Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
  • B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
  • B32B3/12—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a layer of regularly- arranged cells, e.g. a honeycomb structure
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
  • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
• • 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
• • 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
• • 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
  • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/16—Solid spheres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
  • B32B2260/02—Composition of the impregnated, bonded or embedded layer
  • B32B2260/021—Fibrous or filamentary layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
  • B32B2260/04—Impregnation, embedding, or binder material
  • B32B2260/046—Synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
  • B32B2262/10—Inorganic fibres
  • B32B2262/106—Carbon fibres, e.g. graphite fibres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2605/00—Vehicles
  • B32B2605/08—Cars
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24149—Honeycomb-like
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24149—Honeycomb-like
  • Y10T428/24157—Filled honeycomb cells [e.g., solid substance in cavities, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249994—Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
  • Y10T428/292—In coating or impregnation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2964—Artificial fiber or filament
  • Y10T428/2967—Synthetic resin or polymer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2971—Impregnation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer

Definitions

• the present invention relates to an epoxy resin composition for fiber-reinforced composite materials, and more particularly to an epoxy resin composition used for a self-adhesive prepreader for a honeycomb panel face plate.
• Fiber-reinforced composite materials that use an epoxy resin composition as a matrix resin are widely used in aircraft, automobiles, and industrial applications due to their excellent mechanical properties. Particularly in aircraft structural materials and interior materials, there are an increasing number of cases where fiber reinforced composite materials are used as face plates for her cam panels from the viewpoint of light weight.
• a hard cam panel is configured by laminating a pre-preda (uncured fiber reinforced composite resin material) to be a face plate on both sides of a her-cam core with a film adhesive interposed therebetween. It is manufactured by so-called co-curing, which simultaneously cures fat and bonds the face plate and the hard cam core.
• pre-preda uncured fiber reinforced composite resin material
• co-curing which simultaneously cures fat and bonds the face plate and the hard cam core.
• the joint surface between the hard core and the pre-predder is wetted with the pre-predder grease during the heat curing to form a fillet, so-called fillet is formed. It is important to improve shape and strength.
• the fillet is formed in the thickness direction of the hard cam core from the pre-predder in a state where the fat is dripped or raised along the hard cam wall, and its shape is deeply related to the viscosity of the fat.
• the strength of the fillet depends on the toughness of the matrix resin constituting the pre-preda.
• Patent Document 1 describes a thermosetting resin composition comprising a thermosetting resin and a thermoplastic resin so that the cured form becomes a co-continuous phase. It discloses improving the toughness of greaves. However, this thermosetting resin composition improves the toughness of the thermosetting resin to some extent, but is formed when directly bonding the hard cam and the pre-preda. It was not always sufficient to improve the toughness to improve the strength of the fillet formed.
• Patent Document 1 Japanese Patent Laid-Open No. 2-305860
• An object of the present invention is to provide an epoxy resin composition for a fiber-reinforced composite material in which the toughness required for improving the self-adhesion strength of a matrix resin used in a pre-preda for a honeycomb panel face plate is improved. There is to do.
• the epoxy resin composition for fiber-reinforced composite material according to the present invention that achieves the above object comprises epoxy resin (A), thermoplastic resin (B), solid resin fine particles (C), and a curing agent.
• the solid resin fine particles (C) are dispersed in at least the continuous phase of the epoxy resin (A) in the co-continuous phase.
• the epoxy resin composition for fiber-reinforced composite material of the present invention has a co-continuous phase having a three-dimensional network structure in which the epoxy resin (A) and the thermoplastic resin (B) are mixed finely.
• the solid and fine resin particles (C) dissolved and refined are finely dispersed in at least the continuous phase of the epoxy resin (A). It is possible to improve the toughness. Therefore, the self-adhesive strength of the pre-preda can be further improved by using this epoxy resin composition for matrix resin.
• the epoxy resin (A) is not particularly limited, but is not limited to bisphenol A type epoxy resin, bisphenol F type epoxy resin, Naphthalene type epoxy resin, diphenol fluorene type epoxy resin, triglycidyl aminophenol resin, triglycidylaminocresol resin, tetraglycidyl diaminodiphenol -Lumethane resin, Tetraglycidinole m-xylyleneamine, N, N-Diaminocresol resin, phenol novolac epoxy resin, Cresol novolac epoxy resin, biphenyl epoxy resin Preferred examples include dicyclopentagen type epoxy resins and various modified epoxy resins thereof, crystalline epoxy resins, monomolecular crystalline epoxy resins, and the like.
• liquid epoxy resin can be used in order to increase the compatibility with the thermoplastic resin (B) and to ensure that the thermoplastic resin (B) is dissolved during heating and mixing. It is preferable to select an epoxy resin having a low molecular weight from among the above-mentioned preferable ones.
• epoxy resin (A) is used alone or in combination of two or more so that the cured form will exhibit the above morphology according to the required properties of the pre-preda. I prefer that.
• the properties of the epoxy resin (A) are preferably liquid at room temperature, and the viscosity at a temperature of 25 ° C is preferably 1 to: LOO boise, more preferably 5 to 50 boise.
• the viscosity of the epoxy resin composition can be easily adjusted to an appropriate range when the thermoplastic resin (B) is blended, and a co-continuous phase is obtained after curing. Can be formed.
• the viscosity at a temperature of 25 ° C is a value measured using a BH type rotational viscometer. Specifically, a can containing epoxy resin is placed in a thermostatic bath at a temperature of 25 ° C and a BH rotational viscometer. This value is measured with a stable scale.
• a semi-solid or solid epoxy resin may be blended with the epoxy resin (A) as long as the effects of the present invention are not impaired.
• semi-solid or solid epoxy resin may be blended at a ratio of 20 parts by weight or less with respect to 100 parts by weight of epoxy resin (A).
• thermoplastic resin (B) dissolves in the epoxy resin (A) when heated and mixed, and phase-separates when cured to form a finely mixed co-continuous phase.
• the thermoplastic resin (B) is required to have high compatibility with the epoxy resin (A), and preferably has a reactive functional group at the molecular end.
• the reactive functional group is not particularly limited, but preferably includes a hydroxyl group, a force propyl group, an amino group, and the like, and particularly preferably a hydroxyl group.
• the type of the thermoplastic resin (B) is not particularly limited, but may be a polyether sulfonate resin, a polyether imide resin, a polyimide resin, a polyamide resin, a polyether resin, It is preferably at least one selected from a polyester resin, a polysulfone resin, a polyamide-imide resin, a polyacrylate resin, a polyether polyol, a polyether ether resin and a polyether ether ketone resin.
• polyethersulfone resin or polyetherimide resin is preferred, and in particular, polyethersulfone resin has excellent compatibility with epoxy resin and can form a co-continuous phase and improve toughness quickly. I like it because I can.
• a particulate thermoplastic resin (B) more preferably the particle diameter is 200 / zm or less, and more preferably 5 to: LOO / zm.
• the thermoplastic resin (B) when blended in epoxy resin, large particles are prevented from remaining undissolved and dissolved quickly and uniformly. It becomes easy to form a co-continuous phase after conversion.
• the particle size of the fine particles 200 m or less the dissolution of the thermoplastic resin (B) in the epoxy resin (A) becomes uniform, and a co-continuous phase is easily formed and the toughness is sufficiently improved.
• the method for preparing fine particles having a particle diameter of 200 m or less is not particularly limited, but it is preferable to make fine particles by impact pulverization or spray drying.
• the epoxy resin composition of the present invention forms a co-continuous phase in which the epoxy resin (A) and the thermoplastic resin (B) interpenetrate after curing, and at least the epoxy resin in the co-continuous phase.
• Solid resin fine particles (C) are dispersed in a continuous phase of white resin (A). At least in the continuous phase of the epoxy resin (A), the solid resin particles (C) form a finer dispersed phase, so that the stress concentration inside the epoxy resin (A) phase is totally reduced.
• the toughness can be improved by dispersing. By improving the toughness of the epoxy resin composition, the strength of the fillet is improved, and the self-adhesion strength of the pre-preda can be improved.
• the solid resin fine particles (C) may be dispersed at least in the continuous phase of the epoxy resin (A), or may be dispersed in the continuous phase of the thermoplastic resin (B). Yo ...
• the resin constituting the solid resin fine particles (C) may be either a thermosetting resin or a thermoplastic resin as long as it has at least a high affinity with the epoxy resin (A). You may use both.
• thermosetting resin epoxy resin is more preferable, among which epoxy resin, maleimide resin, cyanate resin and the like are preferable.
• Yepo Xylose resin is not particularly limited, but bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, talesol novolac type epoxy resin, dicyclopentagen skeleton Type epoxy resin or naphthalene skeleton epoxy resin, and bisphenol A type epoxy resin is particularly preferred.
• the epoxy resin constituting the solid resin fine particles (C) is prepared by purifying bisphenol-type epoxy resin to increase its purity and increasing its molecular weight, thereby providing an epoxy group at the molecular end.
• the phenoxy skeleton-type rosin having is more preferable.
• the affinity with the epoxy resin (A) can be increased, and the phenoxy skeleton type resin is preferably selected from bisphenol A skeleton and bisphenol F skeleton at least. It is a phenoxy-type resin that can be used as a single force, and can increase the softness point and improve toughness.
• thermoplastic resin constituting the solid resin fine particles (C) is not particularly limited, but those having a reactive functional group at the molecular end are preferred because of their high toughness-improving effect. Yes.
• the molecular weight of the resin constituting the solid resin fine particles (C) is preferably 10,000 to LOO, 000.
• the molecular weight is in the range of 10,000 to 100,000, it is possible to prevent the solid resin particles from remaining undissolved when the epoxy resin composition is cured, and to dissolve the solid resin particles uniformly. By uniformly dispersing the fat particles, the toughness of the epoxy resin composition can be improved.
• the molecular weight is a weight average molecular weight measured by GPC analysis.
• the epoxy resin constituting the solid resin fine particles (C) is preferably of a high molecular weight type.
• An epoxy resin having a weight average molecular weight of 10,000 to 35,000 is more preferable.
• the weight average molecular weight is in the range of 10,000 to 35,000, it is easy to produce fine particles by impact pulverization or the like, and the particles are easily dispersed during the heat curing process of the epoxy resin composition. The reason power is preferable.
• the weight average molecular weight of the phenoxy skeletonized resin having an epoxy group at the molecular terminal used as the solid resin fine particles (C) is preferably 50,000-60,000.
• the weight average molecular weight of the phenoxy skeleton type resin is rubbed within the range of 50,000 to 60,000, fine particles are produced by impact pulverization or the like. It is easy to disperse.
• the epoxy equivalent of the phenoxy skeleton type resin having an epoxy group at the molecular terminal is preferably set to an epoxy equivalent of 8,000 to 20,000 g / eq! /.
• the epoxy equivalent is 8,000 g / eq or more
• the epoxy resin (A) has a dispersed phase separated in the continuous phase of the epoxy resin (A) after curing. It is possible to form it, and when it is less than 20, OOOgZeq, it can be easily dissolved in epoxy resin (A) during heat curing.
• the epoxy resin constituting the solid resin fine particles (C) is preferably composed of a bisphenol A type epoxy resin that is solid at room temperature.
• a bisphenol A type epoxy resin can be prepared by refining bisphenol type epoxy resin to increase its purity and increase its molecular weight, and has a high soft point and improves the workability of the pre-preda. It is preferable because it improves and improves the toughness.
• the bisphenol A type epoxy resin preferably has an epoxy equivalent of 1000 to 8000 gZ eq, more preferably 2000 to 6000 g / eq! /.
• the epoxy equivalent is 1000 g / eq or more
• the epoxy resin (A) is formed into a dispersed phase in the continuous phase of the epoxy resin (A) after curing that does not completely dissolve before heat curing. If it is 8 OOOgZeq or less, it can be easily dissolved in epoxy resin (A) during heat curing.
• the solid resin fine particles (C) In order that the solid resin fine particles (C) are completely dissolved in the epoxy resin (A) at the time of heat curing, the solid resin fine particles (C) have a particle diameter of preferably 100 m or less. More preferably 5 ⁇ m to 100 ⁇ m!
• the particle diameter of the solid resin fine particles (C) By setting the particle diameter of the solid resin fine particles (C) within such a range, the solid resin fine particles (C) are easily dissolved in the epoxy resin (A) when the heat curing process reaches a predetermined temperature. Therefore, the viscosity of the epoxy resin composition can be adjusted appropriately and can be dispersed in the epoxy resin phase to improve the toughness of the cured product.
• the particle diameter of the solid resin particles (C) is preferably 0.1. ⁇ 2 111, preferably 0.1 to 0.5 m. If the particle diameter of the solid resin fine particles (C) is in the range of 0.1 to 2 m and dispersed in the continuous phase of the epoxy resin (A), the effect of improving the toughness of the cured resin resin is preferably increased.
• the type of the curing agent (D) is not particularly limited as long as it is a compound having an active group capable of reacting with an epoxy group, but is not limited to aromatic polyamines, aliphatic polyamines, imidazole compounds, Preferred examples include tetramethyldazine, thiourea addition amine, carboxylic acid anhydride, carboxylic acid hydrazide, carboxylic acid amide, polyphenol compound, novolac resin, and polymercabutane.
• aromatic polyamines are preferred, especially 3, 3 'diaminodiphenyl sulfone (3, 3' — DDS) or 4,4 'diaminodiphenyl sulfone (4 , 4′-DDS) and the like are preferably used.
• a latent curing agent as the curing agent (D).
• the latent curing agent is preferably at least one selected from organic acid dihydrazide, dicyandiamide, aminimide, tertiary amine salt, imidazole salt, Lewis acid and Bronsted acid power, especially organic acid dihydrazide or dicyandiamide. I like it.
• the latent curing agent By using the latent curing agent, the toughness of the cured resin can be improved, that is, the strength of the fillet can be improved and the self-adhesion strength of the pre-preda can be improved.
• the curing agent (D) it is particularly preferable to use at least one curing agent selected from diaminodiphenyl sulfone and a latent hardener.
• the epoxy resin composition of the present invention is preferably 20 to 60 parts by weight, more preferably 30 to 50 parts by weight of the thermoplastic resin (B) with respect to 100 parts by weight of the epoxy resin (A).
• Parts, and the solid sallow fine particles (C) are preferably contained in a proportion of 2 to 20 parts by weight, more preferably 5 to 15 parts by weight.
• the blending amount of the thermoplastic resin (B) in the range of 20 to 60 parts by weight, the viscosity of the epoxy resin composition can be optimized and the shape of the fillet can be made good. By doing so, workability of the pre-preparer such as tackiness and drape can be improved.
• the blending amount of the solid fine resin particles (C) is 2 parts by weight or more, the effect of improving the toughness of the cured product is obtained. It is possible to improve the loop property.
• the curing agent (D) is preferably added in an amount of 25 to 50 parts by weight, more preferably 30 to 45 parts by weight, based on 100 parts by weight of the epoxy resin (A).
• the blending amount of the curing agent (D) is preferably added to 25 to 50 parts by weight, physical properties such as strength, toughness and heat resistance required for the cured resin can be improved.
• the epoxy resin composition for fiber-reinforced composite material according to the present invention has the above-mentioned components (A) to (D) as essential forces.
• Various additives such as known curing agents, fillers, stabilizers, flame retardants, and pigments other than the components (A) to (D) may be blended.
• the epoxy resin composition of the present invention has a fracture toughness value measured according to ASTM D5045-91 of the cured product, preferably 1.8 MPa'm or more, more preferably 1. 8 to 2.5 MPa 'm, more preferably 2.0 to 2.5 MPa-m. Fracture toughness value of cured product of epoxy resin composition 1. In a peel test after self-adhesion between face plate (prepreda) and hard core, where the toughness of the fillet portion is higher than 8 MPa'm. The peel strength can be improved as the material breakage of the hard cam core occurs.
• the epoxy resin composition of the present invention has a minimum viscosity of preferably 10 to 150 Pa's, more preferably 20 to 150 Pa's, as measured by dynamic viscoelasticity at a temperature rising rate of 2 ° CZ. Good to have. It is necessary to make the minimum viscosity of dynamic viscoelasticity measured in the temperature rising process within the above range in order to develop the productivity of the prepreg and self-adhesiveness. Fillet can be formed and self-adhesiveness is improved. If it is 150 Pa's or less, the resin composition can be easily impregnated into the reinforcing fiber during the preparation of the pre-preda while maintaining the formability of the fillet.
• the minimum viscosity by dynamic viscoelasticity measurement is determined by using an epoxy resin composition as a sample, at a temperature from 25 ° C to 200 ° C, at a rate of temperature increase of 2 ° CZ, and at a frequency of lOmdZ seconds.
• the epoxy resin composition for fiber-reinforced composite material of the present invention has a three-dimensional network in which the epoxy resin (A) and the thermoplastic resin (B) are mixed with each other in the form of the cured product. A continuous phase of the structure is formed, and the solid resin is contained in the continuous phase of at least the epoxy resin (A). Since the fine particles (C) form a fine dispersed phase !, they are significantly better than when the epoxy resin (A) and the thermoplastic resin (B) form a co-continuous phase. Exhibits toughness.
• the epoxy resin (A) and the thermoplastic resin (B) form a co-continuous phase with a three-dimensional network structure, so that stress is concentrated and the interface between the two resins is three-dimensional.
• a continuous structure is formed, the stress is easily dispersed as a whole, the adhesive strength of the resin interface is improved by the good compatibility of both resins, and the thermoplastic has excellent toughness.
• the toughness of the cured resin is improved by making the resin (B) into a continuous phase.
• solid resin fine particles (C) become a fine dispersed phase and dispersed in the continuous phase of epoxy resin (A)!
• the toughness of the epoxy resin (A) phase is improved, thereby further increasing the toughness of the cured resin. This is considered to be improving.
• the raw material used in the epoxy resin composition for fiber-reinforced composite material of the present invention is not particularly limited, but liquid epoxy resin (A) has a reactive functional group at the molecular end. It is also preferable that the thermoplastic resin (B), the solid resin fine particles (C) having a particle diameter of 100 IX m or less, and the curing agent (D) can also be used.
• the compatibility with the thermoplastic resin (B) is increased, and the thermoplastic resin (B) can be reliably dissolved during heating and mixing.
• thermoplastic resin having a reactive functional group at the molecular end for the thermoplastic resin (B) the compatibility with the epoxy resin (A) is improved, and the thermoplastic resin (C) is mutually compatible during curing. It becomes easier to form a co-continuous phase.
• a particulate thermoplastic resin (B) it is preferable to use a particulate thermoplastic resin (B), and it is more preferable that the particle diameter is 200 m or less.
• the method for producing the epoxy resin composition for fiber-reinforced composite material is not particularly limited.
• the thermoplastic resin (B) is heated and mixed with the epoxy resin (A) and dissolved. After that, the temperature of the mixed resin is lowered, and it may be blended so that the solid resin fine particles (C) are dispersed therein.
• the obtained prepredder is heat-cured, the solid fine resin particles (C) are dissolved in the epoxy resin (A) during heating, and after curing, at least the continuous phase of the epoxy resin (A) is used as the sea. It becomes islands (dispersed phase) that are more finely and uniformly dispersed.
• the temperature at which the thermoplastic resin (B) is heated and mixed with the epoxy resin (A) and dissolved is preferably 95 to 150 ° C, more preferably 100 to 125 ° C. Mix with a planetary mixer for about 0.5 to 3 hours until homogeneous dissolution. After cooling this mixed resin, preferably at a temperature of 60 to 90 ° C, more preferably at a temperature of 70 to 80 ° C, the solid resin fine particles (C) and the curing agent (D) are added, and the mixed resin is mixed. It is preferable to prepare an epoxy resin composition by uniformly dispersing and mixing in it.
• thermoplastic resin (B) is surely dissolved and the solid resin particles (C) are uniformly dispersed to form a specific form after curing and toughness is improved. This can improve the self-adhesive strength of the pre-preda.
• the fiber reinforced pre-preda of the present invention is obtained by using the above-described epoxy resin composition for a fiber reinforced composite material as a matrix resin and combining the matrix resin with reinforcing fibers.
• the reinforcing fiber carbon fiber, graphite fiber, aramid fiber, glass fiber and the like can be preferably mentioned, and carbon fiber and a carbon fiber woven fabric comprising the same are particularly preferable.
• the fiber reinforced pre-preda is preferably 30 to 50% by weight, more preferably 35 to 45% by weight, of the content of the matrix resin.
• Matrix resin specific force in fiber reinforced pre-predators S within this range, the self-adhesion of the pre-preda is improved, workability and appearance quality are improved, and the mechanical properties of the carbon fiber reinforced composite material are further improved. It can be fully utilized.
• a method for producing a fiber-reinforced pre-preder includes a so-called resin film in which the epoxy resin composition of the present invention is applied in a thin film form on a release paper, and is disposed above and below the reinforcing fiber.
• a hot melt method in which the reinforcing fiber is impregnated with the epoxy resin composition by heating and pressing is preferred. Since the prepredder obtained in this way uses a specific epoxy resin composition, it is excellent in tackiness and draping property, and improves the prepreader workability, so that the prepredder production efficiency can be improved. .
• a fiber-reinforced composite material is produced by laminating the fiber-reinforced pre-predder thus obtained on both sides of a knot-cam core and thermosetting such as ordinary autoclave molding or hot press molding. be able to.
• This fiber reinforced composite material has excellent fillet formation, excellent pre-predder's hard core adhesion, excellent pre-predder surface smoothness, excellent appearance and surface with less porosity. Have sex.
• the hard cam core used in the present invention is preferably aramid hard cam, among which aramid hard cam, aluminum hard cam, paper hammer cam and glass hard cam force are selected.
• the solid resin fine particles (C) are dispersed with a particle size of 100 ⁇ m or less. It is dissolved uniformly, so that the viscosity of the epoxy resin composition is properly adjusted and dispersed in the epoxy resin phase when the curing is completed to further improve the toughness of the resin resin cured product. Can do.
• Examples 1 to 5 in Table 1 were compared.
• an epoxy resin composition was prepared and its properties were evaluated. First, all of the epoxy resin (A) and the thermoplastic resin (B) were stirred and mixed for 75 minutes using a planetary mixer set at a temperature of 125 ° C. until a uniform solution was obtained. Then, the temperature of this planetary mixer was set to 70 ° C, and when the temperature of the resin became uniform, all the solid fine resin particles (C) and the curing agent (D) were added to this solution and stirred and mixed. Epoxy resin composition was prepared.
• Resin A— 1 N, N, O—Triglycidyl mono-p-aminophenol resin (MY- 0510 manufactured by Normanman Advanced) Materials, liquid at room temperature, viscosity at 25 ° C is 7 Boise.
• Oil A-2 Triglycidyl alkylaminophenol oil (Sumitomo Chemical ELM—100), liquid at room temperature, viscosity of 10 boise at 25 ° C.
• Resin A-3 Bisphenol F-type epoxy resin (YDF-170, manufactured by Tohto Kasei Co., Ltd.), liquid at room temperature, viscosity of 25 boise at 25 ° C.
• Resin B-1 Polyethersulfone resin (Sumitomo Chemical Co., Ltd. Sumika Etacel PES5003P), made into fine particles with a particle size of 100 ⁇ m or less by impact grinding.
• Particle C-1 Bisphenol A type epoxy resin (YD-019 manufactured by Tohto Kasei Co., Ltd.), made into fine particles with a particle size of 100 ⁇ m or less by impact grinding.
• Particle C-2 Bisphenol A type epoxy resin (YD-020N manufactured by Toto Kasei Co., Ltd.), made into fine particles with a particle size of 100 ⁇ m or less by impact grinding.
• Particle C-3 Phenoxy bisphenol epoxy resin (YP-70, manufactured by Tohto Kasei Co., Ltd.), made into fine particles with a particle size of 100 ⁇ m or less by impact grinding.
• Curing agent D 1, 3, 3 ′ —Diaminodiphenyl sulfone (Nordmann 'advanced' Materials ARADUR9719— 1)
• Curing agent D-2 Dicyandiamide (Epicure DICY 15 from Japan Epoxy Resin), latent curing agent o
• a resin film was formed on the release paper, and this film was added to a carbon fiber plain weave fabric (T-300-3K manufactured by Toray Industries Inc.) with a resin content of 41% by weight. Then, it was transferred by heating and pressing to obtain a pre-preda.
• a carbon fiber plain weave fabric T-300-3K manufactured by Toray Industries Inc.
• the obtained pre-preda was evaluated with tentacles, and tackiness and drapeability were evaluated according to the following three-stage criteria.
• the obtained epoxy resin composition was cured in a program oven at a temperature of 180 ° C. for 2 hours to produce a resin-cured product.
• the obtained cured resin was ruptured with a sharp blade, and the fractured surface was 5,000 times magnified by a scanning electron microscope with an epoxy resin (A) and a thermoplastic resin (B). The morphology was observed with respect to the dispersion diameter of the solid fat microparticles (C).
• a test sample was prepared from the cured resin obtained above according to ASTM D5045-91, and the fracture toughness value (MPa'm) at 23 ° C (dry state) was measured.
• the obtained hard cam panel was processed into a predetermined size for the face plates disposed on the upper side and the lower side of the hard core in the heat curing process, and the temperature was 23 ° C (drying The peel strength (lb—inZ3in) of the test pieces on the upper side plate and the lower side plate in the state) was measured.
• Example 15 of the present invention From the results of Table 1, in Example 15 of the present invention, the epoxy resin (A) and the thermoplastic resin (B) form a fine co-continuous phase, and the solid resin particles (C) It was confirmed that the particles were dispersed in the continuous phase of epoxy resin (A) with a particle size of 0.2 ⁇ .
• the fracture toughness values of Examples:! To 5 were found to be as extremely high as 2. 1 2. 2 MPa'm.
• the epoxy resin (A) and the thermoplastic resin (B) form a fine co-continuous phase, but contain the solid resin fine particles (C). Therefore, the epoxy resin (A) is not strengthened and the fracture toughness value is as low as 1.8 MPa'm. Since the thermoplastic resin (B) was not blended, a co-continuous phase was not formed, and the fracture toughness value was even lower.
• Examples 1 to 5 of the present invention exhibited excellent properties in all of the tackiness and drape of the pre-preda and the peel strength of the honeycomb panel.
• Comparative Example 1 in which the solid resin fine particles (C) are not compounded and Comparative Example 2 in which the thermoplastic resin (B) is not compounded are found to result in poor peel strength of the hard cam panel. It was.

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