KR20160055983A - Sizing agent for carbon-fiber, and carbon-fiber manufactured by using the same - Google Patents
Sizing agent for carbon-fiber, and carbon-fiber manufactured by using the same Download PDFInfo
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- KR20160055983A KR20160055983A KR1020140154832A KR20140154832A KR20160055983A KR 20160055983 A KR20160055983 A KR 20160055983A KR 1020140154832 A KR1020140154832 A KR 1020140154832A KR 20140154832 A KR20140154832 A KR 20140154832A KR 20160055983 A KR20160055983 A KR 20160055983A
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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- D06M14/36—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to carbon fibres
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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Abstract
Description
본 발명은, 탄소섬유용 사이징제, 및 이를 이용하여 제조된 탄소섬유에 관한 것이다.The present invention relates to a sizing agent for carbon fibers, and carbon fibers produced using the same.
탄소 섬유는 취성이 있고, 집속성 및 내마찰성이 부족하기 때문에, 고차 가공 공정에 있어서 보풀이나 실끊김이 발생하기 쉽다.Since the carbon fiber is brittle and lacks the property of housing and friction resistance, the fluff and yarn breakage tend to occur in the higher-order processing step.
통상적으로, 이러한 문제점을 해결하기 위해, 탄소 섬유에 사이즈제를 도포하는 방법이 행해지고 있다.Conventionally, in order to solve such a problem, a method of applying a sizing agent to carbon fibers has been carried out.
예를 들어, 사이즈제로서 비스페놀 A의 디글리시딜에테르를 탄소 섬유에 도포하거나(특허문헌 1 참조), 사이즈제로서 비스페놀 A의 폴리알킬렌옥시드 부가물을 탄소 섬유에 도포하거나(특허문헌 2 참조), 사이즈제로서 비스페놀 A의 폴리알킬렌옥시드 부가물에 에폭시기를 부가시킨 것을 탄소 섬유에 도포하는 방법(특허문헌 3 참조) 등 이다. 이로써, 상기 언급된 특허문헌 1 내지 3의 내용 전부는 모두 본 발명 명세서의 배경기술로서, 인용·합체된다.For example, as a sizing agent, diglycidyl ether of bisphenol A is applied to a carbon fiber (see Patent Document 1), or a polyalkylene oxide adduct of bisphenol A is applied to a carbon fiber as a sizing agent (Patent Document 2 , A method of applying an epoxy group to a polyalkylene oxide adduct of bisphenol A as a sizing agent to a carbon fiber (see Patent Document 3), and the like. As a result, all of the above-mentioned Patent Documents 1 to 3 are cited as a background art of the specification of the present invention.
그러나, 이러한 종래 기술의 제안 방법으로도 집속성과 내마찰성은 향상되지만, 이들 종래의 제안에는 사이즈제에 의해 탄소 섬유와 매트릭스 수지의 접착성을 적극적으로 향상시킨다고 하는 기술적 사상은 없어, 실제로 탄소 섬유와 매트릭스 수지의 접착성을 대폭 향상시킬 수는 없었다.However, the proposed method of this prior art also improves the collecting property and the frictional resistance. However, these conventional proposals do not have a technical idea that the adhesion between the carbon fibers and the matrix resin is actively improved by the sizing agent, And the adhesive property of the matrix resin could not be significantly improved.
탄소 섬유는 경량이면서 강도 및 탄성률이 우수하기 때문에, 여러가지 매트릭스 수지와 조합한 복합 재료는 항공기 부재, 우주선 부재, 자동차 부재, 선박 부재, 토목 건축재 및 스포츠용품 등의 많은 분야에 이용되고 있는데, 탄소 섬유를 이용한 복합 재료에 있어서, 탄소 섬유의 우수한 특성을 살리기 위해서는, 탄소 섬유와 매트릭스 수지의 접착성은 우수한 것이 중요한 요소이다.Since carbon fibers are lightweight and excellent in strength and elastic modulus, composite materials combined with various matrix resins are used in many fields such as aircraft members, spacecraft members, automobile members, ship members, civil engineering construction materials and sports goods. It is an important factor that the adhesion between the carbon fiber and the matrix resin is excellent in order to take advantage of the excellent properties of the carbon fiber.
특히, 탄소섬유용 사이징(Sizing)제로 에폭시(Epoxy) 및 이와 유사한 성분이 사이징제로 사용되어 왔다. 탄소섬유 복합재료 매트릭스(matrix) 수지를 에폭시로 하는 경우 물성저하가 발행하지 않으나, 비닐 에스터(vinyl ester), 폴리에스터(polyester)수지를 매트릭스 수지로하는 복합재료에 있어서는 복합재료 물성저하의 원인이 된다.In particular, epoxy sizing agents for carbon fibers have been used as sizing agents. Carbon fiber composite material matrix resin does not cause property deterioration when epoxy resin is used. However, in composite materials using vinyl ester or polyester resin as a matrix resin, do.
또한, 에폭시 수지를 매트릭스 수지로 하는 경우에 있어서도 에폭시 수지를 사이징제로 사용하는 경우 낮은 강인성이 문제가 되어왔다.In addition, even when an epoxy resin is used as a matrix resin, low toughness has been a problem when an epoxy resin is used as a sizing agent.
따라서, 본 발명의 목적은, 상기의 종래 기술에서의 문제점을 해결하여 탄소 섬유와 매트릭스 수지의 접착성이 우수하고, 또한 고차 가공성이 우수한 사이징제 도포 탄소 섬유의 제조 방법 및 사이징제 도포 탄소 섬유를 제공하는 데 있다.Accordingly, an object of the present invention is to provide a sizing agent-coated carbon fiber excellent in adhesiveness between a carbon fiber and a matrix resin, excellent in high order formability, and a sizing agent- .
본 발명은 상술한 종래기술의 문제점을 해결하기 위해 안출된 것으로서,SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art,
에폭시 레진, 및 불포화 폴리에스터를 포함하고,Epoxy resins, and unsaturated polyesters,
상기 불포화에스터는 불포화 지방산과 디에폭시다이즈드 하이드로제네이티드 비스페놀 A와 반응시킨 것임을 특징으로 하는 탄소섬유용 사이징제를 제공한다.Wherein the unsaturated ester is reacted with an unsaturated fatty acid and a diepoxy dihydrogen bisphenol A.
또한 본 발명에 있어서, 상기 불포화 지방산은, 하기 화학식 1로 표현되는 화합물에서 1종 이상인 것을 특징으로 하는 탄소섬유용 사이징제를 제공한다.In the present invention, the unsaturated fatty acid may be at least one compound represented by the following general formula (1).
[화학식 1][Chemical Formula 1]
여기서, R1은 H이고, R2 내지 R8은, 각각 독립적으로, 수소, 메틸기, 또는 페닐기이며, n은 0 내지 5의 정수이다.Here, R 1 is H, R 2 to R 8 are each independently hydrogen, a methyl group, or a phenyl group, and n is an integer of 0 to 5.
또한 본 발명에 있어서, 상기 불포화 지방산은, 신남산, 크로톤산, 아크릴산, 및 메타크릴산에서 선택되는 1종 이상인 것을 특징으로 하는 탄소섬유용 사이징제를 제공한다.In the present invention, the unsaturated fatty acid is at least one selected from the group consisting of cinnamic acid, crotonic acid, acrylic acid, and methacrylic acid.
또한 본 발명에 있어서, 상기 에폭시 레진 80 내지 97 중량%, 및 불포화 폴리에스터 3 내지 20 중량% 포함하는 것임을 특징으로 하는 탄소섬유용 사이징제를 제공한다.The present invention also provides a sizing agent for a carbon fiber, which comprises 80 to 97% by weight of the epoxy resin, and 3 to 20% by weight of an unsaturated polyester.
또한 본 발명에 있어서, 25℃에서의 점도가 1.0ⅹ108~1.0ⅹ106이며, 80℃에서의 점도가 1.0ⅹ102~1.0ⅹ104임을 특징으로 하는 탄소섬유용 사이징제를 제공한다.Also, the present invention provides a sizing agent for carbon fibers, wherein the viscosity at 25 ° C is 1.0 x 10 8 to 1.0 x 10 6 , and the viscosity at 80 ° C is 1.0 x 10 2 to 1.0 x 10 4 .
또한 본 발명에 있어서, 25℃의 점도와 80℃의 점도비가 하기 수학식 1을 만족함을 특징으로 하는 탄소섬유용 사이징제를 제공한다.In the present invention, there is also provided a sizing agent for a carbon fiber characterized in that the viscosity at 25 캜 and the viscosity ratio at 80 캜 satisfy the following formula (1).
[수학식 1][Equation 1]
η(at25℃)/η(at 80℃) ≤ 1ⅹ103 + 100 × 중량%(에폭시 레진)/중량%(불포화 폴리 에스터)(at 25 ° C) /? (at 80 ° C)? 1 x 10 3 + 100 x% by weight (epoxy resin) /% by weight (unsaturated polyester)
또한, 본 발명의 사이징제가 도포된 탄소섬유를 제공한다.Further, the carbon fiber to which the sizing agent of the present invention is applied is provided.
또한, 본 발명의 탄소섬유를 포함하는 매트릭스 수지 내에 포함하는 복합 재료를 제공한다.Further, a composite material contained in a matrix resin containing the carbon fiber of the present invention is provided.
본 발명의 탄소섬유는, 에폭시를 매트릭스 수지로 하는 복합재료 뿐 아니라, 비닐 에스터(vinyl ester), 또는 폴리에스터(polyester)수지를 매트릭스 수지로하는 복합재료에 있어서도 물성저하가 발생하지 않으며, 에폭시만을 사이징 처리한 탄소섬유 적용 복합재료 대비하여 우수한 충격강도를 가지는 효과가 있다.The carbon fiber of the present invention does not cause deterioration of physical properties even in a composite material comprising a matrix resin of a vinyl ester or a polyester resin as well as a composite material of an epoxy resin of a matrix resin, It has an effect of providing excellent impact strength as compared with a sizing-treated carbon fiber-applied composite material.
도 1은, 본 발명 실시예 1의 불포화 폴리에스터 함량에 따른 물성 변화를 나타낸 그래프이다.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing changes in physical properties according to the unsaturated polyester content of Example 1 of the present invention. FIG.
이하, 본 발명에 대하여 상세히 설명한다.
Hereinafter, the present invention will be described in detail.
본 발명은, 에폭시 레진, 및 불포화 폴리에스터를 포함하고,The present invention relates to an epoxy resin composition comprising an epoxy resin, and an unsaturated polyester,
상기 불포화에스터는 불포화 지방산과 디에폭시다이즈드 하이드로제네이티드 비스페놀 A(Diepoxized hydrogenated bisphenol A)와 반응시킨 것임을 특징으로 하는 탄소섬유용 사이징제이다.Wherein the unsaturated ester is prepared by reacting an unsaturated fatty acid with a diepoxized hydrogenated bisphenol A (diepoxidized hydrogenated bisphenol A).
상기 불포화 지방산은, 하기 화학식 1로 표현되는 화합물에서 선택되는 1종 이상을 사용할 수 있다.The unsaturated fatty acid may be at least one selected from compounds represented by the following general formula (1).
[화학식 1][Chemical Formula 1]
여기서, R1은 H이고, R2 내지 R8은, 각각 독립적으로, 수소, 메틸기, 또는 페닐기이며, n은 0 내지 5의 정수이다.Here, R 1 is H, R 2 to R 8 are each independently hydrogen, a methyl group, or a phenyl group, and n is an integer of 0 to 5.
상기 화삭식 1로 표현되는 화합물의 예시로, 신남산(cinnamic acid), 크로톤산(crotonic acid), 아크릴산(acrylic acid), 및 메타크릴산(methacrylic acid)등을 들 수 있다. Examples of the compound represented by the formula 1 include cinnamic acid, crotonic acid, acrylic acid, and methacrylic acid.
상기 에폭시 레진 80 내지 97 중량%, 및 불포화 폴리에스터 3 내지 20 중량% 포함하는 것이 바람직하다. 상기 범위를 벗어나, 에폭시 레진이 더 많은 경우, ㅍ폴리에스터 또는 비닐에스터 수지와의 계면 접착력 저하로, 폴리에스터 또는 비닐에스터 복합재료의 기계적 물성이 저하될 수 있고, 불포화 폴리에스터가 더 많은 경우, 에폭시 수지와의 계면 접착력의 저하로 Epoxy 계 복합재료의 기계적 물성이 저하될 수 있다.80 to 97% by weight of the epoxy resin, and 3 to 20% by weight of the unsaturated polyester. If the amount of the epoxy resin is more than the above range, the mechanical properties of the polyester or vinyl ester composite material may be deteriorated due to a decrease in the interfacial adhesion between the polyester resin and the vinyl ester resin. When the number of the unsaturated polyester is larger, The mechanical properties of the epoxy-based composite material may deteriorate due to a decrease in the interfacial adhesion with the epoxy resin.
본 발명의 사이징제는 25℃에서의 점도가 1.0ⅹ108~1.0ⅹ106이며, 80℃에서의 점도가 1.0ⅹ102~1.0ⅹ104임을 특징으로 한다. 상기 점도 범위에서 상온에서의 탄소섬유의 사폭을 안정적으로 유지할 수 있어 프리프레그(Prepreg), 필라멘트 ㅇ와인딩(lament winding) 등 복합재료 중간재 공정에서의 사폭 변형을 최소하 할 수 있어 복합재료 외관의 안정성을 확보할 수 있으며, 개섬성이 필요한 경우 열을 가하여 요구특성을 만족시킬수 있기 때문이다.The sizing agent of the present invention has a viscosity at 25 ° C of 1.0 x 10 8 to 1.0 x 10 6 and a viscosity at 80 ° C of 1.0 x 10 2 to 1.0 x 10 4 . It is possible to stably maintain the width of the carbon fiber at room temperature in the above range of viscosity and to minimize the warpage deformation in the intermediate process of composite materials such as prepreg and filament windings, And it is possible to satisfy the required characteristics by applying heat when the openability is required.
또한 본 발명의 사이징제는, 25℃의 점도와 80℃의 점도비가 하기 수학식 1을 만족함을 특징으로 한다. 이 범위를 만족하는 경우 복합재료 제조 공정에서의 탄소섬유 사폭을 안정적으로 유지할 수 있으며, 필요한 경우 열을 가하여 개섬할 수있어 탄소섬유의 집속성과 개섬성을 동시에 만족시킬 수 있다.The sizing agent of the present invention is characterized in that the viscosity at 25 DEG C and the viscosity ratio at 80 DEG C satisfy the following formula (1). If this range is satisfied, the carbon fibers can be stably maintained in the composite material manufacturing process, and if necessary, heat can be applied to open the carbon fibers, which can simultaneously satisfy the aggregation and openability of the carbon fibers.
[수학식 1][Equation 1]
η(at25℃)/η(at 80℃) ≤ 1ⅹ103 + 100 × 중량%(에폭시 레진)/중량%(불포화 폴리 에스터)
(at 25 ° C) /? (at 80 ° C)? 1 x 10 3 + 100 x% by weight (epoxy resin) /% by weight (unsaturated polyester)
이하, 본 발명에 대하여 실시예를 들어 보다 더 상세히 설명한다. 이하의 실시예는 발명의 상세한 설명을 위한 것일 뿐, 이에 의해 권리범위를 제한하려는 의도가 아님을 분명히 해둔다.
Hereinafter, the present invention will be described in more detail by way of examples. It is to be understood that the following embodiments are for the purpose of illustration only and are not intended to limit the scope of the present invention.
실시예Example
실시예Example 1 One
하기 화학식 2과 같이 표현되는 에폭시 화합물의 혼합물(하기 화학식 2에 있어서, n=0 : n=1 : n=2 : n=3 : n=4 = 17 : 10 : 35 : 20 : 18의 중량비로 섞인 것) 90중량%, 및A mixture of epoxy compounds represented by the following general formula (2) (in the general formula (2) shown below) at a weight ratio of n = 0: n = 1: n = 2: n = 3 = n = 4 = 17:10:35:20:18 90% by weight), and
[화학식 2](2)
하기 화학식 3와 같이 표현되는 에폭시 화합물(하기 화학식 3에 있어서, n=4인 것)과 아크릴산을 1:1 중량비로 반응시켜 얻어진 불포화 폴리에스터 10중량%10% by weight of an unsaturated polyester obtained by reacting an epoxy compound represented by the following formula (3) (n = 4 in the following formula (3)) and acrylic acid in a weight ratio of 1:
[화학식 3](3)
를 혼합하고 물에 분산시켜 사이징제 조성물을 제조하였다.Were mixed and dispersed in water to prepare a sizing agent composition.
상기 사이징제 조성물에 기제조된 탄소섬유를 함침시킨 것과 매트릭스 수지로서 에폭시 수지를 사용하여, 복합 재료를 수득하였다.
A composite material was obtained by impregnating the carbon fiber prepared earlier with the sizing composition and using an epoxy resin as a matrix resin.
실시예Example 2 2
실시예 1에서, 매트릭스 수지로 비닐 에스터를 사용한 것을 제외하고는, 모두 동일하게 하여 복합 재료를 수득하였다.
A composite material was obtained in the same manner as in Example 1, except that a vinyl ester was used as the matrix resin.
실시예Example 3 3
실시예 1에서, 매트릭스 수지로 폴리에스터를 사용한 것을 제외하고는, 모두 동일하게 하여 복합 재료를 수득하였다.
A composite material was obtained in the same manner as in Example 1, except that polyester was used as the matrix resin.
실시예Example 4 4
실시예 1에서, 불포화 폴리에스터 5중량%를 사용한 것을 제외하고는, 모두 동일하게 하여 복합 재료를 수득하였다.
A composite material was obtained in the same manner as in Example 1, except that 5 wt% of an unsaturated polyester was used.
실시예Example 5 5
실시예 1에서, 불포화 폴리에스터 15중량%를 사용한 것을 제외하고는, 모두 동일하게 하여 복합 재료를 수득하였다.
A composite material was obtained in the same manner as in Example 1, except that 15 wt% of the unsaturated polyester was used.
실시예Example 6 6
실시예 1에서, 불포화 폴리에스터 20중량%를 사용한 것을 제외하고는, 모두 동일하게 하여 복합 재료를 수득하였다.
A composite material was obtained in the same manner as in Example 1, except that 20 wt% of an unsaturated polyester was used.
실시예Example 7 7
실시예 1에서, 불포화 폴리에스터 25중량%를 사용한 것을 제외하고는, 모두 동일하게 하여 복합 재료를 수득하였다.
A composite material was obtained in the same manner as in Example 1, except that 25 wt% of an unsaturated polyester was used.
실시예Example 8 8
실시예 1에서, 불포화 폴리에스터 30중량%를 사용한 것을 제외하고는, 모두 동일하게 하여 복합 재료를 수득하였다.
A composite material was obtained in the same manner as in Example 1, except that 30 wt% of an unsaturated polyester was used.
비교예Comparative Example 1 One
실시예 1에서, 사이징제에 불포화 폴리에스터가 포함되지 않는 점을 제외하고는 모두 동일하게 하여 복합 재료를 수득하였다.
In Example 1, a composite material was obtained in the same manner except that unsaturated polyester was not included in the sizing agent.
비교예Comparative Example 2 2
실시예 2에서, 사이징제에 불포화 폴리에스터가 포함되지 않는 점을 제외하고는 모두 동일하게 하여 복합 재료를 수득하였다.
In Example 2, a composite material was obtained in the same manner except that the sizing agent did not contain an unsaturated polyester.
비교예Comparative Example 3 3
실시예 3에서, 사이징제에 불포화 폴리에스터가 포함되지 않는 점을 제외하고는 모두 동일하게 하여 복합 재료를 수득하였다.
In Example 3, a composite material was obtained in the same manner except that the sizing agent did not contain an unsaturated polyester.
상기 실시예 1 내지 3, 및 비교예 1 내지 3에 대해서 강도, 충격강도 등의 물성을 측정하였다. 즉, 사이징제에 포함함 된 불포화 폴리에스터 함량 및 매트릭스 수지 변화에 따른 물성 변화를 측정하였다.The properties such as strength and impact strength were measured for Examples 1 to 3 and Comparative Examples 1 to 3. That is, the unsaturated polyester content included in the sizing agent and the change in the physical properties according to the change of the matrix resin were measured.
결과는 하기 표 1 및 도 1과 같았다.The results are shown in Table 1 and FIG.
표 1에서 확인할 수 있듯이, 풀포화 폴리에스터가 포함되는 경우가 매트릭스 수지의 종류에 관계없이 인장강도 및 충격강도에 있어서 보다 유리한 효과를 나타냄을 알 수 있었고,As can be seen from Table 1, it was found that the case where the fully saturated polyester was included had a more favorable effect on the tensile strength and the impact strength regardless of the type of the matrix resin,
도 1에서 확인할 수 있듯이, 충격강도는 약 5중량% 전후 범위에서 가장 좋았고, 인장강도 약 10중량% 범위에서 가장 좋았며, 불포화 폴리에스터가 너무 과량 첨가되는 경우, 오히려, 물성치가 저하되는 경향을 보였는데, 불포화 폴리에스터의 함량의 최적비가 있는 것으로 보인다.
As can be seen from FIG. 1, the impact strength was the best in the range of about 5 wt%, and the tensile strength was the best in the range of about 10 wt%, and when the unsaturated polyester was added in an excessively large amount, It seems that there is an optimum ratio of unsaturated polyester content.
Claims (8)
상기 불포화에스터는 불포화 지방산과 디에폭시다이즈드 하이드로제네이티드 비스페놀 A와 반응시킨 것임을 특징으로 하는 탄소섬유용 사이징제.Epoxy resins, and unsaturated polyesters,
Wherein said unsaturated ester is obtained by reacting unsaturated fatty acid with diepoxy dihydrogen bisphenol A.
[화학식 1]
여기서, R1은 H이고, R2 내지 R8은, 각각 독립적으로, 수소, 메틸기, 또는 페닐기이며, n은 0 내지 5의 정수이다.The sizing agent for carbon fiber according to claim 1, wherein the unsaturated fatty acid is at least one compound represented by the following formula (1).
[Chemical Formula 1]
Here, R 1 is H, R 2 to R 8 are each independently hydrogen, a methyl group, or a phenyl group, and n is an integer of 0 to 5.
[수학식 1]
η(at25℃)/η(at 80℃) ≤ 1ⅹ103 + 100 × 중량%(에폭시 레진)/중량%(불포화 폴리 에스터)The sizing agent for carbon fiber according to claim 1, characterized in that the viscosity at 25 캜 and the viscosity ratio at 80 캜 satisfy the following formula (1).
[Equation 1]
(at 25 ° C) /? (at 80 ° C)? 1 x 10 3 + 100 x% by weight (epoxy resin) /% by weight (unsaturated polyester)
A composite material contained in a matrix resin comprising the carbon fiber of claim 7.
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| EP3519165A4 (en) * | 2016-09-27 | 2019-10-02 | Magna Exteriors Inc. | Optimized sizing for carbon fiber-sheet molding compound |
| CN111005229A (en) * | 2019-12-27 | 2020-04-14 | 鸿羽腾风材料科技有限公司 | Carbon fiber sizing agent and preparation method thereof |
| CN112469860A (en) * | 2018-08-02 | 2021-03-09 | 三洋化成工业株式会社 | Sizing composition for fibers, fiber bundle, fiber product and composite material |
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| KR102193671B1 (en) | 2019-03-19 | 2020-12-21 | 한국과학기술연구원 | Method and apparatus for surface-treating of carbon fiber coated with compound having benzene ring through rapid plasma treatment, and method for improving physical property of carbon fiber thereby and carbon fiber having improved physical property thereby |
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