WO2017222339A1 - Composition de résine époxyde pour matériau composite renforcé par des fibres, et préimprégné l'utilisant - Google Patents

Composition de résine époxyde pour matériau composite renforcé par des fibres, et préimprégné l'utilisant Download PDF

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Publication number
WO2017222339A1
WO2017222339A1 PCT/KR2017/006658 KR2017006658W WO2017222339A1 WO 2017222339 A1 WO2017222339 A1 WO 2017222339A1 KR 2017006658 W KR2017006658 W KR 2017006658W WO 2017222339 A1 WO2017222339 A1 WO 2017222339A1
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Prior art keywords
epoxy resin
prepreg
component
resin composition
formula
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PCT/KR2017/006658
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English (en)
Korean (ko)
Inventor
이재원
정훈희
김현석
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에스케이케미칼주식회사
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Priority to CN201780034156.3A priority Critical patent/CN109312057B/zh
Priority claimed from KR1020170079636A external-priority patent/KR20180001487A/ko
Publication of WO2017222339A1 publication Critical patent/WO2017222339A1/fr

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    • 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
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • 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
    • C08L63/06—Triglycidylisocyanurates

Definitions

  • the present invention relates to an epoxy resin composition suitable for mass production of fiber reinforced composites and a prepreg using the same.
  • Fiber-reinforced composites have high specific strength and inelasticity, so they are widely used in sports leisure applications, aviation applications, automotive and railway applications, electronics applications, and general industrial applications.
  • molding methods such as filament winding, infusion, res in transfer molding, pultrusion, and press are applied.
  • molding methods such as autoclave, vacuum bag, sheet winding, and bladder molding are used in the preprep, an intermediate product in which matrix resin is impregnated with reinforcing fibers. He is being applied.
  • the prepreg is cut, the prepreg is laminated on a mold of a desired shape, and then vacuum-backed, followed by heat curing for several hours. It takes a long process time, and is not suitable for mass production, but also has the disadvantage of requiring expensive autoclave equipment investment.
  • a press molding method which does not need a vacuum bag operation and can be automated is preferable.
  • the press molding method does not require expensive equipment such as an autoclave, and it is possible to utilize a press equipment that is commonly used.
  • Curing time of 1 hour to 3 hours is required at a temperature of 125 ° C to 175 ° C.
  • the flow of resin is rapidly increased during press molding, causing defects on the surface or inside of the molded article, or the straightness of the fiber. Defects such as disturbing will occur /
  • the storage stability of the prepreg may decrease rapidly.
  • the physical properties are lowered and the physical properties of the finally molded fiber reinforced composites are lowered.
  • the present invention is excellent in workability and storage stability required as a prepreg, heat curing within a few minutes to be suitable for mass production, the resin flow control is adjusted during press molding does not cause defects inside and outside the molded article It is to provide a resin composition and a prepreg using the same.
  • the present invention also provides a method for producing a fiber-reinforced composite using the prepreg.
  • the present invention provides an epoxy resin composition comprising the following components (A), (B), (C), and (D).
  • Component (A) may be composed of 50 to 100 parts by weight of the tetrafunctional glycidyl amine type epoxy resin with respect to 100 parts by weight of the bifunctional BPA type epoxy resin.
  • Dicyandiamide of component (B) is used as an epoxy hardening
  • the content of dicyandiamide may be used so that the ratio of active hydrogen equivalent of dicyandiamide to the average equivalent of component (A) epoxy resin is 30% to 80%.
  • Component (C) comprises 40% to 60% of an aliphatic tertiary amine air duct latent curing agent by weight, formula (1), (2), or an imidazole represented by the formula (3) coming from "60% to 40% It can be a complex mixture, including.
  • the aliphatic tertiary amine adduct type latent curing agent has an effect of lowering the temperature at which the curing reaction is initiated, and the imidazole represented by Formula 1, Formula 2, or Formula 3 increases the rate of the disclosed curing reaction within minutes.
  • the curing reaction can be completed so that the combined use of these can satisfy the fast curing property with excellent storage stability.
  • Component (D) is a polyvinyl acetal resin containing a carboxyl group as a thermoplastic polymer, which may be included in 3 to 10 parts by weight based on 100 parts by weight of component (A). This invention also provides the prepreg manufactured using the epoxy resin composition.
  • the invention also provides a method for producing a fiber-reinforced composite material to press molding for 2 to 5 minutes the prepreg in the mold of 140 ° C to 160 ° C.
  • the present invention by optimizing the components and composition of the epoxy resin, the curing agent, the curing agent, the thermoplastic resin, etc. in the epoxy resin composition, excellent storage stability at room temperature, heat curing within a few minutes to be suitable for mass production, press
  • the resin flowability during molding may be adjusted to provide a prepreg in which defects do not occur inside or outside the molded article.
  • the prepreg using the epoxy resin composition of the present invention is cured at least 90% within 3 minutes at a temperature of 150 ° C, exhibits a glass transition temperature (T g ) of more than 140 ° C, viscosity and tackiness for 1 month or more at room temperature (Tacky) It has storage stability without change.
  • T g glass transition temperature
  • Tacky room temperature
  • it even under press molding conditions with a pressure of 10 kgf / cm 2 , it exhibits moderate resin flowability, which does not cause surface and internal defects, and minimizes bleeding of the resin near the edge of the molded product. Can be used as a leg.
  • FIG. 1 is a photomicrograph of a cross section of a central portion of a carbon fiber composite prepared according to Example 1.
  • FIG. 2 is a photomicrograph of a cross section of a central portion of a carbon fiber composite prepared according to Comparative Example 2.
  • FIG. 3 is a photomicrograph of a cross section of a central portion of a carbon fiber composite prepared according to Comparative Example 4.
  • FIG. 3 is a photomicrograph of a cross section of a central portion of a carbon fiber composite prepared according to Comparative Example 4.
  • Figure 4 is a graph measuring the degree of cure of the prepreg prepared according to Example 1, Comparative Example 5, Comparative Example 6
  • Comparative Example 6 When using only aliphatic tertiary amine adduct type latent curing agent (Amine adduct), Comparative example 5: using only imidazole Case (Imidazole),
  • Example 1 When an aliphatic tertiary amine adduct latent hardener is mixed with imidazole (Amine adduct + Imi dazole), TemP: the actual temperature at which the actual prepreg is heated to heat. [Specific contents to carry out invention]
  • first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.
  • the curing degree is 90% or more or 91% or more, preferably 93% or more or 95% or more when press-molded using a 150 r mold for 3 minutes, fiber reinforced
  • the glass transition temperature (T g ) of the composite molded article is at least 140 ° C or at least 141 ° C, preferably at least 143 ° C or at least 147 ° C. It provides to the epoxy resin composition which can obtain favorable quality without an external defect, and the prepreg manufacturing method using the same.
  • an epoxy resin composition comprising the following components (A), (B), (C), and (D) is provided.
  • Component (A) gives semi-astringent, adhesive property to a resin composition, and after hardening It provides heat resistance, toughness, chemical resistance, etc. to a resin composition.
  • Examples of the epoxy resin applicable to the prepreg include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenyl epoxy resins, novolak type epoxy resins, naphthalene type epoxy resins, and glycidyl ester types.
  • Epoxy resin, glycidyl amine type epoxy resin, polycyclopentadiene type epoxy resin, alicyclic epoxy resin, etc. are mentioned, The epoxy resin etc. which modified these are mentioned.
  • Epoxy resins of bifunctional group have excellent toughness but low heat resistance, and epoxy resins of more than 3 functional groups have high heat resistance due to high crosslinking density, low toughness, and deformation due to high shrinkage during curing. This is more likely to occur. Therefore, it is preferable to use a bifunctional bisphenol A epoxy and a trifunctional or higher epoxy resin in combination, and the epoxy having a trifunctional or higher functional group is a glycidyl amine epoxy resin having a tetrafunctional group in consideration of the curing rate, heat resistance and viscosity. Should be used.
  • the epoxy resin composition of this invention contains the mixture of such bifunctional bisphenol A epoxy resin (bifunctional BPA type epoxy resin) and glycidyl amine type epoxy resin as (A) component.
  • Component (A) is based on 100 parts by weight of the bifunctional BPA epoxy resin.
  • T g glass transition temperature
  • the component of the tetrafunctional glycidyl amine-type epoxy resin exceeds 100 parts by weight based on the difunctional BPA-type epoxy resin increase, the resin ' flowability is excessively increased during press molding and the adhesion of the surface of the prepreg ( Tacky) can be excessively high.
  • the difunctional BPA-type epoxy resin can be classified into liquid, semi-solid, solid, etc. according to the equivalent weight and molecular weight, of which solid-state BPA-type epoxy
  • the use of the resin in an amount of 2 to 30% or more by weight is preferable in view of ensuring proper viscosity and tackiness for prepreg production.
  • Tetraglycidyl diamino diphenyl methane tetraglycidyl diamino diphenyl ether
  • tetraglycidyl diamino diphenylamide tetraglycidyl xylenediamine And halogen substituted products thereof, hydrogenated products thereof, and the like, and one or more thereof
  • Tetraglycidyldiaminodiphenyl methane and the like are preferable in view of the thickening, heat resistance and compatibility with the BPA type epoxy.
  • Examples of commercially available products relating to tetraglycidyl diaminodiphenyl methane include ELM434 from Sumitomo Chemical, Nippon Steel Chemical Company ⁇ YH434L, JER 604 from Mitsubishi Chemical Corporation, Araldite MY9655, MY720, etc., from Huntsman Advanced Materials. Can be mentioned.
  • dicyandiamide is used as a curing agent, in which case the epoxy resin composition has excellent storage stability, and the cured epoxy resin composition has high heat resistance.
  • the content of dicyandiamide may be 3 to 8 parts by weight based on 100 parts by weight of component (A). This can be used so that the ratio of the active hydrogen equivalent of dicyandiamide to the average equivalent of the mixed epoxy resin (A) component is 30% to 80%.
  • the epoxy of component (A) may not participate in the curing reaction, and thus, the heat resistance and mechanical properties of the cured product may be deteriorated.
  • the amount of the cyan die die amide exceeds 8 weight parts, or more than equivalent weight ratio is "80%, fragile and easily becomes high as the cured brittle over, there is a fear that the heat resistance decreases.
  • Examples of commercially available products related to these dicyandiamides include Dicy-7 and Dicy-15 from Mitusbishi Chemical, Dyhard 100S and 100SF from Alzchem, CG1400 from Air product, DDA5 from CVC Thermoset Specialties.
  • an aliphatic tertiary amine adduct type latent curing agent and an imidazole having a structure of Formula (1), (2) or (3) are used in combination. Used as a curing accelerator to promote the reaction of epoxy resin and curing agent.
  • the aliphatic tertiary amine adduct type latent curing agent is a reactant obtained by polymerizing an amine compound, such as a tertiary amine compound, with an epoxy compound, an isocyanate compound, etc., and may be in the form of finely divided powder. It exhibits a low solubility in the epoxy resin at room temperature, but when heated, reacts with the epoxy resin from the surface of the particles to dissolve and causes uniform curing reaction.
  • the aliphatic tertiary amine air duct latent curing agent is cured while it is banung this is the start lowering the temperature at which the effect of the curing accelerator acts to be a curing reaction starts at temperatures above 100 ° C, of less than 80 ° C In silver road, hardening reaction does not occur and shows high storage stability.
  • the aliphatic tertiary amine adduct type latent curing agent of the present invention using aliphatic tertiary amine has a low calorific value during curing and excellent storage stability.
  • the resin composition is cured, its color is relatively transparent.
  • the amount of heat generated during curing is large, there is a possibility that the cured product may deteriorate, and in order to secure the appearance quality, the cured product may be transparent. This appearance quality is a very important characteristic in terms of aesthetics of the user, unless a separate color coating.
  • the fiber reinforced composite material when used as an exterior part such as an automobile, and a separate colored coating is not applied, the woven form of the fiber is exposed to the outside, and when the resin composition is cured, the surface becomes cloudy or cloudy.
  • the problem is that the aesthetic function is significantly degraded.
  • the imidazole represented by Formula 1, Formula 2, or Formula 3 maintains a high storage stability at temperatures below 80 ° C., but at a high temperature above 130 ° C., the rate of curing reaction is very fast and the T g of the cured product is high. have.
  • aliphatic tertiary amine adduct type latent curing agents in combination with 60% to 40% of imidazole represented by the formula (1), (2) or (3).
  • the aliphatic tertiary amine adduct type latent curing agent and the formula (1), (2) or (3) can be used in mixture of 4 to 55%, respectively.
  • the aliphatic tertiary amine adduct type latent curing agent and the imidazole of Formula 1, Formula 2, or Formula 3 are used in combination, the aliphatic tertiary amine adduct type in the process of raising the temperature to the press molding temperature
  • the curing reaction is initiated by the effect of the latent curing agent, and after reaching the press molding temperature, the rapid curing reaction proceeds and is completed by the effect according to the imidazole of Formula 1, Formula 2, or Formula 3 and stored. It is possible to satisfy both stability and fast curing.
  • the aliphatic tertiary amine adduct type latent curing agent may be prepared by reacting an aliphatic tertiary amine compound with an epoxy compound or an isocyanate compound as described above.
  • aliphatic tertiary amines used in such aliphatic tertiary amine adduct type latent curing agents include diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclonuxylamine, And 4,4'-diamino-dicyclonucleomethane and the like
  • examples of the epoxy compound include 1, 2-epoxybutane, 1, 2-epoxynucleic acid, 1, 2-epoxyoctane, styrene oxide and n -butylglycol.
  • Cylyl ether nucleosilglycidyl ether, phenylglycidyl ether, glycidyl acetate and the like.
  • the amine adduct type latent hardener made by Ajinomoto Fine Techno Co., Ltd. (trade name: Amicure MY-24, MY-H), a latent hardener made by T & K TOKA (brand name: Fujicure FXR-1020, FXR-1030) etc.
  • T & K TOKA brand name: Fujicure FXR-1020, FXR-1030
  • the imidazole used as a curing accelerator together with an aliphatic tertiary amine adduct type latent curing agent is 4'hydroxymethyl-5-methyl-2- Phenylimidazole (4-hydroxymethyl-5-methyl-2-phenyl imidazole, 2P4MHZ) and 2,4-diamino-6- [2'-methylimidazoli- (1 ')]-ethyl -3_ triazine isocyanuric acid adduct dihydrate (2,4-diamino_6- [2'-methylimidazol i ⁇ ( ⁇ )] _ ethyl ⁇ s ⁇ triazine isocyanuric adic adduct dehydrate, 2MA-0K), Formula 3 2-phenyl-4,5-dihydroxymethyl imidazole of (2-phenyl-4,5-dihydroxymethyl imidazole, 2PHZ) is preferable in terms of curing rate and storage stability. As these commercial items,
  • the present invention is a component '(C) by using a mixture of an aliphatic tertiary amine adduct type latent curing agent and imidazole having a structure of Formula 1, Formula 2, or Formula 3, to increase the reaction speed and the prepreg molding process time At the same time, the stability of the room temperature is significantly improved, and the mass production process is effectively performed. This is because the urea-based or imida (1 ⁇ (132016; 2MI, 2E4MI, 2P4MI, 2PI, etc.) curing accelerators known in the related art are used alone or at room temperature storage stability when using a compound having a sulfur atom epoxy alone. This remarkably falling problem can be clearly solved.
  • thermoplastic polymer having a hydrogen bond functional group that can be dissolved in an epoxy resin is used as the component (D).
  • the thermoplastic polymer may be dissolved in an epoxy resin, thereby improving the interfacial adhesion between the resin and the reinforcing fiber, thereby increasing the toughness and mechanical properties of the fiber reinforced composite material.
  • the flowability of the resin at high temperature and high pressure during press molding is reduced.
  • Thermoplastic polymers having a hydrogen bond functional group include those having a hydroxyl group, an amide group, and a sulfonyl group.
  • thermoplastic resins having hydroxyl groups include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol and phenoxy resins.
  • thermoplastic resins having amide bonds include polyamides, polyimides and polyvinyl pyridones.
  • An example of a thermoplastic resin having sulfonyl groups is polysulfone.
  • Polyamides, polyimides and polysulfones may have functional groups such as ether bonds and carbonyl groups in their backbone.
  • Polyamide is the nitrogen atom of the amide group It may have a substituent on the phase.
  • thermoplastic resin having a hydrogen bonding functional group that can be dissolved in an epoxy resin is polyvinyl acetal resin.
  • the grade containing a carboxyl group is especially preferable in the polyvinyl acetal resin which has a hydroxyl group, and it is preferable to contain this at 3-10 weight part with respect to 100 weight part of component (A).
  • the thermoplastic polymer of the component (D) controls the resin flowability during press molding, and when the content is less than 3 parts by weight, there is no effect of reducing the resin flowability, and the straightness of the fibers on the surface during the press molding is disturbed and near the edges. Resin and bleeding may become excessive. In addition, even inside the molded article, it is possible to generate voids so that the resin is rapidly pulled out before the resin is cured.
  • the content of the component (D) is included in excess of 10 parts by weight, the flowability of the resin is very small, and voids are not removed sufficiently during press molding, and when dissolved in an epoxy resin, the viscosity becomes very high, and thus prepreg production is performed. It can be difficult.
  • Epoxy resin composition of the present invention using a Brookfield viscometer (e.g., CAP-2000), the viscosity set at 80 ° C. can be 15,000 to 30,000 cps black silver 18,000 to 28,000 cps, to prepare a hot melt prepreg Suitable viscosity ranges can be.
  • the epoxy resin composition is 40 ° C. When stored for a long time under constant temperature conditions, even if more than 30 days or more than 40 days elapses, the viscosity is maintained at less than twice the initial viscosity and can exhibit excellent storage stability.
  • the epoxy resin composition of the present invention is used as a matrix resin for the production of hot melt prepreg without a solvent, it is prepared by the following method.
  • component (A), component (B), and component (E) were put into a container, and stirred for several hours at a temperature of 80 ° C to 180 ° C to prepare a base resin in which component (E) was dissolved in an epoxy resin. do.
  • the base resin is cooled to 60 ° C. to 90 ° C.
  • the components (C) and (D) are stirred together with the curing agent paste in which a part of the component (A) is dispersed.
  • an epoxy resin composition having excellent storage stability can be obtained.
  • a prepreg prepared using the epoxy resin composition as described above.
  • the prepreg can be obtained by impregnating the reinforcing fibers in the epoxy resin composition, and methods of impregnating the prepreg include a dry method (hot melt method) and a wet method (solution method).
  • the wet method is a method in which a prepreg is prepared by immersing reinforcing fibers in an epoxy resin composition solution in which an epoxy resin composition is dissolved in a ketone or alcohol solvent, and then passing through a drying furnace to remove the solvent.
  • the prepreg of the present invention can be produced by applying a hot melt method, which is a dry method, using the epoxy resin composition, and an example of the hot melt method may be mentioned as follows.
  • Hot-melt method has the advantage that can be prepared prepreg containing no residual solvent.
  • the coating method comma coating, roll coating, slot die coating, or the like can be used.
  • carbon fibers such as tow (Tow), continuous fibers such as fabric (Fabr ic), chopped / long fibers (Chopped Fiber), mat
  • tow tow
  • Fabr ic continuous fibers
  • chopped Fiber chopped Fiber
  • carbon fibers or abrasion fibers are preferred because they exhibit excellent specific strength and inelasticity, which can result in light weight properties of fiber-reinforced composites.
  • the fiber content (FAW, Fiber Areal Weight) per unit area of the prepreg is suitable from 50 to 300 g / m 2 . If the FAW is less than 50 g / ra 2 , the work time and cost increase because the number of prepreg stacks is increased to produce molded articles of desired thickness. If the FAW is 300 g / m 2 or more, the drape of the prepreg may be deteriorated, which may be unsuitable for the manufacture of a molded article having a complex shape including a curved surface, and the thickness of the prepreg cross section may increase, making it difficult to impregnate completely.
  • the resin content (RC, Res in Content) in the prepreg is suitable from 25% to 35%.
  • the RC is less than 25%, there is a possibility that the reinforcing fibers are not completely impregnated in the resin and voids remain in the prepreg production. In addition, the fiber is exposed to the surface after molding, it is difficult to ensure excellent surface quality. When RC is more than 35%, the fiber content is relatively low, which lowers the mechanical strength such as specific strength and inelasticity.In addition, the excess resin flows during press molding, which disturbs the arrangement of fibers and near the edge of the molded product. This may cause problems such as resin leaking out.
  • the resin flow to the prepreg prepared using the epoxy composition of the present invention within 12%, preferably within 11% within 5% or less than 6% to 11%, or less than 10% or less than 10% 10% can be exhibited, and it can maintain a favorable state with the appearance that the fiber is not disturbed and resin bleeding to an edge.
  • the resin flow rate of the prepreg is higher than 12%, the straightness of the fiber is disturbed due to the pressure, and the mechanical properties are reduced.
  • the fibers are pulled together (Bl eeding) and the desired product thickness cannot be achieved. This can cause many problems, such as the need for further trimming.
  • more than 6% may be good in terms of removing voids inside the product.
  • Such resin flowability can be derived by measuring the initial weight Wi and the post-molding weight W f under normal press molding conditions, and calculating it according to the following formula (1).
  • Resin Flowability (%) [(W,-W f ) / Wi] x 100
  • Wi shows the initial weight (Wi) measured by laminating four layers of prepregs having a size of 300 mm x 300 mm before press forming.
  • W f is press-molded for 3 minutes at a temperature of 150 ° C and pressure of 10 kgf / cm 2 using a flat tube mold to produce a carbon fiber-reinforced composite. It shows the measured weight (w f ) by processing the initial weight (Wi) to the same size as the measurement.
  • the 'gel time (Gel t ime) measured under conditions of a press-molding temperature of 150 ° C in accordance with the American Society for Testing and Materials method ASTM D 3532 with respect to the prepreg is from about 75 seconds within black is from about 30 seconds to about 75 seconds, Preferably, within about 63 seconds, the black may be about 30 seconds to about 63 seconds, more preferably about 53 seconds or about 30 seconds to about 53 seconds.
  • the gel time (Gel t ime) is the time until the flow of the resin decreases rapidly and the curing reaction proceeds rapidly, that is, the storage modulus of the resin is lost due to the progress of the curing reaction. It means the time it takes to get bigger than).
  • the prepreg prepared using the epoxy composition of the present invention may exhibit a significantly shorter gel time than the conventional one, and thus may be molded in a short time to be suitable for mass production due to a high degree of curing in a certain time and a fast reaction speed. Can be.
  • a method for producing a fiber-reinforced composite using the prepreg as described above a method of manufacturing a part using a prepreg may be applied to any type of molding method such as an existing autoclave, vacuum bag, press molding, but in particular press molding. Through this, it is possible to manufacture a fiber reinforced composite having high productivity and excellent surface quality.
  • the present invention may be prepared by preparing a prepreg using the epoxy resin composition, and press-molded it for 2 to 5 minutes in a mold at a temperature of 140 to 160 ° C, wherein the pressure conditions are 5 to 10 kgf / cm 2 can be applied.
  • the glass fiber-reinforced composite transition low temperature press molding temperature or more than 20 ° C than the temperature in the mold to remove a molded fiber-reinforced composite material from the mold, so components can result in failure to be bent or deformed, pressed at 150 ° C
  • the glass transition temperature should be at least 130 ° C.
  • An epoxy resin composition was prepared at a blending ratio as shown in Table 1 below.
  • the epoxy resin in the component (A) and the thermoplastic resin of the component (D) were weighed and introduced into a glass flask, followed by stirring at 150 ° C. for 2 hours or more to prepare a base resin in which the thermoplastic resin of the component (D) was completely dissolved. It was.
  • 12 phr of EP0N 828, a liquid bisphenol A epoxy resin, and (B) and (C) in the component (A) were weighed and mixed, and then uniformly dispersed through 3 Rol l Mi 11 to prepare a curing agent paste. .
  • the base resin and the hardener paste were mixed at a temperature of about 80 ° C. to prepare an epoxy resin composition.
  • the epoxy resin composition thus prepared is resin basis weight using a comma coater.
  • the prepared prepreg is cut at 300 ⁇ X 300 ⁇ , cross-prepreg is laminated in the direction of the fiber, and 5 sheets are laminated in the order of lamination angle [0/90/0/90/0].
  • the resultant was placed in a mold and press-molded for 3 minutes under conditions of a temperature of 150 T and a pressure of 10 kgf / cm 2 to prepare a carbon fiber reinforced composite.
  • the epoxy resin composition was prepared in the same manner as in Examples 1 to 4, and a prepreg and a carbon fiber reinforced composite were prepared using the same.
  • the epoxy resin composition prepared was measured at 80 ° C. using a Brookfield viscometer (CAP-2000). In addition, the epoxy resin composition was stored in a 40 ° C oven (oven) and the viscosity was measured, the time (days, days) to double the initial viscosity was measured and based on this, the storage stability was evaluated.
  • CAP-2000 Brookfield viscometer
  • Gel time of the prepreg was measured by the method of ASTM D 3532. Gel time cuts the prepreg sample into a size of 6 mm 2 , puts it on a hot plate and cover glass set to a press forming temperature of 150 ° C, and then places the sample. Covered with another cover glass, stirred with a wooden stick and the gelation time was measured in seconds.
  • the heat resistance of the epoxy resin composition was measured using a differential scanning calorimetry device (DSC, Q2000, TA Instruments). First, the sample was heated to 25 ° C. to 250 ° C. at a temperature increase rate of 10 ° C./min, completely cured, cooled, and the glass transition temperature (T g ) that appeared while heating up was measured in the same manner.
  • d) degree of cure of prepreg The degree of curing of the prepreg was measured at 150 ° C isothermal conditions after the sample was heated from 25 ° C to 150 ° C at a rate of 100 ° C / min using a differential scanning calorimetry (DSC, Q2000, TA Instruments). It was. It took 1 minute to reach 150 ° C., then the degree of cure was calculated when staying at 150 ° C. for 3 minutes.
  • resin flowability DSC, Q2000, TA Instruments
  • the resin flow of the prepreg using the epoxy resin composition was measured according to the method of ASTM D 3531 of the American Society for Testing and Materials. However, in order to simulate the actual press molding conditions, the resin flowability was measured by discharging the resin from the front and rear sides of the prepreg, leaving the resin to the outside (edge), and weighing the remaining weight.
  • the prepreg was cut to 300 ⁇ X 300 ⁇ , and then the prepregs were cross-laminated in the direction of the fibers, and 4 sheets were laminated in the lamination angle [0/90/90/0], and the weight was measured. (Wi). This was placed in a flat die, press-molded for 3 minutes under the condition of temperature 150 ° C, pressure 10 kgf / cm 2 to prepare a carbon fiber reinforced composite. After removing the cured resin from the edge of the carbon fiber composite material was processed to an initial size of 300 ⁇ X 300mm (W f ) was weighed again. Resin flowability was calculated according to the following formula (1).
  • Resin Flowability (3 ⁇ 4>) [(W;-W f ) / Wi] x 100
  • Wi shows the initial weight (Wi) measured by laminating four layers of prepregs having a size of 300 mm x 300 mm before press forming.
  • the appearance of the fabricated carbon fiber composite was visually observed to observe whether the one-way carbon fiber was kept straight and undisturbed, and the color of the resin exiting the surface and the edge was observed. In addition, the center portion was cut, the cross section was observed under a microscope, and no voids (vo i d) remained inside.
  • FIGS. 1 to 3 micrographs of cross sections obtained by cutting the central portion of the carbon fiber composites prepared according to Example 1, Comparative Examples 2 and 4 are shown in FIGS. 1 to 3, respectively.
  • the carbon fiber composite of Example 1 according to the present invention can be seen that the voids (void) hardly remain inside the center portion has very excellent properties in terms of formability and mechanical properties.
  • the carbon fiber composites of Comparative Examples 2 and 4 did not optimize the flowability of the resin did not remove the voids (voi d) inside during press molding It can be confirmed directly, in this case it can be seen that very poor in terms of formability and mechanical properties.
  • FIG. 1 the carbon fiber composite of Example 1 according to the present invention can be seen that the voids (void) hardly remain inside the center portion has very excellent properties in terms of formability and mechanical properties.
  • the carbon fiber composites of Comparative Examples 2 and 4 did not optimize the flowability of the resin did not remove the voids (voi d) inside during press molding It can be confirmed directly, in this case it can be
  • Temp shown in FIG. 4 means an actual temperature at which the actual prepreg is heated by receiving heat, and in about 1 minute, the temperature is raised from room temperature to 150 ° C under actual molding conditions or curing degree measurement conditions. This means that after 3 minutes after the temperature rise, the degree of curing is shown.
  • Example 4 in the case of Example 1 in which an aliphatic tertiary amine adduct-type latent hardener and imidazole are mixed according to the present invention, based on a molding time of 2 to 3 minutes (X-axis) (Amine It can be seen that the degree of curing (y-axis, convers ion) is the highest in adduct + imidazo), which is suitable for mass production using presses. In addition, at least 80% of this degree of conv. It can be said that the mold can be demoulded in the press mold, and in the case of Example 1, the curing degree is achieved by 80% or more before 2 minutes 30 seconds has elapsed, and thus it can be seen that it is very suitable for mass production.
  • the viscosity of the epoxy resin composition obtained in Examples 1 to 4 is 15, 000 to 30, 000 cps (at 80 ° C), a viscosity range suitable for the production of hot melt prepreg ,
  • the storage time at 40 ° C was increased to twice the initial viscosity time was more than 30 days was excellent storage stability.
  • it exhibited a curing degree of 90% or more in the curing time of 3 minutes at 150 ° C to implement fast curing suitable for mass production, the glass transition temperature after curing showed a high heat resistance of 140 ° C or more.
  • the resin flowability through the above press molding conditions was within 10%, so that the appearance was maintained in a good state with little fiber bleeding and resin bleeding to the edges.
  • both prepreg and gel time (Gel t ime) prepared using the epoxy resin composition of Examples 1 to 4 were short within 53 seconds, thereby high curing rate within a certain time and fast reaction rate for mass production. It can be seen that molding is possible within a suitable short time.
  • Comparative Examples 1 and 2 by using only conventionally known urea-based or imidazole-type curing accelerators, the storage stability of the epoxy resin composition is not good, and it is not completely cured under the above press molding conditions. I could't.
  • the glass transition temperature was less than 140 ° C, causing deformation of the molded article when demolding.
  • Comparative Example 3 does not use a glycidyl amine-type epoxy resin, the reaction rate is slow, it can be seen that the gel time is long, the heat resistance (T g ) is low.
  • Comparative Example 4 the flow of the resin was very high due to the change of the thermoplastic resin, resulting in fiber disturbance on the surface, excessive resin bleeding to the edges, and voids were not removed inside.
  • Comparative Example 5 when using only the imidazole compound of Formula 1 alone as in Comparative Example 5, not only high molding temperature of 160 ° C or more, but also room temperature storage stability is lowered, there is a problem that can not be used as a prepreg.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

La présente invention concerne une composition de résine époxyde appropriée pour la production en masse d'un composite renforcé par des fibres, et un préimprégné l'utilisant. La composition de résine époxyde comprend : un constituant (A), qui est un mélange d'une résine époxyde de type BPA difonctionnelle et d'une résine époxyde de type glycidylamine tétrafonctionnelle ; un constituant (B), qui est un dicyandiamide en tant qu'agent de durcissement de résine époxyde ; un constituant (C), qui est, en tant qu'accélérateur de durcissement, un mélange d'un agent de durcissement latent de type produit d'addition d'amine tertiaire aliphatique et d'amidazole ; et un constituant (D), qui est une résine de poly(acétal de vinyle) ayant un groupe carboxyle comme polymère thermoplastique. Selon la présente invention, un préimprégné est décrit qui présente une excellente stabilité au stockage à température ambiante, peut être thermodurci en plusieurs minutes de façon à convenir pour une production en masse, et ne génère pas de défauts à l'intérieur et à l'extérieur d'un produit moulé, étant donné que l'aptitude à l'écoulement de la résine est régulée pendant le moulage à la presse.
PCT/KR2017/006658 2016-06-24 2017-06-23 Composition de résine époxyde pour matériau composite renforcé par des fibres, et préimprégné l'utilisant WO2017222339A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111138636A (zh) * 2019-12-31 2020-05-12 浙江华正新材料股份有限公司 一种树脂组合物、预浸料及层压板
CN114015197A (zh) * 2021-11-19 2022-02-08 中航复合材料有限责任公司 一种适用于非热压罐成型的基体树脂及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05230185A (ja) * 1991-10-29 1993-09-07 Kobe Steel Ltd 可撓性に優れた電気絶縁性複合シート材料
JPH0641396A (ja) * 1992-07-24 1994-02-15 Toray Ind Inc エポキシ樹脂組成物
WO2004096885A1 (fr) * 2003-04-28 2004-11-11 The Yokohama Rubber Co. Ltd. Composition de resine pour preimpregne
JP2006160953A (ja) * 2004-12-09 2006-06-22 Sekisui Chem Co Ltd エポキシ系硬化性組成物及び電子部品
JP2010202862A (ja) * 2009-02-05 2010-09-16 Chisso Corp エポキシ樹脂組成物、およびその硬化物
KR20150104120A (ko) * 2013-01-07 2015-09-14 도레이 카부시키가이샤 에폭시 수지 조성물, 프리프레그, 섬유 강화 플라스틱 물질, 및 섬유 강화 플라스틱 물질 제조 방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05230185A (ja) * 1991-10-29 1993-09-07 Kobe Steel Ltd 可撓性に優れた電気絶縁性複合シート材料
JPH0641396A (ja) * 1992-07-24 1994-02-15 Toray Ind Inc エポキシ樹脂組成物
WO2004096885A1 (fr) * 2003-04-28 2004-11-11 The Yokohama Rubber Co. Ltd. Composition de resine pour preimpregne
JP2006160953A (ja) * 2004-12-09 2006-06-22 Sekisui Chem Co Ltd エポキシ系硬化性組成物及び電子部品
JP2010202862A (ja) * 2009-02-05 2010-09-16 Chisso Corp エポキシ樹脂組成物、およびその硬化物
KR20150104120A (ko) * 2013-01-07 2015-09-14 도레이 카부시키가이샤 에폭시 수지 조성물, 프리프레그, 섬유 강화 플라스틱 물질, 및 섬유 강화 플라스틱 물질 제조 방법

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111138636A (zh) * 2019-12-31 2020-05-12 浙江华正新材料股份有限公司 一种树脂组合物、预浸料及层压板
CN114015197A (zh) * 2021-11-19 2022-02-08 中航复合材料有限责任公司 一种适用于非热压罐成型的基体树脂及其制备方法

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