TWI663223B - Solvent-free photocurable inkjet composition and transparent cured film - Google Patents

Solvent-free photocurable inkjet composition and transparent cured film Download PDF

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TWI663223B
TWI663223B TW106133471A TW106133471A TWI663223B TW I663223 B TWI663223 B TW I663223B TW 106133471 A TW106133471 A TW 106133471A TW 106133471 A TW106133471 A TW 106133471A TW I663223 B TWI663223 B TW I663223B
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alkyl
solvent
substituted
inkjet composition
light
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TW201819554A (en
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朴陳圭
權純昱
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南韓商胡網加成股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C08L2203/162—Applications used for films sealable films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Polymerisation Methods In General (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

提供了一種不含溶劑的可光固化的噴墨組合物。該噴墨組合物是環境友善的，可以被應用於噴墨程序，且具有良好的物理特性諸如透光率、耐熱性、對無機屏障層的黏附性、噴射穩定性以及儲存穩定性。該噴墨組合物可以用於提供具有增强的表面固化程度的透光的固化薄膜。因此，該噴墨組合物可以被有效地用作保護材料或封裝劑以提供用於顯示器的製造程序中的電子設備。A solvent-free, photocurable inkjet composition is provided. The inkjet composition is environmentally friendly, can be applied to an inkjet process, and has good physical properties such as light transmittance, heat resistance, adhesion to an inorganic barrier layer, ejection stability, and storage stability. The inkjet composition can be used to provide a light-transmissive cured film having an enhanced degree of surface curing. Therefore, the inkjet composition can be effectively used as a protective material or an encapsulant to provide an electronic device used in a manufacturing process of a display.

Description

不含溶劑的可光固化的噴墨組合物和透光的固化膜Solvent-free photocurable inkjet composition and light-transmissive cured film

本發明涉及一種不含溶劑的可光固化的噴墨組合物以及使用該噴墨組合物形成的透光的固化膜，該噴墨組合物是環境友善的，可以被應用於噴墨程序，且具有極佳的物理特性，諸如透光率(transmittance)、耐熱性，對無機屏障層的黏附性、噴射穩定性以及儲存穩定性。更具體地，本發明涉及可以用於提供具有增强的表面固化程度的透光的固化膜，且因而適於用作顯示器的製造程序中的保護材料(overcoat material)或封裝劑的不含溶劑的可光固化的噴墨組合物，以及使用該噴墨組合物形成的透光的固化膜。The invention relates to a solvent-free photocurable inkjet composition and a light-transmissive cured film formed using the inkjet composition. The inkjet composition is environmentally friendly and can be applied to an inkjet process. It has excellent physical properties, such as transmittance, heat resistance, adhesion to inorganic barrier layers, spray stability, and storage stability. More specifically, the present invention relates to a solvent-free curing film that can be used to provide a light-transmissive cured film having an enhanced degree of surface curing, and is therefore suitable for use as an overcoat material or an encapsulant in the manufacturing process of a display. A photocurable inkjet composition, and a light-transmissive cured film formed using the inkjet composition.

噴墨程序廣泛用於製造濾光片和液晶顯示器、有機發光顯示器、電漿顯示器以及其他顯示器的多個互聯件。The inkjet process is widely used to manufacture filters and multiple interconnects of liquid crystal displays, organic light emitting displays, plasma displays, and other displays.

在典型的噴墨程序中，液體原材料使用諸如噴墨印刷機的合適的印刷設備沿著預先設計的圖案被印刷在基材上，且隨後被乾燥形成期望的薄膜。與其他常規程序相比，噴墨程序需要使用非常少量的材料，且因而就經濟效率和環境友善性而言被認爲是革新性的。In a typical inkjet process, a liquid raw material is printed on a substrate along a predesigned pattern using a suitable printing device such as an inkjet printer, and then dried to form a desired film. Compared to other conventional procedures, inkjet procedures require a very small amount of material and are therefore considered innovative in terms of economic efficiency and environmental friendliness.

蠟油墨、基於有機溶劑的油墨、水基油墨以及可光固化的油墨被用在噴墨設備中。蠟油墨在室溫下是固體。可光固化的油墨在受光照射時被固化。許多基於溶劑的油墨已為習知。例如，韓國專利公開第2016-7009125號公開了一種基於溶劑的噴墨油墨，其含有至少一種顔料、有機溶劑、黏合劑樹脂以及分散劑，其中分散劑具有5,000到小於50,000的重均分子量(Mw)、5到20 mgKOH/g的酸值以及5到50 mgKOH/g的胺值。然而，此基於溶劑的油墨不是環境友善的，原因是需要透過乾燥去除溶劑。Wax inks, organic solvent-based inks, water-based inks, and photocurable inks are used in inkjet equipment. Wax inks are solid at room temperature. Photocurable inks are cured when exposed to light. Many solvent-based inks are known. For example, Korean Patent Publication No. 2016-7009125 discloses a solvent-based inkjet ink containing at least one pigment, an organic solvent, a binder resin, and a dispersant, wherein the dispersant has a weight average molecular weight (Mw ), An acid value of 5 to 20 mgKOH / g, and an amine value of 5 to 50 mgKOH / g. However, this solvent-based ink is not environmentally friendly because the solvent needs to be removed by drying.

基於此原因，對可以應用於噴墨程序的不含溶劑的透光的可光聚合的油墨存在需求。透光的油墨通常被用作顯示器製造程序中的保護材料或封裝劑。保護層和封裝膜覆蓋下面的層以維持下面的層的高度在一致的水平。保護層和封裝膜的另一個作用是保護下面的層免受熱和化學品的影響。此外，保護層和封裝膜需要具有足以防止透光的薄膜在後處理加工期間變性的固有特徵。For this reason, there is a need for solvent-free, light-transmittable photopolymerizable inks that can be applied to inkjet processes. Light-transmitting inks are often used as protective materials or encapsulants in display manufacturing processes. The protective layer and the packaging film cover the underlying layers to maintain the height of the underlying layers at a consistent level. Another role of protective layers and packaging films is to protect the underlying layers from heat and chemicals. In addition, the protective layer and the packaging film need to have inherent characteristics sufficient to prevent the light-transmitting thin film from being denatured during post-processing processing.

然而，空氣中的氧或水淬滅來自不含溶劑的透光油墨中的自由基。此自由基淬滅使得使用不含溶劑的透光油墨形成的固化膜的表面固化的程度變劣。However, oxygen or water in the air quenches free radicals from solvent-free light-transmitting inks. This radical quenching deteriorates the degree of surface curing of a cured film formed using a solvent-free light-transmitting ink.

本發明的一個目的是提供一種包含光響應氣體發生劑的、不含溶劑的可光固化的噴墨組合物，該組合物可以被應用於噴墨程序中，具有良好的噴射穩定性，受光照射時産生氣體以及可以透過該氣體的作用增强固化膜的表面固化程度。本發明的另外的目的是提供一種不含溶劑的噴墨組合物的透光的固化膜。An object of the present invention is to provide a solvent-free, photocurable inkjet composition containing a photoresponsive gas generating agent. The composition can be used in an inkjet process, has good ejection stability, and is exposed to light. A gas is generated from time to time and the effect of permeating the gas can enhance the degree of surface curing of the cured film. Another object of the present invention is to provide a light-transmissive cured film of a solvent-free inkjet composition.

本發明的一個方面提供了包含(A)光響應氣體發生劑的不含溶劑的可光固化的噴墨組合物，所述光響應氣體發生劑由含雜原子的主鏈和結合到主鏈的且含有至少一個氮原子的支鏈組成，其中光響應氣體發生劑(A)在受到光照射時産生氣體。One aspect of the present invention provides a solvent-free photocurable inkjet composition comprising (A) a light-responsive gas generating agent consisting of a heteroatom-containing backbone and a In addition, the composition includes a branched chain containing at least one nitrogen atom, and the photo-responsive gas generating agent (A) generates a gas when irradiated with light.

本發明的另外的方面提供了一種用於光聚合含有烯屬不飽和雙鍵的化合物的方法，該方法包括用150 nm到600 nm波長範圍內的電磁輻射照射該組合物，其中由光照射産生的氣體的作用提供了增强的表面固化程度。Another aspect of the present invention provides a method for photopolymerizing a compound containing an ethylenically unsaturated double bond, the method comprising irradiating the composition with electromagnetic radiation in a wavelength range of 150 nm to 600 nm, wherein The effect of the gas provides an enhanced degree of surface curing.

本發明的另一個方面提供了一種電子設備，該電子設備在其一個或更多個表面上包括組合物的透光的固化膜。Another aspect of the invention provides an electronic device that includes a light-transmissive cured film of the composition on one or more surfaces thereof.

本發明的不含溶劑的可光固化的噴墨組合物可以被用於噴墨程序中，且具有就透光率、耐熱性、對無機屏障層的黏附性、噴射穩定性以及儲存穩定性而言極佳的物理特性。此外，本發明的不含溶劑的可光固化的噴墨組合物使薄膜表面上的自由基淬滅最小化，這確保了透光的固化膜的增强的表面固化程度。The solvent-free photocurable inkjet composition of the present invention can be used in an inkjet process, and has the advantages of light transmittance, heat resistance, adhesion to an inorganic barrier layer, ejection stability, and storage stability. Excellent physical properties. In addition, the solvent-free photocurable inkjet composition of the present invention minimizes radical quenching on the film surface, which ensures an enhanced degree of surface curing of the light-transmissive cured film.

現在將更詳細地描述本發明。The present invention will now be described in more detail.

根據本發明一個方面的不含溶劑的可光固化的噴墨組合物包括(A)光響應氣體發生劑，其在受到光照射時産生氣體。The solvent-free photocurable inkjet composition according to one aspect of the present invention includes (A) a photo-responsive gas generating agent that generates a gas when exposed to light.

光響應氣體發生劑指的是在受到光照射時産生氣體的材料。例如，光響應氣體發生劑可以具有作爲基本結構的(酮)肟酯部分。在此情形中，光響應氣體發生劑在受到光照射時産生CO2 氣體，如反應1所描述的： The photo-responsive gas generating agent refers to a material that generates a gas when irradiated with light. For example, the photo-responsive gas generating agent may have a (keto) oxime ester moiety as a basic structure. In this case, the photo-responsive gas generating agent generates CO 2 gas when exposed to light, as described in Reaction 1:

CO2 氣體有效地保護與空氣中的水接觸時産生的自由基，因此可以抑制自由基的淬滅，實現了使用不含溶劑的組合物形成的固化膜的表面固化程度的增强。The CO 2 gas effectively protects free radicals generated when it comes into contact with water in the air, so quenching of the free radicals can be suppressed, and the degree of surface curing of a cured film formed using a composition containing no solvent is enhanced.

在一個實施方式中，光響應氣體發生劑由含雜原子的主鏈和結合到主鏈的且含有至少一個氮原子的支鏈組成。含雜原子的主鏈並不受限制且可以，例如具有苯并咔唑部分或苯基硫代苯基部分。In one embodiment, the photo-responsive gas generating agent is composed of a heteroatom-containing main chain and a branch chain bound to the main chain and containing at least one nitrogen atom. The heteroatom-containing main chain is not limited and may, for example, have a benzocarbazole moiety or a phenylthiophenyl moiety.

支鏈可以具有由式1表示的結構：(1) 其中X是CO或直接鍵(即X不存在或是CO連接基)， R1 是氫、C3 -C8 環烷基、C2 -C5 烯基、C1 -C20 烷氧基或未被取代的或被鹵素、苯基、C1 -C20 烷基苯基以及CN中的一個或更多個取代的C1 -C20 烷基；R1 選自苯基和萘基，它們中的每一個是未被取代的或被C1 -C6 烷基、C1 -C4 鹵代烷基、鹵素、CN、OR4 、SR5 和/或NR6 R7 中的一個或更多個取代的；或R1 是C3 -C20 雜芳基、C1 -C8 烷氧基、未被取代的或被C1 -C6 烷基、C1 -C4 鹵代烷基和/或鹵素中的一個或更多個取代的苄氧基，或未被取代的或被C1 -C6 烷基、C1 -C4 鹵代烷基和/或鹵素中的一個或更多個取代的苯氧基， R2 選自C6 -C20 芳基和C3 -C20 雜芳基，它們中的每一個是未被取代的或被苯基、鹵素、C1 -C4 鹵代烷基、CN、NO2 、OR4 、SR5 、NR6 R7 、PO(OCk H2k+1 )2 、SO-C1 -C10 烷基、SO2 -C1 -C10 烷基以及由O、S以及NR13 中的一個或更多個中斷的C2 -C20 烷基中的一個或更多個取代的，或它們中的每一個是未被取代的或被鹵素、COOR4 、CONR6 R7 、苯基、C3 -C8 環烷基、C3 -C20 雜芳基、C6 -C20 芳氧基羰基、C3 -C20 雜芳氧基羰基、OR4 、SR5 ，以及被NR6 R7 取代的C1 -C20 烷基中的一個或更多個取代的；R2 是氫，C2 -C12 烯基或任選地被O、CO以及NR13 中的一個或更多個中斷的C3 -C8 環烷基；R2 是未被取代的或被鹵素、OR4 、SR5 、C3 -C8 環烷基、C3 -C20 雜芳基、C6 -C20 芳氧基羰基、C3 -C20 雜芳氧基羰基、NR6 R7 、COOR4 、CONR6 R7 、PO(OCk H2k+1 )2 、、以及苯基中的一個或更多個取代的C1 -C20 烷基，烷基是被C1 -C20 鹵素、C1 -C20 烷基、C1 -C4 鹵代烷基、OR4 、SR5 或被NR6 R7 取代的苯基取代的；R2 是由O、SO以及SO2 中的一個或更多個中斷的且未被取代的或被鹵素、OR4 、COOR4 、CONR6 R7 、苯基、以及被OR4 、SR5 或NR6 R7 取代的苯基中的一個或更多個取代的C2 -C20 烷基；R2 是C2 -C20 烷醯基或是未被取代的或被C1 -C6 烷基、鹵素、苯基、OR4 、SR5 以及NR6 R7 中的一個或更多個取代的苄醯基；R2 是未被取代的或被一個或更多個OR4 取代的萘甲醯基或是C3 -C14 雜芳基羰基；R2 是任選地由一個或更多個O中斷的且未被取代的或被一個或更多個羥基取代的C2 -C12 烷氧基羰基；R2 是未被取代的或被C1 -C6 烷基、鹵素、C1 -C4 鹵代烷基、苯基、OR4 、SR5 以及NR6 R7 中的一個或更多個取代的苯氧基羰基；R2 是CN、CONR6 R7 、NO2 、C1 -C4 鹵代烷基或S(O)m -C1 -C6 烷基；R2 是未被取代的或被C1 -C12 烷基取代的S(O)m -苯基或SO2 -C1 -C6 烷基；R2 是未被取代的或被C1 -C12 烷基取代的SO2 O-苯基；或R2 是二苯基膦醯基或二(C1 -C4 烷氧基)-膦醯基， m是1或2， R’1 具有關於R1 給出的意義中的一個， R’2 具有關於R2 給出的意義中的一個， X1 是O、S、SO或SO2 ， X2 是O、CO、S或直接鍵， R3 選自C6 -C20 芳基和C3 -C20 雜芳基，它們中的每一個是未被取代的或被苯基、鹵素、C1 -C4 鹵代烷基、CN、NO2 、OR4 、SR5 、NR6 R7 以及由O、S以及NR13 中的一個或更多個中斷的C1 -C20 烷基中的一個或更多個取代的，或它們中的每一個是未被取代的或被鹵素、COOR4 、CONR6 R7 、苯基、C3 -C8 環烷基、C3 -C20 雜芳基、C6 -C20 芳基氧羰基、C3 -C20 雜芳基氧羰基、OR4 、SR5 以及被NR6 R7 取代的C1 -C20 烷基中的一個或更多個取代的；R3 是氫或被鹵素、苯基、OH、SH、CN、C3 -C6 烯氧基、OCH2 CH2 CN、OCH2 CH2 (CO)O(C1 -C4 烷基)、O(CO)-(C1 -C4 烷基)、O(CO)-苯基、(CO)OH以及(CO)O(C1 -C4 烷基)中的一個或更多個取代的C1 -C20 烷基；或R3 是被O、S以及R13 中的一個或更多個取代的C2 -C12 烷基；R3 是(CH2 CH2 O)n+1 H、(CH2 CH2 O)n (CO)-(C1 -C8 烷基)、C2 -C12 烯基或C3 -C8 環烷基；或R3 是被SR5 取代的苯基(其中自由基R5 表示至咔唑部分的苯基或萘基環的連接有COR3 的直接鍵， n是1到20的整數， R4 是氫、苯基-C1 -C3 烷基或未被取代的或被鹵素、OH、SH、CN、C3 -C6 烯氧基、OCH2 CH2 CN、OCH2 CH2 (CO)O(C1 -C4 烷基)、O(CO)-(C1 -C4 烷基)、O(CO)-(C2 -C4 )烯基、O(CO)-苯基、(CO)OH、(CO)O(C1 -C4 烷基)、C3 -C20 環烷基、SO2 -(C1 -C4 鹵代烷基)、O(C1 -C4 鹵代烷基)以及由一個或更多個O中斷的C3 -C20 環烷基中的一個或更多個取代的C1 -C20 烷基；R4 是由O、S以及NR13 中的一個或更多個中斷的C2 -C20 烷基；R4 是(CH2 CH2 O)n+1 H、(CH2 CH2 O)n (CO)-(C1 -C8 烷基)、C1- C8 烷醯基、C2- C12 烯基、C3- C6 烯基醯基或任選地由O、S、CO以及NR13 中的一個或更多個中斷的C3 -C20 環烷基；R4 是任選地由一個或更多個O中斷的C1 -C8 烷基-C3 -C10 環烷基；R4 是未被取代的或被C1 -C6 烷基、鹵素、OH以及C1 -C3 烷氧基中的一個或更多個取代的苄醯基；R4 選自苯基、萘基以及C3- C20 雜芳基，它們中的每一個是未被取代的或被鹵素、OH、C1 -C12 烷基、C1 -C12 烷氧基、CN、NO2 、苯基-C1 -C3 烷基氧、苯氧基、C1 -C12 烷基巰基、苯基巰基、N(C1 -C12 烷基)2 、二苯基氨基，以及中的一個或更多個取代的；或R4 形成至或所處的苯基或萘基環的碳原子的其中一個的直接鍵， R5 是氫、C2 -C12 烯基、C3 -C20 環烷基或未被取代的或被O、S、CO、NR13 以及COOR4 中的一個或更多個取代的苯基-C1 -C3 烷基；R5 是未被取代的或被OH、SH、CN、C3 -C6 烯氧基、OCH2 CH2 CN、OCH2 CH2 (CO)O(C1 -C4 烷基)、O(CO)-(C2 -C4 )烯基、O(CO)-(C1 -C4 烷基)、O(CO)-苯基以及(CO)OR4 中的一個或更多個取代的C1 -C20 烷基；R5 是被O、S、CO、NR13 以及COOR4 中的一個或更多個取代的C2 -C20 烷基；R5 是(CH2 CH2 O)n H、(CH2 CH2 O)n (CO)-(C1 -C8 烷基)、C2 -C8 烷醯基或C3 -C6 烯基醯基；R5 是未被取代的或被C1 -C6 烷基、鹵素、OH、C1 -C4 烷氧基以及C1 -C4 烷基巰基中的一個或更多個取代的苄醯基；或R5 選自苯基、萘基以及C3 -C20 雜芳基，它們中的每一個是未被取代的或被鹵素、C1 -C12 烷基、C1 -C4 鹵代烷基、C1 -C12 烷氧基、CN、NO2 、苯基-C1 -C3 烷基氧、苯氧基、C1 -C12 烷基巰基、苯基巰基、N(C1 -C12 烷基)2 、二苯基氨基、(CO)O(C1 -C8 烷基)、(CO)-C1 -C8 烷基、 (CO)N(C1 -C8 烷基)2 以及中的一個或更多個取代的， R6 和R7 各自獨立地是氫、C1 -C20 烷基、C2 -C4 羥基烷基、C2 -C10 烷氧基烷基、C2 -C5 烯基、C3 -C20 環烷基、苯基-C1 -C3 烷基、C1 -C8 烷醯基、C1 -C8 烷醯氧基、C3 -C12 烯基醯基、SO2 -(C1 -C4 鹵代烷基)或苄醯基；R6 和R7 各自獨立地選自苯基、萘基以及C3 -C20 雜芳基，它們中的每一個是未被取代的或被鹵素、C1 -C4 鹵代烷基、C1 -C20 烷氧基、C1 -C12 烷基、苄醯基以及C1 -C12 烷氧基中的一個或更多個取代的；R6 和R7 連同它們所附接的氮原子一起形成5元或6元飽和環或不飽和環，該5元或6元飽和環或不飽和環任選地由O、S或NR4 中斷且未被取代的或被C1 -C20 烷基、C1 -C20 烷氧基、=O、OR4 、SR5 、NR8 R9 、(CO)R10 、NO2 、鹵素、C1 -C4 -鹵代烷基、CN、苯基以及任選地由O、S、CO以及NR4 中的一個或更多個中斷的C3 -C20 環烷基中的一個或更多個取代的；或R6 和R7 連同它們所附接的氮原子一起形成雜芳環系統，該雜芳環系統是未被取代的或被C1 -C20 烷基、C1 -C4 鹵代烷基、C1 -C20 烷氧基、=O、OR4 、SR5 、NR8 R9 、(CO)R10 、、鹵素、NO2 、CN、苯基以及任選地由O、S、CO以及NR4 中的一個或更多個中斷的C3 -C20 環烷基中的一個或更多個取代的， R8 和R9 各自獨立地是氫、C1 -C20 烷基、C1 -C4 鹵代烷基、C3 -C10 環烷基或苯基；或R8 和R9 連同它們所附接的氮原子一起形成5元或6元飽和環或不飽和環，該5元或6元飽和環或不飽和環任選地由O、S或NR13 中斷，該5元或6元飽和環或不飽和環不與苯環稠合或與苯環稠合， R10 是氫、OH、C1 -C20 烷基、C1 -C4 鹵代烷基、任選地由O、CO以及NR13 中的一個或更多個中斷的C2 -C20 烷基、任選地由O、S、CO或NR13 中斷的C3 -C20 環烷基；或R10 是苯基、萘基、苯基-C1 -C4 烷基、OR4 、SR5 或NR8 R9 ， R11 是(CO)OR4 、CONR6 R7 或(CO)R4 ；或R11 具有關於R6 或R7 給出的意義中的一個， R12 是COOR4 、CONR6 R7 或(CO)R4 ；或R12 具有關於R4 給出的意義中的一個，以及 R13 是氫、C1 -C20 烷基、C1 -C4 鹵代烷基、由O和CO中的一個或更多個中斷的C2 -C20 烷基、苯基-C1 -C4 烷基、由O和CO中的一個或更多個中斷的C3 -C8 環烷基、(CO)R6 、或未被取代的或被C1 -C20 烷基、鹵素、C1 -C4 鹵代烷基、OR4 、SR5 、NR6 R7 以及中的一個或更多個取代的苯基。The branch chain may have a structure represented by Formula 1: (1) where X is CO or a direct bond (ie X is absent or CO linker), R 1 is hydrogen, C 3 -C 8 cycloalkyl, C 2 -C 5 alkenyl, C 1 -C 20 alkane group or substituted or unsubstituted halogen, phenyl, C 1 -C 20 alkylphenyl group and a CN or more substituents of C 1 -C 20 alkyl group; R 1 is selected from phenyl and naphthyl Each of them is unsubstituted or one of C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, halogen, CN, OR 4 , SR 5 and / or NR 6 R 7 More substituted; or R 1 is C 3 -C 20 heteroaryl, C 1 -C 8 alkoxy, unsubstituted or C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, and / Or one or more substituted benzyloxy groups in halogen, or unsubstituted or substituted with one or more of C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, and / or halogen R 2 is selected from C 6 -C 20 aryl and C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted by phenyl, halogen, C 1 -C 4 haloalkyl , CN, NO 2 , OR 4 , SR 5 , NR 6 R 7 , PO (OC k H 2k + 1 ) 2 , SO-C 1 -C 10 alkyl, SO 2 -C 1 -C 10 alkyl, and by the O, S and NR 13 One or more interrupted C 2 -C 20 alkyl substituted with one or more of, or each of them is unsubstituted or substituted by halogen, COOR 4, CONR 6 R 7 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 3 -C 20 heteroaryloxycarbonyl, OR 4 , SR 5 , and NR 6 R 7 substituted one or more of C 1 -C 20 alkyl; R 2 is hydrogen, C 2 -C 12 alkenyl or optionally one or more of O, CO and NR 13 Interrupted C 3 -C 8 cycloalkyl; R 2 is unsubstituted or halogen, OR 4 , SR 5 , C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 3 -C 20 heteroaryloxycarbonyl, NR 6 R 7 , COOR 4 , CONR 6 R 7 , PO (OC k H 2k + 1 ) 2 , , And one or more substituted C 1 -C 20 alkyl groups in phenyl, alkyl is C 1 -C 20 halogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, OR 4 , SR 5 or phenyl substituted with NR 6 R 7 ; R 2 is interrupted and unsubstituted by one or more of O, SO and SO 2 or halogen, OR 4 , COOR 4 , CONR 6 R 7 , phenyl, and one or more substituted C 2 -C 20 alkyl groups of phenyl substituted by OR 4 , SR 5 or NR 6 R 7 ; R 2 is a C 2 -C 20 alkyl group Is either unsubstituted or substituted by one or more of C 1 -C 6 alkyl, halogen, phenyl, OR 4 , SR 5 and NR 6 R 7 ; R 2 is unsubstituted Substituted naphthylmethyl or substituted with one or more OR 4 or C 3 -C 14 heteroarylcarbonyl; R 2 is optionally interrupted by one or more O and unsubstituted or C 2 -C 12 alkoxycarbonyl substituted by one or more hydroxyl groups; R 2 is unsubstituted or substituted by C 1 -C 6 alkyl, halogen, C 1 -C 4 haloalkyl, phenyl, OR 4, in a 7 SR 5 and NR 6 R or more substituted phenoxycarbonyl group; R 2 is CN, CONR 6 R 7, NO 2 C 1 -C 4 haloalkyl or S (O) m -C 1 -C 6 alkyl group; R 2 is unsubstituted or substituted by C 1 -C 12 alkyl substituted with S (O) m - phenyl, or SO 2 -C 1 -C 6 alkyl; R 2 is SO 2 O-phenyl which is unsubstituted or substituted by C 1 -C 12 alkyl; or R 2 is diphenylphosphinofluorenyl or di (C 1 -C 4 alkoxy) -phosphonium group, m is 1 or 2, R ' 1 has one of the meanings given for R 1 , R' 2 has one of the meanings given for R 2 , X 1 Is O, S, SO or SO 2 , X 2 is O, CO, S or a direct bond, and R 3 is selected from C 6 -C 20 aryl and C 3 -C 20 heteroaryl, each of which is unsubstituted Substituted or interrupted by one or more of phenyl, halogen, C 1 -C 4 haloalkyl, CN, NO 2 , OR 4 , SR 5 , NR 6 R 7 and by O, S and NR 13 One or more of the C 1 -C 20 alkyl groups, or each of them is unsubstituted or halogen, COOR 4 , CONR 6 R 7 , phenyl, C 3 -C 8 cycloalkane , C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 3 -C 20 heteroaryloxycarbonyl, OR 4 , SR 5 and C 1 -C 20 substituted with NR 6 R 7 One or more substitutions in an alkyl group ; R 3 is hydrogen or halogen, phenyl, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO) O (C 1 -C 4 alkyl) , O (CO)-(C 1 -C 4 alkyl), O (CO) -phenyl, (CO) OH, and (CO) O (C 1 -C 4 alkyl) C 1 -C 20 alkyl; or R 3 is C 2 -C 12 alkyl substituted with one or more of O, S, and R 13 ; R 3 is (CH 2 CH 2 O) n + 1 H, (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl), C 2 -C 12 alkenyl, or C 3 -C 8 cycloalkyl; or R 3 is substituted with SR 5 Phenyl (where radical R 5 represents a phenyl or naphthyl ring connected to a carbazole moiety with a direct bond of COR 3 , n is an integer from 1 to 20, R 4 is hydrogen, phenyl-C 1 -C 3 Alkyl or unsubstituted or halogen, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO) O (C 1 -C 4 alkyl), O (CO)-(C 1 -C 4 alkyl), O (CO)-(C 2 -C 4 ) alkenyl, O (CO) -phenyl, (CO) OH, (CO) O (C 1 -C 4 alkyl), C 3 -C 20 cycloalkyl, SO 2- (C 1 -C 4 haloalkyl), O (C 1 -C 4 haloalkyl), and C interrupted by one or more O One or more substituted C 1 -C in 3 -C 20 cycloalkyl 20 alkyl; R 4 is a C 2 -C 20 alkyl interrupted by one or more of O, S, and NR 13 ; R 4 is (CH 2 CH 2 O) n + 1 H, (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl), C 1- C 8 alkyl, C 2 -C 12 alkenyl, C 3 -C 6 alkenyl fluorenyl or optionally from O C 3 -C 20 cycloalkyl interrupted by one or more of R, S, CO, and NR 13 ; R 4 is C 1 -C 8 alkyl-C 3 optionally interrupted by one or more O -C 10 cycloalkyl; R 4 is unsubstituted or substituted by one or more of C 1 -C 6 alkyl, halogen, OH, and C 1 -C 3 alkoxy; R 4 is selected from phenyl, naphthyl, and C 3 -C 20 heteroaryl, each of which is unsubstituted or halogen, OH, C 1 -C 12 alkyl, C 1 -C 12 alkoxy , CN, NO 2 , phenyl-C 1 -C 3 alkyloxy, phenoxy, C 1 -C 12 alkyl mercapto, phenyl mercapto, N (C 1 -C 12 alkyl) 2 , diphenyl Amino, and One or more of these are substituted; or R 4 forms to or A direct bond to one of the carbon atoms of the phenyl or naphthyl ring, R 5 is hydrogen, C 2 -C 12 alkenyl, C 3 -C 20 cycloalkyl or unsubstituted or O, S One or more substituted phenyl-C 1 -C 3 alkyl groups in CO, NR 13 and COOR 4 ; R 5 is unsubstituted or substituted by OH, SH, CN, C 3 -C 6 alkoxy OCH 2 CH 2 CN, OCH 2 CH 2 (CO) O (C 1 -C 4 alkyl), O (CO)-(C 2 -C 4 ) alkenyl, O (CO)-(C 1- C 4 alkyl), O (CO) -phenyl, and (CO) OR 4 one or more substituted C 1 -C 20 alkyl; R 5 is substituted by O, S, CO, NR 13 and COOR 4 is a more or substituted C 2 -C 20 alkyl group; R 5 is (CH 2 CH 2 O) n H, (CH 2 CH 2 O) n (CO) - (C 1 -C 8 alkyl ), C 2 -C 8 alkylfluorenyl or C 3 -C 6 alkenylfluorenyl; R 5 is unsubstituted or substituted by C 1 -C 6 alkyl, halogen, OH, C 1 -C 4 alkoxy Or one or more substituted benzamidine groups of C 1 -C 4 alkyl mercapto; or R 5 is selected from phenyl, naphthyl, and C 3 -C 20 heteroaryl, each of which is unsubstituted unsubstituted or substituted with halogen, C 1 -C 12 alkyl, C 1 -C 4 haloalkyl, C 1 -C 12 alkoxy, CN, NO 2, Group -C 1 -C 3 alkyloxy, phenoxy, C 1 -C 12 alkylmercapto, phenylmercapto, N (C 1 -C 12 alkyl) 2, diphenylamino, (CO) O ( C 1 -C 8 alkyl), (CO) -C 1 -C 8 alkyl, (CO) N (C 1 -C 8 alkyl) 2 and One or more substituted, R 6 and R 7 are each independently hydrogen, C 1 -C 20 alkyl, C 2 -C 4 hydroxyalkyl, C 2 -C 10 alkoxyalkyl, C 2- C 5 alkenyl, C 3 -C 20 cycloalkyl, phenyl-C 1 -C 3 alkyl, C 1 -C 8 alkylfluorenyl, C 1 -C 8 alkylfluorenyl, C 3 -C 12 alkenylfluorenyl, SO 2- (C 1 -C 4 haloalkyl) or benzamidine; R 6 and R 7 are each independently selected from phenyl, naphthyl, and C 3 -C 20 heteroaryl, among them Each is unsubstituted or substituted by halogen, C 1 -C 4 haloalkyl, C 1 -C 20 alkoxy, C 1 -C 12 alkyl, benzamidine, and C 1 -C 12 alkoxy R 6 and R 7 together with the nitrogen atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring, the 5- or 6-membered saturated or unsaturated ring optionally Ground is interrupted by O, S or NR 4 and is unsubstituted or substituted by C 1 -C 20 alkyl, C 1 -C 20 alkoxy, = O, OR 4 , SR 5 , NR 8 R 9 , (CO) R 10 , NO 2 , halogen, C 1 -C 4 -haloalkyl, CN, phenyl, and C 3 -C 20 cycloalkane optionally interrupted by one or more of O, S, CO, and NR 4 One or more of the bases Substituted; or R 6 and R 7 together with the nitrogen atom to which they are attached together form a heteroaromatic ring system, which heteroaromatic ring system is unsubstituted or substituted by C 1 -C 20 alkyl, C 1 -C 4 haloalkoxy Group, C 1 -C 20 alkoxy group, = O, OR 4 , SR 5 , NR 8 R 9 , (CO) R 10 , , Halogen, NO 2 , CN, phenyl, and optionally substituted with one or more of C 3 -C 20 cycloalkyl groups interrupted by one or more of O, S, CO, and NR 4 , R 8 and R 9 are each independently hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 3 -C 10 cycloalkyl or phenyl; or R 8 and R 9 together with them Nitrogen atoms together form a 5- or 6-membered saturated or unsaturated ring, the 5- or 6-membered saturated or unsaturated ring is optionally interrupted by O, S or NR 13 , the 5- or 6-membered saturated ring or Unsaturated ring is not fused with benzene ring or benzene ring, R 10 is hydrogen, OH, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, optionally from O, CO and NR 13 One or more interrupted C 2 -C 20 alkyl, optionally C 3 -C 20 cycloalkyl interrupted by O, S, CO or NR 13 ; or R 10 is phenyl, naphthyl, benzene -C 1 -C 4 alkyl, OR 4 , SR 5 or NR 8 R 9 , R 11 is (CO) OR 4 , CONR 6 R 7 or (CO) R 4 ; or R 11 has about R 6 or R 7 is one of the meanings given by R 12 is COOR 4 , CONR 6 R 7 or (CO) R 4 ; or R 12 is one of the meanings given by R 4 and R 13 is hydrogen, C 1- C 20 alkyl, C 1 -C 4 haloalkyl, C 2 -C 20 alkyl interrupted by one or more of O and CO, phenyl-C 1 -C 4 alkyl, O and One or more interrupted C 3 -C 8 cycloalkyl, (CO) R 6 , or unsubstituted or C 1 -C 20 alkyl, halogen, C 1 -C 4 haloalkyl, OR 4 , SR 5 , NR 6 R 7, and One or more substituted phenyl.

具體地，R1 是C1 -C20 烷基、苯基或C1 -C8 烷氧基，R2 選自C1 -C20 烷基、苯基、萘基以及C3 -C20 雜芳基，它們中的每一個是被OR4 和C1 -C20 烷基中的一個或更多個取代的；R2 是噻吩基、氫或未被取代的或被OR4 、SR5 、C3 -C8 環烷基、NR6 R7 以及COOR4 中的一個或更多個取代的C1 -C20 烷基；或R2 是由SO2 中斷的C2 -C20 烷基，R3 選自苯基和萘基，它們的每一個是未被取代的或被OR4 、SR5 、NR6 R7 以及C1 -C20 烷基中的一個或更多個取代的；或R3 是噻吩基，R4 是氫、C1 -C8 烷醯基、未被取代的或被鹵素、O(CO)-(C1 -C4 烷基)、O(CO)-(C2 -C4 )烯基以及由一個或更多個O中斷的C3 -C20 環烷基中的一個或更多個取代的C1 -C20 烷基；或R4 是由一個或更多個O中斷的C2 -C20 烷基，R5 是未被取代的或被OH、O(CO)-(C2 -C4 )烯基以及(CO)OR4 中的一個或更多個取代的C3 -C20 環烷基或C1 -C20 烷基；或R5 是未被取代的或被一種或更多種鹵素取代的苯基，且R6 和R7 各自獨立地是C1 -C8 烷醯基或C1 -C8 烷醯氧基；或R6 和R7 連同它們所連接的氮原子形成5元或6元飽和環。Specifically, R 1 is C 1 -C 20 alkyl, phenyl or C 1 -C 8 alkoxy, and R 2 is selected from C 1 -C 20 alkyl, phenyl, naphthyl, and C 3 -C 20 hetero Aryl groups, each of which is substituted by one or more of OR 4 and C 1 -C 20 alkyl; R 2 is thienyl, hydrogen or unsubstituted or OR 4 , SR 5 , One or more substituted C 1 -C 20 alkyl groups in C 3 -C 8 cycloalkyl, NR 6 R 7 and COOR 4 ; or R 2 is a C 2 -C 20 alkyl group interrupted by SO 2 , R 3 is selected from phenyl and naphthyl, each of which is unsubstituted or substituted with one or more of OR 4 , SR 5 , NR 6 R 7 and C 1 -C 20 alkyl; or R 3 is thienyl, R 4 is hydrogen, C 1 -C 8 alkylfluorenyl, unsubstituted or halogen, O (CO)-(C 1 -C 4 alkyl), O (CO)-(C 2 -C 4 ) alkenyl and one or more substituted C 1 -C 20 alkyl groups in a C 3 -C 20 cycloalkyl group interrupted by one or more O; or R 4 is substituted by one or more Multiple O-interrupted C 2 -C 20 alkyl groups, R 5 is unsubstituted or substituted by one or more of OH, O (CO)-(C 2 -C 4 ) alkenyl, and (CO) OR 4 Substituted C 3 -C 20 cycloalkyl or C 1 -C 20 alkyl; Or R 5 is phenyl which is unsubstituted or substituted with one or more halogens, and R 6 and R 7 are each independently C 1 -C 8 alkylfluorenyl or C 1 -C 8 alkylfluorenyloxy; Or R 6 and R 7 together with the nitrogen atom to which they are attached form a 5- or 6-membered saturated ring.

具體地，當含雜原子的主鏈具有苯并咔唑結構且支鏈由式1表示時，光響應氣體發生劑(A)可以具有由式1-1表示的結構：(1-1) 其中R0 是-H、、 ，以及X是按照式1中定義的。Specifically, when the hetero atom-containing main chain has a benzocarbazole structure and the branched chain is represented by Formula 1, the photo-responsive gas generating agent (A) may have a structure represented by Formula 1-1: (1-1) where R 0 is -H, , , And X are defined according to Equation 1.

可選擇地，含雜原子的主鏈具有苯基硫代苯基結構且支鏈由式1表示。在此情形中，光響應氣體發生劑(A)可以具有由式1-2表示的結構：(1-2) 其中R1 、R2 以及X是按照式1中定義的。 光響應氣體發生劑(A)選自由下述結構(a1-1)到(a1-70)組成的群組： 。Alternatively, the heteroatom-containing main chain has a phenylthiophenyl structure and the branched chain is represented by Formula 1. In this case, the photo-responsive gas generating agent (A) may have a structure represented by Formula 1-2: (1-2) wherein R 1 , R 2 and X are as defined in Formula 1. The photo-responsive gas generating agent (A) is selected from the group consisting of the following structures (a1-1) to (a1-70): .

在受到光照射時，氮自由基和CO2 氣體從結構(a1-1)到(a1-60)的支鏈産生。使用結構(a1-1)到(a1-30)是特別較佳的，原因是確保了透光的固化膜的高透光率。When exposed to light, nitrogen radicals and CO 2 gas are generated from the branches of the structures (a1-1) to (a1-60). The use of the structures (a1-1) to (a1-30) is particularly preferable because a high light transmittance of the light-transmitting cured film is ensured.

具體地，光響應氣體發生劑(A)可以是(E)-1-(((1-(9-乙基-6-(噻吩-2-羰基)-9H-咔唑-3-基)亞乙基)氨基)氧)乙酮或(E)-2-(乙醯氧基亞氨基)-1-(4-(苯基硫代)苯基)-2-(鄰甲苯基)乙酮。相比之下，目前使用的酮-型光響應氣體發生劑，例如1-羥基環己基(苯基)甲酮(Irgacure 184)和二苯基磷醯基(均三甲苯基)甲酮，在受光照射時不會産生任何氣體，且因此，不會期望他們的透過氣體作用增强表面固化程度的效果，這不同於本發明。因此，酮型光響應氣體發生劑不適用於本發明。Specifically, the photo-responsive gas generating agent (A) may be (E) -1-(((1- (9-ethyl-6- (thiophen-2-carbonyl) -9H-carbazol-3-yl) Ethyl) amino) oxy) ethanone or (E) -2- (ethoxymethylimino) -1- (4- (phenylthio) phenyl) -2- (o-tolyl) ethanone. In contrast, currently used ketone-type photo-responsive gas generating agents, such as 1-hydroxycyclohexyl (phenyl) methanone (Irgacure 184) and diphenylphosphonium (mesityl) methanone, No gas is generated when irradiated with light, and therefore, their effect of enhancing the degree of surface curing by the action of the transmitted gas is not expected, which is different from the present invention. Therefore, a ketone-type photo-responsive gas generating agent is not suitable for the present invention.

光響應氣體發生劑(A)可以以按重量計基於組合物的總重量的0.1到10%的量被使用。如果光響應氣體發生劑的含量按重量計小於0.1%，則組合物可能未被充分光固化。同時，如果光響應氣體發生劑的含量按重量計超過10%，則烯屬不飽和的可光聚合的化合物作爲組合物的其他組分可能由於它們降低的溶解度而被沉澱。因此，光響應氣體發生劑(A)的含量被調整至按重量計基於組合物的總重量的0.1%到10%，較佳按重量計0.5%到7%，更佳按重量計1%到5%。The photo-responsive gas generating agent (A) may be used in an amount of 0.1 to 10% by weight based on the total weight of the composition. If the content of the photo-responsive gas generating agent is less than 0.1% by weight, the composition may not be sufficiently photo-cured. Meanwhile, if the content of the photo-responsive gas generating agent exceeds 10% by weight, the ethylenically unsaturated photopolymerizable compounds as other components of the composition may be precipitated due to their reduced solubility. Therefore, the content of the photo-responsive gas generating agent (A) is adjusted to 0.1% to 10% by weight based on the total weight of the composition, preferably 0.5% to 7% by weight, and more preferably 1% to 5%.

根據一個實施方式，組合物可以包括(B)一種或更多種烯屬不飽和的可光聚合的化合物。烯屬不飽和的可光聚合的化合物可以以按重量計基於組合物的總重量的40%到98.9%的量被使用。在此範圍之外，不可能將組合物的黏度調整至適合於噴墨程序的值。組合物具有25°C下5到30 cPs，較佳8到25 cPs，更佳8到20 cPs的黏度，這在考慮到噴射穩定性時適合於噴墨程序。因此，烯屬不飽和的可光聚合的化合物(B)的含量被調節至按重量計基於組合物的總重量的40%到98.9%，較佳按重量計50%到95%，更佳按重量計75%到95%。According to one embodiment, the composition may include (B) one or more ethylenically unsaturated photopolymerizable compounds. The ethylenically unsaturated photopolymerizable compound may be used in an amount of 40% to 98.9% by weight based on the total weight of the composition. Outside this range, it is impossible to adjust the viscosity of the composition to a value suitable for the inkjet process. The composition has a viscosity of 5 to 30 cPs, preferably 8 to 25 cPs, and more preferably 8 to 20 cPs at 25 ° C, which is suitable for an inkjet process in consideration of ejection stability. Therefore, the content of the ethylenically unsaturated photopolymerizable compound (B) is adjusted to 40% to 98.9% by weight based on the total weight of the composition, preferably 50% to 95% by weight, more preferably 75% to 95% by weight.

根據一個實施方式，烯屬不飽和的可光聚合的化合物(B)可以是單官能的可聚合的單體、多官能的可聚合的單體或其低聚物。烯屬不飽和的單官能的可聚合的化合物可以被用作單官能的可聚合的單體。較佳之單官能的可聚合的單體具有稠合的環狀或多環烴基，由式2表示：(2)。According to one embodiment, the ethylenically unsaturated photopolymerizable compound (B) may be a monofunctional polymerizable monomer, a polyfunctional polymerizable monomer, or an oligomer thereof. Ethylenically unsaturated monofunctional polymerizable compounds can be used as monofunctional polymerizable monomers. The preferred monofunctional polymerizable monomer has a fused cyclic or polycyclic hydrocarbon group, which is represented by Formula 2: (2).

其中R8 是氫或甲基，R9 是具有稠合的環狀或多環烴基的C7 -C30 一價有機基團，且n是0到10的整數。Wherein R 8 is hydrogen or methyl, R 9 is a C 7 -C 30 monovalent organic group having a fused cyclic or polycyclic hydrocarbon group, and n is an integer from 0 to 10.

使用由式2表示的單官能的可聚合的單體導致低黏度和改進的組合物的光固化效率。The use of the monofunctional polymerizable monomer represented by Formula 2 results in low viscosity and improved photo-curing efficiency of the composition.

式2中的R9 並不受限制且可以是下述結構(b1-1)到(b1-4)中的一個：其中每一個R10 獨立地是氫或C1 -C6 烷基且每一個*表示鍵合手。R 9 in Formula 2 is not limited and may be one of the following structures (b1-1) to (b1-4): Wherein each R 10 is independently hydrogen or C 1 -C 6 alkyl and each * represents a bonding hand.

具有稠合的環狀或多環烴基的單官能的可聚合的單體可以以按重量計基於烯屬不飽和的可光聚合的化合物(B)的重量的20%到50%的量被使用。使用按重量計小於20%或按重量計超過50%的量的單官能的可聚合的單體在噴射穩定性，黏度以及光固化效率方面是不期望的。The monofunctional polymerizable monomer having a fused cyclic or polycyclic hydrocarbon group may be used in an amount of 20% to 50% by weight based on the weight of the ethylenically unsaturated photopolymerizable compound (B). . The use of monofunctional polymerizable monomers in an amount of less than 20% by weight or more than 50% by weight is undesirable in terms of spray stability, viscosity, and light curing efficiency.

例如，多官能的可聚合的單體可以選自由下述組成的群組：三環癸烷二甲醇二(甲基)丙烯酸酯、雙酚F環氧乙烷-改性的二(甲基)丙烯酸酯、雙酚A環氧乙烷-改性的二(甲基)丙烯酸酯、異氰脲酸環氧乙烷-改性的二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷-改性的三羥甲基丙烷三(甲基)丙烯酸酯、環氧丙烷-改性的三羥甲基丙烷三(甲基)丙烯酸酯、己內酯-改性的二季戊四醇六(甲基)丙烯酸酯、環氧乙烷-改性的磷酸三(甲基)丙烯酸酯、參[(甲基)丙烯醯氧乙基]異氰脲酸酯、己內酯-改性的參[(甲基)丙烯醯氧乙基]異氰脲酸酯、由式3表示的化合物、由式4表示的化合物及其混合物：(3)For example, the polyfunctional polymerizable monomer may be selected from the group consisting of: tricyclodecane dimethanol di (meth) acrylate, bisphenol F ethylene oxide-modified bis (methyl) Acrylate, bisphenol A ethylene oxide-modified di (meth) acrylate, isocyanurate ethylene oxide-modified di (meth) acrylate, pentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (methyl) ) Acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified phosphate tri (meth) acrylate, ginseng [(meth) acrylic acid oxyethyl] Isocyanurate, caprolactone-modified para [(meth) acryloxyethyl] isocyanurate, a compound represented by Formula 3, a compound represented by Formula 4, and Mixture: (3)

其中R11 是氫或甲基，R12 是m價有機基團，且m是2到20的整數，(4)Where R 11 is hydrogen or methyl, R 12 is an m-valent organic group, and m is an integer from 2 to 20, (4)

其中R13 是氫或甲基，R14 是二價有機基團，R15 是l-價有機基團，且l是2到20的整數。Where R 13 is hydrogen or methyl, R 14 is a divalent organic group, R 15 is a 1-valent organic group, and l is an integer from 2 to 20.

多官能的可聚合的單體可以以按重量計基於烯屬不飽和的可光聚合的化合物(B)的重量的50%到80%的量被使用。使用按重量計小於50%或按重量計超過80%的量的多官能的可聚合的單體在噴射穩定性、黏度以及光固化效率方面是不期望的。The polyfunctional polymerizable monomer may be used in an amount of 50% to 80% by weight based on the weight of the ethylenically unsaturated photopolymerizable compound (B). The use of polyfunctional polymerizable monomers in an amount of less than 50% by weight or more than 80% by weight is undesirable in terms of spray stability, viscosity, and light curing efficiency.

組合物還可以包括(C)聚合物樹脂。聚合物樹脂(C)可以以按重量計基於組合物的總重量的1%到50%範圍內的量使用。在此範圍之外，不可能合適地控制在期望的黏度範圍內的組合物的固化膜的物理特性(例如透光率、耐熱性以及對無機屏障層的黏附性)。組合物具有25°C下5到30 cPs，較佳8到25 cPs，更佳8到20 cPs的黏度，這在考慮到噴射穩定性時適合於噴墨程序。因此，聚合物樹脂(C)的含量被調節至按重量計基於組合物總重量的1%到50%，較佳按重量計1%到30%。The composition may further include (C) a polymer resin. The polymer resin (C) may be used in an amount ranging from 1% to 50% by weight based on the total weight of the composition. Outside this range, it is impossible to properly control the physical characteristics (such as light transmittance, heat resistance, and adhesion to the inorganic barrier layer) of the cured film of the composition within a desired viscosity range. The composition has a viscosity of 5 to 30 cPs, preferably 8 to 25 cPs, and more preferably 8 to 20 cPs at 25 ° C, which is suitable for an inkjet process in consideration of ejection stability. Therefore, the content of the polymer resin (C) is adjusted to 1 to 50% by weight based on the total weight of the composition, preferably 1 to 30% by weight.

聚合物樹脂(C)不受限制且可以是例如選自由(甲基)丙烯酸酯共聚物、聚異戊二烯、聚丁二烯、聚氨酯、聚酯、聚醯亞胺、聚醯胺酸、含硫的聚醯亞胺以及聚矽氧烷組成的群組。The polymer resin (C) is not limited and may be, for example, selected from a (meth) acrylate copolymer, polyisoprene, polybutadiene, polyurethane, polyester, polyimide, polyamic acid, A group of sulfur-containing polyfluorene and polysiloxane.

(甲基)丙烯酸酯共聚物可以例如是30-50:20-40:5-15:15-25的莫耳比的具有稠合的環狀或多環烴基的，由式2表示的單官能的可聚合的單體、具有芳族烴基的C7 -C30 (甲基)丙烯酸酯、羥基-C1 -C4 -烷基(甲基)丙烯酸酯以及(甲基)丙烯酸酯的共聚物：(2) 其中R8 是氫或甲基，R9 是具有稠合的環狀或多環烴基的C7 -C30 一價有機基團，且n是0到10的整數。此莫耳比使組合物具有25°C下5到30 cP的黏度。具有稠合的環狀或多環烴基，由式2表示的單官能的可聚合的單體、具有芳族烴基的C7 -C30 (甲基)丙烯酸酯、羥基-C1 -C4 -烷基(甲基)丙烯酸酯以及(甲基)丙烯酸酯較佳以35-45:25-35:5-15:15-25的莫耳比，更佳38-42:28-32:8-12:18-22的莫耳比。The (meth) acrylate copolymer may be, for example, a molar ratio of 30-50: 20-40: 5-15: 15-25 having a fused cyclic or polycyclic hydrocarbon group, a monofunctional represented by Formula 2 Polymerizable monomers, C 7 -C 30 (meth) acrylates with aromatic hydrocarbon groups, copolymers of hydroxy-C 1 -C 4 -alkyl (meth) acrylates and (meth) acrylates : (2) wherein R 8 is hydrogen or methyl, R 9 is a C 7 -C 30 monovalent organic group having a fused cyclic or polycyclic hydrocarbon group, and n is an integer of 0 to 10. This molar ratio gives the composition a viscosity of 5 to 30 cP at 25 ° C. A fused cyclic or polycyclic hydrocarbon group, a monofunctional polymerizable monomer represented by Formula 2, a C 7 -C 30 (meth) acrylate having an aromatic hydrocarbon group, a hydroxy-C 1 -C 4- The alkyl (meth) acrylate and (meth) acrylate preferably have a molar ratio of 35-45: 25-35: 5-15: 15-25, more preferably 38-42: 28-32: 8- 12: 18-22 Moreby.

具體地，(甲基)丙烯酸酯共聚物可以是以30-50:20-40:5-15:15-25的莫耳比的丙烯酸異冰片酯、苄基甲基丙烯酸酯、羥基乙基甲基丙烯酸酯以及甲基丙烯酸酯單體的共聚物。Specifically, the (meth) acrylic acid ester copolymer may be isobornyl acrylate, benzyl methacrylate, hydroxyethyl methylate at a molar ratio of 30-50: 20-40: 5-15: 15-25. Copolymer of methacrylate and methacrylate monomers.

根據一個實施方式，組合物還可以包括光引發劑和/或一種或多種不會不利地影響本發明的添加劑。According to one embodiment, the composition may further include a photoinitiator and / or one or more additives that do not adversely affect the invention.

光引發劑和/或添加劑可以以按重量計基於組合物的總重量的0.001%到10%範圍內的量被使用。在此範圍之外，組合物的固化膜的物體特性(例如透光率、耐熱性、對無機屏障層的黏附性以及噴射穩定性)可能變劣。The photoinitiator and / or additive may be used in an amount ranging from 0.001% to 10% by weight based on the total weight of the composition. Outside this range, the object characteristics (such as light transmittance, heat resistance, adhesion to the inorganic barrier layer, and spray stability) of the cured film of the composition may deteriorate.

添加劑可以是例如表面活性劑、用於增强對基材的黏附性的黏附助劑、穩定劑、黏附促進劑、固化促進劑、熱聚合抑制劑、分散劑、增塑劑、填料以及消泡劑。Additives may be, for example, surfactants, adhesion aids for enhancing adhesion to a substrate, stabilizers, adhesion promoters, curing accelerators, thermal polymerization inhibitors, dispersants, plasticizers, fillers, and defoamers .

表面活性劑可以改善組合物的可塗覆性、消泡特性以及流平特性。表面活性劑的非限制性的示例包括以商品名BM-1000和BM-1100 (B.M. Chemie)；MEGAFAC F142D、MEGAFAC F172、MEGAFAC F173以及MEGAFAC F183 (Dainippon Inc & Chemicals, Inc.)；FLUORAD FC-135、FLUORAD FC-170C、FLUORAD FC-430以及FLUORAD FC-431 (Sumitomo 3M Ltd.)；SURFRON S-112、SURFRON S-113、SURFRON S-131、SURFRON S-141以及SURFRON S-145 (Asahi Glass Co., Ltd.)和SH-28PA、SH-190、SH- 193、SZ-6032以及SF-8428 (Toray Silicone Co., Ltd.)市售的氟化表面活性劑。Surfactants can improve the coatability, defoaming properties, and leveling properties of the composition. Non-limiting examples of surfactants include under the trade names BM-1000 and BM-1100 (BM Chemie); MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, and MEGAFAC F183 (Dainippon Inc & Chemicals, Inc.); FLUORAD FC-135 , FLUORAD FC-170C, FLUORAD FC-430, and FLUORAD FC-431 (Sumitomo 3M Ltd.); SURFRON S-112, SURFRON S-113, SURFRON S-131, SURFRON S-141, and SURFRON S-145 (Asahi Glass Co ., Ltd.) and SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (Toray Silicone Co., Ltd.) are commercially available fluorinated surfactants.

黏附助劑不受限制且可以例如是官能性矽烷偶聯劑，其具有反應性取代基如羧基、甲基丙烯醯基、異氰酸酯基或環氧基。官能性矽烷偶聯劑的具體示例包括三甲氧基甲矽烷基苯甲酸、γ-甲基丙烯醯氧丙基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三甲氧基矽烷、γ-縮水甘油醚基丙基三甲氧基矽烷以及β-(3,4-環氧環己基)乙基三甲氧基矽烷。The adhesion assistant is not limited and may be, for example, a functional silane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group, or an epoxy group. Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ -Glycidyl ether propyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

不含溶劑的可光固化的噴墨組合物可以透過本領域已知的合適的攪拌技術充分混合所有組分來製備。所得到的混合物可以在使用之前透過過濾器被過濾。The solvent-free photocurable inkjet composition can be prepared by adequately mixing all components by suitable agitation techniques known in the art. The resulting mixture can be filtered through a filter before use.

根據一個實施方式，提供了一種用於聚合含有烯屬不飽和雙鍵的化合物的方法，該方法包括用150 nm到600 nm波長範圍內的電磁輻射照射組合物，其中由光照射産生的氣體的作用提供了增强的表面固化程度。According to one embodiment, there is provided a method for polymerizing a compound containing an ethylenically unsaturated double bond, the method comprising irradiating a composition with electromagnetic radiation in a wavelength range of 150 nm to 600 nm, wherein The effect provides an enhanced degree of surface curing.

電磁輻射不受限制且其示例包括微波、紅外光、紫外光、X-射線、γ-射線、電子束、光束、中子束以及離子束。電磁輻射源的示例包括低壓汞燈、高壓汞燈、超高壓汞燈、金屬鹵化物燈、氬氣雷射以及LED燈。輻射可以根據下述因素變化，諸如組合物中各組分的量和待形成的透光的固化膜的厚度。例如，當LED燈被用作電磁輻射的源時，輻射劑量可以從30到1000 mJ/cm2 ，較佳100到1000 mJ/cm2 。Electromagnetic radiation is not limited and examples thereof include microwave, infrared light, ultraviolet light, X-ray, γ-ray, electron beam, light beam, neutron beam, and ion beam. Examples of electromagnetic radiation sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, and LED lamps. The radiation may vary depending on factors such as the amount of each component in the composition and the thickness of the light-transmissive cured film to be formed. For example, when an LED lamp is used as a source of electromagnetic radiation, the radiation dose may be from 30 to 1000 mJ / cm 2 , preferably 100 to 1000 mJ / cm 2 .

根據一個實施方式，提供了一種電子設備，在該電子設備的一個或更多個表面上包括該組合物的透光的固化膜。According to one embodiment, there is provided an electronic device including a light-transmissive cured film of the composition on one or more surfaces of the electronic device.

例如，該可光固化的噴墨組合物可以用於多種應用，包括印刷油墨、印刷板、封裝劑、用於電子器件的光致抗蝕劑、電鍍抗蝕劑、抗蝕阻劑、液體膜和乾燥膜、焊接抗蝕劑、用於生産用於不同顯示應用的濾光器的抗蝕劑、用於生産電漿顯示板、電致發光顯示器以及LCD的製造過程中的結構的抗蝕劑。該可光固化的噴墨組合物可以被用作用於生産LCD的間隔件的組合物、用於全像數據儲存(HDS)的組合物或用於封裝電部件和電子部件的組合物。該可光固化的噴墨組合物還可以被用於生産磁性記錄材料、微機械部件、波導、光學開關、鍍覆遮罩、蝕刻遮罩、彩色校樣系統、玻璃纖維電纜塗層以及網版印刷模板。該可光固化的噴墨組合物還可以用於透過立體光刻製造3維物體。該可光固化的噴墨組合物還可以被用作圖像記錄材料、全像記錄材料、用於微電子電路的材料、脫色材料、用於圖像記錄的脫色材料、用於使用微囊的圖像記錄的材料、用於UV和可見光雷射直接成像系統的光致抗蝕劑，或用於形成在印刷電路板的順序累積層中的介電層的光致抗蝕劑材料。For example, the photocurable inkjet composition can be used in a variety of applications including printing inks, printing plates, encapsulants, photoresists for electronic devices, plating resists, resists, liquid films And dried films, solder resists, resists used to produce filters for different display applications, resists used in the manufacture of plasma display panels, electroluminescent displays, and structures in LCD manufacturing structures . The photocurable inkjet composition can be used as a composition for producing an LCD spacer, a composition for Holographic Data Storage (HDS), or a composition for encapsulating electrical and electronic components. The photocurable inkjet composition can also be used to produce magnetic recording materials, micromechanical components, waveguides, optical switches, plating masks, etching masks, color proofing systems, fiberglass cable coatings, and screen printing template. The photocurable inkjet composition can also be used to make a three-dimensional object through stereolithography. The photocurable inkjet composition can also be used as an image recording material, a holographic recording material, a material for microelectronic circuits, a decoloring material, a decoloring material for image recording, and a microcapsule using Image recording materials, photoresists for UV and visible laser direct imaging systems, or photoresist materials for forming a dielectric layer in a sequential build-up layer of a printed circuit board.

透光的固化膜具有超過98%的透光率，正如根據ASTM D1003的一般方法測量的，且具有比常規的透光固化膜的顯著改善的表面固化程度。The light-transmitting cured film has a light transmittance of more than 98%, as measured according to the general method of ASTM D1003, and has a significantly improved degree of surface curing than the conventional light-transmissive cured film.

根據一個實施方式，電子設備的透光的固化膜被用作封裝劑或保護材料。透光的固化膜的基材的非限制性示例包括用於電子部件的基材，其可以形成有互聯圖案。作爲基材，存在示例性的玻璃或塑料基材，這些基材可以塗覆有矽、氮化矽、氧化矽、鈦、鉭、鈀、鈦鎢、銅、鉻、鋁、AlNd、ITO或IGZO。According to one embodiment, a light-transmissive cured film of an electronic device is used as an encapsulant or a protective material. Non-limiting examples of the substrate of the light-transmitting cured film include a substrate for an electronic component, which may be formed with an interconnection pattern. As substrates, there are exemplary glass or plastic substrates, which can be coated with silicon, silicon nitride, silicon oxide, titanium, tantalum, palladium, titanium tungsten, copper, chromium, aluminum, AlNd, ITO, or IGZO .

將參考下面的實施例更詳細地解釋本發明。基於闡釋性的目的，而不是預期限制本發明來提供這些實施例。The present invention will be explained in more detail with reference to the following examples. These examples are provided for illustrative purposes, and are not intended to limit the invention.

[[ 實施例Examples ]]

採用下面的組分製備不含溶劑的可光固化的噴墨組合物。(E)-1-(((1-(9-乙基-6-(噻吩-2-羰基)-9H-咔唑-3-基)亞乙基)氨基)氧)乙酮(L5, Takoma Technology Co., Ltd.)，這對應於由式1-1表示的結構，其中R0 =、R1 =CH3 、R2 =CH3 、X=直接鍵(具體是(a1-63)，以下稱爲(A-1) )和(E)-2-(乙醯氧基亞氨基)-1-(4-(苯基硫代)苯基)-2-(鄰甲苯基)乙酮(TPM-P07, Takoma Technology, Co., Ltd.)，這對應於由式1-2表示的結構，其中R1 =CH3 、R2 =甲苯以及X=CO，下文稱爲(A-2) )被用作光響應氣體發生劑。The following components were used to prepare a solvent-free photocurable inkjet composition. (E) -1-(((1- (9-ethyl-6- (thiophen-2-carbonyl) -9H-carbazol-3-yl) ethylene) amino) oxy) ethanone (L5, Takoma Technology Co., Ltd.), which corresponds to the structure represented by Formula 1-1, where R 0 = , R 1 = CH 3 , R 2 = CH 3 , X = direct bond (specifically (a1-63), hereinafter referred to as (A-1) ) and (E) -2- (ethoxyimino) -1- (4- (phenylthio) phenyl) -2- (o-tolyl) ethanone (TPM-P07, Takoma Technology, Co., Ltd.), which corresponds to the formula represented by Formula 1-2 A structure in which R 1 = CH 3 , R 2 = toluene, and X = CO (hereinafter referred to as (A-2) ) is used as a photo-responsive gas generating agent.

丙烯酸異冰片酯(黏度7.40 cPs)作爲具有稠合的環狀或多環烴基的，由式2表示的單官能的可聚合的單體(其中R8 =CH3 、n=0、R9 =結構(b1-3)以及R10 =H: 下文稱爲(B-1) )，三羥甲基丙烷三丙烯酸酯(黏度57 cPs)作爲多官能的可聚合的單體(下文稱爲(B-2) )，以及1,6-己二醇二丙烯酸酯(黏度4 cPs：下文稱爲(B-3) )被用作烯屬不飽和的可光聚合的化合物。Isobornyl acrylate (viscosity 7.40 cPs) is a monofunctional polymerizable monomer represented by Formula 2 having a fused cyclic or polycyclic hydrocarbon group (where R 8 = CH 3 , n = 0, R 9 = Structure (b1-3) and R 10 = H: hereinafter referred to as (B-1) ), trimethylolpropane triacrylate (viscosity 57 cPs) as a polyfunctional polymerizable monomer (hereinafter referred to as (B -2) ), and 1,6-hexanediol diacrylate (viscosity 4 cPs: hereinafter referred to as (B-3) ) are used as the ethylenically unsaturated photopolymerizable compound.

丙烯酸異冰片酯(黏度7.40 cPs)作爲具有稠合的環狀或多環烴基的、由式2表示的單官能的可聚合的單體、苄基丙烯酸酯(黏度2.68 cPs)作爲具有芳族烴基的C7 -C30 (甲基)丙烯酸酯、羥基乙基甲基丙烯酸酯(黏度6.79 cPs)作爲羥基-C1 -C4 -烷基(甲基)丙烯酸酯以及甲基丙烯酸酯(黏度0.58 cPs)被以40:30:10:20的莫耳比使用以便進行共聚合。所得到的共聚物被浸漬在甲醇中並純化以製備呈粉末形式的聚合物樹脂。Isobornyl acrylate (viscosity 7.40 cPs) as a monofunctional polymerizable monomer having a fused cyclic or polycyclic hydrocarbon group represented by Formula 2, and benzyl acrylate (viscosity 2.68 cPs) as an aromatic hydrocarbon group C 7 -C 30 (meth) acrylate, hydroxyethyl methacrylate (viscosity 6.79 cPs) as hydroxy-C 1 -C 4 -alkyl (meth) acrylate and methacrylate (viscosity 0.58 cPs) was used at a molar ratio of 40: 30: 10: 20 for copolymerization. The obtained copolymer was immersed in methanol and purified to prepare a polymer resin in powder form.

爲了比較，1-羥基環己基(苯基)甲酮(Irgacure184: 下文稱爲(D-1) )和二苯基磷醯基(均三甲苯基)甲酮(TPO: 以下稱爲(D-2) )作爲通常的酮基光引發劑被用於替代光響應氣體發生劑。For comparison, 1-hydroxycyclohexyl (phenyl) methanone (Irgacure184: hereinafter referred to as (D-1) ) and diphenylphosphonium (mesityl) methyl ketone (TPO: hereinafter referred to as (D- 2) ) As a common ketone-based photoinitiator, it is used instead of a photo-responsive gas generating agent.

實施例Examples 1-21-2 和比較實施例And comparative examples 1-21-2 ：:

以表1中顯示的量混合各組分持續4h以製備不含溶劑的可光固化的噴墨組合物。The components were mixed in the amounts shown in Table 1 for 4 h to prepare a solvent-free photocurable inkjet composition.

表table 11

實施例1-2和比較實施例1-2中製備的不含溶劑的可光固化的噴墨組合物用於形成透光的固化膜。The solvent-free photocurable inkjet composition prepared in Examples 1-2 and Comparative Examples 1-2 was used to form a light-transmissive cured film.

具體地，每一種噴墨組合物被噴射到玻璃基材和塗覆氮化矽(SiNx)的基材上以形成具有30 mm (寬) × 30 mm (長) × 10 μm (厚)尺寸的塗層。塗層被暴露於來自1000 mJ/cm2 (365 nm波長)的LED燈的光以形成透光的固化膜。測試了透光的固化膜的下述測試參數。Specifically, each inkjet composition was sprayed onto a glass substrate and a silicon nitride (SiNx) -coated substrate to form a substrate having a size of 30 mm (width) × 30 mm (length) × 10 μm (thickness). coating. The coating was exposed to light from 1000 mJ / cm 2 (365 nm wavelength) LED lamps to form a light-transmissive cured film. The following test parameters of the cured light-transmitting film were tested.

＜測試參數＞＜ Test parameters ＞

評價透光膜的表面固化的程度： 用玻璃棒刮擦每一種透光膜的表面。當玻璃棒沾染油墨時，透光的膜被認爲是“未固化的”，而當玻璃棒未沾染油墨時，被認爲是“固化的”。 The degree of surface curing of the light-transmitting films was evaluated: the surface of each light-transmitting film was scraped with a glass rod. When the glass rod is stained with ink, the light-transmitting film is considered "uncured", and when the glass rod is stained with ink, it is considered "cured".

評價透光膜的透光率： 根據ASTM D1003的一般方法，使用分光光度計測量形成在玻璃基材上的透光膜的透光率。 Evaluation of the light transmittance of the light-transmitting film: According to the general method of ASTM D1003, the light transmittance of the light-transmitting film formed on the glass substrate was measured using a spectrophotometer.

評價透光膜的黏附强度： 透過使用UTM測量透光膜在塗覆氮化矽(SiNx)的玻璃基材與玻璃基材之間的黏附强度來評價每一種透光膜的黏附强度。 Evaluation of the adhesion strength of the light-transmitting film: The adhesion strength of each light-transmitting film was evaluated by measuring the adhesion strength of the light-transmitting film between the silicon substrate (SiNx) -coated glass substrate and the glass substrate using UTM.

具體地，使用0.3 mm的膠帶將6 mm寬的塗層空間形成在塗覆氮化矽(SiNx)的玻璃基材(25 mm (寬) × 70 mm (長) × 3 mm (厚))上。實施例1-2和比較實施例1-2中製備的每一種噴墨組合物被塗覆在塗層空間上且具有相同尺寸的玻璃基材被覆蓋在其上，以便與下面的玻璃基材相交。所得到的結構被暴露於1000 mJ/cm2 (365 nm波長)的LED燈以製備試樣。Specifically, a 6 mm wide coating space was formed on a silicon substrate (SiNx) -coated glass substrate (25 mm (width) × 70 mm (length) × 3 mm (thickness)) using 0.3 mm tape. . Each of the inkjet compositions prepared in Examples 1-2 and Comparative Examples 1-2 was coated on a coating space and a glass substrate having the same size was covered thereon so as to match the glass substrate below intersect. The obtained structure was exposed to an LED lamp of 1000 mJ / cm 2 (365 nm wavelength) to prepare a sample.

在覆蓋的玻璃基材固定後，下面的帶塗層的玻璃基材的兩側被以50 mm/min的速率向下按壓。測量了使兩個玻璃基材彼此分離所需的最大力。After the covered glass substrate was fixed, the underside of the coated glass substrate was pressed down at a rate of 50 mm / min. The maximum force required to separate the two glass substrates from each other was measured.

評價噴墨穩定性 ( 噴射穩定性 ) ： 評價了實施例1-2和比較實施例1-2中製備的每一種噴墨組合物對噴墨程序的適用性且觀察了是否形成伴生物，所暴露的表面被潤濕/乾燥，且組合物被正常噴射。 Evaluation of Inkjet Stability ( Ejection Stability ) : The applicability of each inkjet composition prepared in Examples 1-2 and Comparative Examples 1-2 to the inkjet process was evaluated and whether companions were formed was observed. The exposed surface is wetted / dried and the composition is sprayed normally.

儲存穩定性的評價： 測量了實施例1-2和比較實施例1-2中製備的噴墨組合物在45°C下儲存5天期間的黏度的變化。當5天的黏度變化是10%或更小，則組合物的儲存穩定性被評價爲是“極佳的”。 Evaluation of storage stability: The change in viscosity of the inkjet compositions prepared in Examples 1-2 and Comparative Examples 1-2 during storage at 45 ° C. for 5 days was measured. When the viscosity change over 5 days was 10% or less, the storage stability of the composition was evaluated as "excellent".

表面固化程度、透光率、黏附强度、噴射穩定性以及儲存穩定性的測試結果顯示在表2中。Test results of the degree of surface curing, light transmittance, adhesion strength, spray stability, and storage stability are shown in Table 2.

表table 22

正如可以從表2中的結果看出，實施例1-2的使用光響應氣體發生劑的不含溶劑的可光固化的噴墨組合物被完全固化，這驗證了在光固化期間産生的氣體影響表面固化。此外，實施例1-2的不含溶劑的可光固化的噴墨組合物顯示出就透光率、黏附强度、噴射穩定性以及儲存穩定性而言的極佳的特性。As can be seen from the results in Table 2, the solvent-free photocurable inkjet composition using the photo-responsive gas generating agent of Examples 1-2 was completely cured, which verified the gas generated during photo-curing Affects surface curing. In addition, the solvent-free, photocurable inkjet composition of Examples 1-2 showed excellent characteristics in terms of light transmittance, adhesion strength, ejection stability, and storage stability.

比較實施例1-2的使用通常的酮型光引發劑而不是光響應氣體發生劑的組合物顯示出表面固化程度的差的結果和非常低的黏附强度。The composition of Comparative Example 1-2 using a general ketone-type photoinitiator instead of a photo-responsive gas generating agent showed a result of a poor degree of surface curing and a very low adhesive strength.

＜< 額外的實驗實施例Additional experimental examples ＞＞

爲了參考，四種不含溶劑的可光固化的噴墨組合物被按照表3中顯示的進行製備。For reference, four solvent-free photocurable inkjet compositions were prepared as shown in Table 3.

表table 33

按照與實施例1相同的方式形成透光的固化膜，除了使用參考實施例1-4的不含溶劑的可光固化的噴墨組合物。根據與上述相同的測試方法測量了透光的固化膜的表面固化程度、透光率、黏附强度、噴射穩定性以及儲存穩定性。結果概述在表4中。A light-transmitting cured film was formed in the same manner as in Example 1, except that the solvent-free, photocurable inkjet composition was used in Reference Examples 1-4. The degree of surface curing, light transmittance, adhesion strength, spray stability, and storage stability of the light-transmissive cured film were measured according to the same test methods as described above. The results are summarized in Table 4.

表table 44

正如可以從表4中的結果看到的，參考實施例1-4的不含溶劑的可光固化的噴墨組合物在所測量的包括黏附强度、表面固化程度、噴射穩定性以及儲存穩定性的物理特性中的一個或更多個方面顯示出不令人滿意的結果。As can be seen from the results in Table 4, the solvent-free photocurable inkjet composition of Reference Examples 1-4 measured adhesion strength, degree of surface curing, spray stability, and storage stability. One or more aspects of the physical characteristics of the resin show unsatisfactory results.

無no

無no

Claims (16)

一種不含溶劑的可光固化的噴墨組合物，包含：(A)光響應氣體發生劑，所述光響應氣體發生劑係具有作為基本結構的(酮)肟酯部分，且由含雜原子的主鏈和結合到所述主鏈的且含有至少一個氮原子的支鏈組成，其中所述光響應氣體發生劑(A)在受到光照射時產生氣體；以及烯屬不飽和的可光聚合的化合物(B)，其係包括具有稠合的環狀或多環烴基的單官能的可聚合的單體，且由式2表示：其中R8是氫或甲基，且R9是具有稠合的環狀或多環烴基的C7-C30一價有機基團，且n是0到10的整數。A solvent-free, photocurable inkjet composition comprising: (A) a light-responsive gas generating agent having a (keto) oxime ester moiety as a basic structure and comprising a hetero atom Consisting of a main chain and a branch chain bound to the main chain and containing at least one nitrogen atom, wherein the photo-responsive gas generating agent (A) generates a gas when exposed to light; and an ethylenically unsaturated photopolymerizable polymer Compound (B), which is a monofunctional polymerizable monomer having a fused cyclic or polycyclic hydrocarbon group, and is represented by Formula 2: Wherein R 8 is hydrogen or methyl, and R 9 is a C 7 -C 30 monovalent organic group having a fused cyclic or polycyclic hydrocarbon group, and n is an integer of 0 to 10. 如請求項1所述的不含溶劑的可光固化的噴墨組合物，其中所述含雜原子的主鏈具有苯并咔唑部分或苯基硫代苯基部分。The solvent-free photocurable inkjet composition according to claim 1, wherein the heteroatom-containing main chain has a benzocarbazole moiety or a phenylthiophenyl moiety. 如請求項1所述的不含溶劑的可光固化的噴墨組合物，其中所述支鏈具有由式1表示的結構：其中X是CO或直接鍵，R1是C1-C20烷基、苯基或C1-C8烷氧基，R2選自C1-C20烷基、苯基、萘基以及C3-C20雜芳基，它們中的每一個被OR4和C1-C20烷基中的一個或更多個取代；R2是噻吩基、氫或未被取代的或被OR4、SR5、C3-C8環烷基、NR6R7以及COOR4中的一個或更多個取代的C1-C20烷基；或R2是由SO2中斷的C2-C20烷基，R3選自苯基和萘基，它們中的每一個是未被取代的或被OR4、SR5、NR6R7以及C1-C20烷基中的一個或更多個取代的；或R3是噻吩基，R4是氫、C1-C8烷醯基、未被取代的或被鹵素、O(CO)-(C1-C4烷基)、O(CO)-(C2-C4)烯基、由一個或更多個O中斷的C3-C20環烷基中的一個或更多個取代的C1-C20烷基；或R4是由一個或更多個O中斷的C2-C20烷基，R5是未被取代的或被OH、O(CO)-(C2-C4)烯基以及(CO)OR4中的一個或更多個取代的C3-C20環烷基或C1-C20烷基；或R5是未被取代的或被一種或多種鹵素取代的苯基，以及R6和R7各自獨立地是C1-C8烷醯基或C1-C8烷醯氧基；或R6和R7連同它們所連接的氮原子一起形成5元或6元飽和環。The solvent-free photocurable inkjet composition according to claim 1, wherein the branched chain has a structure represented by Formula 1: Where X is CO or a direct bond, R 1 is C 1 -C 20 alkyl, phenyl or C 1 -C 8 alkoxy, and R 2 is selected from C 1 -C 20 alkyl, phenyl, naphthyl, and C 3 -C 20 heteroaryl, each of which is substituted by one or more of OR 4 and C 1 -C 20 alkyl; R 2 is thienyl, hydrogen or unsubstituted or OR 4 , One or more substituted C 1 -C 20 alkyl groups in SR 5 , C 3 -C 8 cycloalkyl, NR 6 R 7 and COOR 4 ; or R 2 is C 2 -C 20 interrupted by SO 2 Alkyl, R 3 is selected from phenyl and naphthyl, each of which is unsubstituted or one or more of OR 4 , SR 5 , NR 6 R 7 and C 1 -C 20 alkyl Substituted; or R 3 is thienyl, R 4 is hydrogen, C 1 -C 8 alkylfluorenyl, unsubstituted or halogen, O (CO)-(C 1 -C 4 alkyl), O (CO )-(C 2 -C 4 ) alkenyl, one or more substituted C 1 -C 20 alkyl groups in a C 3 -C 20 cycloalkyl group interrupted by one or more O; or R 4 is C 2 -C 20 alkyl interrupted by one or more O, R 5 is unsubstituted or substituted by OH, O (CO)-(C 2 -C 4 ) alkenyl and (CO) OR 4 One or more substituted C 3 -C 20 cycloalkyl or C 1 -C 20 Alkyl; or R 5 is phenyl which is unsubstituted or substituted with one or more halogens, and R 6 and R 7 are each independently C 1 -C 8 alkylfluorenyl or C 1 -C 8 alkylfluorenyl ; Or R 6 and R 7 together with the nitrogen atom to which they are attached form a 5- or 6-membered saturated ring. 如請求項1所述的不含溶劑的可光固化的噴墨組合物，其中所述光響應氣體發生劑(A)選自由下述結構(a1-1)到(a1-70)組成的群組： The solvent-free photocurable inkjet composition according to claim 1, wherein the photo-responsive gas generating agent (A) is selected from the group consisting of the following structures (a1-1) to (a1-70) group: 如請求項1所述的不含溶劑的可光固化的噴墨組合物，其中所述光響應氣體發生劑(A)以按重量計基於所述組合物的總重量的0.1%到10%的量存在。The solvent-free photocurable inkjet composition according to claim 1, wherein the photo-responsive gas generating agent (A) is from 0.1% to 10% by weight based on the total weight of the composition The amount exists. 如請求項1所述的不含溶劑的可光固化的噴墨組合物，其中所述組合物包含按重量計基於所述組合物的總重量的40%到98.9%的烯屬不飽和的可光聚合的化合物(B)，且具有25℃下5cPs到30cPs的黏度。The solvent-free photocurable inkjet composition according to claim 1, wherein the composition comprises from 40% to 98.9% by weight based on the total weight of the composition of an ethylenically unsaturated Photopolymerized compound (B), and has a viscosity of 5 cPs to 30 cPs at 25 ° C. 如請求項1所述的不含溶劑的可光固化的噴墨組合物，其中式2中的R9是下述結構(b1-1)到(b1-4)中的一個：其中每一個R10獨立地是氫或C1-C6烷基且每一個*表示鍵合的手。The solvent-free photocurable inkjet composition according to claim 1, wherein R 9 in Formula 2 is one of the following structures (b1-1) to (b1-4): Wherein each R 10 is independently hydrogen or C 1 -C 6 alkyl and each * represents a bonded hand. 如請求項1所述的不含溶劑的可光固化的噴墨組合物，其中具有稠合的環狀或多環烴基的所述單官能的可聚合的單體以按重量計基於所述烯屬不飽和的可光聚合的化合物(B)的重量的20%到50%的量存在。The solvent-free photocurable inkjet composition according to claim 1, wherein the monofunctional polymerizable monomer having a fused cyclic or polycyclic hydrocarbon group is based on the olefin by weight The unsaturated photopolymerizable compound (B) is present in an amount of 20 to 50% by weight. 如請求項1所述的不含溶劑的可光固化的噴墨組合物，還包含按重量計基於所述組合物的總重量的1%到50%的(C)聚合物樹脂，且具有25℃下5cPs到30cPs的黏度。The solvent-free photocurable inkjet composition according to claim 1, further comprising (C) a polymer resin of 1% to 50% by weight based on the total weight of the composition, and having 25 Viscosity from 5cPs to 30cPs at ℃. 如請求項9所述的不含溶劑的可光固化的噴墨組合物，其中所述聚合物樹脂(C)選自由(甲基)丙烯酸酯共聚物、聚異戊二烯、聚丁二烯、聚氨酯、聚酯、聚醯亞胺、聚醯胺酸、含硫的聚醯亞胺以及聚矽氧烷組成的群組。The solvent-free photocurable inkjet composition according to claim 9, wherein the polymer resin (C) is selected from the group consisting of (meth) acrylate copolymer, polyisoprene, polybutadiene , Polyurethane, polyester, polyimide, polyamic acid, sulfur-containing polyimide, and polysiloxane. 如請求項10所述的不含溶劑的可光固化的噴墨組合物，其中所述(甲基)丙烯酸酯共聚物是具有稠合的環狀或多環烴基的，由下述式2表示的單官能的可聚合的單體、具有芳族烴基的C7-C30(甲基)丙烯酸酯、羥基-C1-C4-烷基(甲基)丙烯酸酯以及(甲基)丙烯酸酯以30-50：20-40：5-15：15-25的莫耳比的共聚物，其中R8是氫或甲基，R9是具有稠合的環狀或多環烴基的C7-C30一價有機基團，且n是0到10的整數。The solvent-free photocurable inkjet composition according to claim 10, wherein the (meth) acrylate copolymer has a fused cyclic or polycyclic hydrocarbon group and is represented by the following formula 2 Monofunctional polymerizable monomers, C 7 -C 30 (meth) acrylates with aromatic hydrocarbon groups, hydroxy-C 1 -C 4 -alkyl (meth) acrylates, and (meth) acrylates Copolymers with a molar ratio of 30-50: 20-40: 5-15: 15-25, Wherein R 8 is hydrogen or methyl, R 9 is a C 7 -C 30 monovalent organic group having a fused cyclic or polycyclic hydrocarbon group, and n is an integer from 0 to 10. 一種不含溶劑的可光固化的噴墨組合物，包含：(A)光響應氣體發生劑，所述光響應氣體發生劑係具有作為基本結構的(酮)肟酯部分，且由含雜原子的主鏈和結合到所述主鏈的且含有至少一個氮原子的支鏈組成，其中所述光響應氣體發生劑(A)在受到光照射時產生氣體；以及(甲基)丙烯酸酯共聚物，其係具有稠合的環狀或多環烴基的，由下述式2表示的單官能的可聚合的單體、具有芳族烴基的C7-C30(甲基)丙烯酸酯、羥基-C1-C4-烷基(甲基)丙烯酸酯以及(甲基)丙烯酸酯以30-50：20-40：5-15：15-25的莫耳比的共聚物：其中R8是氫或甲基，R9是具有稠合的環狀或多環烴基的C7-C30一價有機基團，且n是0到10的整數。A solvent-free, photocurable inkjet composition comprising: (A) a light-responsive gas generating agent having a (keto) oxime ester moiety as a basic structure and comprising a hetero atom Consisting of a main chain and a branch chain bound to the main chain and containing at least one nitrogen atom, wherein the photo-responsive gas generating agent (A) generates a gas when irradiated with light; and a (meth) acrylate copolymer , Which is a fused cyclic or polycyclic hydrocarbon group, a monofunctional polymerizable monomer represented by the following formula 2, a C 7 -C 30 (meth) acrylate having an aromatic hydrocarbon group, a hydroxy- Copolymers of C 1 -C 4 -alkyl (meth) acrylates and (meth) acrylates with a molar ratio of 30-50: 20-40: 5-15: 15-25: Wherein R 8 is hydrogen or methyl, R 9 is a C 7 -C 30 monovalent organic group having a fused cyclic or polycyclic hydrocarbon group, and n is an integer from 0 to 10. 一種用於光聚合含有烯屬不飽和雙鍵的化合物的方法，所述方法包括用150nm到600nm波長範圍內的電磁輻射照射如請求項1至12中任一項所述的組合物，其中由光照射產生的氣體的作用提供了增强的表面固化程度。A method for photopolymerizing a compound containing an ethylenically unsaturated double bond, the method comprising irradiating the composition according to any one of claims 1 to 12 with electromagnetic radiation in a wavelength range of 150 nm to 600 nm, wherein The effect of gas generated by light irradiation provides an enhanced degree of surface curing. 一種電子設備，所述電子設備在其一個或更多個表面上包括如請求項1至12中任一項所述的組合物的透光的固化膜。An electronic device including a light-transmissive cured film of the composition according to any one of claims 1 to 12 on one or more surfaces thereof. 如請求項14所述的電子設備，其中所述固化膜具有按照根據通用方法ASTM D1003測得的超過98%的透光率。The electronic device according to claim 14, wherein the cured film has a light transmittance of more than 98% measured according to a general method ASTM D1003. 如請求項14所述的電子設備，其中所述固化膜是封裝膜或保護層。The electronic device according to claim 14, wherein the cured film is a packaging film or a protective layer.
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