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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
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  • 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
  • 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
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4014—Nitrogen containing compounds
  • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
• • 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
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4078—Curing agents not provided for by the groups C08G59/42 - C08G59/66 boron containing compounds
• • 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
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
  • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
  • C08G59/4253—Rubbers
• • 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
• • 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
  • C08G59/68—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 catalysts used
• • 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
  • C08G59/68—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 catalysts used
  • C08G59/72—Complexes of boron halides
• • 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
• • 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
  • C08J5/249—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
  • 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
  • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
  • C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/53—Core-shell polymer

Definitions

• the present invention relates to an epoxy resin composition preferably used as a matrix resin for a fiber-reinforced composite material suitable for sports applications and general industrial applications, an intermediate base material such as tow prepreg and prepreg using the same as a matrix resin, and fiber reinforced. It is about composite materials.
• the epoxy resin composition is widely used as a matrix resin for fiber-reinforced composite materials, taking advantage of its characteristics of high heat resistance, adhesiveness, and mechanical strength.
• an intermediate base material in which the reinforcing fibers are impregnated with a matrix resin in advance is often used for ease of transportation and shape imparting.
• Examples of the form of the intermediate base material include a prepreg in which reinforcing fibers are arranged in a sheet shape, and a narrow intermediate base material (hereinafter referred to as tow prepreg) such as tow prepreg and yarn prepreg in which the reinforcing fibers are impregnated with a matrix resin. Be done.
• Patent Document 1 describes a technique for improving the surface quality and fracture toughness of a tow prepreg made of the epoxy resin composition by using an epoxy resin composition containing a large amount of core-shell type rubber particles.
• Patent Document 2 describes a low-viscosity epoxy resin composition in which the breaking toughness value of a cured epoxy resin is increased by using fine particles containing a rubber component and insoluble in an epoxy resin in combination with a 1- to bifunctional epoxy resin. The thing is disclosed.
• Patent Document 3 describes an epoxy resin composition for tow prepreg in which a low-viscosity epoxy resin and a core-shell type rubber particle are used in combination to increase the fracture toughness value of a cured resin product.
• Patent Document 4 discloses a technique for improving the storage stability of a prepreg by using a particulate amine compound and a boric acid ester compound in combination.
• a method of lowering the crosslink density of the cured epoxy resin is known.
• a technique of adding insoluble particles to an epoxy resin is known.
• the mechanical strength and heat resistance of the fiber-reinforced composite material are insufficient because the elastic modulus and heat resistance of the cured epoxy resin product are significantly reduced.
• the method of adding a large amount of particles increases the viscosity of the epoxy resin composition, so that the amount of particles added is limited from the viewpoint of the manufacturing process. Therefore, it is desired to construct a technique that achieves both deformation ability and fracture toughness without impairing mechanical strength and heat resistance.
• the epoxy resin compositions described in Patent Documents 2 and 3 show a relatively high fracture toughness value, but probably because the epoxy resin composition uses a large amount of a 1-2 functional epoxy resin and the cross-linking is insufficient. The tensile elongation and heat resistance were low.
• Patent Document 4 discloses an epoxy resin composition having excellent storage stability and a relatively high fracture toughness value, but there is no suggestion or mention of the elongation of the cured resin product.
• the present invention is an epoxy resin composition capable of improving the drawbacks of the prior art, exhibiting deformability and breaking toughness at a high level, and obtaining a cured resin product maintaining heat resistance, and the epoxy resin composition.
• An object of the present invention is to provide an intermediate base material composed of a product and reinforcing fibers, and a fiber-reinforced composite material obtained by curing the intermediate base material.
• the epoxy resin composition of the present invention is an epoxy resin composition satisfying the following condition 1 or condition 2, and the tensile elongation at break of the cured resin obtained by reacting the epoxy resin composition at 150 ° C. for 60 minutes. Is 7% or more.
• Condition 1 A bifunctional aliphatic epoxy resin represented by the formula (I), which contains all of the following components [A], [B], and [C] [A]:
• R 1 represents a hydrogen atom or a methyl group, and n and m each independently represent an integer of 1 to 6.
• those satisfying the above condition 1 are those satisfying the aspect 1 of the epoxy resin composition of the present invention
• those satisfying the above condition 2 are the epoxy resin compositions of the present invention. It may be referred to as aspect 2.
• the intermediate base material of the present invention is obtained by impregnating reinforcing fibers with the epoxy resin composition of the present invention.
• the fiber-reinforced composite material of the present invention is obtained by curing the intermediate base material of the present invention.
• an epoxy resin composition capable of obtaining a cured resin product which exhibits deformability and fracture toughness at a high level and maintains heat resistance.
• the epoxy resin composition of the present invention has a tensile elongation at break of 7% or more of a cured resin product obtained by reacting the epoxy resin composition at 150 ° C. for 60 minutes.
• the tensile elongation at break of the cured resin is lower than 7%, the mechanical properties of the fiber-reinforced composite material using the epoxy resin composition as the matrix resin, particularly the deformation ability, are reduced, so that the breaking strength and the long-term Durability (fatigue characteristics) becomes insufficient.
• the upper limit of the tensile elongation at break is not particularly limited, but is about 20%.
• aspects 1 and 2 of the epoxy resin composition of the present invention may be simply referred to as aspects 1 and 2 of the present invention.
• the term "the present invention” is simply used without specifying the aspect, it means all the aspects of the first aspect and the second aspect.
• Aspect 1 of the present invention satisfies condition 1. That is, it contains a bifunctional aliphatic epoxy resin represented by the component [A] formula (I), a component [B] terminal carboxy-modified acrylic rubber, and a component [C] dicyandiamide as essential components. First, these components will be described.
• the component [A] in the present invention is a bifunctional aliphatic epoxy resin represented by the following formula (I).
• R 1 represents a hydrogen atom or a methyl group. Further, n and m each independently represent an integer of 1 to 6.
• component [A] examples include aliphatic epoxy resins such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, trimethylene glycol diglycidyl ether, and hexamethylene glycol diglycidyl ether.
• ethylene glycol diglycidyl ether "Denacol” (registered trademark) EX-850, EX-851, EX-821 (all manufactured by Nagase ChemteX Corporation) and the like can be used.
• propylene glycol diglycidyl ether examples include “Denacol” (registered trademark) EX-911, EX-941, EX-920 (all manufactured by Nagase ChemteX Corporation), and "ADEKA Glycyrrol” (registered trademark) ED-506. (Manufactured by ADEKA Corporation) or the like can be used.
• hexamethylene glycol diglycidyl ether "Denacol” (registered trademark) EX-212 or the like can be used.
• Aspect 1 of the present invention preferably contains 3 to 20 parts by mass of the component [A], and more preferably 6 to 10 parts by mass, out of 100 parts by mass of the total epoxy resin.
• the component [B] contained in the first aspect of the present invention is a terminal carboxy-modified acrylic rubber.
• the fracture toughness can be increased without lowering the tensile elongation at break of the cured resin product.
• Aspect 1 of the present invention needs to include the component [A] and the component [B] at the same time. It is not possible to achieve both tensile elongation at break and resin toughness value at a high level with only component [A] or component [B], but by including both at the same time, tensile elongation at break and resin toughness value can be achieved at a high level. It can be compatible. The reason is not clear, but it can be inferred that, for example, since the component [B] has a reactive carboxy group at the terminal, it forms a flexible crosslinked structure after the curing reaction.
• the tensile elongation at break, the tensile elastic modulus, and the tensile strength of the cured product obtained by curing the epoxy resin composition of the present invention are such that a resin cured plate processed into a dumbbell shape is tensioned according to JIS K7161 (1994). Evaluate by conducting a test.
• the resin toughness value of the cured epoxy resin product of the present invention is evaluated from the K1c value obtained from the SENB test described in ASTM D5045-99.
• the heat resistance of the cured epoxy resin product of the present invention is evaluated from the glass transition temperature calculated from the heat flow obtained by performing the temperature rise measurement of DSC measurement (differential scanning calorimetry).
• the glass transition temperature is measured by the method described in JIS K7121 (1987).
• the component [C] of the present invention is dicyandiamide.
• Dicyandiamide is excellent in that it can impart high mechanical properties and heat resistance to an epoxy resin cured product obtained as a curing agent, and is widely used as a curing agent for epoxy resins. Examples of commercially available products of such dicyandiamide include DICY7T and DICY15 (all manufactured by Mitsubishi Chemical Corporation).
• Aspect 1 of the present invention preferably contains a component [H]: a curing accelerator.
• the component [C] is used in combination with a curing accelerator (component [H]) such as an aromatic urea compound to lower the curing temperature of the epoxy resin composition as compared with the case where the component [C] is blended alone.
• a curing accelerator such as an aromatic urea compound
• Examples of such component [H] include 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU), 3- (4-chlorophenyl) -1,1-dimethylurea, and phenyldimethylurea (PDMU). ), 2,4-Toluene bis (3,3-dimethylurea) (TBDMU) and the like.
• aromatic urea compounds include DCMU99 (manufactured by Hodogaya Chemical Industry Co., Ltd.), "Omicure” (registered trademark) 24 (manufactured by PTI Japan Co., Ltd.), and “Dyhard” (registered).
• Trademarks UR505 (4,4'-methylenebis (phenyldimethylurea), manufactured by AlzChem) and the like can be mentioned.
• the first aspect of the present invention it is preferable to use TBDMU as the component [H].
• TBDMU the component [C] and TBDMU in combination, heat resistance and tensile elongation at break can be further enhanced at the same time.
• the first aspect of the present invention preferably contains 1.2 to 4.0 parts by mass of TBDMU, and more preferably 2.5 to 3.5 parts by mass, based on 100 parts by mass of the total epoxy resin.
• the gelation start time of the epoxy resin composition of the present invention is evaluated according to ASTM E2039, using the time until the degree of curing of the epoxy resin composition obtained from the dielectric measurement reaches 20% as an index. Can be done.
• Component [D] Aspect 1 of the present invention preferably contains 4 to 18 parts by mass of core-shell type rubber particles as the component [D] with respect to 100 parts by mass of the total epoxy resin.
• the mass ratio of the content of the component [B] to the content of the component [D] is within the range of 0.1 to 0.8.
• the core-shell type rubber particles are particles in which the shell component is modified on the surface of the particulate core component, and a part or the whole of the surface of the core component is coated with the shell component.
• the components of the core and shell components are not particularly limited, and may have core and shell components.
• An epoxy resin composition satisfying the above range has remarkably improved fracture toughness and tensile elongation at break of the cured epoxy resin, so that the fracture strength and fatigue characteristics of the fiber-reinforced composite material are particularly excellent.
• the effect further exceeds the level that can be expressed by the combination of the components [A] and [B], and the specific effect of improving fracture elongation and fracture toughness found in the presence of the component [D]. Is.
• Examples of such component [D] include “Kaneka” (registered trademark) MX-125, MX-150, MX-154, MX-257, MX-267, MX-416, MX-451, MX-EXP (HM5) ( As described above, Kaneka Corporation), “PARALOID” (registered trademark) EXL-2655, EXL-2668 (all manufactured by Dow Chemical Co., Ltd.) and the like can be used.
• Component [G] Aspect 1 of the present invention preferably contains 5 to 30 parts by mass of the component [G]: dicyclopentadiene type epoxy resin out of 100 parts by mass of the total epoxy resin.
• the heat resistance of the cured resin can be improved without increasing the viscosity of the epoxy resin composition, and therefore, it is suitably used as an epoxy resin composition for tow prepreg. be able to.
• Examples of such component [G] include HP7200L, HP7200, HP7200H, HP7200HH, HP7200HHH (all manufactured by DIC Corporation) and the like.
• Aspect 2 of the present invention comprises an epoxy resin and satisfies condition 2. That is, component [D]: core-shell type rubber particles, component [E]: boric acid ester compound, and component [F]: curing agent are contained as essential components.
• Aspect 2 of the present invention contains 9 to 18 parts by mass of the component [D] with respect to 100 parts by mass of the total epoxy resin (condition [a]).
• condition [a] contains 9 to 18 parts by mass of the component [D] with respect to 100 parts by mass of the total epoxy resin.
• the fracture toughness value of the cured resin product is insufficient, so that the durability of the fiber-reinforced composite material becomes insufficient.
• the elastic modulus is significantly reduced, so that the mechanical strength of the fiber-reinforced composite material is insufficient.
• the viscosity of the epoxy resin composition is increased, it becomes difficult to use it in a tow prepreg, which requires a low viscosity epoxy resin composition from the viewpoint of a manufacturing process.
• the core-shell type rubber particles listed in the above description of the first aspect can be used.
• the component [E] in aspect 2 of the present invention is a boric acid ester compound.
• component [E] include alkyl borates such as trimethylborate, triethylborate, tributylborate, tri-n-octylborate, tri (triethylene glycol methyl ether) borate, tricyclohexylborate, and trimentylborate.
• alkyl borates such as trimethylborate, triethylborate, tributylborate, tri-n-octylborate, tri (triethylene glycol methyl ether) borate, tricyclohexylborate, and trimentylborate.
• Aromatic borates such as trio-cresylborate, trim-cresylborate, trip-cresylborate, triphenylborate, tri (1,3-butanediol) viborate, tri (2-methyl- 2,4-Pentanediol) Vivorate, trioctylene glycol diborate and the like.
• a cyclic boric acid ester having a cyclic structure in the molecule can also be used.
• the cyclic borate include tris-o-phenylene bisbolate, bis-o-phenylene pyrobolate, bis-2,3-dimethylethylenephenylene pyrobolate, bis-2,2-dimethyltrimethylene pyroborate and the like. ..
• Examples of products containing such boric acid ester include “Cureduct” (registered trademark) L-01B (Shikoku Kasei Kogyo Co., Ltd.) and “Cureduct” (registered trademark) L-07N (Shikoku Kasei Kogyo Co., Ltd.). ) (Composition containing 5% by mass of boric acid ester compound), “Cureduct” (registered trademark) L-07E (Shikoku Kasei Kogyo Co., Ltd.) (Composition containing 5% by mass of boric acid ester compound), etc. Be done.
• Aspect 2 of the present invention satisfies the following condition [b].
• the content of the component [D] / the content of the component [E] is a mass ratio.
• the fracture toughness of the cured epoxy resin product composed of the epoxy resin composition is remarkably high, and the deformability is high.
• the effect is not a level that can be expressed by the component [D] alone, but is a specific effect of improving fracture toughness that is expressed by containing [D] and [E] in a specific compounding ratio.
• the bonding mode of the crosslinked structure and the component [D] formed by curing the epoxy resin composition by containing a specific amount of boric acid ester is in an optimum state for improving fracture toughness. I'm guessing that it will be.
• the component [F] of the second aspect of the present invention is a curing agent.
• the curing agent is a component that reacts with the epoxy resin at a predetermined temperature to form a crosslinked structure, and is not particularly limited.
• component [F] examples include amine compounds such as diaminodiphenylmethane, diaminodiphenylsulfone, diethyltoluenediamine, aliphatic amines, imidazole compounds, and dicyandiamide, hydrogenated methylnadic acid anhydride, and methylhexahydrophthalic acid anhydride. And so on.
• amine compounds such as diaminodiphenylmethane, diaminodiphenylsulfone, diethyltoluenediamine, aliphatic amines, imidazole compounds, and dicyandiamide, hydrogenated methylnadic acid anhydride, and methylhexahydrophthalic acid anhydride. And so on.
• an imidazole compound as the component [F], and the heat resistance of the epoxy resin composition can be enhanced.
• an imidazole compound As a commercially available product of such an imidazole compound, "Cure Duct” (registered trademark) P-0505 (manufactured by Shikoku Chemicals Corporation) can be used.
• dicyandiamide (component [C]), which is particularly preferably used as the component [F], is excellent in giving high mechanical properties and heat resistance to the cured resin product.
• Aspect 2 of the present invention preferably contains a component [C] and a component [H]: a curing accelerator, similarly to the first aspect.
• a component [H] a curing accelerator
• the curing accelerators listed in the above-mentioned description of the first aspect can be used.
• TBDMU is preferably used in order to further enhance the heat resistance and the tensile elongation at break of the epoxy resin cured product.
• the storage stability of the intermediate base material is specifically improved.
• the mechanism for improving the stability is not clear, since the component [E] has Lewis acidity, the imidazole compound or the amine compound liberated from the component [H] interacts with the component [E] at room temperature. It is speculated that this is to reduce the reactivity of.
• the storage stability of the intermediate base material can be evaluated using the change in the glass transition temperature as an index after the epoxy resin composition is stored under certain conditions.
• the storage stability of the epoxy resin composition according to the second aspect of the present invention is that when the change in the glass transition temperature after storage at 40 ° C. and 75% RH for 14 days is 20 ° C. or less, the epoxy resin composition is intermediate. It is preferable because the base material exhibits excellent storage stability even at room temperature.
• the storage stability of the epoxy resin composition according to the second aspect of the present invention can be evaluated by tracking the change in the glass transition temperature by differential scanning calorimetry (DSC).
• DSC differential scanning calorimetry
• the epoxy resin composition can be stored in a constant temperature and humidity chamber for a predetermined period of time, and the change in the glass transition temperature before and after storage can be measured and determined from the temperature rise measurement of DSC.
• Aspect 2 of the present invention preferably contains 3 to 20 parts by mass of the component [A], and more preferably 6 to 10 parts by mass, out of 100 parts by mass of the total epoxy resin.
• the viscosity of the epoxy resin composition can be effectively lowered without impairing the heat resistance of the cured epoxy resin, so that a low viscosity epoxy resin composition is required in the manufacturing process. It is particularly preferably used when applied to toe prepregs.
• the second aspect of the present invention preferably contains 5 to 30 parts by mass of the component [G]: dicyclopentadiene type epoxy resin out of 100 parts by mass of the total epoxy resin.
• the component [G] in the above range, the heat resistance of the cured resin can be improved without increasing the viscosity of the epoxy resin composition, so that it can be suitably used as an epoxy resin composition for tow prepreg. ..
• an epoxy resin different from the components [A] and [G] may be used as the component [I].
• Examples of commercially available products of the aniline type epoxy resin include GAN (N, N-diglycidyl aniline) and GOT (N, N-diglycidyl-o-toluidine) (all manufactured by Nippon Kayaku Co., Ltd.).
• Examples of commercially available products of the diaminodiphenyl sulfone type epoxy include TG3DAS (manufactured by Konishi Chemical Industry Co., Ltd.).
• Examples of commercially available products of the bisphenol A type epoxy resin include "jER” (registered trademark) 828, 1001, 1007 (all manufactured by Mitsubishi Chemical Corporation).
• phenol novolac type epoxy resins examples include "jER” (registered trademark) 152, 154, 180S (all manufactured by Mitsubishi Chemical Corporation).
• Examples of commercially available products of the xylene diamine type epoxy resin include TETRAD-X (manufactured by Mitsubishi Gas Chemical Company, Inc.).
• an antifoaming agent may be added to the epoxy resin composition of the present invention as long as the effects of the present invention are not lost.
• defoaming agents include non-silicon polymer-based defoaming agents and silicone-based defoaming agents.
• non-silicon polymer antifoaming agent "BYK” (registered trademark) 1788, 1790, 1791, A535 (all manufactured by Big Chemie Japan Co., Ltd.) and the like can be used.
• silicon-based defoaming agent "BYK” (registered trademark) 1798, 1799 (all manufactured by Big Chemie Japan Co., Ltd.), DOWNSIL SH200 (manufactured by Dow Toray Co., Ltd.) and the like can be used.
• the epoxy resin composition of the present invention may be kneaded using a machine such as a kneader, a planetary mixer, a three-roll and a twin-screw extruder, or if uniform kneading is possible, a beaker is used. You may mix it by hand using a spatula or the like.
• a machine such as a kneader, a planetary mixer, a three-roll and a twin-screw extruder, or if uniform kneading is possible, a beaker is used. You may mix it by hand using a spatula or the like.
• the epoxy resin composition of the present invention can be used as an intermediate base material that is compositely integrated with reinforcing fibers.
• Examples of the form of the intermediate base material include prepreg, slit tape, and toe prepreg. These intermediate base materials are made by impregnating reinforcing fibers with an epoxy resin composition.
• a prepreg made by arranging reinforcing fibers in a sheet shape and impregnating with a matrix resin, a slit tape made by cutting the prepreg into a narrow width, and a reinforcing fiber made of 1,000 to 70,000 filaments impregnated with a matrix resin.
• Examples include toe prepreg.
• the manufacturing method and the viscosity suitable for the matrix resin differ depending on the form.
• the prepreg can be obtained by impregnating a reinforcing fiber base material with the epoxy resin composition of the present invention.
• the impregnation method include a hot melt method (dry method).
• the hot melt method is a method in which the reinforcing fibers are directly impregnated with the epoxy resin composition whose viscosity has been reduced by heating, or a film in which the epoxy resin composition is coated on a release paper or the like is prepared, and then both sides of the reinforcing fibers are prepared.
• the film is laminated from one side and the reinforcing fibers are impregnated with the resin by heating and pressurizing, it is necessary to appropriately increase the viscosity of the epoxy resin composition so as to be suitable for the pressurizing step.
• the epoxy resin composition of the present invention may further contain a thermoplastic resin as long as the effects of the present invention are not lost. By containing the thermoplastic resin, it becomes easy to prepare the viscosity suitable for the embodiment as a prepreg.
• the epoxy resin composition preferably has a viscosity at 25 ° C. in the range of 8,000 to 30,000 Pa ⁇ s from the viewpoint of good handleability at room temperature, that is, at 25 ° C.
• thermoplastic resins include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol, phenoxy resin, polyvinylpyrrolidone, polysulfone, polyethersulfone, and triblock copolymers.
• Aspect 2 of the present invention preferably contains 2 to 10 parts by mass of the triblock copolymer with respect to 100 parts by mass of the total epoxy resin composition, and particularly preferably contains 4 to 8 parts by mass.
• the triblock copolymer in such a range, it is possible to prepare an epoxy resin composition having a viscosity suitable for producing a prepreg while increasing the fracture toughness of the cured epoxy resin composition composed of the epoxy resin composition.
• Nanostrength (registered trademark) M22N, M52N, M65N (all manufactured by Arkema Co., Ltd.) and the like can be used.
• the epoxy resin composition containing the triblock copolymer may contain 40 to 70 parts by mass of the component [G]: dicyclopentadiene type epoxy resin out of 100 parts by mass of the total epoxy resin. It is preferable, and particularly preferably contains 45 to 65 parts by mass.
• the epoxy resin composition can effectively increase the viscosity at 25 ° C. while increasing the heat resistance. Therefore, the prepreg obtained by impregnating the reinforcing fibers with the epoxy resin composition is excellent in handleability at room temperature.
• the above-mentioned tow prepreg can be produced by various known methods. For example, while immersing the epoxy resin composition of the present invention in reinforcing fibers at a temperature of about 40 ° C. from room temperature without using an organic solvent. A method of impregnation, a method of coating the epoxy resin composition on a rotating roll or a release paper, then transferring the reinforcing fiber to one side or both sides, and then applying pressure to impregnate the fiber by passing it through a bending roll or a pressure roll. Can be manufactured with.
• the intermediate base material of the present invention is obtained by impregnating reinforcing fibers with the epoxy resin composition of the present invention.
• the form of the intermediate base material can take the above-mentioned various forms and is not particularly limited.
• the viscosity of the epoxy resin composition impregnated in the reinforcing fibers at 25 ° C. is preferably 0.5 to 100 Pa ⁇ s.
• the epoxy resin composition tends to be highly impregnated into the reinforcing fibers.
• the viscosity of the epoxy resin composition at 25 ° C. is particularly preferably 3 to 30 Pa ⁇ s.
• the impregnation property of the reinforcing fibers is further improved, so that it is not necessary to install a special heating mechanism in the resin bath or dilute with an organic solvent.
• the viscosity of the epoxy resin composition of the present invention can be measured by, for example, a cone-plate type rotational viscometer (E-type viscometer).
• E-type viscometer cone-plate type rotational viscometer
• the epoxy resin composition is placed on an E-type viscometer set at 25 ° C., and can be evaluated as an average value of viscosities observed at a certain rotation speed.
• the reinforcing fiber used in the present invention is not particularly limited, and glass fiber, carbon fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like can be used. Two or more of these fibers may be mixed and used. It is preferable to use carbon fiber from the viewpoint of obtaining a lightweight and highly rigid fiber-reinforced composite material.
• the fiber-reinforced composite material of the present invention is obtained by curing the intermediate base material of the present invention.
• the fiber-reinforced composite material of the present invention can be obtained, for example, by heat-curing an intermediate base material or tow prepreg in which the epoxy resin composition prepared by the above method and the reinforcing fibers are compositely integrated.
• the fiber-reinforced composite material of the present invention can also be obtained by wrapping a tow prepreg around a mandrel, a liner, or the like and heat-curing it.
• a fiber-reinforced composite material using a liner it is composed of a liner, a cured epoxy resin coating the liner, and reinforcing fibers.
• the epoxy resin composition of the present invention is suitably used for general industrial applications such as pressure vessels where long-term durability is required by taking advantage of its excellent deformability and fracture toughness.
• the fiber-reinforced composite material of the present invention can be obtained by appropriately using a method of laminating and molding a prepreg and applying heat and pressure, for example, an autoclave molding method, a press molding method, a bagging molding method, a wrapping molding method and the like. You can also.
• the obtained fiber-reinforced composite material can be preferably used for structural materials such as automobiles, bicycles, ships and railroad vehicles by taking advantage of its excellent deformability and fracture toughness.
• ⁇ Preparation method of epoxy resin composition A predetermined amount of components other than the component [D] core-shell type rubber particles, the component [E] borate ester compound, the component [H] curing accelerator, the component [C] dicyandiamide, and the component [F] curing agent are added to the stainless beaker. The mixture was added, the temperature was raised to 60 to 150 ° C., and the mixture was appropriately kneaded until each component was compatible.
• ⁇ Epoxy resin cured product tensile properties evaluation method> After defoaming the uncured epoxy resin composition obtained according to the above ⁇ Method for preparing epoxy resin composition> in a vacuum, the thickness is set to 2 mm with a 2 mm thick "Teflon" (registered trademark) spacer. In the molded mold, the resin was cured at a temperature of 150 ° C. for 1 hour to obtain a resin cured plate having a thickness of 2 mm. The obtained cured resin plate was processed into a 1BA type dumbbell shape according to JIS K7161 (1994).
• ⁇ Epoxy resin composition gelation start time evaluation method> The uncured epoxy resin composition obtained according to the above ⁇ Method for preparing an epoxy resin composition> was allowed to stand in 2 mL on a micropress preheated to 150 ° C., and was subjected to a cure monitor LT-451 (manufactured by Lambient Technologies). The ionic viscosity was measured. The ionic viscosity of the epoxy resin composition reaches a minimum value at the start of curing, increases with the progress of the curing reaction, and then saturates with completion.
• the cure index (Cd) is calculated from the measured value of the ionic viscosity under the conditions of 150 ° C. and 1 hour according to the ASTM E2039 standard, and the time until the Cd reaches 20% is adopted as the gelation start time. did.
• ⁇ Epoxy resin composition storage stability evaluation method> After weighing 3 g of the epoxy resin composition obtained according to the above ⁇ Epoxy resin composition preparation method> in an aluminum cup and allowing it to stand in a constant temperature and humidity chamber for 14 days in an environment of 40 ° C. and 75% RH.
• the glass transition temperature was Ta and the initial glass transition temperature Tb
• the storage stability was determined by the value of ⁇ Tg.
• For the glass transition temperature weigh 3 mg of the epoxy resin after storage into a sample pan and use a differential scanning calorimeter (Q-2000: manufactured by TA Instruments) at 5 ° C / min from -20 ° C to 150 ° C. The temperature was raised and measured. The midpoint of the inflection point of the obtained heat generation curve was acquired as the glass transition temperature.
• Example 1 As an epoxy resin, "Denacol” (registered trademark) EX-911 is 2 parts by mass, “jER” (registered trademark) 828 is 90 parts by mass, “jER” (registered trademark) 1001 is 8 parts by mass, and the terminal carboxy-modified acrylic rubber is used. Using 15 parts by mass of "Hypro” (registered trademark) 1300X8, 7.3 parts by mass of DICY7T as dicyandiamide, and 2.5 parts by mass of DCMU99 as an aromatic urea compound, an epoxy resin was used according to the above ⁇ Method for preparing epoxy resin composition>. The composition was prepared.
• the viscosity of the epoxy resin composition was measured according to the above ⁇ Viscosity measurement of the epoxy resin composition at 25 ° C.> and found to be 28 Pa ⁇ s, which was an appropriate viscosity when producing the tow prepreg.
• the time for the cure index (Cd) of the epoxy resin composition to reach 20% was measured according to the above ⁇ method for evaluating the gelation start time of the epoxy resin composition> and found to be 4.1 minutes.
• Examples 2 to 19 An epoxy resin composition and a cured resin were prepared in the same manner as in Example 1 except that the resin compositions were changed as shown in Tables 1 to 3, respectively.
• Example 20 to 28, 31, 32 An epoxy resin composition and a cured resin were prepared in the same manner as in Example 1 except that the resin compositions were changed as shown in Tables 3 and 4, respectively.
• Examples 29, 30, 33 to 37 The epoxy resin composition and the cured resin were prepared in the same manner as in Example 1 except that the resin compositions were changed as shown in Tables 4 and 5, respectively, and a thermoplastic resin was added.
• the glass transition temperature of this epoxy resin composition was measured according to the above ⁇ Measurement of glass transition temperature> and found to be 138 ° C. Further, when the viscosity was measured according to the above ⁇ Viscosity measurement of the epoxy resin composition at 25 ° C.>, it was 29 Pa ⁇ s. When the time for Cd to reach 20% was measured according to the above ⁇ Method for evaluating the gelation start time of the epoxy resin composition>, it was 6.7 minutes, which was insufficient. Moreover, when the storage stability was evaluated according to the above ⁇ Method for evaluating the storage stability of the epoxy resin composition>, ⁇ Tg was insufficient at 32 ° C.
• the fracture toughness value of this epoxy resin composition was evaluated according to the above ⁇ Method for evaluating the fracture toughness value of the cured epoxy resin product>, the fracture toughness value was 1. because the components [A] and [B] were not contained. It was as low as 7 MPa ⁇ m 0.5 .
• Comparative Example 2 Regarding the resin composition shown in Table 6, an epoxy resin composition was prepared by the method described in Example 5 of Patent Document 2 (Japanese Unexamined Patent Publication No. 9-227693), and at 25 ° C. by the same method as in Comparative Example 1. The viscosity, the time it takes for Cd to reach 20% at 150 ° C., tensile properties, fracture toughness, and heat resistance were evaluated.
• the epoxy resin composition does not contain the component [A], the component [B], and the component [D], the tensile elongation at break and the fracture toughness value are insufficient.
• the viscosity at 25 ° C. was 72 Pa ⁇ s.
• the time required for Cd to reach 20% was 4.8 minutes. Further, ⁇ Tg was insufficient at 27 ° C.
• Comparative Example 3 With respect to the resin composition shown in Table 6, an epoxy resin composition was prepared by the method described in Example 1 of Patent Document 3 (Japanese Unexamined Patent Publication No. 2011-157491), and at 25 ° C. by the same method as in Comparative Example 1. The viscosity, the time it takes for Cd to reach 20% at 150 ° C., tensile properties, fracture toughness, and heat resistance were evaluated.
• the cured resin product made of the epoxy resin composition had insufficient tensile properties, fracture toughness, and heat resistance.
• Comparative Example 4 For the resin compositions shown in Table 6, an epoxy resin composition was prepared in the same manner as in Example 1 until the viscosity at 25 ° C. and Cd reached 20% at 150 ° C. in the same manner as in Comparative Example 1. Time, tensile properties, fracture toughness, and heat resistance were evaluated.
• Comparative Example 6 For the resin compositions shown in Table 6, an epoxy resin composition was prepared in the same manner as in Example 1 until the viscosity at 25 ° C. and Cd reached 20% at 150 ° C. in the same manner as in Comparative Example 1. Time, tensile properties, fracture toughness, and heat resistance were evaluated.
• Comparative Example 7 For the resin compositions shown in Table 6, an epoxy resin composition was prepared in the same manner as in Example 1 until the viscosity at 25 ° C. and Cd reached 20% at 150 ° C. in the same manner as in Comparative Example 1. Time, tensile properties, fracture toughness, and heat resistance were evaluated.
• the epoxy resin composition had a significantly low tensile elongation at break.
• the viscosity at 25 ° C. was 103 Pa ⁇ s, which was an inappropriate viscosity for producing a tow prepreg.
• Comparative Example 8 For the resin compositions shown in Table 6, an epoxy resin composition was prepared in the same manner as in Example 1 until the viscosity at 25 ° C. and Cd reached 20% at 150 ° C. in the same manner as in Comparative Example 1. Time, tensile properties, fracture toughness, and heat resistance were evaluated.
• component [A] but does not contain [B]. Further, instead of containing the component [D], YP-50 and "Sumika Excel" PES5003P are contained as thermoplastic resins, but the fracture toughness and tensile elongation at break of the cured product made of the epoxy resin composition are remarkably low. It was a thing.
• Comparative Example 9 Regarding the resin composition shown in Table 7, an epoxy resin composition was prepared by the method described in Example 4 of Patent Document 2 (Japanese Unexamined Patent Publication No. 9-157498), and at 25 ° C. by the same method as in Comparative Example 1. Viscosity, storage stability, tensile properties, fracture toughness, and heat resistance were evaluated.
• the epoxy resin composition had an insufficient fracture toughness value, probably because it contained only 7 parts by mass of the component [D] with respect to 100 parts by mass of the total epoxy resin. In addition, the tensile elongation at break was 4.0%, which was extremely low.
• ⁇ Tg was 5 ° C. and the storage stability was good, but the viscosity at 25 ° C. was 800 Pa ⁇ s, which was an inappropriate viscosity in the production of tow prepreg and prepreg.
• Comparative Example 10 For the resin compositions shown in Table 7, an epoxy resin composition was prepared in the same manner as in Example 1, and the viscosity, storage stability, tensile properties, fracture toughness, and fracture toughness at 25 ° C. were prepared in the same manner as in Comparative Example 1. The heat resistance was evaluated.
• the component [E] contains 10 parts by mass of the component [D], but the component [E] is as small as 0.01 parts by mass (0.2 parts by mass for L-07E).
• the mass ratio of the content of the component [E] to the content of the component [D] was 0.001, and the fracture toughness was 1.6 MPa ⁇ m 0.5, which was insufficient.
• ⁇ Tg was 32 ° C., which was insufficiently stable.
• the viscosity at 25 ° C. was 22 Pa ⁇ s.
• Comparative Example 11 For the resin compositions shown in Table 7, an epoxy resin composition was prepared in the same manner as in Example 1, and the viscosity, storage stability, tensile properties, fracture toughness, and fracture toughness at 25 ° C. were prepared in the same manner as in Comparative Example 1. The heat resistance was evaluated.
• the unit of each component in the table is the mass part.
• the fiber-reinforced composite material composed of the epoxy resin composition is excellent in fracture strength and fracture characteristics.
• the epoxy resin composition of the present invention can adjust the viscosity at room temperature to a range suitable for producing a tow prepreg or a state suitable for handling the prepreg, and thus is an intermediate for producing a fiber-reinforced composite material. It is preferably used as a base material.

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