Ink and application thereof

Abstract

The invention provides printing ink and application thereof. The ink comprises a photocuring free radical monomer, a photocuring cationic monomer, a free radical photoinitiator and a cationic photoinitiator, the photocuring free radical monomer comprises a first free radical monomer and a second free radical monomer, the first free radical monomer comprises an acrylate monomer, and the second free radical monomer is selected from a compound shown in a formula 1; the photocuring cationic monomer comprises a first cationic monomer and a second cationic monomer, and the first cationic monomer comprises a vinyl monomer; the second cationic monomer is selected from a compound shown in a formula 2. The ink has high refractive index, curing rate and light transmittance and low curing shrinkage rate, and a formed film can effectively block water and oxygen, so that the performance of a light extraction layer of an optical element and a photoelectronic device is remarkably improved.

Description

Technical Field

[0001] The invention relates to the technical field of ink packaging, and in particular to an ink and application thereof. Background Art

[0002] Organic Light-Emitting Diodes (OLED) have the characteristics of all-solid-state, active luminescence, high brightness, high contrast, ultra-thin and ultra-light, low cost, low power consumption, no viewing angle limitation, and a wide operating temperature range. They can also be made on flexible, lightweight, and durable plastic substrates, and can achieve truly flexible displays. They are the technology that best meets people's requirements for future displays.

[0003] Compared with liquid crystal display (LCD), organic electroluminescent device (OLED) has the advantages of low driving voltage, high luminous brightness and luminous efficiency, wide luminous viewing angle, fast response speed, ultra-thin, and can be made on flexible panels. It is known as the third generation of flat panel display technology. As the organic electroluminescent diode for the next generation of flat panel display applications, organic optoelectronic semiconductor materials require: 1. High luminous efficiency; 2. Excellent electron and hole stability; 3. Suitable luminous color; 4. Excellent processability. The various types of light-emitting diodes currently used are mainly organic small molecule light-emitting diodes (OLED), polymer organic light-emitting diodes (POLED), organic phosphorescent light-emitting diodes (PHOLED), and organic thermal delayed luminescence materials (TADF). Among them, organic phosphorescent light-emitting diode materials use the luminescence mechanism of singlet excited state (fluorescence) and triplet excited state (phosphorescence), and the quantum efficiency and luminescence efficiency are 3 to 4 times that of fluorescent OLED materials. Therefore, phosphorescent materials obviously have much higher luminous efficiency than small molecule fluorescent materials, while also reducing the heat generated, increasing the competitiveness of OLED display panels. This makes it possible for OLED displays or lighting to surpass LCD displays and traditional light sources in general.

[0004] Based on the demand for high luminous efficiency and long service life of OLED devices, thin film encapsulation has become the current trend of encapsulation. Thin film encapsulation is to grow a single layer or multilayer thin film on the prepared OLED device substrate to achieve the effect of blocking water vapor. The study of OLED thin film usually adopts the method of organic-inorganic composite thin film. Inorganic thin film can effectively block water vapor and oxygen, but the film forming property and interface matching are poor and defects are easily formed; organic thin film has good flexibility, good film forming property and high flatness due to its large free volume and average degree of freedom of chain segments. The role of organic thin film can cover the defects of inorganic thin film. Taking advantage of the high barrier property of inorganic film to water vapor and oxygen and the good surface morphology of organic film, the method of alternating organic and inorganic film film formation can obtain a more satisfactory effect.

[0005] Thin film encapsulation is represented by a three-layer structure, and its excellent performance has become the mainstream method of flexible OLED encapsulation. The three-layer structure is a smooth substrate with a first inorganic layer (SiNX), an organic polymer buffer layer is obtained by inkjet printing and then curing on this substrate, and the third inorganic layer (SiNX) is the last inorganic layer. The organic polymer buffer layer (organic UV-curable resin) is considered to be a conventional and effective encapsulation material because of its good curing characteristics, stability, bonding strength, transmittance and high purity. Commonly used organic polymer buffer layers include acrylic resins, methacrylic resins, isoprene resins, ethylene resins, epoxy resins, polyurethane resins, cellulose resins, perylene resins, imide resins or a mixture of two or more. When the refractive index of the ink used for OLED encapsulation is low, the total internal reflection phenomenon generated inside the OLED reduces the light extraction efficiency. Therefore, increasing the refractive index of the encapsulation ink will reduce the occurrence of total reflection, thereby improving the light extraction efficiency. Therefore, on the premise of playing a good encapsulation role, how to increase the light extraction efficiency is the key to developing ink compositions. The ink can show higher light transmittance and light extraction efficiency. However, the current ink composition is rarely applied to OLED display devices and it is difficult to simultaneously meet the performance index requirements of high light transmittance, high light curing rate, low shrinkage and the like required by the growing demand for thin film encapsulation.

[0006] With the continuous development of science and technology, the demand for ink is growing. Ink can be widely used in optical lenses, electronic components, biomedicine, photovoltaics and other fields, especially in the field of optoelectronics, where it plays an important role. However, existing inks often have problems such as low refractive index, poor stability or complicated preparation process, which makes it difficult to meet market demand. Therefore, developing a new type of ink composition to improve the quality and stability of the product is an urgent problem to be solved in the current field. Pure organic monomer type ink composition is a good research direction. The development of pure organic monomer type ink composition has largely overcome the risk of instability and easy precipitation of inorganic filler type ink composition, and has also improved the stability of inkjet printing to a certain extent. However, there are still problems such as low refractive index, large curing shrinkage, and low transmittance, so it is increasingly important to develop a stable pure organic ink composition. Summary of the invention

[0007] The present invention aims to solve one of the technical problems in the prior art at least to a certain extent. To this end, one object of the present invention is to provide an ink and its application.

[0008] In a first aspect of the present invention, the present invention provides an ink. According to an embodiment of the present invention, the ink comprises a photocurable free radical monomer, a photocurable cationic monomer, a free radical photoinitiator and a cationic photoinitiator; The photocurable free radical monomer includes a first free radical monomer and a second free radical monomer, the first free radical monomer includes an acrylate monomer, and the second free radical monomer is selected from the compound represented by Formula 1, and the compound represented by Formula 1 is selected from at least one of the following structures; , , ,

[0009] Among them, the A group is , group B is , wherein a and i are independently 0 or 1, and a+i is not 0; b, c, d, e, f, g, h, u, and v are independently 0 or 1, and at least one of d, e, f, and g is 1; R1, R 10 are independently hydrogen, substituted or unsubstituted C1~C 20 Alkyl or substituted or unsubstituted C1~C 20 R2, R3, R8, and R9 are independently a single bond, oxygen, sulfur, a substituted or unsubstituted C1~C 20 Alkylene or substituted or unsubstituted C7~C 20 R4, R5, R6, R7 are independently chlorine, bromine or iodine; R 11 , R 12 are independently oxygen or sulfur; The photocurable cationic monomer includes a first cationic monomer and a second cationic monomer, wherein the first cationic monomer includes a vinyl monomer; the second cationic monomer is selected from a compound represented by Formula 2, wherein the compound represented by Formula 2 is selected from at least one of the following structures; , , ,

[0010] Among them, the M group is , N group is , wherein k and L are independently 0 or 1, and k+L is not 0; m, n, p, q, t, w, r, x, y, z are independently 0 or 1, and at least one of m, n, p, q is 1; R 13 , R 14 , R 15 , R 16 are independently chlorine, bromine or iodine; R 17 , R 18 , R 19 , R 24 are independently a single bond, oxygen, sulfur, a substituted or unsubstituted C1~C 20 Alkylene or substituted or unsubstituted C7~C 20 Arylalkylene; R 20 , R 22 are independently a single bond, a substituted or unsubstituted C1~C 20 Alkylene or substituted or unsubstituted C7~C 20 Arylalkylene; R 21 , R 23 are independently oxygen or sulfur.

[0011] The ink according to the above embodiment of the present invention includes a photocurable free radical monomer, a photocurable cationic monomer, a free radical photoinitiator and a cationic photoinitiator, which adopts a pure organic component to avoid the risk of instability such as precipitation caused by the inorganic filler system. The photocurable free radical monomer includes a first free radical monomer and a second free radical monomer, the second free radical monomer is a halogen-modified free radical monomer, and the photocurable cationic monomer includes a first cationic monomer and a second cationic monomer, the second cationic monomer is a halogen-modified cationic monomer, and the combination and compounding of the second free radical monomer and the second cationic monomer can work synergistically, significantly improving the refractive index, curing performance, and light transmittance of the ink, and reducing the curing shrinkage of the ink. The formed film can effectively block water and oxygen, thereby significantly improving the performance of the light extraction layer of optical elements and optoelectronic devices. At the same time, through the interaction of the first free radical monomer, the second free radical monomer, the first cationic monomer and the second cationic monomer, the ink has a suitable viscosity, thereby having excellent printing performance. Specifically, the ink has a refractive index of no less than 1.67, a transmittance of greater than 98%, a volume shrinkage of no more than 8%, a photocuring rate of greater than 90%, a viscosity of less than 31 cP, and can be inkjet printed.

[0012] In some embodiments of the present invention, the compound represented by Formula 1 comprises at least one of the following structures: , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , .

[0013] As an example, the compound shown in Formula 1 is not limited to 2,4,6-trichloro-1-acrylic acid (benzyloxy) ester, 2,4,6-trichloro-1-acrylic acid (benzylthio) ester, 2,4,6-trichloro-1-acrylic acid (benzylthio) ethyl ester, 2,4,6-trichloro-1-acrylic acid (benzylthio) ethyl thioester, 2,3,4,6-tetraiodo-1-methylacrylate (benzyloxy) ethyl ester, 2,3,4,6-tetraiodo-1-methylacrylate (benzylthio) ethyl ester , 3,4-diiodo-1-methylacrylate (phenylmethylthio) ethylthioate, 3,6-dichloro-1,5-dimethylacrylate (phenylenedithio) dimethyl ester, 2,3-dichloro-1,5-dimethylacrylate (phenylenedithio) dimethyl ester, 2,3,4-trichloro-1,5-dimethylacrylate (phenylenedithio) dimethyl ester, 2,3,4-trichloro-1,5-dimethylacrylate (phenylenedithio) diethyl ester, 2,3,4,6-tetrachloro-1,5-dimethylacrylate 、2,3,4,6-tetrachloro-1,5-dimethacrylate benzyl dimethyl thioester、3,6-dibromo-1,5-dimethacrylate (phenylenedithio) dimethyl ester、2,3-dibromo-1,5-dimethacrylate (phenylenedithio) dimethyl ester、2,3,4-tribromo-1,5-dimethacrylate (phenylenedithio) dimethyl ester、2,3,4-tribromo-1,5-dimethacrylate benzyl dimethyl ester、2,3,4,6-tetrabromo-1,5-dimethacrylate benzyl dimethyl thioester、 2,3,4,6-tetrabromo-1,5-dimethacrylate benzyl dimethyl ester, 2,3,4,6-tetrabromo-1,5-dimethacrylate (phenylenedimethylthio) ethyl ester, 2,3,4,6-tetrabromo-1,5-dimethacrylate (phenylenedimethylthio) ethyl thioester, 2,3,4-triiodo-1,5-dimethacrylate benzyl dimethylthioester, 2,3,4-triiodo-1,5-dimethacrylate benzyl dimethyl ester or 3,4-diiodo-1,5-acrylate (phenylenedimethylthio) diethyl ester.

[0014] In some embodiments of the present invention, the compound represented by Formula 2 comprises at least one of the following structures: , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , .

[0015] As an example, the compounds shown in Formula 2 are not limited to 2,4,6-trichloro-1-(phenylmethylthio) vinyl sulfide, 2,4,6-trichloro-1-(phenylmethylthio) vinyl ether, 3-bromo-1-(phenylmethylthio) ethyl vinyl ether, 3-bromo-1-(phenylmethylthio) ethyl vinyl sulfide, 2,3,4,6-tetraiodo-1-(phenylmethylthio) vinyl sulfide, 2,3,4,6-tetraiodo-1-(phenylmethylthio) ethyl vinyl sulfide. 2-iodo-1-(phenylmethylthio)ethyl vinyl sulfide, 3,4-diiodo-1-(phenylmethylthio)ethyl vinyl ether, 3,4-diiodo-1-(phenylmethylthio)ethyl vinyl sulfide, 2,3,5,6-tetrachloro-1,4-(phenylenedimethylthio) divinyl sulfide, 2,3,5,6-tetrachloro-1,4-(phenylenedimethoxy) divinyl ether, 2,3,5,6-tetrachloro-1,4-(phenylenedimethoxy) divinyl ether, 2,3,5,6-tetrachloro-1,4-(phenylenedimethylthio)diethyl vinyl ether, 3,4-dibromo-1,5-(phenylenedimethylthio)diethyl vinyl ether, 3,4-dibromo-1,5-(phenylenedimethylthio)diethyl vinyl ether, 3,4,5-tribromo-1,5-(phenylenedimethylthio)divinyl ether, 3,4,5-tribromo-1,5-(phenylenedimethylthio)divinyl ether, 2,3,4,5 -tetrabromo-1,5-(phenylenedimethoxy) divinyl ether, 2,3,4,5-tetrabromo-1,5-(phenylenedimethylthio) divinyl sulfide, 2,4-diiodo-1,5-(phenylenedimethylthio) vinyl sulfide, 2,4-diiodo-1,5-(phenylenedimethoxy) divinyl ether, 3,4-diiodo-1,5-(phenylenedimethylthio) diethyl vinyl ether or 3,4-diiodo-1,5-(phenylenedimethylthio) diethyl vinyl sulfide.

[0016] In some embodiments of the present invention, based on the total mass of the photocurable free radical monomer, the mass proportion of the second free radical monomer is 10-60wt%. For example, the mass proportion of the second free radical monomer is 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, etc. The inventors have found that when the mass proportion of the second free radical monomer is controlled within the above range, it has a more obvious effect on reducing the viscosity of the ink, increasing the refractive index, increasing the curing rate, and increasing the hardness, and can effectively meet the requirements of inkjet printing and rapid curing.

[0017] In some embodiments of the present invention, based on the total mass of the photocurable cationic monomer, the mass proportion of the second cationic monomer is 10-60wt%. For example, the mass proportion of the second cationic monomer is 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, etc. The inventors have found that when the mass proportion of the second cationic monomer is controlled within the above range, it has a more obvious effect on reducing the viscosity of the ink, increasing the refractive index, and reducing the curing shrinkage, and can effectively meet the requirements of inkjet printing and low curing shrinkage after curing.

[0018] In some embodiments of the present invention, the acrylate monomer includes at least one of a monofunctional acrylate monomer, a difunctional acrylate monomer, and a multifunctional acrylate monomer.

[0019] By way of example, acrylate monomers include, but are not limited to, lauryl acrylate (LA), ethoxyethoxyethyl acrylate ((EOEOEA)-KPX A007), butyl acrylate (BA), hydroxyethyl acrylate and isobornyl acrylate, ethoxylated tetrahydrofuran acrylate ((THF(EO)A)-KPX A015), methacrylate phosphate, isobornyl methacrylate, phenyl thioacrylate, methyl phenyl thioacrylate, ethyl phenyl thioacrylate, propyl phenyl thioacrylate, diphenyl thioacrylate, triphenyl thioacrylate, 2-phenoxyethyl acrylate, 2-phenylthioethyl acrylate, 4-methylthio phenylthioacrylate, 1-bicyclo[2.2.1]heptane-2,5-di(methylthio)-4-methacrylate, diethylene glycol diacrylate (DEGDA), dimethacrylate, Ethylene glycol di(meth)acrylate, triethylene glycol diacrylate (TEGDA), triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol diacrylate, polyethylene glycol (200) diacrylate [PEG(200)DA], polyethylene glycol (400) diacrylate [PEG(400)DA], polyethylene glycol (600) diacrylate [PEG(600)DA], neopentyl glycol diacrylate and propoxy neopentyl glycol diacrylate, 1,6-Hexanediol diacrylate (HDDA), 1,6-Hexanediol di(meth)acrylate, 1,4-Butanediol diacrylate (BDDA), 1,4-Butanediol di(meth)acrylate, 20(ethoxy)bisphenol A diacrylate [BPA(EO)20DA], propylene glycol diacrylate (TPGDA), octanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, undecanediol di(meth)acrylate, dodecanediol di(meth)acrylate, 1,4-benzylthiodiacrylate, 4,4-[isopropylbis(p-phenyloxy)]diethanol methacrylate, 2,4,6-trithio-1,3-dimethyldipropylene ester, 2-(1,3-disulfanyl)-1,3-disulfide-1,4-dimethacrylate, 4,4-[disulfide-biphenyl]diethanol methacrylate, 1,9-nonanediacrylate benzyl thioester, 3,7-dithia-1,9-nonanediacrylate thioester, cyclohexanedimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), trimethylolpropane triol triacrylate (TMPTMA), trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tripropenyl ester, propoxylated pentaerythritol propenyl ester or di(trimethylolpropane) tetraacrylate.

[0020] In some embodiments of the present invention, the vinyl monomer includes at least one of bis(4-(vinyloxy)phenyl)oxyethane, bis(4-(vinylthio)phenyl)oxyethane, bis(4-(vinylthio)phenyl)sulfane, 2,5-(vinyloxy)-1,4-dithiane, 2,5-(vinylthio)-1,4-dithiane, 4,4'-bis(vinyloxy)-diphenyl sulfone, 4,4'-bis(vinyloxy)-diphenylmethane, bis[4-(vinyloxy)phenyl]ether, bis[4-(vinyloxy)phenyl]sulfone, 4,4'-bis(vinyloxy)-benzophenone, bis[4-(vinyloxy)phenyl]dimethylsilane, 4,4'-bis(vinyloxy)-diphenylamine, 4,4'-bis(vinyloxy)-ethyl dibenzoate, bis[4-(vinyloxy)phenyl]phosphate and 1,4-(vinylthio)benzene.

[0021] In some embodiments of the present invention, the free radical photoinitiator includes at least one of benzoin and its derivatives initiators, benzil and its derivatives initiators, acetophenone derivatives initiators, α-hydroxyketone derivatives initiators, α-aminoketone derivatives initiators, benzoylformate initiators, acylphosphine oxide initiators, benzophenone initiators, thioxanthone initiators, anthraquinone and anthraquinone derivatives initiators.

[0022] In some embodiments of the present invention, the cationic photoinitiator includes at least one of an aromatic diazonium salt initiator, a diaryl iodonium salt initiator, a triaryl sulfonium salt initiator, a triaryl sulfonium salt initiator, an alkyl sulfonium salt initiator, an iron aromatic salt initiator and a triaryl siloxane ether initiator.

[0023] In some embodiments of the present invention, the ink comprises, by weight percentage: 10-70 wt% of the photocurable free radical monomer, 10-70 wt% of the photocurable cationic monomer, 0.1-6 wt% of the free radical photoinitiator, and 0.1-6 wt% of the cationic photoinitiator. The inventors have found that controlling the mass proportion of each monomer within the above range has a significant effect on reducing the viscosity of the ink, increasing the refractive index, increasing the curing rate, increasing the hardness, and reducing the curing shrinkage, and can effectively meet the requirements of inkjet printing, rapid curing, and low shrinkage after curing.

[0024] In some embodiments of the present invention, the ink further comprises no more than 5 wt % of an auxiliary agent by mass percentage.

[0025] In some embodiments of the present invention, the auxiliary agent includes at least one of a photosensitizer, a co-initiator, an inhibitor, an antioxidant, a substrate wetting agent, a defoamer and a leveling agent. Preferably, the auxiliary agent includes a photosensitizer or a co-initiator.

[0026] In some embodiments of the present invention, the photosensitizer includes but is not limited to diphenyliodonium hexafluorophosphate, 4-tert-butylphenyliodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tri(4-methoxyphenyl)sulfonium hexafluorophosphate, bis(4-tert-butylphenyl)sulfonium hexafluorophosphate, bis(4-tert-butylphenyl)sulfonium hexafluorophosphate, bis(4-tert-butylphenyl)sulfonium hexafluorophosphate, tri(4-methoxyphenyl)sulfonium hexafluorophosphate anthracene, 4-isopropylthioxanthone, benzophenone or phenothiazine.

[0027] In some embodiments of the present invention, the co-initiator includes but is not limited to ethyl 4-dimethylaminobenzoate, isooctyl p-dimethylaminobenzoate, dimethylaminoethyl benzoate or ethyl 4-dimethylaminobenzoate.

[0028] In some embodiments of the present invention, the polymerization inhibitor includes, but is not limited to, p-hydroxyanisole, hydroquinone, tris[N-nitroso-N-phenylhydroxylamine]aluminum salt or p-benzoquinone.

[0029] In some embodiments of the present invention, the antioxidant includes, but is not limited to, 2,6-di-tert-butyl-4-methylphenol, bis(3,5-di-tert-butylphenyl)pentaerythritol diphosphite or (2,4-di-tert-butylphenyl)phosphite.

[0030] In a second aspect of the present invention, the present invention proposes the application of the above-mentioned ink in optical lenses, electronic components, biomedicine or photovoltaic fields.

[0031] The present invention has at least the following technical effects: (1) The second free radical monomer and the second cationic monomer used in the present invention are new halogenated high refractive index monomers. The combination of the second free radical monomer and the second cationic monomer can work synergistically to significantly improve the refractive index, curing performance, and light transmittance of the ink, and reduce the curing shrinkage of the ink. The formed film can effectively block water and oxygen, ensure the performance of the product, and thus significantly improve the performance of the light extraction layer of optical components and optoelectronic devices.

[0032] (2) The present invention uses a purely organic ink composition, thus avoiding the risk of instability such as precipitation caused by an inorganic filler system.

[0033] (3) The raw materials for preparing the ink are easily available, the preparation is simple, the cost is low, and it is conducive to large-scale production. DETAILED DESCRIPTION

[0034] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. The present invention is described below with reference to specific embodiments. It should be noted that these embodiments are merely illustrative and do not limit the present invention in any way.

[0035] The free radical photoinitiator used in the embodiments and comparative examples is TPO, the cationic photoinitiator is bis(4-tert-butylphenyl)iodonium hexafluorophosphate, the photosensitizer is 4-isopropylthioxanthone, the first free radical monomer is methylphenyl acrylate thioester (denoted as Y), the first cationic monomer is bis(4-(vinylthio)phenyl)oxane (denoted as W), the specific structures of the second free radical monomer and the second cationic monomer are shown in Table 1, and the weight parts of the above components are shown in Table 1.

[0036] Table 1

[0037] The ink properties of the embodiments and comparative examples were measured in the following manner: (1) Transmittance test: A UV-visible spectrophotometer test system (Carry 5000, manufactured by Agilent Technologies, Inc., USA) was used. The photocurable composition was sprayed or ink-jet printed on a glass substrate and the light was measured at 200 mW / cm 2 The film was subjected to UV curing for 180 seconds by UV irradiation at 400°C to produce a cured sample having a 10 μm thick layer. The transmittance of the film was measured in the range of 400 to 800 nm using a UV-visible spectrophotometer test system (Carry 5000, manufactured by Agilent Technologies, Inc., USA).

[0038] (2) Photocuring rate: FT-IR (Nicolet iS10, Thermo) at 1635 cm -1 (C=C) and 1720cm -1 The absorption peak intensity of the photocurable composition was measured near (C=O). First, the photocurable composition was sprayed or ink-jet printed on a glass substrate and heated at 200 mW / cm 2 The cured film was subjected to UV curing for 180 seconds by UV irradiation to produce a sample with a size of 20 cm x 20 cm x 3 μm (width x length x thickness). The cured film was cut into samples, which were then used to measure the wavelength at 1635 cm using FT-IR (Nicoleti S10, by Thermo). -1 (C=C) and 1720cm -1 The absorption peak intensity of (C=O). The photocuring rate is calculated by formula 1: Photocuring rate (%) = |1-(A / B)|x100 Formula 1; Where A is the cured film at 1635cm -1 The absorption peak intensity near 1720cm -1 is the ratio of the absorption peak intensities near 1635 cm -1 The absorption peak intensity near 1720cm -1 The ratio of the absorption peak intensities near

[0039] (3) Hardness: The composition was applied to a glass substrate using a sprayer, and then heated at 150 mW / cm 2 The samples were irradiated with a UV lamp for 10 seconds for UV curing, and then placed in an oven at 80°C for 0.5 h to allow the samples to be completely cured, and then tested according to GB / T 6739-2006.

[0040] (4) Volume shrinkage (%): The composition was placed in a polytetrafluoroethylene mold and heated to 150 mW / cm 2 The composition was cured by irradiating with a UV lamp for 10 seconds and then placed in an oven at 80°C for 0.5 hours to completely cure the composition. After curing, the volume of the sample was measured using the water displacement method. The curing shrinkage of the encapsulation composition was calculated according to the following equation, where C is the volume of the liquid before curing and D is the volume of the sample after UV curing: Curing shrinkage (%) = (|C-D|÷C) × 100%.

[0041] (5) Viscosity: The viscosity of the composition at 25°C was tested using a TA Discovery HR-1 rheometer with 60 mm parallel plates.

[0042] (6) Refractive index: The refractive index of the liquid ink composition is tested using an Abbe refractometer. Take an appropriate amount of liquid ink and evenly apply it on the observable surface of the prism table. Use a white light source to illuminate it. The corresponding value read in the readable area is the refractive index of the liquid at 589nm. The cured layer film is tested using an ellipsometer. First, the liquid ink is evenly applied on the smooth surface of a silicon wafer or optical frosted glass with a thickness of 1~10nm. After the film is cured, the full-band refractive index is tested on the ellipsometer to obtain the full-band refractive index.

[0043] The results of the ink properties of the embodiments and comparative examples are shown in Table 2.

[0044] Table 2

[0045] It can be seen from Table 2 that the ink of the present application has a high refractive index, which is above 1.60, and has a high light transmittance, a small volume shrinkage, a high photocuring rate, and an appropriate viscosity, which improves the printing performance of the ink.

[0046] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An ink, characterized in that: Including photocurable free radical monomers, photocurable cationic monomers, free radical photoinitiators and cationic photoinitiators; The photocurable free radical monomer includes a first free radical monomer and a second free radical monomer, the first free radical monomer includes an acrylate monomer, and the second free radical monomer is selected from the compound represented by Formula 1, and the compound represented by Formula 1 is selected from at least one of the following structures; 、 、 ， Among them, the A group is , group B is , wherein a and i are independently 0 or 1, and a+i is not 0; b, c, d, e, f, g, h, u, v are independently 0 or 1, and at least one of d, e, f, g is 1; R1, R 10 are independently hydrogen, substituted or unsubstituted C1~C 20 Alkyl or substituted or unsubstituted C1~C 20 R2, R3, R8, and R9 are independently a single bond, oxygen, sulfur, a substituted or unsubstituted C1~C 20 Alkylene or substituted or unsubstituted C7~C 20 R4, R5, R6, R7 are independently chlorine, bromine or iodine; R 11 , R 12 are independently oxygen or sulfur; The photocurable cationic monomer includes a first cationic monomer and a second cationic monomer, wherein the first cationic monomer includes a vinyl monomer; the second cationic monomer is selected from a compound represented by Formula 2, wherein the compound represented by Formula 2 is selected from at least one of the following structures; 、 、 ， Among them, the M group is , N group is , wherein k and L are independently 0 or 1, and k+L is not 0; m, n, p, q, t, w, r, x, y, z are independently 0 or 1, and at least one of m, n, p, q is 1; R 13 , R 14 , R 15 , R 16 are independently chlorine, bromine or iodine; R 17 , R 18 , R 19 , R 24 are independently a single bond, oxygen, sulfur, a substituted or unsubstituted C1~C 20 Alkylene or substituted or unsubstituted C7~C 20 Arylalkylene; R 20 , R 22 are independently a single bond, a substituted or unsubstituted C1~C 20 Alkylene or substituted or unsubstituted C7~C 20 Arylalkylene; R 21 , R 23 are independently oxygen or sulfur.

2. The ink according to claim 1, characterized in that: The compound represented by Formula 1 includes at least one of the following structures: ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， 。 3. The ink according to claim 1, characterized in that: The compound represented by Formula 2 includes at least one of the following structures: ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， 。 4. The ink according to claim 1, characterized in that: Based on the total mass of the photocurable free radical monomer, the mass proportion of the second free radical monomer is 10-60wt%.

5. The ink according to claim 1, characterized in that: Based on the total mass of the photocurable cationic monomer, the mass proportion of the second cationic monomer is 10-60wt%.

6. The ink according to any one of claims 1 to 5, characterized in that: The acrylic acid ester monomer includes at least one of a monofunctional acrylic acid ester monomer, a bifunctional acrylic acid ester monomer, and a multifunctional acrylic acid ester monomer; and / or, the vinyl monomer includes at least one of bis(4-(vinyloxy)phenyl)oxyethane, bis(4-(vinylthio)phenyl)oxyethane, bis(4-(vinylthio)phenyl)sulfane, 2,5-(vinyloxy)-1,4-dithiane, 2,5-(vinylthio)-1,4-dithiane, 4,4'-bis(vinyloxy)-diphenyl sulfone, 4,4'-bis(vinyloxy)-diphenylmethane, bis[4-(vinyloxy)phenyl]ether, bis[4-(vinyloxy)phenyl]sulfone, 4,4'-bis(vinyloxy)-benzophenone, bis[4-(vinyloxy)phenyl]dimethylsilane, 4,4'-bis(vinyloxy)-diphenylamine, 4,4'-bis(vinyloxy)-ethyl dibenzoate, bis[4-(vinyloxy)phenyl]phosphate and 1,4-(vinylthio)benzene; And / or, the free radical photoinitiator includes at least one of benzoin and its derivatives, benzil and its derivatives, acetophenone derivatives, α-hydroxyketone derivatives, α-aminoketone derivatives, benzoylformate esters, acylphosphine oxides, benzophenones, thioxanthones, anthraquinones and anthraquinone derivatives; And / or, the cationic photoinitiator includes at least one of an aromatic diazonium salt initiator, a diaryl iodonium salt initiator, a triaryl sulfonium salt initiator, a triaryl sulfonium salt initiator, an alkyl sulfonium salt initiator, an iron aromatic salt initiator and a triaryl siloxane ether initiator.

7. The ink according to any one of claims 1 to 5, characterized in that: Calculated by mass percentage, it includes: 10-70wt% of the photocurable free radical monomer, 10-70wt% of the photocurable cationic monomer, 0.1-6wt% of the free radical photoinitiator, and 0.1-6wt% of the cationic photoinitiator.

8. The ink according to claim 7, characterized in that: Calculated by mass percentage, it also includes no more than 5wt% of auxiliary agents.

9. The ink according to claim 8, characterized in that: The auxiliary agent includes at least one of a photosensitizer, a co-initiator, an inhibitor, an antioxidant, a substrate wetting agent, a defoamer and a leveling agent.

10. Use of the ink according to any one of claims 1 to 9 in the fields of optical lenses, electronic components, biomedicine or photovoltaics.

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