent mechanical properties. And fiber reinforced composite materials can be obtained. Further, it is possible to suppress the generation of voids and the deterioration of mechanical properties in the obtained fiber-reinforced composite material.
• the boiling point is a value at normal pressure (101 kPa). If the boiling point at normal pressure cannot be measured, the converted boiling point converted to 101 kPa in the boiling point conversion chart can be used.
• the molecular weight m of the component [C] is 50 or more and 250 or less, more preferably 70 or more and 120 or less, and further preferably 70 or more and 110 or less. By setting m to such a range, the component [C] is appropriately held in the voids of the crosslinked structure formed by the reaction of the epoxy resin and the aromatic diamine, and is excellent in elastic modulus, strength, and elongation. A cured product is obtained.
• the component [C] has a sum ( ⁇ P + ⁇ H) of a polar component ( ⁇ P) and a hydrogen bond component ( ⁇ H) in the Hansen solubility parameter (HSP) of 10.0. It is important to satisfy the above (condition (1)), more preferably 15.0 or more, still more preferably 20.0 or more.
• the Hansen solubility parameter is a kind of dissolution parameter represented by three components of a dispersion component ( ⁇ D), a polar component ( ⁇ P), and a hydrogen bond component ( ⁇ H), and is expressed as a three-dimensional vector. Can be done.
• the HSP can uniquely calculate the value at 25 ° C. from the chemical structure of each component by using the computer software Hansen Solubility Parameter in Practice (HSPiP) (http://www.hansen-solubility.com).
• HSPiP ver. Using 5.0.06 (a product sold by Video Studio Question Co., Ltd.), calculate the value of the target compound at 25 ° C. and use it.
• the epoxy resin composition of the present invention satisfies that at least a part of the component [C] has a Hansen solubility parameter distance (HSP distance) L from the component [A] of 20.0 or less. (Condition (2)), preferably 17.0 or less, more preferably 10.0 or less.
• HSP distance L between the component [A] and the component [C] the higher the affinity between the component [A] and the component [C], and the easier it is to uniformly dissolve the epoxy resin composition. It is possible to prevent these from separating separately when curing. Therefore, the component [C] is easily held in the gap portion of the crosslinked structure, and an excellent elastic modulus and strength improving effect can be obtained.
• the HSP distance is a three-dimensional vector ( ⁇ D , ⁇ P , ⁇ H ) whose coordinates are the three components of HSP possessed by a certain substance, and the coordinates are each of the three components of two different substances. It is a parameter corresponding to the distance between three-dimensional vectors. It can be estimated that the smaller the HSP distance L, the higher the affinity between the two substances.
• the HSP of the first substance is ⁇ D1 , ⁇ P1 , ⁇ H1 and the HSP of the second substance is ⁇ D2 , ⁇ P2 , ⁇ H2
• the HSP distance L is calculated by the formula (1). be able to.
• the HSP value of the mixed epoxy resin calculated by the following method is used as the HSP of the component [A].
• the epoxy resin 1 having the HSP of ⁇ Da , ⁇ Pa , and ⁇ Ha as the component [A] and the epoxy resin 2 having the HSP of ⁇ Db , ⁇ Pb , and ⁇ Hb were mixed in a mass ratio of Wa: Wb.
• the HSP ( ⁇ Dm , ⁇ Pm , ⁇ Hm ) of the mixed epoxy resin is a value calculated by the formula (2).
• the HSP value of the mixed epoxy resin expressed by adding the three-dimensional vectors of the HSPs of each component is also used as the component [A].
• A] can be used as an HSP.
• the HSP distance L from the component [A] is calculated for each of the compounds of the component [C], and the above condition (2) is satisfied. Determine if you are satisfied. It is preferable that the HSP distance L between each compound of the component [C] and the component [A] is 20.0 or less.
• the molecular weight m of the component [C] is 70 or more and 110 or less, and the C / E is 0.01 or more and 0.20 or less so that either or both of the elastic modulus and the strength can be obtained.
• a particularly excellent cured product can be obtained, and the molecular weight m of the component [C] is preferably 70 or more and 110 or less, more preferably 0.07 or more and 0.13 or less, so that the elastic modulus and strength can be increased. In each case, a particularly excellent cured product can be obtained.
• the viscosity of the resin composition of the present invention when held at 70 ° C. for 2 hours is 5.0 times or less the initial viscosity at 70 ° C. (condition (4)).
• a ratio also referred to as “viscosity increase ratio”
• the step of kneading the resin composition and the resin composition In the step of impregnating the reinforcing fiber with the material, the change in viscosity of the resin composition becomes small, and the pot life can be lengthened. Further, it is possible to reduce the variation in the flow amount of the resin composition during molding, suppress the variation in the resin content contained in the fiber-reinforced composite material, and obtain a fiber-reinforced composite material having stable dimensions and mechanical properties. ..
• the viscosity increase ratio is effectively suppressed by using a solid aromatic diamine of the component [B], particularly at least one of 3,3'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl sulfone. be able to.
• the epoxy resin composition of the present invention has excellent elastic modulus, strength, and elongation, and is suitably used as a matrix resin for a fiber-reinforced composite material.
• Methods for obtaining a fiber-reinforced composite material include a method of impregnating a reinforcing fiber with a resin composition in a molding process such as a hand lay-up method, an RTM method, a filament winding method, and a drawing molding method, or a method of preliminarily converting a resin composition into a reinforcing fiber.
• a method of molding the impregnated prepreg by an autoclave method or a press molding method.
• the reinforcing fiber used for the prepreg and the fiber-reinforced composite material of the present invention carbon fiber, graphite fiber, aramid fiber, glass fiber and the like can be preferably mentioned, but carbon fiber is particularly preferable.
• the form and arrangement of the reinforcing fibers are not limited, and for example, fibrous structures such as long fibers aligned in one direction, a single tow, a woven fabric, a knit, and a braid are used.
• the reinforcing fibers two or more types of carbon fibers, glass fibers, aramid fibers, boron fibers, PBO fibers, high-strength polyethylene fibers, alumina fibers, silicon carbide fibers and the like may be used in combination.
• carbon fibers include acrylic, pitch and rayon carbon fibers, and acrylic carbon fibers having particularly high tensile strength are preferably used.
• the form of the carbon fiber twisted yarn, untwisted yarn, untwisted yarn and the like can be used, but in the case of twisted yarn, the orientation of the filaments constituting the carbon fiber is not parallel, so that the obtained carbon fiber reinforced composite material can be used. Since it causes deterioration of the mechanical properties of the carbon fiber reinforced composite material, untwisted or untwisted yarn having a good balance between formability and strength characteristics of the carbon fiber reinforced composite material is preferably used.
• the carbon fiber preferably has a tensile elastic modulus of 200 GPa or more and 440 GPa or less.
• the tensile elastic modulus of the carbon fiber is affected by the crystallinity of the graphite structure constituting the carbon fiber, and the higher the crystallinity, the higher the elastic modulus. Within this range, the rigidity and strength of the carbon fiber reinforced composite material are all balanced at a high level, which is preferable.
• a more preferable elastic modulus is 230 GPa or more and 400 GPa or less, and more preferably 260 GPa or more and 370 GPa or less.
• the tensile elastic modulus of the carbon fiber is a value measured according to JIS R7608 (2008).
• the prepreg of the present invention can be produced by various known methods.
• a prepreg can be produced by a hot melt method in which the resin composition is reduced in viscosity by heating and impregnated into reinforcing fibers without using an organic solvent.
• a method of directly impregnating the reinforcing fibers with a resin composition whose viscosity has been reduced by heating or a method of first producing a release paper sheet with a resin film in which the resin composition is once coated on a release paper or the like. Then, a method can be used in which a resin film is laminated on the reinforcing fiber side from both sides or one side of the reinforcing fiber, and the reinforcing fiber is impregnated with the resin composition by heating and pressurizing.
• the content of the reinforcing fibers in the prepreg is preferably 30% by mass or more and 90% by mass or less.
• the content is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 65% by mass or more.
• the advantages of the fiber-reinforced composite material having excellent specific strength and specific elastic modulus can be easily obtained. Further, when molding the fiber-reinforced composite material, it is possible to prevent the amount of heat generated during curing from becoming too high.
• the content to 90% by mass or less, more preferably 85% by mass or less, it is possible to suppress the generation of voids in the composite material due to poor resin impregnation. Moreover, the tackiness of the prepreg can be maintained.
• the fiber-reinforced composite material of the present invention can be produced, for example, by laminating the above-mentioned prepreg of the present invention in a predetermined form and pressurizing and heating to cure the resin.
• a method of applying heat and pressure a press molding method, an autoclave molding method, a bagging molding method, a lapping tape method, an internal pressure molding method and the like are adopted.
• the fiber-reinforced composite material of the present invention can be widely used for aerospace applications, general industrial applications and sports applications. More specifically, in general industrial applications, it is suitably used for structures such as automobiles, ships, and railroad vehicles. In sports applications, it is suitably used for golf shafts, fishing rods, tennis and badminton rackets.
• the unit "part" of the composition ratio means a mass part unless otherwise specified.
• the various characteristics (physical properties) were measured in an environment with a temperature of 23 ° C. and a relative humidity of 50% unless otherwise specified.
• Component [C] A compound having a boiling point of 130 ° C. or higher and a molecular weight m of 50 to 250, which does not have an epoxy group in the molecule and has a substantially curable ability of an epoxy resin.
• 1,2-Hexanediol (boiling point: 245 ° C., molecular weight m: 118, ⁇ D: 16.7, ⁇ P: 7.1, ⁇ H: 17.5, manufactured by Tokyo Chemical Industry Co., Ltd.)
• N-Methylpropionamide (boiling point: 223 ° C., molecular weight m: 87, ⁇ D: 17.2, ⁇ P: 13.6, ⁇ H: 10.1, manufactured by
• the ratio H / E of the number of moles H of active hydrogen of the component [B] to the number of moles E of the epoxy group of the component [A] is 1.00, and the number of moles E of the epoxy group of the component [A] is 1.00.
• the ratio C / E of the number of moles C of the component [C] to C was 0.05, and the Hansen solubility parameter distance L between the component [A] and the component [C] was 15.1.
• Examples 2 to 8> The respective components [A], [B] and [C] were blended in the same procedure as in Example 1 above according to the blending ratios in Table 1 to obtain a resin composition.
• Example 8 a two-component epoxy resin was mixed and used as the component [A].
• the HSP ( ⁇ Dm, ⁇ Pm, ⁇ Hm) of these mixed epoxy resins was calculated as (19.0, 7.5, 6.4) according to the formula (2).
• Comparative Example 1 the component [C] was not mixed. Comparing Comparative Example 1 and Example 1, the elastic modulus, strength, and elongation of the cured resin product are improved by blending the component [C], and the strength and elongation are particularly dramatic. It can be seen that it has improved.
• Comparative Example 2 also does not contain the component [C]. Comparing Comparative Example 2 and Example 6, it can be seen that the elastic modulus and strength of the cured resin product are dramatically improved by blending the component [C].
• Comparative Example 3 also does not contain the component [C]. From the comparison between Comparative Example 3 and Example 8, it can be seen that the elastic modulus and strength of the cured resin product are dramatically improved by blending the component [C].
• Comparative Example 4 glycidol was blended as an additive of the component [A] instead of the component [C]. Glycidol has an epoxy group in the molecule. Comparing Comparative Example 4 and Example 1, it can be seen that the elastic modulus, strength, and elongation of the obtained cured resin product are improved because the component [C] does not have an epoxy group in the molecule.
• Comparative Example 5 ethanol was blended instead of the component [C]. Ethanol does not satisfy the condition that the boiling point of the component [C] is 130 ° C. or higher and that the molecular weight m is 50 or more and 250 or less. Comparing Comparative Example 5 and Example 1, the elasticity of the cured resin product obtained by blending the component [C] satisfying the conditions of a boiling point of 130 ° C. or higher and a molecular weight m of 50 or higher and 250 or lower. It can be seen that the rate, strength, and elongation improve.
• 1,4-diphenylbenzene was blended as a component [C]. 1,4-Diphenylbenzene does not satisfy the condition that the sum of the polar component and the hydrogen bond component in the Hansen solubility parameter is 10.0 or more. Comparing Comparative Example 7 and Example 1, when the sum of the polar component and the hydrogen bond component in the Hansen solubility parameter of the component [C] is 10.0 or more, the elastic modulus and strength of the obtained cured resin product, It can be seen that the elongation improves.
• Comparative Example 8 glycerol was blended as a component [C].
• the condition that the Hansen solubility parameter distance L between the component [A] and the component [C] is 20.0 or less is not satisfied. Comparing Comparative Example 8 and Example 1, when the Hansen solubility parameter distance L between the component [A] and the component [C] is 20.0 or less, the elastic modulus, strength, and elongation of the obtained cured resin product are obtained. You can see that the degree improves.
• Comparative Example 9 the condition that the number of moles E of the epoxy group of the component [A] and the number of moles C of the component [C] are 0.01 or more and 0.20 or less is not satisfied. Comparing Comparative Example 9 and Example 1, it can be seen that the elastic modulus, strength, and elongation of the obtained cured resin product are improved by satisfying the above conditions.
• Comparative Example 10 does not satisfy the condition that the viscosity of the epoxy resin composition when held at 70 ° C. for 2 hours is 5.0 times or less of the initial viscosity at 70 ° C. Therefore, the composition has a large increase in viscosity in the step of mixing the epoxy resin and has a short pot life. Comparing Comparative Example 10 and Example 1, it can be seen that the pot life of the obtained resin composition is long and the handleability is excellent by satisfying the above conditions.

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• 2020
  • 2020-11-05 US US17/773,694 patent/US12460044B2/en active Active
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  • 2020-11-11 TW TW109139279A patent/TWI871375B/zh active

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