KR101207124B1 - Inorganic nano particle coating solution containing hydrophilic group-modified acrylic resin, and inorganic nano particle film - Google Patents
Inorganic nano particle coating solution containing hydrophilic group-modified acrylic resin, and inorganic nano particle film Download PDFInfo
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- KR101207124B1 KR101207124B1 KR1020060116829A KR20060116829A KR101207124B1 KR 101207124 B1 KR101207124 B1 KR 101207124B1 KR 1020060116829 A KR1020060116829 A KR 1020060116829A KR 20060116829 A KR20060116829 A KR 20060116829A KR 101207124 B1 KR101207124 B1 KR 101207124B1
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Abstract
본 발명은 유리전이온도가 -85 내지 22 ℃인 아크릴계 단량체 45 내지 95 중량%, 친수성기 도입 단량체 1 내지 30 중량%, 및 유리전이온도가 8 내지 153 ℃인 비닐기 함유 단량체 1 내지 40 중량%로부터 중합된 친수기로 개질된 아크릴계 수지, 이를 포함하는 무기 나노 입자 코팅액, 및 상기 코팅액으로 제조된 무기 나노 입자 필름에 관한 것이다.The present invention is made from 45 to 95% by weight of an acrylic monomer having a glass transition temperature of -85 to 22 ° C, 1 to 30% by weight of a hydrophilic group introducing monomer, and 1 to 40% by weight of a vinyl group containing monomer having a glass transition temperature of 8 to 153 ° C. It relates to an acrylic resin modified with a polymerized hydrophilic group, an inorganic nanoparticle coating solution comprising the same, and an inorganic nanoparticle film prepared from the coating solution.
본 발명의 친수기로 개질된 아크릴계 수지는 무기 나노 입자 필름의 제조시 바인더로 사용되어, 무기 나노 입자의 분산성을 크게 향상시켜 장기간 보관에도 침전되지 않는 무기 나노 입자 코팅액을 제공하며, 적은 함량으로 사용됨에도 필름에서의 무기 나노 입자 간의 접착력을 향상시키고, 습도에 따른 필름의 특성을 균일하게 제어하여, 공정상의 유연성을 증가시키는 효과가 있다. The acrylic resin modified with the hydrophilic group of the present invention is used as a binder in the preparation of the inorganic nanoparticle film, thereby greatly improving the dispersibility of the inorganic nanoparticles to provide an inorganic nanoparticle coating solution which does not precipitate even in long-term storage, and is used in a small amount. It improves the adhesion between the inorganic nanoparticles in the Edo film, and uniformly controls the properties of the film according to humidity, thereby increasing the flexibility in the process.
아크릴계 수지, 친수기, 무기 나노 입자, 필름, 기판, 바인더 Acrylic resin, hydrophilic group, inorganic nanoparticles, film, substrate, binder
Description
도 1은 본 발명의 실시예 및 비교예에서 제조한 무기 나노 입자 코팅액의 분산 안정성 거동을 나타낸 그래프이다. 1 is a graph showing the dispersion stability behavior of the inorganic nanoparticle coating liquid prepared in Examples and Comparative Examples of the present invention.
본 발명은 무기 나노 입자 필름의 제조시 바인더로 사용되는 친수기로 개질된 아크릴계 수지, 이를 포함하여 무기 나노 입자의 분산성이 크게 향상된 무기 나노 입자 코팅액, 및 상기 코팅액으로 제조되어 무기 나노 입자 간의 접착력이 향상되고, 습도에 따른 필름 특성이 균일하게 제어된 무기 나노 입자 필름에 관한 것이다. The present invention is an acrylic resin modified with a hydrophilic group used as a binder in the preparation of the inorganic nanoparticle film, the inorganic nanoparticle coating liquid which greatly improves the dispersibility of the inorganic nanoparticles, and the coating liquid is produced by the adhesion between the inorganic nanoparticles The present invention relates to an inorganic nanoparticle film having improved and uniformly controlled film properties according to humidity.
일반적으로 유/무기 기판 위에 무기 나노 입자 필름을 제조하기 위한 무기 나노 입자 코팅액은 고분자 바인더를 포함하는 유기 용매에 무기 나노 입자를 첨가하고, 기계적인 분쇄방법을 이용하여 제조하여 왔다. 특히, 무기 나노 입자를 코팅하기 위한 바인더로서 종래에는 폴리불화비닐리덴 수지 및 합성 고무를 포함하는 수지 등이 사용되었다. 그러나, 이러한 수지를 사용하는 경우, 코팅액 내에서의 무기 나노 입자의 분산 안정성이 좋지 않으며, 습도에 따라 코팅성이 영향을 많이 받게되는 문제점이 있어, 코팅성을 유지하기 위해서는 무기 나노 입자의 함량 대비하여 고분자 바인더의 함량이 10 중량% 이상으로 첨가되어야만 했다. 이와 같이, 고분자 바인더의 함량이 증가되면 필름 내의 무기 나노 입자의 함량이 감소되기 때문에 코팅을 통하여 얻고자 하는 특성을 충분히 얻을 수 없다는 문제점이 있었다. In general, the inorganic nanoparticle coating liquid for preparing the inorganic nanoparticle film on the organic / inorganic substrate has been prepared by adding inorganic nanoparticles to an organic solvent including a polymer binder and using a mechanical grinding method. In particular, a resin including polyvinylidene fluoride resin and synthetic rubber has been conventionally used as a binder for coating inorganic nanoparticles. However, in the case of using such a resin, the dispersion stability of the inorganic nanoparticles in the coating solution is not good, there is a problem that the coating properties are affected by the humidity, in order to maintain the coating properties compared to the content of the inorganic nanoparticles Therefore, the content of the polymer binder had to be added at 10% by weight or more. As such, when the content of the polymer binder is increased, the content of the inorganic nanoparticles in the film is decreased, and thus there is a problem in that it is not possible to sufficiently obtain the desired characteristics through the coating.
따라서, 습도에 관계없이 균일한 코팅성을 유지할 수 있으며, 고분자 바인더의 함량을 감소시킴으로써 고농도의 무기 입자 코팅이 가능한 코팅액이 필요한 실정이다. Therefore, a uniform coating property can be maintained regardless of humidity, and a coating liquid capable of coating inorganic particles at a high concentration by reducing the content of the polymer binder is required.
상기와 같은 종래기술의 문제점을 해결하고자, 본 발명은 무기 나노 입자 필름의 제조시 바인더로 사용되어 무기 나노 입자의 분산성을 크게 향상시키는 친수기로 개질된 아크릴계 수지를 제공하는 것을 목적으로 한다. In order to solve the problems of the prior art as described above, an object of the present invention is to provide an acrylic resin modified with a hydrophilic group to be used as a binder in the preparation of the inorganic nanoparticle film to greatly improve the dispersibility of the inorganic nanoparticles.
또한, 본 발명은 상기 아크릴계 수지를 포함하는 무기 나노 입자 코팅액, 및 이로부터 제조되어 무기 나노 입자 간의 접착력이 향상되고, 습도에 따른 필름 특성이 균일하게 제어된 무기 나노 입자 필름을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide an inorganic nanoparticle coating liquid comprising the acrylic resin, and an inorganic nanoparticle film prepared therefrom to improve adhesion between inorganic nanoparticles and uniformly controlled film properties according to humidity. do.
본 발명의 상기 목적 및 기타 목적들은 하기 설명된 본 발명에 의하여 모두 달성될 수 있다.These and other objects of the present invention can be achieved by the present invention described below.
상기의 목적을 달성하기 위하여, 본 발명은 a) 유리전이온도가 -85 내지 22 ℃인 아크릴계 단량체 45 내지 95 중량%, b) 친수성기 도입 단량체 1 내지 30 중량%, 및 c) 유리전이온도가 8 내지 153 ℃인 비닐기 함유 단량체 1 내지 40 중량%로부터 중합됨을 특징으로 하는 친수기로 개질된 아크릴계 수지를 제공한다.In order to achieve the above object, the present invention is a) 45 to 95% by weight acrylic monomer having a glass transition temperature of -85 to 22 ℃, b) 1 to 30% by weight of a hydrophilic group introduced monomer, and c) the glass transition temperature of 8 It provides a hydrophilic group-modified acrylic resin characterized in that it is polymerized from 1 to 40% by weight of a vinyl group-containing monomer which is from 153 ℃.
또한, 본 발명은 유기 용매에 무기 나노 입자와 상기 친수기로 개질된 아크릴계 수지가 90:10 내지 99:1의 중량비로 분산된 것을 특징으로 하는 무기 나노 입자 코팅액을 제공한다. The present invention also provides an inorganic nanoparticle coating liquid, wherein the inorganic nanoparticles and the acrylic resin modified with the hydrophilic group are dispersed in a weight ratio of 90:10 to 99: 1 in an organic solvent.
또한, 본 발명은 상기 무기 나노 입자 코팅액으로부터 제조된 무기 나노 입자 필름을 제공한다. The present invention also provides an inorganic nanoparticle film prepared from the inorganic nanoparticle coating solution.
이하 본 발명을 상세하게 설명한다. Hereinafter, the present invention will be described in detail.
본 발명자들은 유/무기 기판 위에 1 내지 100 ㎛ 두께의 무기 나노 입자 필름을 코팅함에 있어서, 친수기로 개질된 아크릴계 수지를 바인더로 포함하는 코팅액을 사용하는 경우, 습도에 관계없이 균일한 코팅성을 유지할 수 있으며, 바인더의 함량을 무기 나노 입자 함량 대비하여 10 중량% 미만으로 유지함으로써 고농도의 무기 입자 코팅이 가능하며, 상기와 같이 코팅된 무기 나노 입자가 기판으로부 터 탈락되는 현상을 방지할 수 있음을 확인하고, 이를 토대로 본 발명을 완성하게 되었다. The present inventors, when coating the inorganic nanoparticle film of 1 to 100 ㎛ thickness on the organic / inorganic substrate, when using a coating liquid containing a hydrophilic-modified acrylic resin as a binder, it maintains a uniform coating regardless of humidity In addition, by maintaining the content of the binder less than 10% by weight compared to the inorganic nanoparticles content can be coated with a high concentration of inorganic particles, it is possible to prevent the coated inorganic nanoparticles from falling off from the substrate. After confirming this, the present invention was completed.
본 발명의 친수기로 개질된 아크릴계 수지는 a) 유리전이온도가 -85 내지 22 ℃인 아크릴계 단량체 45 내지 95 중량%, b) 친수성기 도입 단량체 1 내지 30중량%, 및 c) 유리전이온도가 8 내지 153 ℃인 비닐기 함유 단량체 1 내지 40 중량%로부터 중합된 수지이다. Acrylic resin modified with a hydrophilic group of the present invention is a) 45 to 95% by weight of the acrylic monomer having a glass transition temperature of -85 to 22 ℃, b) 1 to 30% by weight of the hydrophilic group introduced monomer, and c) 8 to It is resin polymerized from 1-40 weight% of vinyl group containing monomers which are 153 degreeC.
상기 a) 유리전이온도가 -85 내지 22 ℃인 아크릴계 단량체는 에틸아크릴레이트, n-부틸아크릴레이트, 2-에틸헥실아크릴레이트, 이소프로필아크릴레이트, n-헥실메타크릴레이트, 라우릴메타크릴레이트 및 2-히드록시에틸아크릴레이트로 이루어지는 군으로부터 선택되는 1종 이상이 바람직하다. A) The acrylic monomer having a glass transition temperature of -85 to 22 ° C is ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isopropyl acrylate, n-hexyl methacrylate, lauryl methacrylate. And at least one selected from the group consisting of 2-hydroxyethyl acrylate.
또한, 상기 아크릴계 단량체는 본 발명의 친수기로 개질된 아크릴계 수지 총 함량에 대하여 45 내지 95 중량%로 중합되는 것이 바람직하다. 상기 함량으로 중합되는 경우에는 필름 제조시 기판과의 접착성이 높고, 동시에 응집력도 적당하여 필름이 부분 박리되는 현상을 방지하고, 필름의 열특성을 향상시키는 효과가 있다. In addition, the acrylic monomer is preferably polymerized to 45 to 95% by weight relative to the total content of the acrylic resin modified with a hydrophilic group of the present invention. When the polymerization is carried out in the above content, the adhesiveness with the substrate during the film production is high, and at the same time, the cohesion force is also suitable to prevent the film from being partially peeled off and to improve the thermal properties of the film.
상기 b) 친수성기 도입 단량체는 무기 나노 입자 코팅액의 분산 안정성을 향상시키며, 습도에 영향을 받지 않는 균일한 코팅성을 부여하기 위한 것으로, 구체적으로 아크릴산, 메타크릴산, 2-하이드록시에틸메타크릴산, 말레인산, 말레산무수물 및 이타콘산으로 이루어지는 군으로부터 선택되는 1종 이상이 바람직하다. The b) hydrophilic group introduction monomer is to improve the dispersion stability of the inorganic nanoparticle coating liquid, to impart a uniform coating property is not affected by humidity, specifically acrylic acid, methacrylic acid, 2-hydroxyethyl methacrylate , At least one selected from the group consisting of maleic acid, maleic anhydride and itaconic acid is preferred.
또한, 상기 친수성기 도입 단량체는 본 발명의 친수기로 개질된 아크릴계 수지 총 함량에 대하여 1 내지 30 중량%로 중합되는 것이 바람직하다. 상기 함량으 로 중합되는 경우에는 높은 습도에서 건조하는 경우에도 응집력과 접착력이 저하되지 않으며, 기판에서 필름이 들뜨는 현상이 발생하지 않는 효과가 있다. In addition, the hydrophilic group introduction monomer is preferably polymerized to 1 to 30% by weight relative to the total content of the acrylic resin modified with a hydrophilic group of the present invention. When the polymerization is carried out in the above content, the cohesion force and the adhesive force do not decrease even when dried at a high humidity, and there is an effect that the film is not lifted from the substrate.
상기 c) 유리전이온도가 8 내지 153 ℃인 비닐기 함유 단량체는 본 발명의 친수기로 개질된 아크릴계 수지의 열특성을 향상시키고 경도를 부여하기 위한 것으로, 구체적으로 메틸아크릴레이트, 메틸메타크릴레이트, 에틸메타크릴레이트, 이소부틸아크릴레이트, 아크릴아미드, 디아세톤아크릴아미드, 스티렌, 비닐톨루엔, 비닐아세테이트 및 아크릴로니트릴로 이루어지는 군으로부터 선택되는 1종 이상이 바람직하다. C) The vinyl group-containing monomer having a glass transition temperature of 8 to 153 ° C. is for improving the thermal properties and imparting hardness of the acrylic resin modified with the hydrophilic group of the present invention. Specifically, methyl acrylate, methyl methacrylate, At least one selected from the group consisting of ethyl methacrylate, isobutyl acrylate, acrylamide, diacetone acrylamide, styrene, vinyltoluene, vinyl acetate and acrylonitrile is preferred.
또한, 상기 비닐기 함유 단량체는 본 발명의 친수기로 개질된 아크릴계 수지 총 함량에 대하여 1 내지 40 중량%로 중합되는 것이 바람직하다. 상기 함량으로 중합되는 경우에는 기판과의 접착성을 감소시키지 않으면서도, 건조 후 필름의 응집력과 열특성을 향상시키는 효과가 있다. In addition, the vinyl group-containing monomer is preferably polymerized to 1 to 40% by weight relative to the total content of the acrylic resin modified with a hydrophilic group of the present invention. When polymerized to the above content, there is an effect of improving the cohesion and thermal properties of the film after drying, without reducing the adhesion to the substrate.
상기와 같은 단량체 성분 이외에 높은 분자량의 아크릴계 수지가 요구되는 경우, 중합시 가교성 단량체가 본 발명의 친수기로 개질된 아크릴계 수지 총 함량에 대하여 0.01 내지 2.0 중량%로 더 포함될 수도 있다. 상기 가교성 단량체로는 에틸렌글리콜디메타크릴레이트, 디비닐벤젠, 및 이들의 혼합물일 수 있다.When a high molecular weight acrylic resin is required in addition to the monomer component as described above, the crosslinkable monomer may be further included as 0.01 to 2.0% by weight based on the total content of the acrylic resin modified with the hydrophilic group of the present invention. The crosslinkable monomer may be ethylene glycol dimethacrylate, divinylbenzene, and mixtures thereof.
상기 중합은 괴상중합 방법으로 실시되는 것이 바람직하며, 이때 중합에 통상적으로 사용되는 중합개시제, 분자량조절제, 용매 등을 사용할 수 있다. The polymerization is preferably carried out by a bulk polymerization method, and may include a polymerization initiator, a molecular weight regulator, a solvent, and the like, which are usually used for polymerization.
상기 용매는 톨루엔, 에틸벤젠, 자이렌 또는 메틸에틸케톤 등을 단독 또는 2종 이상 혼합하여 사용할 수 있다.The solvent may be used alone or in combination of two or more kinds of toluene, ethylbenzene, xylene or methyl ethyl ketone.
상기 중합개시제는, 구체적으로 t-부틸퍼옥시-2-에틸헥사노에이트(t-butylperoxy-2-ethylhexanoate), 1,1-비스(t-부틸퍼옥시)-3,3,5-트리메틸 사이클로헥산{1,1-bis(t-butylperoxy)-3,3,5-trimethyl cyclohexane}, 1,1-비스(t-부틸퍼옥시) 사이클로헥산{1,1-bis(t-butylperoxy) cyclohexane}, 1,1-비스(t-부틸퍼옥시)-2-메틸 사이클로헥산{1,1-bis(t-butylperoxy)-2-methyl cyclohexane}, 2,2-비스(4,4-디-t-부틸퍼옥시 사이클로헥실)프로판{2,2-bis(4,4-di-t-butylperoxy cyclohexyl) propane} 또는 아조비스이소부티로니트릴 등을 사용할 수 있다. 중합개시제의 사용량은 상기 a) 내지 c)의 단량체 및 용매를 포함하는 혼합용액 100 중량부에 대하여 0.01 내지 0.1 중량부인 것이 바람직하다. 그 사용량이 0.01 중량부 미만일 경우에는 중합의 진행이 불가능해져 전체 수지의 물성 균형이 어려우며, 0.1 중량부를 초과하는 경우에는 과도한 점도 상승으로 인하여 공정상 불리하고 위험하다. Specifically, the polymerization initiator, t-butylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl cyclo Hexane {1,1-bis (t-butylperoxy) -3,3,5-trimethyl cyclohexane}, 1,1-bis (t-butylperoxy) cyclohexane {1,1-bis (t-butylperoxy) cyclohexane} , 1,1-bis (t-butylperoxy) -2-methyl cyclohexane {1,1-bis (t-butylperoxy) -2-methyl cyclohexane}, 2,2-bis (4,4-di-t -Butyl peroxy cyclohexyl) propane {2,2-bis (4,4-di-t-butylperoxy cyclohexyl) propane} or azobisisobutyronitrile and the like can be used. The amount of the polymerization initiator is preferably 0.01 to 0.1 parts by weight based on 100 parts by weight of the mixed solution containing the monomers of a) to c) and a solvent. If the amount is less than 0.01 parts by weight, it is impossible to proceed with polymerization, and it is difficult to balance the physical properties of the entire resin, and if it exceeds 0.1 parts by weight, it is disadvantageous and dangerous in the process due to excessive viscosity increase.
상기 분자량조절제는, 구체적으로 t-도데실 메르캅탄(t-dodecyl mercaptan) 또는 n-옥틸 메르캅탄(n-octyl mercaptane) 등의 메르캅탄류를 사용할 수 있다. 분자량조절제의 사용량은 혼합용액 100 중량부에 대하여 0.01 내지 1 중량부인 것이 바람직하다. 그 사용량이 0.01 중량부 미만일 경우에는 과도한 점도 상승으로 공정상 불리하여 수지의 물성 저하를 초래하고, 1 중량부를 초과하는 경우에는 중합반응이 진행되지 않아 전체 수지의 물성 균형을 이루기 어렵다. Specifically, the molecular weight regulator may be used mercaptans such as t-dodecyl mercaptan or n-octyl mercaptane. It is preferable that the usage-amount of a molecular weight modifier is 0.01-1 weight part with respect to 100 weight part of mixed solutions. If the amount is less than 0.01 parts by weight, excessive viscosity rise is disadvantageous in the process, leading to a decrease in the physical properties of the resin. If the amount is more than 1 part by weight, the polymerization reaction does not proceed and it is difficult to balance the physical properties of the entire resin.
상기 친수기로 개질된 아크릴계 수지는 무기 나노 입자의 코팅용 바인더로 사용될 수 있다. The acrylic resin modified with the hydrophilic group may be used as a binder for coating inorganic nanoparticles.
본 발명의 무기 나노 입자 코팅액은 유기 용매에 무기 나노 입자와 바인더로 상기 친수기로 개질된 아크릴계 수지가 분산된 코팅액이다.The inorganic nanoparticle coating liquid of the present invention is a coating liquid in which an acrylic resin modified with the hydrophilic group by inorganic nanoparticles and a binder in an organic solvent is dispersed.
상기 유기 용매는 무기 나노 입자와 바인더를 분산시키기고, 고형분 함량을 조절하기 위한 것으로, 당업계에서 통상적으로 사용되는 유기 용매라면 그 종류가 특별히 제한되지 않으며, 끓는점이 비교적 낮은 에탄올, 메탄올, 아세톤, 톨루엔, 벤젠 및 에틸렌 글리콜로 이루어지는 군으로부터 선택되는 1종 이상이 바람직하다. The organic solvent is to disperse the inorganic nanoparticles and the binder, and to control the solid content, and the organic solvent is not particularly limited as long as it is an organic solvent commonly used in the art, ethanol, methanol, acetone, which has a relatively low boiling point, At least one selected from the group consisting of toluene, benzene and ethylene glycol is preferred.
상기 무기 나노 입자는 그 종류가 특별히 제한되지 않으며, 구체적으로 BaTiO3, PbZrO3, PbTiO3, Pb1-xLaxZr1-yTiyO3(여기서, x와 y는 각각 0 또는 1), Pb(Mg3Nb2/3)O3-PbTiO3(PMN-PT), HfO2, SrTiO3, SnO2, CeO2, MgO, NiO, CaO, ZnO, ZrO2, Y2O3, Al2O3, TiO2 및 SiC로 이루어지는 군으로부터 선택되는 1종 이상이다. The inorganic nanoparticles are not particularly limited in kind, and specifically, BaTiO 3 , PbZrO 3 , PbTiO 3 , Pb 1-x La x Zr 1-y Ti y O 3 (where x and y are each 0 or 1). , Pb (Mg 3 Nb 2/3 ) O 3 -PbTiO 3 (PMN-PT), HfO 2 , SrTiO 3 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3, it is at least one member selected from the group consisting of TiO 2 and SiC.
상기 무기 나노 입자는 평균입경이 1 내지 1000 ㎚인 것일 수 있다. The inorganic nanoparticles may have an average particle diameter of 1 to 1000 nm.
상기 무기 나노 입자와 상기 친수기로 개질된 아크릴계 수지는 90:10 내지 99:1의 중량비로 분산되는 것이 바람직하다. The inorganic nanoparticles and the acrylic resin modified with the hydrophilic group are preferably dispersed in a weight ratio of 90:10 to 99: 1.
즉, 상기 무기 나노 입자 코팅액은 유기 용매에 고형분으로 무기 나노 입자와 바인더인 친수기로 개질된 아크릴계 수지가 분산된 것으로, 이때 고형분 중, 상기 친수기로 개질된 아크릴계 수지가 10 중량% 미만으로 포함되는 것이 바람직하며, 보다 바람직하게는 5 중량% 미만으로 포함되는 것이다. 상기와 같은 성분을 포함하는 무기 나노 입자 코팅액은 코팅액에서 무기 나노 입자의 분산성을 혁신적 으로 향상시키는 동시에 코팅시 무기 입자 간의 접착력 또는 기판과 무기 입자 필름 간의 접착력을 향상시키는 역할을 하며, 바인더인 친수기로 개질된 아크릴계 수지가 10 중량% 미만, 보다 바람직하게 5 중량% 미만으로 포함되어도 코팅성이 향상되며, 습도에 관계없이 균일한 코팅성을 얻을 수 있는 효과가 있다.That is, the inorganic nanoparticle coating liquid is an acrylic resin in which the inorganic nanoparticles and the hydrophilic group modified as a binder are dispersed in solids in an organic solvent, wherein the acrylic resin modified with the hydrophilic group is included in the solid content in less than 10% by weight. Preferably, it is more preferably contained less than 5% by weight. Inorganic nanoparticle coating liquid containing the above components innovatively improve the dispersibility of inorganic nanoparticles in the coating solution and at the same time serves to improve the adhesion between the inorganic particles or the adhesion between the substrate and the inorganic particle film, the binder hydrophilic group Even if the modified acrylic resin is contained in less than 10% by weight, more preferably less than 5% by weight, the coating property is improved, there is an effect that can obtain a uniform coating regardless of humidity.
상기 무기 나노 입자 코팅액은 부직포 등의 다공성 기재에 코팅되어 공기 정화 필터, 및 다공성 필름이 필요한 수계 1차 또는 2차 전지 등에 사용될 수 있다. The inorganic nanoparticle coating liquid may be coated on a porous substrate such as a nonwoven fabric and used for an air purification filter and an aqueous primary or secondary battery requiring a porous film.
본 발명은 상기 무기 나노 입자 코팅액으로부터 제조된 필름을 제공한다.The present invention provides a film prepared from the inorganic nanoparticle coating liquid.
또한, 본 발명은 상기 무기 나노 입자 코팅액이 코팅된 기판을 제공한다. In addition, the present invention provides a substrate coated with the inorganic nanoparticle coating solution.
상기 기판은 금속, 합금, 목재, 플라스틱, 또는 가죽재 등을 포함하는 유기 또는 무기 기판일 수 있다. The substrate may be an organic or inorganic substrate including metal, alloy, wood, plastic, leather, or the like.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.
[실시예][Example]
실시예 1Example 1
친수기로 개질된 부틸아크릴레이트/스티렌 수지 제조Preparation of butyl acrylate / styrene resin modified with hydrophilic group
교반기 및 온도계 등이 부착된 3구 플라스크에 아조비스이소부티로니트릴 0.1 g, 아크릴산 10 g, 부틸아크릴레이트 300 g, 스티렌 30 g을 넣고, 불활성 질소가스도 연속적으로 주입하면서 괴상중합하였다. 이때, 플라스크 내부온도는 80 ℃로, 교반속도는 분당 150 rpm였다. 5 시간 동안 중합반응하였으며, 반응이 완료된 후, 실온으로 냉각시켜 메탄올에 침전 잡아 수지를 수득하였다. 0.1 g of azobisisobutyronitrile, 10 g of acrylic acid, 300 g of butyl acrylate, and 30 g of styrene were added to a three-necked flask equipped with a stirrer and a thermometer, and subjected to bulk polymerization while continuously injecting inert nitrogen gas. At this time, the flask internal temperature was 80 ° C. and the stirring speed was 150 rpm. The polymerization was carried out for 5 hours, and after the reaction was completed, the mixture was cooled to room temperature and precipitated in methanol to obtain a resin.
무기 나노 입자 코팅액 제조Inorganic nanoparticle coating solution preparation
상기 제조한 친수기로 개질된 부틸아크릴레이트/스티렌 수지를 벤젠에 녹인 용액에 BaTiO3 분말을 전체 고형분 20 중량% 농도로 첨가하고 분산시켜 BaTiO3와 개질된 부틸아크릴레이트/스티렌 수지의 중량비가 95:5인 무기 나노 입자 코팅액을 제조하였다. The weight ratio of BaTiO 3 and the modified butyl acrylate / styrene resin was added by dispersing BaTiO 3 powder at a concentration of 20% by weight of the total solids in a solution of butyl acrylate / styrene resin modified with hydrophilic groups prepared in benzene. An inorganic nanoparticle coating solution of 5 was prepared.
무기 나노 입자 필름 제조Inorganic Nanoparticle Film Manufacturing
상기 제조한 무기 나노 입자 코팅액을 닥터블레이드로 유리 기판 위에 각각 4가지 다른 습도 조건에서 코팅한 후 건조하여 두께가 약 8 ㎛인 무기 나노 입자 필름을 제조하였다. 이때, 코팅시 온도는 23 ℃로 고정하였으며, 20, 30, 40, 50 %의 습도 하에서 각각 코팅하였다. The inorganic nanoparticle coating liquid prepared above was coated on a glass substrate with a doctor blade at four different humidity conditions, and then dried to prepare an inorganic nanoparticle film having a thickness of about 8 μm. At this time, the temperature at the time of coating was fixed at 23 ℃, were coated under humidity of 20, 30, 40, 50%, respectively.
실시예 2Example 2
상기 실시예 1에서 부틸아크릴레이트/스티렌 수지 제조시 아크릴산을 20 g으로 증량하여 첨가한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. In preparing the butyl acrylate / styrene resin in Example 1 was carried out in the same manner as in Example 1, except that the acrylic acid was increased by 20 g.
실시예 3Example 3
상기 실시예 1에서 무기 나노 입자 코팅액 제조시 BaTiO3와 개질된 부틸아크릴레이트/스티렌 수지의 중량비가 90:10인 코팅액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. The preparation of the inorganic nanoparticle coating solution in Example 1 was carried out in the same manner as in Example 1, except that a coating solution having a weight ratio of BaTiO 3 and the modified butyl acrylate / styrene resin was 90:10.
실시예 4Example 4
상기 실시예 1에서 무기 나노 입자 코팅액 제조시 BaTiO3 대신 TiO2를 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. The preparation of the inorganic nanoparticle coating solution in Example 1 was carried out in the same manner as in Example 1, except that TiO 2 was used instead of BaTiO 3 .
비교예 1Comparative Example 1
상기 실시예 1에서 부틸아크릴레이트/스티렌 수지 제조시 아크릴산을 첨가하지 않고 중합하여, 친수기를 포함하지 않는 부틸아크릴레이트/스티렌 수지를 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. In Example 1, the polymerization was carried out in the same manner as in Example 1 except that the butyl acrylate / styrene resin was polymerized without adding acrylic acid to prepare a butyl acrylate / styrene resin, thereby producing a butyl acrylate / styrene resin containing no hydrophilic group.
비교예 2Comparative Example 2
상기 실시예 1에서 친수기로 개질된 부틸아크릴레이트/스티렌 수지가 아닌 폴리불화비닐리덴 수지를 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. Except for using a polyvinylidene fluoride resin other than the butyl acrylate / styrene resin modified in the hydrophilic group in Example 1 was carried out in the same manner as in Example 1.
[시험예][Test Example]
상기 실시예 1 내지 4, 및 비교예 1 내지 2에서 제조한 무기 나노 입자 코팅액의 분산안정성, 및 무기 나노 입자 필름의 물성을 하기의 방법으로 측정하였다. The dispersion stability of the inorganic nanoparticle coating liquids prepared in Examples 1 to 4 and Comparative Examples 1 and 2, and the physical properties of the inorganic nanoparticle film were measured by the following method.
시험예 1. 무기 나노 입자 코팅액의 분산 안정성 측정Test Example 1. Measurement of dispersion stability of inorganic nanoparticle coating liquid
무기 나노 입자 코팅액을 높이가 일정한 유기관에 넣은 후, 시간에 따른 침전 거동을 조사하여, 침전에 대한 안정성을 평가하고, 그 결과를 도 1에 나타내었다. After the inorganic nanoparticle coating liquid was placed in a constant organic tube, the precipitation behavior was investigated over time to evaluate the stability to precipitation, and the results are shown in FIG. 1.
도 1에 나타낸 바와 같이, 본 발명에 따라 제조한 친수기로 개질된 부틸아크릴레이트/스티렌 수지를 바인더로 사용한 실시예 1 내지 4의 무기 나노 입자 코팅액은 비교예 1 및 2와 비교하여 침전율이 낮아 상대적으로 분산 안정성이 우수한 것을 확인할 수 있었다.As shown in FIG. 1, the inorganic nanoparticle coating liquids of Examples 1 to 4 using the hydrophilic group-modified butyl acrylate / styrene resin prepared as a binder have a relatively low precipitation rate compared to Comparative Examples 1 and 2. It was confirmed that the dispersion stability is excellent.
시험예 2. 무기 나노 입자 필름의 패킹(packing) 밀도 측정Test Example 2 Measurement of Packing Density of Inorganic Nanoparticle Film
8 ㎛로 동일한 두께의 무기 나노 입자 필름의 외부 습도 변화에 따른 단위 면적당 무게를 측정하여 패킹 밀도를 측정하고, 그 결과를 하기 표 1에 나타내었다. The packing density was measured by measuring the weight per unit area according to the external humidity change of the inorganic nanoparticle film having the same thickness as 8 μm, and the results are shown in Table 1 below.
상기 표 1에 나타낸 바와 같이, 본 발명에 따라 제조한 친수기로 개질된 부틸아크릴레이트/스티렌 수지를 바인더로 사용한 실시예 1 내지 4의 무기 나노 입자 필름은 외부 습도 변화에 관계없이 일정한 패킹 밀도를 나타내는 것을 확인할 수 있었다. As shown in Table 1, the inorganic nanoparticle films of Examples 1 to 4 using a butyl acrylate / styrene resin modified with a hydrophilic group prepared according to the present invention as a binder exhibit a constant packing density regardless of external humidity change. I could confirm that.
반면, 바인더로 친수기로 개질되지 않은 부틸아크릴레이트/스티렌 수지를 사용한 비교예 1, 및 종래의 폴리불화비닐리덴을 사용한 비교예 2의 무기 나노 입자 필름은 외부 습도의 변화에 따라 그 패킹 밀도가 상당히 감소되는 것을 확인할 수 있었다. On the other hand, the inorganic nanoparticle films of Comparative Example 1 using a butyl acrylate / styrene resin which is not modified with a hydrophilic group as a binder, and Comparative Example 2 using a conventional polyvinylidene fluoride have a significant packing density according to changes in external humidity. It was confirmed that the decrease.
시험예 2. 무기 나노 입자 필름의 기판과의 접착력 측정Test Example 2 Measurement of Adhesion of Inorganic Nanoparticle Film with Substrate
8 ㎛로 동일한 두께의 무기 나노 입자 필름의 외부 습도 변화에 따른 기판과의 접착력을 필 테스터기(peel tester)를 이용하여 측정하고, 그 결과를 하기 표 2에 나타내었다.Adhesion to the substrate according to the change in the external humidity of the inorganic nanoparticle film of the same thickness to 8 ㎛ was measured using a peel tester (peel tester), the results are shown in Table 2 below.
상기 표 2에 나타낸 바와 같이, 본 발명에 따라 제조한 친수기로 개질된 부틸아크릴레이트/스티렌 수지를 바인더로 사용한 실시예 1 내지 4의 무기 나노 입자 필름은 외부 습도 변화에 관계없이 일정한 접착력을 나타내는 것을 확인할 수 있었다. As shown in Table 2, the inorganic nanoparticle films of Examples 1 to 4 using a butyl acrylate / styrene resin modified with a hydrophilic group prepared according to the present invention as a binder exhibit a constant adhesive force regardless of the change in external humidity. I could confirm it.
반면, 바인더로 친수기로 개질되지 않은 부틸아크릴레이트/스티렌 수지를 사용한 비교예 1, 및 종래의 폴리불화비닐리덴을 사용한 비교예 2의 무기 나노 입자 필름은 외부 습도가 증가함에 따라 접착력이 현저하게 저하되는 것을 확인할 수 있었다. On the other hand, the inorganic nanoparticle films of Comparative Example 1 using a butyl acrylate / styrene resin which is not modified with a hydrophilic group as a binder, and Comparative Example 2 using a conventional polyvinylidene fluoride significantly decrease the adhesive strength as the external humidity increases. It could be confirmed.
상기에서 살펴본 바와 같이, 본 발명의 친수기로 개질된 아크릴계 수지는 무기 나노 입자 필름의 제조시 바인더로 사용되어, 무기 나노 입자의 분산성을 크게 향상시켜 장기간 보관에도 침전되지 않는 무기 나노 입자 코팅액을 제공하며, 적은 함량으로 사용됨에도 필름에서의 무기 나노 입자 간의 접착력을 향상시키고, 습도에 따른 필름의 특성을 균일하게 제어하여, 공정상의 유연성을 증가시키는 효과가 있다. As described above, the hydrophilic-modified acrylic resin of the present invention is used as a binder in the preparation of the inorganic nanoparticle film, thereby greatly improving the dispersibility of the inorganic nanoparticles, thereby providing an inorganic nanoparticle coating solution that does not precipitate even in long-term storage. And, even when used in a small amount to improve the adhesion between the inorganic nanoparticles in the film, uniformly control the properties of the film according to the humidity, there is an effect of increasing the flexibility in the process.
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| US10155361B2 (en) | 2011-11-09 | 2018-12-18 | Corning Incorporated | Method of binding nanoparticles to glass |
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