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WO2004096885A1 - Composition de resine pour preimpregne - Google Patents

Composition de resine pour preimpregne Download PDF

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Publication number
WO2004096885A1
WO2004096885A1 PCT/JP2004/006126 JP2004006126W WO2004096885A1 WO 2004096885 A1 WO2004096885 A1 WO 2004096885A1 JP 2004006126 W JP2004006126 W JP 2004006126W WO 2004096885 A1 WO2004096885 A1 WO 2004096885A1
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WO
WIPO (PCT)
Prior art keywords
epoxy resin
resin composition
preda
resin
honeycomb core
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2004/006126
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English (en)
Japanese (ja)
Inventor
Mitsuhiro Iwata
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Yokohama Rubber Co Ltd
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Yokohama Rubber Co Ltd
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Filing date
Publication date
Application filed by Yokohama Rubber Co Ltd filed Critical Yokohama Rubber Co Ltd
Publication of WO2004096885A1 publication Critical patent/WO2004096885A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers

Definitions

  • the present invention relates to a resin composition for a prepredder field which retains heat resistance and water resistance, and has excellent flow control properties and adhesion to a honeycomb core. More specifically, the present invention relates to a copure adhesive for bonding a honeycomb core to a prepredder. The present invention relates to a resin composition for a prepreg having (self-adhesive) properties. Background art
  • Epoxy resin compositions are used in the fields of construction, civil engineering, automobiles, aircraft, and the like as resins having excellent heat resistance. Fiber-reinforced composite materials using an epoxy resin composition as a matrix resin have excellent mechanical properties, heat resistance and water resistance, and so far pre-preparers have been proposed using combinations of epoxy resins with various compositions and reinforcing fibers. Have been.
  • the pre-preda is generally in the form of a sheet, and includes a sheet plane in which continuous fibers are arranged in one direction in parallel, a continuous fiber woven fabric, a discontinuous fiber arranged in an arbitrary direction, and the like. is there.
  • a honeycomb core having a honeycomb structure is often formed into a structure in which a cross-section of a pre-preda is joined to a cross-section. Adhesion to the pre-preda has been conventionally achieved by interposing a sheet-like adhesive between the honeycomb core and the pre-preda. P2004 / 006126.
  • a pre-preda is laminated on both sides of the 82-cam core without using an adhesive sheet, and the pre-preda itself is cured and adhered to the honeycomb core at the same time and without an adhesive.
  • Precure molding has been required for pre-preda, and as a resin composition for pre-preda impregnation (resin composition for pre-preda), an epoxy resin having co-curability has been studied and disclosed in various inventions for defining viscosity characteristics. I have.
  • JP-A-5-239317 discloses an epoxy resin comprising an epoxy resin, a curing agent, and a solid rubber for the purpose of avoiding the generation of porosity (voids and voids generated during curing of the resin).
  • the composition is a complex viscosity ⁇ measured at 80 ° C. at an oscillation frequency of 0.02 Hz. .. 2 is 500 Pa ⁇ s or more, and complex viscosity TU and 7? Measured at vibration frequency 2 Hz. .. The relationship between 2 is log ??. .. An epoxy resin composition satisfying 2 — log 7 2 ⁇ 0.5 is disclosed.
  • 9-1196461 discloses that a reinforcing fiber and a matrix resin are used for the purpose of improving the duckability and drapability, the matrix resin is a thermosetting resin, and the measurement frequency is 0.
  • the complex viscosity ⁇ * of the matrix resin in the dynamic viscoelasticity measurement at 5 Hz and 50 ° C is in the range of 200 to 2000 Pa ⁇ s, and the energy loss t &: 16 is 0.3 to 5
  • a range of pre-preda is disclosed.
  • JP-A-11-254435 discloses that the minimum viscosity is 0.01 to 30 Pa ⁇
  • a resin film for producing a pre-preda prepared by applying a thermosetting resin of s on a release sheet.
  • the minimum viscosity If the ratio is less than 0.1Pas, the resin film will not be produced uniformly, which will cause problems such as flow and repelling. If it exceeds 30 Pas, the film will not be evenly formed, and when transferring the resin from the coating roll to release paper, transfer unevenness will occur and a uniform resin film will not be obtained.
  • the present invention provides a resin composition for a prepreg, which is excellent in heat resistance, water repellency, flow control properties and adhesion to a honeycomb core, and clarifies the relationship between the formability of the fillet and the complex viscosity of the resin. It is an object of the present invention to provide a structure obtained by adhering a pre-preda using a resin composition for a pre-preda to a honeycomb core.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a group consisting of an epoxy resin, an aromatic amine, an imidazole-based catalyst, a boron trifluoride-amine salt catalyst, and dicyandiamide.
  • Complex viscosity of the resin composition for a pre-preda containing at least one selected from the group consisting of a solid rubber and / or a thermoplastic polymer.
  • the resin composition for a pre-preda is an excellent composition which is excellent in heat resistance, water resistance and flow control as a matrix resin for the pre-preda, and also satisfies the adhesiveness to a honeycomb core.
  • the present invention was found to be a product. That is, the present invention provides the following resin compositions (1) to (3) for a pre-preda and the structure (4).
  • the content of the solid rubber and Z or the thermoplastic polymer (cl) is not less than 1 part by mass and less than 10 parts by mass with respect to 100 parts by mass of the epoxy resin (a);
  • a resin composition for a pre-preda resin whose complex viscosity measured at a vibration frequency of 0.02 Hz satisfies the relationship represented by the following formula (1).
  • ⁇ represents the temperature rise rate
  • ⁇ represents the temperature difference between the measurement points in the measurement temperature range of 25 to 250 ° C.
  • FIG. 1 is a perspective view of a structure including a honeycomb core and a pre-preda.
  • FIG. 2 is a cross-sectional view of a structure including a honeycomb core and a pre-preda.
  • the resin composition for a pre-preda of the present invention comprises: (a) an epoxy resin; (b) an aromatic amine; (c) an imidazole-based catalyst, boron trifluoride'amine salt catalyst, and disiandiamide. At least one selected (hereinafter, also simply referred to as component (c)) and (d) solid rubber and Z or a thermoplastic polymer, and the content of the solid rubber and Z or thermoplastic polymer (d) But not less than 1 part by mass and less than 10 parts by mass with respect to 100 parts by mass of the epoxy resin (a),
  • the resin composition for a pre-preda is characterized in that the complex viscosity 7? Measured at a vibration frequency of 0.02 Hz satisfies the relationship represented by the following formula (1).
  • A represents the temperature rise rate
  • ⁇ represents the temperature difference between the measurement points in the measurement temperature range of 25 to 250 ° C.
  • the epoxy resin (a) used in the present invention is not particularly limited as long as it is a polyepoxy compound having an average of two or more epoxy groups in one molecule.
  • epoxy compounds having a bisphenyl group such as bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, and piphenyl type, etc.
  • Bifunctional glycidyl ether epoxy resins such as polyalkylene glycol type, alkylene glycol type epoxy compounds, epoxy compounds having a naphthylene ring, and epoxy compounds having a fluorene group;
  • Polyfunctional dalicidyl ether type epoxy resin such as phenol nopolak type, orthocresol nopolak type, DPP nopolak type, tris-hydroxyphenylmethane type, trifunctional type, tetraphenylolethane type, etc .;
  • TGDDM tetraglycidyl m-xylyl
  • Aromatic epoxy resin having a glycidylamino group such as rangedamine, triglycidyl-1-P-aminophenol, N, N-diglycidyldiline;
  • Alicyclic epoxy resin epoxy resin represented by Flep 10 manufactured by Toray Recoal Co., Ltd. epoxy resin having a sulfur atom in the main chain; urethane-modified epoxy resin having urethane bond; polybutadiene, liquid polyacrylonitrile-butadiene rubber or A rubber-modified epoxy resin containing acrylonitrile-butadiene rubber (NBR) is exemplified. These may be used alone or in combination of two or more.
  • the resin composition for a pre-preda of the present invention preferably contains an epoxy resin having a skeleton and an aromatic epoxy resin having a Z or dalicidylamino group, because it is excellent in heat resistance and water resistance. .
  • epoxy resin having a dicyclopentene skeleton for example, commercially available products such as TACTIX-556 from Dow Chemical and HP-720 from Dainippon Ink & Chemicals, Inc.
  • aromatic epoxy resins having a glycidylamino group can be used. Specifically, for example, Sumitomo Chemical's ELM-434, Mitsubishi Gas Chemical's TET RAD—X etc. can be used.
  • the resin composition for a pre-preda may include, as an epoxy resin, In addition to an epoxy resin having a Tajene skeleton and / or an aromatic epoxy resin having a glycidylamino group, an epoxy resin having two or more epoxy groups in one molecule (polyfunctional epoxy resin) However, heat resistance, water resistance, and adhesion to the honeycomb core and the carbon fiber are preferable because they are good.
  • the polyfunctional epoxy resin the above-mentioned daricidyl ether type epoxy resin is preferably used, and specifically, for example, glycidyl ether type epoxy resins represented by the following formulas (4) and (5) and the like are mentioned.
  • epoxy resin (a) used in the present invention As the epoxy resin (a) used in the present invention,
  • the aromatic epoxy resin having a glycidylamino group accounts for 30% by mass of all epoxy resins constituting the epoxy resin (a) (hereinafter, simply referred to as epoxy resin (a)).
  • the content of the epoxy resin having a dicyclopentene skeleton is preferably 25% by mass or more from the viewpoint of maintaining a balance between water resistance and heat resistance.
  • the total content is 55 to 95% by mass with respect to the epoxy resin (a), Preferably it is 65 to 95% by mass. This range is preferred because it is excellent in water resistance and heat resistance.
  • the epoxy resin (a) includes, in addition to the above-mentioned epoxy resin having a dicyclopentene skeleton and the above-mentioned aromatic epoxy resin having a dalycidylamino group, a general epoxy resin such as the above-mentioned polyfunctional epoxy resin.
  • the composition contains 5 to 45% by mass, preferably 5 to 35% by mass of a general-purpose epoxy resin used for the composition. When the content of the other epoxy resin is within this range, heat resistance and water resistance are maintained, and an appropriate viscosity can be obtained, which is preferable.
  • aromatic amine (b) used in the present invention include, for example, diaminodiphenylsulfone (DDS), diaminodiphenylmethane (DDM), and diaminodiphenylene represented by the following formula (6).
  • DDS diaminodiphenylsulfone
  • DDM diaminodiphenylmethane
  • diaminodiphenylene represented by the following formula (6).
  • Monoter (D AD PE) bisaniline
  • benzyldimethylaniline and the like.
  • aromatic amines having one or more amino groups in the molecule are preferred from the viewpoint that the resulting composition of the present invention has excellent heat resistance.
  • Such aromatic amines having one or more amino groups Preferred examples of the diamine diphenyl sulfone (DDS), diamino diphenyl methane (DDM), diamino diphenyl ether (DADPE), bisaniline, etc. It is preferable to use it as an agent because it is particularly excellent in heat resistance. These aromatic amines may be used alone or as a mixture of two or more.
  • the resin composition for a prepredder of the present invention may comprise, as a curing agent, an imidazole-based catalyst or boron trifluoride as a component (c), in addition to the aromatic amine (b), as long as the object of the present invention is not impaired.
  • ⁇ Contains at least one selected from the group consisting of amine salt catalysts and dicyandiamide.
  • component (c) examples include those commonly used as a curing agent and a curing catalyst for an epoxy resin.
  • dicyandiamide DI CY
  • various derivatives of imidazole eg, Shikoku Chemicals
  • 2MA—OK 2 ⁇ - ⁇
  • boron trifluoride-amine salt catalyst eg, boron trifluoride-monoethylamine, boron trifluoride'pirazine salt, boron trifluoride-aniline
  • the solid rubber and / or thermoplastic polymer (d) used in the present invention is as described above.
  • Specific examples of the solid rubber include various rubbers such as acrylonitrile-butadiene rubber and its hydride, acryl rubber, ethylene-acrylic rubber, epichlorohydrin rubber, and ethylene-vinyl acetate rubber.
  • thermoplastic polymer examples include, for example, PES (polyether sulfone), PPS (polyphenylene sulfide), PEEK (polyether ethyl ketone), PI (polyimide), PEI (polyetherimide), PAI (Polyamide imide), and the like, and the thermal decomposition onset temperature (Td) is preferably 160 ° C. or more.
  • Examples of the functional group capable of reacting with the epoxy resin include a hydroxyl group, an amino group, and the like.
  • the solid rubber is preferably an acrylonitrile butadiene rubber (NBR) among the above examples, and a functional group capable of reacting with an epoxy resin or a curing agent, in particular, a carboxy-modified acrylonitrile butadiene rubber having a carboxyl group and More preferably, it is Z or carboxy-modified hydrogenated acrylonitrile-butadiene rubber (hereinafter, referred to as carboxy-modified (hydrogenated) acrylonitrile-butadiene rubber).
  • NBR acrylonitrile butadiene rubber
  • a functional group capable of reacting with an epoxy resin or a curing agent in particular, a carboxy-modified acrylonitrile butadiene rubber having a carboxyl group and More preferably, it is Z or carboxy-modified hydrogenated acrylonitrile-butadiene rubber (hereinafter, referred to as carboxy-modified (hydrogenated) acrylonitrile-butadiene rubber).
  • the carboxy-modified (hydrogenated) acrylonitrile-butadiene rubber may be one or both of a non-hydrogenated rubber and a hydrogenated rubber.However, when the hydrogenated rubber is used, the weather resistance of the composition, Good heat resistance and water resistance. Cal The modified oxy group can easily react with an epoxy resin or a curing agent because it has a hydroxyl group.
  • the carboxy-modified (hydrogenated) acrylonitrile-butadiene rubber (d) used in the present invention may be one type or a mixture of two or more types.
  • the carboxy-modified (hydrogenated) acrylonitrile-butadiene rubber is a carboxy-modified (hydrogenated) acrylonitrile-butadiene rubber having 20% to 40% by mass of nitrile and 0.5% to 6% by mass of carboxy. It is preferable that there is.
  • the content of solid rubber and Z or thermoplastic polymer (d) compatible with the epoxy resin is 1 part by weight or more and less than 10 parts by weight with respect to 100 parts by weight of the epoxy resin (a). It is preferably less than 5 parts by mass from the viewpoint of the viscosity (complex viscosity) of the obtained prepreg resin composition of the present invention and the formability of fillets described later.
  • the resin composition for a prepreg of the present invention further comprises a complex measured at a vibration frequency of 0.02 Hz.
  • ⁇ is the heating rate and ⁇ is between the measurement points in the measurement temperature range of 25 to 250 ° C. 6126 Indicates the temperature difference.
  • the complex viscosity is a value measured as follows using a dynamic mechanical analyzer (dynamic viscoelasticity measuring device; DMA).
  • DMA dynamic viscoelasticity measuring device
  • the complex viscosity is measured by a plate-to-plate type (parallel plate method) using a disk-shaped plate with a diameter of 25 mm or 50 mm. It is measured from a torque and a phase difference generated when the resin composition for a pre-preda of the present invention is filled and one plate is subjected to a vibration having a predetermined vibration frequency of 0.02 Hz and an amplitude of 1 Hz.
  • the present inventor uses this as a parameter indicating the distance at which the upper fillet flows out during the co-curing of the pre-preda, and integrates 1Z within the temperature range in which the resin composition for the pre-preda flows out and hardens, so that the upper fillet is sufficiently large.
  • ⁇ / ( ⁇ ? ⁇ ) obtained by integrating the complex viscosity of the resin composition for pre-preda measured in a specific measurement temperature range (25 to 250 ° C) and the measured value of the upper fillet.
  • the parameter represented by the above formula (1) is different from that of the resin composition for a pre-reader. Since a continuous change in a wide temperature range in the outflow hardening can be reflected, this is an excellent parameter when selecting a resin composition having a certain viscosity range capable of obtaining a sufficiently large fillet shape.
  • the resin composition for a prepreg of the present invention comprises, as essential components, an epoxy resin (a), an aromatic amine (b), an imidazole catalyst, a boron trifluoride / amine salt catalyst and dicyandiamide. It contains at least one selected material (c) and a solid rubber and / or a thermoplastic polymer (d), but it does not impair the curing of the resin composition for a prepreg of the present invention. And various additives such as an anti-aging agent and a solvent.
  • Examples of the filler include Ribon Bonplatsk, calcium carbonate, titanium oxide, silica, aluminum hydroxide and the like.
  • Examples of the anti-aging agent include hindered amines and hindered phenols.
  • Examples of the solvent include methanol, ethanol, propanol, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK).
  • the resin composition for a prepreg of the present invention comprises at least one selected from the group consisting of an epoxy resin (a), an aromatic amine (b), an imidazole-based catalyst, a boron trifluoride-amine salt catalyst, and dicyandiamide.
  • One (c), the solid rubber and Z or the thermoplastic polymer (d), and the additives to be added as required, are added using a Dalton-type mixer, a paint roll, a grinder, or the like. It is manufactured by mixing in a conventional manner.
  • the carboxy-modified (hydrogenated) acrylonitrile When the gen rubber component is mixed as a solid rubber, it may be mixed by dissolving it in the above solvent, or may be mixed by a paint roll. However, both of them must be well dispersed in the epoxy resin (a). is necessary.
  • the cured product obtained from the resin composition for a prepreg of the present invention is excellent in heat resistance and water resistance and also excellent in adhesion between the prepreg and the honeycomb core. It is useful to use it as an object.
  • the use of the resin composition for a pre-preda of the present invention as a matrix resin composition refers to a carbon fiber, an aramide fiber such as Kevlar, a fiber woven fabric such as a glass fiber, or a unidirectional fiber thereof. This is to impregnate the resin composition for a prepreg of the present invention, or to laminate a plurality of woven fabrics impregnated with the resin composition, thereby producing a prepreg.
  • the resin composition for a pre-preda of the present invention is dissolved in a solvent to prepare a varnish and then impregnated.
  • a solvent used in preparing the varnish a solvent of alcohols such as methanol, ethanol, and propanol, or a solvent of ketones such as methyl ethyl ketone (MEK) is preferably dissolved.
  • MEK methyl ethyl ketone
  • a varnish containing the resin composition for pre-preda may be prepared and then impregnated into a woven fabric.
  • the addition amount of the solvent is 100 to 200 parts by mass with respect to 100 parts by mass of the solid content of the resin composition for a prepredder, so that the drying step is optimized.
  • Examples of the fiber woven fabric used in the prepreg using the resin composition for a prepreg of the present invention as a matrix resin include carbon fibers, aramide fibers such as Kepler, fiber woven fabrics such as glass fibers, and unidirectional fibers (long fibers) thereof. And the like. Specific examples include Rikibon fiber T-300 manufactured by Toray Co., Ltd. and HTA grade manufactured by Toho Rayon Co., Ltd., and the basis weight of the fiber is 140 to 200 g. / m 2 is preferred.
  • the pre-preda using the resin composition for a pre-preda of the present invention as a matrix resin is a pre-preda prepared by impregnating the above-described epoxy resin (a) as a varnish with or without a solvent into a woven fabric of carbon fiber.
  • a pre-preda prepared by impregnating the above-described epoxy resin (a) as a varnish with or without a solvent into a woven fabric of carbon fiber.
  • Such prepregs can be manufactured using equipment such as a UD (unidirect) machine.
  • the content of the impregnated resin composition for a prepreg is not particularly limited as long as it is a value suitable for each application, but is 30 to 50% by mass, particularly 35 to 45% by mass in the prepreg. Preferably it is.
  • the resin composition for a pre-preda of the present invention can be an adhesive to a honeycomb core as well as a matrix resin for a pre-preda. Therefore, if the prepreg is applied as it is, it is not necessary to use another adhesive between the prepreg and the honeycomb core. This indicates that so-called cure molding, in which a prepreg is prepared using the prepreg resin composition of the present invention and curing of the prepreg itself and adhesion to the honeycomb core can be performed simultaneously.
  • any composition may be used as long as it is a non-metallic 82-cam core such as a resin-based or paper-based material.
  • a Nomex honeycomb core impregnated with is most preferred when applied to aircraft.
  • Various sizes of hexagonal pillars in the honeycomb structure of the honeycomb core can be used, but it is preferable to use a honeycomb core having a cell size of 1/8 to 38 inches. It is preferable in terms of strength and weight reduction.
  • FIG. 1 and 2 show an example of a structure in which a pre-preda and a honeycomb core are bonded, and a method of bonding the pre-preda and the honeycomb core will be described.
  • FIG. 1 is a perspective view of the structure 1.
  • FIG. 2 is a cross-sectional view of the structure 1 cut in parallel with the side surfaces of the prisms of the honeycomb core 11.
  • Part a of FIG. 2 shows a structure using a pre-preparer formed of a conventional matrix resin
  • part b shows a structure using a pre-preda using a resin composition for a pre-preda of the present invention as a matrix resin.
  • the structure 1 is obtained by bonding the pre-predator 10 and the honeycomb core 11 to each other, and the present invention is applied to one or both end faces of the end 12 of the honeycomb core having a honeycomb structure. It is produced by bonding a pre-predator 10 using the above composition as a matrix resin and heat-curing with an autoclave or the like while pressing from both ends.
  • the solid rubber and / or the thermoplastic polymer (d), preferably, propyloxy-modified (hydrogenated) acrylonitrile By containing butadiene rubber
  • d propyloxy-modified (hydrogenated) acrylonitrile
  • An appropriate amount of the resin composition for prepreg can be present in the prepreg without the resin component flowing out of the prepreg due to excessive outflow. Therefore, curing can be completed while maintaining the appropriate shape of the upper fillet 14. Also, on the lower surface, when the viscosity once decreases, the lower fillet 14 'is formed by the surface tension, and the resin composition for pre-preda is appropriately held, whereby the curing can be completed.
  • the fillet refers to the shape of the resin layer formed between the pre-preda and the honeycomb core when the pre-preda and the honeycomb core are joined and cured. (14, 14 'in Figure 2)
  • the structure of the present invention does not impair the heat resistance of the epoxy resin, and is more water-resistant than before. Also, it has excellent adhesion between the pre-preda and the honeycomb core.
  • Curing conditions at the time of bonding the honeycomb core and Puripureda is, 2 to 5 ° CZ min, at pressure 2. 5 ⁇ 4. O k gZ cm 2, 1 5 0 ⁇ 1 8 5. It is preferable to raise the temperature to C, maintain the temperature at 150 to 185 ° C for 1 to 2 hours, and then lower the temperature to room temperature in 2 to 5 ° C for Z minutes.
  • the resulting structure of the prepredder and the honeycomb core has excellent heat resistance and water resistance, and has an adhesive property between the prepredder and the honeycomb core.
  • the size of the upper fillet is preferably 400 m or more because of excellent adhesion between the pre-preda and the honeycomb core.
  • the raw material components were mixed at the ratios (parts by mass) shown in Table 1 below, or various dalton type mixers were used to produce various pre-preda resin compositions.
  • each composition was heated at a minute and cured at 180 ° C for 2 hours, and the cured product obtained was cut into a 5 x 5 x 15 mm rod shape.
  • the inflection point of the curve obtained by measuring the sample obtained under the conditions of a heating rate of 10 ° CZ and a load of 100 g using the penetration method of a thermomechanical analyzer (TMA) is used as the glass transition point (Tg).
  • TMA thermomechanical analyzer
  • the cured product cured at 180 ° C for 2 hours was immersed in warm water at 93 ° C for 14 days, and immediately after being taken out, the glass transition point (Tg) was determined using the above-mentioned (1) for the Venetration by TMA. )). In this measurement, if the glass transition point is less than 165 ° C, it is not suitable for use after water resistance. (3) Pre-preda moldability
  • the prepredder prepared in (3) above was joined to both cross sections of a Nomex honeycomb core manufactured by Showa Aircraft Co., Ltd., exhibiting a honeycomb pattern, pre-assembled by the vacuum back method, and then heated to 2 ° CZ by autoclave.
  • the temperature was raised to 180 ° C. at a molding pressure of S kgZcm 2 and then kept at 180 ° C. for 2 hours to obtain a test piece.
  • the obtained test piece was cut parallel to the prism of the honeycomb core, and a case where fillets of 400 m or more were formed at the top and bottom of both ends of the honeycomb core was evaluated as “ ⁇ ”, and a fillet was formed below 400 m. If the fillet was not filled or had a fillet biased only on the lower surface, it was evaluated as “X”.
  • the prepredder prepared in (3) was joined to both cross sections of the Nomex honeycomb core manufactured by Showa Aircraft Co., Ltd., which had a honeycomb-like pattern, and pre-assembled by the vacuum back method.
  • the temperature was raised to 180 ° C at a temperature rising rate of 2 ° C / min and a molding pressure of 3 kg / cm 2 , and then kept at 180 ° C for 2 hours to obtain a test piece.
  • the obtained test piece was cut parallel to the prism of the 82 cam core, and the fillet size of the fillet (upper fillet) formed at the upper end of the 82 cam core was measured.
  • Epoxy resin> 'ELM-434 Daricidylamine type epoxy resin of the above formula (2) manufactured by Sumitomo Chemical Co., Ltd. (epoxy equivalent: 120)
  • HP-7200 Epoxy resin having a dicyclopentene group manufactured by Dainippon Ink and Chemicals, Inc. (epoxy equivalent 250-280)
  • EP-154 Phenol-nopolak type epoxy resin manufactured by Yuka Shell Chemical (epoxy equivalent 180)
  • YD-128 Bisphenol A type epoxy resin manufactured by Toto Kasei (epoxy equivalent 190)
  • DDS 4,4,1-diaminodiphenyl sulfone manufactured by Sumitomo Chemical Co., Ltd.
  • BF 3 / MEA Boron trifluoride monoethylamine, manufactured by Stella Chemifa DI CY-15: Dicyandiamide manufactured by Yuka Shell Chemical
  • DCMU-99 3- (3,4-dichlorophenyl) 1-1,1-dimethylperyl manufactured by Hodogaya Chemical Co., Ltd.
  • N ipo 1— 1041 Acrylonitrile butadiene rubber manufactured by Zeon Corporation
  • N ip 01-1072 Carboxy-modified acrylonitrile rubber manufactured by Zeon Corporation ⁇ Thermoplastic polymer>
  • the resin composition for prepreg of the present invention that satisfies the relationship represented by the above formula (1) has excellent prepreg moldability and fillet moldability, and furthermore, the upper fillet 1, It has been found that the size of 400 m or more results in excellent adhesion to the honeycomb core.
  • the resin composition for a prepreg of the present invention can maintain the heat resistance and water resistance of the resin.
  • the prepreg using the resin composition for a prepreg has excellent adhesiveness with a honeycomb core, and has excellent adhesion to a honeycomb core. This is useful because a sufficiently large fillet can be formed between them.
  • the pre-preda can be provided with cocurability, which is useful because it exhibits flow control properties.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention se rapporte à la résolution du rapport entre la moulabilité de congés et la viscosité complexe d'une résine. Elle concerne une composition de résine pour préimprégnés présentant d'excellentes caractéristiques de résistance thermique, de résistance à l'eau, de régulation de l'écoulement et d'adhérence aux noyaux alvéolaires, et une structure obtenue par liaison des préimprégnés formés avec cette composition de résine sur une âme en nid d'abeilles. Cette composition de résine pour préimprégnés contient (a) une résine époxyde, (b) une amine aromatique, (c) au moins un élément choisi dans le groupe constitué par les catalyseurs imidazole, les catalyseurs au trifluorure de bore/sel d'amine, et le dicyandiamide, et (d) un caoutchouc solide et/ou un polymère thermoplastique. La proportion de caoutchouc solide et/ou de polymère thermoplastique (d) est comprise entre 1 et 10 parties en poids, à l'exclusion de 10 parties en poids, pour 100 parties en poids de résine époxyde (a), et la viscosité complexe θ de la composition de résine mesurée à une fréquence de 0,02 Hz, obéit à une relation donnée.
PCT/JP2004/006126 2003-04-28 2004-04-28 Composition de resine pour preimpregne Ceased WO2004096885A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2307136C1 (ru) * 2006-03-01 2007-09-27 Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") Эпоксидное связующее, препрег на его основе и изделие, выполненное из препрега
WO2017222339A1 (fr) * 2016-06-24 2017-12-28 에스케이케미칼주식회사 Composition de résine époxyde pour matériau composite renforcé par des fibres, et préimprégné l'utilisant
EP3623406A4 (fr) * 2017-05-10 2020-12-16 Toray Industries, Inc. Composition de résine époxyde, préimprégné, matériau composite renforcé de fibres et procédé de production associé

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JP2016210860A (ja) * 2015-05-01 2016-12-15 三菱レイヨン株式会社 エポキシ樹脂組成物および繊維強化複合材料用プリプレグ
KR20180001487A (ko) * 2016-06-24 2018-01-04 에스케이디스커버리 주식회사 섬유강화 복합재료용 에폭시 수지 조성물 및 이를 이용한 프리프레그
JP7028276B2 (ja) * 2020-04-15 2022-03-02 横浜ゴム株式会社 繊維強化複合材料用エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0625446A (ja) * 1992-03-02 1994-02-01 Toray Ind Inc クロスプリプレグおよびその製造法
JPH06345884A (ja) * 1993-06-10 1994-12-20 Toray Ind Inc ヤーンプリプレグ用エポキシ樹脂組成物およびヤーンプリプレグ
JPH09132636A (ja) * 1995-11-09 1997-05-20 Yokohama Rubber Co Ltd:The エポキシ樹脂組成物
JPH09143249A (ja) * 1995-11-24 1997-06-03 Yokohama Rubber Co Ltd:The エポキシ樹脂組成物
JP2001031838A (ja) * 1999-07-22 2001-02-06 Toho Rayon Co Ltd 自己接着性表面材用エポキシ樹脂組成物及びプリプレグ
JP2002194054A (ja) * 2000-12-27 2002-07-10 Yokohama Rubber Co Ltd:The エポキシ樹脂組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0625446A (ja) * 1992-03-02 1994-02-01 Toray Ind Inc クロスプリプレグおよびその製造法
JPH06345884A (ja) * 1993-06-10 1994-12-20 Toray Ind Inc ヤーンプリプレグ用エポキシ樹脂組成物およびヤーンプリプレグ
JPH09132636A (ja) * 1995-11-09 1997-05-20 Yokohama Rubber Co Ltd:The エポキシ樹脂組成物
JPH09143249A (ja) * 1995-11-24 1997-06-03 Yokohama Rubber Co Ltd:The エポキシ樹脂組成物
JP2001031838A (ja) * 1999-07-22 2001-02-06 Toho Rayon Co Ltd 自己接着性表面材用エポキシ樹脂組成物及びプリプレグ
JP2002194054A (ja) * 2000-12-27 2002-07-10 Yokohama Rubber Co Ltd:The エポキシ樹脂組成物

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2307136C1 (ru) * 2006-03-01 2007-09-27 Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") Эпоксидное связующее, препрег на его основе и изделие, выполненное из препрега
WO2017222339A1 (fr) * 2016-06-24 2017-12-28 에스케이케미칼주식회사 Composition de résine époxyde pour matériau composite renforcé par des fibres, et préimprégné l'utilisant
EP3623406A4 (fr) * 2017-05-10 2020-12-16 Toray Industries, Inc. Composition de résine époxyde, préimprégné, matériau composite renforcé de fibres et procédé de production associé

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