Effect of Total Acrylic/Fluorinated Acrylic Monomer Contents on the Properties of Waterborne Polyurethane/Acrylic Hybrid Emulsions

이성원,이영희,박현,김한도 한국고분자학회 2013 Macromolecular Research Vol.21 No.6

Stable emulsions of waterborne poly(urethane-urea) (WBPU, soft segment content: 57 wt%, dimethylol propionic acid: 19 mol%/5.8 wt%)/n-butyl acrylate (BA)/glycidyl methacrylate (GMA)/perfluorodecyl acrylate (PFA)(weight ratio of BA/GMA/PFA: 5/3/2) hybrid materials containing 0-30 wt% of acrylate content (fluorinated acrylate content: 0-6 wt%) were successfully prepared by an emulsifier-free/solvent-free prepolymer mixing process. However, the as-polymerized hybrid emulsion containing 40 wt% of acrylic monomer content was found to be unstable, indicating that near 40 wt% in acrylic monomer content was beyond the limit of the self-emulsifying ability. By the curve fitting analysis of IR-peaks and X-ray photoelectron spectroscopy (XPS) analysis, the C-F content was found to increase with the increase in acrylate content. The average particle size of emulsion, young modulus/yield point in stress-strain curve, hardness, thermostability, and water/methylene iodide-contact angles of the film sample increased with increasing acrylate content. However, the viscosity of emulsion, the elongation at break, water swelling and surface energy of film samples were significantly decreased with increasing acrylate content. The tensile strength of film sample decreased a little with increasing acrylate content. These results point to the strong potential of WBPU (70 wt%)/acrylate copolymer (30 wt%) hybrid as a coating material with the lowest surface energy (18.18 mN/m) and the highest contact angles (water: 111.76o, and methylene iodide: 79.95o).

천연유래 멘톨을 함유한 투명 아크릴 감압성 점착제 제조 및 점착특성

백승석(Seung-Suk Beak),홍세흠(Seheum Hong),황석호(Seok-Ho Hwang) 한국고분자학회 2016 폴리머 Vol.40 No.5

본 연구는 2-ethylhexyl acrylate와 2-hydroxyethyl acrylate 기본 조성물에 천연물질인 menthol로부터 합성한 menthyl acrylate(MnA)와 석유화학 기반 isobornyl acrylate(IBOA)의 조성비를 변화시키면서 광중합된 공중합체를 이용하여 자외선 경화형 투명 감압성 점착제를 제조하였다. 시럽의 기본 물성인 고형분 및 분자량 분석뿐만 아니라 제조된 감압성 점착제의 점착특성과 광학특성을 고찰하였다. 모든 아크릴 감압성 점착제는 약 3.5 kgf/25 mm의 180° 박리력과 약 0.25 kgf의 초기점착력을 IBOA와 MnA 조성비에 상관없이 거의 유지하였다. 또한 모든 아크릴 감압성 점착제에서 93% 이상의 광투과도와 1.0% 이하의 haze 값, 그리고 1.0 이하의 색차값을 보여주었다. Transparent acrylic pressure sensitive adhesives (PSAs) were successfully prepared by photopolymerization with 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate as a default constituent and with isobornyl acrylate and biomass-derived menthyl acrylate as a variable constituent. The concentration effect of menthyl acrylate in the acrylic PSAs was investigated on adhesion and the optical properties as well as the characteristics (solid content, and molecular weight) of the syrups were also investigated. Regardless of increasing menthyl acrylate concentration in the acrylic PSAs, the acrylic PSAs exhibited almost the same adhesion performance such as 180° peel strength (~3.5 kgf/25 mm) and probe tack (~0.25 kgf). All acrylic PSA samples also showed high transmittance (more than 93%), low haze (less than 1.0%) and low color-difference (less than 1.0).

아크릴계 점착제의 제조와 가교물성에 대한 모노머의 영향

김판수 ( Pan Soo Kim ),이원기 ( Won-ki Lee ) 한국접착및계면학회 2016 접착 및 계면 Vol.17 No.2

본 연구에서는 아크릴 접착제의 물성에 대한 주 모노머의 영향을 비교하기 위하여 2-ethylhexylacrylate 대신에 butyl acrylate를 사용하여 acrylic acid와 2-hydroxyethyl methacrylate의 공중합체를 합성하고 2종의 경화제를 이용하여 접착 물성을 연구하였다. 선형의 측쇄사슬을 가진 butyl acrylate계 점착제는 가지형태의 측쇄를 가진 2-ethylhexyl acrylate계 접착제에 비해 낮은 접착특성을 보였다. 경화제의 경우 가교점이 많고 가교반응을 통해 유연한 ether나 ester그룹을 생성하는 epoxy형 경화제에서 우수한 물성을 보였고 관능기인 산의 농도가 높을수록 접착특성이 향상되는 것을 관찰하였다. This study was to investigate the effect of main monomer, butyl acrylate instead of 2-ethylhexyl acrylate, of acrylic PSAs on adhesive properties. The copolymers of butyl acrylate, acrylic acid and 2 hydroxyethyl acrylate were synthesized and their adhesive properties were investigated after crosslinking with two different agents. Comparing to 2-hydroxyethyl acrylate-based one which has branch-like side groups, butyl acrylate-based PSA with linear side groups show poor adhesive properties. In case of crosslinking agent, epoxy- typed agent than isocyanate-typed one showed better properties than isocyanate-typed one because epoxy- typed agent has more crosslinking sites and produces more flexible bonds, ester and ether, than isocynate- typed one. Most adhesive properties of PSAs were increased with acid content

Preparation of dual curable acryl/epoxy resin using various acrylic monomer

황태성,임승호,김하은,김정수,김동현 한국공업화학회 2020 한국공업화학회 연구논문 초록집 Vol.2020 No.-

The acryl/epoxy dual curing system is a good way to improve the adhesive strength. In the acryl / epoxy dual curing system, the acrylate polymer chain is formed through the primary UV curing, and the additional curing reaction between the functional group of the acrylate and the epoxy occurs through the secondary thermal curing. The adhesion properties of the dual curable adhesive can be adjusted by the type of acrylic monomer. Butyl acrylate and 2-ethyl hexyl acrylate are used for the enhancement of adhesion. Isobornyl methacrylate and cyclo hexyl acrylate are used to improve heat resistance. Acrylic acid, 2-hydroxy ethyl acrylate, and hydroxyl propyl acrylate are used for the thermal curing with epoxy. The UV and thermal curing behaviors of the dual curable adhesives were investigated using photo-differential scanning calorimetry, fourier transform infrared spectrophotometer, and the determination of the gel fraction, pendulum hardness and adhesion strength.

미립자공학,유동층,고분자,재료 : 무기, 유기 ; 금속코팅용 광경화 코팅필름의 물성에 대한 아크릴산(Acrylic acid)의 영향

서종철 ( Jong Chul Seo ),최준석 ( Jun Suk Choi ),장츼성 ( Eui Sung Jang ),서광원 ( Kwang Won Seo ),한학수 ( Ha Ksoo Han ) 한국화학공학회 2011 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.49 No.1

본 연구에서는 스테인레스 스틸(stainless steel)의 표면 코팅용 광경화 필름 개발을 위하여 isophorone diisocyanate (IPDI), polycaprolactone triol(PCLT), 2-hydroxyethyl acrylate(HEA), 그리고, 희석제로서 trimethylolpropane triacrylate (TMPTA)와 acrylic acid(AA)의 첨가비율을 달리한 광경화형 poly(urethane acrylate-co-acrylic acid)(PU-co-AA) 필름을 성공적으로 제조하였으며, 제조한 PU-co-AA 필름의 모폴로지, 접착특성, 기계적 특성, 전기적 특성 등에 대한 AA 첨 가량의 영향을 조사하였다. 모든 PU-co-AA 필름은 비정형 구조를 나타내었으나, AA의 함량이 증가할수록 분자 규칙 및 패킹밀도는 감소하였다. 접착특성은 AA 함량 50% 이상에서는 접착력 5B 수준으로 스테인레스 스틸에 대한 우수 한 접착특성을 나타내었으며, AA 함유량이 0%에서 66%까지 증가함에 따라 Pull-off strength법 접착력은 6~31 kgf/cm2로 선형적으로 증가하였다. 광경화 폴리우레탄 아크릴레이트의 접착력을 증가시키기 위한 유연한 사슬구조와 2관능기를 가진 AA의 도입은 다관능기의 TMPTA의 높은 가교밀도를 줄임으로써 효과적인 것을 확인할 수 있었으며, AA 함량 이 증가함에 따라 접촉각의 감소와 젖음성의 향상을 확인하였다. 한편, 유연한 사슬 및 곁사슬 -COOH를 가진 AA의 도입은 규칙성 및 패킹밀도의 감소를 나타내며, 이는 PU-co-AA 필름의 경도 저하를 나타내며, 또한 AA의 분자 내의 작용기 -COOH는 고분자 필름 내의 분극현상을 증가시킴으로써 유전상수의 증가 경향을 나타내었다. 결론적으로 PUco- AA 필름의 물리적 특성은 첨가한 AA의 함량에 크게 의존함을 확인할 수 있었다. 또한, 광경화 폴리우레탄 아크릴 레이트에 아크릴산 AA의 도입은 사슬의 유연성 증가와 가교밀도의 감소 영향으로 스테인레스 스틸과의 접착력을 향상시키는데 매우 효과적인 방법임을 확인할 수 있었다. Five different composition UV-cured poly(urethane acrylate-co-acrylic acid) (PU-co-AA) films have been prepared by reacting isophorone diisocyanate(IPDI), polycaprolactone triol(PCLT), 2-hydroxyethyl acrylate(HEA), and different weight ratio trimethylolpropane triacrylate(TMPTA) and acrylic acid(AA) as diluents, and characterized using a Fourier transform infrared spectroscopy(FT-IR). The adhesion properties onto the stainless steel, morphology, mechanical hardness, and electrical property of UV-cured PU-co-AA films were investigated as a function of acrylic acid(AA) content. All the PU-co-AA films are structure-less and the molecular ordering and packing density decreased with increasing content of AA due to the flexible structure and -COOH side chains in AA. The crosscut test showed that PUco-AA films without AA and with low content of AA showed 0% adhesion(OB) and the adhesion of PU-co-AA films in the range of 4()""`50"10 AA increased dramatically as the content of AA increases. The pull-off measurements showed that the adhesion force of PU-co-AA films to stainless steel substrate varied from 6 to 31 kg/cm2 and increased linearly with increasing AA content. The mechanical hardness also decreased as the content of AA increases. This may come from relatively linear and flexible structure in AA and low crystallinity in PU-co-AA films with higher content of AA. The higher AA-containing PU-co-AA films showed higher dielectric constant due to the increase of polarization by intra-ducing AA monomer. In conclusion, the physical properties of UV-cured PU-co-AA films are strongly dependent upon the content of AA and the incorporation of AA in polyurethane acrylate is very useful way to increase the adhesion strength of UV-curable polymers on the stainless steel substrate.

수분산 폴리우레탄 아크릴 접착제의 합성 및 물성 연구

이승환 ( Seung Hwan Lee ),천정미 ( Jung Mi Cheon ),정부영 ( Boo Young Jeong ),김한도 ( Han Do Kim ),천제환 ( Jae Hwan Chun ) 한국접착및계면학회 2015 접착 및 계면 Vol.16 No.4

본 연구에서는 수분산 폴리우레탄 아크릴레이트의 접착력 및 물성을 향상시키기 위하여 polyester polyol, 4,4-dicyclohexylmethane diisocyanate (H12MDI), dimethylol propionic acid (DMPA), acrylate monomer를 사용하여 수분산 폴리우레탄 아크릴레이트를 합성하였다. 또한 합성된 수분산 폴리우레탄 아크릴레이트의 물성은 FT-IR, 입도분석, UTM, 접착력 등을 평가하였다. 입도 분석에서 아크릴산의 함량이 증가함에 따라 입자의 크기가 증가하였고, 기계적 물성을 평가한 결과, 아크릴산의 함량이 증가함에 따라 인장강도는 증가하였고 신율은 감소하였다. 접착강도는 PU/acryl 비율 중 acryl의 함량이 증가, 아크릴산의 함량이 증가할수록 증가하였다. 아크릴산의 함량이 0.5 wt%일 때가장 높은 접착강도를 나타내었다. In this study, waterborne polyurethane acrylate were synthesized with polyester polyol, 4,4-dicyclohexylmethane diisocyanate (H12MDI), dimethylol propionic acid (DMPA), acrylate monomer to improve the properties and peel strength. In addition, the properties of the synthesized waterborne polyurethane acylate was evaluated through FT-IR, particle size analysis, UTM, peel strength. As the acrylic acid content increased, particle size increased. In the results of mechanical properties, when the acrylic acid contents increased, tensile strength was increased but elongation was decreased. All peel strength was improved as the acrylic acid contents of WPUA and acrylate ratio of PU/acrylate increased. Optimum peel strength obtained when acrylic acid was 0.5 wt%.

Poly(2-trialkylstannylthioethyl acrylate) 필름의 표면 활성화를 통한 발색단 도입

도정윤(Jung Yun Do),윤종철(Jong Chul Yun) 한국고분자학회 2012 폴리머 Vol.36 No.6

소수성 고분자 표면을 화학적 처리를 통해 활성화시키고 화학반응을 통해 발색단을 도입하는 연구를 진행하 였다. 2-Triphenylstannylthioethyl acrylate를 자외선 조사시켜 고분자 필름을 만들었다. 필름 표면에 노출된 주석치환 체를 불소이온으로 처리하여 SH를 형성함으로써 필름표면에 많은 SH를 생성시켰고 적외석 흡수스펙트럼으로 이를 확 인하였다. 아크릴 유도체로 만든 발색단 물질을 노출된 SH와 반응시켜 필름 표면에 여러 발색단을 도입할 수 있었고 이를 자외선-가시광선 흡수스펙트럼으로 관찰할 수 있었다. 2-Triphenylstannylthioethyl acrylate와 tris(hydroxymethyl) ethane에서 유도된 triacrylate를 혼합하여 얻은 광경화 필름에서 단분자 함량 변화에 따른 SH의 표면 노출량을 변화 시킬 수 있음을 흡수스펙트럼을 통해 관찰하였다. 유사하게, 2-tributylstannylthioethyl acrylate를 이용한 광경화 필름 을 만들어 표면반응 연구를 진행하였다. 이 경우, 불소이온 처리를 통한 표면 활성화는 약 5분 이내로 빠르게 진행 되었다. 이소시안 작용기를 갖는 발색단을 합성하여 필름과 반응시켜 표면에 발색단 도입하는 비교연구를 진행하였 다. 아크릴 유도체가 표면 SH와 반응이 24시간 이상을 요구하는 반면 이소시안 유도체는 10분 이내에 결합반응이 완료되었다. Surface modification of a hydrophobic acrylic polymer film has been performed through simple chemical treatment to give a reactive surface. 2-Triphenylstannylthioethyl acrylate was polymerized under UV-illumination with various contents of a comonomer. When the polymer film was treated with fluoride ion, thiol functional group (SH) was generated on the film surface, which was observed through infrared absorption spectroscopy. The surface was functionalized by thiol addition reaction to acrylic chromophores. The SH content on the surface was controlled with a comonomer, tris(hydroxymethyl)ethane triacrylate, and examined with UV-Vis absorbance of the chromophore attached film. Similarly, a polymer film from 2-tributylstannylthioethyl acrylate was prepared. Destannylation from the triphenylstannyl and tributylstannyl surface completed after 30 and 5 min, respectively. The SH-exposed surface was modified with an isocyanate attached chromophore within 10 min, while acrylic chromophore required 24 h.

Uv-Curable Urethane Acrylate/Silica Hybrid Coating: Introducing Modified Silane Using Urethane Reaction

신은진,강상호,정일두 한국공업화학회 2017 한국공업화학회 연구논문 초록집 Vol.2017 No.1

Although multifunctional acrylate/silica hybrid materials have been widely studied as hard coating for high hardness of materials in many fields, the formation of crack on bending of UV-cured film has restricted to be used as hard coating materials. In this work, long-chain silane1 was synthesized by the reaction of equimolar amount of isophorone diisocyanate (IPDI) with 2-hydroxyethyl acrylate (HEA) and (3-mercaptopropyl) trimethoxy silane, then it was hydrolyzed and condensed to be introduced onto the surface of a silica particle which was also synthesized by Stober method. The silica and long-chain silane were formulated to make the optimum ratio and finally blended with urethane acrylate, dipentaerythritol penta-/hexa-acrylate and dilute acrylate. They were coated on the glass or PMMA by spin-coating followed by UV-cured. Finally, it was characterized by Fourier transform infrared spectroscopy, pencil hardness, impact strength, transmittance, yellowing resistance, and contact angle.

2P-537 Synthesis and evaluation of hybrid zinc/silyl acrylate SPC resins

박라희,박현 한국공업화학회 2017 한국공업화학회 연구논문 초록집 Vol.2017 No.1

Alkylsilyl (meth)acrylate-based polymers which are used in the development of environmentally friendly antifouling paints, can give the coatings self-smoothing properties. However, it has a low erosion rate in a static environment and perform poorly against diatoms which are major component of primary colonizers. In this study, we compared two different types of silyl acrylate, and then synthesized SPC resins using silyl acrylate with better performance. When we synthesized SPC resins, we used Zn/Si-acrylate copolymers composed of different ratios to improve the disadvantages of silyl acrylate. The SPC structures of the synthesized polymers were confirmed using FT-IR spectroscopy. Also, we investigated basic properties which are NV(Nonvolatile Content), viscosity, and hardness and self-polishing ability of the developed resins. ^**This work was supported by the National Research Foundation of Korea(NFR) grant funded by the Korea government(MSIP) through GCRC-SOP (No. 2011-0030013)

아크릴 변성 부틸아크릴레이트 올리고머가 광경화 수지 물성에 미치는 영향

리종위,김광언,배진영 한국고분자학회 2022 폴리머 Vol.46 No.5

The purpose of this study is to investigate acrylic oligomer with excellent flexibility which can be used as aphotocurable crosslinking agent. In this study, the acrylate oligomer with the epoxy group was synthesized by free radicalpolymerization of butyl acrylate (BA) and glycidyl methacrylate (GMA) as reactants. Also, the acryl-modified oligomerwith hydroxyl group was synthesized by the reaction of acrylic acid with the epoxy-containing oligomer. Various acrylmodified acrylate oligomers were prepared by changing the concentration of GMA and employing different acrylatemonomers such as hexyl acrylate and octyl acrylate with different chain lengths. Photo-cured films were prepared fromthe synthesized acryl-modified oligomers, reactive diluents, and photoinitiator. And the corresponding curing degree, thermal properties and mechanical properties of the cured film were investigated.