KR20200073326A - Epoxy resin composition for fiber impregnation with excellent water resistance - Google Patents
Epoxy resin composition for fiber impregnation with excellent water resistance Download PDFInfo
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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
- C08G59/50—Amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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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
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
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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
- C08G59/50—Amines
- C08G59/54—Amino amides>
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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
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
Abstract
Description
본 발명은 내수성이 우수한 섬유 함침용 에폭시 수지 조성물에 관한 것이다. The present invention relates to an epoxy resin composition for impregnating fibers having excellent water resistance.
일반적으로 노후화된 구조물은 콘크리트나 강판을 사용하여 보수 및 보강 공사를 하지만, 해양 구조물의 경우, 콘크리트나 강판 대신에 강도 증진과 표면 보호 기능을 갖는 섬유강화 복합소재를 사용하여 보수 및 보강 공사를 한다.In general, aging structures are repaired and reinforced using concrete or steel plates, but in the case of offshore structures, instead of concrete or steel plates, fiber reinforced composites with strength and surface protection functions are used to repair and reinforce them. .
이러한 섬유강화 복합소재는 기존의 금속 및 무기물 재료에서 섬유를 사용한 재료로 빠르게 전환되고 있다. 섬유강화 복합소재는 수중에 노출된 해양 구조물의 보수 보강 시 시간적, 경제적 비용을 획기적으로 절감시킬 수 있어 여러 분야에 널리 사용되고 있다. 섬유강화 복합소재에 사용되는 수지 조성물은 내수성, 접착성 및 내약품성이 우수한 에폭시 수지를 기반으로 한 조성물이 사용되고 있다. These fiber-reinforced composite materials are rapidly converting from conventional metal and inorganic materials to materials using fibers. Fiber-reinforced composite materials are widely used in various fields because they can dramatically reduce the time and economic costs when repairing and reinforcing marine structures exposed to water. As the resin composition used in the fiber-reinforced composite material, a composition based on an epoxy resin having excellent water resistance, adhesion and chemical resistance is used.
에폭시 수지는 분자 내에 에폭시기를 2개 이상 가지는 수지로, 에폭시기와 경화제 간의 열경화 반응에 의해 경화되어 바닥재, 벽재 등과 같은 마감재로 형성된다. 에폭시 수지는 굴곡강도 등의 기계적 성질이 우수하고 경화 시 접착성이 우수하여 도료로서도 폭넓게 사용되고 있다. 이러한 에폭시 수지 기반의 조성물은 경화성과 작업성을 향상시키기 위해 희석제와 경화제가 더 포함된다. Epoxy resin is a resin having two or more epoxy groups in a molecule, and is cured by a thermal curing reaction between an epoxy group and a curing agent to form a finishing material such as a flooring material or a wall material. Epoxy resins are widely used as paints because they have excellent mechanical properties such as flexural strength and excellent adhesion during curing. The epoxy resin-based composition further includes a diluent and a curing agent to improve curability and workability.
한편, 에폭시 수지, 희석제 및 경화제의 종류와 함량을 달리하여 에폭시 수지 조성물을 제조하지만, 종래 에폭시 수지 조성물로는 염수, 습윤, 저온 환경에서 장시간 노출되는 경우, 경화성 및 내수성이 우수한 효과를 제공하기 어려운 문제점이 있다.On the other hand, an epoxy resin composition is prepared by varying the type and content of an epoxy resin, a diluent, and a curing agent, but it is difficult to provide an excellent effect of curability and water resistance when exposed to salt water, wet, and low temperature environments for a long time with conventional epoxy resin compositions. There is a problem.
본 발명의 목적은 내수성이 우수한 섬유 함침용 에폭시 수지 조성물을 제공하는 것이다.An object of the present invention is to provide an epoxy resin composition for impregnating fibers having excellent water resistance.
본 발명의 목적들은 이상에서 언급한 목적으로 제한되지 않으며, 언급되지 않은 본 발명의 다른 목적 및 장점들은 하기의 설명에 의해서 이해될 수 있고, 본 발명의 실시예에 의해 보다 분명하게 이해될 것이다. 또한, 본 발명의 목적 및 장점들은 특허 청구 범위에 나타낸 수단 및 그 조합에 의해 실현될 수 있음을 쉽게 알 수 있을 것이다.The objects of the present invention are not limited to the above-mentioned objects, and other objects and advantages of the present invention not mentioned can be understood by the following description, and will be more clearly understood by embodiments of the present invention. In addition, it will be readily appreciated that the objects and advantages of the present invention can be realized by means of the appended claims and combinations thereof.
본 발명에 따르면 비스페놀계 에폭시 수지 100중량부에 대하여, 노볼락계 에폭시 수지 10~30중량부, 페놀계 용매 5~20중량부 및 실리콘계 소포제 0.1~1중량부를 포함하는 주제; 및 비스페놀계 에폭시 수지 100중량부에 대하여, 아민계 경화제 200~400중량부를 포함하는 경화제;를 포함하고, 상기 주제 100중량부에 대하여, 경화제 50~100중량부를 포함하는 섬유 함침용 에폭시 수지 조성물을 제공한다.According to the present invention, with respect to 100 parts by weight of a bisphenol-based epoxy resin, a subject comprising 10 to 30 parts by weight of a novolac-based epoxy resin, 5 to 20 parts by weight of a phenolic solvent, and 0.1 to 1 part by weight of a silicone antifoaming agent; And a curing agent comprising 200 to 400 parts by weight of an amine-based curing agent with respect to 100 parts by weight of a bisphenol-based epoxy resin; and, with respect to 100 parts by weight of the subject, an epoxy resin composition for impregnating fibers comprising 50 to 100 parts by weight of a curing agent. to provide.
본 발명에 따른 섬유 함침용 에폭시 수지 조성물은 비스페놀계 에폭시 수지와 노볼락계 에폭시 수지를 기반으로 하여, 우수한 경화성과 내수성을 나타낼 수 있다. The epoxy resin composition for fiber impregnation according to the present invention is based on a bisphenol-based epoxy resin and a novolac-based epoxy resin, and may exhibit excellent curability and water resistance.
또한, 에폭시 수지 조성물은 섬유 보강재에 함침되어 우수한 계면 접착력과 내구성을 나타낼 수 있어, 해양 구조물에 적용 가능하다.In addition, the epoxy resin composition is impregnated in the fiber reinforcement can exhibit excellent interfacial adhesion and durability, it is applicable to marine structures.
상술한 효과와 더불어 본 발명의 구체적인 효과는 이하 발명을 실시하기 위한 구체적인 사항을 설명하면서 함께 기술한다.In addition to the above-described effects, the concrete effects of the present invention will be described together while describing the specific matters for carrying out the invention.
전술한 목적, 특징 및 장점은 첨부된 도면을 참조하여 상세하게 후술되며, 이에 따라 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 본 발명의 기술적 사상을 용이하게 실시할 수 있을 것이다. 본 발명을 설명함에 있어서 본 발명과 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 상세한 설명을 생략한다. 이하, 첨부된 도면을 참조하여 본 발명에 따른 바람직한 실시예를 상세히 설명하기로 한다. 도면에서 동일한 참조부호는 동일 또는 유사한 구성요소를 가리키는 것으로 사용된다.The above-described objects, features, and advantages will be described in detail below with reference to the accompanying drawings, and accordingly, a person skilled in the art to which the present invention pertains can easily implement the technical spirit of the present invention. In the description of the present invention, when it is determined that detailed descriptions of known technologies related to the present invention may unnecessarily obscure the subject matter of the present invention, detailed descriptions will be omitted. Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The same reference numbers in the drawings are used to indicate the same or similar components.
또한 어떤 구성요소가 다른 구성요소에 "연결", "결합" 또는 "접속"된다고 기재된 경우, 상기 구성요소들은 서로 직접적으로 연결되거나 또는 접속될 수 있지만, 각 구성요소 사이에 다른 구성요소가 "개재"되거나, 각 구성요소가 다른 구성요소를 통해 "연결", "결합" 또는 "접속"될 수도 있는 것으로 이해되어야 할 것이다. Also, when a component is described as being "connected", "coupled" or "connected" to another component, the components may be directly connected to or connected to each other, but other components may be "interposed" between each component. It should be understood that "or, each component may be "connected", "coupled" or "connected" through other components.
이하에서는, 본 발명의 실시예에 따른 내수성이 우수한 섬유 함침용 에폭시 수지 조성물을 설명하도록 한다.Hereinafter, an epoxy resin composition for impregnating fibers excellent in water resistance according to an embodiment of the present invention will be described.
본 발명에 따른 섬유 함침용 에폭시 수지 조성물은 용제형 조성물로서, 섬유강화 복합소재의 섬유 보강재에 함침되어 해양 구조물 등의 보수, 보강용으로 사용될 수 있다. 상기 섬유는 유리섬유, 탄소섬유, 아라미드 섬유, 천연섬유 등을 가리킨다.The epoxy resin composition for impregnating fibers according to the present invention is a solvent-based composition, and is impregnated with a fiber reinforcement material of a fiber-reinforced composite material, and may be used for repairing and reinforcing marine structures. The fiber refers to glass fiber, carbon fiber, aramid fiber, natural fiber, and the like.
본 발명에 따른 섬유 함침용 에폭시 수지 조성물은 주제와 경화제를 포함한다. 상기 에폭시 수지 조성물은 주제 100중량부에 대하여, 경화제 50~100중량부를 포함한다.The epoxy resin composition for impregnating fibers according to the present invention includes a subject and a curing agent. The epoxy resin composition contains 50 to 100 parts by weight of the curing agent with respect to 100 parts by weight of the subject.
주제는 비스페놀계 에폭시 수지 100중량부에 대하여, 노볼락 에폭시 수지 10~30중량부, 페놀계 용매 5~20중량부 및 실리콘계 소포제 0.1~1중량부를 포함하는 한다.The subject matter includes 10 to 30 parts by weight of a novolac epoxy resin, 5 to 20 parts by weight of a phenolic solvent, and 0.1 to 1 part by weight of a silicone antifoaming agent based on 100 parts by weight of a bisphenol-based epoxy resin.
상기 비스페놀계 에폭시 수지는 상온에서 액상으로 존재하고, 내수성, 접착성 등이 우수하다. 그 예로 비스페놀 A형 에폭시 수지 또는 비스페놀 F형 에폭시 수지 등이 있다. 상기 비스페놀계 에폭시 수지의 당량은 170~180g/eq일 수 있으며, 이 범위를 벗어나는 경우, 아민브러싱, 미경화, 물성저하 등의 문제점이 발생한다.The bisphenol-based epoxy resin exists as a liquid at room temperature, and has excellent water resistance, adhesion, and the like. Examples include bisphenol A-type epoxy resins or bisphenol F-type epoxy resins. The equivalent of the bisphenol-based epoxy resin may be 170 to 180 g/eq, and if it is outside this range, problems such as amine brushing, uncured, and deterioration of properties occur.
상기 노볼락계 에폭시 수지는 페놀 노볼락 에폭시 수지, o-크레졸 노볼락 에폭시 수지 및 디사이클로펜타디엔 노볼락 에폭시 수지 중 1종 이상을 포함한다.The novolac-based epoxy resin includes at least one of phenol novolac epoxy resin, o -cresol novolac epoxy resin, and dicyclopentadiene novolac epoxy resin.
상기 노볼락계 에폭시 수지는 10~30중량부로 포함되는 것이 바람직하다. 이 범위를 벗어나는 경우, 수지 조성물의 내수성 및 접착강도가 다소 저하될 수 있다.The novolak-based epoxy resin is preferably included in 10 to 30 parts by weight. If it is out of this range, the water resistance and adhesive strength of the resin composition may be lowered somewhat.
상기 페놀계 용매는 노닐 페놀 용매 및 도데실 페놀 용매 중 1종 이상을 포함한다. 상기 페놀계 용매는 5~20중량부로 포함되는 것이 바람직하다. 이 범위를 벗어나는 경우, 조성물의 분산성이 저하되면서 점도 조절이 어려울 수 있다. 그리고 조성물의 접착 강도가 저하될 수 있다.The phenolic solvent includes at least one of nonyl phenol solvent and dodecyl phenol solvent. The phenolic solvent is preferably included in 5 to 20 parts by weight. If it is outside this range, viscosity may be difficult to control while the dispersibility of the composition is lowered. And the adhesive strength of the composition may be lowered.
상기 실리콘계 소포제는 실리콘이 함유된 아크릴 중합물로, 0.1~1중량부로 포함되는 것이 바람직하다. 그 함량이 0.1중량부 미만이거나, 1중량부를 초과하는 경우, 경화물의 요구되는 물성을 보다 향상시키기 어려울 수 있고, 경화물의 표면이 불균일해질 수 있다.The silicone-based antifoaming agent is an acrylic polymer containing silicone, and is preferably included in 0.1 to 1 part by weight. If the content is less than 0.1 part by weight, or more than 1 part by weight, it may be difficult to further improve the required physical properties of the cured product, and the surface of the cured product may be uneven.
본 발명의 에폭시 수지 조성물은 비스페놀계 에폭시 수지 100중량부에 대하여, 아민계 경화제 200~400중량부를 포함하는 경화제를 포함한다.The epoxy resin composition of the present invention contains a curing agent comprising 200 to 400 parts by weight of an amine curing agent relative to 100 parts by weight of a bisphenol-based epoxy resin.
아민계 경화제는 지방족 아민계 경화제, 아미도아민계 경화제 및 페날카민(phenalkamine)계 경화제 중 1종 이상을 포함할 수 있다. 지방족 아민계 경화제는 에폭시 수지와의 경화 반응이 빠르고 접착성이 우수하며, 그 예로 에틸렌 디아민, 디에틸렌 트리아민 등이 있다. 아미도아민계 경화제는 화학적 내성과 강한 접착력을 가지며, 그 예로 폴리아미도아민, 폴리키탈 아미도아민 등이 있다. 페날카민계 경화제는 에폭시 수지와의 상용성이 우수하고, 5℃ 이하의 저온에서 경화되며, 경화 속도가 빠른 특징이 있다. The amine-based curing agent may include at least one of an aliphatic amine-based curing agent, an amidoamine-based curing agent, and a phenalkamine-based curing agent. The aliphatic amine-based curing agent has a fast curing reaction with an epoxy resin and excellent adhesion, and examples thereof include ethylene diamine and diethylene triamine. The amidoamine-based curing agent has chemical resistance and strong adhesion, and examples thereof include polyamidoamine and polykital amidoamine. The phenalamine-based curing agent has excellent compatibility with an epoxy resin, cures at a low temperature of 5° C. or less, and has a fast curing speed.
에폭시 수지 조성물은 아민계 경화제 200~400중량부를 포함하는 것이 바람직하다. 함량이 200중량부 미만인 경우, 경화 속도가 지나치게 느려지는 문제점이 있고, 400중량부를 초과하는 경우 경화 속도가 너무 빨라지게 되어 바람직하지 않다.It is preferable that the epoxy resin composition contains 200 to 400 parts by weight of an amine curing agent. When the content is less than 200 parts by weight, there is a problem that the curing rate is too slow, and when it exceeds 400 parts by weight, the curing rate becomes too fast, which is not preferable.
이러한 아민계 경화제의 당량은 200~400g/eq일 수 있으며, 이들 범위를 벗어나는 경우, 물성저하 및 외관상의 문제점이 발생한다.Equivalent of the amine-based curing agent may be 200 ~ 400g / eq, when out of these ranges, physical properties and appearance problems occur.
또한, 본 발명의 섬유 함침용 에폭시 수지 조성물은 주제 또는 경화제에 비스페놀계 에폭시 수지 100중량부에 대하여, 테트라부틸포스포늄 말로네이트(Tetrabutylphosphonium malonate) 0.1~1중량부를 더 포함할 수 있다. 주제 또는 경화제에 테트라부틸포스포늄 말로네이트를 더 포함하는 경우, 점도 조절이 용이하며, 습윤 환경에서 우수한 접착강도를 나타낼 수 있다.In addition, the epoxy resin composition for impregnating the fiber of the present invention may further include 0.1 to 1 part by weight of tetrabutylphosphonium malonate (Tetrabutylphosphonium malonate) with respect to 100 parts by weight of the bisphenol-based epoxy resin in the main or curing agent. When the subject or the curing agent further includes tetrabutylphosphonium malonate, viscosity control is easy, and excellent adhesive strength can be exhibited in a wet environment.
전술한 바와 같이, 본 발명의 섬유 함침용 에폭시 수지 조성물은 비스페놀계 에폭시 수지와 노볼락계 에폭시 수지, 수중 환경에서 우수한 경화성을 나타내는 아민계 경화제를 포함함으로써, 섬유 보강재에 함침되기에 용이하고, 섬유 계면과의 접착력 및 내구성이 우수한 효과가 있다. As described above, the epoxy resin composition for impregnating the fibers of the present invention includes a bisphenol-based epoxy resin, a novolac-based epoxy resin, and an amine-based curing agent that exhibits excellent curing properties in an underwater environment, so that it is easy to be impregnated into the fiber reinforcement material and the fibers It has an excellent effect of adhesion and durability with the interface.
아울러, 본 발명의 섬유 함침용 에폭시 수지 조성물은 섬유 보강재에 함침됨에 따라, 수중 환경에 존재하는 해양 구조물 등에 보수, 보강용으로 적용 가능하다.In addition, the epoxy resin composition for impregnating fibers of the present invention is impregnated with a fiber reinforcement material, and can be applied to repair and reinforce marine structures existing in an underwater environment.
이와 같이 내수성이 우수한 섬유 함침용 에폭시 수지 조성물에 대하여 그 구체적인 실시예를 살펴보면 다음과 같다.Looking at the specific embodiment of the epoxy resin composition for impregnating fibers having excellent water resistance as described above is as follows.
1. 섬유 함침용 에폭시 수지 조성물의 제조1. Preparation of epoxy resin composition for fiber impregnation
실시예 1Example 1
1g당량이 170g/eq인 비스페놀 A형 에폭시 수지(Huntsman 사) 100중량부에 대하여, 페놀 노볼락 에폭시 수지(Huntsman 사) 10중량부, 도데실 페놀 용매 20중량부를 혼합하고 100℃까지 승온하여 1시간 동안 교반하였다. 그리고 반응온도를 60℃까지 낮추고, 실리콘 소포제(알드리치) 1중량부를 투입하여 10분간 교반하여 주제를 제조하였다.With respect to 100 parts by weight of bisphenol A-type epoxy resin (Huntsman) having a 1 g equivalent of 170 g/eq, 10 parts by weight of phenol novolac epoxy resin (Huntsman) and 20 parts by weight of dodecyl phenol solvent were mixed and heated to 100° C. 1 Stir for hours. Then, the reaction temperature was lowered to 60° C., and 1 part by weight of a silicone antifoaming agent (Aldrich) was added thereto, followed by stirring for 10 minutes to prepare a subject.
비스페놀 A형 에폭시 수지 100중량부에 대하여, 1g당량이 300g/eq인 아민계 경화제(디에틸렌 트리아민:폴리아미도아민=2:1의 혼합비) 400중량부를 혼합하고 100℃까지 승온하여 3시간 동안 교반하여 경화제를 제조하였다.With respect to 100 parts by weight of bisphenol A-type epoxy resin, 400 parts by weight of an amine-based curing agent (diethylene triamine:polyamidoamine = 2:1 mixing ratio) having an equivalent weight of 300 g/eq is mixed and heated to 100° C. for 3 hours. The curing agent was prepared by stirring.
상기 주제 100중량부에 대하여, 경화제 100중량부를 혼합하여 수지 조성물을 제조하였다.With respect to 100 parts by weight of the subject, a resin composition was prepared by mixing 100 parts by weight of a curing agent.
실시예 2Example 2
페놀 노볼락 에폭시 수지 대신 o-크레졸 노볼락 에폭시 수지(Huntsman 사)를 혼합하여 주제를 제조한 점을 제외하고는 실시예 1과 동일한 조건으로 수지 조성물을 제조하였다.Phenol novolac epoxy resin Instead, a resin composition was prepared under the same conditions as in Example 1, except that the subject was prepared by mixing o -cresol novolac epoxy resin (Huntsman).
실시예 3Example 3
페놀 노볼락 에폭시 수지(Huntsman 사) 30중량부를 혼합하여 주제를 제조한 점을 제외하고는 실시예 1과 동일한 조건으로 수지 조성물을 제조하였다.A resin composition was prepared under the same conditions as in Example 1, except that 30 parts by weight of a phenol novolac epoxy resin (Huntsman) was mixed to prepare a subject.
실시예 4Example 4
아민계 경화제(디에틸렌 트리아민:폴리아미도아민=2:1의 혼합비) 200중량부를 혼합하여 경화제를 제조한 점을 제외하고는 실시예 1과 동일한 조건으로 수지 조성물을 제조하였다.A resin composition was prepared under the same conditions as in Example 1, except that a curing agent was prepared by mixing 200 parts by weight of an amine-based curing agent (diethylene triamine:polyamidoamine = 2:1 mixing ratio).
실시예 5Example 5
주제에 테트라부틸포스포늄 말로네이트(알드리치) 1중량부를 더 포함한 점을 제외하고는 실시예 1과 동일한 조건으로 수지 조성물을 제조하였다.A resin composition was prepared under the same conditions as in Example 1, except that 1 part by weight of tetrabutylphosphonium malonate (Aldrich) was added to the subject.
비교예 1Comparative Example 1
페놀 노볼락 에폭시 수지(Huntsman 사) 5중량부를 혼합하여 주제를 제조한 점을 제외하고는 실시예 1과 동일한 조건으로 수지 조성물을 제조하였다.A resin composition was prepared under the same conditions as in Example 1, except that the subject was prepared by mixing 5 parts by weight of a phenol novolac epoxy resin (Huntsman).
비교예 2Comparative Example 2
페놀 노볼락 에폭시 수지(Huntsman 사) 37중량부를 혼합하여 주제를 제조한 점을 제외하고는 실시예 1과 동일한 조건으로 수지 조성물을 제조하였다.A resin composition was prepared under the same conditions as in Example 1, except that the subject was prepared by mixing 37 parts by weight of a phenol novolac epoxy resin (Huntsman).
비교예 3Comparative Example 3
아민계 경화제(디에틸렌 트리아민:폴리아미도아민=2:1의 혼합비) 180중량부를 혼합하여 경화제를 제조한 점을 제외하고는 실시예 1과 동일한 조건으로 수지 조성물을 제조하였다.A resin composition was prepared under the same conditions as in Example 1 except that a curing agent was prepared by mixing 180 parts by weight of an amine-based curing agent (diethylene triamine:polyamidoamine = 2:1 mixing ratio).
비교예 4Comparative Example 4
아민계 경화제(디에틸렌 트리아민:폴리아미도아민=2:1의 혼합비) 450중량부를 혼합하여 경화제를 제조한 점을 제외하고는 실시예 1과 동일한 조건으로 수지 조성물을 제조하였다A resin composition was prepared under the same conditions as in Example 1, except that a curing agent was prepared by mixing 450 parts by weight of an amine curing agent (a mixing ratio of diethylene triamine:polyamidoamine = 2:1).
2. 물성 평가 방법 및 그 결과2. Method for evaluating physical properties and results
상기 실시예 1~5 및 비교예 1~4에서 제조된 조성물을 이용하여 다음과 같이, 물성 평가를 실시하였다.Using the compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4, physical properties were evaluated as follows.
1) 접착강도(kgf/cm2) : JIS K 5400 에 의거하여 측정하였다.1) Adhesive strength (kgf/cm 2 ): Measured according to JIS K 5400.
2) 경화도(%) 측정: 콘크리트 면에 롤러를 사용하여 조성물을 도포한 후, 25℃ 및 수분 85%의 조건 하에 24시간 방치하여 초기 무게 대비 방치한 후의 무게의 비율을 측정하여 경화도(%)를 도출하였다. 그 결과는 하기 표 1에 기재한 바와 같다.2) Curing degree (%) measurement: After applying the composition using a roller on the concrete surface, it is allowed to stand for 24 hours under the condition of 25°C and 85% moisture to measure the ratio of the weight after being left to stand for the initial weight. %). The results are shown in Table 1 below.
3) 경화시간(min) : KSM ISO 6721-10에 의거하여 측정하였다.3) Curing time (min): measured according to KSM ISO 6721-10.
4) 쇼어경도(shore D) : ASTM D2240에 의거하여 측정하였다.4) Shore hardness (shore D): It was measured according to ASTM D2240.
[표 1][Table 1]
표 1을 참조하면, 본 발명에 따른 에폭시 수지 조성물의 경화물은 접착강도가 40~60 kgf/cm2, 경화도 90~98%, 경화시간 10분 이하, 쇼어경도 85D~90D를 나타낸다.Referring to Table 1, the cured product of the epoxy resin composition according to the present invention exhibits an adhesive strength of 40 to 60 kgf/cm 2 , a curing degree of 90 to 98%, a curing time of 10 minutes or less, and a shore hardness of 85D to 90D.
에폭시 수지와 아민계 경화제의 함량을 만족한 실시예 1~5는 접착강도, 경화도, 경화시간, 경도 항목에서 비교예 1~4에 비하여 상대적으로 높은 결과값을 보여주었다.Examples 1 to 5, which satisfied the content of the epoxy resin and the amine-based curing agent, showed relatively high results compared to Comparative Examples 1 to 4 in terms of adhesive strength, curing degree, curing time, and hardness.
특히, 실시예 5는 테트라부틸포스포늄 말로네이트 성분을 더 포함함으로써, 실시예 1~4에 비하여 접착강도와 경화도가 더 높은 결과를 보여준다. Particularly, Example 5 further shows a higher adhesion strength and hardenability than Examples 1 to 4 by further including a tetrabutylphosphonium malonate component.
따라서, 염수, 수중, 저온 환경에서 우수한 경화성 및 내수성을 나타내기 위해서는 에폭시 수지 조성물에 비스페놀계 에폭시 수지, 노볼락 에폭시 수지, 아민계 경화제를 필수적으로 포함시키는 것이 바람직하다.Therefore, it is preferable to essentially include a bisphenol-based epoxy resin, a novolac epoxy resin, and an amine-based curing agent in an epoxy resin composition in order to exhibit excellent curability and water resistance in a saline, underwater, and low temperature environment.
이상과 같이 본 발명에 대해서 실시예를 참조로 하여 설명하였으나, 본 명세서에 개시된 실시예에 의해 본 발명이 한정되는 것은 아니며, 본 발명의 기술사상의 범위 내에서 통상의 기술자에 의해 다양한 변형이 이루어질 수 있음은 자명하다. 아울러 앞서 본 발명의 실시 예를 설명하면서 본 발명의 구성에 따른 작용 효과를 명시적으로 기재하여 설명하지 않았을 지라도, 해당 구성에 의해 예측 가능한 효과 또한 인정되어야 함은 당연하다.As described above, the present invention has been described with reference to Examples, but the present invention is not limited by the Examples disclosed herein, and various modifications can be made by those skilled in the art within the scope of the technical idea of the present invention. It is obvious that it can. In addition, although the operation and effect according to the configuration of the present invention is not explicitly described while describing the embodiment of the present invention, it is natural that the predictable effect by the configuration should also be recognized.
Claims (4)
비스페놀계 에폭시 수지 100중량부에 대하여, 아민계 경화제 200~400중량부를 포함하는 경화제;를 포함하고,
상기 주제 100중량부에 대하여, 경화제 50~100중량부를 포함하는 섬유 함침용 에폭시 수지 조성물.
A subject comprising 10 to 30 parts by weight of a novolac-based epoxy resin, 5 to 20 parts by weight of a phenolic solvent, and 0.1 to 1 part by weight of a silicone antifoaming agent based on 100 parts by weight of a bisphenol-based epoxy resin; And
Contains a curing agent containing 200 to 400 parts by weight of an amine-based curing agent, based on 100 parts by weight of the bisphenol-based epoxy resin,
The epoxy resin composition for impregnating fibers comprising 50 to 100 parts by weight of the curing agent, based on 100 parts by weight of the subject.
상기 노볼락계 에폭시 수지는 페놀 노볼락 에폭시 수지, o-크레졸 노볼락 에폭시 수지 및 디사이클로펜타디엔 노볼락 에폭시 수지 중 1종 이상을 포함하는 섬유 함침용 에폭시 수지 조성물.
According to claim 1,
The novolac-based epoxy resin is a phenol novolac epoxy resin, o -cresol novolac epoxy resin and dicyclopentadiene novolac epoxy resin fiber impregnating epoxy resin composition comprising at least one.
상기 페놀계 용매는 노닐 페놀 용매 및 도데실 페놀 용매 중 1종 이상을 포함하는 섬유 함침용 에폭시 수지 조성물.
According to claim 1,
The phenolic solvent is an epoxy resin composition for impregnating fibers comprising at least one of a nonyl phenol solvent and a dodecyl phenol solvent.
상기 아민계 경화제는 지방족 아민계 경화제, 아미도아민계 경화제 및 페날카민계 경화제 중 1종 이상을 포함하는 섬유 함침용 에폭시 수지 조성물.
According to claim 1,
The amine-based curing agent is an epoxy resin composition for impregnating fibers comprising at least one of an aliphatic amine-based curing agent, an amidoamine-based curing agent and a phenalamine-based curing agent.
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| JP2003041093A (en) * | 2001-07-27 | 2003-02-13 | Nippon Oil Corp | Resin composition for composite material, intermediate material for composite material and composite material |
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| KR20070108384A (en) | 2005-02-25 | 2007-11-09 | 니폰 가야꾸 가부시끼가이샤 | Epoxy resin, hardenable resin composition containing the same and use thereof |
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| KR101779089B1 (en) * | 2016-04-20 | 2017-09-18 | 주식회사 제일화성 | Epoxy resin composition having excellent water-proof and curing property in wet conditions |
| KR101791136B1 (en) * | 2017-02-10 | 2017-10-30 | (주)그린텍컴 | Composition for solvent-free lining coating for odorless coating |
| JP2017203142A (en) * | 2016-05-13 | 2017-11-16 | 三菱ケミカル株式会社 | Epoxy resin composition, prepreg, fiber-reinforced composite material, and method for producing the same |
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2018
- 2018-12-13 KR KR1020180160863A patent/KR102133400B1/en active IP Right Grant
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| JP2003041093A (en) * | 2001-07-27 | 2003-02-13 | Nippon Oil Corp | Resin composition for composite material, intermediate material for composite material and composite material |
| KR20050033184A (en) * | 2003-10-06 | 2005-04-12 | (주)크린텍 | Epoxy resin composition for repairing non-excavating sewer pipe |
| KR20070108384A (en) | 2005-02-25 | 2007-11-09 | 니폰 가야꾸 가부시끼가이샤 | Epoxy resin, hardenable resin composition containing the same and use thereof |
| KR100682369B1 (en) * | 2005-12-30 | 2007-02-15 | 삼화페인트공업주식회사 | Thermally hardening two fluid type epoxy paints composite |
| KR20130024259A (en) * | 2011-08-31 | 2013-03-08 | 주식회사 케이씨씨 | Solvent free epoxy coating composition for internal gas transmission pipelines |
| KR20160001860A (en) * | 2014-06-27 | 2016-01-07 | 한국건설생활환경시험연구원 | Impregnated resine composition well impregnated for wooden boat |
| KR101779089B1 (en) * | 2016-04-20 | 2017-09-18 | 주식회사 제일화성 | Epoxy resin composition having excellent water-proof and curing property in wet conditions |
| JP2017203142A (en) * | 2016-05-13 | 2017-11-16 | 三菱ケミカル株式会社 | Epoxy resin composition, prepreg, fiber-reinforced composite material, and method for producing the same |
| KR101791136B1 (en) * | 2017-02-10 | 2017-10-30 | (주)그린텍컴 | Composition for solvent-free lining coating for odorless coating |
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| KR102133400B1 (en) | 2020-07-14 |
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