KR101398971B1 - Coated film with high-hydrophilic and ir shield characteristic, and preparing method thereof - Google Patents

Coated film with high-hydrophilic and ir shield characteristic, and preparing method thereof Download PDF

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KR101398971B1
KR101398971B1 KR1020130085706A KR20130085706A KR101398971B1 KR 101398971 B1 KR101398971 B1 KR 101398971B1 KR 1020130085706 A KR1020130085706 A KR 1020130085706A KR 20130085706 A KR20130085706 A KR 20130085706A KR 101398971 B1 KR101398971 B1 KR 101398971B1
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film
coating
oxide
group
inorganic particles
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김영주
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주식회사 케이닉스공사
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Priority to PCT/KR2013/008414 priority patent/WO2015008894A1/en
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Abstract

The present invention relates to an antibacterial coating composition for anti-fog comprising copolymers consisting of organic silicon polymers having an amide group, and mass production of anti-dew infrared-cut off coating films through one-time coating by coating olefin-based polymers, polyethylene terephthalate (PET) and polyamide-based polymers with the composition by a roll-to-roll method using gravure, micro gravure and slot-die and lip-die coaters.

Description

고 친수성 및 적외선 차단 특성을 갖는 코팅 필름 및 이의 제조 방법{Coated film with high-hydrophilic and IR shield characteristic, and preparing method thereof}[0001] The present invention relates to a coating film having high hydrophilicity and infrared shielding property and a method for producing the same,

본 발명은 아미드기를 갖는 유기 실리콘 고분자로 이루어지는 공중합체를 포함하는 고 친수성 및 적외선 차단 특성을 갖는 코팅 조성물 및 상기 조성물을 올레핀계 고분자, 폴리에틸렌테레프탈레이트(PET) 및 폴리아미드계 고분자에 그라비어(gravure), 마이크로 그라비어(micro gravure), 슬롯다이(slot-die)및 립 다이(lip-die) 코터를 이용한 롤-투-롤(roll-to-roll)방법으로 코팅하여 고 친수성 및 적외선 차단 특성을 갖는 필름을 대량 생산하는 기술에 관한 것이다. 또한, 상기 고 친수성 적외선 차단 코팅 조성물을 이용하여 건축물 및 자동차 등의 에너지 절감 및 결로 현상 방지의 두 가지 기능을 동시에 발현하는 특성을 기대할 수 있는 복합 기능성 필름 등을 제조하는 방법에 관한 것이다.The present invention relates to a coating composition having a high hydrophilicity and an infrared shielding property, comprising a copolymer comprising an organosilicon polymer having an amide group, and a method for gravure coating the composition with an olefin polymer, polyethylene terephthalate (PET) and polyamide- Roll-to-roll process using a micro-gravure, slot-die and lip-die coater to produce a film having high hydrophilicity and infrared blocking properties The present invention relates to a technique for mass-producing a film. In addition, the present invention relates to a method for producing a composite functional film or the like that can simultaneously exhibit two functions of energy saving and dew condensation prevention in buildings and automobiles by using the high-hydrophilic infrared barrier coating composition.

기존의 친수(hydrophilic), 초친수(super-hydrophilic) 및 적외선 차단 기능은 각기 다른 기능으로, 코팅 기재(필름, 유리 및 금속 등)에 각각 여러 번 코팅하여 다 기능성(multi function)을 구현하는 필름을 제조 하였다(특허 출원번호 제10-2010-0129001호 등). 이러한 다 기능성 필름은 각각의 기능성 코팅 조성물을 두 번 이상 코팅 기재에 코팅하여 제품의 대량 제조 시 낮은 수율 문제와 기능성의 제한이 있었다.Conventional hydrophilic, super-hydrophilic and infrared blocking functions are different functions, and each film is coated with a coating material (film, glass and metal) several times to realize a multi-function film (Patent Application No. 10-2010-0129001 etc.). These multifunctional films have a low yield problem and limited functionality in mass production of the product by coating each functional coating composition on the coated substrate more than once.

이를 보완하기 위하여 본 발명에서는 물과 화학적인 친화성이 강한 아미드기(-CONH-)갖는 실리콘 고분자와, 하이드록시기(-OH)를 다량 포함하는 무기 산화 나노 입자를 이용하여 새로운 1 액형 유-무기 나노 실리콘 복합체의 고 친수성 및 적외선 차단 기능을 동시에 갖는 코팅 조성물을 합성하였다. 한편, 이를 이용한 고 친수성 적외선 차단 코팅 필름은 촉진 내후성 시험의 약 500시간에서 색 변색율이 3% 이하인 내구성을 갖고 있으며, 상기 복합 기능성 코팅 조성물을 이용하여 롤-투-롤 방법에 의하여 코팅한다면 한 번의 코팅으로 고 친수성 및 적외선 차단 특성의 두 가지 기능을 동시에 갖는 코팅 필름의 대량생산이 가능하다는 장점이 있다. In order to compensate for this, the present invention uses a silicon polymer having an amide group (-CONH-) having a strong chemical affinity for water and an inorganic oxide nanoparticle containing a large amount of a hydroxyl group (-OH) A coating composition having both a high hydrophilic property and an infrared ray blocking function of an inorganic nano silicone composite was synthesized. On the other hand, the high-hydrophilic infrared barrier coating film using the same has durability with a color change rate of less than 3% at about 500 hours of the accelerated weathering test. If the coating is applied by the roll-to-roll method using the above- It is possible to mass-produce a coating film having both functions of high hydrophilicity and infrared ray blocking property at the same time.

본 발명은 상기와 같은 문제점을 해결하기 위하여 완성된 것으로, 결로 방지와 적외선 차단 기능을 보유한 첨가물질을 동시에 바인딩할 수 있는 바인더에 의하여 단일 조성물로부터 복합 기능(결로 방지 기능과 적외선 차단 기능)을 발휘될 수 있는 코팅 조성물을 제공하는데 그 목적이 있다.Disclosure of the Invention The present invention has been completed in order to solve the above-mentioned problems, and it is an object of the present invention to provide a multi-function (a dew condensation preventing function and an infrared ray blocking function) from a single composition by a binder capable of simultaneously binding an additive material having anti- And to provide a coating composition which can be used as a coating composition.

본 발명의 다른 목적은 상기 코팅 조성물을 기재에 코팅하는 방법 및 이에 의하여 수득되는 촉진 내후성 시험의 500시간에서 색 변색율이 3% 이하인 내구성을 갖는 결로 방지 및 적외선 차단 필름을 제공하는 것이다.Another object of the present invention is to provide a method of coating the above coating composition on a substrate and a dew condensation preventing and infrared ray shielding film having a durability with a color discoloration rate of 3% or less at 500 hours of the accelerated weathering test obtained thereby.

본 발명의 또 다른 목적은 결로 방지 적외선 차단 기능이 코팅된 필름이나 쉬트(sheet)를 이용하여 건축물이나 자동차의 에너지 유리에 부착하여 에너지 절약용품에 응용하는 방법을 제공하는 것이다.It is another object of the present invention to provide a method of applying to an energy saving article by attaching to an energy glass of a building or an automobile by using a film or a sheet coated with the anti-condensation infrared ray blocking function.

상기 목적을 달성하기 위하여, 본 발명의 코팅 조성물은 하기 화학식 1로 표시되는 화합물, 하기 화학식 2로 표시되는 화합물 및 하기 화학식 3으로 표시되는 화합물로 이루어지는 랜덤 공중합체를 포함하는 것을 특징으로 한다.In order to achieve the above object, the coating composition of the present invention is characterized by including a random copolymer comprising a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3)

[화학식 1][Chemical Formula 1]

Figure 112013065504424-pat00001
Figure 112013065504424-pat00001

[화학식 2](2)

Figure 112013065504424-pat00002
Figure 112013065504424-pat00002

[화학식 3](3)

Figure 112013065504424-pat00003
Figure 112013065504424-pat00003

(상기 식들에서, R1, R2, 및 R3은 C1 내지 C18의 알킬기, C3 내지 C10의 시클로알킬기, C6 내지 C15의 아릴기 또는 C2 내지 C12의 불포화 탄화수소 결합을 갖는 알킬기를 나타낸다.)(In the above formulas, R 1 , R 2 , and R 3 represent a C1 to C18 alkyl group, a C3 to C10 cycloalkyl group, a C6 to C15 aryl group, or an alkyl group having a C2 to C12 unsaturated hydrocarbon bond.)

상기 코팅 조성물은 나노 무기 입자를 추가로 포함하는 것을 특징으로 한다.The coating composition is characterized by further comprising nano-inorganic particles.

상기 나노 무기 입자는 티타니아(TiO2), 안티몬틴옥사이드(ATO), 인듐틴옥사이드(ITO), 카본 나노 튜브(CNT), 삼산화 제이철(Fe2O3), 바나듐옥사이드(V2O3), 실리카 (SiO2), 산화아연(ZnO), 산화 세슘(Cs2O), 산화텅스텐(WO3), 이산화 몰르브덴(MoO2) 및 알루미나(Al2O3)로 이루어지는 군으로부터 선택되는 하나 이상임을 특징으로 한다.The nano inorganic particles are of titania (TiO 2), antimony tin oxide (ATO), indium tin oxide (ITO), carbon nanotubes (CNT), trioxide, ferric (Fe 2 O 3), vanadium oxide (V 2 O 3), silica (SiO 2), zinc oxide (ZnO), cesium oxide (Cs 2 O), tungsten oxide (WO 3), dioxide Moldova beuden (MoO 2) and alumina (Al 2 O 3) at least one member selected from the group consisting of .

상기 나노 무기 입자의 크기는 3 ~ 100nm의 범위인 것을 특징으로 한다.The size of the nano-inorganic particles is in the range of 3 to 100 nm.

필름 또는 쉬트(sheet)와의 부착력을 높이기 위하여, 상기 코팅 조성물에 3관능기 유기 알콕시실란 또는 4관능기 알콕시실란 화합물이 첨가될 수 있다.In order to increase adhesion to a film or a sheet, a trifunctional organic alkoxysilane or a four-function alkoxysilane compound may be added to the coating composition.

상기 3관능기 알콕시실란은 2-(트리메톡시실릴에틸)피리딘, (3-트리메톡시실릴프로필)디에틸렌트리아민, n-(3-트리메톡시실릴프로필)피롤, n-트리에톡시실릴프로필퀴닌우레탄, (S)-n-트리에톡시실릴프로필-오-멘토카바매이트, n-(3-트리에톡시실릴프로필)-4-하이드록시부틸아미드, n-(3-트리에톡시실릴프로필)-4,5-디하이드로이미다졸, 트리에톡시실릴프로필에틸카바매이트, 2-(트리에톡시실릴에틸)-5-(아세톡시)바이사이클로헵탄, 비닐트리-티.-부톡시실란, 비닐트리이소프로폭시실란 또는 이들의 혼합물인 것을 특징으로 한다.The trifunctional alkoxysilane may be selected from the group consisting of 2- (trimethoxysilylethyl) pyridine, (3-trimethoxysilylpropyl) diethylenetriamine, n- (3-trimethoxysilylpropyl) Propyl quinine urethane, (S) -n-triethoxysilylpropyl-o-mentocarbamate, n- (3-triethoxysilylpropyl) -4-hydroxybutylamide, n- Propyl) -4,5-dihydroimidazole, triethoxysilylpropylethyl carbamate, 2- (triethoxysilylethyl) -5- (acetoxy) bicycloheptane, vinyltri- , Vinyltriisopropoxysilane, or a mixture thereof.

상기 4관능기 알콕시실란은 비스(메틸디에톡시실릴)에탄, 비스(에틸메톡시실릴)부탄, 비스(프로필메톡시실릴)부탄, 비스(헵틸에톡시실릴)헵탄, 테트라에틸오소실리케이트, 테트라메틸오소실리케이트 또는 이들의 혼합물인 것을 특징으로 한다.The tetrafunctional alkoxysilane may be at least one selected from the group consisting of bis (methyldiethoxysilyl) ethane, bis (ethylmethoxysilyl) butane, bis (propylmethoxysilyl) butane, bis (heptylethoxysilyl) heptane, tetraethylorthosilicate, Silicates or mixtures thereof.

상기 코팅 조성물은 유리 비산 방지 필름, 안전 방범 필름, 방탄 필름 또는 실사 인쇄가 적용된 필름에 코팅하여 복합 기능성 코팅 필름을 생산할 수 있는 것을 특징으로 한다.The coating composition is characterized by being able to produce a composite functional coating film by coating on a glass shatterproof film, a security security film, a bulletproof film, or a film to which actual printing is applied.

본 발명의 코팅 필름은 하기 화학식 1로 표시되는 화합물, 하기 화학식 2로 표시되는 화합물 및 하기 화학식 3으로 표시되는 화합물로 이루어지는 랜덤 공중합체 화합물, 및 세가지 이상의 무기 산화 나노입자를 포함하는 코팅 조성물이 플라스틱필름이나 쉬트에 코팅되어 결로 방지 기능과 적외선 차단 기능을 동시에 발현하는 것을 특징으로 한다.The coating film of the present invention comprises a random copolymer compound comprising a compound represented by the following formula (1), a compound represented by the following formula (2) and a compound represented by the following formula (3), and a coating composition comprising three or more inorganic oxide nano- And is coated on a film or a sheet to simultaneously exhibit a dew condensation preventing function and an infrared ray blocking function.

[화학식 1][Chemical Formula 1]

Figure 112013065504424-pat00004
Figure 112013065504424-pat00004

[화학식 2](2)

Figure 112013065504424-pat00005
Figure 112013065504424-pat00005

[화학식 3](3)

Figure 112013065504424-pat00006

Figure 112013065504424-pat00006

(상기 식들에서, R1, R2 및 R3는 C1 내지 C18의 알킬기, C3 내지 C10의 시클로알킬기, C6 내지 C15의 아릴기 또는 C2 내지 C12의 불포화 탄화수소 결합을 갖는 알킬기를 나타낸다.)(In the above formulas, R 1 , R 2 and R 3 represent an alkyl group having a C1 to C18 alkyl group, a C3 to C10 cycloalkyl group, a C6 to C15 aryl group or a C2 to C12 unsaturated hydrocarbon bond.)

상기 무기 산화 나노입자는티타니아(TiO2), 안티몬틴옥사이드(ATO), 인듐틴옥사이드(ITO), 카본 나노 튜브(CNT), 삼산화 제이철(Fe2O3), 바나듐옥사이드(V2O3), 실리카 (SiO2), 산화아연(ZnO), 산화 세슘(Cs2O), 삼산화텅스텐(WO3), 이산화 몰르브덴(MoO2) 및 알루미나(Al2O3)로 이루어진 군으로부터 선택되는 하나 이상임을 특징으로 한다.The inorganic oxide nanoparticles may include at least one selected from the group consisting of titania (TiO 2 ), antimony tin oxide (ATO), indium tin oxide (ITO), carbon nanotube (CNT), ferric trioxide (Fe 2 O 3 ), vanadium oxide (V 2 O 3 ) , silica (SiO 2), zinc oxide (ZnO), cesium oxide (Cs 2 O), trioxide, tungsten (WO 3), dioxide Moldova beuden (MoO 2) and alumina one selected from the group consisting of (Al 2 O 3) Or more.

상기 플라스틱 필름이나 쉬트는 폴리에틸렌(PE), 폴리프로필렌(PP), 폴리스티렌(PS), 폴리염화비닐(PVC) 및 폴리메틸메타아크릴레이트(PMMA)의 폴리올레핀계 고분자, 폴리올레핀계 고분자의 공중합체 또는 축중합 고분자인 폴리에틸렌테레프탈레이트(PET), 지방족아미드 및 방향족아미드를 모두 포함하는 폴리아미드계인 것을 특징으로 한다.The plastic film or sheet may be a polyolefin-based polymer of polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC) and polymethylmethacrylate (PMMA), a copolymer or polyolefin- (PET) which is a polymeric polymer, an aliphatic amide and an aromatic amide.

또한, 본 발명의 코팅 필름의 제조 방법은 하기 화학식 1로 표시되는 화합물, 하기 화학식 2로 표시되는 화합물 및 하기 화학식 3으로 표시되는 화합물로 이루어지는 랜덤 공중합체 화합물, 및 둘 이상의 무기 산화 나노 입자를 포함하는 코팅 조성물을 플라스틱 필름이나 쉬트에 코팅하여 결로 방지 기능과 적외선 차단 기능을 부여하는 것을 특징으로 한다.The method for producing a coating film of the present invention includes a random copolymer compound comprising a compound represented by the following formula (1), a compound represented by the following formula (2) and a compound represented by the following formula (3), and two or more inorganic oxide nanoparticles Is coated on a plastic film or sheet to impart a dew condensation preventing function and an infrared ray blocking function.

[화학식 1][Chemical Formula 1]

Figure 112013065504424-pat00007
Figure 112013065504424-pat00007

[화학식 2](2)

Figure 112013065504424-pat00008
Figure 112013065504424-pat00008

[화학식 3](3)

Figure 112013065504424-pat00009
Figure 112013065504424-pat00009

(상기 식들에서, R1, R2 및 R3는 C1 내지 C18의 알킬기, C3 내지 C10의 시클로알킬기, C6 내지 C15의 아릴기 또는 C2 내지 C12의 불포화 탄화수소 결합을 갖는 알킬기를 나타낸다.)(In the above formulas, R 1 , R 2 and R 3 represent an alkyl group having a C1 to C18 alkyl group, a C3 to C10 cycloalkyl group, a C6 to C15 aryl group or a C2 to C12 unsaturated hydrocarbon bond.)

상기 코팅은 그라비아(gravure), 마이크로 그라비아(micro gravure), 슬롯 다이(slot-die) 또는 립 다이(lip-die) 코팅법을 이용하여 롤-투-롤(roll-to-roll) 방식으로 이루어지는 것을 특징으로 한다.The coating may be applied in a roll-to-roll fashion using gravure, micro gravure, slot-die or lip-die coating techniques. .

본 발명에 의하면, 결로 방지기능과 적외선 차단 기능을 동시에 발현할 수 있는 새로운 아미드기를 갖는 유기 실리콘 고분자를 기재로 하는 유-무기 복합체 코팅 조성물이 합성된다. 이러한 코팅제는 롤-투-롤 코팅 법으로 상기에 표시한 여러 종류의 필름 기재에 한 번의 코팅으로 대량 생산이 가능하게 하여 생산성 증대를 통한 원가 절감을 가능하게 하였다.According to the present invention, an organic-inorganic hybrid coating composition based on an organic silicon polymer having a novel amide group capable of simultaneously exhibiting a dew condensation preventing function and an infrared ray blocking function is synthesized. Such a coating agent can be mass-produced by coating on various types of film substrates described above by a roll-to-roll coating method, thereby making it possible to reduce costs by increasing productivity.

또한, 결로 방지기능과 적외선 차단 기능을 동시에 발현하여 건축물이나 자동차의 유리창으로 손실되는 에너지를 절약하고, 결로 현상을 방지 하여 습기로 인한 건축물이나 자동차의 2차 손상을 억제하는데 많은 기여를 할 것으로 예상된다.In addition, it is expected to contribute to the prevention of condensation and the secondary damage of buildings and automobiles due to moisture by saving the energy lost in buildings or automobile windows by simultaneously exhibiting condensation prevention function and infrared ray blocking function. do.

도 1은 실시예 3의 수 접촉각 테스트 사진을 나타낸다.
도 2는 실시예 1의 결로 방지 적외선 차단코팅 필름의 코팅 두께에 따른 적외선 차단 특성을 나타내는 그래프이다.
1 shows a water contact angle test photograph of Example 3. Fig.
FIG. 2 is a graph showing infrared blocking characteristics according to coating thickness of the anti-condensation infrared blocking coating film of Example 1. FIG.

하기 화학식 1, 하기 화학식 2 또는 하기 화학식 3으로 표시되는 아미드기를 갖는 유기 실리콘 화합물과 무기 산화 나노 입자를 이용하여 아미드기를 갖는 유-무기 하이브리드 복합 고분자를 합성하여 결로 방지 및 적외선 차단 코팅 조성물을 합성하였다. 또한 상기의 아미드기를 갖는 유-무기 하이브리드 복합 고분자 코팅 조성물을 여러 종류의 필름에 롤-투-롤 방식으로 코팅하여, 결로 방지 및 적외선 차단 코팅 필름을 1번의 코팅으로 대량 생산에 성공하였다.
Inorganic hybrid composite polymer having an amide group was synthesized using an organosilicon compound having an amide group represented by the following formula (1), (2) or (3) and inorganic oxide nanoparticles to prepare a dew condensation preventing and infrared ray blocking coating composition . In addition, the above-mentioned organic-inorganic hybrid composite coating composition having an amide group was coated on various kinds of films in a roll-to-roll manner to successfully produce a large number of anti-condensation and infrared ray-blocking coating films by one coating.

[화학식 1][Chemical Formula 1]

Figure 112013065504424-pat00010
Figure 112013065504424-pat00010

[화학식 2](2)

Figure 112013065504424-pat00011
Figure 112013065504424-pat00011

[화학식 3](3)

Figure 112013065504424-pat00012

Figure 112013065504424-pat00012

(상기 식들에서, R1, R2, 및 R3 은 C1 내지 C18의 알킬기, C3 내지 C10의 시클로알킬기, C6 내지 C15의 아릴기 또는 C2 내지 C12의 불포화 탄화수소 결합을 갖는 알킬기를 나타낸다.)(In the above formulas, R 1 , R 2 , and R 3 represent a C1 to C18 alkyl group, a C3 to C10 cycloalkyl group, a C6 to C15 aryl group, or an alkyl group having a C2 to C12 unsaturated hydrocarbon bond.)

본 발명의 핵심 기술인 결로 방지 및 적외선 차단 코팅 필름을 제조하기 위한 방법으로 아미드기를 갖는 유기 실리콘 화합물과 무기 산화 나노 입자를 이용한 아미드기를 갖는 유-무 하이브리드 실리콘 고분자 코팅 조성물을 제조하고 이를 이용하여 결로 방지 및 적외선 차단 코팅 필름을 롤-투-롤 방식으로 제조하였다. 상기 코팅필름의 제조 방법은 하기 단계에 의한다.As a method for manufacturing a dew condensation preventing and infrared ray blocking coating film which is a core technology of the present invention, an organic-silicone hybrid coating composition having an amide group using an amide group-containing organosilicon compound and inorganic oxide nanoparticles is prepared, And an infrared barrier coating film were produced in a roll-to-roll manner. The method for producing the coating film is as follows.

(a) 상기 화학식 1, 화학식 2 또는 화학식 3으로 표시되는 아미드기를 갖는 유기 실리콘 화합물을 유기용매에 혼합한 후, 무기산을 첨가하여 김서림 방지 항균 기능을 동시에 발현하는 하기 화학식 4로 표시되는 아미드기를 갖는 유-무기 하이브리드 고분자를 합성하는 단계:(a) mixing an organic silicon compound having an amide group represented by the above formula (1), (2) or (3) in an organic solvent, and then adding an inorganic acid to simultaneously express anti- The step of synthesizing the organic-inorganic hybrid polymer:

[화학식 4][Chemical Formula 4]

Figure 112013065504424-pat00013
Figure 112013065504424-pat00013

(상기 식에서, n은 100 ~ 200 범위의 정수이며, R1, R2, R3은 C1 내지 C18의 알킬기, C3 내지 C10의 시클로알킬기, C6 내지 C15의 아릴기 또는 C2 내지 C12의 불포화 탄화수소 결합을 갖는 알킬기를 나타낸다.)Wherein R 1 , R 2 and R 3 are independently selected from the group consisting of a C1 to C18 alkyl group, a C3 to C10 cycloalkyl group, a C6 to C15 aryl group or a C2 to C12 unsaturated hydrocarbon bond Lt; / RTI >

상기 화학식 1, 화학식 2 또는 화학식 3으로 표시되는 아미드기를 갖는 유기 실리콘 화합물을 총 중량의 1 내지 20배의 유기 용매의 혼합물에서 약 10~30분간 교반 후, 염산(HCl) 수용액을 총 몰수의 0.001 내지 0.02배를 넣는다. The organic silicon compound having an amide group represented by the above formula (1), (2) or (3) is stirred for about 10 to 30 minutes in a mixture of an organic solvent having a total weight of 1 to 20 times the total weight. To 0.02 times.

본 단계의 온도는 70℃ 이상이어야 반응이 진행되며, 특히 130℃ 이상으로 12시간 이상 가열하는 것이 보다 바람직하다.The reaction should be carried out at a temperature of 70 ° C or higher in this step, more preferably at 130 ° C or higher for at least 12 hours.

또한, pH는3~4에서 반응이 이루어진다.The reaction is carried out at a pH of 3 to 4.

(b) 상기 아미드화 유기 실리콘 고분자의 코팅성 및 기재에 따른 부착력을 높이기 위하여 유기 알콕시실란 화합물을 아미드화 유기 실리콘 고분자의 몰비의 약 0.01배~0.1배의 비율로 혼합하는 단계:(b) mixing the organoalkoxysilane compound in an amount of about 0.01 to 0.1 times the molar ratio of the amidated organosilicon polymer in order to increase the coating property and the adhesion of the amidated organosilicon polymer according to the substrate;

여기에서 사용되는 유기 알콕시실란 화합물은 3관능기 알콕시실란과 4관능기알콕시실란이며, 상기 3관능기알콕시실란은 2-(트리메톡시실릴에틸)피리딘, (3-트리메톡시실릴프로필)디에틸렌트리아민, n-(3-트리메톡시실릴프로필)피롤, n-트리에톡시실릴프로필퀴닌우레탄, (S)-n-트리에톡시실릴프로필-오-멘토카바매이트, n-(3-트리에톡시실릴프로필)-4-하이드록시부틸아미드, n-(3-트리에톡시실릴프로필)-4,5-디하이드로이미다졸, 트리에톡시실릴프로필에틸카바매이트, 2-(트리에톡시실릴에틸)-5-(아세톡시)바이사이클로헵탄, 비닐트리-티-부톡시실란, 비닐트리이소프로폭시실란 중 2 또는 3개의 화합물을 혼합하여 사용한다.The organic alkoxysilane compound used herein is a trifunctional alkoxysilane and a tetrafunctional alkoxysilane, and the trifunctional alkoxysilane is preferably 2- (trimethoxysilylethyl) pyridine, (3-trimethoxysilylpropyl) diethylenetriamine , n - (3-trimethoxysilylpropyl) pyrrole, n-triethoxysilylpropylquinine urethane, (S) -n-triethoxysilylpropyl-o-mentocarbamate, n- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, triethoxysilylpropylethyl carbamate, 2- (triethoxysilylethyl) -5- (acetoxy) bicycloheptane, vinyltri-thi-butoxysilane, and vinyltriisopropoxysilane are mixed and used.

또한, 상기 4관능기 알콕시실란은비스(메틸디에톡시실릴)에탄, 비스(에틸메톡시실릴)부탄, 비스(프로필메톡시실릴)부탄, 비스(헵틸에톡시실릴)헵탄, 테트라에틸오소실리케이트, 테트라메틸오소실리케이트 중 하나의 화합물을 혼합하여 사용한다.The tetrafunctional alkoxysilane may be at least one selected from the group consisting of bis (methyldiethoxysilyl) ethane, bis (ethylmethoxysilyl) butane, bis (propylmethoxysilyl) butane, bis (heptylethoxysilyl) heptane, tetraethylorthosilicate, tetra Methyl oxysilicate are mixed and used.

(c) 상기 혼합 용액을 400rpm으로 교반하면서 무기 산화 나노 입자를 서서히 첨가한 후 가열 반응시켜 최종 코팅 조성물을 완성시키는 단계:(c) slowly adding the inorganic oxide nanoparticles while stirring the mixed solution at 400 rpm, and then heating to complete the final coating composition;

여기서, 무기 산화 나노 입자는 티타니아(TiO2), 안티몬틴옥사이드(ATO), 인듐틴옥사이드(ITO), 카본 나노 튜브(CNT), 삼산화 제이철(Fe2O3), 바나듐옥사이드(V2O3), 실리카 (SiO2), 산화아연(ZnO), 산화 세슘(Cs2O), 산화텅스텐(WO3), 이산화 몰르브덴(MoO2) 및 알루미나(Al2O3)로 이루어지는 군으로부터 선택되는 하나 이상이다. 또한, 상기 무기 산화 나노 입자의 크기는 3 ~ 100nm의 범위이다.Here, the inorganic oxide nanoparticles of titania (TiO 2), antimony tin oxide (ATO), indium tin oxide (ITO), carbon nanotubes (CNT), trioxide, ferric (Fe 2 O 3), vanadium oxide (V 2 O 3 ), silica (SiO 2), zinc oxide (ZnO), cesium oxide (Cs 2 O), tungsten oxide (WO 3), dioxide Moldova beuden (MoO 2) and alumina (Al 2 O 3) selected from the group consisting of More than one. The size of the inorganic oxide nanoparticles ranges from 3 to 100 nm.

(d) 상기 코팅 조성물을 플라스틱 필름이나 쉬트에 그라비아(gravures), 마이크로 그라비아(microgravure), 슬롯 다이(slot-die) 또는 립 다이(lip-die) 코팅법을 이용하여 롤-투-롤 방식으로 코팅하여, 결로 방지및 적외선 차단 코팅 기능을 동시에 발현하는 필름 또는 쉬트(sheet)제품을 생산하는 단계:(d) applying the coating composition to a plastic film or sheet in a roll-to-roll fashion using gravures, microgravure, slot-die or lip- Coating to produce a film or sheet product that simultaneously exhibits anti-condensation and infrared barrier coating functions:

상기 플라스틱 필름이나 쉬트는 폴리에틸렌(PE), 폴리프로필렌(PP), 폴리스티렌(PS), 폴리염화비닐(PVC) 및 폴리메틸메타아크릴레이트(PMMA)의 폴리올레핀계 고분자, 폴리올레핀계 고분자의 공중합체 또는 축중합 고분자인 폴리에틸렌테레프탈레이트(PET), 지방족아미드 및 방향족아미드를 모두 포함하는 폴리아미드계인 것을 특징으로 한다.The plastic film or sheet may be a polyolefin-based polymer of polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC) and polymethylmethacrylate (PMMA), a copolymer or polyolefin- (PET) which is a polymeric polymer, an aliphatic amide and an aromatic amide.

또한, 결로 방지 및 적외선 차단 기능을 동시에 발현하는 필름 또는 쉬트 제품을 생산할 수 있다.In addition, film or sheet products that simultaneously exhibit dew condensation prevention and infrared ray blocking function can be produced.

또한, 유리창 파손 시 발생하는 유리 파편의 비산을 방지해주는 비산 방지 필름, 안전 방범 필름, 방탄 필름 및 실사 인쇄가 적용된 필름 등에도 상기 복합 기능성 코팅 조성물을 코팅하여 기능성 필름을 생산할 수 있고, 다양한 용도에 사용할 수 있다.
In addition, a functional film can be produced by coating the above-mentioned composite functional coating composition on a shatterproof film, a security crime film, a bulletproof film, and a film to which real printing is applied, which prevents scattering of glass fragments generated when a window is broken, Can be used.

이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시 예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 요지에 따라 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 당 업계에서 통상의 지식을 가진 자에 있어서 자명할 것이다.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .

화학식 1의 2관능기의 아미노산 유기 실리콘 화합물 0.1몰과 화학식 2의 3관능기 아미노산 유기 실리콘 화합물 0.5몰과 화학식 3의 3관능기 아미노산 유기 실리콘 화합물 0.5몰을 총 중량의 5배의 메틸에틸케톤, 톨루엔, 물과 염산의 혼합물에 녹인 후 약 30분간 교반한다. 여기에 화학식 1, 화학식 2와 화학식 3의 아미노산 유기 실리콘 화합물의 총 몰수의 0.02배에 해당하는 n-(3-트리에톡시실릴프로필)-4,5-디히드로이미다졸, 및 화학식 1, 화학식 2와 화학식 3의 아미노산 유기 실리콘 화합물의 총 몰수의 0.01배에 해당하는 트리에톡시실릴프로필에틸카바매이트를 10배의 중량비의 메틸에틸케톤과 톨루엔에 녹여 위 반응물에 첨가한다. 약 1시간 정도 교반한 후, 용액 고형분의 약 3%의 질량비로 10nm의 산화아연(ZnO)를 100mL/분의 속도로 서서히 적가하고, 용액 고형분의13%의 질량비로 50nm의 안티몬옥사이드(ATO)을 100mL/분의 속도로 서서히 적가하고, 용액 고형분의 15%의 질량비로 20nm의 산화세슘(Cs2O)를 100mL/분의 속도로 적가하고, 용액 고형분의 18%의 질량비로 20nm의 삼산화 텅스텐(WO3)를 100mL/분의 속도로 적가한다. 위 혼합 용액을 400rpm으로 교반하면서 130℃까지 가열하여 12시간 동안 반응시켰다. 반응 종결 후 상온으로 냉각시킨 후 중탄산나트륨을 사용하여 중화시켰다. 이 용액을 립-코터(lip-coater)를 이용하여 폴리에틸렌테레프탈레이트(PET)필름에 약 40mL/분의 속도로 코팅하여 코팅필름을 생산하였다. 0.1 mol of the amino acid organic silicon compound of the formula (1), 0.5 mol of the trifunctional amino acid organic silicon compound of the formula (2) and 0.5 mol of the trifunctional amino acid organic silicon compound of the formula (3) were dissolved in methyl ethyl ketone, toluene, And hydrochloric acid, and the mixture is stirred for about 30 minutes. (3-triethoxysilylpropyl) -4,5-dihydroimidazole corresponding to 0.02 times the total number of moles of the amino acid organosilicon compounds of formulas (1), (2) and (3) Triethoxysilylpropyl ethyl carbamate corresponding to 0.01 times the total number of moles of the amino acid organosilicon compound of formula (2) and (3) is dissolved in methyl ethyl ketone and toluene in a weight ratio of 10 times and added to the reaction product. After stirring for about 1 hour, zinc oxide (ZnO) of 10 nm was slowly added dropwise at a rate of 100 mL / min at a mass ratio of about 3% of the solid content of the solution, and 50 nm of antimony oxide (ATO) was added at a mass ratio of 13% (Cs 2 O) was added dropwise at a rate of 100 mL / min at a mass ratio of 15% of the solid content of the solution, and 20 nm of tungsten trioxide (20 nm) was added thereto at a mass ratio of 18% (WO 3 ) is added dropwise at a rate of 100 mL / min. The above mixed solution was heated to 130 DEG C while stirring at 400 rpm and reacted for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and then neutralized with sodium bicarbonate. The solution was coated on a polyethylene terephthalate (PET) film at a rate of about 40 mL / min using a lip-coater to produce a coating film.

화학식 1의 2관능기의 아미노산 유기 실리콘 화합물 0.1몰과 화학식 2의 3 관능기 아미노산 유기 실리콘 화합물 0.5몰과 화학식 3의 3관능기 아미노산 유기 실리콘 화합물 0.5몰을 총 중량의 5배의 메틸에틸케톤, 톨루엔, 물과 염산의 혼합물에 녹인 후 약 30분간 교반한다. 여기에 화학식 1, 화학식 2와 화학식 3의 아미노산 유기 실리콘 화합물의 총 몰수의 0.02배의 n-(3-트리에톡시실릴프로필)-4,5-디하이드로이미다졸, 및 화학식 1, 화학식 2와 화학식 3의 아미노산 유기 실리콘 화합물의 총 몰수의 0.01배의 트리에톡시실릴프로필에틸카바매이트를 10배의 중량비의 메틸에틸케톤과톨루엔에 녹여 위 반응물에 첨가한다. 약 1시간 정도 교반한 후, 용액 고형분의 약 5%의 질량 비로 10nm의 인듐틴옥사이드(ITO)를 100mL/분의 속도로 서서히 적가하고, 용액 고형분의 15%의 질량비로 20nm의 산화세슘(Cs2O)를 100mL/분의 속도로 적가하고, 용액 고형분의 18%의 질량비로 20nm의 삼산화 텅스텐(WO3)를 100mL/분의 속도로 적가하고, 용액 고형분의 12%의 질량비로 12nm의 안티몬틴옥사이드(ATO)를 100mL/분의 속도로 서서히 적가한다. 위 혼합 용액을 400rpm으로 교반하면서 130℃까지 가열하여 12시간 동안 반응시켰다. 반응 종결 후 상온으로 냉각시킨 후 중탄산나트륨을 사용하여 중화시켰다. 이 용액을 립-코터(lip-coater)를 이용하여 폴리에틸렌테레프탈레이트(PET)필름에 약 40mL/분의 속도로 코팅하여 코팅필름을 생산하였다.0.1 mol of the amino acid organic silicon compound of the formula (1), 0.5 mol of the trifunctional amino acid organic silicon compound of the formula (2) and 0.5 mol of the trifunctional amino acid organic silicon compound of the formula (3) were dissolved in methyl ethyl ketone, toluene, And hydrochloric acid, and the mixture is stirred for about 30 minutes. (3-triethoxysilylpropyl) -4,5-dihydroimidazole of 0.02 times the total number of moles of the amino acid organosilicon compounds of the formulas (1), (2) and (3) Triethoxysilylpropyl ethyl carbamate having a molecular weight of 0.01 times the total number of moles of the amino acid organic silicon compound of formula (3) is dissolved in methyl ethyl ketone and toluene in a weight ratio of 10 times and added to the reaction product. After stirring for about 1 hour, 10 nm of indium tin oxide (ITO) was slowly added dropwise at a mass ratio of about 5% of the solid content of the solution at a rate of 100 mL / min, and 20 nm of cesium oxide 2 O) was added dropwise at a rate of 100 mL / min, 20 nm of tungsten trioxide (WO 3 ) was added dropwise at a rate of 100 mL / min at a mass ratio of 18% of the solid content of the solution, and 12 nm of antimony Tin oxide (ATO) is added dropwise at a rate of 100 mL / min. The above mixed solution was heated to 130 DEG C while stirring at 400 rpm and reacted for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and then neutralized with sodium bicarbonate. The solution was coated on a polyethylene terephthalate (PET) film at a rate of about 40 mL / min using a lip-coater to produce a coating film.

화학식 1의 2 관능기의 아미노산 유기 실리콘 화합물 0.1몰과 화학식 2의 3 관능기 아미노산 유기 실리콘 화합물 0.5몰과 화학식 3의 3 관능기 아미노산 유기 실리콘 화합물 0.5몰을 총 중량의 5배의 메틸에틸케톤, 톨루엔, 물과 염산의 혼합물에 녹인 후 약 30분간 교반한다. 여기에 화학식 1, 화학식 2와 화학식 3의 아미노산 유기 실리콘 화합물의 총 몰수의 0.02배의 n-(3-트리에톡시실릴프로필)-4,5-디하이드로이미다졸, 및 화학식 1, 화학식 2와 화학식 3의 아미노산 유기 실리콘 화합물의 총 몰수의 0.01배의 트리에톡시실릴프로필에틸카바매이트를 10배의 중량비의 메틸에틸케톤과 톨루엔에 녹여 위 반응물에 첨가한다. 약 1시간 정도 교반한 후, 용액 고형분의 약 12%의 질량 비로 25nm의 알루미나(Al2O3)를 100mL/분의 속도로 서서히 적가하고, 용액 고형분의 15%의 질량비로 20nm의 산화세슘(Cs2O)를 100mL/분의 속도로 적가하고, 용액 고형분의 7%의 질량비로 50nm의 산화몰리브덴(MoO2)를 100mL/분의 속도로 적가하고, 용액 고형분의 18%의 질량비로 20nm의 삼산화 텅스텐(WO3)를 100mL/분의 속도로 적가한다. 위 혼합 용액을 400rpm으로 교반하면서 130℃까지 가열하여 12시간 동안 반응시켰다. 반응 종결 후 상온으로 냉각시킨 후 중탄산나트륨을 사용하여 중화시켰다. 이 용액을 립-코터(lip-coater)를 이용하여 폴리에틸렌테레프탈레이트(PET)필름에 약 40mL/분의 속도로 코팅하여 코팅필름을 생산하였다.0.1 mol of the amino acid organic silicon compound of the formula (1), 0.5 mol of the trifunctional amino acid organic silicon compound of the formula (2) and 0.5 mol of the trifunctional amino acid organic silicon compound of the formula (3) were dissolved in methyl ethyl ketone, toluene, And hydrochloric acid, and the mixture is stirred for about 30 minutes. (3-triethoxysilylpropyl) -4,5-dihydroimidazole of 0.02 times the total number of moles of the amino acid organosilicon compounds of the formulas (1), (2) and (3) Triethoxysilylpropyl ethyl carbamate having a molecular weight of 0.01 times the total number of moles of the amino acid organic silicon compound of formula (3) is dissolved in methyl ethyl ketone and toluene in a weight ratio of 10 times and added to the reaction product. After stirring for about 1 hour, 25 nm of alumina (Al 2 O 3 ) was slowly added dropwise at a mass ratio of about 12% of the solid content of the solution at a rate of 100 mL / min, and 20 nm of cesium oxide Cs 2 O) was added dropwise at a rate of 100 mL / min, and 50 nm of molybdenum oxide (MoO 2 ) was added dropwise at a rate of 100 mL / min at a mass ratio of 7% of the solid content of the solution. Tungsten trioxide (WO 3 ) is added dropwise at a rate of 100 mL / min. The above mixed solution was heated to 130 DEG C while stirring at 400 rpm and reacted for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and then neutralized with sodium bicarbonate. The solution was coated on a polyethylene terephthalate (PET) film at a rate of about 40 mL / min using a lip-coater to produce a coating film.

화학식 1의 2 관능기의 아미노산 유기 실리콘 화합물 0.1몰과 화학식 2의 3관능기 아미노산 유기 실리콘 화합물 0.5몰과 화학식 3의 3관능기 아미노산 유기 실리콘 화합물 0.5몰을 총 중량의 5배의 메틸에틸케톤, 톨루엔, 물과 염산의 혼합물에 녹인 후 약 30분간 교반한다. 여기에 화학식 1, 화학식 2와 화학식 3의 아미노산 유기 실리콘 화합물의 총 몰수의 0.02배의 n-(3-트리에톡시실릴프로필)-4,5-디하이드로이미다졸(n-(3-Triethoxysilylpropyl)-4,5-dihydroimidazole) 및 화학식 1, 화학식 2와 화학식 3의 아미노산 유기 실리콘 화합물의 총 몰수의 0.01배의 트리에톡시실릴프로필에틸카바매이트(Triethoxysilylpropylethylcarbamate)를 10배의 중량비의 메틸에틸케톤과 톨루엔에 녹여 위 반응물에 첨가한다. 약 1시간 정도 교반한 후, 용액 고형분의 약 11%의 질량비로 34nm의 실리카(SiO2)를 100mL/분의 속도로 서서히 적가하고, 용액 고형분의 15%의 질량비로 20nm의 산화세슘(Cs2O)를 100mL/분의 속도로 적가하고, 용액 고형분의 18%의 질량비로 20nm의 삼산화 텅스텐(WO3)를 100mL/분의 속도로 적가한다. 용액 고형분의 12%의 질량비로 41nm의 오산화바나듐(V2O5)를 100mL/분의 속도로 서서히 적가한다. 위 혼합 용액을 400rpm으로 교반하면서 130℃까지 가열하여 12시간 동안 반응시켰다. 반응 종결 후 상온으로 냉각시킨 후 중탄산나트륨을 사용하여 중화시켰다. 이 용액을 립-코터(lip-coater)를 이용하여 폴리에틸렌테레프탈레이트(PET)필름에 약 40mL/분의 속도로 코팅하여 코팅필름을 생산하였다.0.1 mol of the amino acid organic silicon compound of the formula (1), 0.5 mol of the trifunctional amino acid organic silicon compound of the formula (2) and 0.5 mol of the trifunctional amino acid organic silicon compound of the formula (3) were dissolved in methyl ethyl ketone, toluene, And hydrochloric acid, and the mixture is stirred for about 30 minutes. (3-triethoxysilylpropyl) -4,5-dihydroimidazole of 0.02 times the total number of moles of the amino acid organosilicon compounds of the formulas (1), (2) and (3) -4,5-dihydroimidazole) and triethoxysilylpropylethylcarbamate (triethoxysilylpropylethylcarbamate) in an amount of 0.01 times the total number of moles of the amino acid organosilicon compounds of the formulas (1), (2) and (3) were dissolved in methyl ethyl ketone and toluene And added to the above reaction product. After about 1 hour of stirring, 34 nm of silica (SiO 2 ) was slowly added dropwise at a rate of 100 mL / min at a mass ratio of about 11% of the solid content of the solution, and 20 nm cesium oxide (Cs 2 O) is added dropwise at a rate of 100 mL / min, and 20 nm of tungsten trioxide (WO 3 ) is added dropwise at a rate of 100 mL / min at a mass ratio of 18% of the solid content of the solution. Vanadium pentoxide (V 2 O 5 ) at 41 nm is slowly added dropwise at a rate of 100 mL / min at a mass ratio of 12% of the solid content of the solution. The above mixed solution was heated to 130 DEG C while stirring at 400 rpm and reacted for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and then neutralized with sodium bicarbonate. The solution was coated on a polyethylene terephthalate (PET) film at a rate of about 40 mL / min using a lip-coater to produce a coating film.

결로 방지 및 적외선 차단 기능을 보유하고 있는 첨가물질은 그 범위가 제한되지 않으며, 티타니아(TiO2), 안티몬틴옥사이드(ATO), 인듐틴옥사이드(ITO), 카본 나노 튜브(CNT), 삼산화 제이철(Fe2O3), 바나듐옥사이드(V2O3), 실리카 (SiO2), 산화아연(ZnO), 산화 세슘(Cs2O), 산화텅스텐(WO3), 이산화 몰르브덴(MoO2) 또는 알루미나(Al2O3)와 같은 무기 산화 나노 입자를 포함할 수 있으며, 나노 무기 입자의 크기는 3 ~ 100nm의 범위인 것이 포함될 수 있다.
The additive materials that have anti-condensation and infrared ray blocking function are not limited in their range, and include TiO 2 , antimony tin oxide (ATO), indium tin oxide (ITO), carbon nanotube (CNT) Fe 2 O 3), vanadium oxide (V 2 O 3), silica (SiO 2), zinc (ZnO), cesium oxide (Cs 2 O), tungsten oxide (WO 3), dioxide Moldova beuden (MoO 2) or And inorganic oxide nanoparticles such as alumina (Al 2 O 3 ). The size of the nano-inorganic particles may be in the range of 3 to 100 nm.

[시험예][Test Example]

실시예 1내지 4에서 제조된 코팅 필름의 가시광 투과율(%), 적외선 차단율(%), 표면경도 및 수 접촉각을 측정한 결과는 하기 [표 1]과 같다.
The visible light transmittance (%), the infrared cut-off rate (%), the surface hardness and the water contact angle of the coating films prepared in Examples 1 to 4 are shown in Table 1 below.

시편Psalter 가시광선 투과율(%)Visible light transmittance (%) 적외선 차단율(%) (780nm~2500nm)Infrared cutoff (%) (780nm ~ 2500nm) 연필경도Pencil hardness 수 접촉각Water contact angle 실시예 1Example 1 65%65% 86%86% 2H2H 15°15 ° 실시예 2Example 2 70%70% 78%78% 2H2H 16°16 ° 실시예 3Example 3 40%40% 60%60% 2H2H 11°11 ° 실시예 4Example 4 35%35% 67%67% 2H2H 10°10 °

* 가시광 투과율은 380nm~780nm범위를 측정하였다.* Visible light transmittance was measured in the range of 380 nm to 780 nm.

** 모든 실시예의 코팅 두께는 3~4㎛로 정하였다.
** The coating thicknesses of all examples were set at 3-4 μm.

상기 표 1에 의하면, 본원발명의 코팅필름은 높은 적외선 차단율 및 고친수성의 특성을 가지므로, 본원발명의 코팅필름은 무기 산화 나노 입자들의 종류 및 특성에 따라서 결로 방지 및 적외선 차단 기능을 동시에 모두 발현하는 우수한 특징이 있음을 알 수 있다.
According to the above Table 1, since the coating film of the present invention has high infrared ray blocking rate and high hydrophilicity, the coating film of the present invention exhibits both anti-condensation and infrared ray blocking functions simultaneously depending on the kind and characteristics of the inorganic oxide nanoparticles It can be seen that there are excellent features of

또한, 실시예 1 내지 4에서 제조된 코팅 필름의 500시간 촉진 내후성 시험 방법에 따른 색 변화율(%)을 측정한 데이터를 [표 2] 및 [표 3]에 정리 하였다.
The data of the color change rate (%) according to the 500-hour accelerated weathering test of the coating films prepared in Examples 1 to 4 are summarized in [Table 2] and [Table 3].

초기Early 100hr100hr 300hr300hr 500hr500 hr 실시예 1Example 1 65.30%65.30% 66.70%66.70% 66.80%66.80% 66.90%66.90% 실시예 2Example 2 70.10%70.10% 71.30%71.30% 71.50%71.50% 71.70%71.70% 실시예 3Example 3 40.50%40.50% 41.70%41.70% 41.90%41.90% 42.00%42.00% 실시예 4Example 4 35.40%35.40% 36.50%36.50% 36.70%36.70% 36.9%36.9%

* 시험 방법: ASTM G 155:2005, KS L 2016:2007 * Test method: ASTM G 155: 2005, KS L 2016: 2007

** 가시광선 투과율 파장 500nm 기준
** Visible light transmittance based on wavelength 500nm

초기Early 100hr100hr 300hr300hr 500hr500 hr 실시예 1Example 1 91.10%91.10% 89.80%89.80% 89.70%89.70% 89.60%89.60% 실시예 2Example 2 83.00%83.00% 82.20%82.20% 82.10%82.10% 81.90%81.90% 실시예 3Example 3 65.20%65.20% 63.70%63.70% 63.40%63.40% 63.30%63.30% 실시예 4Example 4 74.90%74.90% 73.70%73.70% 73.40%73.40% 73.20%73.20%

* 시험 방법: ASTM G 155:2005, KS L 2016:2007 * Test method: ASTM G 155: 2005, KS L 2016: 2007

** 적외선 차단율 파장 1000nm 기준** Infrared cutoff wavelength based on 1000nm wavelength

상기 표 2 및 표 3에 의하면, 본원발명의 코팅필름은 500hr 제논 램프 촉진 내후성 시험 후에도 가시 광선 및 적외선 영역에서 색 변화율이 3% 미만으로 무기 산화 입자의 높은 내후성 특성을 잘 나타냄을 알 수 있다.According to Tables 2 and 3, the coating film of the present invention exhibits high weatherability of inorganic oxide particles with a color change rate of less than 3% in visible and infrared regions even after 500 hr of xenon lamp promoting weathering test.

Claims (12)

하기 화학식 1로 표시되는 화합물, 하기 화학식 2로 표시되는 화합물 및 하기 화학식 3으로 표시되는 화합물로 이루어지는 랜덤 공중합체와 산화 세슘(Cs2O) 무기입자 및 산화텅스텐(WO3) 무기입자를 포함하는 코팅 조성물이 플라스틱 필름이나 쉬트에 코팅되어 형성되고, 상기 산화 세슘(Cs2O) 무기입자의 함량은 코팅 조성물 용액 고형분의 15 질량%, 그리고 상기 산화텅스텐(WO3) 무기입자의 함량은 코팅 조성물 용액 고형분의 18 질량%로 이루어져, 결로 방지 기능과 적외선 차단 기능을 동시에 발현하는 코팅 필름.
[화학식 1]
Figure 112014026585050-pat00014

[화학식 2]
Figure 112014026585050-pat00015

[화학식 3]
Figure 112014026585050-pat00016

(상기 식들에서, R1, R2 및 R3은 C1 내지 C18의 알킬기, C3 내지 C10의 시클로알킬기, C6 내지 C15의 아릴기 또는 C2 내지 C12의 불포화 탄화수소 결합을 갖는 알킬기를 나타낸다.)
(Cs 2 O) inorganic particles and tungsten oxide (WO 3 ) inorganic particles comprising a random copolymer comprising a compound represented by the following formula (1), a compound represented by the following formula (2) and a compound represented by the following formula The content of the cesium oxide (Cs 2 O) inorganic particles is 15% by mass of the solid content of the coating composition solution, and the content of the inorganic particles of tungsten oxide (WO 3 ) And 18% by mass of the solid content of the solution, thereby simultaneously exhibiting a dew condensation preventing function and an infrared ray blocking function.
[Chemical Formula 1]
Figure 112014026585050-pat00014

(2)
Figure 112014026585050-pat00015

(3)
Figure 112014026585050-pat00016

(In the above formulas, R 1 , R 2 and R 3 represent an alkyl group having a C1 to C18 alkyl group, a C3 to C10 cycloalkyl group, a C6 to C15 aryl group or a C2 to C12 unsaturated hydrocarbon bond.)
제 1항에 있어서,
필름 또는 쉬트(sheet)와의 부착력을 높이기 위하여, 상기 코팅 조성물에 3 관능기 알콕시실란 또는 4 관능기 알콕시실란 화합물이 첨가되는 것을 특징으로 하는 코팅 필름.
The method according to claim 1,
Characterized in that a trifunctional alkoxysilane or a tetrafunctional alkoxysilane compound is added to the coating composition in order to increase adhesion to a film or a sheet.
제 2항에 있어서,
상기 3 관능기 알콕시실란은 2-(트리메톡시실릴에틸)피리딘, (3-트리메톡시실릴프로필)디에틸렌트리아민, n-(3-트리메톡시실릴프로필)피롤, n-트리에톡시실릴프로필퀴닌우레탄, (S)-n-트리에톡시실릴프로필-오-멘토카바매이트, n-(3-트리에톡시실릴프로필)-4-하이드록시부틸아미드, n-(3-트리에톡시실릴프로필)-4,5-디하이드로이미다졸, 트리에톡시실릴프로필에틸카바매이트, 2-(트리에톡시실릴에틸)-5-(아세톡시)바이사이클로헵탄, 비닐트리-티-부톡시실란, 비닐트리이소프로폭시실란 또는 이들의 혼합물인 것을 특징으로 하는 코팅 필름.
3. The method of claim 2,
The trifunctional alkoxysilane may be selected from the group consisting of 2- (trimethoxysilylethyl) pyridine, (3-trimethoxysilylpropyl) diethylenetriamine, n- (3-trimethoxysilylpropyl) Propyl quinine urethane, (S) -n-triethoxysilylpropyl-o-mentocarbamate, n- (3-triethoxysilylpropyl) -4-hydroxybutylamide, n- Propyl) -4,5-dihydroimidazole, triethoxysilylpropylethyl carbamate, 2- (triethoxysilylethyl) -5- (acetoxy) bicycloheptane, vinyltri- Vinyltriisopropoxysilane, or a mixture thereof.
제 2항에 있어서,
상기 4관능기 알콕시실란은 비스(메틸디에톡시실릴)에탄, 비스(에틸메톡시실릴)부탄, 비스(프로필메톡시실릴)부탄, 비스(헵틸에톡시실릴)헵탄, 테트라에틸오소실리케이트, 테트라메틸오소실리케이트 또는 이들의 혼합물인 것을 특징으로 하는 코팅 필름.
3. The method of claim 2,
The tetrafunctional alkoxysilane may be at least one selected from the group consisting of bis (methyldiethoxysilyl) ethane, bis (ethylmethoxysilyl) butane, bis (propylmethoxysilyl) butane, bis (heptylethoxysilyl) heptane, tetraethylorthosilicate, Silicate, or a mixture thereof.
제 1항에 있어서,
상기 코팅 조성물은 티타니아(TiO2), 안티몬틴옥사이드(ATO), 인듐틴옥사이드(ITO), 카본 나노 튜브(CNT), 삼산화 제이철(Fe2O3), 바나듐옥사이드(V2O3), 실리카 (SiO2), 산화아연(ZnO), 알루미나(Al2O3), 이산화 몰르브덴(MoO2) 또는 이들의 혼합물인 나노 무기 입자를 추가로 포함하는 것을 특징으로 하는 코팅 필름.
The method according to claim 1,
The coating composition may comprise at least one selected from the group consisting of titania (TiO 2 ), antimony tin oxide (ATO), indium tin oxide (ITO), carbon nanotubes (CNT), ferric trioxide (Fe 2 O 3 ), vanadium oxide (V 2 O 3 ) Wherein the coating film further comprises nano-inorganic particles which are silicon oxide (SiO 2 ), zinc oxide (ZnO), alumina (Al 2 O 3 ), molybdenum dioxide (MoO 2 ) or a mixture thereof.
삭제delete 제 5항에 있어서,
상기 나노 무기 입자의 크기는 3 ~ 100nm의 범위인 것을 특징으로 하는 코팅 필름.
6. The method of claim 5,
Wherein the size of the nano-inorganic particles is in the range of 3 to 100 nm.
삭제delete 삭제delete 제 1항에 있어서
상기 플라스틱 필름이나 쉬트는 폴리에틸렌(PE), 폴리프로필렌(PP), 폴리스티렌(PS), 폴리염화비닐(PVC) 및 폴리메틸메타아크릴레이트(PMMA)의 폴리올레핀계 고분자, 폴리올레핀계 고분자의 공중합체 또는 축중합 고분자인 폴리에틸렌테레프탈레이트(PET), 지방족아미드 및 방향족아미드를 모두 포함하는 폴리아미드계인 것을 특징으로 하는 코팅 필름.
The method of claim 1, wherein
The plastic film or sheet may be a polyolefin-based polymer of polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC) and polymethylmethacrylate (PMMA), a copolymer or polyolefin- A coating film characterized by being a polyamide-based polymer including both polyethylene terephthalate (PET), an aliphatic amide, and an aromatic amide.
제 1항에 기재된 코팅 필름을 제조하는 방법에 있어서,
상기 코팅은 그라비아(gravures), 마이크로 그라비아(microgravure), 슬롯 다이(slot-die) 또는 립 다이(lip-die) 코팅법을 이용하여 롤-투-롤 방식으로 이루어지는 것을 특징으로 하는 코팅필름을 제조하는 방법.
A method for producing a coating film according to claim 1,
Characterized in that the coating is performed in a roll-to-roll fashion using gravures, microgravures, slot-die or lip-die coating methods. How to.
제 1항 내지 제 5항 및 제 7항 중 어느 한 항에 있어서,
상기 코팅 조성물은 유리 비산 방지 필름, 안전 방범 필름, 방탄 필름 또는 실사 인쇄가 적용된 필름에 코팅하여 복합 기능성 코팅 필름을 생산할 수 있는 것을 특징으로 하는 코팅 필름.
8. The method according to any one of claims 1 to 5 and 7,
Wherein the coating composition is capable of producing a composite functional coating film by coating on a glass shatterproof film, a security security film, a bulletproof film, or a film to which real printing is applied.
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