TW201841970A - Epoxy resin composition for fiber-reinforced composite materials, fiber-reinforced composite material and molded body - Google Patents

Epoxy resin composition for fiber-reinforced composite materials, fiber-reinforced composite material and molded body Download PDF

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TW201841970A
TW201841970A TW107111252A TW107111252A TW201841970A TW 201841970 A TW201841970 A TW 201841970A TW 107111252 A TW107111252 A TW 107111252A TW 107111252 A TW107111252 A TW 107111252A TW 201841970 A TW201841970 A TW 201841970A
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epoxy resin
resin composition
fiber
reinforced composite
composite material
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TWI778041B (en
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三宅力
中西哲也
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日商新日鐵住金化學股份有限公司
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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
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Abstract

Provided is an epoxy resin composition for fiber-reinforced composite materials, which has a good balance between storage stability and impregnation ability during the production of a prepreg, and which enables the achievement of a molded article that has excellent mechanical characteristics. An epoxy resin composition for fiber-reinforced composite materials, which contains, as essential ingredients, (A) an epoxy resin, (B) dicyandiamide, (C) an imidazole-based curing assistant and (D) a core-shell rubber, and which is characterized in that the imidazole-based curing assistant (C) makes the epoxy resin composition have an exothermic onset temperature of 135 DEG C or higher as determined by DSC at a heating rate of 10 DEG C/minute. Also, an epoxy resin composition which contains, as essential ingredients, (A) an epoxy resin, (B) an epoxy resin curing agent and (C) an imidazole compound, and which is characterized in that: the epoxy resin (A) contains a liquid bisphenol A epoxy resin and/or a liquid bisphenol F epoxy resin, while having a viscosity (25 DEG C) of from 1 Pa.s to 100 Pa.s (inclusive); and both of the epoxy resin curing agent (B) and the imidazole compound (C) are solids that have a melting point or a decomposition temperature of 200 DEG C or higher, while having an average particle diameter (D50) of 2 [mu]m or less.

Description

纖維強化複合材料用環氧樹脂組成物、纖維強化複合材料及成形體Epoxy resin composition, fiber reinforced composite material and molded body for fiber reinforced composite material

本發明係關於纖維強化複合材料及使用在該複合材料之環氧樹脂組成物。本發明係關於成為絲束預浸料(Tow prepreg)時之捲繞性優異，且可減低孔洞(void)的發生之環氧樹脂組成物及使用該組成物之纖維強化複合材料。The present invention relates to a fiber reinforced composite material and an epoxy resin composition used in the composite material. The present invention relates to an epoxy resin composition which is excellent in winding property in the case of a tow prepreg and which can reduce the occurrence of voids, and a fiber-reinforced composite material using the same.

以往，碳纖維、玻璃纖維等之強化纖維、與由環氧樹脂、酚樹脂等之熱硬化性樹脂所構成之纖維強化複合材料，雖為輕量，但由於強度或剛性等之力學特性或耐熱性、且耐腐蝕性優異，已被應用在航空暨宇宙、汽車、鐵道車輛、船舶、土木建築及運動用品等之多數領域。尤其是於要求高性能之用途，使用已使用經連續之強化纖維的纖維強化複合材料，使用比強度、比彈性率優異之碳纖維作為強化纖維，而且使用熱硬化性樹脂作為基質樹脂，其中，多數使用尤其是與碳纖維之接著性優異的環氧樹脂。惟，一般而言由於環氧樹脂(硬化物)有脆弱，亦即韌性或伸長低的缺點，導致降低將此直接使用之纖維強化複合材料的力學特性並非可滿足者。Conventionally, a fiber-reinforced composite material composed of a reinforcing fiber such as carbon fiber or glass fiber and a thermosetting resin such as an epoxy resin or a phenol resin is lightweight, but mechanical properties such as strength and rigidity or heat resistance. It has excellent corrosion resistance and has been used in many fields such as aerospace and space, automobiles, railway vehicles, ships, civil engineering and sporting goods. In particular, for applications requiring high performance, fiber-reinforced composite materials using continuous reinforcing fibers are used, carbon fibers excellent in specific strength and specific modulus are used as reinforcing fibers, and thermosetting resins are used as matrix resins, among which most An epoxy resin which is excellent in adhesion to carbon fibers in particular is used. However, in general, due to the disadvantage that the epoxy resin (hardened material) is weak, that is, the toughness or elongation is low, it is not satisfactory to reduce the mechanical properties of the fiber-reinforced composite material used directly.

作為提昇環氧樹脂之韌性或伸長之方法，已嘗試摻合韌性優異之橡膠成分或熱塑性樹脂之方法等。例如，藉由將如含有羧基之丙烯腈-丁二烯橡膠之橡膠成分摻合在環氧樹脂，改善環氧樹脂之韌性已自1970年代被研究，為一般眾所周知。然而，橡膠成分除了引起耐熱性降低或彈性率降低，為了充分得到藉由橡膠成分之韌性改質效果，有必要大量摻合橡膠成分。因此，有降低環氧樹脂原本之耐熱性或力學特性，得不到具有良好之物性的複合材料的缺點。As a method of improving the toughness or elongation of an epoxy resin, a method of blending a rubber component or a thermoplastic resin excellent in toughness has been attempted. For example, it has been known from the 1970s to improve the toughness of epoxy resins by blending a rubber component such as a carboxyl group-containing acrylonitrile-butadiene rubber with an epoxy resin. However, in addition to the rubber component, the heat resistance is lowered or the modulus of elasticity is lowered, and in order to sufficiently obtain the toughness-modifying effect by the rubber component, it is necessary to blend a large amount of the rubber component. Therefore, there is a disadvantage that the original heat resistance or mechanical properties of the epoxy resin are lowered, and a composite material having good physical properties cannot be obtained.

又，作為於環氧樹脂摻合熱塑性樹脂之方法，係藉由將如聚醚碸、聚碸及聚醚醯亞胺之熱塑性樹脂溶解在環氧樹脂，或以微粉末摻合進行溶解，於環氧樹脂中使熱塑性樹脂均勻分散之方法，已知有不損害環氧樹脂所具有之機械物性，且提昇韌性，而得到耐衝撃性優異之纖維強化複合材料(專利文獻1)。Further, as a method of blending a thermoplastic resin with an epoxy resin, a thermoplastic resin such as polyether oxime, polyfluorene, and polyether sulfimide is dissolved in an epoxy resin, or dissolved by fine powder blending. In the method of uniformly dispersing a thermoplastic resin in an epoxy resin, a fiber-reinforced composite material excellent in impact resistance is obtained without impairing the mechanical properties of the epoxy resin and improving the toughness (Patent Document 1).

然而，於此方法，為了充分得到韌性改質效果，有必要大量摻合此等之熱塑性樹脂。其結果，有如大幅上昇環氧樹脂組成物的黏度，得到預浸料時之製程性的大幅降低，或產生在所得之預浸料之樹脂未含浸部，硬化預浸料所得之纖維強化複合材料產生孔洞的缺點。However, in this method, in order to sufficiently obtain the toughness-modifying effect, it is necessary to blend a large amount of these thermoplastic resins. As a result, the viscosity of the epoxy resin composition is greatly increased, the processability at the time of obtaining the prepreg is greatly reduced, or the resin is not impregnated in the obtained prepreg, and the fiber reinforced composite material obtained by hardening the prepreg is obtained. The disadvantage of creating holes.

對於此問題，提案有使用實質上不溶於環氧樹脂之聚合物粒子的方法。其中，提案有使將聚合物作為主成分之粒子狀的核部分、與和核部分不同之聚合物接枝聚合等之方法，摻合被覆核部分之表面的一部分或全體之核殼橡膠粒子的方法(例如專利文獻2、3)。於此方法，已知可抑制環氧樹脂組成物之黏度上昇、環氧樹脂硬化物之Tg低下。For this problem, a method of using polymer particles substantially insoluble in epoxy resin has been proposed. Among them, there is proposed a method of graft-polymerizing a core portion having a polymer as a main component and a polymer different from a core portion, and blending a part or the entire core-shell rubber particles of the surface of the coated core portion. Method (for example, Patent Documents 2 and 3). In this method, it is known that the viscosity of the epoxy resin composition is suppressed and the Tg of the cured epoxy resin is lowered.

然而，為了得到充分之韌性提昇效果，有必要大量之核殼橡膠粒子的摻合，此結果，依然殘留降低環氧樹脂硬化物之彈性率，從而引起纖維強化複合材料之力學特性的降低的問題。However, in order to obtain a sufficient toughness-improving effect, it is necessary to mix a large amount of core-shell rubber particles, and as a result, the elastic modulus of the cured epoxy resin is still remaining, thereby causing a problem of lowering the mechanical properties of the fiber-reinforced composite material. .

作為彌補該等之手段，亦提案有併用核殼橡膠與分子量大之長鏈環氧樹脂的手法(專利文獻4)。然而，長鏈環氧樹脂除了提昇組成物的黏度之外，亦招致儲藏穩定性的惡化，無法滿足韌性之提昇。As a means of making up for this, a method of using a core-shell rubber and a long-chain epoxy resin having a large molecular weight in combination has been proposed (Patent Document 4). However, in addition to increasing the viscosity of the composition, the long-chain epoxy resin also causes deterioration in storage stability and cannot satisfy the improvement in toughness.

環氧樹脂係被分類成熱硬化性樹脂的樹脂之一。對於材料之接著性強一事作為特徵列舉，其用途被廣泛使用在塗料、電子材料、土木暨接著等。又，與碳纖維、玻璃纖維等之強化纖維之複合化的纖維強化複合材料雖為輕量，但由於強度或剛性等之力學特性或耐熱性、耐腐蝕性優異，被應用在航空暨宇宙、汽車、鐵道車輛、船舶、土木建築及運動用品等之多數領域。The epoxy resin is one of resins which are classified into a thermosetting resin. As a feature enumeration, the use of materials is widely used in coatings, electronic materials, civil engineering, and the like. In addition, the fiber-reinforced composite material which is composited with reinforcing fibers such as carbon fiber or glass fiber is lightweight, but it is excellent in mechanical properties such as strength and rigidity, heat resistance and corrosion resistance, and is used in aviation and the universe and automobiles. Most areas such as railway vehicles, ships, civil engineering and sporting goods.

纖維強化複合材料之加工，雖可列舉高壓釜法、拉擠成型法、長絲纏繞法、編結法、樹脂移轉成型法等之方法，但加工方法可藉由作為目的之構造體的形狀或所要求之生產性等選擇。Examples of the processing of the fiber-reinforced composite material include a method such as an autoclave method, a pultrusion method, a filament winding method, a braiding method, and a resin transfer molding method, but the processing method can be formed by the shape of the intended structure. Or the choice of productivity required.

長絲纏繞法係對於被稱為心軸之型，將含浸環氧樹脂或其他硬化性樹脂之碳纖維束或其他纖維束(單絲)進行纏繞(Wind)而成型之製程，將此硬化可得到複合材料。此方法可大致分成乾法與濕法2種。The filament winding method is a process in which a carbon fiber bundle or other fiber bundle (monofilament) impregnated with an epoxy resin or other curable resin is wound and formed by a method called a mandrel, and the hardening can be obtained. Composite material. This method can be roughly divided into two types, dry method and wet method.

濕法係於長絲纏繞步驟之中，捲出碳纖維，於捲繞在心軸為止之間設置樹脂含浸槽之手法。此方法作為製程簡單之外，由於必須配合纏繞速度含浸樹脂，故有被限定在黏度低，含浸性優異之樹脂的問題。又，有由於在單位重量產生變動，有必須使用額外的樹脂、樹脂於步驟中落下而污染，會因纏繞之速度或角度導致偏離所瞄準的地點等之問題。The wet method is carried out in the filament winding step, and the carbon fiber is taken up, and a resin impregnation groove is provided between the mandrels and the mandrel. Since this method is simple in the process, since it is necessary to impregnate the resin at the winding speed, there is a problem that it is limited to a resin having a low viscosity and excellent impregnation properties. Further, there is a problem that the unit weight is changed, and it is necessary to use an extra resin or a resin to fall in the step to be contaminated, which may cause a deviation from the intended location due to the speed or angle of the winding.

另一乾法係於碳纖維使用提前含浸樹脂之絲束預浸料(Tow prepreg)。藉由此製程分成含浸步驟與捲繞步驟，不需要分別精度良好地實施，而是作為中間構件之絲束預浸料的儲藏穩定性成必要。儲藏穩定性優異之樹脂，通常已知成為犧牲硬化反應性折衷。這種折衷是該業界廣泛認可的一個課題。Another dry method is to use a tow prepreg in which the carbon fiber is preliminarily impregnated with a resin. By this process, it is divided into an impregnation step and a winding step, and it is not necessary to perform the precision separately, but the storage stability of the tow prepreg as an intermediate member is necessary. A resin excellent in storage stability is generally known as a sacrificial hardening reactivity compromise. This trade-off is a subject that is widely recognized in the industry.

作為用以兼具環氧樹脂之儲藏穩定性與硬化反應性的技術，一般已知有使用粉末之硬化劑或硬化促進劑(以下為硬化劑等)之方法。藉由於硬化劑等採用固體者，可將接觸環氧樹脂與硬化劑等之機會限定於固液界面。又，由於硬化劑等藉由加熱而溶解、擴散以引起反應，所以已知作為能夠消除折衷的技術。As a technique for combining the storage stability and the curing reactivity of the epoxy resin, a method of using a hardener for a powder or a curing accelerator (hereinafter, a curing agent or the like) is generally known. By using a solid such as a hardener or the like, the chance of contacting the epoxy resin and the hardener can be limited to the solid-liquid interface. Further, since the curing agent or the like is dissolved and diffused by heating to cause a reaction, it is known as a technique capable of eliminating the tradeoff.

欲將此技術適用在複合材料時，因成型之時機與溶解硬化劑等之粒子的時機，導致是否適用完全不同。亦即，即使大量含有粉末的情況，進行高壓釜成型時，除了可得到缺陷較少之硬化物之外，在長絲纏繞法，有成為孔洞等之缺陷多之硬化物的問題，尤其是依樹脂含有率(Rc)縮小，有增大此問題的傾向。When this technique is applied to a composite material, the timing of the molding and the timing of dissolving the particles such as the hardener cause a completely different application. In other words, even when a large amount of powder is contained, in the case of autoclave molding, in addition to a cured product having few defects, a filament winding method has a problem of a cured product having many defects such as voids, in particular, The resin content ratio (Rc) is reduced, which tends to increase the problem.

專利文獻5中，記載有關於可兼具儲藏穩定性與速硬化性的環氧樹脂組成物，於實施例揭示樹脂含有率41重量%之碳纖維交叉預浸料。專利文獻6中雖針對組合特定之尿素衍生物與二氰二胺的促進劑有記載，但無纖維複合材料之實施例。專利文獻7中亦針對可兼具儲藏穩定性與速硬化性的樹脂組成物有記載，於實施例揭示樹脂含有率66重量%之玻璃纖維預浸料。 　　在任一專利文獻，針對在減低樹脂含有率時之孔洞減低技術並未有任何記載。Patent Document 5 describes an epoxy resin composition which can have both storage stability and rapid curing properties, and discloses a carbon fiber cross prepreg having a resin content of 41% by weight in the examples. Patent Document 6 describes an example of a fiber-free composite material, although it is described as a combination of a specific urea derivative and a dicyandiamide accelerator. Patent Document 7 also discloses a resin composition which can achieve both storage stability and quick-curing properties, and discloses a glass fiber prepreg having a resin content of 66% by weight in the examples. In any of the patent documents, there is no description of the technique for reducing pores when the resin content is reduced.

專利文獻8中，雖揭示有作為保存穩定性及硬化性良好之環氧樹脂組成物，係於環氧樹脂含有平均粒徑10μm以下之胺系化合物的粒子及含有硼酸酯化合物者，即使參照實施例等，亦無成為預浸料時之樹脂含有率的記載。 [先前技術文獻] [專利文獻]In the case of the epoxy resin composition containing an amine compound having an average particle diameter of 10 μm or less and a boronic acid ester compound, the epoxy resin composition is excellent in storage stability and curability. In the examples and the like, there is no description of the resin content rate when the prepreg is used. [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本特公平6-43508號公報 　　[專利文獻2]日本特開平5-65391號公報 　　[專利文獻3]日本特開2003-277579號公報 　　[專利文獻4]日本專利第5293629號 　　[專利文獻5]日本特開2004-075914號公報 　　[專利文獻6]日本特表2007-504341號公報 　　[專利文獻7]日本特表2015-516497號公報 　　[專利文獻8]日本特開平9-157498號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Bulletin

於本發明，由於提供一種可兼具預浸料製造時之含浸性與儲藏穩定性，並且成形物之力學特性優異之纖維強化複合材料用環氧樹脂組成物，尤其是提供一種可提昇在長絲纏繞法使用之絲束預浸料的保存穩定性之纖維強化複合材料用環氧樹脂組成物。 　　又，提供一種碳纖維複合材料所使用之環氧樹脂組成物，且儲藏穩定性與硬化反應性優異，即使在低樹脂含有率Rc，亦可減低孔洞等之缺陷的樹脂組成物。According to the present invention, it is possible to provide an epoxy resin composition for a fiber-reinforced composite material which has both impregnation properties and storage stability in the production of a prepreg and excellent mechanical properties of the molded article, and in particular, provides an improvement in length An epoxy resin composition for a fiber-reinforced composite material having a storage stability of a tow prepreg used in the wire winding method. In addition, the epoxy resin composition used for the carbon fiber composite material is excellent in storage stability and curing reactivity, and the resin composition can be reduced in defects such as voids even at a low resin content rate Rc.

亦即，第一本發明為一種纖維強化複合材料用環氧樹脂組成物，其係將環氧樹脂(A)、二氰二胺(B)、咪唑系硬化輔助劑(C)及核殼橡膠(D)作為必須成分之環氧樹脂組成物，其特徵為咪唑系硬化輔助劑(C)為將環氧樹脂組成物在DSC以昇溫速度10℃/分鐘的條件測定時之發熱起始溫度成為135℃以上者。That is, the first invention is an epoxy resin composition for a fiber-reinforced composite material, which is an epoxy resin (A), a dicyandiamide (B), an imidazole-based hardening auxiliary (C), and a core-shell rubber. (D) an epoxy resin composition which is an essential component, and the imidazole-based hardening aid (C) is a heat-generating starting temperature when the epoxy resin composition is measured at a temperature rising rate of 10 ° C /min. Above 135 °C.

第一本發明之纖維強化複合材料用環氧樹脂組成物，期望滿足以下任一種。 　　1)相對於環氧樹脂(A)之環氧基當量，含有二氰二胺(B)0.2～0.8當量，相對於二氰二胺(B)100質量份，含有咪唑系硬化輔助劑(C)50～250質量份、 　　2)環氧樹脂(A)於1分子中具有2個環氧基，且使用E型黏度計所測定在25℃之黏度為1～50Pa･s、 　　3)咪唑系硬化輔助劑(C)為2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三嗪異氰脲酸加成物或2-苯基-4-甲基-5-羥基甲基咪唑、 　　4)核殼橡膠(D)之體積平均粒子徑為1～500nm、 　　5)使用E型黏度計所測定在25℃之黏度為1～50Pa･s。The epoxy resin composition for a fiber-reinforced composite material according to the first aspect of the invention is desirably satisfying any of the following. 1) 0.2 to 0.8 equivalent of dicyandiamide (B) based on the epoxy equivalent of epoxy resin (A), and an imidazole hardening adjuvant (C) with respect to 100 parts by mass of dicyandiamide (B) 50 to 250 parts by mass, 2) epoxy resin (A) has two epoxy groups in one molecule, and the viscosity at 25 ° C is 1 to 50 Pa·s as measured by an E-type viscometer, 3) imidazole system The hardening aid (C) is 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid The volume average particle diameter of the product or 2-phenyl-4-methyl-5-hydroxymethylimidazole, 4) core-shell rubber (D) is 1 to 500 nm, 5) measured at 25 ° C using an E-type viscometer The viscosity is 1 to 50 Pa·s.

第一本發明之另一態樣為一種纖維強化複合材料，其特徵為於上述環氧樹脂組成物摻合強化纖維而成。強化纖維之體積含有率較佳為30～75%。 　　本發明之進而又一態樣為一種成形體，其係將上述纖維強化複合材料以長絲纏繞法進行成形及硬化而得。Another aspect of the first aspect of the invention is a fiber-reinforced composite material characterized in that the epoxy resin composition is blended with reinforcing fibers. The volume content of the reinforcing fibers is preferably from 30 to 75%. Still another aspect of the present invention provides a molded body obtained by molding and hardening the fiber-reinforced composite material by a filament winding method.

又，本發明者們為了解決上述課題進行努力研究的結果，發現藉由使用低黏度之液狀環氧樹脂作為環氧樹脂，作為環氧樹脂所摻合之硬化劑及硬化促進劑，在任何情況下，藉由將熔點等為高之固體，且平均粒子徑為一定值以下者作為必須成分摻合，可充分減低孔洞，而終至完成第二本發明。In order to solve the above problems, the inventors of the present invention have found that a liquid epoxy resin having a low viscosity is used as an epoxy resin, and a curing agent and a curing accelerator which are blended as an epoxy resin are used. In the case where a solid having a high melting point or the like is high and the average particle diameter is equal to or less than a certain value, the pores can be sufficiently reduced, and the second invention can be completed.

亦即，第二本發明為一種環氧樹脂組成物，其係將環氧樹脂(A)、環氧樹脂硬化劑(B)、咪唑化合物(C)作為必須成分之環氧樹脂組成物，其特徵為環氧樹脂(A)為含有液狀雙酚A型環氧樹脂及/或液狀雙酚F型環氧樹脂，黏度(25℃)1Pa･s以上100Pa･s以下，環氧樹脂硬化劑(B)及咪唑化合物(C)皆為熔點或分解溫度200℃以上之固體，平均粒徑(D50)2μm以下。That is, the second invention is an epoxy resin composition which is an epoxy resin composition containing an epoxy resin (A), an epoxy resin hardener (B), and an imidazole compound (C) as essential components. Epoxy resin (A) is a liquid bisphenol A type epoxy resin and/or liquid bisphenol F type epoxy resin, and has a viscosity (25 ° C) of 1 Pa·s or more and 100 Pa·s or less. Both the agent (B) and the imidazole compound (C) are solids having a melting point or a decomposition temperature of 200 ° C or higher, and an average particle diameter (D50) of 2 μm or less.

在第二本發明，上述環氧硬化劑(B)可為二氰二胺。上述咪唑化合物(C)可為下述式(1)或式(2)表示之化合物。又，環氧硬化劑(B)與咪唑化合物(C)的合計量，相對於環氧樹脂組成物，較佳為成為10重量%以下。 In the second invention, the epoxy hardener (B) may be dicyandiamide. The above imidazole compound (C) may be a compound represented by the following formula (1) or formula (2). Further, the total amount of the epoxy curing agent (B) and the imidazole compound (C) is preferably 10% by weight or less based on the epoxy resin composition.

第二本發明之環氧樹脂組成物可含有橡膠成分(D)。作為此橡膠成分(D)，適合具有核殼構造之橡膠粒子。又，少量含有穩定劑亦佳。The epoxy resin composition of the second invention may contain a rubber component (D). As the rubber component (D), rubber particles having a core-shell structure are suitable. Also, a small amount of a stabilizer is also preferred.

第二本發明之另一態樣為一種絲束預浸料，其係將上述環氧樹脂組成物含浸在碳纖維(E)而成。作為碳纖維(E)，適合平均直徑為7.5μm以下。Another aspect of the second invention is a tow prepreg obtained by impregnating the above epoxy resin composition with carbon fibers (E). As the carbon fiber (E), it is suitable for an average diameter of 7.5 μm or less.

第二本發明之另一態樣為一種碳纖維強化塑料，其係成型上述絲束預浸料，進行硬化而成。Another aspect of the second aspect of the invention is a carbon fiber reinforced plastic obtained by molding the tow prepreg and hardening it.

以下，首先針對第一本發明之實施形態進行說明。Hereinafter, first, an embodiment of the first invention will be described.

第一本發明之纖維強化複合材料用環氧樹脂組成物(以下，亦單稱為環氧樹脂組成物)係將環氧樹脂(A)、二氰二胺(B)、咪唑系硬化輔助劑(C)、核殼橡膠(D)作為必須成分。以下，亦分別將環氧樹脂(A)、二氰二胺(B)、咪唑系硬化輔助劑(C)、核殼橡膠(D)稱為(A)成分、(B)成分、(C)成分及(D)成分。The epoxy resin composition for fiber-reinforced composite material according to the first aspect of the present invention (hereinafter also referred to simply as epoxy resin composition) is an epoxy resin (A), dicyandiamide (B), and an imidazole-based hardening auxiliary agent. (C), core-shell rubber (D) as an essential component. Hereinafter, the epoxy resin (A), the dicyandiamide (B), the imidazole-based hardening aid (C), and the core-shell rubber (D) are referred to as (A) component, (B) component, and (C), respectively. Ingredients and (D) ingredients.

於本發明使用之環氧樹脂(A)的摻合量，於(A)～(D)成分的合計100質量份之內，為40～75質量份，較佳為40～70質量份，更佳為50～70質量份。 　　作為環氧樹脂，可使用於1分子中具有2個環氧基之雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚E型環氧樹脂、雙酚S型環氧樹脂、雙酚Z型環氧樹脂、異佛爾酮雙酚型環氧樹脂等之雙酚型環氧樹脂，或不限於此等雙酚型環氧樹脂之鹵素、烷基取代體、氫化產品、單體且具有複數之重複單元的高分子量體、環氧烷(alkylene oxide)加成物之縮水甘油基醚或酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂等之酚醛清漆型環氧樹脂，或3,4-環氧基-6-甲基環己基甲基-3,4-環氧基-6-甲基環己烷羧酸酯、3,4-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯、1-環氧基乙基-3,4-環氧基環己烷等之脂環式環氧樹脂，或三羥甲基丙烷聚縮水甘油基醚、季戊四醇聚縮水甘油基醚、聚氧伸烷基二縮水甘油基醚等之脂肪族環氧樹脂，或鄰苯二甲酸二縮水甘油基酯、與四氫鄰苯二甲酸二縮水甘油基酯、與二聚酸縮水甘油基酯等之縮水甘油基酯，或四縮水甘油基二胺基二苯基甲烷、四縮水甘油基二胺基二苯基碸、三縮水甘油基胺基酚、三縮水甘油基胺基甲酚、四縮水甘油基二甲苯二胺等之縮水甘油基胺類等。此等之環氧樹脂中，從黏度增加率的觀點來看，較佳為於1分子中具有2個環氧基之環氧樹脂，較該環氧基更多之多官能的環氧樹脂為不佳。其中，最佳為雙酚F型環氧樹脂。此等可單獨1種使用，亦可組合2種以上使用。The blending amount of the epoxy resin (A) used in the present invention is 40 to 75 parts by mass, preferably 40 to 70 parts by mass, based on 100 parts by mass of the total of the components (A) to (D). It is preferably 50 to 70 parts by mass. As the epoxy resin, it can be used for a bisphenol A type epoxy resin having two epoxy groups in one molecule, a bisphenol F type epoxy resin, a bisphenol E type epoxy resin, a bisphenol S type epoxy resin, a bisphenol type epoxy resin such as a bisphenol Z type epoxy resin or an isophorone bisphenol type epoxy resin, or a halogen, an alkyl substituent, a hydrogenated product, or a single bisphenol type epoxy resin a high molecular weight body having a plurality of repeating units, a glycidyl ether of an alkylene oxide adduct or a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol A novolac a novolac type epoxy resin such as an epoxy resin, or 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, An alicyclic ring of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane or the like An oxy-resin, or an aliphatic epoxy resin such as trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, polyoxyalkylene diglycidyl ether, or diglycidyl phthalate And a glycidyl ester of tetrahydrophthalic acid diglycidyl ester, a dimer acid glycidyl ester, or the like, or a tetraglycidyldiamine diphenylmethane or a tetraglycidyldiamine group A glycidylamine such as phenylhydrazine, triglycidylaminophenol, triglycidylamino cresol or tetraglycidyl xylylenediamine. Among these epoxy resins, from the viewpoint of the viscosity increase rate, an epoxy resin having two epoxy groups in one molecule is preferable, and a polyfunctional epoxy resin having more epoxy groups than the epoxy group is preferably Not good. Among them, the best is bisphenol F type epoxy resin. These may be used alone or in combination of two or more.

於本發明使用之環氧樹脂(A)，使用在25℃之E型黏度計(錐板型)所測定之黏度較佳為1～50Pa･s的範圍，更佳為5～30Pa･s，再更佳為6～25Pa･s，特佳為7～20Pa･s。藉此，具有對良好之強化纖維的含浸性，且成為含浸後亦難以從纖維引起樹脂之液體滴落者。又，環氧樹脂(A)可為數種類之混合物，較佳為其混合物的黏度為上述範圍。The epoxy resin (A) used in the present invention has a viscosity of preferably 1 to 50 Pa·s, more preferably 5 to 30 Pa·s, as measured by an E-type viscometer (cone-plate type) at 25 ° C. More preferably, it is 6 to 25 Pa·s, and particularly preferably 7 to 20 Pa·s. Thereby, it has the impregnation property with respect to a favorable reinforced fiber, and it is also difficult to drip the liquid of the resin from the fiber after impregnation. Further, the epoxy resin (A) may be a mixture of several kinds, and it is preferred that the viscosity of the mixture is in the above range.

本發明之環氧樹脂組成物中，使用二氰二胺(B)作為硬化劑。二氰二胺於常溫為固體之硬化劑，係於室溫雖幾乎不溶解於環氧樹脂，但加熱至180℃以上時進行溶解，具有與環氧基進行反應之特性的於室溫保存穩定性優異之潛在性硬化劑。作為使用的量，較佳為相對於環氧樹脂(A)之環氧基當量，以0.2～0.8當量(將二氰二胺1莫耳作為4當量計算)的範圍摻合。更佳為0.2～0.5當量。相對於環氧基當量，未滿0.2當量時，降低硬化物之交聯密度，變容易降低破壞韌性，超過0.8當量時，由於未反應之二氰二胺變容易殘留，有機械物性惡化的傾向。In the epoxy resin composition of the present invention, dicyandiamide (B) is used as a curing agent. The dicyandiamide is a solid hardener at room temperature. It is hardly soluble in epoxy resin at room temperature, but is dissolved when heated to 180 ° C or higher. It has a property of reacting with an epoxy group and is stable at room temperature. A potential hardener with excellent properties. The amount to be used is preferably blended in a range of 0.2 to 0.8 equivalents (calculated as dicyandiamide 1 molar as 4 equivalents) with respect to the epoxy equivalent of the epoxy resin (A). More preferably, it is 0.2 to 0.5 equivalent. When the amount is less than 0.2 equivalent, the crosslinking density of the cured product is lowered, and the fracture toughness is easily lowered. When the amount is more than 0.8 equivalent, the unreacted dicyandiamide tends to remain and the mechanical properties tend to deteriorate. .

本發明之環氧樹脂組成物的製造可用各種周知之方法製造。例如，有將各成分在捏合機進行混練之方法。又，可使用二軸之擠出機進行混練。二氰二胺(B)雖以固體狀態直接分散於各成分中，但一度混練全部之成分時，有二氰二胺凝集成為分散不佳的情況。分散不佳之環氧樹脂組成物由於在硬化物中產生物性不均，或產生硬化不佳故不佳。因此，二氰二胺較佳為使用環氧樹脂之一部分，在三輥進行預備混練，作為母料批次使用。The epoxy resin composition of the present invention can be produced by various known methods. For example, there is a method in which each component is kneaded in a kneader. Further, the two-axis extruder can be used for kneading. Although dicyandiamide (B) is directly dispersed in each component in a solid state, when all the components are once kneaded, dicyandiamide is condensed into a poor dispersion. The poorly dispersed epoxy resin composition is not preferable because it causes unevenness in physical properties in the hardened material or poor hardening. Therefore, it is preferred to use a part of the epoxy resin as the dicyandiamide, and to perform preliminary kneading on the three rolls, and use it as a master batch.

本發明之環氧樹脂組成物所包含之咪唑系硬化輔助劑(C)的摻合量，相對於二氰二胺(B)之量100質量份，較佳為成為50～250質量份，更佳為50～100質量份。咪唑系硬化輔助劑少於50質量份時，速硬化性的表現變困難，較250質量份更多時，速硬化性雖無變化，有硬化物變脆弱的傾向。The blending amount of the imidazole-based curing aid (C) contained in the epoxy resin composition of the present invention is preferably 50 to 250 parts by mass based on 100 parts by mass of the dicyandiamide (B). It is preferably 50 to 100 parts by mass. When the amount of the imidazole-based hardening aid is less than 50 parts by mass, the performance of the quick-curing property becomes difficult, and when it is more than 250 parts by mass, the quick-curing property does not change, and the cured product tends to be weak.

作為咪唑系硬化輔助劑(C)，為了提昇黏度增加率之抑制(保存穩定性)，使用作為環氧樹脂組成物時之DSC(差示掃描熱量分析)發熱起始溫度為135℃以上者。咪唑系硬化輔助劑(C)，其發熱起始溫度較佳為137℃以上，更佳為140℃以上者即可。發熱起始溫度較135℃更低時，不僅降低於室溫之保存穩定性，而且於含浸時硬化反應已進行，無法充分表現流動性提昇效果。此DSC發熱起始溫度，係將摻合作為硬化觸媒之咪唑系硬化輔助劑(C)的環氧樹脂組成物，以昇溫速度10℃/分鐘之條件DSC測定時之每一小時之發熱量的外插表示之溫度，於圖1表示由實測值所求出之溫度。 　　在圖1，外插每一小時之發熱量，將其交點定義為發熱起始溫度，且將表示發熱量之最大值的溫度定為發熱峰值溫度。As the imidazole-based hardening aid (C), in order to improve the viscosity increase rate (storage stability), the DSC (differential scanning calorimetry) when the epoxy resin composition is used is a heating initiation temperature of 135 ° C or higher. The imidazole-based hardening aid (C) preferably has a heat-generating starting temperature of 137 ° C or higher, more preferably 140 ° C or higher. When the starting temperature of the heat is lower than 135 ° C, the storage stability is not only lowered at room temperature, but also the hardening reaction proceeds during impregnation, and the fluidity improving effect cannot be sufficiently exhibited. The DSC heating initiation temperature is an epoxy resin composition which is a mixture of an imidazole-based hardening aid (C) which is a hardening catalyst, and the calorific value per hour measured by a DSC at a temperature rising rate of 10 ° C /min. The extrapolated temperature indicates the temperature obtained from the measured values in Fig. 1. In Fig. 1, the calorific value per hour is extrapolated, the intersection point thereof is defined as the heat generation onset temperature, and the temperature indicating the maximum value of the calorific value is set as the heat generation peak temperature.

進而，作為咪唑系硬化輔助劑(C)，為了抑制硬化時之發熱，作為環氧樹脂組成物時之DSC發熱峰值溫度較佳為145℃～160℃，更佳為148℃～155℃者即可。咪唑系硬化輔助劑(C)之發熱峰值溫度較145℃更低時，不僅降低於室溫之保存穩定性，而且於含浸時硬化反應已進行，無法充分表現流動性提昇效果。又，超過160℃時，由於藉由硬化時之硬化發熱，引起樹脂本身之異常發熱、分解故不佳。此DSC發熱峰值溫度，係將摻合作為硬化觸媒之咪唑系硬化輔助劑(C)的環氧樹脂組成物，以昇溫速度10℃/分鐘之條件DSC測定時之發熱峰值溫度。Further, as the imidazole-based curing assistant (C), in order to suppress heat generation during curing, the DSC heat generation peak temperature in the case of the epoxy resin composition is preferably 145 to 160 ° C, more preferably 148 to 155 ° C. can. When the peak temperature of the heat of the imidazole-based hardening aid (C) is lower than 145 ° C, the storage stability is not only lowered at room temperature, but also the hardening reaction proceeds during impregnation, and the fluidity-improving effect cannot be sufficiently exhibited. Moreover, when it exceeds 160 ° C, it is not preferable because the heat generation at the time of hardening causes heat generation and decomposition of the resin itself. The peak temperature of the DSC heat generation is an epoxy resin composition which is a mixture of an imidazole-based hardening aid (C) which is a hardening catalyst, and a peak temperature of heat generation measured by DSC at a temperature rising rate of 10 ° C /min.

作為咪唑系硬化輔助劑(C)，除了對在本發明之混合時的強化纖維之含浸性，為了更加滿足在硬化時之耐熱性，較佳為2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三嗪異氰脲酸加成物、2-苯基-4-甲基-5-羥基甲基咪唑。又，若為成為顯示發熱峰值溫度為145℃以上之組成者，可將其他咪唑系化合物作為硬化輔助劑成分之一部分組合1種或2種以上使用。例如作為此等之其他咪唑系硬化輔助劑(C1)，可使用2-甲基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、1-苄基-2-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基6-4′,5′-二羥基甲基咪唑、1-氰基乙基-2-乙基-4甲基咪唑等之咪唑系化合物。進而，作為含有三嗪環之咪唑化合物，例如可列舉2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-十一烷基咪唑基-(1’)]-乙基-s-三嗪等。As the imidazole-based hardening aid (C), in addition to the impregnation property of the reinforcing fibers in the mixing of the present invention, in order to more satisfy the heat resistance at the time of curing, 2,4-diamino-6-[2 is preferable. '-Ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenyl-4-methyl-5-hydroxymethylimidazole . In addition, when it is a composition which shows that the peak temperature of the heat generation is 145 ° C or more, one or two or more kinds of other imidazole-based compounds may be used in combination as one of the curing auxiliary components. For example, as such other imidazole-based hardening aids (C1), 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2- can be used. Methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl 6-4', 5'-di An imidazole compound such as hydroxymethylimidazole or 1-cyanoethyl-2-ethyl-4-methylimidazole. Further, examples of the imidazole compound containing a triazine ring include 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine and 2,4. -Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine or the like.

由於咪唑系硬化輔助劑(C)亦為固體，由於容易引起分散不佳，故較佳為與二氰二胺(B)相同，使用環氧樹脂之一部分，在三輥進行預備混練，作為母料批次使用。Since the imidazole-based hardening aid (C) is also a solid, since it is liable to cause poor dispersion, it is preferably the same as dicyandiamide (B), and a part of the epoxy resin is used, and the preliminary mixing is performed on the three rolls as a mother. Material batch use.

作為核殼橡膠(D)，係藉由於將經交聯之橡膠狀聚合物或彈性體作為主成分之粒子狀核成分的表面，接枝聚合與核成分為異種之殼成分聚合物，而將粒子狀核成分的表面之一部分或全體以殼成分被覆者。The core-shell rubber (D) is a shell component of a particulate component which has a cross-linked rubbery polymer or an elastomer as a main component, and the graft polymerization and the core component are heterogeneous shell component polymers. One or both of the surfaces of the particulate core component are covered with a shell component.

作為構成核殼聚合物之核成分，雖可使用由選自乙烯基單體、共軛二烯系單體、(甲基)丙烯酸酯系單體中之1種或複數種所聚合之聚合物或聚矽氧樹脂等，但芳香族系乙烯基單體與共軛二烯系單體，其中，由苯乙烯與丁二烯所構成之交聯橡膠狀聚合物提高韌性提昇效果故可優選使用。As the core component constituting the core-shell polymer, one or a plurality of polymers polymerized from one selected from the group consisting of a vinyl monomer, a conjugated diene monomer, and a (meth) acrylate monomer can be used. Or a polysiloxane resin, etc., but an aromatic vinyl monomer and a conjugated diene monomer, wherein a crosslinked rubber-like polymer composed of styrene and butadiene improves the toughness-improving effect, so that it can be preferably used. .

構成核殼聚合物之殼成分，較佳為已被接枝聚合於前述之核成分，與構成核成分之聚合物進行化學鍵結。作為構成如此之殼成分之成分，例如可使用由選自(甲基)丙烯酸酯、芳香族乙烯化合物等中之1種或複數種所聚合之聚合物。使用由苯乙烯與丁二烯所構成之交聯橡膠狀聚合物作為核成分時，可適合使用(甲基)丙烯酸酯之甲基丙烯酸甲酯與芳香族乙烯化合物之苯乙烯的混合體。The shell component constituting the core-shell polymer is preferably graft-polymerized to the above-described core component and chemically bonded to the polymer constituting the core component. As the component constituting such a shell component, for example, a polymer obtained by polymerizing one or more selected from the group consisting of (meth) acrylate, aromatic vinyl compound, and the like can be used. When a crosslinked rubber-like polymer composed of styrene and butadiene is used as a core component, a mixture of methyl methacrylate of a (meth) acrylate and styrene of an aromatic vinyl compound can be suitably used.

又，於殼成分為了使分散狀態穩定化，較佳為導入與本發明之環氧樹脂組成物進行反應之官能基。作為如此之官能基，例如可列舉羥基、羧基、環氧基，其中，較佳為環氧基。作為導入環氧基之方法，係於殼成分例如併用甲基丙烯酸2,3-環氧基丙酯，接枝聚合在核成分之方法。Further, in order to stabilize the dispersion state of the shell component, it is preferred to introduce a functional group which reacts with the epoxy resin composition of the present invention. Examples of such a functional group include a hydroxyl group, a carboxyl group, and an epoxy group. Among them, an epoxy group is preferred. As a method of introducing an epoxy group, a method of graft-polymerizing a core component to a shell component, for example, 2,3-epoxypropyl methacrylate in combination is used.

作為可適用在本發明之環氧樹脂組成物的核殼聚合物，若為上述者，則並未特別限制，可使用以周知之方法製造者。然而，通常，核殼聚合物粉碎以塊狀取出者被作為粉體操作，使粉體狀核殼聚合物再度分散於環氧樹脂中雖多，但於此方法，以一次粒子的狀態穩定分散有困難。因此，較佳為從核殼聚合物之製造過程，完全未以塊狀取出，最終可用於環氧樹脂中以一次粒子分散之母料批次的狀態操作者。例如，可使用日本特開2004-315572號公報所記載之方法，亦即，可使用將核殼聚合物以乳化聚合、分散聚合、懸濁聚合所代表之水媒體中進行聚合之方法進行聚合，而得到分散核殼聚合物之懸濁液，於所得之懸濁液混合水與顯示部分溶解性之有機溶劑，例如丙酮或甲基乙基酮等之醚系溶劑後，接觸水溶性電解質，例如接觸氯化鈉或氯化鉀，使有機溶劑層與水層進行相分離，於分離去除水層所得之核殼聚合物分散有機溶劑，適當混合環氧樹脂後，蒸發去除有機溶劑之方法等。例如，作為核殼聚合物分散環氧基母料批次，可適合使用由Kaneka公司所市售之“Kane ace”。The core-shell polymer which can be used in the epoxy resin composition of the present invention is not particularly limited as long as it is the above, and it can be produced by a known method. However, in general, the core-shell polymer is pulverized as a powder, and the powder-like core-shell polymer is dispersed in the epoxy resin. However, in this method, the state of the primary particles is stably dispersed. Difficulties. Therefore, it is preferred that the core-shell polymer is not taken out in a block form during the manufacturing process of the core-shell polymer, and finally can be used in the state of the master batch of the primary particle dispersed in the epoxy resin. For example, a method described in JP-A-2004-315572, that is, a method in which a core-shell polymer is polymerized by an aqueous medium represented by emulsion polymerization, dispersion polymerization or suspension polymerization, can be used. A suspension of the dispersed core-shell polymer is obtained, and the obtained suspension is mixed with water and an organic solvent which exhibits partial solubility, for example, an ether solvent such as acetone or methyl ethyl ketone, and then contacted with a water-soluble electrolyte, for example, The method of contacting sodium chloride or potassium chloride to phase separate the organic solvent layer from the aqueous layer, separating the core-shell polymer obtained by separating the aqueous layer, dispersing the organic solvent, appropriately mixing the epoxy resin, and evaporating the organic solvent. For example, as a core-shell polymer dispersed epoxy master batch, a "Kane ace" commercially available from Kaneka Corporation can be suitably used.

於本發明之環氧樹脂組成物適用核殼聚合物時，核殼聚合物較佳為平均粒子徑以體積平均粒子徑為1～500nm，若為3～300nm更佳。尚，體積平均粒子徑可使用奈米軌道粒度分布測定裝置(日機裝製)測定。於本發明使用之核殼聚合物的體積平均粒子徑為1nm以下時，製造困難，或變非常高價無法實質上使用，體積平均粒子徑為500nm以上時，在絲束預浸料之製造步驟，在含浸環氧樹脂組成物之步驟，由於以數千條水準存在之強化纖維成為如網的狀態，以此強化纖維進行濾別，由於有在絲束預浸料中成為分散狀態不均勻的情況，故不佳。When the core-shell polymer is used in the epoxy resin composition of the present invention, the core-shell polymer preferably has an average particle diameter of from 1 to 500 nm in terms of volume average particle diameter, more preferably from 3 to 300 nm. Further, the volume average particle diameter can be measured using a nano-orbital particle size distribution measuring apparatus (daily machine). When the volume-average particle diameter of the core-shell polymer used in the present invention is 1 nm or less, production is difficult, or it is too expensive to be substantially used, and when the volume average particle diameter is 500 nm or more, in the production step of the tow prepreg, In the step of impregnating the epoxy resin composition, since the reinforcing fibers existing in the thousands of levels become in a state such as a net, the reinforcing fibers are filtered, and the dispersion state is uneven in the tow prepreg. So it is not good.

核殼橡膠(D)的摻合量，較佳為於環氧樹脂組成物100質量份中摻合0.5～15質量份，若為1～10質量份更佳。若為摻合量為0.5質量份以上，易得到成形後之纖維強化複合材料所必須之破壞韌性，進而，若摻合量為15質量份以下，抑制所得之環氧樹脂組成物的黏度提高，由於可毫無困難含浸在強化纖維，故成為更適合在纖維強化複合材料用者。The blending amount of the core-shell rubber (D) is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the epoxy resin composition. When the blending amount is 0.5 parts by mass or more, the fracture toughness necessary for the fiber-reinforced composite material after molding is easily obtained, and when the blending amount is 15 parts by mass or less, the viscosity of the obtained epoxy resin composition is suppressed from increasing. Since it can be impregnated with reinforcing fibers without any difficulty, it is more suitable for users of fiber-reinforced composite materials.

本發明之環氧樹脂組成物可進一步包含其他穩定劑、改質劑等。作為較佳之穩定劑，較佳為B(OR)3 (惟，R表示氫原子、烷基或芳基)表示之硼酸化合物。硼酸化合物的摻合量相對於樹脂組成物全體100質量份，為0.01～10質量份，較佳為0.1～3質量份。未滿0.01質量份之添加量時，無法確保儲藏時之穩定性，且超過10質量份時，由於導致阻礙硬化反應的效果變大，誘發硬化不良，故不佳。The epoxy resin composition of the present invention may further contain other stabilizers, modifiers, and the like. As a preferred stabilizer, a boronic acid compound represented by B(OR) 3 (wherein R represents a hydrogen atom, an alkyl group or an aryl group) is preferred. The blending amount of the boric acid compound is 0.01 to 10 parts by mass, preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total of the resin composition. When the amount is less than 0.01 parts by mass, the stability at the time of storage cannot be ensured, and when it exceeds 10 parts by mass, the effect of hindering the curing reaction is increased, and the curing failure is induced, which is not preferable.

本發明之環氧樹脂組成物中，作為添加劑，以提昇表面平滑性為目的可添加消泡劑、整平劑。此等添加劑相對於樹脂組成物全體100質量份，可摻合0.01～3質量份，較佳為0.01～1質量份。摻合量未滿0.01質量份時，無法顯示表面變平滑的效果，超過3質量份時，由於引起添加劑滲出表面，反而成為損害平滑性的要因，故不佳。In the epoxy resin composition of the present invention, as an additive, an antifoaming agent and a leveling agent may be added for the purpose of improving surface smoothness. These additives may be blended in an amount of 0.01 to 3 parts by mass, preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total of the resin composition. When the blending amount is less than 0.01 parts by mass, the effect of smoothing the surface cannot be exhibited. When the amount is more than 3 parts by mass, the additive bleeds out of the surface, which in turn causes damage to smoothness, which is not preferable.

本發明之環氧樹脂組成物係藉由均勻混合上述之(A)成分～(D)成分等製造。所得之纖維強化複合材料用環氧樹脂組成物，具有對良好之強化纖維的含浸性，且含浸後亦難以引起樹脂之液體從纖維滴落。進而，本發明之纖維強化複合材料用環氧樹脂組成物係於室溫23℃穩定，幾乎無黏度變化，在溫度40℃、大氣環境或惰性氣體環境的條件下，經過72小時後之黏度增加率為20%以下，不僅可擔保於對具有長時間之含浸步驟之預浸料的製造時穩定之強化纖維的含浸性，而且由於於保管時不會增黏，起因於樹脂流動性惡化之硬化時空隙少，而得到表面平滑性優異之纖維強化複合材料。The epoxy resin composition of the present invention is produced by uniformly mixing the above components (A) to (D). The obtained epoxy resin composition for a fiber-reinforced composite material has impregnation properties with good reinforcing fibers, and it is also difficult to cause the liquid of the resin to drip from the fibers after impregnation. Further, the epoxy resin composition for a fiber-reinforced composite material of the present invention is stable at room temperature of 23 ° C, has almost no viscosity change, and has an increased viscosity after 72 hours at a temperature of 40 ° C, an atmospheric environment or an inert gas atmosphere. The rate of 20% or less is not only guarantored by the impregnation property of the reinforcing fiber which is stable at the time of manufacture of the prepreg having a long-term impregnation step, but also due to the deterioration of the fluidity of the resin due to no stickiness during storage. When the void is small, a fiber-reinforced composite material excellent in surface smoothness is obtained.

本發明之環氧樹脂組成物中，可摻合其他硬化性樹脂。作為如此之硬化性樹脂，雖可列舉不飽和聚酯樹脂、硬化性丙烯酸樹脂、硬化性胺基樹脂、硬化性三聚氰胺樹脂、硬化性脲樹脂、硬化性氰酸酯樹脂、硬化性胺基甲酸酯樹脂、硬化性環氧丙烷樹脂、硬化性環氧基/環氧丙烷複合樹脂等，但並非被限定於此等。In the epoxy resin composition of the present invention, other curable resins may be blended. Examples of such a curable resin include an unsaturated polyester resin, a curable acrylic resin, a curable amine-based resin, a curable melamine resin, a curable urea resin, a curable cyanate resin, and a curable urethane. The ester resin, the curable propylene oxide resin, the curable epoxy group/propylene oxide composite resin, and the like are not limited thereto.

本發明之環氧樹脂組成物使用E型黏度計所測定之黏度較佳為1～50Pa･s/25℃，更佳為5～30Pa･s/25℃，再更佳為6～25Pa･s/25℃，特佳為7～20Pa･s/25℃。黏度過高時，對碳纖維之含浸性惡化，黏度過低時，招致二氰二胺或咪唑系硬化輔助劑的沉澱。The viscosity of the epoxy resin composition of the present invention measured by an E-type viscometer is preferably from 1 to 50 Pa·s / 25 ° C, more preferably from 5 to 30 Pa·s / 25 ° C, still more preferably from 6 to 25 Pa·s. /25 ° C, especially good 7 ~ 20Pa · s / 25 ° C. When the viscosity is too high, the impregnation of the carbon fiber is deteriorated, and when the viscosity is too low, precipitation of the dicyandiamide or the imidazole-based hardening aid is caused.

本發明之環氧樹脂組成物適合使用在絲束預浸料纖維強化複合材料。於此使用之絲束預浸料之製造方法雖並未特別限定，但可用使該環氧樹脂組成物溶解在甲基乙基酮或甲醇等之有機溶劑，進行低黏度化，邊浸漬強化纖維束邊含浸後，使用烤箱等使有機溶劑蒸發，而成為絲束預浸料之濕法，或不使用有機溶劑，進行加熱，將經低黏度化之該環氧樹脂組成物薄膜化在輥或脫模紙上，其次，藉由轉印至強化纖維束之單面或兩面後，通過彎輥或壓力輥進行加壓，而含浸之熱熔法、將該環氧樹脂組成物藉由加熱進行低黏度化，邊浸漬強化纖維束邊含浸之長絲纏繞法等製造，絲束預浸料中所殘留之有機溶劑實質上皆無，由於可製造生產性高且高品位之絲束預浸料，故可優選使用長絲纏繞法。藉由使用如此之製造法，可得到樹脂經含浸之絲束預浸料。The epoxy resin composition of the present invention is suitably used in a tow prepreg fiber reinforced composite material. The method for producing the tow prepreg used herein is not particularly limited, but the epoxy resin composition may be dissolved in an organic solvent such as methyl ethyl ketone or methanol to carry out low-viscosity and impregnated reinforcing fibers. After the bundle is impregnated, the organic solvent is evaporated by using an oven or the like to form a wet pre-dip of the tow, or heated without using an organic solvent, and the low-viscosity epoxy resin composition is thinned on a roll or On the release paper, secondly, after being transferred to one side or both sides of the reinforcing fiber bundle, pressurization is performed by a bending roll or a pressure roll, and the hot melt method of impregnation is performed, and the epoxy resin composition is low by heating. It is manufactured by a filament winding method in which the viscosity is immersed and impregnated with a fiber bundle, and the organic solvent remaining in the tow prepreg is substantially absent, since a high-grade tow prepreg can be produced, A filament winding method can be preferably used. By using such a manufacturing method, a resin impregnated tow prepreg can be obtained.

作為本發明之纖維強化複合材料用環氧樹脂組成物所使用之強化纖維，雖選自玻璃纖維、芳綸纖維、碳纖維、硼纖維等，但為了得到強度優異之纖維強化複合材料，較佳為使用碳纖維。The reinforcing fiber used for the epoxy resin composition for a fiber-reinforced composite material of the present invention is selected from the group consisting of glass fiber, aramid fiber, carbon fiber, and boron fiber. However, in order to obtain a fiber-reinforced composite material having excellent strength, it is preferably Use carbon fiber.

在藉由本發明之環氧樹脂組成物與強化纖維構成之成形體，強化纖維之體積含有率較佳為30～75%，更佳為45～75%，為此範圍時，由於得到空隙少，且強化纖維之體積含有率高之成形體，而得到優異強度之成形材料。In the molded article comprising the epoxy resin composition of the present invention and the reinforced fiber, the volume fraction of the reinforcing fibers is preferably from 30 to 75%, more preferably from 45 to 75%, and in this range, since voids are obtained, Further, a molded body having a high volume content of the reinforcing fibers is obtained, and a molding material having excellent strength is obtained.

本發明之環氧樹脂組成物藉由以80～180℃，較佳為135℃以上之溫度的任意溫度，以0.5～10小時的範圍之任意時間進行加熱，使交聯反應進行，可得到硬化物。加熱條件可為1階段，亦可為組合複數加熱條件之多階段條件。尤其是假設填充如燃料電池所使用般之氫氣體等之高壓力容器的情況下，藉由以80～150℃之溫度的範圍的任意溫度，以0.5～5小時的範圍之任意時間進行加熱硬化，可得到所期望之硬化物的物性。The epoxy resin composition of the present invention can be hardened by heating at any temperature in the range of from 0.5 to 10 hours at any temperature of from 80 to 180 ° C, preferably from 135 ° C or higher. Things. The heating condition may be one stage or a multi-stage condition in which a plurality of heating conditions are combined. In particular, in the case of a high-pressure vessel filled with a hydrogen gas or the like as used in a fuel cell, heat hardening is performed at any temperature in the range of 0.5 to 5 hours at any temperature in the range of 80 to 150 °C. The physical properties of the desired cured product can be obtained.

其次，針對第二本發明之實施形態進行說明。Next, an embodiment of the second invention will be described.

第二本發明之環氧樹脂組成物係將環氧樹脂(A)、環氧樹脂硬化劑(B)及咪唑化合物(C)作為必須成分包含。以下，亦分別將環氧樹脂(A)、環氧樹脂硬化劑(B)及咪唑化合物(C)稱為(A)成分、(B)成分及(C)成分。The epoxy resin composition of the second aspect of the invention contains the epoxy resin (A), the epoxy resin hardener (B), and the imidazole compound (C) as essential components. Hereinafter, the epoxy resin (A), the epoxy resin curing agent (B), and the imidazole compound (C) are also referred to as the component (A), the component (B), and the component (C), respectively.

環氧樹脂(A)係含有液狀雙酚A型環氧樹脂、液狀雙酚F型環氧樹脂或兩者，在25℃之黏度為1Pa･s以上100Pa･s以下之環氧樹脂。 　　此黏度係使用在25℃之E型黏度計(錐板型)所測定之黏度。較佳之黏度為30Pa･s以下，更佳為15Pa･s以下。又，為4Pa･s以上，再更佳為8Pa･s以上。黏度超過100Pa･s時，對碳纖維之含浸時無法充分含浸，且於長絲纏繞成形時容易產生孔洞。未滿1Pa･s時，有穿線時或纏繞時之液體滴落、纏繞時之捲繞偏差等，故不佳。The epoxy resin (A) contains an epoxy resin having a liquid bisphenol A type epoxy resin, a liquid bisphenol F type epoxy resin, or both, and having a viscosity at 25 ° C of 1 Pa·s or more and 100 Pa·s or less. This viscosity is the viscosity measured by an E-type viscometer (cone-plate type) at 25 °C. The viscosity is preferably 30 Pa·s or less, more preferably 15 Pa·s or less. Further, it is 4 Pa·s or more, and more preferably 8 Pa·s or more. When the viscosity exceeds 100 Pa·s, the carbon fiber is not sufficiently impregnated during impregnation, and pores are likely to be formed when the filament is wound and formed. When it is less than 1 Pa·s, there is a case where the liquid is dropped during the threading or winding, and the winding deviation at the time of winding, etc., which is not preferable.

環氧樹脂(A)雖為單獨或包含液狀雙酚A型環氧樹脂、液狀雙酚F型環氧樹脂兩者之成分，但若在25℃之黏度滿足上述範圍，則可含有其他液狀或固體環氧樹脂。The epoxy resin (A) may be a component of both a liquid bisphenol A type epoxy resin and a liquid bisphenol F type epoxy resin, but may have other components if the viscosity at 25 ° C satisfies the above range. Liquid or solid epoxy resin.

作為其他環氧樹脂，可使用於1分子中具有2個環氧基之雙酚E型環氧樹脂、雙酚S型環氧樹脂、雙酚Z型環氧樹脂、異佛爾酮雙酚型環氧樹脂等之雙酚型環氧樹脂，或不限於此等雙酚型環氧樹脂之鹵素、烷基取代體、氫化品、單體且具有複數之重複單元之高分子量體、伸烷基氧化物加成物之縮水甘油基醚或酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂等之酚醛清漆型環氧樹脂，或3,4-環氧基-6-甲基環己基甲基-3,4-環氧基-6-甲基環己烷羧酸酯、3,4-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯、1-環氧基乙基-3,4-環氧基環己烷等之脂環式環氧樹脂，或三羥甲基丙烷聚縮水甘油基醚、季戊四醇聚縮水甘油基醚、聚氧伸烷基二縮水甘油基醚等之脂肪族環氧樹脂，或鄰苯二甲酸二縮水甘油基酯與四氫鄰苯二甲酸二縮水甘油基酯與二聚酸縮水甘油基酯等之縮水甘油基酯，或四縮水甘油基二胺基二苯基甲烷、四縮水甘油基二胺基二苯基碸、三縮水甘油基胺基酚、三縮水甘油基胺基甲酚、四縮水甘油基二甲苯二胺等之縮水甘油基胺類等。此等可單獨1種使用，亦可組合2種以上使用。As another epoxy resin, it can be used for a bisphenol E type epoxy resin having two epoxy groups in one molecule, a bisphenol S type epoxy resin, a bisphenol Z type epoxy resin, and an isophorone bisphenol type. a bisphenol type epoxy resin such as an epoxy resin, or a high molecular weight body having a repeating unit of a halogen, an alkyl substituent, a hydrogenated product, a monomer of the bisphenol type epoxy resin, or an alkyl group a novolak type epoxy resin such as a glycidyl ether or a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, or a bisphenol A novolak type epoxy resin, or 3, 4 -Epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-ring An alicyclic epoxy resin such as oxycyclohexane carboxylate or 1-epoxyethyl-3,4-epoxycyclohexane, or trimethylolpropane polyglycidyl ether or pentaerythritol poly An aliphatic epoxy resin such as glycidyl ether or polyoxyalkylene diglycidyl ether, or diglycidyl phthalate and diglycidyl tetrahydrophthalate and dimer acid condensate A glycidyl ester such as a water glyceryl ester, or a tetraglycidyldiaminodiphenylmethane, a tetraglycidyldiaminediphenylphosphonium, a triglycidylaminophenol, or a triglycidylamino group. A glycidylamine such as cresol or tetraglycidyl xylene diamine. These may be used alone or in combination of two or more.

環氧樹脂硬化劑(B)係熔點或熱分解溫度為200℃以上之固體環氧樹脂硬化劑。藉由為固體，雖於室溫幾乎未溶解在環氧樹脂，但加熱至100℃以上時則溶解，可成為具有與環氧基進行反應之特性，且於室溫之保存穩定性優異之潛在性硬化劑。 　　作為環氧樹脂硬化劑，例如較佳為使用二氰二胺、二醯肼化合物、胍化合物、二胺基二苯基碸等。使用二氰二胺時，作為摻合量，較佳為相對於環氧樹脂(A)之環氧基1莫耳，以0.3～1.2當量(為二氰二胺時，將1莫耳作為4當量計算)的範圍進行摻合。更佳為0.4～0.6當量。未滿0.3當量時，硬化物之交聯密度降低，容易降低破壞韌性，超過1.2當量時，由於容易殘留未反應之二氰二胺，有機械物性惡化的傾向。從另一觀點來看，相對於環氧樹脂組成物，較佳為1～15wt%，更佳為3～7wt%。The epoxy resin hardener (B) is a solid epoxy resin hardener having a melting point or a thermal decomposition temperature of 200 ° C or higher. When it is a solid, it is hardly dissolved in the epoxy resin at room temperature, but it is dissolved when heated to 100 ° C or higher, and it has a property of reacting with an epoxy group and has excellent storage stability at room temperature. Sex hardener. As the epoxy resin curing agent, for example, dicyandiamide, a diterpene compound, an anthracene compound, a diaminodiphenylphosphonium or the like is preferably used. When dicyandiamide is used, the blending amount is preferably from 0.3 to 1.2 equivalents per 1 part of the epoxy group of the epoxy resin (A) (for dicyandiamide, 1 mole is used as 4) The range of equivalent calculations is blended. More preferably, it is 0.4 to 0.6 equivalent. When the amount is less than 0.3 equivalent, the crosslinking density of the cured product is lowered, and the fracture toughness is likely to be lowered. When the amount is more than 1.2 equivalents, the unreacted dicyandiamide tends to remain, and the mechanical properties tend to deteriorate. From another point of view, it is preferably from 1 to 15% by weight, more preferably from 3 to 7% by weight, based on the epoxy resin composition.

咪唑化合物(C)作為硬化促進劑進行作用，除了對於混合時之強化纖維的含浸性，另為了更加滿足在硬化時之耐熱性，例如可使用2-甲基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、1-苄基-2-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基6-4′,5′-二羥基甲基咪唑、1-氰基乙基-2-乙基-4甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑等之咪唑系化合物。進而，亦可優選使用含有三嗪環之咪唑化合物，例如可列舉式(2)表示之2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-十一烷基咪唑基-(1’)]-乙基-s-三嗪、式(1)表示之2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-S-三嗪異氰脲酸加成物等。此等可1種或組合2種以上使用，尤其是優選使用式(1)或式(2)表示之咪唑化合物。若為化學性穩定，且於常溫未溶解在環氧樹脂者，則並非被限定於上述者。 　　咪唑化合物(C)的使用量相對於環氧樹脂組成物100重量份，較佳為0.01～7重量份。更佳為1～5重量份。超過7重量份時，由於粉末成分增多，產生孔洞容易增多的問題。未滿0.01重量份時，產生無法實現速硬化性的問題。The imidazole compound (C) acts as a hardening accelerator, in addition to the impregnation property of the reinforcing fibers at the time of mixing, and in order to further satisfy the heat resistance at the time of hardening, for example, 2-methylimidazole, 1,2-dimethyl group can be used. Imidazole, 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-4-methylimidazole, 2-phenyl-4-methyl An imidazole compound such as a 5-hydroxymethylimidazole. Further, an imidazole compound containing a triazine ring can also be preferably used, and for example, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl represented by the formula (2) can be used. -s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, represented by formula (1) a diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-S-triazine isocyanuric acid adduct or the like. These may be used alone or in combination of two or more. In particular, an imidazole compound represented by the formula (1) or the formula (2) is preferably used. If it is chemically stable and is not dissolved in an epoxy resin at normal temperature, it is not limited to the above. The amount of the imidazole compound (C) used is preferably 0.01 to 7 parts by weight based on 100 parts by weight of the epoxy resin composition. More preferably, it is 1 to 5 parts by weight. When it exceeds 7 parts by weight, there is a problem that the number of pores tends to increase due to an increase in the powder component. When it is less than 0.01 part by weight, there is a problem that the quick-curing property cannot be achieved.

環氧樹脂硬化劑(B)及咪唑化合物(C)之合計的添加量，從孔洞減低效果來看，較佳為相對於環氧樹脂組成物為10重量%以下。更佳為相對於環氧樹脂組成物為1～5重量%。The total amount of the epoxy resin hardener (B) and the imidazole compound (C) is preferably 10% by weight or less based on the effect of reducing the pores with respect to the epoxy resin composition. More preferably, it is 1 to 5% by weight based on the epoxy resin composition.

藉由環氧樹脂硬化劑(B)及咪唑化合物(C)皆成為平均粒徑D50為2μm以下，較佳為D90成為3μm以下，顯示良好之含浸性，於硬化物作成時可減低孔洞。然而，粒徑過細時，具體而言，D90成為1μm以下時，恐有顯著損害儲藏穩定性之虞。該情況下，可藉由添加硼酸三丁酯等之路易斯酸，進行技術性改善。於長絲纏繞時由於硬化劑粉末收納在碳纖維之間隙，並未阻礙來自絲束預浸料之樹脂成分的滲出，可將在長絲纏繞製程必然產生之碳纖維的段差以樹脂埋入。作為結果，即使在低Rc條件，亦可抑制孔洞之生成。理想的情況下，藉由硬化劑等之粒子直徑相對於碳纖維之直徑成為(2/√3-1)以下，不會影響碳的收緊。因此，較佳為D50為此直徑以下，更理想為D90為此直徑以下。理想的情況下，D100雖為此直徑以下，但精度良好地實現此有困難，且粒徑變過細時，儲藏穩定性惡化。D50較此直徑更大時，在長絲纏繞步驟無法得到充分之樹脂的滲出，無法將碳纖維之段差藉由樹脂埋入。因此，變容易殘留空氣，有於硬化物中殘留孔洞之虞。The epoxy resin hardener (B) and the imidazole compound (C) have an average particle diameter D50 of 2 μm or less, preferably D90 of 3 μm or less, and exhibit good impregnation, and the void can be reduced when the cured product is formed. However, when the particle diameter is too small, specifically, when D90 is 1 μm or less, there is a fear that the storage stability is remarkably impaired. In this case, technical improvement can be performed by adding a Lewis acid such as tributyl borate. When the filament is entangled, since the hardener powder is accommodated in the gap between the carbon fibers, the bleed out of the resin component from the tow prepreg is not hindered, and the step of the carbon fiber which is inevitably generated in the filament winding process can be buried in the resin. As a result, the formation of voids can be suppressed even under low Rc conditions. In an ideal case, the particle diameter of the hardener or the like is (2/√3-1) or less with respect to the diameter of the carbon fiber, and does not affect the tightening of carbon. Therefore, it is preferred that D50 be below this diameter, and more desirably D90 is below this diameter. In the case of D100, the D100 is preferably not more than the diameter, but it is difficult to achieve this with high precision, and when the particle diameter is too small, the storage stability is deteriorated. When D50 is larger than this diameter, sufficient resin bleed is not obtained in the filament winding step, and the step of carbon fiber cannot be buried by the resin. Therefore, it is easy to leave air, and there is a flaw in the hole in the hardened material.

硬化劑等之粉碎例如可藉由噴磨機進行。經粉碎之硬化劑等之粒度分布，例如可使用日機裝製微軌道粒度分布測定裝置MT3300EXII進行評估。分散劑雖藉由粉末的種類進行選擇，但於本說明書，係分散在2-丙醇進行測定。The pulverization of the hardener or the like can be carried out, for example, by a jet mill. The particle size distribution of the pulverized hardener or the like can be evaluated, for example, using a daily-mounted micro-track particle size distribution measuring apparatus MT3300EXII. Although the dispersing agent is selected by the kind of the powder, in the present specification, it is measured by dispersing in 2-propanol.

硬化劑等藉由縮小粉末之粒徑，由於增大表面積，有降低儲藏穩定性的懸念。該情況下，可藉由周知慣用之手法改善儲藏穩定性。作為穩定劑，具體而言，可列舉添加少量硼酸三丁酯等之路易斯酸，例如相對於環氧樹脂組成物100重量份，添加1.0重量份以下之方法。A hardener or the like has a suspense which lowers the storage stability by reducing the particle diameter of the powder and increasing the surface area. In this case, the storage stability can be improved by a conventionally known method. Specific examples of the stabilizer include a Lewis acid such as a small amount of tributyl borate, and a method of adding 1.0 part by weight or less to 100 parts by weight of the epoxy resin composition.

本發明之環氧樹脂組成物中可包含橡膠成分(D)。作為橡膠成分，將丙烯腈與丁二烯作為原料之共聚物由於相對於環氧樹脂之溶解性優異，故優選使用。尤其是使用具有可與羧基、胺基、環氧基等之環氧樹脂或其硬化劑進行反應之官能基者時，由於硬化物之韌性提昇效果大，故特佳。 　　又，亦可優選使用含有不溶環氧樹脂之橡膠成分之粒子。雖亦使用經交聯之橡膠粒子本身，但尤其適合具有將不溶環氧樹脂之橡膠粒子的表面以非橡膠成分被覆之核殼構造的橡膠粒子。此情況下，被覆之成分為如聚甲基丙烯酸甲酯般溶解、或膨潤於環氧樹脂亦可，反倒是由於粒子在環氧樹脂中之分散變良好，故較佳。使用具有不溶環氧樹脂之核殼構造的橡膠粒子時，樹脂硬化物之耐熱性有較通常之橡膠成分更優異之優勢。The rubber component (D) may be contained in the epoxy resin composition of the present invention. As a rubber component, a copolymer containing acrylonitrile and butadiene as a raw material is preferably used because it is excellent in solubility with respect to an epoxy resin. In particular, when a functional group having an epoxy resin such as a carboxyl group, an amine group or an epoxy group or a curing agent thereof is used, the effect of improving the toughness of the cured product is particularly high. Further, particles containing a rubber component of an insoluble epoxy resin can also be preferably used. Although the crosslinked rubber particles themselves are also used, rubber particles having a core-shell structure in which the surface of the rubber particles insoluble epoxy resin is coated with a non-rubber component are particularly suitable. In this case, the coated component may be dissolved as in the case of polymethyl methacrylate or may be swelled in the epoxy resin. On the other hand, since the dispersion of the particles in the epoxy resin is good, it is preferable. When rubber particles having a core-shell structure of an insoluble epoxy resin are used, the heat resistance of the cured resin has an advantage superior to that of a usual rubber component.

於橡膠成分之添加，有韌性之提昇效果及預浸料之黏性的提昇效果，平均粒子徑以體積平均粒子徑較佳為1～500nm，若為3～300nm更佳。 　　核殼橡膠等之橡膠成分(D)的摻合量，較佳為於環氧樹脂組成物100重量份中摻合0.5～15重量份，若為1～10重量份更佳。若摻合量為0.5重量份以上，容易得到成形後之纖維強化複合材料所必要之破壞韌性，進而，若摻合量為15重量份以下，抑制所得之纖維強化複合材料用環氧樹脂組成物的黏度提高，由於可合理地含浸在強化纖維，成為更適合在纖維強化複合材料用者。The addition of the rubber component has an effect of improving the toughness and an effect of improving the viscosity of the prepreg. The average particle diameter is preferably from 1 to 500 nm in terms of volume average particle diameter, and more preferably from 3 to 300 nm. The blending amount of the rubber component (D) such as the core-shell rubber is preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the epoxy resin composition. When the blending amount is 0.5 parts by weight or more, the fracture toughness required for the fiber-reinforced composite material after molding is easily obtained, and when the blending amount is 15 parts by weight or less, the obtained epoxy resin composition for fiber-reinforced composite material is suppressed. The viscosity is improved, and since it can be reasonably impregnated with reinforcing fibers, it becomes more suitable for users of fiber-reinforced composite materials.

本發明之環氧樹脂組成物中，作為添加劑，以提昇表面平滑性為目的可添加消泡劑、整平劑。此等添加劑相對於樹脂組成物全體100重量份，可摻合0.01～3重量份，較佳為0.01～1重量份。摻合量未滿0.01重量份時，未表現使表面平滑的效果，超過3重量份時，引起添加劑滲出於表面，反而，成為損害平滑性的要因。又，視必要亦可摻合顏料其他添加劑。惟，本發明之環氧樹脂組成物作為全體，以保持液狀的方式，可將(A)成分的摻合量設為50wt%以上，較佳為定為80wt%以上。尚，溶劑不作為添加劑處理。In the epoxy resin composition of the present invention, as an additive, an antifoaming agent and a leveling agent may be added for the purpose of improving surface smoothness. These additives may be blended in an amount of 0.01 to 3 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the total of the resin composition. When the blending amount is less than 0.01 part by weight, the effect of smoothing the surface is not exhibited, and when it exceeds 3 parts by weight, the additive is caused to permeate the surface, and conversely, it is a factor that impairs smoothness. Further, other additives of the pigment may be blended as necessary. In the epoxy resin composition of the present invention, the amount of the component (A) blended may be 50% by weight or more, and preferably 80% by weight or more, as a whole. Still, the solvent is not treated as an additive.

本發明之環氧樹脂組成物中可摻合其他硬化性樹脂。作為如此之硬化性樹脂，雖可列舉不飽和聚酯樹脂、硬化性丙烯酸樹脂、硬化性胺基樹脂、硬化性三聚氰胺樹脂、硬化性脲樹脂、硬化性氰酸酯樹脂、硬化性胺基甲酸酯樹脂、硬化性環氧丙烷樹脂、硬化性環氧基/環氧丙烷複合樹脂等，但並非被限定於此等。Other curable resins may be blended in the epoxy resin composition of the present invention. Examples of such a curable resin include an unsaturated polyester resin, a curable acrylic resin, a curable amine-based resin, a curable melamine resin, a curable urea resin, a curable cyanate resin, and a curable urethane. The ester resin, the curable propylene oxide resin, the curable epoxy group/propylene oxide composite resin, and the like are not limited thereto.

本發明之環氧樹脂組成物係藉由均勻混合上述之(A)成分～(C)成分等製造。原料的混合可藉由周知慣用之方法混合。例如，可使用自轉公轉式離心攪拌裝置，可用分散器等進行分散，亦可進行輥分散。可為其他方法，亦可組合此等。惟，提高溫度時，由於硬化劑等溶解在環氧樹脂中，使儲藏穩定性惡化。以較佳為40℃以下，理想為以30℃以下的條件迅速混合。The epoxy resin composition of the present invention is produced by uniformly mixing the above components (A) to (C). The mixing of the raw materials can be carried out by a conventionally known method. For example, a self-rotating revolution type centrifugal stirring device can be used, and dispersion can be carried out by a disperser or the like, or roll dispersion can be performed. It can be other methods or combined. However, when the temperature is raised, the curing property is deteriorated because the curing agent or the like is dissolved in the epoxy resin. It is preferably mixed at a temperature of preferably 40 ° C or lower, preferably at 30 ° C or lower.

本發明之環氧樹脂組成物係(A)成分以液狀存在，(B)成分、(C)成分之至少一部分以粉末狀存在。(B)成分、(C)成分之一部分雖溶解在液體中，環氧樹脂的硬化控制在無法充分進行的程度。據此，作為預浸料的製造所使用之環氧樹脂組成物，或作為存在於預浸料中之環氧樹脂組成物有用。The epoxy resin composition (A) component of the present invention is present in a liquid form, and at least a part of the component (B) and the component (C) is present in a powder form. When one of the components (B) and (C) is dissolved in a liquid, the hardening of the epoxy resin is not sufficiently controlled. Accordingly, it is useful as an epoxy resin composition used for the production of a prepreg or as an epoxy resin composition present in a prepreg.

本發明之環氧樹脂組成物可以藉由加熱進行低黏度化，邊浸漬強化纖維束邊含浸之長絲纏繞法等製造絲束預浸料，由於絲束預浸料中所殘留之有機溶劑實質上可能皆無，故可製造生產性高且高品位之絲束預浸料，於此使用之強化纖維束可列舉碳纖維，較佳為使用10.0μm以下，更佳為使用平均直徑為7.5μm以下，特佳為使用6.5μm以下之碳纖維。較平均直徑更大時，針對本發明的效果之顯著差異縮小。The epoxy resin composition of the present invention can be used to produce a tow prepreg by heating and low viscosity, and impregnating a fiber bundle impregnated filament winding method, etc., due to the organic solvent remaining in the tow prepreg. It is possible to produce a high-grade tow prepreg, and the reinforcing fiber bundle used herein may be carbon fiber, preferably 10.0 μm or less, more preferably 7.5 μm or less. It is particularly preferable to use carbon fibers of 6.5 μm or less. When the average diameter is larger, the significant difference with respect to the effect of the present invention is reduced.

本發明之環氧樹脂組成物適合使用在絲束預浸料纖維強化複合材料。於此使用之絲束預浸料的製造方法，雖並未特別限定，但可用使環氧樹脂組成物溶解在甲基乙基酮或甲醇等之有機溶劑，進行低黏度化，邊浸漬強化纖維束邊含浸後，使用烤箱等使有機溶劑蒸發，而成為絲束預浸料之濕法，或不使用有機溶劑，進行加熱，將經低黏度化之該環氧樹脂組成物薄膜化在輥或脫模紙上，其次，藉由轉印至強化纖維束之單面或兩面後，通過彎輥或壓力輥進行加壓，而含浸之熱熔法、將該環氧樹脂組成物藉由加熱進行低黏度化，邊浸漬強化纖維束邊含浸之長絲纏繞法等製造，不使用有機溶劑或使用低沸點之溶劑時，絲束預浸料中所殘留之有機溶劑實質上皆無，由於可製造生產性高且高品位之絲束預浸料，故可優選使用長絲纏繞法。藉由使用如此之製造法，可得到樹脂含浸之絲束預浸料。The epoxy resin composition of the present invention is suitably used in a tow prepreg fiber reinforced composite material. The method for producing the tow prepreg used herein is not particularly limited, but the epoxy resin composition may be dissolved in an organic solvent such as methyl ethyl ketone or methanol to carry out low-viscosity and impregnated reinforcing fibers. After the bundle is impregnated, the organic solvent is evaporated by using an oven or the like to form a wet pre-dip of the tow, or heated without using an organic solvent, and the low-viscosity epoxy resin composition is thinned on a roll or On the release paper, secondly, after being transferred to one side or both sides of the reinforcing fiber bundle, pressurization is performed by a bending roll or a pressure roll, and the hot melt method of impregnation is performed, and the epoxy resin composition is low by heating. It is produced by a filament winding method in which the viscosity is immersed and impregnated with a fiber bundle, and when an organic solvent or a solvent having a low boiling point is used, the organic solvent remaining in the tow prepreg is substantially absent, since productivity can be produced. A high-grade and high-grade tow prepreg is preferred, and a filament winding method can be preferably used. By using such a manufacturing method, a resin impregnated tow prepreg can be obtained.

本發明之環氧樹脂組成物係作為纖維強化複合材料有用，作為於此使用之強化纖維，雖選自玻璃纖維、芳綸纖維、碳纖維、硼纖維等，但為了得到強度優異之纖維強化複合材料，較佳為使用碳纖維。The epoxy resin composition of the present invention is useful as a fiber-reinforced composite material, and the reinforcing fiber used herein is selected from glass fiber, aramid fiber, carbon fiber, boron fiber, etc., but a fiber-reinforced composite material excellent in strength is obtained. Preferably, carbon fiber is used.

碳纖維例如雖可列舉東麗製T700SC-12000-50C(直徑7μm、密度1.8g/cm3 、纖度802TEX)、東麗製T720SC-36000-50C(直徑6μm、密度1.8g/cm3 、纖度1650TEX)等，但在本發明，並非被限定於此等。Examples of the carbon fiber include Toray T700SC-12000-50C (diameter 7 μm, density 1.8 g/cm 3 , fineness 802TEX), Toray T720SC-36000-50C (diameter 6 μm, density 1.8 g/cm 3 , fineness 1650 TEX) Etc., but in the present invention, it is not limited to this.

本發明之絲束預浸料可將上述之環氧樹脂組成物含浸在碳纖維。該方法可將碳纖維浸漬在樹脂浴，亦可將塗佈在鼓輪(Drum)之樹脂轉印在碳纖維。可藉由其他周知慣用之手法獲得。The tow prepreg of the present invention can impregnate the above epoxy resin composition with carbon fibers. In this method, the carbon fiber is immersed in a resin bath, and the resin coated on the drum (Drum) may be transferred to the carbon fiber. It can be obtained by other well-known methods.

在藉由本發明之環氧樹脂組成物與強化纖維構成之成形體，強化纖維之含有率雖因作為目的之材料而異，但在車載用之高壓氣體容器，為了實現輕量化，Rc為18～28重量%，較佳為20～26重量%，更佳為21～24重量%。Rc較18重量%更低時，孔洞易增多，較28重量%更高時，由於製品重量增大，例如作為車載用之氣體容器不佳。In the molded article comprising the epoxy resin composition of the present invention and the reinforcing fiber, the content of the reinforcing fiber varies depending on the intended material. However, in order to reduce the weight of the high-pressure gas container for use in the vehicle, Rc is 18 to 28% by weight, preferably 20 to 26% by weight, more preferably 21 to 24% by weight. When the Rc is lower than 18% by weight, the pores tend to increase, and when it is higher than 28% by weight, the weight of the product is increased, for example, it is not preferable as a gas container for use in a vehicle.

本發明之環氧樹脂組成物可藉由以80～180℃，較佳為以135℃以上之溫度的任意溫度，以0.5～10小時的範圍之任意時間進行加熱，使交聯反應進行，而得到硬化物。加熱條件可為1階段，亦可為組合複數加熱條件之多階段條件。尤其是假設填充如燃料電池所使用般之氫氣體等之高壓力容器的情況下，藉由以80～150℃之溫度的範圍的任意溫度，以0.5～5小時的範圍之任意時間進行加熱硬化，可得到所期望之硬化物的物性。 [實施例]The epoxy resin composition of the present invention can be subjected to heating at any temperature in the range of 0.5 to 10 hours at any temperature of 80 to 180 ° C, preferably 135 ° C or higher, to carry out the crosslinking reaction. A hardened product is obtained. The heating condition may be one stage or a multi-stage condition in which a plurality of heating conditions are combined. In particular, in the case of a high-pressure vessel filled with a hydrogen gas or the like as used in a fuel cell, heat hardening is performed at any temperature in the range of 0.5 to 5 hours at any temperature in the range of 80 to 150 °C. The physical properties of the desired cured product can be obtained. [Examples]

以下，藉由實施例，進一步具體說明本發明。Hereinafter, the present invention will be further specifically described by way of examples.

首先，針對第一本發明，藉由實施例具體說明。 　　在第一本發明，為了得到各實施例之樹脂組成物，使用下述之樹脂原料。First, the first invention will be specifically described by way of examples. In the first aspect of the invention, in order to obtain the resin composition of each of the examples, the following resin materials are used.

(A)環氧樹脂 　　･液狀雙酚F型環氧樹脂：YDF-170(新日鐵住金化學製)(環氧基當量160～180g/eq、黏度2～5Pa･s) 　　･液狀雙酚A型環氧樹脂：YD-128(新日鐵住金化學製)(環氧基當量184～194g/eq、黏度11～15Pa･s) (B)二氰二胺 　　･二氰二胺：DICYANEX1400F(AIRPRODUCT公司製) (C)咪唑系硬化輔助劑 　　･2MZA-PW(四國化成工業製) 2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三嗪 　　･2MAOK-PW(四國化成工業製) 2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三嗪異氰脲酸加成物 　　･2P4MHZ-PW(四國化成工業製) 2-苯基-4-甲基-5-羥基甲基咪唑 　　･PN-23J(味之素精細技術製) 　　･PN-50J(味之素精細技術製) (D)核殼橡膠 　　･MX-154(Kaneka製)：環氧基母料批次 　　(核殼橡膠摻合量40wt%、BPA型環氧樹脂摻合量60wt%、平均粒徑100nm)(A) Epoxy resin/liquid bisphenol F-type epoxy resin: YDF-170 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) (epoxy equivalent 160-180 g/eq, viscosity 2 to 5 Pa·s) ・Liquid double Phenol A type epoxy resin: YD-128 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) (epoxy equivalent: 184 to 194 g/eq, viscosity: 11 to 15 Pa·s) (B) dicyandiamide and dicyandiamide: DICYANEX1400F (manufactured by AIRPRODUCT Co., Ltd.) (C) Imidazole-based hardening aid, 2MZA-PW (manufactured by Shikoku Chemicals Co., Ltd.) 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-( 1')]-Ethyl-s-triazine·2MAOK-PW (manufactured by Shikoku Chemicals Co., Ltd.) 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1) ')]-Ethyl-s-triazine isocyanuric acid adduct, 2P4MHZ-PW (manufactured by Shikoku Chemicals Co., Ltd.) 2-Phenyl-4-methyl-5-hydroxymethylimidazole, PN-23J ( Ajinomoto Fine Technology) ・PN-50J (Ajinomoto Fine Technology) (D) Core Shell Rubber, MX-154 (Kaneka): Epoxy Masterbatch Batch (core shell rubber blending amount 40% by weight) , BPA type epoxy resin blending amount 60wt%, average particle diameter 100nm)

將測定方法示於以下。 　　(1)環氧基當量：係依照JIS K 7236規格測定。具體而言，使用電位差滴定裝置，使用四氫呋喃作為溶劑，加入溴化四乙基銨乙酸溶液，使用0.1mol/L高氯酸-乙酸溶液。 　　(2)黏度：係依JIS K7117-1。具體而言，將硬化前樹脂組成物在25℃之黏度以E型黏度計測定。 　　(3)增黏率：於40℃之熱風循環式烤箱靜置3天後，依照JIS K7177-1測定。 　　(4)反應峰值溫度：在差示掃描熱量測定裝置(SII Nano Technology製 EXSTAR6000 DSC6200)，以10℃/分鐘之昇溫條件進行測定時之每一小時之發熱量成為最大時之溫度表示。 　　(5)反應起始溫度：在差示掃描熱量測定裝置(SII Nano Technology製 EXSTAR6000 DSC6200)，以10℃/分鐘之昇溫條件進行測定時之每一小時之發熱量的外插表示。 　　(6)Tg：在差示掃描熱量測定裝置(SII Nano Technology製 EXSTAR6000 DSC6200)，以10℃/分鐘之昇溫條件進行測定時之DSC外插值的溫度表示。 　　(7)破壞韌性(K1c)：係依ASTM E399。具體而言，作成寬10mm、厚度4mm、長度50mm之試驗片，以室溫23℃下、十字頭速度0.5 mm/分鐘測定。 　　(8)拉伸彈性率、拉伸強度、拉伸伸長：依JIS K7161。具體而言，使用萬能材料試驗機(島津科學製 Autograph AGS-H)。在室溫，將包含握持部分之全長215mm、寬10mm、厚度4mm之尺寸的啞鈴試驗片，以吸盤間114mm、速度50mm/min.進行拉伸試驗，從所得之應力-應變圖，求出拉伸強度、拉伸彈性率、拉伸伸長。The measurement method is shown below. (1) Epoxy equivalent: It is measured in accordance with JIS K 7236. Specifically, a potentiometric titration apparatus was used, tetrahydrofuran was used as a solvent, and a tetraethylammonium bromide acetic acid solution was added, and a 0.1 mol/L perchloric acid-acetic acid solution was used. (2) Viscosity: according to JIS K7117-1. Specifically, the viscosity of the resin composition before hardening at 25 ° C was measured by an E-type viscosity meter. (3) Viscosity increasing ratio: After standing in a hot air circulating oven at 40 ° C for 3 days, it was measured in accordance with JIS K7177-1. (4) Peak temperature of reaction: The temperature at which the calorific value per hour of the differential scanning calorimeter (EXSTAR6000 DSC6200 manufactured by SII Nano Technology) was measured at a temperature rise of 10 ° C /min. (5) Reaction initiation temperature: An extrapolation of the calorific value per hour of the measurement by a differential scanning calorimeter (EXSTAR6000 DSC6200, manufactured by SII Nano Technology) at a temperature rise of 10 ° C /min. (6) Tg: The temperature of the DSC extrapolated value measured by a differential scanning calorimeter (EXSTAR6000 DSC6200, manufactured by SII Nano Technology) under the temperature rising condition of 10 ° C / min. (7) Destructive toughness (K1c): according to ASTM E399. Specifically, a test piece having a width of 10 mm, a thickness of 4 mm, and a length of 50 mm was prepared and measured at a room temperature of 23 ° C at a crosshead speed of 0.5 mm/min. (8) Tensile modulus, tensile strength, and tensile elongation: according to JIS K7161. Specifically, a universal material testing machine (Autograph AGS-H manufactured by Shimadzu Scientific) was used. At room temperature, a dumbbell test piece including a grip portion having a total length of 215 mm, a width of 10 mm, and a thickness of 4 mm was subjected to a tensile test at 114 mm between the suction cups and a speed of 50 mm/min, and the obtained stress-strain diagram was obtained. Tensile strength, tensile modulus, and tensile elongation.

參考例 　　咪唑系硬化輔助劑之發熱起始溫度及反應峰值溫度的測定所使用之環氧樹脂組成物係依以下調製。 　　將YD-128(A)/二氰二胺(B)/咪唑系硬化輔助劑(C)，以表1A之摻合(wt%)加入進行混練，來作為環氧樹脂組成物。在差示掃描熱量測定裝置，將從以10℃/分鐘之昇溫條件進行測定時之每一小時之發熱量，集合外插之發熱起始溫度及發熱峰值溫度的測定結果示於表1A。Reference Example The epoxy resin composition used for the measurement of the heat initiation temperature and the reaction peak temperature of the imidazole-based hardening aid was prepared as follows. YD-128(A)/dicyandiamine (B)/imidazole-based hardening aid (C) was added as a resin composition by blending (wt%) of Table 1A. In the differential scanning calorimeter, the calorific value of the heat generation temperature and the peak value of the exothermic temperature of each hour when the calorific value was measured at a temperature rising condition of 10 ° C /min is shown in Table 1A.

實施例1A～4A、比較例1A～8A (1)環氧樹脂組成物之調製 　　加入(A)環氧樹脂、(B)二氰二胺、(C)咪唑系硬化輔助劑及(D)核殼橡膠，使用THINKY PLANETARY VACUUM MIXER(Thinky製)，以2000rpm、4.0mmhg之條件下進行6分鐘混練，調製表1A及2A所示之組成(wt%)的環氧樹脂組成物。(B)二氰二胺係使用與環氧樹脂之一部分進行預備混練者，(D)核殼橡膠亦使用於核殼聚合物之製造過程分散在環氧樹脂中之母料批次。Examples 1A to 4A and Comparative Examples 1A to 8A (1) Preparation of epoxy resin composition (A) epoxy resin, (B) dicyandiamide, (C) imidazole hardening auxiliary agent, and (D) core The shell rubber was kneaded by a THINKY PLANETARY VACUUM MIXER (manufactured by Thinky Co., Ltd.) under conditions of 2000 rpm and 4.0 mmhg for 6 minutes to prepare a composition (wt%) of the epoxy resin composition shown in Tables 1A and 2A. (B) The dicyandiamide is used as a preliminary kneading with one part of the epoxy resin, and (D) the core-shell rubber is also used as a master batch for the dispersion of the core-shell polymer in the epoxy resin.

(2)試驗片之製作 　　將於上述(1)製作之環氧樹脂組成物加熱至80℃之溫度，注入模子，以50℃之溫度的烤箱以3℃/分鐘昇溫至150℃後進行45分鐘硬化，製作厚度4mm之環氧樹脂硬化物的板。其次，切出所得之環氧樹脂硬化物的板，使用在試驗分析。將結果示於表2A及3A。(2) Preparation of test piece The epoxy resin composition prepared in the above (1) was heated to a temperature of 80 ° C, poured into a mold, and heated at a temperature of 50 ° C in an oven at 3 ° C / min to 150 ° C for 45 minutes. After hardening, a plate of a cured epoxy resin having a thickness of 4 mm was produced. Next, the obtained plate of the cured epoxy resin was cut out and used for experimental analysis. The results are shown in Tables 2A and 3A.

其次，針對第二本發明，藉由實施例具體說明。 　　在第二本發明，將於各實施例及比較例使用之材料示於以下。為了得到樹脂組成物，使用下述之樹脂原料。Next, the second invention will be specifically described by way of examples. In the second invention, the materials used in the respective examples and comparative examples are shown below. In order to obtain a resin composition, the following resin raw materials are used.

(A)成分 　　･液狀雙酚F型環氧樹脂：YDF-170(新日鐵住金化學製)(環氧基當量160～180g/eq、黏度2～5Pa･s) 　　･液狀雙酚A型環氧樹脂：YD-128(新日鐵住金化學製)(環氧基當量184～194g/eq、黏度11～15Pa･s) 　　･核殼橡膠含有液狀BPA型環氧樹脂：Kane ace MX-154(Kaneka公司製)(橡膠含量40重量%、環氧基當量301g/eq、黏度30Pa･s-50℃) (B)成分 　　･二氰二胺：DICYANEX1400F(分解溫度250℃以上；AIRPRODUCT公司製) 　　･二乙基甲基苯二胺：ETHACURE100(室溫液狀；Albemarle公司製) (C)成分 　　･2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三嗪異氰脲酸加成物：2MAOK-PW(分解溫度250℃以上；四國化成工業製)(A) Ingredients and liquid bisphenol F-type epoxy resin: YDF-170 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) (epoxy equivalent: 160 to 180 g/eq, viscosity: 2 to 5 Pa·s) ・Liquid bisphenol A Epoxy resin: YD-128 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) (epoxy equivalent: 184 to 194 g/eq, viscosity: 11 to 15 Pa·s) ・ Core-shell rubber contains liquid BPA-type epoxy resin: Kane ace MX -154 (manufactured by Kaneka Co., Ltd.) (40% by weight of rubber, 301 g/eq of epoxy equivalent, viscosity: 30 Pa·s - 50 ° C) (B) Component: dicyandiamide: DICYANEX 1400F (decomposition temperature: 250 ° C or higher; AIR PRODUCT )) ・Diethylmethylphenylenediamine: ETHACURE 100 (room temperature liquid; manufactured by Albemarle) (C) component・2,4-diamino-6-[2'-ethyl-4'-methyl Imidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct: 2MAOK-PW (decomposition temperature above 250 ° C; manufactured by Shikoku Chemicals Co., Ltd.)

碳纖維 　　T7μm：東麗製T700SC-12000-50C(直徑7μm) 　　T6μm：東麗製SC-36000-50C(直徑6μm)Carbon fiber T7μm: Toray T700SC-12000-50C (diameter 7μm) T6μm: Toray SC-36000-50C (diameter 6μm)

將測定方法示於以下。 　　平均粒徑之測定： 　　作為分散劑，係使用2-丙醇，使用日機裝製微軌道粒度分布測定裝置MT3300EXII評估。The measurement method is shown below. Measurement of Average Particle Diameter: As a dispersing agent, 2-propanol was used, and it was evaluated using a daily-mounted micro-orbital particle size distribution measuring apparatus MT3300EXII.

黏度： 　　依JIS K7117-1，使用東機產業製E型黏度計RE-85進行。Viscosity: According to JIS K7117-1, the E-type viscometer RE-85 manufactured by Toki Sangyo Co., Ltd. was used.

儲藏穩定性： 　　追蹤黏度的變化進行評估。其條件係作成50g樹脂組成物，放入50mL之小玻璃瓶，測定於25℃之初期黏度及經指定時間(24h、48h、96h或168h)保管後之黏度，以黏度上昇率評估。黏度上昇率Z係從於25℃指定時間保管後之黏度VZ 、與初期黏度Vi，以下式計算之值。針對保管時間24h、48h、96h或168h，分別求出黏度上昇率。 　　黏度上昇率(%)=(VZ /Vi-1)×100 　　尚，將作為全體之儲藏穩定性評估為◎：優、○：良、×：不可。Storage stability: Track changes in viscosity for evaluation. The conditions were as follows: 50 g of a resin composition was placed in a 50 mL vial, and the initial viscosity at 25 ° C and the viscosity after storage for a specified time (24h, 48h, 96h or 168h) were measured and evaluated as the viscosity increase rate. The viscosity increase rate Z is a value calculated from the following formula from the viscosity V Z after storage at a predetermined time of 25 ° C and the initial viscosity Vi. The viscosity increase rate was determined for the storage time of 24h, 48h, 96h or 168h, respectively. The viscosity increase rate (%) = (V Z /Vi-1) × 100. The storage stability of the whole is evaluated as ◎: excellent, ○: good, ×: not.

硬化性(硬化發熱殘量)： 　　藉由差示掃描熱量分析(DSC)進行。將樹脂組成物封入樣品盤後，以10℃/min之昇溫速度昇溫至300℃，測定作為基準之硬化發熱量A。同樣，將樹脂組成物封入樣品盤後，以10℃/min之昇溫速度昇溫至指定的溫度(140℃、150℃或160℃)，保持30分鐘後急冷至室溫，而得到硬化物。將此等之硬化物以10℃/min之昇溫速度昇溫至300℃，測定硬化發熱量B。將所得之各硬化物的硬化發熱量B，以作為基準之樹脂組成物的硬化發熱量A去除，藉由下述式求出硬化發熱殘量。顯示硬化發熱殘量(%)越低，硬化性越良好。 　　硬化發熱殘量(%)=B/A×100 　　尚，將作為全體之硬化性評估為◎：優、○：良、×：不可。Hardenability (hardening heat generation residual): Performed by differential scanning calorimetry (DSC). After the resin composition was sealed in the sample pan, the temperature was raised to 300 ° C at a temperature increase rate of 10 ° C / min, and the calorific calorific value A as a reference was measured. Similarly, after sealing the resin composition into the sample pan, the temperature was raised to a predetermined temperature (140 ° C, 150 ° C or 160 ° C) at a temperature increase rate of 10 ° C / min, and after 30 minutes, it was quenched to room temperature to obtain a cured product. The cured product was heated to 300 ° C at a temperature increase rate of 10 ° C / min, and the calorific calorific value B was measured. The hardening calorific value B of each of the obtained cured products is removed by the hardening calorific value A of the resin composition as a standard, and the hardening heat generation amount is obtained by the following formula. The lower the hardening residual amount (%) is, the better the hardenability is. The amount of hardening heat generation (%) = B / A × 100 is still evaluated as the overall hardenability: ◎: excellent, ○: good, ×: not.

樹脂含有率 　　藉由以下之計算求出。 　　樹脂含有率Rc=(附樹脂之碳纖維g-碳纖維g)/附樹脂之碳纖維gThe resin content was determined by the following calculation. Resin content rate Rc = (carbon fiber g-carbon fiber g with resin) / carbon fiber g with resin

孔洞率： 　　藉由以下之式求出。 　　孔洞率=1-(實測密度)/(理論密度) 　　於此，實測密度在阿基米德法進行評估。 　　理論密度係藉由以下，由計算求出 　　理論密度=環氧樹脂硬化物之密度×Rc+碳纖維之密度×(1-Rc)Hole ratio: It is obtained by the following formula. Hole rate = 1 - (measured density) / (theoretical density) Here, the measured density is evaluated by the Archimedes method. The theoretical density is calculated by the following theoretical density = density of epoxy resin cured material × Rc + density of carbon fiber × (1-Rc)

實施例1B 　　於混練容器混合暨分散MX-154 25重量份、YDF-170 66.9重量份、二氰二胺(DICYANEX1400F之微粉碎品、粒徑D50=1.2μm,D90=2.1μm)5.1重量份、2MAOK(2MAOK-PW之微粉碎品、粒徑D50=1.2μm,D90=2.3μm)3重量份，得到環氧樹脂組成物(C1)，進行儲藏穩定性與硬化發熱殘量之評估。將結果示於表1B。Example 1B was mixed and dispersed in a kneading vessel, 25 parts by weight of MX-154, 66.9 parts by weight of YDF-170, and 5.1 parts by weight of dicyandiamide (finely pulverized product of DICYANEX 1400F, particle diameter D50 = 1.2 μm, D90 = 2.1 μm). 3 parts by weight of 2 MAOK (2MAOK-PW finely pulverized product, particle diameter D50 = 1.2 μm, D90 = 2.3 μm) was obtained, and an epoxy resin composition (C1) was obtained, and the storage stability and the hardening residual amount were evaluated. The results are shown in Table 1B.

實施例2B 　　作為穩定劑，除了加入硼酸三丁酯0.3重量份之外，其他與實施例1B同樣進行，得到環氧樹脂組成物(C2)，並進行評估。集中結果示於表1B。Example 2B An epoxy resin composition (C2) was obtained and evaluated in the same manner as in Example 1B except that 0.3 parts by weight of tributyl borate was added as a stabilizer. The results of the concentration are shown in Table 1B.

比較例1B～4B 　　作為表1B所示之組成，在與實施例1B相同之手法，得到環氧樹脂組成物(R1、R2、R3、R4)，評估物性。集中結果示於表1B。 　　尚，表中，硬化劑及咪唑化合物之粒徑係如以下。 　　二氰二胺(D50=2.5)為D50=2.5μm,D90=4.7μm，二氰二胺(D50=1.2)為D50=1.2μm,D90=2.1μm，2MAOK(D50=3.5)為D50=3.5μm,D90=5.5μm，2MAOK(D50=1.2)為D50=1.2μm,D90=2.3μm。Comparative Examples 1B to 4B As the compositions shown in Table 1B, in the same manner as in Example 1B, epoxy resin compositions (R1, R2, R3, and R4) were obtained, and physical properties were evaluated. The results of the concentration are shown in Table 1B. Further, in the table, the particle diameters of the hardener and the imidazole compound are as follows. Dicyanamide (D50=2.5) is D50=2.5μm, D90=4.7μm, dicyandiamide (D50=1.2) is D50=1.2μm, D90=2.1μm, 2MAOK(D50=3.5) is D50=3.5 Μm, D90 = 5.5 μm, 2 MAOK (D50 = 1.2) was D50 = 1.2 μm, and D90 = 2.3 μm.

實施例3B～8B 　　將於實施例1B所得之環氧樹脂組成物(C1)含浸在直徑6μm或7μm之碳纖維，而得到樹脂含有率Rc為0.20～0.28之附樹脂之碳纖維。進而，邊將所得之附樹脂的碳纖維施加反張力10kN，邊於直徑140mm之管狀心軸藉由纏繞橫動(Traverse)及重複層合，而得到6mm厚度之層合體。以120℃×2小時+160℃×1小時的條件進行硬化，而得到纖維強化塑料，測定孔洞率。將結果示於表2B。[Examples 3B to 8B] The epoxy resin composition (C1) obtained in Example 1B was impregnated with carbon fibers having a diameter of 6 μm or 7 μm to obtain a resin-attached carbon fiber having a resin content Rc of 0.20 to 0.28. Further, while the obtained resin-attached carbon fiber was subjected to a back tension of 10 kN, a tubular mandrel having a diameter of 140 mm was wound by traverse and repeated lamination to obtain a laminate having a thickness of 6 mm. The fiber was reinforced by 120 ° C × 2 hours + 160 ° C × 1 hour to obtain a fiber reinforced plastic, and the porosity was measured. The results are shown in Table 2B.

比較例5B～16B 　　除了將使用之環氧樹脂組成物變更為比較例1B～4B之樹脂組成物(R1～R4)之外，其他在與實施例3B相同之手法，得到附樹脂之碳纖維及纖維強化塑料，測定孔洞率。將結果示於表3B。Comparative Examples 5B to 16B In addition to the resin composition (R1 to R4) of Comparative Examples 1B to 4B, the resin composition was used, and in the same manner as in Example 3B, carbon fibers and fibers with resin were obtained. Strengthen the plastic and measure the hole rate. The results are shown in Table 3B.

第二發明之實施例與比較例相比較，得到孔洞率減低的結果。又，碳纖維之直徑變細時，雖有易提高孔洞率的傾向，但實施例與比較例相比較，得到抑制孔洞率上昇的結果。The examples of the second invention were compared with the comparative examples to obtain a result of a decrease in the void ratio. Further, when the diameter of the carbon fiber is reduced, the porosity tends to increase, but the examples show a result of suppressing an increase in the void ratio as compared with the comparative example.

實施例1B之環氧樹脂組成物，得到接近比較例4B之環氧樹脂組成物之孔洞率的結果。實施例1B之環氧樹脂組成物較比較例4B，非常清楚得到抑制黏度之上昇，改善儲藏穩定性的結果。進而，得到硬化反應所需要之時間明顯短縮的結果。The epoxy resin composition of Example 1B was obtained as a result of the porosity of the epoxy resin composition of Comparative Example 4B. The epoxy resin composition of Example 1B was more clearly obtained as a result of suppressing an increase in viscosity and improving storage stability as compared with Comparative Example 4B. Further, the time required for the hardening reaction is significantly shortened.

實施例1B之環氧樹脂組成物與比較例1B～3B之環氧樹脂組成物相比較，雖儲藏穩定性降低若干，將極少量之硼酸三丁酯添加在絲之實施例2B得到可改變此之結果。 [產業上之可利用性]The epoxy resin composition of Example 1B was compared with the epoxy resin compositions of Comparative Examples 1B to 3B, and although the storage stability was somewhat lowered, a very small amount of tributyl borate was added to Example 2B of the yarn to obtain a change. The result. [Industrial availability]

根據本發明，得到預浸料製造時之含浸性優異、兼具高儲藏穩定性及高破壞韌性與伸長之纖維強化複合材料用環氧樹脂組成物。又，可提供一種兼具高儲藏穩定性與高硬化反應性，且實現低樹脂含有率，可抑制硬化物中之孔洞等之缺陷的纖維強化複合材料用環氧樹脂組成物。 　　因此，可適合利用在各種之纖維強化複合材料用途。According to the present invention, an epoxy resin composition for a fiber-reinforced composite material which is excellent in impregnation properties at the time of production of a prepreg and which has both high storage stability and high fracture toughness and elongation is obtained. Further, it is possible to provide an epoxy resin composition for a fiber-reinforced composite material which has high storage stability and high curing reactivity, and which has a low resin content and can suppress defects such as voids in the cured product. Therefore, it can be suitably used for various fiber reinforced composite materials.

[圖1]表示由DSC圖表所求出之發熱起始溫度與發熱峰值溫度的圖形。Fig. 1 is a graph showing the heat generation onset temperature and the heat generation peak temperature obtained from the DSC chart.

Claims (19)

一種纖維強化複合材料用環氧樹脂組成物，其係將環氧樹脂(A)、二氰二胺(B)、咪唑系硬化輔助劑(C)及核殼橡膠(D)作為必須成分之環氧樹脂組成物，其特徵為咪唑系硬化輔助劑(C)為將環氧樹脂組成物在DSC以昇溫速度10℃/分鐘的條件測定時之發熱起始溫度成為135℃以上者。An epoxy resin composition for a fiber-reinforced composite material, which comprises an epoxy resin (A), a dicyandiamide (B), an imidazole-based hardening auxiliary (C), and a core-shell rubber (D) as essential components. The oxy-resin composition is characterized in that the imidazole-based hardening aid (C) is a heat-generating starting temperature of 135 ° C or higher when the epoxy resin composition is measured under the conditions of a temperature increase rate of 10 ° C /min. 如請求項1之纖維強化複合材料用環氧樹脂組成物，其中，相對於環氧樹脂(A)之環氧基當量，含有二氰二胺(B)0.2～0.8當量，相對於二氰二胺(B)100質量份，含有咪唑系硬化輔助劑(C)50～250質量份。The epoxy resin composition for a fiber-reinforced composite material according to claim 1, wherein the epoxy group equivalent of the epoxy resin (A) contains 0.2 to 0.8 equivalents of dicyandiamide (B) relative to dicyandiamide. 100 parts by mass of the amine (B) contains 50 to 250 parts by mass of the imidazole-based curing assistant (C). 如請求項1之纖維強化複合材料用環氧樹脂組成物，其中，環氧樹脂(A)係於1分子中具有2個環氧基，使用E型黏度計所測定之在25℃之黏度為1～50Pa･s。The epoxy resin composition for a fiber-reinforced composite material according to claim 1, wherein the epoxy resin (A) has two epoxy groups in one molecule, and the viscosity at 25 ° C measured by an E-type viscometer is 1 to 50 Pa·s. 如請求項1之纖維強化複合材料用環氧樹脂組成物，其中，咪唑系硬化輔助劑(C)為2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三嗪異氰脲酸加成物或2-苯基-4-甲基-5-羥基甲基咪唑。An epoxy resin composition for a fiber-reinforced composite material according to claim 1, wherein the imidazole-based hardening auxiliary (C) is 2,4-diamino-6-[2'-ethyl-4'-methylimidazole Base-(1')]-ethyl-s-triazine isocyanuric acid adduct or 2-phenyl-4-methyl-5-hydroxymethylimidazole. 如請求項1之纖維強化複合材料用環氧樹脂組成物，其中，核殼橡膠(D)之體積平均粒子徑為1～500nm。The epoxy resin composition for a fiber-reinforced composite material according to claim 1, wherein the core-shell rubber (D) has a volume average particle diameter of from 1 to 500 nm. 如請求項1之纖維強化複合材料用環氧樹脂組成物，其中，使用E型黏度計所測定之在25℃之黏度為1～50 Pa･s。The epoxy resin composition for a fiber-reinforced composite material according to claim 1, wherein the viscosity at 25 ° C measured by an E-type viscometer is 1 to 50 Pa·s. 一種纖維強化複合材料，其特徵為於如請求項1之纖維強化複合材料用環氧樹脂組成物摻合強化纖維而成。A fiber-reinforced composite material characterized by blending a reinforcing fiber with an epoxy resin composition for a fiber-reinforced composite material according to claim 1. 如請求項7之纖維強化複合材料，其中，強化纖維之體積含有率為30～75%。The fiber-reinforced composite material according to claim 7, wherein the reinforcing fiber has a volume content of 30 to 75%. 一種成形體，其係將如請求項7之纖維強化複合材料以長絲纏繞法進行成形及硬化而得。A molded body obtained by forming and hardening a fiber-reinforced composite material according to claim 7 by a filament winding method. 一種環氧樹脂組成物，其係將環氧樹脂(A)、環氧樹脂硬化劑(B)、咪唑化合物(C)作為必須成分之環氧樹脂組成物，其特徵為 　　環氧樹脂(A)含有液狀雙酚A型環氧樹脂及/或液狀雙酚F型環氧樹脂，黏度(25℃)1Pa･s以上100Pa･s以下， 　　環氧樹脂硬化劑(B)及咪唑化合物(C)皆為熔點或分解溫度200℃以上之固體，平均粒徑(D50)2μm以下。An epoxy resin composition which is an epoxy resin composition containing an epoxy resin (A), an epoxy resin hardener (B), and an imidazole compound (C) as essential components, and is characterized by an epoxy resin (A) Contains liquid bisphenol A type epoxy resin and/or liquid bisphenol F type epoxy resin, viscosity (25 ° C) 1 Pa·s or more and 100 Pa·s or less, epoxy resin hardener (B) and imidazole compound (C All are solids having a melting point or a decomposition temperature of 200 ° C or higher, and an average particle diameter (D50) of 2 μm or less. 如請求項10之環氧樹脂組成物，其中，環氧樹脂硬化劑(B)為二氰二胺。The epoxy resin composition of claim 10, wherein the epoxy resin hardener (B) is dicyandiamide. 如請求項10之環氧樹脂組成物，其中，咪唑化合物(C)為式(1)或式(2)所示之化合物，。The epoxy resin composition of claim 10, wherein the imidazole compound (C) is a compound represented by the formula (1) or the formula (2), . 如請求項10之環氧樹脂組成物，其係進一步含有橡膠成分(D)。The epoxy resin composition of claim 10, which further contains a rubber component (D). 如請求項10之環氧樹脂組成物，其中，環氧樹脂硬化劑(B)與咪唑化合物(C)的合計量，相對於環氧樹脂組成物為10重量%以下。The epoxy resin composition of claim 10, wherein the total amount of the epoxy resin hardener (B) and the imidazole compound (C) is 10% by weight or less based on the epoxy resin composition. 如請求項10之環氧樹脂組成物，其中，橡膠成分(D)為具有核殼構造之橡膠粒子。The epoxy resin composition of claim 10, wherein the rubber component (D) is a rubber particle having a core-shell structure. 如請求項10之環氧樹脂組成物，其係含有穩定劑。The epoxy resin composition of claim 10 which contains a stabilizer. 一種絲束預浸料，其係將如請求項10之環氧樹脂組成物含浸在碳纖維(E)而成。A tow prepreg obtained by impregnating the epoxy resin composition of claim 10 with carbon fibers (E). 如請求項17之絲束預浸料，其中，碳纖維(E)之平均直徑為7.5μm以下。The tow prepreg according to claim 17, wherein the carbon fibers (E) have an average diameter of 7.5 μm or less. 一種碳纖維強化塑料，其係成型如請求項17之絲束預浸料，並硬化而成。A carbon fiber reinforced plastic formed by the tow prepreg of claim 17 and hardened.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3950251A4 (en) * 2019-03-29 2023-01-04 Sekisui Chemical Co., Ltd. Open carbon fiber bundle, fiber-reinforced composite material, and method for manufacturing open carbon fiber bundle

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7186711B2 (en) * 2017-09-29 2022-12-09 日鉄ケミカル＆マテリアル株式会社 Curable resin composition and Tuprepreg using the same
KR20220009940A (en) * 2019-05-17 2022-01-25 오츠카 가가쿠 가부시키가이샤 Composite laminate and manufacturing method thereof
CN111138636A (en) * 2019-12-31 2020-05-12 浙江华正新材料股份有限公司 Resin composition, prepreg and laminated board
US20230030598A1 (en) * 2020-01-30 2023-02-02 Toray Industries, Inc. Epoxy resin composition, molding material for fiber-reinforced composite material, and fiber-reinforced composite material
CN111690233B (en) * 2020-07-22 2023-05-23 黑龙江省科学院石油化学研究院 Low-temperature curing high-toughness epoxy resin system and preparation method thereof
MY196339A (en) * 2020-09-29 2023-03-24 Furukawa Electric Co Ltd Transparent Adhesive Composition, Film-Shaped Transparent Adhesive, Method of Producing Transparent Adhesive Cured Layer-Attached Member, and Electronic Component and Method of Producing the Same
CN114031896B (en) * 2021-11-20 2024-01-05 山西宇德新材料科技有限公司 Epoxy resin composition for carbon fiber winding and preparation method thereof

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61210076A (en) * 1985-03-14 1986-09-18 Shikoku Chem Corp Novel adduct of 2-substituted-4,6-diamino-s-triazine and isocyanuric acid, synthesis of said adduct, and curing of polyepoxide resin using said adduct
JPH0693084A (en) * 1992-09-10 1994-04-05 Toray Chiokoole Kk Solution type polysulfide-modified epoxy resin, and epoxy resin for carbon fiber prepregs
JP4238124B2 (en) * 2003-01-07 2009-03-11 積水化学工業株式会社 Curable resin composition, adhesive epoxy resin paste, adhesive epoxy resin sheet, conductive connection paste, conductive connection sheet, and electronic component assembly
JP4639766B2 (en) * 2004-11-16 2011-02-23 横浜ゴム株式会社 Two-component room temperature curable epoxy resin composition and metal adhesive composition
JP5233091B2 (en) * 2006-08-01 2013-07-10 住友ベークライト株式会社 Liquid resin composition and semiconductor device produced using liquid resin composition
JP2009079128A (en) * 2007-09-26 2009-04-16 Sekisui Chem Co Ltd Resin composition, prepreg, cured product, sheet-like laminated body, laminate and multilayer laminate
US8042976B2 (en) * 2007-11-30 2011-10-25 Taiyo Holdings Co., Ltd. White hardening resin composition, hardened material, printed-wiring board and reflection board for light emitting device
US20110319525A1 (en) * 2009-03-25 2011-12-29 Yuki Maeda Epoxy resin composition, prepreg, carbon fiber reinforced composite material, and housing for electronic or electrical component
JP5229252B2 (en) * 2009-03-25 2013-07-03 東レ株式会社 Epoxy resin composition for carbon fiber reinforced composite material, prepreg, carbon fiber reinforced composite material, and electronic / electrical component casing
CN103827741B (en) * 2011-09-27 2016-06-22 日本化药株式会社 Liquid crystal sealing agent and use its liquid crystal display
KR101616659B1 (en) * 2011-11-29 2016-04-28 미쯔비시 레이온 가부시끼가이샤 Prepreg, fiber-reinforced composite material, method for producing same, and epoxy resin composition
TWI545155B (en) * 2012-06-05 2016-08-11 三菱麗陽股份有限公司 Epoxy resin composition, tow prepreg, pressure vessel reinforced by composite material and tendon
KR101687394B1 (en) * 2013-06-17 2016-12-16 주식회사 엘지화학 Photo-curable and thermo-curable resin composition and dry film solder resist
JP5757309B2 (en) * 2013-09-04 2015-07-29 三菱レイヨン株式会社 Epoxy resin composition, tow prepreg and pressure vessel
JP6433651B2 (en) * 2013-11-21 2018-12-05 スリーエム イノベイティブ プロパティズ カンパニー Adhesive, adhesive-attached member, and connection method between members
EP3075785B1 (en) * 2013-11-26 2019-09-11 Toho Tenax Co., Ltd. Heat-curable resin composition, prepreg, and method for producing fiber-reinforced composite using each of same
JP6347684B2 (en) * 2014-07-07 2018-06-27 京セラ株式会社 Thermosetting resin composition for semiconductor bonding and semiconductor device
JP2016117869A (en) * 2014-12-24 2016-06-30 京セラケミカル株式会社 Resin composition for semiconductor adhesion and semiconductor device
JP6771884B2 (en) * 2015-02-09 2020-10-21 東レ株式会社 Epoxy resin compositions, prepregs and fiber reinforced composites
JP6241549B2 (en) * 2015-05-13 2017-12-06 三菱ケミカル株式会社 Sheet molding compounds and fiber reinforced composite materials
TWI591109B (en) * 2015-06-11 2017-07-11 Mitsubishi Rayon Co Epoxy resin composition, molded article, prepreg, fiber reinforced Composites and structures
JP6723698B2 (en) * 2015-07-23 2020-07-15 東京応化工業株式会社 Fine particle-containing composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3950251A4 (en) * 2019-03-29 2023-01-04 Sekisui Chemical Co., Ltd. Open carbon fiber bundle, fiber-reinforced composite material, and method for manufacturing open carbon fiber bundle

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