KR102419869B1 - Method for manufacturing the quick hardening epoxy resin prepreg - Google Patents
Method for manufacturing the quick hardening epoxy resin prepreg Download PDFInfo
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- KR102419869B1 KR102419869B1 KR1020200133134A KR20200133134A KR102419869B1 KR 102419869 B1 KR102419869 B1 KR 102419869B1 KR 1020200133134 A KR1020200133134 A KR 1020200133134A KR 20200133134 A KR20200133134 A KR 20200133134A KR 102419869 B1 KR102419869 B1 KR 102419869B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/105—Coating or impregnating independently of the moulding or shaping step of reinforcement of definite length with a matrix in solid form, e.g. powder, fibre or sheet form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
- B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
- B29B15/125—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex by dipping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
- B29B15/14—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length of filaments or wires
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2009/00—Use of rubber derived from conjugated dienes, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
- B29K2105/0872—Prepregs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
- B29K2105/165—Hollow fillers, e.g. microballoons or expanded particles
- B29K2105/167—Nanotubes
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- Mechanical Engineering (AREA)
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- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
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Abstract
이 발명의 실시 예에 따른 속경화 에폭시 수지 프리프레그 제조방법은 고형 에폭시 수지 48~52중량%, 액상 에폭시 수지 30~34중량% 및 CNT 0.5~2중량%을 3롤밀을 통해 고르게 배합하는 수지 조성물 1차 배합단계; 수지 조성물 1차 배합단계에서 배합된 수지 조성물을 용탕 믹서에 옮겨 담은 후, 용탕 믹서에 입자가 분산된 개질 러버 8~10중량%, 경화제 4~6중량%, 경화촉진제 2~4중량%를 투입하고, 용탕 믹서의 내부온도가 50~70℃ 조건으로 유지되게 하는 가운데 용탕 믹서를 100~200RPM의 속도로 5~10분간 저속회전시켜 수지 조성물을 2차 배합하는 수지 조성물 2차 배합단계; 및 수지 조성물 2차 배합단계에서 배합된 수지 조성물에 직물 또는 섬유를 함침시킨 후 일정 두께의 프리프레그를 형성하는 프리프레그 형성단계; 를 포함하여 이루어진다.The rapid curing epoxy resin prepreg manufacturing method according to an embodiment of the present invention is a resin composition in which 48 to 52% by weight of a solid epoxy resin, 30 to 34% by weight of a liquid epoxy resin, and 0.5 to 2% by weight of CNT are uniformly blended through a 3-roll mill first mixing step; After transferring the resin composition blended in the first mixing step of the resin composition to the molten metal mixer, 8 to 10% by weight of the particle-dispersed modified rubber, 4 to 6% by weight of the curing agent, and 2 to 4% by weight of the curing accelerator are added to the molten metal mixer. and a resin composition secondary mixing step of secondary mixing the resin composition by rotating the molten metal mixer at a low speed of 100 to 200 RPM for 5 to 10 minutes while maintaining the internal temperature of the molten metal mixer at a condition of 50 to 70° C.; and a prepreg forming step of forming a prepreg of a certain thickness after impregnating the fabric or fiber in the resin composition blended in the resin composition secondary blending step; is made including
Description
이 발명은 자동차부품, 항공부품, 스포츠용품 등을 복합재료로 제작하는 과정에서 기계적 물성을 충분히 만족하면서도 제품 성형 시에 신속한 경화가 가능하여 생산성이 향상될 수 있는 속경화 에폭시 수지 프리프레그 및 그 제조방법 관한 것이다.The present invention relates to a fast-curing epoxy resin prepreg capable of improving productivity by allowing rapid curing during product molding while sufficiently satisfying mechanical properties in the process of manufacturing automobile parts, aviation parts, sports goods, etc. with composite materials, and manufacturing thereof it's about how
섬유강화 복합재료는 강철에 비하여 우수한 물성을 지니면서도 플라스틱에 비하여 가벼운 특성을 갖기 때문에 항공기, 자동차, 건축 부자재, 스포츠 용품 등을 포함한 각종 산업용품의 제작에 사용되고 있다. 한편, 이와 같은 섬유강화 복합재료를 이용한 제품의 제조는 대량 생산할 수 있는 금형 및 성형 공정의 구현에 어려움이 있을 뿐만 아니라 제품의 성형 공정에서는 수작업이 필요해 생산량이 낮고 가격이 비싼 단점이 있다.Fiber-reinforced composite materials have superior physical properties compared to steel and lighter than plastics, so they are used in the manufacture of various industrial products, including aircraft, automobiles, construction materials, and sports goods. On the other hand, manufacturing a product using such a fiber-reinforced composite material has disadvantages in that it is difficult to implement a mold and a molding process that can be mass-produced, but also requires manual work in the molding process of the product, resulting in low production and high price.
프리프레그(prepreg)는 섬유강화 복합재료를 이용한 제품의 성형 공정을 단축하기 위하여 직물 또는 섬유를 플라스틱 수지에 함침하거나 뿌린 후에 시트 형태이며 반경화 상태로 미리 제작되는 것을 통칭한다. 프리프레그는 성형할 제품 및 용도에 따라서, 또는 복합재료의 종류에 따라서, 또는 직물 또는 섬유의 종류에 따라서 다양하게 제공되고 있다.A prepreg is a sheet form after impregnating or sprinkling a fabric or fiber in a plastic resin in order to shorten the molding process of a product using a fiber-reinforced composite material. Prepregs are provided in various ways according to the product and use to be molded, or the type of composite material, or the type of fabric or fiber.
이 발명은 리프 스프링, 제트 스프링 등의 자동차 부품과 양궁의 날개 등과 같은 스포츠용품을 복합재료로 제작하는데 있어 요구되는 기계적 물성을 충분하게 만족하면서도 제품 성형 시에 5~10분 이내에 신속하게 경화될 수 있는 속경화 에폭시 수지 프리프레그 및 그 제조방법를 제공하는데 목적이 있다.This invention satisfies the mechanical properties required for producing composite materials for automobile parts such as leaf springs and jet springs and sporting goods such as archery wings, and can be cured quickly within 5 to 10 minutes during product molding. An object of the present invention is to provide a fast curing epoxy resin prepreg and a method for manufacturing the same.
전술한 바와 같은 발명의 목적을 달성하기 위한 수단으로 이 발명은 다음과 같은 구성으로 이루어질 수 있다.As a means for achieving the object of the invention as described above, the present invention may be configured as follows.
이 발명의 실시 예에 따른 속경화 에폭시 수지 프리프레그 제조방법은 a) Acrylate-Butadiene 러버 및/또는 Nitrile-Butadiene 러버 일정량을 호모 믹서에 투입하고, 호모 믹서에 투입된 러버 중량에 대하여 톨루엔 10Phr을 혼합한 후, 호모 믹서를 6,000~8,000RPM으로 고속회전시켜 입자를 분산시키는 러버입자 분산단계; b) 고형 에폭시 수지 48~52중량%, 액상 에폭시 수지 30~34중량% 및 CNT 0.5~2중량%을 3롤밀(Three roll mill)을 통해 고르게 배합하는 수지 조성물 1차 배합단계; c) 수지 조성물 1차 배합단계에서 배합된 수지 조성물을 용탕 믹서에 옮겨 담은 후, 용탕 믹서에 러버입자 분산단계에서 입자가 분산된 개질 러버 8~10중량%, 경화제 4~6중량%, 경화촉진제 2~4중량%를 투입하고, 용탕 믹서의 내부온도가 50~70℃ 조건으로 유지되게 하는 가운데 용탕 믹서를 100~200RPM의 속도로 5~10분간 저속회전시켜 수지 조성물을 2차 배합하는 수지 조성물 2차 배합단계; 및 d) 수지 조성물 2차 배합단계에서 배합된 수지 조성물에 직물 또는 섬유를 함침시킨 후 일정 두께의 프리프레그를 형성하는 프리프레그 형성단계; 를 포함하여 이루어진다.The method for manufacturing a fast-curing epoxy resin prepreg according to an embodiment of the present invention comprises: a) adding a certain amount of Acrylate-Butadiene rubber and/or Nitrile-Butadiene rubber to a homo mixer, and mixing 10 Phr of toluene with respect to the weight of the rubber injected into the homo mixer. Then, a rubber particle dispersing step of dispersing the particles by rotating the homo mixer at a high speed of 6,000 to 8,000 RPM; b) a first mixing step of a resin composition in which 48 to 52% by weight of a solid epoxy resin, 30 to 34% by weight of a liquid epoxy resin, and 0.5 to 2% by weight of CNT are uniformly blended through a three roll mill; c) After transferring the resin composition blended in the first mixing step of the resin composition to the molten metal mixer, 8 to 10 wt % of the modified rubber in which the particles are dispersed in the rubber particle dispersing step in the molten metal mixer, 4 to 6 wt % of the curing agent, and a curing accelerator 2 to 4% by weight is added, and while the internal temperature of the molten metal mixer is maintained at 50 to 70° C., the molten metal mixer is rotated at a low speed for 5 to 10 minutes at a speed of 100 to 200 RPM to secondary compound the resin composition. secondary mixing step; And d) a prepreg forming step of forming a prepreg of a certain thickness after impregnating the fabric or fiber in the resin composition blended in the resin composition secondary mixing step; is made including
이 발명의 실시 예에 따른 속경화 에폭시 수지 프리프레그 제조방법에서 수지 조성물 1차 배합단계에서 고형 에폭시 수지는 50중량%, 액상 에폭시 수지는 32중량%, CNT는 1중량%로 이루어지고, 수지 조성물 2차 배합단계에서 개질 러버는 9중량%, 경화제는 5중량%, 경화촉진제는 3중량%로 이루어진다.In the method for manufacturing a fast-curing epoxy resin prepreg according to an embodiment of the present invention, in the first mixing step of the resin composition, the solid epoxy resin is 50% by weight, the liquid epoxy resin is 32% by weight, and the CNT is 1% by weight, and the resin composition In the second mixing step, the modified rubber is composed of 9 wt%, the curing agent is 5 wt%, and the curing accelerator is 3 wt%.
이 발명의 실시 예에 따른 속경화 에폭시 수지 프리프레그 제조방법에서 프리프레그 형성단계에서의 직물 또는 섬유는 탄소섬유, 유리섬유, 아라미드 섬유 또는 붕소 섬유로 이루어진 군으로부터 선택되는 1종 이상의 섬유로 이루어진다.In the method for manufacturing a fast curing epoxy resin prepreg according to an embodiment of the present invention, the fabric or fiber in the prepreg forming step is made of one or more fibers selected from the group consisting of carbon fibers, glass fibers, aramid fibers or boron fibers.
이 발명의 실시 예에 따른 속경화 에폭시 수지 프리프레그 제조방법에서 수지 조성물 2차 배합단계에서 사용되는 용탕 믹서는 이중벽 구조의 내부에 가온을 위한 물이 수용되고, 이중벽 구조에 수용된 물온도 조절에 의해 가온이 이루어진다.In the method for manufacturing a fast curing epoxy resin prepreg according to an embodiment of the present invention, in the molten metal mixer used in the secondary mixing step of the resin composition, water for heating is accommodated in the double-walled structure, and the temperature of the water accommodated in the double-walled structure is controlled by warming takes place
이 발명의 실시 예에 따른 속경화 에폭시 수지 프리프레그 제조방법에서 러버입자 분산단계에서 Acrylate-Butadiene 러버와 Nitrile-Butadiene 러버의 혼합은 Acrylate-Butadiene 러버 40~60중량%, Nitrile-Butadiene 러버 60~40중량%의 비율로 이루어진다.In the method for manufacturing a fast curing epoxy resin prepreg according to an embodiment of the present invention, the mixing of Acrylate-Butadiene rubber and Nitrile-Butadiene rubber in the rubber particle dispersion step is 40 to 60 wt% of Acrylate-Butadiene rubber, 60 to 40 wt% of Nitrile-Butadiene rubber It consists of a percentage by weight.
이 발명은 자동차의 리프 스프링, 제트 스프링 등의 자동차 부품과 양궁의 날개 등과 같은 스포츠용품을 복합재료로 제작하는데 있어 요구되는 기계적 물성을 충분하게 만족하면서도 제품 성형 시에 5~10분 이내에 신속하게 경화되어 생산상을 높일 수 있는 효과가 있다.This invention sufficiently satisfies the mechanical properties required for manufacturing automobile parts such as leaf springs and jet springs of automobiles and sporting goods such as archery wings with composite materials, while rapidly curing within 5 to 10 minutes during product molding. This has the effect of increasing the productivity.
도1은 이 발명에 따른 속경화 에폭시 수지 프리프레그 제조방법을 설명하기 위한 도면.1 is a view for explaining a method for manufacturing a fast curing epoxy resin prepreg according to the present invention.
이하에서는 첨부된 도면을 참조하면서 이 발명의 실시 예에 따른 속경화 에폭시 수지 프리프레그 및 그 제조방법에 대하여 구체적으로 설명한다.Hereinafter, a fast curing epoxy resin prepreg and a manufacturing method thereof according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.
도1은 이 발명에 따른 속경화 에폭시 수지 프리프레그 제조방법을 설명하기 위한 도면이다.1 is a view for explaining a method for manufacturing a fast curing epoxy resin prepreg according to the present invention.
이 발명의 실시 예에 따른 속경화 에폭시 수지 프리프레그는 자동차의 리프 스프링, 자동차의 제트 스프링, 양궁의 날개를 제작하는데 주로 사용되기 위한 것으로, 수지 조성물은 고형 에폭시 수지 48~52중량%, 액상 에폭시 수지 30~34중량%, 개질 러버 8~10중량%, 경화제 4~6중량%, 경화촉진제 2~4중량% 및 CNT 0.5~2중량%을 포함하여 이루어진다.The fast-curing epoxy resin prepreg according to an embodiment of the present invention is mainly used for manufacturing leaf springs of automobiles, jet springs of automobiles, and wings of archery. 30 to 34% by weight of resin, 8 to 10% by weight of modified rubber, 4 to 6% by weight of a curing agent, 2 to 4% by weight of a curing accelerator, and 0.5 to 2% by weight of CNT.
특히, 이 발명의 실시 예에 따른 속경화 에폭시 수지 프리프레그를 제조하는 공정에는 도1에서 보이는 바와 같이 접착력 증진을 포함되는 개질 러버가 수지 조성물에 고르게 배합될 수 있도록 하는 러버입자 분산단계가 포함되며, 수지 조성물을 배합하는 공정으로 수지 조성물 1차 배합단계와 수지 조성물 2차 배합단계가 포함되고, 최종적으로 배합된 수지 조성물로 프리프레그를 형성하는 프리프레그 형성단계가 포함된다.In particular, the process of manufacturing a fast-curing epoxy resin prepreg according to an embodiment of the present invention includes a rubber particle dispersing step so that the modified rubber including adhesion enhancement can be evenly mixed in the resin composition as shown in FIG. , a process of blending the resin composition includes a first blending step of a resin composition and a second blending step of the resin composition, and includes a prepreg forming step of forming a prepreg with the finally blended resin composition.
< < 러버입자 분산단계rubber particle dispersion step > >
이 발명의 실시 예에 따른 러버입자 분산단계에서는 Acrylate-Butadiene 러버 및/또는 Nitrile-Butadiene 러버 일정량을 호모 믹서(Homo mixer)에 투입하고, 호모 믹서에 투입된 러버 중량에 대하여 톨루엔(Toluene) 10Phr(Parts per hundreds of rubber)을 혼합한 후, 호모 믹서를 6,000~8,000RPM으로 고속회전시켜 러버 입자를 분산시킨다.In the rubber particle dispersing step according to an embodiment of the present invention, a certain amount of Acrylate-Butadiene rubber and/or Nitrile-Butadiene rubber is added to a homo mixer, and 10 Phr of toluene (Toluene) with respect to the weight of the rubber injected into the homo mixer (Parts) per hundreds of rubber), and then high-speed rotation of the homo mixer at 6,000~8,000RPM to disperse the rubber particles.
러버입자 분산단계에 사용되는 러버 제품으로는 Goodrich사(U.S.A.)의 Hycar 1300 타입인 Acrylate-Butadiene Rubber를 사용하거나 Goodrich사의 Hycar 4021 타입인 Nitrile-Butadiene Rubber을 사용한다. 한국의 국도화학 제품으로는 KR-450과 KR-628이 사용될 수 있다.As a rubber product used in the rubber particle dispersing step, Goodrich's (U.S.A.) Hycar 1300 type Acrylate-Butadiene Rubber or Goodrich's Hycar 4021 type Nitrile-Butadiene Rubber is used. KR-450 and KR-628 can be used as Korea's Kukdo Chemical products.
Acrylate-Butadiene Rubber와 Nitrile-Butadiene Rubber를 혼합하여 사용할 경우에, Acrylate-Butadiene 러버 40~60중량%, Nitrile-Butadiene 러버 60~40중량%의 비율로 이루어지는 것이 바람직하다.When mixing Acrylate-Butadiene Rubber and Nitrile-Butadiene Rubber, it is preferable to consist of 40 to 60% by weight of Acrylate-Butadiene Rubber and 60 to 40% by Weight of Nitrile-Butadiene Rubber.
Acrylate-Butadiene 러버 및/또는 Nitrile-Butadiene 러버, 톨루엔(Toluene)이 담긴 호모 믹서를 6,000~8,000RPM으로 고속회전시키면 러버 입자가 분산되면서 개질 러버로 준비된다.Acrylate-Butadiene rubber and/or Nitrile-Butadiene rubber, and a homomixer containing toluene are rotated at a high speed of 6,000 to 8,000 RPM to disperse the rubber particles and prepare a modified rubber.
전술한 러버입자 분산단계를 통해서 입자가 분산된 개질 러버는 이 발명에 따른 속경화 에폭시 수지 프리프레그를 반경화 상태(B-stage)로 성형하는데 필요한 수지 조성물을 구성하는 각 성분들의 전체 중량을 기준으로 하여 8~10중량%의 용량이 준비되도록 한다.The modified rubber in which the particles are dispersed through the above-described rubber particle dispersing step is based on the total weight of each component constituting the resin composition required for molding the fast-curing epoxy resin prepreg according to the present invention to a semi-cured state (B-stage). to prepare a capacity of 8 to 10% by weight.
< < 수지 조성물 1차 배합단계Resin composition first mixing step > >
수지 조성물 1차 배합단계에서는 이 발명에 따른 속경화 에폭시 수지 프리프레그를 반경화 상태(B-stage)로 성형하는데 필요한 수지 조성물의 각 성분들의 전체 중량을 기준으로 고형 에폭시 수지 48~52중량%, 액상 에폭시 수지 30~34중량% 및 CNT(Carbon nanp tube) 0.5~2중량%를 별도의 용기에서 혼합한다. 3롤밀(Three roll mill)을 이용하여 고형 에폭시 수지, 액상 에폭시 수지 및 CNT가 고르게 혼합되도록 한다.In the first compounding step of the resin composition, 48 to 52% by weight of a solid epoxy resin based on the total weight of each component of the resin composition required for molding the fast curing epoxy resin prepreg according to the present invention to a semi-cured state (B-stage), 30 to 34% by weight of the liquid epoxy resin and 0.5 to 2% by weight of CNT (Carbon nanp tube) are mixed in a separate container. Using a three roll mill, the solid epoxy resin, liquid epoxy resin and CNT are mixed evenly.
고형 에폭시 수지는 비스페놀-A타입 에폭시 수지(bisphenol-A type epoxy resin) 또는 페놀 노블락 에폭시 수지(phenol novolac epoxy resin)이 사용될 수 있으며, 필요에 따라서는 비스페놀-A 에폭시 수지와 페놀 노블락 에폭시 수지를 균등한 비율로 혼합하여 사용될 수 있다. 특히, 비스페놀-A타입 에폭시 수지는 국도화학의 제품인 YD-011이나 YDPN-638을 사용될 수 있다. 액상 에폭시 수지 대비 고형 에폭시 수지가 차지하는 분량은 10~80%의 범위로 이루어질 수 있다.For the solid epoxy resin, bisphenol-A type epoxy resin or phenol novolac epoxy resin can be used. It can be used by mixing in one ratio. In particular, as the bisphenol-A type epoxy resin, YD-011 or YDPN-638 manufactured by Kukdo Chemical may be used. The proportion of the solid epoxy resin compared to the liquid epoxy resin may be in the range of 10 to 80%.
액상 에폭시 수지로는 액상 비스페놀-A타입 에폭시 수지(liquid bisphenol-A type epoxy resin)가 사용될 수 있다. 액상 비스페놀-A타입 에폭시 수지로는 국토화학의 제품인 YD-128이 사용될 수 있다. 고상 에폭시 수지 대비 액상 에폭시 수지가 차지하는 분량은 10~60%의 범위로 이루어질 수 있다.As the liquid epoxy resin, a liquid bisphenol-A type epoxy resin may be used. As the liquid bisphenol-A type epoxy resin, YD-128, a product of Hokji Chemical, can be used. The proportion of the liquid epoxy resin compared to the solid epoxy resin may be in the range of 10 to 60%.
수지 조성물 1차 배합단계에서 혼합되는 각 혼합물의 바람직한 함량은 고형 에폭시 수지는 50중량%, 액상 에폭시 수지는 32중량%, CNT는 1중량%이다.The preferred content of each mixture to be mixed in the first mixing step of the resin composition is 50 wt% of a solid epoxy resin, 32 wt% of a liquid epoxy resin, and 1 wt% of CNT.
수지 조성물 1차 배합단계에서 CNT가 수지 조성물에 배합되는 과정에서 마치 고무 가류공정 등에서와 같이 수지 조성물에 고르게 배합이 이루어짐으로써 프리프레그의 층간접착력이 향상되고 성형된 제품의 충격방지 및 진동감쇄 효과 측면에서 유리해질 수 있다.In the process of mixing CNTs with the resin composition in the first compounding step of the resin composition, as in the rubber vulcanization process, the mixture is evenly mixed with the resin composition, thereby improving the interlayer adhesion of the prepreg and preventing the impact and vibration damping of the molded product. can be advantageous in
이와 같이 수지 조성물 1차 배합단계에서 배합된 수지 조성물은 속경화 에폭시 수지 프리프레그를 반경화 상태로 성형하는데 필요한 수지 조성물의 각 성분들의 전체 중량을 기준으로 하여 83중량%의 용량이 준비된다.As such, the resin composition blended in the first compounding step of the resin composition has a capacity of 83% by weight based on the total weight of each component of the resin composition required for molding the fast-curing epoxy resin prepreg into a semi-cured state.
< < 수지 조성물 2차 배합단계Secondary compounding step of resin composition > >
수지 조성물 1차 배합단계에서 배합된 수지 조성물 일정량을 내부온도가 50~70℃ 조건으로 유지될 수 있게 구성된 용탕 믹서에 담고, 용탕 믹서에 앞의 러버입자 분산단계를 통해 준비해둔 개질 러버 8~10중량%, 경화제 4~6중량%, 경화촉진제 2~4중량%를 추가한다.Put a certain amount of the resin composition blended in the first compounding step of the resin composition in a molten metal mixer configured to maintain the internal temperature at 50 to 70°C, and the modified rubber 8 to 10 prepared through the rubber particle dispersing step in the molten metal mixer % by weight, 4 to 6% by weight of a curing agent, and 2 to 4% by weight of a curing accelerator are added.
수지 조성물 2차 배합단계에서 입자가 분산된 개질 러버는 9중량%, 경화제는 5중량%, 경화촉진제는 3중량%의 비율로 혼합되는 것이 바람직하다.In the secondary compounding step of the resin composition, it is preferable that the modified rubber in which the particles are dispersed is mixed in a ratio of 9% by weight, the curing agent is 5% by weight, and the curing accelerator is 3% by weight.
이후, 용탕 믹서의 내부온도가 50~70℃ 조건으로 유지되게 하는 가운데 용탕 믹서를 100~200RPM의 속도로 5~10분간 저속회전시켜 각 혼합물들이 고르게 배합되도록 한다.Then, while the internal temperature of the molten metal mixer is maintained at a condition of 50 to 70 ℃, the molten metal mixer is rotated at a low speed for 5 to 10 minutes at a speed of 100 to 200 RPM so that each mixture is evenly mixed.
수지 조성물 2차 배합단계에서 사용되는 용탕 믹서는 이중벽 구조의 내부에 가온을 위한 물이 수용되고, 이중벽 구조에 수용된 물온도 조절에 의해 가온이 이루어지도록 구성된 것이 사용된다.As for the molten metal mixer used in the secondary mixing step of the resin composition, water for heating is accommodated in the double-wall structure, and heating is performed by controlling the temperature of the water accommodated in the double-wall structure.
< < 프리프레그 형성단계Prepreg Formation Step > >
수지 조성물 2차 배합단계에서 배합이 완료된 수지 조성물에 탄소섬유, 유리섬유, 아라미드 섬유 또는 붕소 섬유로 이루어진 군으로부터 선택되는 1종 이상의 섬유 또는 직물을 함침하여 일정 두께를 갖는 시트형태의 반경화 프리프레그를 형성한다.Semi-hardened prepreg in the form of a sheet having a certain thickness by impregnating one or more fibers or fabrics selected from the group consisting of carbon fibers, glass fibers, aramid fibers or boron fibers in the resin composition that has been blended in the resin composition secondary mixing step to form
또한, 전술한 공정들을 통해 제조된 수지 조성물은 60~80℃의 온도조건에서 UD 기계를 통해 UD 프리프레그를 제조될 수 있다.In addition, the resin composition prepared through the above-described processes may be prepared by using a UD machine at a temperature of 60 ~ 80 ℃ UD prepreg.
< < 제품 성형product molding > >
이 발명의 실시 예에 따른 방법에 의해서 제조된 프리프레그를 사용하여 자동차의 리프 스프링, 제트 스프링 등의 자동차 부품과 양궁의 날개 등과 같은 스포츠용품을 복합재료로 제작하게 된다.By using the prepreg manufactured by the method according to the embodiment of the present invention, automobile parts such as leaf springs and jet springs of automobiles and sporting goods such as archery wings are manufactured from composite materials.
제품을 성형하는 과정에서 140~160℃의 온도조건에서 5~10분이면 경화가 이루어짐에 따라 제품 생산성이 향상될 뿐만 아니라 복합재료에서 요구되는 기계적 물성 또한 충분하게 확보할 수 있다.In the process of molding the product, curing occurs in 5 to 10 minutes at a temperature of 140 to 160 ° C. As a result, product productivity is improved as well as mechanical properties required for composite materials can be sufficiently secured.
< < 실시예Example > >
앞에 설명한 단계들을 통해서 고형 에폭시수지 50중량%, 액상 에폭시 수지 32중량%, 개질 러버 9중량%, 경화제 5중량%, 경화촉진제 3중량%, CNT 1중량%의 혼합비율로 프리프레그 제작을 위한 에폭시 수지 조성물을 제조(표1 참조)하였다.Epoxy for prepreg production at a mixing ratio of 50% by weight of solid epoxy resin, 32% by weight of liquid epoxy resin, 9% by weight of modified rubber, 5% by weight of curing agent, 3% by weight of curing accelerator, and 1% by weight of CNT through the steps described above. A resin composition was prepared (see Table 1).
위의 혼합비율로 제조된 에폭시 수지 조성물을 이용하여 복합재료용 프리프레그를 형성하였으며, 그 물성은 다음의 표2 및 표3과 같이 나타났다.A prepreg for a composite material was formed using the epoxy resin composition prepared in the above mixing ratio, and its physical properties were shown in Tables 2 and 3 below.
한편, 도2는 이 발명의 실시 예에 따른 프리프레그의 경화반응을 DSC(Differential Scanning Calorimetry)로 보인 그래프이며, 도3은 이 발명의 실시 예에 따른 프리프레그의 TG를 보인 그래프이다. 도2 및 도3에서 보이는 바와 같이 이 발명의 실시 예에 따른 프리프레그는 150℃ × 10min 정도에서 제품성형 과정에서의 큐어 사이클(cure cycle)이 끝난다.On the other hand, Figure 2 is a graph showing the curing reaction of the prepreg according to an embodiment of the present invention by DSC (Differential Scanning Calorimetry), Figure 3 is a graph showing the TG of the prepreg according to an embodiment of the present invention. As shown in Figures 2 and 3, the prepreg according to the embodiment of the present invention is finished with a cure cycle in the product molding process at about 150 ℃ × 10min.
이상에서는 첨부된 도면들을 참조하면서 이 발명의 실시 예에 따른 속경화 에폭시 수지 프리프레그 및 그 제조방법에 대하여 설명하였다. 이러한 실시 예들은 이 발명의 청구범위에 기재된 기술 사상에 포함되는 것이다. 또한, 전술한 실시 예들은 예시적인 것에 불과한 것으로 한정 해석되면 안 된다.In the above, a fast curing epoxy resin prepreg and a manufacturing method thereof according to an embodiment of the present invention have been described with reference to the accompanying drawings. These embodiments are included in the technical spirit described in the claims of the present invention. In addition, the above-described embodiments are merely exemplary and should not be construed as being limited.
Claims (6)
a) 호모 믹서(Homo mixer)에 Acrylate-Butadiene 러버 40~60중량% 및 Nitrile-Butadiene 러버 60~40중량%를 투입하여 혼합하되, 상기 호모 믹서에 투입된 러버의 전체 중량에 대하여 톨루엔 10Phr(Parts per hundreds of rubber)을 혼합하고, 상기 호모 믹서를 6,000~8,000RPM으로 고속회전시켜 입자를 분산시키는 러버입자 분산단계;
b) 고형 에폭시 수지 48~52중량%, 액상 에폭시 수지 30~34중량% 및 CNT 0.5~2중량%을 3롤밀(Three roll mill)을 통해 고르게 배합하는 수지 조성물 1차 배합단계;
c) 가온을 위한 물이 수용되는 이중벽 구조의 용탕 믹서에 상기 수지 조성물 1차 배합단계에서 배합된 수지 조성물을 옮겨 담은 후, 상기 용탕 믹서에 상기 러버입자 분산단계에서 입자가 분산된 개질 러버 8~10중량%, 경화제 4~6중량%, 경화촉진제 2~4중량%를 투입하고, 상기 용탕 믹서의 내부온도가 50~70℃ 조건으로 유지되게 하는 가운데 상기 용탕 믹서를 100~200RPM의 속도로 5~10분간 저속회전시켜 수지 조성물을 2차 배합하는 수지 조성물 2차 배합단계; 및
d) 상기 수지 조성물 2차 배합단계에서 배합된 수지 조성물에 직물 또는 섬유를 함침시킨 후 일정 두께의 프리프레그를 형성하는 프리프레그 형성단계; 를 포함하여 이루어지는 속경화 에폭시 수지 프리프레그 제조방법.
In the method of manufacturing a prepreg in a semi-cured (B-stage) state having a certain thickness so that curing can be achieved within 5 to 10 minutes at a temperature of 140 to 160 ° C in the product molding process,
a) 40 to 60% by weight of Acrylate-Butadiene rubber and 60 to 40% by weight of Nitrile-Butadiene rubber are added to a homo mixer and mixed, but toluene 10Phr (Parts per a rubber particle dispersing step of mixing hundreds of rubber) and dispersing the particles by high-speed rotation of the homo mixer at 6,000 to 8,000 RPM;
b) a first mixing step of a resin composition in which 48 to 52% by weight of a solid epoxy resin, 30 to 34% by weight of a liquid epoxy resin, and 0.5 to 2% by weight of CNT are uniformly blended through a three roll mill;
c) After transferring the resin composition blended in the first blending step of the resin composition to a double-walled molten metal mixer containing water for heating, the modified rubber in which particles are dispersed in the rubber particle dispersing step in the melt mixer 8~ 10% by weight, 4 to 6% by weight of the curing agent, and 2 to 4% by weight of the curing accelerator are added, and while the internal temperature of the molten metal mixer is maintained at 50 to 70° C., the molten metal mixer is operated at a speed of 100 to 200 RPM. A secondary compounding step of a resin composition for secondary compounding of the resin composition by rotating at a low speed for ~10 minutes; and
d) a prepreg forming step of forming a prepreg of a certain thickness after impregnating the fabric or fiber in the resin composition blended in the second blending step of the resin composition; A method for producing a fast curing epoxy resin prepreg comprising a.
상기 수지 조성물 1차 배합단계에서 상기 고형 에폭시 수지는 50중량%, 상기 액상 에폭시 수지는 32중량%, 상기 CNT는 1중량%로 이루어지고,
상기 수지 조성물 2차 배합단계에서 상기 개질 러버는 9중량%, 상기 경화제는 5중량%, 상기 경화촉진제는 3중량%로 이루어지는 것을 특징으로 하는 속경화 에폭시 수지 프리프레그 제조방법.
The method of claim 1,
In the first mixing step of the resin composition, the solid epoxy resin is 50% by weight, the liquid epoxy resin is 32% by weight, and the CNT is 1% by weight,
In the secondary compounding step of the resin composition, the modified rubber is comprised of 9 wt%, the curing agent is 5 wt%, and the curing accelerator is 3 wt%.
프리프레그 형성단계에서의 직물 또는 섬유는 탄소섬유, 유리섬유, 아라미드 섬유 또는 붕소 섬유로 이루어진 군으로부터 선택되는 1종 이상의 섬유로 이루어진 것을 특징으로 하는 속경화 에폭시 수지 프리프레그 제조방법.
The method of claim 1,
The fabric or fiber in the prepreg forming step is a fast curing epoxy resin prepreg manufacturing method, characterized in that it consists of at least one fiber selected from the group consisting of carbon fiber, glass fiber, aramid fiber or boron fiber.
A fast curing epoxy resin prepreg manufactured by the manufacturing method according to any one of claims 1 to 3.
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