KR100275898B1 - Matrix using hybrid system of epoxy/vinyl ester resin - Google Patents
Matrix using hybrid system of epoxy/vinyl ester resin Download PDFInfo
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- KR100275898B1 KR100275898B1 KR1019980024810A KR19980024810A KR100275898B1 KR 100275898 B1 KR100275898 B1 KR 100275898B1 KR 1019980024810 A KR1019980024810 A KR 1019980024810A KR 19980024810 A KR19980024810 A KR 19980024810A KR 100275898 B1 KR100275898 B1 KR 100275898B1
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- vinyl ester
- epoxy
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- 229920001567 vinyl ester resin Polymers 0.000 title claims abstract description 41
- 239000011159 matrix material Substances 0.000 title claims abstract description 36
- 229920005989 resin Polymers 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 title claims abstract description 21
- 239000004593 Epoxy Substances 0.000 title description 26
- 239000003822 epoxy resin Substances 0.000 claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000002787 reinforcement Effects 0.000 claims description 5
- 238000011417 postcuring Methods 0.000 claims description 3
- 239000012779 reinforcing material Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 5
- 229920006241 epoxy vinyl ester resin Polymers 0.000 abstract description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 12
- 229930185605 Bisphenol Natural products 0.000 description 9
- 238000009396 hybridization Methods 0.000 description 8
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 5
- 239000003733 fiber-reinforced composite Substances 0.000 description 4
- 229920006305 unsaturated polyester Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
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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
-
- 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
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
본 발명은 에폭시 수지 80 내지 90중량%와 비닐 에스테르 수지 10 내지 20중량%를 하이브리드시킨 조성물을 포함하는 매트릭스 및 그의 제조방법을 제공한다. 본 발명에 따른 매트릭스는 기존의 열경화성 수지인 에폭시 수지와 비닐 에스테르 수지를 특정 혼합비로 하이브리드시킴으로써 열적, 기계적 및 내화학적 성질은 물론 속경화성과 작업용이성이 우수하다.The present invention provides a matrix comprising a composition obtained by hybridizing 80 to 90% by weight of an epoxy resin and 10 to 20% by weight of a vinyl ester resin, and a method of preparing the same. The matrix according to the present invention is excellent in thermal hardening and workability as well as thermal, mechanical and chemical resistance by hybridizing the existing thermosetting resin epoxy resin and vinyl ester resin in a specific mixing ratio.
Description
본 발명은 에폭시/비닐 에스테르 수지의 하이브리드 시스템을 이용한 매트릭스에 관한 것이다. 더욱 상세하게는, 기존의 열경화성 수지인 에폭시와 비닐 에스테르를 하이브리드시켜 물성을 향상시킨 새로운 매트릭스에 관한 것이다.The present invention relates to a matrix using a hybrid system of epoxy / vinyl ester resins. More specifically, the present invention relates to a new matrix in which physical properties are improved by hybridizing epoxy and vinyl ester, which are existing thermosetting resins.
에폭시 수지는 열적, 기계적 및 내화학적 성질이 우수하여 코팅재료, 전기절연재료, 복합재료의 매트릭스, 토목ㆍ건축재료 등에 널리 사용되고 있다.Epoxy resins are widely used in coating materials, electrical insulating materials, matrix of composite materials, civil engineering and building materials because of their excellent thermal, mechanical and chemical resistance properties.
비닐 에스테르 수지는 에폭시 수지가 갖는 우수한 열적, 기계적 및 내화학적 성질 이외에 불포화 폴리에스테르의 속경화성과 작업 용이성을 함께 갖추고 있어 이미 오래전부터 여러 분야에서 사용되어 왔다. 특히 내식성과 내화학성을 필요로 하는 분야에서 섬유강화 복합재료의 매트릭스로 많이 사용되고 있는 수지이다.In addition to the excellent thermal, mechanical and chemical properties of epoxy resins, vinyl ester resins have been used in various fields for a long time since they have fast curing properties and ease of operation of unsaturated polyesters. In particular, the resin is widely used as a matrix of fiber reinforced composite materials in fields requiring corrosion resistance and chemical resistance.
근래에는 매트릭스에 대한 새로운 성능들이 요구되고 있으며, 이러한 요구에 맞는 매트릭스의 개발이 절실히 필요하게 되었다. 새로운 매트릭스 개발 방법으로는 매트릭스 자체를 개발하는 방법과 기존의 매트릭스들을 선정하여 이들을 하이브리드시킴으로써 개개의 매트릭스가 갖는 장점을 살리고 단점을 보완시켜 향상된 물성을 지니는 매트릭스를 만드는 방법이 있다. 전자의 경우, 많은 연구시간과 연구비용을 필요로 하므로 후자에 관심이 모아지고 있는추세이다.In recent years, new capabilities for matrices are required, and the development of matrices that meet these needs is urgently needed. New matrix development methods include the development of the matrix itself and the selection of existing matrices and hybridization of them to take advantage of the advantages of individual matrices and to compensate for the disadvantages to create matrices with improved physical properties. In the former case, a lot of research time and research costs are required, and the latter is attracting attention.
본 발명은 기존의 열경화성 수지인 에폭시 수지와 비닐 에스테르 수지를 특정 혼합비로 하이브리드시켜 우수한 열적, 기계적 및 내화학적 성질은 물론 속경화성과 작업용이성이 우수한 복합재료용 매트릭스를 제조하는 것을 목적으로 한다.An object of the present invention is to hybridize an epoxy resin and a vinyl ester resin, which is a conventional thermosetting resin, in a specific mixing ratio, and to prepare a matrix for a composite material having excellent thermal, mechanical and chemical resistance properties as well as fast curing and workability.
도 1은 에폭시/비닐 에스테르 수지의 하이브리드 시스템에서 비닐 에스테르의 함량에 따른 굴곡강도 및 굴곡탄성률을 나타낸 도면이다.1 is a view showing the flexural strength and flexural modulus according to the content of the vinyl ester in the hybrid system of epoxy / vinyl ester resin.
도 2는 에폭시/비닐 에스테르 수지의 하이브리드 시스템에서 비닐 에스테르의 함량에 따른 인장강도를 나타낸 도면이다.2 is a view showing the tensile strength according to the content of the vinyl ester in the hybrid system of epoxy / vinyl ester resin.
도 3은 에폭시/비닐 에스테르 수지의 하이브리드 시스템에서 비닐 에스테르의 함량에 따른 충격강도를 나타낸 도면이다.3 is a view showing the impact strength according to the content of the vinyl ester in the hybrid system of epoxy / vinyl ester resin.
종래에는 에폭시 수지의 기계적 특성을 향상시키기 위해서 에폭시 수지에 충전제, 첨가제 및 열가소성 수지 등을 첨가하였다. 그러나, 종래의 경우 에폭시 수지에 대한 모노머의 선정이 용이하지 않고 첨가제에 의한 부반응이 일어날 수 있어 가공성 등에 악영향을 미칠 수 있는 단점이 있다.Conventionally, fillers, additives, thermoplastic resins, and the like have been added to epoxy resins in order to improve the mechanical properties of the epoxy resins. However, in the conventional case, it is not easy to select a monomer for the epoxy resin and side reactions may occur due to additives, which may adversely affect workability.
본 발명자들은 이러한 단점을 해결하고자 연구를 거듭한 결과, 에폭시 비닐 에스테르를 특정 비율로 하이브리드시킴으로써 기계적 특성은 물론 속경화성 및 작업용이성을 향상시켜 작업공정을 단순화시키고 작업시간을 크게 단축시킨다는 사실을 발견하고 본 발명을 완성하기에 이르렀다.The present inventors have conducted research to solve these shortcomings, and found that hybridization of epoxy vinyl esters at a specific ratio improves mechanical properties as well as fast curing and ease of use, which simplifies the work process and greatly shortens the working time. The present invention has been completed.
또한, 본 발명에 따라 에폭시에 값싼 비닐에스테르를 첨가함으로써 매트릭스의 비용을 크게 절감할 수 있는 장점이 있다.In addition, according to the present invention by adding a cheap vinyl ester to the epoxy there is an advantage that can significantly reduce the cost of the matrix.
본 발명에 따라 에폭시에 비닐에스테르를 하이브리드시키면 열경화나 상온경화에 의해 매트릭스를 제조할 수 있는 장점이 있다.Hybridization of vinyl esters to epoxy according to the present invention has the advantage that the matrix can be prepared by thermosetting or room temperature curing.
본 발명은 에폭시 수지 80 내지 90중량%와 비닐 에스테르 수지 10 내지 20중량%를 하이브리드시킨 조성물을 포함하는 매트릭스를 제공한다.The present invention provides a matrix comprising a composition of 80 to 90% by weight epoxy resin and 10 to 20% by weight vinyl ester resin.
도1, 2 및 3에서 나타낸 바와같이, 비닐에스테르의 함량이 20중량%를 초과하면 굴곡강도, 굴곡탄성률, 인장강도 및 충격강도가 급격히 떨어지고, 또한 비닐에스테르의 함량이 10중량% 미만인 경우는 상기 물성치가 약간 떨어진다.1, 2 and 3, when the content of the vinyl ester exceeds 20% by weight, the flexural strength, the flexural modulus, the tensile strength and the impact strength are sharply dropped, and when the content of the vinyl ester is less than 10% by weight, The physical properties drop slightly.
본 발명은 또한 에폭시 수지 80 내지 90중량%와 비닐 에스테르 수지 10 내지 20중량%를 하이브리드시킨 조성물을 로울러에 의해 섬유강화재에 도포시켜 복합재료를 제조하는 방법을 제공한다.The present invention also provides a method for producing a composite material by applying a composition obtained by hybridizing 80 to 90% by weight of an epoxy resin and 10 to 20% by weight of a vinyl ester resin to a fiber reinforcement by a roller.
본 발명에 따른 복합재료는 바인더(binder)로서의 역할을 하기 위해서 섬유강화재에 본 발명에 따른 조성물을 도포시켜 만들 수 있다. 섬유강화재로는 유리섬유를 사용하는 것이 바람직하다.The composite material according to the present invention can be made by applying the composition according to the present invention to a fiber reinforcement in order to act as a binder. It is preferable to use glass fiber as a fiber reinforcing material.
본 발명에 따른 복합재료는 에폭시 수지 80 내지 90중량%와 비닐 에스테르 수지 10 내지 20중량%를 하이브리드시킨 조성물을 로울러에 의해 섬유강화재에 도포시킴으로써 제조된다. 매트릭스 조성물은 100℃~150℃에서 1 내지 2시간 동안 후경화처리시켜 물성을 증가시킨다.The composite material according to the present invention is prepared by applying a composition obtained by hybridizing 80 to 90% by weight of an epoxy resin and 10 to 20% by weight of a vinyl ester resin to a fiber reinforcement by a roller. The matrix composition is post-cured at 100 ° C. to 150 ° C. for 1 to 2 hours to increase physical properties.
후경화 시스템은 경화과정을 거친 경화물의 물성을 증가시키기 위해 실시되는 방법중 하나이다. 인위적으로 열에너지를 가해줌으로써 경화물 내부에 존재하는 용제나 기타 불순물을 제거하고, 소량으로 존재할 수 있는 미반응물에 에너지를 가하여 반응하도록 하여 물성을 증가시키는 것이 목적이다.Post-cure system is one of the methods carried out to increase the properties of the cured cured product. The purpose is to increase the physical properties by removing the solvent or other impurities present in the cured product by artificially applying thermal energy and adding energy to the unreacted material that may be present in a small amount.
이하, 실시예에서 본 발명을 더욱 상세히 설명하지만, 본 실시예가 본 발명의 범위를 한정하는 것은 아니다.Hereinafter, although an Example demonstrates this invention in more detail, this Example does not limit the scope of the present invention.
[실시예 1]Example 1
저점도를 갖는 C12-C14변성타입의 비스페놀-A의 디글리시딜에테르(Diglycidyl Ether of Bisphenol-A, "DGEBA")계 에폭시 "YD-114"[국도화학(주) 제품]에 저점도이며 삼액형으로 제조된 비스페놀계 비닐에스테르 "SR-825L"[세원화성(주) 제품]을 0, 10, 20, 30, 100중량%로 첨가하여 하이브리드시켜 매트릭스 조성물을 제조하였다.Low viscosity C 12 -C 14 -A-modified bisphenol type diglycidyl ether of (Diglycidyl Ether of Bisphenol-A, "DGEBA") based epoxy "YD-114" [Kukdo Chemical Co., Ltd. product; a trough having a The bisphenol-based vinyl ester "SR-825L" (manufactured by Sewon Chemical Co., Ltd.), which was prepared in a three-component form, was added at 0, 10, 20, 30, and 100% by weight to prepare a matrix composition.
이때 사용된 아민계 에폭시 경화제 트리에틸렌테트라민(TETA), 비닐 에스테르 개시제 메틸에틸케톤퍼옥시드(MEKP) 및 비닐 에스테르 촉진제 코발트-옥토에이트(Co-Oct)의 함량은 각각 12phr, 1phr, 0.5phr로 고정하였다. 제조된 비닐 에스테르 함량 변화에 따른 매트릭스 조성물의 변형속도(cross-head speed)를 2mm/분으로 고정하고, 지지대 사이의 거리와 시편 두께의 비율을 16:1로 고정한 후, 만능 시험기(Instron #1125)를 사용하여 굴곡강도 및 굴곡탄성률을 측정하였다. 그 결과, 도 1에서 나타낸 바와같이 비닐 에스테르가 각각 10중량% 및 20중량% 첨가된 경우, 에폭시 자체보다 굴곡강도가 약 1% 및 2% 증가하였으며, 굴곡탄성률의 경우 거의 같은 수준을 나타냈다.The content of the amine epoxy curing agent triethylenetetramine (TETA), vinyl ester initiator methylethyl ketone peroxide (MEKP) and vinyl ester promoter cobalt-octoate (Co-Oct) used was 12 phr, 1 phr, 0.5 phr, respectively. Fixed. After fixing the cross-head speed of the matrix composition according to the produced vinyl ester content change at 2 mm / min, and fixing the ratio of the distance between the supports and the specimen thickness at 16: 1, the universal tester (Instron # 1125 ) Was used to measure flexural strength and flexural modulus. As a result, as shown in Figure 1, when the vinyl ester is added 10% by weight and 20% by weight, respectively, the flexural strength was increased by about 1% and 2% than the epoxy itself, the flexural modulus was almost the same level.
[실시예 2]Example 2
중점도를 갖는 DGEBA계 에폭시 "YD-128"[국도화학(주) 제품]에 저점도이며 삼액형으로 제조된 비스페놀계 비닐에스테르 "SR-825L"[세원화성(주) 제품]을 상기 실시예 1과 같이 하이브리드시켜 매트릭스 조성물을 제조하였다. 변형속도를 5mm/분으로 고정하고, 만능 시험기를 사용하여 인장강도를 측정한 결과 비닐 에스테르가 각각 10중량% 및 20중량% 첨가된 경우, 도 2에서 나타낸 바와같이 에폭시 자체보다 인장강도가 약 4% 및 9% 증가하였다.The bisphenol-based vinyl ester "SR-825L" [Sewon Hwasung Co., Ltd.] produced in a three-pack type with low viscosity in DGEBA epoxy "YD-128" [product of Kukdo Chemical Co., Ltd.] having a medium viscosity is obtained in the above examples. Hybrid as in 1 to prepare a matrix composition. When the strain rate was fixed at 5 mm / min and the tensile strength was measured using a universal testing machine, when the vinyl ester was added 10 wt% and 20 wt%, respectively, as shown in FIG. % And 9% increase.
[실시예 3]Example 3
고점도를 갖는 반고형 타입의 DGEBA계 에폭시 "YD-134"[국도화학(주) 제품]에 저점도이며 삼액형으로 제조된 비스페놀계 비닐에스테르 "SR-825L"[세원화성(주) 제품]을 상기 실시예 1과 같이 하이브리드시켜 매트릭스 조성물을 제조하였다. 플라스틱 충격 시험기를 사용하여 충격강도를 측정하였다. 그 결과, 도 3에서 나타낸 바와같이 역시 비닐 에스테르가 각각 10중량% 및 20중량% 첨가된 경우, 에폭시 자체보다 충격강도가 약 2% 및 3% 증가하였다.Semi-solid type DGEBA epoxy "YD-134" [Kukdo Chemical Co., Ltd.] with high viscosity and low viscosity and three-component bisphenol vinyl ester "SR-825L" manufactured by Sewon Chemical Co., Ltd. Hybridization was carried out as in Example 1 to prepare a matrix composition. Impact strength was measured using a plastic impact tester. As a result, as shown in Figure 3 also when the vinyl ester is added 10% by weight and 20% by weight, respectively, the impact strength was increased by about 2% and 3% than the epoxy itself.
[실시예 4]Example 4
저점도를 갖는 C12-C14변성타입의 DGEBA계 에폭시 "YD-114"[국도화학(주) 제품]에 저점도이며 삼액형으로 제조된 비스페놀계 비닐에스테르 "SR-825L"[세원화성(주) 제품]을 상기 실시예 1과 같이 하이브리드시켜 매트릭스 조성물을 제조한 후, 섬유강화재로 쓰인 네덜란드의 Parabeam B.V.사가 제조한 삼차원 유리직물에 자체 제작한 알루미늄 로울러를 사용하여 도포시켜 시편을 제조하였다. 제조된 매트릭스 변화에 따른 섬유강화 복합재료의 변형속도를 5mm/분으로 고정하고, 만능 시험기를 사용하여 압축강도를 측정한 결과, 매트릭스에 불포화 폴리에스테르가 각각 10중량% 및 20중량% 첨가된 수지를 사용한 경우, 에폭시 자체를 매트릭스로 사용한 경우의 압축강도에 비해 약 1% 및 2%의 증가를 나타냈다.Low viscosity of the C 12 -C 14 DGEBA-type epoxy-modified type "YD-114" [Kukdo Chemical Co., Ltd. product; having a low viscosity is a three-part bisphenol-based vinyl ester "SR-825L" [prepared by the three won Mars ( Note) product] was prepared by hybridization as in Example 1, and then coated on a three-dimensional glass fabric manufactured by Parabeam BV of the Netherlands used as a fiber reinforcement using a self-made aluminum roller to prepare a specimen. The deformation rate of the fiber-reinforced composite material according to the prepared matrix was fixed at 5 mm / min and the compressive strength was measured using a universal testing machine. As a result, resins containing 10% by weight and 20% by weight of unsaturated polyester were added to the matrix. When used, it showed about 1% and 2% increase compared to the compressive strength when epoxy itself was used as a matrix.
[실시예 5]Example 5
중점도를 갖는 DGEBA계 에폭시 "YD-114"[국도화학(주) 제품]에 저점도이며 삼액형으로 제조된 비스페놀계 비닐에스테르 "SR-825L"[세원화성(주) 제품]을 상기 실시예 2와 같이 하이브리드시켜 상기 실시예 4와 같이 시편을 제조하였다. 제조된 매트릭스 변화에 따른 섬유강화 복합재료의 변형속도를 5mm/분으로 고정하고, 만능 시험기를 사용하여 압축강도를 측정한 결과, 매트릭스에 불포화 폴리에스테르가 각각 10중량% 및 20중량% 첨가된 수지를 사용한 경우, 에폭시 자체를 매트릭스로 사용한 경우의 압축강도에 비해 약 2% 및 3%의 증가를 나타냈다.The bisphenol-based vinyl ester "SR-825L" [Sewon Hwaseong Co., Ltd.] produced in a three-pack type with low viscosity in DGEBA epoxy "YD-114" [product of Kukdo Chemical Co., Ltd.] having a medium viscosity is obtained in the above examples. Hybrid as in 2 to prepare a specimen as in Example 4. The deformation rate of the fiber-reinforced composite material according to the prepared matrix was fixed at 5 mm / min and the compressive strength was measured using a universal testing machine. As a result, resins containing 10% by weight and 20% by weight of unsaturated polyester were added to the matrix, respectively. In the case of using, the epoxy resin showed an increase of about 2% and 3% compared to the compressive strength when the epoxy itself was used as the matrix.
[실시예 6]Example 6
고점도를 갖는 반고형 타입의 DGEBA계 에폭시 "YD-134"[국도화학(주) 제품]에 저점도이며 삼액형으로 제조된 비스페놀계 비닐에스테르 "SR-825L"[세원화성(주) 제품]을 상기 실시예 3과 같이 하이브리드시켜 상기 실시예 4와 같이 시편을 제조하였다. 제조된 매트릭스 변화에 따른 섬유강화 복합재료의 변형속도를 5mm/분으로 고정하고, 만능 시험기를 사용하여 압축강도를 측정한 결과, 매트릭스에 불포화 폴리에스테르가 각각 10중량% 및 20중량% 첨가된 수지를 사용한 경우, 에폭시 자체를 매트릭스로 사용한 경우의 압축강도에 비해 약 3% 및 4%의 증가를 나타냈다.Semi-solid type DGEBA epoxy "YD-134" [Kukdo Chemical Co., Ltd.] with high viscosity and low viscosity and three-component bisphenol vinyl ester "SR-825L" manufactured by Sewon Chemical Co., Ltd. The specimen was prepared as in Example 4 by hybridization as in Example 3. The deformation rate of the fiber-reinforced composite material according to the prepared matrix was fixed at 5 mm / min and the compressive strength was measured using a universal testing machine. As a result, resins containing 10% by weight and 20% by weight of unsaturated polyester were added to the matrix, respectively. In the case of using, the increase in compressive strength when using the epoxy itself as a matrix was about 3% and 4%.
[실시예 7]Example 7
저점도를 갖는 C12-C14변성타입의 DGEBA계 에폭시 "YD-114"[국도화학(주) 제품]에 저점도이며 삼액형으로 제조된 비스페놀계 비닐에스테르 "SR-825L"[세원화성(주) 제품]을 상기 실시예 1과 같이 하이브리드시켜 매트릭스 조성물을 제조한 후에 100℃에서 1시간 동안 후경화를 실시하였다. 본 발명에서 후경화 후의 매트릭스를 상기 실시예 1과 같이 측정하였다. 그 결과, 도 1에서 나타낸 바와같이 역시 비닐 에스테르가 각각 10중량% 및 20중량% 첨가된 경우 에폭시 자체의 굴곡강도에 비해 약 1% 및 2%의 증가를 보이며, 굴곡탄성률의 경우 에폭시 자체의 값과 유사한 값을 나타냈다.Low viscosity of the C 12 -C 14 DGEBA-type epoxy-modified type "YD-114" [Kukdo Chemical Co., Ltd. product; having a low viscosity is a three-part bisphenol-based vinyl ester "SR-825L" [prepared by the three won Mars ( NOTE) Products were hybridized as in Example 1 to prepare a matrix composition, and then subjected to post-curing at 100 ° C. for 1 hour. In the present invention, the matrix after the post cure was measured in the same manner as in Example 1. As a result, as shown in FIG. 1, when the vinyl ester was added 10 wt% and 20 wt%, respectively, the flexural strength of the epoxy itself was increased by about 1% and 2%, and the flexural modulus was the value of the epoxy itself. Values similar to
[실시예 8]Example 8
중점도를 갖는 DGEBA계 에폭시 "YD-128"[국도화학(주) 제품]에 저점도이며 삼액형으로 제조된 비스페놀계 비닐에스테르 "SR-825L"[세원화성(주) 제품]을 상기 실시예 1과 같이 하이브리드시켜 매트릭스 조성물을 제조한 후에 120℃에서 1시간 30분 동안 후경화를 실시하였다. 후경화 후의 매트릭스를 상기 실시예 2와 같이 측정하였다. 그 결과, 도 2에서 나타낸 바와같이 역시 비닐 에스테르가 각각 10중량% 및 20중량% 첨가될 경우, 에폭시 자체의 인장강도에 비해 약 3% 및 4% 증가하였다.The bisphenol-based vinyl ester "SR-825L" [Sewon Hwasung Co., Ltd.] produced in a three-pack type with low viscosity in DGEBA epoxy "YD-128" [product of Kukdo Chemical Co., Ltd.] having a medium viscosity is obtained in the above examples After the hybridization as described in 1 to prepare a matrix composition was subjected to post-cure at 120 ℃ 1 hour 30 minutes. The matrix after postcure was measured in the same manner as in Example 2. As a result, as shown in FIG. 2, when 10% by weight and 20% by weight of vinyl ester were added, the tensile strength of the epoxy itself increased by about 3% and 4%.
[실시예 9]Example 9
고점도를 갖는 반고형 타입의 DGEBA계 에폭시 "YD-134"[국도화학(주) 제품]에 저점도이며 삼액형으로 제조된 비스페놀계 비닐에스테르 "SR-825L"[세원화성(주) 제품]을 상기 실시예 1과 같이 하이브리드시켜 매트릭스 조성물을 제조한 후에 150℃에서 2시간 동안 후경화를 실시하였다. 경화 후의 매트릭스를 상기 실시예 3과 같이 측정하였다. 그 결과, 도 3에서 나타낸 바와같이 역시 비닐 에스테르가 각각 10중량% 및 20중량% 첨가될 경우, 에폭시 자체의 충격강도에 비해 약 1% 및 2%의 증가하였다.Semi-solid type DGEBA epoxy "YD-134" [Kukdo Chemical Co., Ltd.] with high viscosity and low viscosity and three-component bisphenol vinyl ester "SR-825L" manufactured by Sewon Chemical Co., Ltd. After the hybridization as in Example 1 to prepare a matrix composition was subjected to post-curing at 150 ℃ for 2 hours. The matrix after curing was measured in the same manner as in Example 3. As a result, as shown in Figure 3 also when the vinyl ester is added 10% by weight and 20% by weight, respectively, compared to the impact strength of the epoxy itself by about 1% and 2% increased.
본 발명에 따른 매트릭스는 기존의 열경화성 수지인 에폭시 수지와 비닐 에스테르 수지를 특정 혼합비로 하이브리드시킴으로써 열적, 기계적 및 내화학적 성질은 물론 속경화성과 작업용이성이 우수하다.The matrix according to the present invention is excellent in thermal hardening and workability as well as thermal, mechanical and chemical resistance by hybridizing the existing thermosetting resin epoxy resin and vinyl ester resin in a specific mixing ratio.
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