TWI758062B - Photo curable ink, method of patterning, and package structure - Google Patents

Abstract

Photo curable ink increases 1 part by weight of resin, 1.5 to 3.5 parts by weight of diluent, and 0.25 to 1.5 parts by weight of photo sensitizer. The resin has a chemical structure of

or

. R ¹is C _2-16alkyl group, phenyl group, tolyl group, benzyl group, or

, and R ⁵is C _2-10alkyl group;R ²is

,

,

,

,

,

, or

; and each of R ³and R ⁴is independently H, C _1-15alkyl group, C _2-15alkenyl group, or phenyl group. The photo curable ink has a viscosity of 4 cps to 50 cps at room temperature, and an acid value of 0 mg/KOH to 60 mg/KOH.

Description

Photocurable ink, patterning method, and packaging structure

The present disclosure relates to photocurable inks used in ink jet printing (IJP) processes, and more particularly, to patterning processes and packaging structures using photocurable inks.

At present, most of the anti-etching materials are screen printing materials or dry film materials, and a few are laser forming materials. If the anti-etching material is applied by means of ink jet printing (IJP), it is usually necessary to dissolve the anti-etching material in a solvent, resulting in the problem of volatile organic compounds (VOCs) and even the environmental protection of waste water. On the other hand, screen printing materials require a screen, while dry film materials require a photomask. Although laser forming has no problems such as waste water, it is relatively slow.

To sum up, there is a need for new anti-etching materials to solve the above problems.

或

，R ¹係C _2-16的烷基、苯基、甲苯基、苯甲基、或

，且R ⁵係C _2-10的烷基；R ²係

、

、

、

、

、

、或

；以及R ³及R ⁴各自為H、C _1-15烷基、C _2-15烯基、或苯基，其中光固化墨水的室溫黏度係4 cps至50 cps，以及其中光固化墨水的酸價係0 mg/KOH至60 mg/KOH。 The light-curable ink provided by an embodiment of the present disclosure includes: 1 weight part of a resin; 1.5 to 3.5 weight parts of a diluent; and 0.25 to 1.5 weight parts of a photosensitive agent, wherein the chemical structure of the resin is

or

, R ¹ is C _2-16 alkyl, phenyl, tolyl, benzyl, or

, and R ⁵ is a C _2-10 alkyl group; R ² is

,

,

,

,

,

,or

and R ³ and R ⁴ are each H, C _1-15 alkyl, C _2-15 alkenyl, or phenyl, wherein the room temperature viscosity of the photocurable ink is 4 cps to 50 cps, and wherein the photocurable ink has a The acid value ranges from 0 mg/KOH to 60 mg/KOH.

In some embodiments, the photocurable ink is solvent-free.

In some embodiments, the diluent comprises (meth)acrylate, tridecyl acrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate Esters, Diethylene Glycol Diacrylate, Tetraethylene Glycol Diacrylate, Tripropylene Glycol Diacrylate, Neopentyl Glycol Diacrylate, 1,4-Butanediol Dimethacrylate, Poly(butylene Glycol) ) diacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol diacrylate, tetraethylene glycol diacrylate, triisopropylene glycol diacrylate, triisopropylene glycol diacrylate, ethoxylate Alkylated bisphenol A diacrylate, isobornyl acrylate, N-vinyl caprolactam, or a combination of the above.

In some embodiments, the sensitizer comprises benzylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,6-dimethoxybenzyl)-2 ,4,4-trimethyl, hydroxycyclohexyl phenyl ketone, hydroxymethyl phenyl acetone, dimethoxyphenyl acetophenone, 2-methyl-1-[4-(methylthio) phenyl ]-2-morpholinopropan-1-yl, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-yl, 1-(4-dodecylphenyl) )-2-hydroxy-2-methylpropan-1-yl, 4-(2-hydroxyethoxy)phenyl-2(2-hydroxy-2-propyl) ketone, diethoxyphenylphenethyl Ketone, 2,4,6-Trimethylbenzyldiphenylphosphine, 2,3-Dihydroxy-6-(2-hydroxy-2-methyl-1-oxypropyl)-1,1 ,3-trimethyl-3-[4-(2-hydroxy-2-methyl-1-oxypropyl)phenyl]-1H-indene, 2-methyl-1-[4-(methylthio) base)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-methylamino)-1-(4-morpholinophenyl)butan-1-one, α-Hydroxycyclohexyl phenyl ketone, methyl phenyl glycidyl ester, 2-hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-propanone, (n ⁵ -2,4-Cyclopentadien-1-yl)[(1,2,3,4,5,6-n)-(1-methylethyl)benzene]-iron(I)-hexafluoroantimony acid salt, methylphenylglyoxylate/hydroxyphenyl(1-hydroxy)cyclohexylphenyl ketone + benzophenone, bis(η ⁵ -cyclopentadiene)-bis(2,6-difluoro) -3-[pyrrol-1-yl]-phenyl)titanate, 2-hydroxy-2-methyl-1-phenyl-1-propyl-1-one, diphenyl(4-phenylthio) base) phenyl perylene hexafluoroantimonate + (mercapto-4,1-phenylene) bis(diphenyl perylene) dihexafluoroantimonate, 2-isopropyl thioxanthone, ethyl (2, 4,6-Trimethylbenzylphenylphosphite, 2,2-dimethyl-1,2-diphenylethan-1-one, 4-benzyl-4'-methyl diphenyl sulfide, 2,4-diethyl thioxanthone, isopropyl thioxanthone, methyl-o-benzyl benzoate, 2,4,6-trimethylbenzyl Acrylodiphenyl hypophosphite oxide, or a combination of the above.

或

，R ¹係C _2-16的烷基、苯基、甲苯基、苯甲基、或

，且R ⁵係C _2-10的烷基；R ²係

、

、

、

、

、

、或

；以及R ³及R ⁴各自為H、C _1-15烷基、C _2-15烯基、或苯基，其中光固化墨水的室溫黏度係4 cps至50 cps，以及其中光固化墨水的酸價係20 mg/KOH至60 mg/KOH。 A patterning method provided by an embodiment of the present disclosure includes inkjet printing of a photocurable ink on an inorganic material layer, and instant photocuring of the photocurable ink to form a pattern; and etching the inorganic material layer not covered by the pattern to form a patterned Inorganic material layer, wherein the photocurable ink comprises: 1 weight part of resin; 1.5 to 3.5 weight part of diluent; and 0.25 to 1.5 weight part of photosensitive agent, wherein the chemical structure of the resin is

or

, R ¹ is C _2-16 alkyl, phenyl, tolyl, benzyl, or

, and R ⁵ is a C _2-10 alkyl group; R ² is

,

,

,

,

,

,or

and R ³ and R ⁴ are each H, C _1-15 alkyl, C _2-15 alkenyl, or phenyl, wherein the room temperature viscosity of the photocurable ink is 4 cps to 50 cps, and wherein the photocurable ink has a The acid value is 20 mg/KOH to 60 mg/KOH.

In some embodiments, the patterning method further includes stripping the pattern on the patterned inorganic material layer.

In some embodiments, the thickness of the pattern is 1 μm to 10 μm.

或

，R ¹係C _2-16的烷基、苯基、甲苯基、苯甲基、或

，且R ⁵係C _2-10的烷基；R ²係

、

、

、

、

、

、或

；以及R ³及R ⁴各自為H、C _1-15烷基、C _2-15烯基、或苯基，其中光固化墨水的室溫黏度係4 cps至50 cps，以及其中光固化墨水的酸價係0 mg/KOH至40 mg/KOH。 An encapsulation structure provided by an embodiment of the present invention includes: a photoelectric element; a protective layer covering the photoelectric element; and a gas barrier layer covering the protective layer, wherein the protective layer is formed by curing a photocurable ink, and the photocurable ink includes: 1. 1.5 to 3.5 parts by weight of a diluent; and 0.25 to 1.5 parts by weight of a sensitizer, wherein the chemical structure of the resin is

or

, R ¹ is C _2-16 alkyl, phenyl, tolyl, benzyl, or

, and R ⁵ is a C _2-10 alkyl group; R ² is

,

,

,

,

,

,or

and R ³ and R ⁴ are each H, C _1-15 alkyl, C _2-15 alkenyl, or phenyl, wherein the room temperature viscosity of the photocurable ink is 4 cps to 50 cps, and wherein the photocurable ink has a The acid value ranges from 0 mg/KOH to 40 mg/KOH.

In some embodiments, the thickness of the protective film is 1 μm to 10 μm.

In some embodiments, the optoelectronic element includes a light emitting diode, a quantum dot light emitting diode, an organic light emitting diode, a liquid crystal display, or a light sensor.

The photocurable ink provided by an embodiment of the present disclosure includes: 1 weight part of resin; 1.5 to 3.5 weight parts of diluent; and 0.25 to 1.5 weight part of photosensitive agent. If the amount of diluent is too low, the synthesized polymer has high room temperature viscosity and cannot be printed. If the amount of the photosensitive agent is too low, the photosensitive ability of the photocurable ink will be deteriorated, which will lead to amortization, and the line width cannot be controlled finely. If the amount of sensitizer is too high, insoluble crystals will be formed, which will lead to blockage of the nozzle and poor storage stability.

或

。R ¹係C _2-16的烷基、苯基、甲苯基、苯甲基、或

，且R ⁵係C _2-10的烷基；R ²係

、

、

、

、

、

、或

；以及R ³及R ⁴各自為H、C _1-15烷基、C _2-15烯基、或苯基。 In one embodiment, the chemical structure of the resin is

or

. R ¹ is C _2-16 alkyl, phenyl, tolyl, benzyl, or

, and R ⁵ is a C _2-10 alkyl group; R ² is

,

,

,

,

,

,or

; and R ³ and R ⁴ are each H, C _1-15 alkyl, C _2-15 alkenyl, or phenyl.

或

In one embodiment, the above-mentioned resin is formed as follows. First, the glycidyl ether is reacted with acrylic acid, and then reacted with acid anhydride to form a resin. It is worth noting that the above three should not be directly mixed and must be reacted sequentially, otherwise the desired structure cannot be synthesized, and the molecular segments will produce a disordered combination, the molecular weight cannot be controlled, the degree of polymerization cannot be controlled, and there is no reproducibility. The above reaction looks like this:

or

The room temperature viscosity of the above photocurable ink is 4 cps to 50 cps, and the acid value of the photocurable ink is 0 mg/KOH to 60 mg/KOH. If the viscosity of the light-curable ink is too low, the nozzle will not be able to absorb ink, and there will be ink leakage and ink droplets, which will lead to more scattered spots. If the room temperature viscosity of the light-curable ink is too high, the inkjet fluency is not good and it is easy to be blocked. If the acid value of the photocurable ink is too high, micro-etching will occur on the surface of the copper foil, resulting in a large roughness that affects the electrical properties. In some embodiments, the photocurable ink is solvent-free. If the photo-curable ink contains solvent, it must be baked to remove the solvent after inkjet, and cannot be photo-cured immediately.

In some embodiments, the diluent comprises (meth)acrylate, tridecyl acrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate Esters, Diethylene Glycol Diacrylate, Tetraethylene Glycol Diacrylate, Tripropylene Glycol Diacrylate, Neopentyl Glycol Diacrylate, 1,4-Butanediol Dimethacrylate, Poly(butylene Glycol) ) diacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol diacrylate, tetraethylene glycol diacrylate, triisopropylene glycol diacrylate, triisopropylene glycol diacrylate, ethoxylate Alkylated bisphenol A diacrylate, isobornyl acrylate, N-vinyl caprolactam, or a combination of the above.

In some embodiments, the sensitizer comprises benzylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,6-dimethoxybenzyl)-2 ,4,4-trimethyl, hydroxycyclohexyl phenyl ketone, hydroxymethyl phenyl acetone, dimethoxyphenyl acetophenone, 2-methyl-1-[4-(methylthio) phenyl ]-2-morpholinopropan-1-yl, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-yl, 1-(4-dodecylphenyl) )-2-hydroxy-2-methylpropan-1-yl, 4-(2-hydroxyethoxy)phenyl-2(2-hydroxy-2-propyl) ketone, diethoxyphenylphenethyl Ketone, 2,4,6-Trimethylbenzyldiphenylphosphine, 2,3-Dihydroxy-6-(2-hydroxy-2-methyl-1-oxypropyl)-1,1 ,3-trimethyl-3-[4-(2-hydroxy-2-methyl-1-oxypropyl)phenyl]-1H-indene, 2-methyl-1-[4-(methylthio) base)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-methylamino)-1-(4-morpholinophenyl)butan-1-one, α-Hydroxycyclohexyl phenyl ketone, methyl phenyl glycidyl ester, 2-hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-propanone, (n ⁵ -2,4-Cyclopentadien-1-yl)[(1,2,3,4,5,6-n)-(1-methylethyl)benzene]-iron(I)-hexafluoroantimony acid salt, methylphenylglyoxylate/hydroxyphenyl(1-hydroxy)cyclohexylphenyl ketone + benzophenone, bis(η ⁵ -cyclopentadiene)-bis(2,6-difluoro) -3-[pyrrol-1-yl]-phenyl)titanate, 2-hydroxy-2-methyl-1-phenyl-1-propyl-1-one, diphenyl(4-phenylthio) base) phenyl perylene hexafluoroantimonate + (mercapto-4,1-phenylene) bis(diphenyl perylene) dihexafluoroantimonate, 2-isopropyl thioxanthone, ethyl (2, 4,6-Trimethylbenzylphenylphosphite, 2,2-dimethyl-1,2-diphenylethan-1-one, 4-benzyl-4'-methyl diphenyl sulfide, 2,4-diethyl thioxanthone, isopropyl thioxanthone, methyl-o-benzyl benzoate, 2,4,6-trimethylbenzyl Acrylodiphenyl hypophosphite oxide, or a combination of the above.

An embodiment of the present disclosure provides a patterning method, which includes inkjet printing the above-mentioned photocurable ink on an inorganic material layer (eg, a metal layer such as Cu or other ceramic materials such as ITO), and then photocuring the photocurable ink immediately to form a pattern. The inorganic material layer uncovered by the pattern is then etched to form a patterned inorganic material layer. The photocurable ink includes: 1 weight part of resin; 1.5 to 3.5 weight part of diluent; and 0.25 to 1.5 weight part of photosensitive agent. The chemical structure of the resin is the same as above, and will not be repeated here. The room temperature viscosity of the photocurable ink is 4 cps to 50 cps, and the acid value of the photocurable ink is 20 mg/KOH to 60 mg/KOH. If the acid value of the photocurable ink is too low, it is difficult to remove after the etching process. If the acid value of the photocurable ink is too high, the surface of the copper foil will be slightly etched, resulting in a large surface roughness that affects the electrical properties. In some embodiments, the thickness of the pattern is between 1 μm and 10 μm. If the thickness of the pattern is too small, the effect of resisting the metal etching solution is poor, and there is a risk of peeling off, which leads to the concern of disconnection of the metal circuit. If the thickness of the pattern is too large, the process time of lye stripping needs to be extended, and the mass production speed will be slowed down.

In some embodiments, the patterning method further includes stripping the pattern on the patterned inorganic material layer after etching the inorganic material layer. The step of peeling off the pattern can use an alkali such as sodium carbonate, or an aqueous solution of 0.05%-5% KOH or 1%-2.3% TMAH.

An encapsulation structure provided by an embodiment of the present invention includes: a photoelectric element; a protective layer covering the photoelectric element; and a gas barrier layer covering the protective layer, wherein the protective layer is formed by curing a photocurable ink, and the photocurable ink includes: 1. 1.5 to 3.5 parts by weight of the resin; 1.5 to 3.5 parts by weight of the diluent; and 0.25 to 1.5 parts by weight of the sensitizer. The chemical structure of the resin is the same as above, and will not be repeated here. The room temperature viscosity of the photocurable ink is 4cps to 50cps, and the acid value of the photocurable ink is 0mg/KOH to 40mg/KOH. If the acid value of the photocurable ink is too high, too many acid groups may damage the photovoltaic element.

In some embodiments, the thickness of the protective film is 1 μm to 10 μm. If the thickness of the protective film is too small, the element cannot be effectively covered, and gas or water molecules may intrude from the side, resulting in damage to the photovoltaic element. If the thickness of the protective film is too large, the stress of the gas barrier layer material will not match, and the light transmittance in the visible area will also decrease. In some embodiments, the optoelectronic element includes a light emitting diode, a quantum dot light emitting diode, an organic light emitting diode, a liquid crystal display, or a light sensor. In some embodiments, the gas barrier layer includes a solution-coated gas barrier layer, silicon oxide (SiO ₂ ) or silicon nitride ( _{Six N y )} . In another embodiment, the gas barrier layer is a solution coated gas barrier, and its composition and formation method can refer to FlexUP ^TM with Solution-coated Gas Barrier Technology ( https://www.itri. org.tw/english/ListStyle.aspx?DisplayStyle=01_content&SiteID=1&MmmID=1037333526356626457&MGID=746506075040501237 ) .

In order to make the above-mentioned content and other objects, features, and advantages of the present disclosure more obvious and easy to understand, preferred embodiments are given below, and are described in detail as follows in conjunction with the accompanying drawings:

[Example]

In the following examples, the measurement method of the room temperature viscosity is the instrument of BROOKFIELD, the Spindle is the viscosity value measured under the rotor of No. 18, under 50~100rpm, and the room temperature is 25℃, and the measurement standard of the acid value The method is to dissolve the test sample in a mixed solution of toluene and ethanol (toluene:ethanol=7:3), and use a potentiometric automatic titrator (AT500N) for titration with 0.1N KOH-ethanol solution.

Preparation Example 1

80 g of glycidyl ether was heated to 120° C. and stirred (rotational speed 250 rpm). 0.05 g of hydroquinone (HQ) was added to glycidyl ether and stirred for 5 minutes. Next, 38 g of acrylic acid was added to the reaction for 6 hours. Then, 81 g of acid anhydride was added and stirred (rotation speed 300 rpm) and reacted for 2 to 6 hours to obtain 199 g of resin with an acid value of 176 mg/KOH, a molecular weight of 570, and a room temperature viscosity of 1845 cps. The above reaction is as follows:

Preparation Example 2

80 g of glycidyl ether was heated to 120° C. and stirred (rotational speed 250 rpm). 0.05 g of HQ was added to glycidyl ether and stirred for 5 minutes. Next, 38 g of acrylic acid was added to the reaction for 6 hours. Then, 90 g of acid anhydride was added and stirred (rotation speed 300 rpm) and reacted for 2 to 6 hours to obtain 208 g of resin with an acid value of 172 mg/KOH, a molecular weight of 570, and a room temperature viscosity of 1400 cps. The above reaction is as follows:

Preparation Example 3 Take 80 g of glycidyl ether, heat it to 120° C. and stir (rotation speed 250 rpm). 0.05 g of HQ was added to glycidyl ether and stirred for 5 minutes. Next, 38 g of acrylic acid was added to the reaction for 6 hours. Then, 83 g of acid anhydride was added and stirred (rotation speed 300 rpm) and reacted for 2 to 6 hours to obtain 201 g of resin with an acid value of 164 mg/KOH, a molecular weight of 564, and a room temperature viscosity of 1038 cps. The above reaction is as follows:

Preparation Example 4 106 g of glycidyl ether was heated to 120° C. and stirred (rotational speed 250 rpm). 0.05 g of HQ was added to glycidyl ether and stirred for 5 minutes. Next, 27 g of acrylic acid was added to the reaction for 2 to 6 hours. Then, 57 g of acid anhydride was added and stirred (rotation speed 300 rpm) and reacted for 6 hours to obtain 190 g of resin with an acid value of 125 mg/KOH, a molecular weight of 685, and a room temperature viscosity of 1260 cps. The above reaction is as follows:

Preparation Example 5 Take 118 g of glycidyl ether (n=9~12), heat it to 120° C. and stir (rotation speed: 250 rpm). 0.05 g of HQ was added to glycidyl ether and stirred for 5 minutes. Next, 27 g of acrylic acid was added to the reaction for 6 hours. Then, 57 g of acid anhydride was added and stirred (rotation speed 300 rpm) and reacted for 2 to 6 hours to obtain 202 g of resin with an acid value of 110 mg/KOH, a molecular weight of 1453, and a room temperature viscosity of 54488 cps. The above reaction is as follows:

Preparation Example 6 81 g of glycidyl ether was heated to 120° C. and stirred (rotational speed 250 rpm). 0.3 g of HQ was added to glycidyl ether and stirred for 5 minutes. Next, 38 g of acrylic acid was added to the reaction for 6 hours. Then, 82 g of acid anhydride was added and stirred (rotation speed 300 rpm) and reacted for 2 to 6 hours to obtain 200 g of resin with an acid value of 115 mg/KOH, a molecular weight of 2578, and a room temperature viscosity of 569000 cps. The above reaction is as follows:

Preparation Example 7 106 g of glycidyl ether was heated to 120° C. and stirred (rotational speed 250 rpm). 0.3 g of HQ was added to glycidyl ether and stirred for 5 minutes. Next, 27 g of acrylic acid was added to the reaction for 6 hours. Then 63 g of acid anhydride was added and stirred (rotation speed 300 rpm) and reacted for 2 to 6 hours to obtain 196 g of resin with an acid value of 116 mg/KOH, a molecular weight of 709, and a room temperature viscosity of 1620 cps. The above reaction is as follows:

Preparation Example 8 106 g of glycidyl ether was heated to 120° C. and stirred (rotational speed 250 rpm). 0.3 g of HQ was added to glycidyl ether and stirred for 5 minutes. Next, 27 g of acrylic acid was added to the reaction for 6 hours. Then, 62 g of acid anhydride was added and stirred (rotation speed 300 rpm) and reacted for 2 to 6 hours to obtain 195 g of resin with an acid value of 121 mg/KOH, a molecular weight of 674, and a room temperature viscosity of 1087 cps. The above reaction is as follows:

Preparation Example 9 70 g of glycidyl ether was heated to 120° C. and stirred (rotational speed 250 rpm). 0.3 g of HQ was added to glycidyl ether and stirred for 5 minutes. Next, 33 g of acrylic acid was added to the reaction for 6 hours. Then, 78 g of acid anhydride was added and stirred (rotation speed 300 rpm) and reacted for 2 to 6 hours to obtain 181 g of resin with an acid value of 164 mg/KOH, a molecular weight of 561, and a room temperature viscosity of 1240 cps. The above reaction is as follows:

Comparative Example 1 Take 35g of dipentaerythritol hexaacrylate (DPHA), 50g of 1,6-hexanediol diacrylate (HDDA) as diluent, and 15g of 2,4,6-trimethylbenzyl Diphenylphosphine oxide (TPO) is used as a sensitizer to form a photocurable ink with a room temperature viscosity of ≦15cps and an acid value of 0 mg/KOH after mixing. Inkjet printing (IJP) inkjet photocurable ink on the 10cm*10cm FR4 copper foil substrate, control the film thickness to 7~8μm. The ink is cured to form a pattern by an exposure light source of LED (395nm wavelength). Then, the copper foil under the ink pattern is removed by a wet etching (FeCl ₃ ) process to form a circuit. The ink pattern is then stripped off with a sodium carbonate solution. The fluidity of inkjet printing ink is good. The cured ink pattern coverage is 2B (100% adhesion is 5B; 95%~90% adhesion is 4B; 90%~80% adhesion is 3B; 80%~ 60% attached as 2B). The cured ink pattern is soluble in butyl ether, so it is not suitable to form a solution coated gas barrier (SGB) on the cured ink pattern to form an encapsulation structure. The cured ink pattern can withstand wet etching (FeCl3 ₎ but cannot be stripped with sodium carbonate solution. To sum up, the above inks are not suitable for the patterning process of inkjet printing, nor are they suitable for forming a package structure with SGB.

Comparative Example 2 50g of DPHA, 35g of HDDA as diluent, and 15g of TPO as photosensitive agent were mixed to form a photocurable ink with room temperature viscosity >15cps and acid value of 0 mg/KOH. Inkjet printing (IJP) inkjet photocurable ink on the 10cm*10cm FR4 copper foil substrate, control the film thickness to 7~8μm. The ink is cured to form a pattern by an exposure light source of LED (395nm wavelength). Then, the copper foil under the ink pattern is removed by a wet etching (FeCl ₃ ) process to form a circuit. The ink pattern is then stripped off with a sodium carbonate solution. The fluidity of the inkjet printing ink is poor. Cured ink pattern coverage was 3B (tested with a 100 grid knife and 3M 610 Scotch® Scotch tape). The cured ink pattern is soluble in butyl ether, so it is not suitable to form SGB on the cured ink pattern to form the encapsulation structure. The cured ink pattern can withstand wet etching (FeCl3 ₎ but cannot be stripped with sodium carbonate solution. To sum up, the above inks are not suitable for the patterning process of inkjet printing, nor are they suitable for forming a package structure with SGB.

Comparative Example 3 20g of the resin obtained in Preparation Example 5, 200g of HDDA as a diluent, and 15g of TPO as a sensitizer were mixed to form a photocurable ink with a room temperature viscosity >15cps and an acid value of 9.3 mg/KOH. Inkjet printing (IJP) inkjet photocurable ink on the 10cm*10cm FR4 copper foil substrate, control the film thickness to 7~8μm. The ink is cured to form a pattern by an exposure light source of LED (395nm wavelength). Then, the copper foil under the ink pattern is removed by a wet etching (FeCl ₃ ) process to form a circuit. The ink pattern is then stripped off with a sodium carbonate solution. The fluidity of the inkjet printing ink is poor. Cured ink pattern coverage was 3B (tested with a 100 grid knife and 3M 610 Scotch® Scotch tape). The cured ink pattern is insoluble in butyl ether, so SGBs can be formed on the cured ink pattern to form an encapsulation structure. The cured ink pattern can withstand wet etching (FeCl3 ₎ but cannot be stripped with sodium carbonate solution. To sum up, the above inks are not suitable for the patterning process of inkjet printing.

Comparative Example 4 20g of the resin obtained in Preparation Example 6, 400g of HDDA as a diluent, and 15g of TPO as a sensitizer were mixed to form a photocurable ink with a room temperature viscosity >15cps and an acid value of 5.2 mg/KOH. Inkjet printing (IJP) inkjet photocurable ink on the 10cm*10cm FR4 copper foil substrate, control the film thickness to 7~8μm. The ink is cured to form a pattern by an exposure light source of LED (395nm wavelength). Then, the copper foil under the ink pattern is removed by a wet etching (FeCl ₃ ) process to form a circuit. The ink pattern is then stripped off with a sodium carbonate solution. The fluidity of the inkjet printing ink is poor. Cured ink pattern coverage was 3B (tested with a 100 grid knife and 3M 610 Scotch® Scotch tape). The cured ink pattern is insoluble in butyl ether, so SGBs can be formed on the cured ink pattern to form an encapsulation structure. The cured ink pattern can withstand wet etching (FeCl3 ₎ but cannot be stripped with sodium carbonate solution. To sum up, the above inks are not suitable for the patterning process of inkjet printing.

Example 1 20g of the resin obtained in Preparation Example 1, 65g of HDDA as a diluent, and 15g of TPO as a sensitizer were mixed to form a photocurable ink with a room temperature viscosity of ≦15cps and an acid value of 35.2 mg/KOH. Inkjet printing (IJP) inkjet photocurable ink on the 10cm*10cm FR4 copper foil substrate, control the film thickness to 7~8μm. The ink is cured to form a pattern by an exposure light source of LED (395nm wavelength). Then, the copper foil under the ink pattern is removed by a wet etching (FeCl ₃ ) process to form a circuit. The ink pattern is then stripped off with a sodium carbonate solution. The fluidity of inkjet printing ink is good. Cured ink pattern coverage was 5B (tested with a 100 grid knife and 3M 610 Scotch® Scotch tape). The cured ink pattern is insoluble in butyl ether, so SGBs can be formed on the cured ink pattern to form an encapsulation structure. The cured ink pattern can withstand wet etching (FeCl3 ₎ and can be stripped off with sodium carbonate solution. To sum up, the above ink is suitable for the patterning process of inkjet printing, and can also be used with SGB to form a package structure.

Example 2 20g of the resin obtained in Preparation Example 2, 60g of HDDA as a diluent, and 15g of TPO as a sensitizer were mixed to form a photocurable ink with a room temperature viscosity of ≦15cps and an acid value of 36.2 mg/KOH. Inkjet printing (IJP) inkjet photocurable ink on the 10cm*10cm FR4 copper foil substrate, control the film thickness to 7~8μm. The ink is cured to form a pattern by an exposure light source of LED (395nm wavelength). Then, the copper foil under the ink pattern is removed by a wet etching (FeCl ₃ ) process to form a circuit. The ink pattern is then stripped off with a sodium carbonate solution. The fluidity of inkjet printing ink is good. Cured ink pattern coverage was 5B (tested with a 100 grid knife and 3M 610 Scotch® Scotch tape). The cured ink pattern is insoluble in butyl ether, so SGBs can be formed on the cured ink pattern to form an encapsulation structure. The cured ink pattern can withstand wet etching (FeCl3 ₎ and can be stripped off with sodium carbonate solution. To sum up, the above ink is suitable for the patterning process of inkjet printing, and can also be used with SGB to form a package structure.

Example 3 Take 20g of the resin obtained in Preparation Example 3, 50g of HDDA as a diluent, and 15g of TPO as a sensitizer, and mixed to form a photocurable ink with a room temperature viscosity of ≦15cps and an acid value of 38.5 mg/KOH. Inkjet printing (IJP) inkjet photocurable ink on the 10cm*10cm FR4 copper foil substrate, control the film thickness to 7~8μm. The ink is cured to form a pattern by an exposure light source of LED (395nm wavelength). Then, the copper foil under the ink pattern is removed by a wet etching (FeCl ₃ ) process to form a circuit. The ink pattern is then stripped off with a sodium carbonate solution. The fluidity of inkjet printing ink is good. Cured ink pattern coverage was 5B (tested with a 100 grid knife and 3M 610 Scotch® Scotch tape). The cured ink pattern is insoluble in butyl ether, so SGBs can be formed on the cured ink pattern to form an encapsulation structure. The cured ink pattern can withstand wet etching (FeCl3 ₎ and can be stripped off with sodium carbonate solution. To sum up, the above ink is suitable for the patterning process of inkjet printing, and can also be used with SGB to form a package structure.

Example 4 20g of the resin obtained in Preparation Example 4, 55g of HDDA as a diluent, and 15g of TPO as a sensitizer were mixed to form a photocurable ink with a room temperature viscosity of ≦15cps and an acid value of 27.7 mg/KOH. Inkjet printing (IJP) inkjet photocurable ink on the 10cm*10cm FR4 copper foil substrate, control the film thickness to 7~8μm. The ink is cured to form a pattern by an exposure light source of LED (395nm wavelength). Then, the copper foil under the ink pattern is removed by a wet etching (FeCl ₃ ) process to form a circuit. The ink pattern is then stripped off with a sodium carbonate solution. The fluidity of inkjet printing ink is good. Cured ink pattern coverage was 5B (tested with a 100 grid knife and 3M 610 Scotch® Scotch tape). The cured ink pattern is insoluble in butyl ether, so SGBs can be formed on the cured ink pattern to form an encapsulation structure. The cured ink pattern can withstand wet etching (FeCl3 ₎ and can be stripped off with sodium carbonate solution. To sum up, the above ink is suitable for the patterning process of inkjet printing, and can also be used with SGB to form a package structure.

Example 5 20g of the resin obtained in Preparation Example 7, 63g of HDDA as a diluent, and 15g of TPO as a sensitizer were mixed to form a photocurable ink with a room temperature viscosity of ≦15cps and an acid value of 23.6 mg/KOH. Inkjet printing (IJP) inkjet photocurable ink on the 10cm*10cm FR4 copper foil substrate, control the film thickness to 7~8μm. The ink is cured to form a pattern by an exposure light source of LED (395nm wavelength). Then, the copper foil under the ink pattern is removed by a wet etching (FeCl ₃ ) process to form a circuit. The ink pattern is then stripped off with a sodium carbonate solution. The fluidity of inkjet printing ink is good. Cured ink pattern coverage was 5B (tested with a 100 grid knife and 3M 610 Scotch® Scotch tape). The cured ink pattern is insoluble in butyl ether, so SGBs can be formed on the cured ink pattern to form an encapsulation structure. The cured ink pattern can withstand wet etching (FeCl3 ₎ and can be stripped off with sodium carbonate solution. To sum up, the above ink is suitable for the patterning process of inkjet printing, and can also be used with SGB to form a package structure.

Example 6 Take 20g of the resin obtained in Preparation Example 8, 50g of HDDA as a diluent, and 15g of TPO as a sensitizer, and mixed to form a photocurable ink with a room temperature viscosity of ≦15cps and an acid value of 28.47 mg/KOH. Inkjet printing (IJP) inkjet photocurable ink on the 10cm*10cm FR4 copper foil substrate, control the film thickness to 7~8μm. The ink is cured to form a pattern by an exposure light source of LED (395nm wavelength). Then, the copper foil under the ink pattern is removed by a wet etching (FeCl ₃ ) process to form a circuit. The ink pattern is then stripped off with a sodium carbonate solution. The fluidity of inkjet printing ink is good. Cured ink pattern coverage was 5B (tested with a 100 grid knife and 3M 610 Scotch® Scotch tape). The cured ink pattern is insoluble in butyl ether, so SGBs can be formed on the cured ink pattern to form an encapsulation structure. The cured ink pattern can withstand wet etching (FeCl3 ₎ and can be stripped off with sodium carbonate solution. To sum up, the above ink is suitable for the patterning process of inkjet printing, and can also be used with SGB to form a package structure.

Example 7 Take 20g of the resin obtained in Preparation Example 9, 55g of HDDA as a diluent, and 15g of TPO as a sensitizer, and mixed to form a photocurable ink with a room temperature viscosity of ≦15cps and an acid value of 36.44 mg/KOH. Inkjet printing (IJP) inkjet photocurable ink on the 10cm*10cm FR4 copper foil substrate, control the film thickness to 7~8μm. The ink is cured to form a pattern by an exposure light source of LED (395nm wavelength). Then, the copper foil under the ink pattern is removed by a wet etching (FeCl ₃ ) process to form a circuit. The ink pattern is then stripped off with a sodium carbonate solution. The fluidity of inkjet printing ink is good. Cured ink pattern coverage was 5B (tested with a 100 grid knife and 3M 610 Scotch® Scotch tape). The cured ink pattern is insoluble in butyl ether, so SGBs can be formed on the cured ink pattern to form an encapsulation structure. The cured ink pattern can withstand wet etching (FeCl3 ₎ and can be stripped off with sodium carbonate solution. To sum up, the above ink is suitable for the patterning process of inkjet printing, and can also be used with SGB to form a package structure.

Although the present disclosure has been disclosed above with several preferred embodiments, it is not intended to limit the present disclosure. Anyone with ordinary knowledge in the technical field may make any changes without departing from the spirit and scope of the present disclosure. Therefore, the scope of protection of this disclosure should be determined by the scope of the appended patent application.

without.

without.

without.

Claims (10)

A photocurable ink, comprising: 1 weight part of resin; 1.5 to 3.5 weight part of diluent; and 0.25 to 1.5 weight part of photosensitive agent, wherein the chemical structure of the resin is

or

, R ¹ is C _2-16 alkyl, phenyl, tolyl, benzyl, or

, and R ⁵ is a C _2-10 alkyl group; R ² is a

,

,

,

,

,

,or

and R ³ and R ⁴ are each H, C _1-15 alkyl, C _2-15 alkenyl, or phenyl, wherein the photocurable ink has a room temperature viscosity of 4 cps to 50 cps, and wherein the photocurable ink The acid value of the ink is 0 mg/KOH to 60 mg/KOH. Such as the photocurable ink of claim 1, it does not contain solvent. The photocurable ink of claim 1, wherein the diluent comprises (meth)acrylate, tridecyl acrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, Ethylene Glycol Diacrylate, Diethylene Glycol Diacrylate, Tetraethylene Glycol Diacrylate, Tripropylene Glycol Diacrylate, Neopentyl Glycol Diacrylate, 1,4-Butanediol Dimethacrylate, Poly(butylene glycol) diacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol diacrylate, tetraethylene glycol diacrylate, triisopropylene glycol diacrylate, triisopropylene glycol diacrylate Acrylates, ethoxylated bisphenol A diacrylate, isobornyl acrylate, N-vinyl caprolactam, or a combination of the above. The photocurable ink of claim 1, wherein the sensitizer comprises acylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,6-dimethoxybenzyl) Acyl)-2,4,4-trimethyl, hydroxycyclohexyl phenyl ketone, hydroxymethyl phenyl acetone, dimethoxyphenyl acetophenone, 2-methyl-1-[4-(methyl phenyl ketone) Thio)phenyl]-2-morpholinopropan-1-yl, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-yl, 1-(4-deca Dialkylphenyl)-2-hydroxy-2-methylpropan-1-yl, 4-(2-hydroxyethoxy)phenyl-2(2-hydroxy-2-propyl)one, diethoxy phenylacetophenone, 2,4,6-trimethylbenzyldiphenylphosphine, 2,3-dihydroxy-6-(2-hydroxy-2-methyl-1-oxypropyl )-1,1,3-trimethyl-3-[4-(2-hydroxy-2-methyl-1-oxypropyl)phenyl]-1H-indene, 2-methyl-1-[ 4-(Methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-methylamino)-1-(4-morpholinophenyl)butane -1-one, α-hydroxycyclohexyl phenyl ketone, methylphenyl glycidyl ester, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1- Acetone, (n ⁵ -2,4-cyclopentadien-1-yl)[(1,2,3,4,5,6-n)-(1-methylethyl)benzene]-iron (I )-hexafluoroantimonate, methylphenylglyoxylate/hydroxyphenyl(1-hydroxy)cyclohexylphenyl ketone + benzophenone, bis(n ⁵ -cyclopentadiene)-bis(2 ,6-difluoro-3-[pyrrol-1-yl]-phenyl) titanate, 2-hydroxy-2-methyl-1-phenyl-1-propyl-1-one, diphenyl ( 4-Phenylthio) Phenyl perionate hexafluoroantimonate + (mercapto-4,1-phenylene) bis(diphenyl perionyl) dihexafluoroantimonate, 2-isopropylthioxanthone, Ethyl (2,4,6-trimethylbenzylphenyl phosphite, 2,2-dimethyl-1,2-diphenylethan-1-one, 4-benzyl -4'-Methyldiphenyl sulfide, 2,4-diethyl thioxanthone, isopropyl thioxanthone, methyl-o-benzyl benzoate, 2,4,6- Trimethylbenzyldiphenyl hypophosphite oxide, or a combination of the above. A patterning method, comprising: inkjet printing a photocurable ink on an inorganic material layer, and photocuring the photocurable ink in real time to form a pattern; and etching the inorganic material layer not covered by the pattern to form a pattern 1.5 to 3.5 parts by weight of a diluent; and 0.25 to 1.5 parts by weight of a sensitizer, wherein the chemical structure of the resin is

or

, R ¹ is C _2-16 alkyl, phenyl, tolyl, benzyl, or

, and R ⁵ is a C _2-10 alkyl group; R ² is a

,

,

,

,

,

,or

and R ³ and R ⁴ are each H, C _1-15 alkyl, C _2-15 alkenyl, or phenyl, wherein the photocurable ink has a room temperature viscosity of 4 cps to 50 cps, and wherein the photocurable ink The acid value of the ink is 20 mg/KOH to 60 mg/KOH. The patterning method of claim 5, further comprising peeling off the pattern on the patterned inorganic material layer. The patterning method of claim 5, wherein the thickness of the pattern is 1 μm to 10 μm. A package structure, comprising: a photoelectric element; a protective layer covering the photoelectric element; and a gas barrier layer covering the protective layer, wherein the protective layer is formed by curing a photocurable ink, and the photocurable ink includes : 1 part by weight of a resin; 1.5 to 3.5 parts by weight of a diluent; and 0.25 to 1.5 parts by weight of a sensitizer, wherein the chemical structure of the resin is

or

, R ¹ is C _2-16 alkyl, phenyl, tolyl, benzyl, or

, and R ⁵ is a C _2-10 alkyl group; R ² is a

,

,

,

,

,

,or

and R ³ and R ⁴ are each H, C _1-15 alkyl, C _2-15 alkenyl, or phenyl, wherein the photocurable ink has a room temperature viscosity of 4 cps to 50 cps, and wherein the photocurable ink The acid value of the ink is 0 mg/KOH to 40 mg/KOH. The package structure of claim 8, wherein the protective film has a thickness of 1 μm to 10 μm. The package structure of claim 8, wherein the optoelectronic element comprises a light emitting diode, a quantum dot light emitting diode, an organic light emitting diode, a liquid crystal display, or a light sensor.