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WO2019065663A1 - Composition de résine durcissable et faisceau de fibres pré-imprégné l'utilisant - Google Patents

Composition de résine durcissable et faisceau de fibres pré-imprégné l'utilisant Download PDF

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Publication number
WO2019065663A1
WO2019065663A1 PCT/JP2018/035541 JP2018035541W WO2019065663A1 WO 2019065663 A1 WO2019065663 A1 WO 2019065663A1 JP 2018035541 W JP2018035541 W JP 2018035541W WO 2019065663 A1 WO2019065663 A1 WO 2019065663A1
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Prior art keywords
resin composition
curable resin
epoxy resin
mass
parts
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Ceased
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PCT/JP2018/035541
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English (en)
Japanese (ja)
Inventor
裕一 谷口
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Chemical and Materials Co Ltd
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Priority to JP2019545147A priority Critical patent/JP7186711B2/ja
Publication of WO2019065663A1 publication Critical patent/WO2019065663A1/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
    • 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
    • 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
    • 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
    • C08G59/56—Amines together with other curing agents
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04—Epoxynovolacs

Definitions

  • the present invention relates to a curable resin composition for toe prepreg which is excellent in viscosity stability, and toe prepreg using the same.
  • the method of producing a fiber reinforced composite material includes an autoclave molding method using a prepreg in which a thermosetting matrix resin is impregnated in advance into reinforcing fibers, a press molding method, a step of impregnating reinforcing fibers with a liquid matrix resin, and thermosetting.
  • a method such as wet lay-up molding method, pultrusion molding method, filament winding molding method, RTM method and the like including the molding process according to the above.
  • fracture toughness of the matrix resin there are various methods for enhancing the fracture toughness of the matrix resin, and examples thereof include addition of low elastic modulus rubbery polymer, block copolymer, core-shell type rubber particles, and the like.
  • fracture toughness can be improved by dispersing rubber particles having an average particle diameter of several tens to several hundreds of nm in a matrix resin. Optimization of the compatibility between the matrix resin and the shell layer of the core-shell type rubber particles is important in enhancing the fracture toughness because it affects the dispersibility of the rubber particles.
  • Patent documents 1 and 2 propose a resin composition using core-shell type rubber particles.
  • Patent Document 3 proposes a resin composition using core-shell rubber particles and urethane-modified or rubber-modified epoxy.
  • Patent Document 4 proposes a resin composition using core-shell rubber particles and solid bisphenol F-type epoxy resin.
  • the present invention provides a resin composition used as a matrix resin for tow prepreg which can obtain a fiber-reinforced composite material having high fracture toughness of a molded product obtained by curing and excellent in impact resistance and fatigue resistance.
  • the purpose is to
  • the above-mentioned bisphenol F-type epoxy resin is represented by the following general formula (1), and has a dinuclear substance content of 75 area% or more and a trinuclear substance content of 6 area% or less in gel permeation chromatography (GPC) measurement It is preferred to be configured in proportions. (Wherein, m is an integer of 0 to 5)
  • the dicyandiamide or its derivative (C) and the solid aromatic urea compound or solid imidazole compound (D) preferably have a D90 particle size of 2 to 8 ⁇ m.
  • the preferred form of tow prepreg is that the reinforcing fibers are blended at a volume content of 48 to 72%.
  • Another embodiment of the present invention is a fiber-reinforced composite material (molded body) obtained by molding, by filament winding molding method, a tow-preg in which reinforcing fibers are mixed with the above-mentioned resin composition.
  • a molded product obtained by curing a prepreg using the same exhibits high fracture toughness.
  • it is suitably used for a fiber reinforced composite material obtained by a filament winding molding method.
  • the GPC chart of bisphenol F-type epoxy resin YDF-170 is shown.
  • the GPC chart of bisphenol F-type epoxy resin YDF-1500 is shown.
  • the curable resin composition according to the present invention for epoxy resin (A), core-shell type rubber particles (B), dicyandiamide or derivative thereof (C), solid aromatic urea compound or solid imidazole compound (D) It is an essential ingredient.
  • epoxy resin (A), core-shell type rubber particles (B), dicyandiamide or its derivative (C), solid aromatic urea compound or solid imidazole compound (D) are respectively component (A) and component (B) It is also referred to as component (C) and component (D).
  • the curable resin composition for tow prepreg is also referred to as a curable resin composition or a resin composition.
  • the epoxy resin (A) used by this invention is bisphenol F-type epoxy resin whose epoxy equivalent (g / eq) is 180 or less 25 mass parts or more of the 100 mass parts. If the content of the bisphenol F-type epoxy resin is 25% by mass or more and the epoxy equivalent is not 180 or less, the dispersibility of the core-shell type rubber component of the cured product becomes too uniform, resulting in a decrease in fracture toughness.
  • the dinuclear-body content rate in a bisphenol F-type epoxy resin is 75 area% or more, and the trinuclear-body content rate is 6 area% or less.
  • the inclusion of the di-nucleus and the tri-nucleus in the above ratio can further enhance the fracture toughness value without excessively dispersing the core-shell type rubber component.
  • polynuclear body content rate of tetranuclear body or more is 1 area% or less in GPC measurement.
  • a bisphenol F type epoxy resin may also form a tetranuclear body generated by a ring opening reaction of an epoxy group as in a normal epoxy resin, this is not calculated as the above-mentioned tetranuclear body.
  • the epoxy resin (A) used in the present invention may contain other epoxy resins (refer to bisphenol F epoxy resin and bisphenol A epoxy resin).
  • the blending amount of the other epoxy resin is 20 parts by mass or less, preferably less than 10 parts by mass, in 100 parts by mass of the component (A).
  • epoxy resins include, for example, bisphenol-type epoxy resins such as bisphenol E-type epoxy resin, bisphenol S-type epoxy resin, bisphenol Z-type epoxy resin, and isophorone bisphenol-type epoxy resin having two or more epoxy groups in one molecule Or a halogen of these bisphenols, an alkyl-substituted product, a hydrogenated product, a polymer having not only a monomer but a plurality of repeating units, a glycidyl ether of an alkylene oxide adduct, a cresol novolac epoxy resin, a bisphenol A novolac Epoxy resins such as epoxy resins, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl- Aliphatic epoxy resins such as 2,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycycl
  • the core-shell rubber particle (B) is composed of a core portion and a shell portion forming an outer layer of the core portion.
  • the core portion is preferably made of a polymer having an elastomeric or rubbery polymer as a main component, and the shell portion is preferably made of a polymer grafted to the core portion.
  • the addition of the core-shell type rubber particles has the effect of improving the toughness and improving the tackiness of the prepreg, and the average particle diameter is preferably 1 to 500 nm as volume average particle diameter, and more preferably 3 to 300 nm. .
  • a solid aromatic urea compound or a solid imidazole compound (D) as a curing accelerator is blended.
  • the component (D) more desirably has a D90 particle size of 2 to 8 ⁇ m.
  • D90 of the particle diameter means a particle diameter corresponding to 90% of the distribution under the integrated sieving.
  • Any method can be adopted as a method for obtaining the above-mentioned small particle diameter.
  • methods such as a method of grinding coarse particles of a curing agent with a jet mill or a mortar, a method of freeze grinding, a method of classifying with a test sieve, and the like can be mentioned, but it is not limited thereto.
  • a solid aromatic urea compound for example, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, N-phenyl-N ' , N'-dimethylurea, N- (4-chlorophenyl) -N ', N'-dimethylurea, N- (3,4-dichlorophenyl) -N', N'-dimethylurea, N- (3-chloro-) 4-Methylphenyl) -N ', N'-dimethylurea, N- (3-chloro-4-ethylphenyl) -N', N'-dimethylurea, N- (3-chloro-4-methoxyphenyl)- N ', N'-dimethylurea, N- (4-methyl-3-nitrophenyl) -N', N'-dimethylurea,
  • solid imidazole compounds include 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl 6-4 ', 5'-dihydroxymethylimidazole, 1-cyanoethyl-2-ethyl-4methylimidazole, 2-phenyl-4-methyl-5 It is preferable to use an imidazole compound such as -hydroxymethylimidazole.
  • imidazole compounds containing a triazine ring can also be preferably used, for example, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6 -[2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-S -Triazine isocyanuric acid adduct etc. are mentioned.
  • the amount of the solid aromatic urea compound or solid imidazole compound (D) used is preferably 0.01 to 7 parts by mass with respect to 100 parts by mass of the curable resin composition. More preferably, it is 1 to 5 parts by mass. If the amount is more than 7 parts by mass, a powder component is increased, which causes a problem that the number of voids tends to be increased. If the amount is less than 0.01 parts by mass, there arises a problem that fast curing can not be realized.
  • An antifoamer and a leveling agent can be added to the curable resin composition of the present invention as an additive for the purpose of improving surface smoothness.
  • These additives can be blended in an amount of 0.01 to 3 parts by mass, preferably 0.01 to 1 parts by mass, with respect to 100 parts by mass of the resin composition.
  • the curable resin composition for tow prepreg of the present invention is produced by uniformly mixing the components (A), (B), (C), (D) and the like described above.
  • the obtained resin composition has a viscosity in the range of 3 to 45 Pa ⁇ s measured using an E-type viscometer cone plate type at 25 ° C. Within this range, the fiber has a good impregnating property to reinforcing fibers, dripping of resin from the fiber does not occur even after impregnation, good toe prepreg is obtained, and a fiber-reinforced composite material with few voids even at curing is obtained.
  • Examples of the conductive filler include carbon black, carbon nanotubes, fullerenes, metal nanoparticles and the like, which may be used alone or in combination.
  • the blending of carbon nanotubes not only improves the conductivity but also that the blending strength of less than 1 wt% to the fiber reinforced composite material can enhance the impact strength of the fiber reinforced composite material. It can be used suitably.
  • the curable resin composition for toe prepreg of the present invention is impregnated into reinforcing fibers or bundles to form toe prepreg.
  • the method of using to-preg may be a known method.
  • the tow prepreg obtained in this manner is suitably used for a fiber reinforced composite material obtained by a filament winding molding method.
  • the method for producing a molded article (also referred to as a fiber reinforced composite material) by processing the curable resin composition for tow prepreg of the present invention to tow prepreg is not particularly limited, but it is desirable as a method for producing a pressure vessel by filament winding method. Applied. A tow prepreg is wound around a metal or resin liner and then thermally cured to obtain a molded article in which a layer of a fiber reinforced composite material is formed to cover the liner. After this, the liner may be removed if necessary. In addition, it is desirably applied as a method for producing a circularly cast hollow fiber-reinforced composite material, such as a shaft or roll-shaped molded article, by a filament winding method. A molded article can be obtained by winding and heat-forming a tow prepreg around a metal or resin mandrel, and the mandrel may be removed depending on the application.
  • Reinforcing fibers used in the toe prepreg of the present invention are selected from glass fibers, aramid fibers, carbon fibers, boron fibers and the like, but carbon fibers are used to obtain a fiber-reinforced composite material excellent in strength. preferable.
  • the volume content of reinforcing fibers in the tow prepreg composed of the curable resin composition for tow prepreg of the present invention and the reinforcing fibers is preferably 48 to 72%, more preferably 53 to 68%. Since a compact having a small amount of voids and a high volume content of reinforcing fibers can be obtained, a molding material having excellent strength can be obtained.
  • the present invention will be specifically described based on examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
  • the part which shows a compounding quantity is a mass part unless there is particular notice.
  • the unit of epoxy equivalent is g / eq.
  • Molecular weight distribution was measured using gel permeation chromatography (GPC).
  • the main body (Tosoh Corporation HLC-8220GPC) with columns (TSKgel G4000HXL, TSKgel G3000HXL, TSKgel G2000 HXL) manufactured in series by Tosoh Corporation is used, the column temperature is set to 40 ° C., and tetrahydrofuran is used as an eluent.
  • the measurement was performed using a RI (differential refractometer) detector as a detector with a flow rate of min, and the binuclear content and trinuclear content were determined from the area% of the peak.
  • RI differential refractometer
  • FIG. 1 shows a GPC chart of YDF-170
  • FIG. 2 shows a GPC chart of YDF-1500.
  • A is a peak showing a dinuclear body
  • B is a peak showing a trinuclear body
  • C is a peak showing a tetranuclear body formed by ring opening and dimerization of an epoxy group.
  • Example 1 27 parts of YDF-170 as component (A), 51 parts of YD-128, 7 parts of MX-154EP in MX-154, 5 parts of MX-154 CSR in MX-154 as component (B), (C ) Put 5.7 parts of DICY as the component, 4.5 parts of DCMU as the component (D), and 150 mL of a poly container, and use a vacuum mixer “Awatori Neritaro” (made by Shinky) at room temperature 5 It mixed, stirring for minutes, and curable resin composition was obtained.
  • the viscosity value at 25 ° C. was measured using an E-type viscometer cone plate type.
  • the curable resin composition was prepared, and 0.8 mL of the composition was used for measurement, and the value after 60 seconds from the start of measurement was taken as the value of viscosity.
  • the curable resin composition is poured into a 120 mm long ⁇ 120 mm long mold provided with a 4 mm thick spacer hollowed out in a flat plate shape, and cured at 120 ° C. for 2 hours to form a molded plate for measurement; And it was used for measurement of flexural strength, and measurement of fracture toughness.
  • the resulting molded plate was cut to a size of 3 mm ⁇ 3 mm with a table-top band saw, and was further polished to a thickness of approximately 1.2 mm using a belt disc sander. Measured using a differential scanning calorimeter under a nitrogen atmosphere at a temperature elevation rate of 10 ° C./min, from the tangent at the inflection point of the DSC curve and the temperature at which the onset of inflection is seen, ie from the inflection point The point of intersection with the tangent at a temperature range of 20 to 30 ° C. lower is taken as the glass transition temperature Tg.
  • the obtained hoop-like carbon fiber reinforced composite material was cut into a size of inner arc length 100 mm ⁇ width 14 mm with a table-top band saw, and the actual density was measured by the Archimedes method. Further, the theoretical density was calculated by the following equation with the density of the cured epoxy resin being 1.2 and the density of carbon fibers being 1.8.
  • Theoretical density weight of cut-out carbon fiber reinforced composite material / (application weight of resin / density of cured epoxy resin + wound weight of carbon fiber / density of carbon fiber)
  • a curable resin composition was produced in the same manner as in Example 1 except that the raw materials were used in the compositions described in Tables 1 and 2 as the components (A) to (D).
  • a carbon fiber reinforced composite material is formed by using this curable resin composition and heat curing followed by obtaining in the same manner as in Example 1 to form a carbon fiber reinforced composite material. The test, the molding plate for fracture toughness measurement, and the porosity were measured.
  • a peak showing a binuclear body A peak showing a trinuclear body

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  • Engineering & Computer Science (AREA)
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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine durcissable adaptée à l'utilisation en tant que résine de matrice pour un matériau composite renforcé par des fibres ayant une excellente résistance à la fatigue, la composition de résine durcissable ayant une faible viscosité, une augmentation minimale de la viscosité même dans une étape d'imprégnation prolongée, et une bonne imprégnation dans des fibres de renfort, et une ténacité élevée étant obtenue dans un article moulé obtenu par durcissement de la composition de résine durcissable. La présente invention concerne une composition de résine durcissable pour un faisceau de fibres pré-imprégné incluant (A) une résine époxy, (B) des particules de caoutchouc de type noyau-enveloppe, (C) du dicyanadiamide ou un dérivé de celui-ci, et (D) un composé d'urée aromatique solide ou un composé d'imidazole solide en tant que composants essentiels de celui-ci, au moins 25 % en masse de la résine époxy (A) étant constitués d'une résine époxy de type bisphénol-F ayant une masse par équivalent époxy de 180 g/éq. la quantité mélangée des particules de caoutchouc de type cœur-enveloppe (B) étant de 2 à 20 % en masse par rapport à la quantité totale des composants (A) à (D), et la viscosité de la composition de résine durcissable pour un faisceau de fibres pré-imprégné à 25 °C étant dans la plage allant de 3 à 45 Pa∙s.
PCT/JP2018/035541 2017-09-29 2018-09-26 Composition de résine durcissable et faisceau de fibres pré-imprégné l'utilisant Ceased WO2019065663A1 (fr)

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JP2021512989A (ja) * 2018-02-09 2021-05-20 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッドＰＰＧ Ｉｎｄｕｓｔｒｉｅｓ Ｏｈｉｏ，Ｉｎｃ． コーティング組成物
JP2021161242A (ja) * 2020-03-31 2021-10-11 日鉄ケミカル＆マテリアル株式会社 硬化性樹脂組成物、及びそれを用いたトウプリプレグ
CN113874441A (zh) * 2019-06-14 2021-12-31 Dic株式会社 环氧树脂组合物、固化物、纤维增强复合材料、预浸料及丝束预浸料
JP2022039266A (ja) * 2020-08-28 2022-03-10 東レ株式会社 エポキシ樹脂組成物、中間基材、トウプレグ、および繊維強化複合材料
WO2022239471A1 (fr) * 2021-05-13 2022-11-17 Dic株式会社 Composition durcissable, objet durci, matériau composite renforcé par des fibres, et article moulé en résine renforcée par des fibres
WO2023032943A1 (fr) * 2021-09-01 2023-03-09 豊田合成株式会社 Composition thermodurcissable
CN120082175A (zh) * 2025-03-28 2025-06-03 北玻院(滕州)复合材料有限公司 一种阻燃型高模量、高韧性缠绕环氧树脂组合物及其制备方法

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