Cyclic-free low viscous silicone acrylates and their synthesis process and photocurable ink composition and cured product thereof

Abstract

The present disclosure is directed to cyclic-free low viscous di- or multi- methacrylate terminated organo-siloxane molecules having viscosity in the range of ~ 10 cps to ~ 180 cps. Additionally, the present disclosure is also directed to methods of making the cyclic-free low viscous di- or multi-methacrylate terminated organo-siloxane molecules. The present disclosure is further directed to a photocurable ink composition applicable to inkjet printing and a cured product thereof.

Description

CYCLIC-FREE LOW VISCOUS SILICONE ACRYLATES AND THEIR SYNTHESIS PROCESS AND PHOTOCURABLE INK COMPOSITION AND CURED PRODUCT THEREOFFIELD OF INVENTION

[0001] The present disclosure is directed to cyclic-free low viscous di- or multimethacrylate terminated organo-siloxane molecules having viscosity in the range of ~ 10 cps to ~ 180 cps. Additionally, the present disclosure is also directed to methods of making the cyclic-free low viscous di- or multi-methacrylate terminated organo-siloxane molecules. The present disclosure is further directed to a photocurable ink composition comprising di- or multi -methacryl ate terminated organo-siloxane molecules applicable to inkjet printing and a cured product thereof.BACKGROUND

[0002] UV-curable silicone acrylate polymers are an important class of polymers as they can be used in many applications such as adhesives, coating, healthcare, display, and many more. The acrylate moieties provide a crosslinking site for the UV curing whereas the polysiloxane backbone gives desired flexibility and temperature resistance to cured material. Conventionally, the silicone acrylate polymer is synthesized directly by ring opening polymerization or equilibrium reaction of cyclic siloxanes using acrylated- disiloxanes as chain stopper or indirectly via initial ring opening polymerization or equilibrium reaction of cyclic siloxanes using tetramethyldisiloxanes, followed by hydrosilylation routes to introduce acrylate groups. Equilibrium reaction of cyclic siloxanes using acid or base generates cyclic siloxanes of different lengths (D4 to D10) due to inherent back-biting reaction. However, in many applications these cyclic siloxanes hamper the efficiency of the end use applications (e.g display, healthcare applications). Additionally, environmental restrictions also come into picture to remove the cyclic siloxanes from the end products. Hence, extra efforts are needed to remove the cyclic siloxanes from the end product. These process to remove cyclics are often stringent experimental conditions (e.g., application of several cycle stripping procedure using low vacuum (0.001-15 mbar) at higher temperature (90-100 °C)) which add additional cost to synthesize these kinds of cyclic free silicone-acrylate molecules.Additionally, these additional processes may increase the chances of gel formation of the final products which would results batch failure.

[0003] In the patents KR 102330855, WO 2021181341, and US 20200347167A1 synthesis of silicone acrylate material with a D unit of 7 to 50 with 2-hydroxyhexylene group, ethylene oxide group, polyethylene oxide group, 2-hydroxypropoxypropylene group, or polypropylene oxide group was provided. These polymers are being use in contact lenses application as hydrogels or in other ophthalmic applications.

[0004] In the patent CN 108794750A synthesis of organo-polysiloxane molecule having a (methyl) acrylate group and the degree of polymerization of 7<(m+n)<600, with methyl, phenyl, hydroxyl functionalized groups, and hydroxyl functionalized esters, and at least two at the side chain was provided. The synthesized silicone composition had excellent low adhesion properties, and its cured coating is used as a release paper in many industrial fields.

[0005] In the patent US 8871861B2 the synthesis of organo-polysiloxane molecules with multi acrylate groups was provided. These materials can be used as a photocurable ink comprising a colouring agents.

[0006] In the non-patent literature, Polymers for Advanced Technologies 24;6; 557-567, 2013 (DOI: 10.1002 / pat.3115) was described a series of novel mono-ethylenically unsaturated polycarbosiloxanes macromonomers as compatibilizer materials for soft silicon hydrogels which were prepared from the anionic ring-opening polymerization of 2,2,5,5-tetramethyl-2,5-disila-l-oxacyclopentane followed by methacrylation. In addition, the novel di-ethylenically unsaturated polycarbosiloxanes were synthesized by cationic polymerization and their structure-property relationship was determined that the modulus and the tensile strength of the formulated material depends on the nature and length of the polycarbosiloxane used and can be tuned for the purpose as needed.

[0007] However, conventional polydisperse PDMS polymer material usually contains volatiles cyclics which do not have a single molecular weight specific chain and low viscosity which is a prerequisite for many other applications.

[0008] Therefore, there is a need for developments of a silicone acrylate with specific chain length (D unit = 3) with below 50 ppm residual cyclic content.

[0009] Furthermore, as the structures of organic light-emitting devices are verified and their uses expand, a problem in the reliability of these products is emerging. In particular, products including organic light-emitting diodes (OLEDs) are sensitive to environmentalfactors, and there is a problem of black spots occurring when a display panel is exposed to visible light due to the penetration of oxygen, moisture, etc. from the outside.

[0010] In addition, organic acrylate crosslinkers commonly used in conventional inkjet printing compositions can be classified as materials subject to the regulation in terms of the environment, and yellowing may occur under visible light.

[0011] In addition, organic solvents have been used in the related art to improve the viscosity of inkjet printing compositions for forming micropatterns. However, volatile materials due to organic solvents during a coating process or curing process of the inkjet printing compositions, volatile materials due to organic solvents and / or impurities that can be generated after forming a panel laminated structure, etc. may adversely affect the reliability of displays.

[0012] Therefore, there is a need for an inkjet printing composition capable of excluding the use of organic solvents and forming micropattems.SUMMARY

[0013] The following presents a summary of this disclosure to provide a basic understanding of some aspects. This summary is intended to neither identify key or critical elements nor define any limitations of embodiments or claims. Furthermore, this summary may provide a simplified overview of some aspects that can be described in greater detail in other portions of this disclosure.

[0014] The present disclosure provides cyclic-free low viscous di- or multi- methacrylate terminated organo-siloxane molecules. The viscosity of the synthesized molecules was in the range of ~ 10 cps to ~ 180 cps. Additionally, the present invention also discussed different processes to make these kinds of cyclic-free siloxane-acrylate molecules.

[0015] In one embodiment, the present disclosure provides a silicone compound represented by Chemical Structure 1 :

[0016] wherein

[0017] R1 and R2 can be Ci-Cio alkyl or C5-C20 aryl;

[0018] X can be Ci-Cio alkyl, optionally substituted with O, N, or a halogen;

[0019] Q can be selected from:

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026] wherein

[0027] XI can be methylene or a direct bond;

[0028] R3 can be from H or Me.

[0029] In another embodiment, the silicone compound is represented by ChemicalStructure 2

[0030]

[0031] wherein

[0032] R1 and R2 can be Ci-Cio alkyl or C5-C20 aryl;

[0033] X can be C1-C10 alkyl; and

[0034] R3 can be H or Me.

[0035] In another embodiment, the silicone compound is represented by ChemicalStructure 3

[0036]

[0037] wherein

[0038] R1 andR2 can be C1-C10 alkyl or C5-C20 aryl;

[0039] X can be C1-C10 alkyl; and

[0040] R3 can be H or Me.

[0041] In another embodiment, the silicone compound is represented by ChemicalStructure 4

[0042]

[0043] wherein

[0044] R1 and R2 can be C1-C10 alkyl or C5-C20 aryl;

[0045] XI can be C1-C10 alkyl;

[0046] X2 can be methylene or a direct bond; and

[0047] R3 can be H or Me.

[0048] In another embodiment, the silicone compound is represented by ChemicalStructure 5

[0049]

[0050] wherein

[0051] R1 andR2 can be Ci-Cio alkyl or C5-C20 aryl;

[0052] XI can be C1-C10 alkyl; and

[0053] R3 can be H or Me.

[0054] In another embodiment, the silicone compound is represented by ChemicalStructure 6

[0055]

[0056] wherein

[0057] R1 and R2 can be C1-C10 alkyl or C5-C20 aryl;

[0058] X can be C1-C10 alkyl; and

[0059] R3 can be H or Me.

[0060] In another embodiment, the silicone compound is represented by ChemicalStructure 7

[0061]

[0062] wherein

[0063] R1 and R2 can be C1-C10 alkyl or C5-C20 aryl;

[0064] X can be C1-C10 alkyl; and

[0065] R3 can be H or Me.

[0066] In another embodiment, provided is a process of preparing the silicone compound of Chemical Structure 2 or Chemical Structure 3 comprising:

[0067] (i) reacting a pentasiloxane dihydride of Chemical Structure 8

[0068]

[0069] with methacrylate of Chemical Structure 9 in presence of a platinum catalyst

[0070]

[0071] wherein

[0072] R1 and R2 can be Ci-Cio alkyl or C5-C20 aryl;

[0073] X can be O or N; and

[0074] R3 can be H or Me;

[0075] (ii) purifying compound obtained from step (i) by air purging at 80-90 °C for 2 hours in vacuum.

[0076] In another embodiment, provided is a process of preparing the silicone compound of Chemical Structure 2 or Chemical Structure 3 comprising

[0077] (i) reacting a pentasiloxane dihydride of Chemical Structure 8

[0078]

[0079] with allyloxyethanol in presence of a platinum catalyst to produce a compound of Chemical Structure 10;

[0080]

[0081] wherein

[0082] R1 and R2 can be C1-C10 alkyl or C5-C20 aryl;

[0083] (ii) reacting compound of Chemical Structure 10 with methacrylic anhydride or methacrylic acid in the presence of catalyst; and

[0084] (iii) purifying by air purging at 85 °C for 2 hours under vacuum.

[0085] In another embodiment, provided is a process of preparing the silicone compound of Chemical Structure 4 comprising

[0086] (i) reacting a pentasiloxane dihydride of Chemical Structure 8

[0087]

[0088] with allylgly cidyl ether in presence of a platinum catalyst

[0089]

[0090] to produce a compound of Chemical Structure 11

[0091]

[0092] wherein

[0093] R1 and R2 can be Ci-Cio alkyl or C5-C20 aryl;

[0094] (ii) reacting compound of Chemical Structure 11 with methacrylic acid anhydride in the presence of catalyst; and

[0095] (iii) purifying compound obtained from step (ii) by air purging at 85 °C for 2 hours in vacuum.

[0096] In another embodiment, provided is a process of preparing the silicone compound of Chemical Structure 4 by

[0097] (i) reacting a pentasiloxane dihydride of Chemical Structure 8

[0098]

[0099] with compound in the presence of a platinum catalyst;

[0100] wherein

[0101] R1 and R2 can be Ci-Cio alkyl or C5-C20 aryl; and

[0102] R3 can be H or Me; and

[0103] (ii) purifying compound obtained from step (i) by air purging at 85-90 °C for 2 hours in vacuum.

[0104] In another embodiment, provided is a process of preparing the silicone compound of Chemical Structure 5 by

[0105] (i) reacting a pentasiloxane dihydride of Chemical Structure 8

[0106]

[0107]

[0108] to produce a compound of Chemical Structure 12

[0109]

[0110] wherein[OHl] R1 and R2 can be C1-C10 alkyl or C5-C20 aryl; and

[0112] (ii) reacting compound of Chemical Structure 12 with methacrylic anhydride in the presence of catalyst; and

[0113] (iii) purifying compound obtained from step (ii) by air purging at 85-90 °C for 2 hours in vacuum.

[0114] In another embodiment, provided is a process of preparing the silicone compound of Chemical Structure 5 by

[0115] (i) reacting a pentasiloxane dihydride of Chemical Structure 8

[0116]

[0117] with in presence of a platinum catalyst;

[0118] wherein

[0119] R1 andR2 can be Ci-Cio alkyl or C5-C20 aryl; and

[0120] R3 can be H or Me.

[0121] In another embodiment, provided is a process of preparing the silicone compound of Chemical Structure 6 by

[0122] reacting a pentasiloxane dihydride of Chemical Structure 8

[0123]

[0124] with compound in presence of a platinum catalyst;

[0125] wherein

[0126] R1 andR2 can be C1-C10 alkyl or C5-C20 aryl; and

[0127] R3 can be H or Me.

[0128] In another embodiment, provided is a process of preparing the silicone compound of Chemical Structure 7 by

[0129] reacting a pentasiloxane dihydride of Chemical Structure 8

[0130]

[0131] with compound in presence of a platinum catalyst;

[0132] wherein

[0133] R1 andR2 can be Ci-Cio alkyl or C5-C20 aryl; and

[0134] R3 can be H or Me.

[0135] In another embodiment, provided is a process of preparing a silicone compound wherein the catalyst is selected from dimethyl amino pyridine, 1 -methyl imidazole, triethyl amine or aluminum triflate.

[0136] In another embodiment, the silicone compound has a viscosity in the range of 5 to 200 centipoise.

[0137] In another embodiment, the silicone compound has a residual cyclosiloxanes (D4- D10) content of less than 50 ppm.

[0138] The present disclosure also provides a photocurable ink composition comprising: a polyorganosiloxane including a trifunctional silicone unit (T unit) bound with a(meth)acrylate group; at least one siloxane oligomer including (meth)acrylate groups at both terminals; and at least one photoinitiator; wherein the photocurable ink has a viscosity 10 cP to 30 cP at 25 °C.

[0139] In an embodiment, the polyorganosiloxane of the photocurable ink composition is represented by the following Chemical Structure 13:

[0140] wherein:

[0141] RIA, R2A, R3A, R4A, and R5A are the same as or different from each other, and are each independently an alkyl group having 1 to 10 carbon atoms;

[0142] R6A is an acrylate group or a methacrylate group; and ml and nl are each independently 1 to 200.

[0143] In an embodiment, the siloxane oligomer of the photocurable ink composition includes at least one of the following:

[0144] (i) Chemical Structure 2

[0145] wherein

[0146] R1 andR2 are each selected from Ci-Cio alkyl and C5-C20 aryl;

[0147] X is selected from C1-C10 alkyl; and

[0148] R3 is H or Me; and

[0149] (ii) Chemical Structure 4

[0150] wherein

[0151] R1 andR2 are each selected from C1-C10 alkyl and C5-C20 aryl;

[0152] XI is selected from C1-C10 alkyl;

[0153] X2 is methylene or a direct bond; and

[0154] R3 is H or Me.

[0155] In an embodiment, the siloxane oligomer of the photocurable ink composition includes Chemical Formula 2 or Chemical Formula 4 alone.

[0156] In an embodiment, the siloxane oligomer of the photocurable ink composition includes both Chemical Formulas 2 and 4, and a weight ratio of Chemical Formula 2: Chemical Formula 4 is 30:70 to 70:30.

[0157] In an embodiment, in the siloxane oligomer of the photocurable ink composition, the content of impurities including cyclic siloxanes D4 to D10 is 50 ppm or less.

[0158] In an embodiment, based on the total weight of the photocurable ink composition, the content of the polyorganosiloxane is 9 wt% to 90 wt%, the content of at least one siloxane oligomer is 9 wt% to 90 wt%, and the content of at least one photoinitiator is 0.1 wt% to 6 wt%.

[0159] In an embodiment, based on the total weight of photocurable ink composition, the content of the polyorganosiloxane is 49 wt% to 90 wt%, the content of the siloxane oligomer including Chemical Formula 2 or 4 is 9 wt% to 50 wt%, and the content of at least one photoinitiator is 0.1 wt% to 6 wt%.

[0160] In an embodiment, the siloxane oligomer of the photocurable ink includes both Chemical Formulas 2 and 4, and based on the total weight of the photocurable ink composition, the content of the polyorganosiloxane is 10 wt% to 90 wt%, the content of the siloxane oligomer including Chemical Formula 2 is 4 wt% to 50 wt%, the content of the siloxane oligomer including Chemical Formula 4 is 4 wt% to 50 wt%, and the content of at least one photoinitiator is 0.1 wt% to 6 wt%.

[0161] In an embodiment, a contact angle of the photocurable ink composition to a glass substrate is 23° or less.

[0162] In an embodiment, a cured product is manufactured by curing the photocurable ink composition.

[0163] In an embodiment, the storage modulus of the cured product is from 0.1 GPa to 10 GPa.

[0164] In an embodiment, an image display device comprises the cured product manufactured by curing the photocurable ink composition.DESCRIPTION OF THE DRAWINGS

[0165] The following figures are included to illustrate some aspects of the present disclosure and should not be viewed as exclusive embodiments. The subject matter disclosed is capable of considerable modifications, alterations, combinations, and equivalents in form and function, without departing from the scope of this disclosure.

[0166] FIG. l is a schematic of a first reaction of allyloxy ethanol with methacrylic acid or methacrylate anhydride in the presence of a catalyst to produce allyloxyethylmethacrylate followed by a second reaction of pentasiloxane dihydride with allyloxy ethylmethacrylate in the presence of a platinum catalyst to produce a difunctional siloxane-methacrylate molecule.

[0167] FIG. 2 is a schematic of a first reaction of pentasiloxane dihydride with allyloxy ethanol in the presence of a platinum catalyst to produce bis-propylhydroxy pentasiloxane followed by a second reaction of bis-propylhydroxy pentasiloxane with methacrylic anhydride or methacrylic acid in the presence of a esterification catalyst to produce a difunctional siloxane-methacrylate molecule.

[0168] FIG. 3 is a schematic of a first reaction of an epoxy containing vinyl / allyl with pentasiloxane dihydride in the presence of a platinum catalyst to produce an epoxy containing siloxane followed by a second reaction of the epoxy containing siloxane with methacrylic acid in the presence of a catalyst to produce a hydroxy containing difunctional siloxane-methacrylate oligomer.

[0169] FIG. 4 is a schematic of a first reaction of an epoxy containing vinyl / allyl with pentasiloxane dihydride in the presence of a platinum catalyst to produce an epoxy containing siloxane followed by a second reaction of the epoxy containing siloxane with methacrylic acid in the presence of a catalyst to produce a hydroxy containing difunctional siloxane-methacrylate oligomer.

[0170] FIG. 5 is a schematic of a first reaction of methacrylic acid with an epoxy terminated allyl in the presence of a catalyst to produce a hydroxyl containing allylmethacrylate followed by a second reaction of the hydroxyl containing allyl-methacrylate with a pentasiloxane dihydride in the presence of a platinum catalyst to produce a hydroxy containing di-functional siloxane-methacrylate oligomer.

[0171] FIG. 6 is a schematic of a first reaction of methacrylic acid with an epoxy terminated allyl in the presence of a catalyst to produce a hydroxyl containing allyl-methacrylate followed followed by a second reaction of the hydroxyl containing allylmethacrylate with a platinum catalyst to produce a hydroxyl containing di-functional siloxane-methacrylate oligomer.

[0172] FIG. 7 is a schematic of a first reaction of an epoxy containing vinyl / allyl with pentasiloxane dihydride in the presence of a platinum catalyst to produce an epoxy terminated siloxane followed by a second reaction of the epoxy terminated siloxane with methacrylic anhydride in the presence of a catalyst to produce an multi-functional siloxane-methacrylate oligomer.

[0173] FIG. 8 is a schematic of a first reaction of an epoxy containing vinyl / allyl with pentasiloxane dihydride in the presence of a platinum catalyst to produce an epoxy terminated siloxane followed by a second reaction of the epoxy terminated siloxane with methacrylic anhydride in the presence of a catalyst to produce an multi-functional siloxane-methacrylate oligomer.

[0174] FIG. 9 is a schematic of a first reaction of an epoxy containing vinyl / allyl with methacrylic anhydride in the presence of a catalyst to produce a tri-vinyl-methacrylate followed by a second reaction of the product of the tri -functional vinyl-methacrylate with pentasiloxane dihydride in the presence of a platinum catalyst to produce multi-functional siloxane-methacrylate oligomer.

[0175] FIG. 10 is a schematic of a first reaction of an epoxy containing vinyl / allyl with methacrylic anhydride in the presence of a catalyst to produce a tri -functional vinyl- methacrylate followed by a second reaction of tri -functional vinyl-methacrylate with pentasiloxane dihydride in the presence of a platinum catalyst to produce an to produce a multi -functi onal sil oxane-methacry 1 ate .DETAILED DESCRIPTION

[0176] Reference will now be made to exemplary embodiments, examples of which are illustrated in the accompanying drawings. It is to be understood that other embodiments can be utilized, and structural and functional changes can be made. Moreover, features of the various embodiments can be combined or altered. As such, the following description is presented by way of illustration only and should not limit in any way the various alternatives and modifications that can be made to the illustrated embodiments. In this disclosure, numerous specific details provide a thorough understanding of the subjectdisclosure. It should be understood that aspects of this disclosure can be practiced with other embodiments not necessarily including all aspects described herein, etc.

[0177] As used herein, the words “example” and “exemplary” means an instance, or illustration. The words “example” or “exemplary” do not indicate a key or preferred aspect or embodiment. The word “or” is intended to be inclusive rather than exclusive, unless context suggests otherwise. As an example, the phrase “A employs B or C,” includes any inclusive permutation (e.g., A employs B; A employs C; or A employs both B and C). As another matter, the articles “a” and “an” are generally intended to mean “one or more” unless context suggest otherwise.

[0178] As used herein, the term:

[0179] “alkyl” includes straight, branched, and cyclic monovalent hydrocarbon groups, which can be substituted with a heteroatom or heteroatom containing group;

[0180] “alkylene” includes straight, branched, and cyclic divalent hydrocarbon groups, which can be substituted with a heteroatom or heteroatom containing group;

[0181] “aryl” includes any monovalent aromatic hydrocarbon group, which can be substituted with a heteroatom or heteroatom containing group; this term also includes fused systems containing an aromatic group;

[0182] “arylene” includes any divalent aromatic hydrocarbon group, which can be substituted with a heteroatom or heteroatom containing group this term also includes fused systems containing an aromatic group;

[0183] “aralkyl” include straight, branched, and cyclic monovalent hydrocarbon groups substituted with an aryl substituent;

[0184] “cyclo” or “cyclic” alkyl includes a monovalent cyclic hydrocarbon and includes, free cyclic groups, bicyclic groups, tricyclic groups, and higher cyclic structures, as well as bridged cyclic groups, fused cyclic groups, and fused cyclic groups containing at least one bridged cyclic group;

[0185] “cyclo” or “cyclic” alkylene includes a divalent cyclic hydrocarbon and includes, free cyclic groups, bicyclic groups, tricyclic groups, and higher cyclic structures, as well as bridged cyclic groups, fused cyclic groups, and fused cyclic groups containing at least one bridged cyclic group;

[0186] “hetero” as used refer to an atom or in conjunction with another group includes atom or group containing an atom such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, etc.

[0187] Provided is cyclic free low viscous di- or multi- methacrylate terminated organo- siloxane molecules. The viscosity of the synthesized molecules was in the range of ~ 10 cps to ~ 180 cps. Additionally, the present disclosure also provides different processes to make these kinds of cyclic-free siloxane-acrylate molecules.

[0188] In one embodiment, the silicone compound is represented by Chemical Structure 1 :

[0189]

[0190] wherein

[0191] R1 andR2 can be Ci-Cio alkyl or C5-C20 aryl;

[0192] X can be C1-C10 alkyl, optionally substituted with O, N, or a halogen;

[0193] Q can be selected from the following

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201] wherein

[0202] XI can be methylene or a direct bond; and

[0203] R3 can be H or Me.

[0204] In another embodiment, the silicone compound is represented by ChemicalStructure 2:

[0205]

[0206] wherein

[0207] R1 andR2 can be Ci-Cio alkyl or C5-C20 aryl;

[0208] X can be C1-C10 alkyl; and

[0209] R3 can be H or Me.

[0210] In another embodiment, the silicone compound is represented by ChemicalStructure 3 :

[0211]

[0212] wherein

[0213] R1 and R2 can be Ci-Cio alkyl or C5-C20 aryl;

[0214] X can be C1-C10 alkyl; and

[0215] R3 can be H or Me.

[0216] In another embodiment, the silicone compound is represented by ChemicalStructure 4:

[0217]

[0218] wherein

[0219] R1 and R2 can be C1-C10 alkyl or C5-C20 aryl;

[0220] XI can be C1-C10 alkyl;

[0221] X2 can be methylene or a direct bond; and

[0222] R3 can be H or Me.

[0223] In another embodiment, the silicone compound is represented by ChemicalStructure 5 :

[0224]

[0225] wherein

[0226] R1 and R2 can be C1-C10 alkyl or C5-C20 aryl;

[0227] XI can be C1-C10 alkyl; and

[0228] R3 can be H or Me.

[0229] In another embodiment, the silicone compound is represented by ChemicalStructure 6:

[0230]

[0231] wherein

[0232] R1 and R2 can be Ci-Cio alkyl or C5-C20 aryl;

[0233] and X can be C1-C10 alkyl; and

[0234] and R3 can be H or Me.

[0235] In another embodiment, the silicone compound is represented by ChemicalStructure 7 :

[0236]

[0237] wherein

[0238] R1 andR2 can be C1-C10 alkyl or C5-C20 aryl;

[0239] X can be C1-C10 alkyl; and

[0240] R3 can be H or Me.

[0241] In another embodiment, provided is a process of preparing the silicone compound of Chemical Structure 2 or Chemical Structure 3 comprising:

[0242] (i) reacting a pentasiloxane dihydride of Chemical Structure 8

[0243]

[0244] with methacrylate of Chemical Structure 9 in presence of a platinum catalyst

[0245]

[0246] wherein

[0247] R1 and R2 can be Ci-Cio alkyl or C5-C20 aryl;

[0248] X can be O or N; and

[0249] R3 can be H or Me; and

[0250] (ii) purifying compound obtained from step (i) by air purging at 80-90 °C for 2 hours in vacuum.

[0251] In another embodiment, provided is a process of preparing the silicone compound of Chemical Structure 2 or Chemical Structure 3 comprising

[0252] (i) reacting a pentasiloxane dihydride of Chemical Structure 8

[0253]

[0254] with allyloxyethanol in presence of a platinum catalyst to produce a compound ofChemical Structure 10:

[0255]

[0256] wherein

[0257] R1 and R2 can be C1-C10 alkyl or C5-C20 aryl;

[0258] (ii) reacting compound of Chemical Structure 10 with methacrylic anhydride or methacrylic acid in the presence of a catalyst; and

[0259] (iii) purifying by air purging at 85 °C for 2 hours under vacuum.

[0260] In another embodiment, provided is a process of preparing the silicone compound of Chemical Structure 4, comprising

[0261] (i) reacting a pentasiloxane dihydride of Chemical Structure 8

[0262]

[0263] with compound in the presence of a platinum catalyst;

[0264] to produce a compound of Chemical Structure 11

[0265]

[0266] wherein

[0267] R1 and R2 can be Ci-Cio alkyl or C5-C20 aryl;

[0268] (ii) reacting compound of Chemical Structure 11 with methacrylic acid anhydride in the presence of catalyst; and

[0269] (iii) purifying compound obtained from step (ii) by air purging at 85 °C for 2 hours in vacuum.

[0270] In another embodiment, provided is a process of preparing the silicone compound of Chemical Structure 4, comprising

[0271] (i) reacting a pentasiloxane dihydride of Chemical Structure 8

[0272]

[0273] with the compoundcatalyst;

[0274] wherein

[0275] R1 and R2 can be C1-C10 alkyl or C5-C20 aryl; and

[0276] R3 can be H or Me; and

[0277] (iii) purifying compound obtained from step (i) by air purging at 85-90° C for 2 hours in vacuum.

[0278] In another embodiment, provided is a process of preparing the silicone compound of Chemical Structure 5, comprising

[0279] (i) reacting a pentasiloxane dihydride of Chemical Structure 8

[0280]

[0281] with the compound in the presence of platinum catalyst to produce a compound of Chemical Structure 12

[0284] R1 andR2 can be Ci-Cio alkyl or C5-C20 aryl; and

[0285] R3 can be H or Me;

[0286] (ii) reacting compound of Chemical Structure 12 with methacrylic anhydride in the presence of catalyst; and

[0287] (iii) purifying compound obtained from step (ii) by air purging at 85-90 °C for 2 hours in vacuum.

[0288] In another embodiment, provided is a process of preparing the silicone compound of Chemical Structure 5 by

[0289] reacting a pentasiloxane dihydride of Chemical Structure 8

[0290]

[0291] catalyst;

[0292] wherein

[0293] R1 andR2 can be Ci-Cio alkyl or C5-C20 aryl; and

[0294] R3 can be H or Me.

[0295] In another embodiment, provided is a process of preparing the silicone compound of Chemical Structure 6 by

[0296] reacting a pentasiloxane dihydride of Chemical Structure 8

[0297]

[0298] with the compound in the presence of a platinum catalyst;

[0299] wherein

[0300] R1 and R2 can be C1-C10 alkyl or C5-C20 aryl and

[0301] R3 can be H or Me.

[0302] In another embodiment, provided is a process of preparing the silicone compound of Chemical Structure 6 by

[0303] reacting a pentasiloxane dihydride of Chemical Structure 8

[0304]

[0305] catalyst;

[0306] wherein

[0307] R1 and R2 can be Ci-Cio alkyl or C5-C20 aryl; and

[0308] R3 can be H or Me.

[0309] In another embodiment, provided is a process of preparing the silicone compound wherein the catalyst is selected from dimethyl amino pyridine, 1 -methyl imidazole, triethyl amine, and aluminum tritiate.

[0310] In another embodiment, the silicone compound has a viscosity in the range of 5 to200 centipoise.

[0311] In another embodiment, the silicone compound has a residual cyclosiloxanes (D4- D10) content less than 50 ppm.

[0312] The present disclosure discloses the synthesis of silicone multi-acrylate with a specific molecular weight.

[0313] The present disclosure also provides a photocurable ink composition and a cured product thereof capable of excluding the use of organic solvents and forming micropatterns.

[0314] In an embodiment, the present disclosure provides a photocurable ink composition including:

[0315] 1) a polyorganosiloxane including a trifunctional silicone unit (T unit) bound with a (meth)acrylate group;

[0316] 2) at least one siloxane oligomer including (meth)acrylate groups at both terminals; and

[0317] 3) at least one photoinitiator,

[0318] wherein the composition has a viscosity of 10 cP to 30 cP at 25 °C.

[0319] In another embodiment, the present disclosure provides a cured product manufactured by curing the photocurable ink composition.

[0320] In another embodiment, the present disclosure provides an image display device including the cured product.

[0321] According to one embodiment of the present disclosure, the photocurable ink composition can reduce the generation of outgas during a curing process by excluding the use of an organic solvent, and implement a low viscosity of 10 cP to 30 cP at 25 °C, thereby forming micropatterns through inkjet printing.

[0322] According to one embodiment of the present disclosure, the cured product of the photocurable ink composition can be applied as an encapsulation layer of an image display device such as an organic light-emitting diode, and the encapsulation layer can effectively block oxygen, moisture, etc. flowing in from the outside.

[0323] In the present disclosure, when a certain member is located “on” the other member, not only a certain member is in contact with the other member, but also another member is present between the two members.

[0324] In the present disclosure, unless specifically stated otherwise, when a certain part “comprises” a certain component, it is meant that another component is not excluded, but another component can be further included.

[0325] As described above, when an organic solvent is used in the inkjet printing composition, the organic solvent may have a negative effect on the reliability of a display. Therefore, an object of the present disclosure is to provide a photocurable ink composition and a cured product thereof capable of excluding the use of an organic solvent and forming micropattems.

[0326] In an embodiment, the present disclosure provides a photocurable ink composition comprising: 1) a polyorganosiloxane including a trifunctional silicone unit (T unit) bound with a (meth)acrylate group; 2) at least one siloxane oligomer including (meth)acrylate groups at both terminals; and 3) at least one photoinitiator; and has a viscosity of 10 cP to 30 cP at 25 °C.

[0327] In an embodiments, the photocurable ink composition comprises a polyorganosiloxane including a trifunctional silicone unit (T unit) bound with a (meth)acrylate group.

[0328] In an embodiment, the (meth)acrylate group includes an acrylate group and a methacrylate group.

[0329] A silicone resin having a siloxane structure (Si-O-Si) is classified into a monofunctional silicone unit (M unit), a difunctional silicone unit (D unit), a trifunctional silicone unit (T unit), and a tetrafunctional silicone unit (Q unit) according to constituent units, and the constituent units are used alone or combined in a copolymerized state. Astructure consisting of only the monofunctional silicone unit and the difunctional silicone unit is a linear siloxane form, and as the content of the difunctional silicone unit increases, the linear length is increased and the viscosity also increases as much. Even if the viscosity increases to the maximum, the silicone resin is not solidified, and the shape at a synthesizable level has a raw rubber-like shape.

[0330] In an embodiment, the polyorganosiloxane is a polyorganosiloxane in which a (meth)acrylate group is bound to a trifunctional silicone unit (T unit), and is different from a polyorganosiloxane in which the (meth)acrylate group is bound to a monofunctional silicone unit (M unit), a difunctional silicone unit (D unit), or a tetrafunctional silicone unit (Q unit) other than the trifunctional silicone unit (T unit), and has different physical properties.

[0331] In one embodiment of the present disclosure, the polyorganosiloxane can be represented by the following Chemical Formula 13:

[0332]

[0333] wherein

[0334] RIA, R2A, R3A, R4A, and R5A are the same as or different from each other, and are each independently an alkyl group having 1 to 10 carbon atoms,

[0335] R6A is an acrylate group or a methacrylate group, and

[0336] ml and nl are each independently 1 to 200.

[0337] The photocurable ink composition according to one embodiment of the present disclosure further comprises at least one siloxane oligomer having (meth)acrylate groups at both terminals.

[0338] Conventional silicone acrylate polymers are synthesized by an equilibrium reaction of cyclic siloxane (Cyclic-D) using acrylate as a chain stopper. In this process, cyclic siloxane is generated by a backbiting reaction. However, such cyclic siloxane reduces efficiency in many application fields such as displays and medical fields.Therefore, considering environmental safety, a process of removing the cyclic siloxane is required in final products.

[0339] In order to remove the cyclic siloxane, a stripping process needs to be applied under strict conditions using low vacuum and high temperature, and a gelation reaction of the final product can be induced by the process of removing the cyclic siloxane. In the present disclosure, the composition was improved using a polydimethylsiloxane (PDMS)- based raw material to improve the thermal stability of the material.

[0340] In one embodiment, in the siloxane oligomer including the (meth)acrylate groups at both terminals, the content of impurities including cyclic siloxanes D4 to D10 can be50 ppm or less, can be from 50 ppm to 1 ppm, can be from 40 ppm to 1 ppm, or can be 0 ppm. When the content of impurities including cyclic siloxanes D4 to DIO in the siloxane oligomer exceeds 50 ppm, fine bubbles can be generated while the cyclic siloxanes D4 to D10 volatilize during the curing process of the ink composition to form pinholes on the surface of the cured product and deteriorate the structural integrity of the product, which is not preferable. In addition, when the content of impurities including cyclic siloxanes D4 to D10 in the siloxane oligomer exceeds 50 ppm, a volume difference before and after curing may occur due to the volatilization characteristics of cyclic siloxanes D4 to D10, and as a result, in the final products, a desired dimension may not be maintained and uneven changes can occur. Therefore, it is important to manage the content of impurities including the cyclic siloxanes D4 to D10 to be 50 ppm or less in the siloxane oligomer including the (meth)acrylate groups at both terminals in order to stably maintain the quality and performance of the final product.

[0341] The siloxane oligomer including the (meth)acrylate groups at both terminals can include one or two or more (meth)acrylate groups at each terminal. That is, the siloxane oligomer can be a siloxane oligomer including a total of two (meth)acrylate groups by including one (meth)acrylate group at each terminal. In addition, the siloxane oligomer can be a siloxane oligomer including a total of at least three (meth)acrylate groups by including one or two or more (meth)acrylate groups at each terminal.

[0342] In one embodiment of the present disclosure, the siloxane oligomer may include at least one of the following Chemical Formulas 14 and 15.

[0343] Chemical Formula 14

[0344]

[0345] Chemical Formula 15

[0347] In Chemical Formulas 14 and 15,

[0348] R7, R8, R9, RIO, R11, R12, R15, R16, R17, R18, R19 and R20 are the same as or different from each other and are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 5 to 20 carbon atoms,

[0349] XI, X2, X3 and X4 are the same as or different from each other and are each independently an alkylene group having 1 to 10 carbon atoms,

[0350] X5 and X6 are the same as or different from each other and are each independently a direct bond or a methylene group, and

[0351] R13, R14, R21, R22, R23 and R24 are the same as or different from each other and are each independently hydrogen or a methyl group.

[0352] In one embodiment of the present disclosure, the siloxane oligomer may include at least one of the following Chemical Formulas 2 and 4.

[0353] Chemical Formula 2

[0354] (i) Chemical Structure 2

[0355]

[0356] wherein

[0357] R1 andR2 are each selected from Ci-Cio alkyl and C5-C20 aryl;

[0358] X is selected from C1-C10 alkyl; and

[0359] R3 is H or Me; and

[0360] (ii) Chemical Structure 4

[0361]

[0362] wherein

[0363] R1 andR2 are each selected from Ci-Cio alkyl and C5-C20 aryl;

[0364] XI is selected from C1-C10 alkyl;

[0365] X2 is methylene or a direct bond; and

[0366] R3 is H or Me.

[0367] The siloxane oligomer including Chemical Formula 2 or 4 (or Chemical Formula14 or 15) has a characteristic of not including cyclic siloxane, which is a synthetic raw material or impurity generated during synthesis, unlike conventional siloxane polymers with similar structures. The siloxane oligomer according to one embodiment of the present disclosure can be used to improve a curing rate and hardness by improving a low degree of crosslinking that is difficult to be expected in silicone materials, and may also be used for dissolving a photoinitiator. Therefore, since the photocurable ink composition according to one embodiment of the present disclosure does not include conventional carbon compounds, silicone-based regulation materials, and furthermore organic solvents, there can be provided an inkjet printing composition that is advantageous in terms of environmental aspects or process speed improvement.

[0368] In one embodiment of the present disclosure, the siloxane oligomer may include Chemical Formula 14 alone, Chemical Formula 15 alone, or both Chemical Formulas 14 and 15.

[0369] In one embodiment of the present disclosure, when the siloxane oligomer includes both Chemical Formulas 14 and 15, a weight ratio of Chemical Formula 14: Chemical Formula 15 can be 30:70 to 70:30, 35:65 to 65:35, or 40:60 to 60:40. When the weight ratio of Chemical Formula 14: Chemical Formula 15 is satisfied, a viscosity of 10 cP to 30 cP can be exhibited to be suitably applied for inkjet printing.

[0370] In one embodiment of the present disclosure, when the siloxane oligomer includes both Chemical Formulas 14 and 15 and the relative content of Chemical Formula 14 is high, the modulus can be lowered, and when the relative content of Chemical Formula 15is high, the viscosity can be increased. Therefore, considering the modulus and viscosity characteristics, an appropriate content ratio of Chemical Formulas 14 and 15 can be adjusted.

[0371] In one embodiment of the present disclosure, the siloxane oligomer can include Chemical Formula 2 alone, Chemical Formula 3 alone, or both Chemical Formulas 2 and 3.

[0372] In one embodiment of the present disclosure, when the siloxane oligomer includes both Chemical Formulas 2 and 3, a weight ratio of Chemical Formula 2: Chemical Formula 3 can be 30:70 to 70:30, 35:65 to 65:35, or 40:60 to 60:40. When the weight ratio of Chemical Formula 2: Chemical Formula 3 is satisfied, a viscosity of 10 cP to 30 cP can be exhibited to be suitably applied for inkjet printing.

[0373] In one embodiment of the present disclosure, when the siloxane oligomer includes both Chemical Formulas 2 and 3 and the relative content of Chemical Formula 2 is high, the modulus can be lowered, and when the relative content of Chemical Formula 3 is high, the viscosity can be increased. Therefore, considering the modulus and viscosity characteristics, an appropriate content ratio of Chemical Formulas 2 and 3 can be adjusted.

[0374] In one embodiment of the present disclosure, the alkyl group can be linear, branched or cyclic, and the number of carbon atoms is not particularly limited, but can be 1 to 30, or 1 to 10. Specific examples of the alkyl group include methyl, ethyl, propyl, n- propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1 -ethylbutyl, pentyl, n-pentyl, cyclopentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, cyclohexyl, 1 -methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3, 3 -dimethylbutyl, 2- ethylbutyl, heptyl, n-heptyl, 1 -methylhexyl, cyclopentyl methyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1 -methylheptyl, 2-ethylhexyl, 2-propyl pentyl, n-nonyl, 2,2- dimethylheptyl, 1 -ethyl -propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4- methylhexyl, and 5-methylhexyl groups, etc., but are not limited thereto.

[0375] The aryl group can be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but can be 5 to 30, 5 to 20, or 6 to 20. Specific examples of the aryl group may include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a triphenylenyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, etc., but are not limited thereto.

[0376] The alkylene group can be applied with the above-mentioned alkyl groups, except for divalent groups.

[0377] In one embodiment of the present disclosure, the viscosity of Chemical Formula 2 can be about 11 cP at 25°C, and the viscosity of Chemical Formula 3 can be about 47 cP.

[0378] The photocurable ink composition according to one embodiment of the present disclosure includes at least one photoinitiator.

[0379] The photoinitiator is thermally inactive, but is excited by receiving light to generate free radicals, and these free radicals impart excitation energy to siloxane to initiate a curing reaction by ultraviolet curing. In terms of reactivity, the photoinitiator may include aromatic hydrocarbons, acetophenone and derivatives thereof, benzophenone and derivatives thereof, o-benzoyl benzoate ester, benzoin, benzoin ether and derivatives thereof, xanthon and derivatives thereof, quinone compounds, halogenated hydrocarbons and amines, organic peroxides, etc. In terms of compatibility with silicone and stability, compounds or organic peroxides containing a substituted or unsubstituted benzoyl group are more preferable. For example, the photoinitiator may include acetophenone, propiophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy- 1 ,2-diphenylethan- 1 - one, 2-hydroxy-2-methyl- 1 -phenyl-propan- 1 -one, 1 -hydroxy-cyclohexyl-phenyl-ketone, ethyl(2,4,6-trimethylbenzoyl)phenyl phosphinate, l-[4-(2-hydroxy ethoxy)-phenyl]-2- hy droxy-2-methyl- 1 -propan- 1 -one, 2-hy droxy- 1 - {4-[4-(2-hydroxy-2-methyl-propionyl)- benzyl]phenyl]-2-methyl-propan-l-one, 2-methyl-l-(4-methylthiophenyl)-2-morpholino propan- 1 -one, 2-Benzyl-2-dimethylamino-(4-morpholinophenyl)-butanone- 1 ,2- (dimethylamino)-2-[(4-m ethylphenyl) methyl]- 1 -[4-(4-morpholinyl) phenyl]- 1 -butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)- phenylphosphine oxide, 1,2-octanedione, l-[4-(phenylthio)-2-(O-benzoyl oxime)], ethanone, l-[9-ethyl-6-(2-methylbenzoyl)-9 H-carbazol-3-yl]-l-(O-acetyloxime), a mixture of oxyphenyl acetic acid, 2-[2-oxo-2-phenyl acetoxy ethoxy] ethyl ester and oxyphenyl acetic acid, 2-(2 -hydroxy ethoxy) ethyl ester, ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate, bis(2,6-dimethoxy benzoyl)-2,4,4-trimethyl- pentyl phosphine oxide, benzoyl peroxide, etc., but is not limited thereto.

[0380] In particular, in one embodiment of the present disclosure, it is more preferable to apply a photoinitiator that enables the silicone-based composition to be UV-cured even at long wavelengths. For example, the photoinitiator may include 2,4,6-trimethylbenzoyldiphenylphosphinate, bis(2,4,6-trimethylbenzoyl)phenylphosphine, or a mixture thereof.

[0381] The photocurable ink composition according to one embodiment of the present disclosure may have a viscosity of 10 cP to 30 cP, and 15 cP to 25 cP at 25 °C.

[0382] In one embodiment of the present disclosure, when the viscosity of the photocurable ink composition exceeds 30 cP, ink does not flow easily, and thus an injection pressure may increase or nozzles can be clogged, so that the printing quality may deteriorate, and printing may not be performed. In addition, the high viscosity exceeding 30 cP may cause an inkjet printer to exceed a required injection pressure, which may cause excessive load on a printer head. In addition, ink having the high viscosity exceeding 30 cP may not spread evenly on the surface, and thus unbalance or blurring of printed products occurs, and the like, thereby lowering the printing quality, which is not preferable. In addition, when the viscosity of the photocurable ink composition is less than 10 cP, it can be advantageous when printing at high speed and printing micropattems, but the ink may easily leak or flow from the inkjet head to cause problems in the printing quality, which is not preferable. Therefore, in one embodiment of the present disclosure, the viscosity of the photocurable ink composition of 10 cP to 30 cP is a preferable viscosity range in which the ink does not spread too quickly on the surface, thereby implementing clear images.

[0383] In one embodiment of the present disclosure, based on the total weight of the photocurable ink composition, the content of the polyorganosiloxane is 9 wt% to 90 wt%, the content of at least one siloxane oligomer is 9 wt% to 90 wt%, and the content of at least one photoinitiator is 0.1 wt% to 6 wt%. In addition, in one embodiment of the present disclosure, when the siloxane oligomer includes Chemical Formula 2 or 3 alone, the content of the polyorganosiloxane is 49 wt% to 90 wt%, the content of the siloxane oligomer including Chemical Formula 2 or 3 is 9 wt% to 50 wt%, and the content of at least one photoinitiator is 0.1 wt% to 6 wt%. In addition, in one embodiment of the present disclosure, when the siloxane oligomer includes both Chemical Formulas 2 and 3, the content of the polyorganosiloxane is 10 wt% to 90 wt%, the content of the siloxane oligomer including Chemical Formula 2 is 4 wt% to 50 wt%, the content of the siloxane oligomer including Chemical Formula 3 is 4 wt% to 50 wt%, and the content of at least one photoinitiator is 0.1 wt% to 6 wt%.

[0384] In one embodiment of the present disclosure, a contact angle of the photocurable ink composition to a glass substrate can be 23° or less, and can be 22° or less. When the contact angle of the photocurable ink composition to the glass substrate exceeds 23°, the photocurable ink composition may not spread well on the glass substrate, and thus may not be evenly distributed on the surface of the glass substrate, but may remain in the form of water droplets. This problem may cause uneven results in coating, printing, or other surface treatment processes, which is not preferable. In addition, when adhesion with other materials is required, if the surface is hydrophobic, the adhesion can be reduced, which may cause a TFE (Thin Film Encapsulation) material to have difficulty in bonding with other substrates or layers, resulting in peeling or damage to the layer.

[0385] Another embodiment of the present disclosure provides a cured product manufactured by curing the photocurable ink composition.

[0386] The cured product according to one embodiment of the present disclosure can be formed using a method known in the art, except for curing the photocurable ink composition described above. More specifically, the photocurable ink composition can be formed using a method such as applying, coating, or printing on a substrate, and a curing method, but is not limited thereto.

[0387] Yet another embodiment of the present disclosure provides an image display device including the cured product.

[0388] In one embodiment of the present disclosure, the storage modulus of the cured product can be 0.1 GPa or more, and can be 0.1 GPa to 10 GPa. The storage modulus of a photocurable inkjet encapsulation material may vary depending on a composition of the materials, the degree of curing, and added additives, but is generally known to be 0.1 GPa to 10 GPa. Low-strength polymer materials have the storage modulus of about 0.5 GPa. When the storage modulus is less than 0.1 GPa, it is not preferable in that the materials can be easily deformed or damaged by external load or stress. The appropriate storage modulus may vary depending on the requirements of the application field, and generally, it is preferable to have a range of 0.1 GPa to 10 GPa that may maintain stability even in high-temperature and high-humidity environments.

[0389] The cured product according to one embodiment of the present disclosure can be applied for coating and protecting various objects. In particular, the cured product can be effective in protecting objects including external components, for example, moisture or moisture-sensitive elements. Examples of objects to which a coating material includingthe cured product can be applied may include image display devices such as an organic light emitting diode (OLED), etc., but are not limited thereto.EXAMPLES

[0390] The base building block of all the synthesized silicone acrylate molecules are the pentasiloxane dihydride which has a specific molecular weight. This pentasiloxane dihydride can be synthesized by ring opening polymerization of hexamethylcyclotrisiloxane (D3) in the presence of 1,1, 3, 3 tetramethyldisiloxane and acid catalyst as described in IntT Publication WO 2017 / 012714 Al. This pentasiloxane dihydride is used to synthesize multi -acrylate siloxane-acrylate molecules and their synthesis procedure are given as follows.Synthesis Example 1. Synthesis of di-functional siloxane-acrylate molecules

[0391] The di-acrylate siloxane-acrylate molecules can be synthesized in two different ways.

[0392] The first process shown in FIG. 1 is the reaction between pentasiloxane dihydride (MHD3MH) with allyloxyethylmethacrylate in the presence of platinum catalyst. Allyloxyethylmethacrylate can be synthesized using allyloxy ethanol with methacrylic acid or methacrylate anhydride in presence of catalyst e.g. dimethyl amino pyridine (DMAP), 1 -methyl imidazole, tri-ethyl amine, aluminum tritiate.

[0393] The obtained molecule was purified via distillation at 90 °C and 1 mbar.

[0394] In a second process shown in FIG. 2, the same material can be synthesized by reacting methacrylic anhydride or methacrylic acid with bis-propylhydroxy pentasiloxane in the presence of different esterification catalysts. The catalyst can be dimethyl amino pyridine, 1 -methyl imidazole, Tri ethyl amine, Aluminum tritiate, etc. Bis-propylhydroxy pentasiloxane can be synthesized by reaction between pentasiloxane dihydride and allyloxy ethanol in presence of platinum as catalystSynthesis Example 2. Synthesis of hydroxy containing di-functional siloxane- acrylate oligomer

[0395] The synthesis of hydroxyl containing di-functional siloxane-acrylate molecule can be synthesized using two different approaches.

[0396] In the first process shown in FIG. 3 and FIG. 4, the aforementioned molecule is synthesized by the reaction of epoxy containing siloxane with methacrylic acid in the presence of a catalyst. The epoxy containing siloxane can be synthesized by epoxy containing vinyl / allyl with pentasiloxane dihydride (MHD3MH) in the presence of platinum catalyst (FIG. 3). The material is further purified by air purging at 85 °C for 2 hours using vacuum.

[0397] In the second process shown in FIG. 5 and FIG. 6, is the reaction of pentasiloxane dihydride with hydroxyl containing allyl / vinyl methacrylate to synthesize hydroxyl containing di-acrylate siloxane in the presence of platinum catalyst. Hydroxyl containing allyl / vinyl methacrylate molecule can be synthesized using reaction of methacrylic / acrylic acid with epoxy containing vinyl / allyl molecules. The material is further purified by air purging at 85 °C for 2 hours in vacuum.Synthesis Example 3. Synthesis of tetra-acrylate siloxane-acrylate molecule

[0398] The synthesis of multi-acrylate siloxane also can be synthesized using two different processes.

[0399] First process shown in FIGs. 7 and 8 includes the synthesis of epoxy terminated siloxane by reaction of epoxy containing vinyl / allyl with pentasiloxane dihydride and followed by reaction of the same with methacrylic anhydride to get tetra-acrylate siloxane (III). The material is further purified by air purging at 85 °C for 2 hours in vacuum.

[0400] In second process shown in FIGs. 9 and 10, first the reaction of methacrylic anhydride and epoxy containing vinyl / allyl alkyl siloxane will be carried out to synthesize allyl / vinyl containing siloxane di-(meth)acrylate. Then, this material will be reacted with pentasiloxane dihydride to get tetra-(meth)acrylate siloxane molecules.Properties of the Silicone Acrylate Molecules

[0401] The synthesized molecules are characterized by1H-NMR and29Si-NMR at Bruker 400 MHz NMR instrument. The viscosity of synthesized molecules is measured by RS600 Haake Rheometer using parallel plate instrument for 180 s. The viscosity of siloxane diacrylate was measured as 10-130 cps whereas for the tetra-acrylate siloxane measured as 54-200 cps. The solid content of the sample was measured by Mettler Toledo solid content analyzer at 150 °C for 15 minutes. pH was measured using pH paper in both neat and with mixing the sample with water.

[0402] Similarly, as the silicone cyclic content of the synthesized molecules are very important for the many applications the cyclic content of the same is measured using the GC-MS analysis (D4-D10). The quantification of cyclics by GC is 50 ppm and the detection limit is ~2 ppm. Anything below the detection limit will be referred as N.D. (Not detected).

[0403] We have demonstrated the method to prepare the siloxane-acrylate molecules with below 50 ppm level.

[0404] Table 1: Viscosity and cyclic value of the synthesized multi-acrylate oligomers.Synthesis Example 4. Preparation of Pentasiloxane Di-methacrylate via Route 1 (Esterification followed by Hydrosilylation).

[0405] Step 1 : Preparation of Allyloxyethylmethacrylate

[0406] In a typical reaction process, Allyloxyethanol (100 g, 0.98 mol) is reacted with Methacrylic anhydride (MAAnh) (136 g, 0.88 mol) in presence of N,N-Di methyl aminopyridine (2.25 g, 0.018 mol) at 60-90 °C for 12 hours till complete consumption of . BHT (71 mg, 300 ppm) is used as polymerization inhibitor. The crude reaction mixture is diluted with Hexane (100 mL) and first washed with 10% NaOH solution to remove generated methacrylic acid followed by washing with water. After concentrating the cleaned product using rotary evaporator, final distillation will result in pure product as colorless liquid. Yield: 110 g.

[0407] Step 2: Reaction of Allyloxy ethyl methacrylate (AOEMA) with Pentasiloxane dihydride.

[0408] In a typical reaction process, purified AOEMA (105 g, 0.62 mol) is reacted with Pentasiloxane dihydride (MHD3MH) (100 g, 0.28 mol) in presence of Pt-catalyst (10ppm) and BHT as polymerization inhibitor (300 ppm) at 65-85 °C. After 3-4 h, complete consumption of Si-H moieties could be confirmed via1H NMR. The crude product is then treated with activated char-coal to remove Pt-catalyst and filtered. Excess AOEMA is removed from Product by stripping at 60-65 °C with Air-flow to yield colorless liquid. Yield: 185 g.Synthesis Example 5. Preparation of Pentasiloxane Di-methacrylate via Route 2 (Hydrosilylation followed by Esterification).

[0409] Step 1 : Reaction of Pentasiloxane dihydride with Allyloxy ethanol

[0410] In a typical reaction process, Pentasiloxane dihydride (200 g, 0.56 mol) is subjected to hydrosilylation with 2-Allyloxy ethanol (130 g, 1.2 mol) in presence of Karstedt’s catalyst (5 ppm, Pt) and 2-(Dibutylamino)ethanol (300 ppm) at a temperature of 65 °C. The reaction mass is then subjected to vacuum stripping to remove excess reagents. The product is isolated as colorless liquid (270 g).

[0411] Step 2. Methacryl ati on of reaction product from step 1.

[0412] In a typical reaction process, the product from step 1 (150 g, 0.27 mol) is reacted with Methacrylic anhydride (90 g, 0.6 mol) in presence of Dimethyl aminopyridine (DMAP, 0.1 mol%) and BHT (300 ppm) at a temperature of 60 °C. The reaction product is purified via a solvent extraction method and removal of solvents yields a colorless liquid (200 g).Synthesis Example 6. Preparation of Pentasiloxane Di-(hydroxy-methacrylate)

[0413] In a typical reaction process, Pentasiloxane dihydride (200 g, 0.56 mol) is subjected to hydrosilylation with Allyl glycidyl ether (AGE) (130 g, 1.2 mol) in presence of Karstedt’s catalyst (5 ppm, Pt) at 75 °C. The reaction product is purified via vacuum stripping with removal of excess AGE, yielding colorless low viscosity liquid (280 g).

[0414] The above reaction product (200 g, 0.34 mol) was further reacted with Methacrylic acid (62g, 0.72 mol) catalyzed by Tetrabutylphosphonium bromide (0.75 wt%, 2 g) in presence of BHT (500 ppm) at 90 °C. The product is purified via solvent extraction using Alcohol-Water mixture. Removal of residual solvents yielded slightly viscous colorless oil as the product (240 g).Synthesis Example 7. Preparation of Pentasiloxane Di-(hydroxy-cyclohexyl- methacrylate)

[0415] In a typical reaction process, Pentasiloxane dihydride (200 g, 0.56 mol) is subjected to hydrosilylation with Vinylcycloheneoxide (VCHO) (140 g, 1.1 mol) in presence of Karstedt’s catalyst (5 ppm, Pt) at 75 °C. The reaction product is isolated as colorless liquid (340 g).

[0416] The Bis-epoxy Pentasiloxane (340 g, 0.56 mol) is further subjected to esterification with Methacrylic acid (106 g, 1.24 mol) in presence of Ti-isopropoxide (2000 ppm) and MEHQ (300 ppm) as polymerization inhibitor at a temperature of 60 °C. The product is purified through washing with Methanol -water mixture, removal of solvents yielded slightly viscous oil (430 g).Synthesis Example 8. Preparation of Pentasiloxane Di-(hydroxy-methacrylate)

[0417] At first, Allyl glycidyl methacrylate (AGM) is prepared via esterification of Allyl glycidyl ether (AGE) (250 g, 2.2 mol) with Methacrylic acid (226 g, 2.6 mol) in presence of Lithium Methacrylate (10 g, 0.1 mol) and MEHQ (2.3g, 1 wt%) at 90 °C. Crude reaction product washed with Bi-carbonate solution and further vacuum-distillation yielded colorless oil as the purified product (420 g).

[0418] AGM (280 g, 1.4 mol) is then subjected to hydrosilylation with Pentasiloxane dihydride (200 g, 0.56 mol) in presence of Karstedt’s catalyst (5 ppm, Pt) and MEHQ (300 ppm) at 65 °C. Further washing of the crude reaction mass with Methanol -Water mixture and vacuum drying yields slightly viscous colorless liquid (430 g).Synthesis Example 9. Preparation of Pentasiloxane Di-(hydroxy-methacrylate)

[0419] At first, Vinyl cyclohexyl methacrylate (VCHMA) is prepared via esterification of Vinyl cyclohexene oxide (VCHO) (250 g, 2.2 mol) with Methacrylic acid (226 g, 2.6 mol) in presence of Lithium Methacrylate (10 g, 0.1 mol) and MEHQ (2.3 g, 1 wt%) at 90 °C. Crude reaction product washed with Bi-carbonate solution and further vacuumdistillation yielded colorless oil as the purified product (420 g).

[0420] VCHMA (260 g, 1.2 mol) is then subjected to hydrosilylation with Pentasiloxane dihydride (200 g, 0.56 mol) in presence of Karstedt’s catalyst (5 ppm, Pt) and MEHQ (300 ppm) at 45 °C. Further washing of the crude reaction mass with Methanol -Water mixture and vacuum drying yields slightly viscous colorless liquid (420 g).Synthesis Example 10. Preparation of Pentasiloxane Tetra-methacrylate via Hydrosilylation followed by Esterification.

[0421] In a typical reaction process, Pentasiloxane dihydride (200 g, 0.56 mol) is subjected to hydrosilylation with Allyl glycidyl ether (AGE) (130 g, 1.2 mol) in presence of Karstedt’s catalyst (5 ppm, Pt) at 75 °C. The reaction product is purified via vacuum stripping with removal of excess AGE, yielding colorless low viscosity liquid (280 g).

[0422] The above reaction product (200 g, 0.34 mol) was further reacted with Methacrylic anhydride (160 g, 1.03 mol) catalyzed by Tetrabutylphosphonium bromide (1 wt%, 3.6 g) in presence of BHT (5000 ppm) at 100 °C. The product is purified via solvent extraction using Alcohol-Water mixture. Removal of residual solvents yielded slightly viscous colorless oil as the product (280 g).Synthesis Example 11. Preparation of Pentasiloxane Tetra-methacrylate via Hydrosilylation followed by Esterification.

[0423] In a typical reaction process, Pentasiloxane dihydride (200 g, 0.56 mol) is subjected to hydrosilylation with Vinylcycloheneoxide (VCHO) (140 g, 1.1 mol) in presence of Karstedt’s catalyst (5 ppm, Pt) at 75 °C. The reaction product is isolated as colorless liquid (340 g).

[0424] The Bis-epoxy Pentasiloxane (200 g, 0.33 mol) is further subjected to esterification with Methacrylic anhydride (153 g, 1 mol) in presence of Tetrabutylphosphonium bromide (1 wt%, 3.5 g) and MEHQ (3000 ppm) as polymerization inhibitor at a temperature of 90 °C. The product is purified through washing with Methanol-water mixture, removal of solvents yielded slightly viscous oil (270 g).Synthesis Example 12. Preparation of Pentasiloxane Tetra-methacrylate via Esterification followed by Hydrosilylation.

[0425] At first, Allyl glycidyl dimethacrylate (AGDiMA) is prepared via esterification of Allyl glycidyl ether (AGE) (200 g, 1.75 mol) with Methacrylic anhydride (325 g, 2.1 mol) in presence of Tetrabutylphosphonium bromide (1 wt%, 5,25g) and Phenothiazine (5.25 g, 1 wt%) at 90 °C. Crude reaction product washed with Bi-carbonate solution and further vacuum-distillation yielded colorless oil as the purified product (440 g).

[0426] AGDiMA (280 g, 1.04 mol) is then subjected to hydrosilylation with Pentasiloxane dihydride (150 g, 0.42 mol) in presence of Karstedt’s catalyst (5 ppm, Pt)and MEHQ (300 ppm) at 65 °C. Further washing of the crude reaction mass with Methanol -Water mixture and vacuum drying yields slightly viscous colorless liquid (350 g)-Synthesis Example 13. Preparation of Pentasiloxane Tetra-methacrylate via Esterification followed by Hydrosilylation.

[0427] At first, Vinyl cyclohexyl Dimethacrylate (VCHDiMA) is prepared via esterification of Vinyl cyclohexene oxide (VCHO) (200 g, 1.6 mol) with Methacrylic anhydride (300 g, 1.9 mol) in presence of Tetrabutylphosphonium bromide (5g, 1 wt%) and Phenothiszine (5g, 1 wt%) at 90 °C. Crude reaction product washed with Bicarbonate solution and further vacuum-distillation yielded colorless oil as the purified product (400 g).

[0428] VCHDiMA (310 g, 1.1 mol) is then subjected to hydrosilylation with Pentasiloxane dihydride (200 g, 0.56 mol) in presence of Karstedt’s catalyst (5 ppm, Pt) and MEHQ (300 ppm) at 45 °C. Further washing of the crude reaction mass with Methanol -Water mixture and vacuum drying yields slightly viscous colorless liquid (480 g)-Comparative Examples Overview

[0429] We compared the residual cyclics (D4-D10) values and GC-MS data between material obtained from above detailed method with the material synthesized using the conventional reaction process as described in many prior arts which is ring opening polymerization or acid catalyzed equilibration reaction of cyclic siloxane using bis- acrylated disiloxane as chain stopper. In first reaction (Comparative Example 1), ring opening polymerization of cyclic D4 (1,1,3,3,5,5,7,7-Octamethylcyclotetrasiloxane) is carried out using acrylate di-siloxane as a chain stopper with trifluoromethanesulfonic acid as catalyst.

[0430] In the second example (Comparative Example 2), ring opening polymerization of cyclic D3 (1,1, 3, 3, 5, 5, hexamethylcyclotrisiloxane) is carried out using acrylate disiloxane as a chain stopper with trifluoromethanesulfonic acid as catalyst.

[0431] Here, also siloxane cyclics were measured using GC-MS instrument as explained in above results section. The cyclics value are measured more than 40,000 ppm for the first example whereas in the second example cyclic value are measured more than 10,000ppm. Apart from this, both the synthesized polymers do not have single molecular weight from GC-MS data unlike previously synthesized polymer.

[0432] Table 2: Viscosity and cyclic value of the comparative examples

[0433] So, the invented reaction procedure offers better quality product in terms of cyclic value as compared to conventionally used reaction procedures. What has been described above includes examples of the present specification.Photocurable Ink Synthesis Example 1. Synthesis of polyorganosiloxane A-l

[0434] In a 5,000 mL three-neck round-bottom flask, 150 g of TSL8370 (Momentive), 1,250 g of TSL8032 (Momentive), 65 g of TSL8031 (Momentive), and 1,600 g of toluene were added and stirred well, and then added with 100 g of water at room temperature and stirred for about 1 hour.

[0435] The mixture was added with 700 g of water, stirred for 2 hours while the temperature was raised to 70 °C, cooled to room temperature, and then a water layer was discarded using a separatory funnel to leave an organic layer.

[0436] The organic layer was heated to 80 °C, and then added with 0.5 g of a 50% KOH solution, and stirred for 2 hours while the temperature was raised to 120 °C. The water was fully removed from a final silicone polymer layer to obtain polyorganosiloxane A-l.

[0437] As a result of measuring the molecular weight by gel permeation chromatography (GPC), the weight average molecular weight based on polystyrene standard was 5,000 g / mol.Photocurable Ink Synthesis Example 2. Synthesis of polyorganosiloxane A-2

[0438] Polyorganosiloxane A-2 was synthesized and obtained in the same manner as in Synthesis Example 1 except for using 288 g instead of 150 g of TSL8370, 1,000 g instead of 1,250 g of TSL8032, and 104 g instead of 65 g of TSL8031. As a result of measuring the molecular weight by GPC, the weight average molecular weight based on polystyrene standard was 3,000 g / mol.Photocurable Ink Synthesis Example 3. Synthesis of Siloxane Oligomer B-l

[0439] In a 500 mL three-necked round-bottomed flask, 2.25 g of N,N- dimethylaminopyridine, 100 g of allyloxy ethanol, and 136 g of methacrylic anhydride were added and stirred and reacted at 60 °C to 90 °C for 12 hours. The reaction was terminated by adding 70 mg of butylhydroxytoluene as a polymerization inhibitor. The reaction mixture was diluted with 100 mL of hexane, washed with a 10% NaOH solution, and an organic layer was separated using a separatory funnel. The solvent was removed from the separated organic layer using a rotary evaporator.

[0440] 1 Equivalent of allyloxyethyl methacrylate obtained from the reaction was added with 10 ppm of a platinum catalyst, 300 ppm of a polymerization inhibitor, butylhydroxytoluene, and 0.5 equivalent of pentasiloxane dihydride, and heated at 70 °C for 3 hours. The mixture was cooled to room temperature, and filtered through activated carbon to obtain a siloxane oligomer B-l as diacrylate siloxane. The viscosity of the siloxane oligomer B-l at 25 °C was 11 cP.Photocurable Ink Synthesis Example 4. Synthesis of Siloxane Oligomer C-l

[0441] 200 g of pentasiloxane dihydride, 130 g of allyl glycidyl ether, and 5 ppm of a platinum catalyst were added, and heated at 70°C for 2 hours. After the reaction, excess allyl glycidyl ether was removed through a vacuum stripping process to obtain a colorless transparent liquid. 200 g of the product, 5,000 ppm of butylhydroxytoluene, 3.6 g of tetrabutylphosphonium bromide, and 160 g of methacrylic anhydride were reacted at 100 °C for 3 hours. The reactant was extracted and purified with a mixture of ethanol and water, and the solvent was removed to obtain a siloxane oligomer C-l as colorless transparent tetra-acrylate siloxane. The viscosity of the siloxane oligomer C-l at 25 °C was 47 cP.Photocurable Ink Comparative Synthesis Example 1. Synthesis of Siloxane Oligomer B-2

[0442] Trifluoromethanesulfonic acid was used as a catalyst and acrylate disiloxane was used as a chain stopper, and a ring-opening reaction of cyclic D4 (1, 1,3, 3, 5, 5,7,7- octamethylcyclotetrasiloxane) was performed to obtain a siloxane oligomer B-2. The viscosity of the siloxane oligomer B-2 at 25 °C was 8 cP.Photocurable Ink Comparative Synthesis Example 2. Synthesis of Siloxane Oligomer C-2

[0443] 200 g of pentasiloxane dihydride was hydrosilylated at 70 °C using 140 g of vinylcyclohexene oxide in the presence of a platinum catalyst (5 ppm) to obtain colorless and transparent oil. 200 g of the intermediate and 150 g of methacrylic anhydride were reacted at 100 °C for 3 hours in the presence of 3.5 g of tetrabutylphosphotium bromide and 3,000 ppm of 4-methoxyphenol. The reactant was extracted and purified with a mixture of ethanol and water, and the solvent was removed to obtain a colorless, transparent, and viscous siloxane oligomer C-2. The viscosity of the siloxane oligomer C- 2 at 25 °C was 180 cP.

[0444] Photocurable ink compositions were prepared by mixing components described in Tables 3 to 7 below.

[0445] Table 3

[0446] Table 4

[0447] Table 5

[0448] Table 6

[0449] Table 7

[0450] In Tables 3 to 7 above, components used were as follows:

[0451] Polyorganosiloxane A-l: Polyorganosiloxane A-l of Photocurable Ink Synthesis Example 1

[0452] Polyorganosiloxane A-2: Polyorganosiloxane A-2 of Photocurable Ink Synthesis Example 2

[0453] Siloxane oligomer B-l: Siloxane oligomer B-l of Photocurable Ink Synthesis Example 3

[0454] Siloxane oligomer B-2: Siloxane oligomer B-2 of Photocurable Ink Comparative Synthesis Example 1

[0455] Siloxane oligomer C-l: Siloxane oligomer C-l of Photocurable Ink Synthesis Example 4

[0456] Siloxane oligomer C-2: Siloxane oligomer C-2 of Photocurable Ink Comparative Synthesis Example 2

[0457] Multifunctional acrylate crosslinker: Trimethylolpropane triacrylate (TMPTA, viscosity at 25°C of 75 cP)

[0458] Photoinitiator D-l: Irgacure 819

[0459] Photoinitiator D-2: Irgacure 2100Photocurable Ink Experimental Example 1

[0460] In the siloxane oligomer B-l prepared in Photocurable Ink Synthesis Example 3 and the siloxane oligomer B-2 prepared in Photocurable Ink Comparative Synthesis Example 1, the content of impurities including cyclic siloxanes D4 to D10 and the oligomer distribution were measured using Gas Chromatography-Mass Spectrometry (GC-MS) equipment, and the results were shown in Table 8 below.

[0461] Table 8

[0462] As shown in the results of Table 8 above, in the siloxane oligomer B-l prepared in Photocurable Ink Synthesis Example 3, the impurities including the cyclic siloxanes D4 to D10 were not detected, and the oligomers were measured with a single molecular weight distribution. However, in the siloxane oligomer B-2 prepared in Photocurable Ink Comparative Synthesis Example 1, the content of impurities including the cyclicsiloxanes D4 to DIO was measured as about 40,000 ppm, and the oligomers were shown in a Gaussian distribution rather than the single molecular weight distribution.Photocurable Ink Experimental Example 2

[0463] The characteristics of the prepared photocurable ink compositions of Examples and Comparative Examples were evaluated and shown in Table 9 below.

[0464] Table 9

[0465] In Table 9 above, measurement methods of the characteristics were as follows:

[0466] Viscosity: The viscosity was measured at 20 rpm under 25°C conditions using a viscometer (DV3T, Brookfield).

[0467] Contact Angle: The composition was dropped on a glass surface using a contact angle measuring device according to a method of ASTM D 5946, and an angle formed between a stationary liquid droplet and the surface was measured.

[0468] Storage Modulus: The storage modulus was confirmed using DMA (TA Q800).The composition was filled into a mold with 5.3 mm in width x 17.7672 mm in length x 2 mm in height, and then irradiated with UV 1 J (@395 nm LED) to produce a specimen. The specimen produced above was analyzed using DMA at a heating rate of 3 °C per minute from -40 °C to 80 °C to obtain the Storage Modulus. Among them, the Storage value at 25 °C was taken.

[0469] Surface characteristics of cured product: The composition was filled into a mold with 5.3 mm in width x 17.7672 mm in length x 2 mm in height, and then irradiated with UV 1 J (@395 nm LED) to produce a specimen. When observing the surface of the specimen produced above, if no pinholes were generated, it was evaluated as O, and if the pinholes were generated, it was evaluated as X.

[0470] In Photocurable Ink Comparative Example 1 above, the siloxane oligomer C-2 with a high viscosity was applied, and it can be confirmed that the viscosity of the composition was high. In Photocurable Ink Comparative Example 2 above, a multifunctional acrylate crosslinker was included instead of multifunctional acrylate siloxane, and it can be confirmed that the viscosity and contact angle of the composition were high.

[0471] In Photocurable Ink Comparative Examples 3 to 5, the siloxane oligomer B-2 was applied, and the content of impurities in the siloxane oligomer B-2 was high, and thus pinholes were generated on the surface of the cured product of the composition including the siloxane oligomer B-2. In addition, in Photocurable Ink Comparative Example 4, a siloxane oligomer C-2 with a high viscosity was applied, and it can be confirmed that the viscosity of the composition was high. In Photocurable Ink Comparative Example 5 above, a multifunctional acrylate crosslinker was included instead of multifunctional acrylate siloxane, and it can be confirmed that the viscosity and contact angle of the composition were high.

[0472] Photocurable Ink Comparative Example 6 included both the siloxane oligomer including Chemical Formula 2 above and the siloxane oligomer including Chemical Formula 4 above, and when the content of Chemical Formula 4 exceeded 50 wt% based on the total weight of the composition, it can be confirmed that the viscosity of the composition was high.

[0473] In Photocurable Ink Comparative Examples 7 and 8, the siloxane oligomer content was less than 9 wt%, and the compositions of Photocurable Ink Comparative Examples 7 and 8 had difficulty in dissolving the photoinitiator, and thus, it was impossible to measure the viscosity, contact angle, and storage modulus. In addition, although curing was performed upon exposure, phenomena such as unevenness or foreign matters in a cured film were observed.

[0474] Photocurable Ink Comparative Examples 9 to 12 included both the siloxane oligomer including Chemical Formula 2 and the siloxane oligomer including Chemical Formula 4, and a weight ratio of Chemical Formula 2: Chemical Formula 4 did not satisfy 30:70 to 70:30, and thus it can be confirmed that the storage modulus value is very low or the viscosity is high.

[0475] Photocurable Ink Comparative Example 13 did not include a photoinitiator, so that curing was impossible, and Photocurable Ink Comparative Example 14 had a total contentof the photoinitiator of more than 6 wt% based on the total weight of the composition, so that it was difficult to dissolve the photoinitiator, and thus the viscosity, contact angle, and storage elastic modulus were not measurable.

[0476] As the results, the photocurable ink composition according to one embodiment of the present disclosure can reduce the generation of outgas during a curing process by excluding the use of an organic solvent, and implement a low viscosity of 10 cP to 30 cP at 25 °C, thereby forming micropatterns through inkjet printing.

[0477] According to one embodiment of the present disclosure, the cured product of the photocurable ink composition can be applied as an encapsulation layer of an image display device such as an organic light-emitting diode, and the encapsulation layer can effectively block oxygen, moisture, etc. that flow in from the outside.

[0478] So, the invented reaction procedure offers better quality product in terms of cyclic value as compared to conventionally used reaction procedures. What has been described above includes examples of the present specification. It is, of course, not possible to describe every conceivable combination of components or methodologies for purposes of describing the present specification, but one of ordinary skill in the art may recognize that many further combinations and permutations of the present specification are possible. Accordingly, the present specification is intended to embrace all such alterations, modifications and variations that fall within the spirit and scope of the appended claims. Furthermore, to the extent that the term “includes” is used in either the detailed description or the claims, such term is intended to be inclusive in a manner similar to the term “comprising” as “comprising” is interpreted when employed as a transitional word in a claim.

[0479] The foregoing description identifies various, non-limiting embodiments of an aromatic-containing silicone compound and curable compositions comprising such compounds. Modifications may occur to those skilled in the art and to those who may make and use the invention. The disclosed embodiments are merely for illustrative purposes and not intended to limit the scope of the invention or the subject matter set forth in the claims.

[0480] Further embodiments of the present invention are provided in the following.

[0481] Embodiment 1 : A silicone compound represented by the Chemical Structure 1 :

[0482] wherein R1 and R2 can be Ci-Cio alkyl or C5-C20 aryl;

[0483] X can be C1-C10 alkyl, optionally substituted with O, N or a halogen;

[0484] Q can be following

[0485]

[0486]

[0487]

[0488]

[0489]

[0490] and

[0491]

[0492] wherein XI can be methylene or a direct bond;

[0493] R3 can be H or Me.

[0494] Embodiment 2: The silicone compound according to Embodiment 1 represented by Chemical Structure 2

[0495] wherein R1 and R2 can be C1-C10 alkyl or C5-C20 aryl;

[0496] X can be C1-C10 alkyl; and

[0497] R3 can be H or Me.

[0498] Embodiment 3 : The silicone compound according to Embodiment 1 represented by Chemical Structure 3

[0499]

[0500] wherein R1 and R2 can be Ci-Cio alkyl or C5-C20 aryl;

[0501] X can be C1-C10 alkyl; and

[0502] R3 can be H or Me.

[0503] Embodiment 4: The silicone compound according to Embodiment 1 represented by Chemical Structure 4

[0504]

[0505] wherein R1 andR2 can be C1-C10 alkyl or C5-C20 aryl;

[0506] XI can be C1-C10 alkyl;

[0507] X2 can be methylene or a direct bond; and

[0508] R3 can be H or Me.

[0509] Embodiment 5: The silicone compound according to Embodiment 1 represented by Chemical Structure 5

[0510]

[0511] wherein R1 andR2 can be C1-C10 alkyl or C5-C20 aryl;

[0512] XI can be C1-C10 alkyl; and

[0513] R3 can be H or Me.

[0514] Embodiment 6: The silicone compound according to Embodiment 1 represented by Chemical Structure 6

[0515]

[0516] wherein R1 and R2 can be C1-C10 alkyl or C5-C20 aryl;

[0517] and X can be C1-C10 alkyl.

[0518] and R3 can be H or Me.

[0519] Embodiment 7: The silicone compound according to Embodiment 1 represented by Chemical Structure 7

[0520]

[0521] wherein R1 and R2 can be C1-C10 alkyl or C5-C20 aryl;

[0522] and X can be C1-C10 alkyl.

[0523] and R3 can be H or Me.

[0524] Embodiment 8: A process of preparing the silicone compound according toEmbodiment 2 or Embodiment 3 by

[0525] (i) reacting a pentasiloxane dihydride of Chemical Structure 8

[0526]

[0527] with methacrylate of Chemical Structure 9 in presence of a platinum catalyst

[0528]

[0529] wherein Ri andR2 can be Ci-Cio alkyl or C5-C20 aryl;

[0530] X can be O orN;

[0531] and R3 can be H or Me

[0532] (ii) purifying compound obtained from step (i) by air purging at 80-90° C for 2 hours in vacuum.

[0533] Embodiment 9: A process of preparing the silicone compound according toEmbodiment 2 or Embodiment 3 by

[0534] (i) reacting a pentasiloxane dihydride of Chemical Structure 8

[0535]

[0536] with allyloxyethanol in presence of a platinum catalyst to produce a compound ofChemical Structure 10;

[0537]

[0538] wherein

[0539] Ri andR2 can be C1-C10 alkyl or C5-C20 aryl;

[0540] (ii) reacting compound of Chemical Structure 10 with methacrylic anhydride or methacrylic acid in the presence of catalyst; and

[0541] (iii) purifying by air purging at 85 ° C for 2 hours under vacuum.

[0542] Embodiment 10: A process of preparing the silicone compound according toEmbodiment 4 by

[0543] (i) reacting a pentasiloxane dihydride of Chemical Structure 8

[0544]

[0545] with compound of following formula

[0546]

[0547] in the presence of platinum catalyst to produce a compound of Chemical Structure11

[0548]

[0549] wherein Ri andR.2 can be Ci-Cio alkyl or C5-C20 aryl;

[0550] (ii) reacting compound of Chemical Structure 11 with methacrylic acid anhydride in the presence of catalyst; and

[0551] (iii) purifying compound obtained from step (ii) by air purging at 85° C for 2 hours in vacuum.

[0552] Embodiment 11 : A process of preparing the silicone compound according toEmbodiment 4 by

[0553] (i) reacting a pentasiloxane dihydride of Chemical Structure 8

[0554]

[0555] wherein Rl and R2 can be C1-C10 alkyl or C5-C20 aryl; and

[0556] R.3 can be H or Me;

[0557] with compound of following formula

[0558] in the presence of a catalyst; and

[0559] (ii) purifying compound obtained from step (i) by air purging at 85-90° C for 2 hours in vacuum.

[0560] Embodiment 12: A process of preparing the silicone compound according to Embodiment 5 by

[0561] (i) reacting a pentasiloxane dihydride of Chemical Structure 8

[0562]

[0563] with the compound of following formula

[0564] in the presence of platinum catalyst to produce a compound of Chemical Structure12

[0565]

[0566] wherein

[0567] Ri andR2 can be Ci-Cio alkyl or C5-C20 aryl; and

[0568] R3 can be H or Me;

[0569] (ii) reacting compound of Chemical Structure 12 with methacrylic anhydride in the presence of catalyst; and

[0570] (iii) purifying compound obtained from step (ii) by air purging at 85-90° C for 2 hours in vacuum.

[0571] Embodiment 13: A process of preparing the silicone compound according to Embodiment 5 by

[0572] reacting a pentasiloxane dihydride of Chemical Structure 8

[0573]

[0574] with compound of following formula

[0575] in presence of a platinum catalyst

[0576] wherein

[0577] Ri andR2 can be Ci-Cio alkyl or C5-C20 aryl; and

[0578] R3 can be H or Me.

[0579] Embodiment 14: A process of preparing the silicone compound according toEmbodiment 6 by

[0580] reacting a pentasiloxane dihydride of Chemical Structure 8

[0581]

[0582] with compound of following formula

[0583]

[0584] wherein

[0585] Ri andR2 can be C1-C10 alkyl or C5-C20 aryl; and

[0586] R.3 can be H or Me.

[0587] Embodiment 15: A process of preparing the silicone compound according toEmbodiment 6 by

[0588] reacting a pentasiloxane dihydride of Chemical Structure 8

[0589]

[0590] with compound of following formula

[0591]

[0592] wherein Ri andR.2 can be Ci-Cio alkyl or C5-C20 aryl; and

[0593] R3 can be H or Me.

[0594] Embodiment 16: The process according to Embodiment 8, 9, 11 or 14 wherein the catalyst is selected from dimethyl amino pyridine, 1 -methyl imidazole, tri-ethyl amine or aluminum triflate.

[0595] Embodiment 17: The silicone compound according to Embodiments 1 to 7 having a viscosity in the range of 5 to 200 centipoise.

[0596] Embodiment 18: The silicone compound according to Embodiments 1 to 7 has a residual cyclosiloxanes (D4-D10) content less than 50 ppm.

[0597] Embodiment 19: A photocurable ink composition comprising:

[0598] a polyorganosiloxane including a trifunctional silicone unit (T unit) bound with a (meth)acrylate group;

[0599] at least one siloxane oligomer including (meth)acrylate groups at both terminals; and

[0600] at least one photoinitiator;

[0601] wherein the photocurable ink has a viscosity 10 cP to 30 cP at 25 °C.

[0602] Embodiment 20: The photocurable ink composition of Embodiment 19, wherein the polyorganosiloxane is represented by the following Chemical Structure 13:

[0603]

[0604] wherein:

[0605] RIA, R2A, R3A, R4A, and R5A are the same as or different from each other, and are each independently an alkyl group having 1 to 10 carbon atoms;

[0606] R6A is an acrylate group or a methacrylate group; and

[0607] ml and nl are each independently 1 to 200.

[0608] Embodiment 21 : The photocurable ink composition of Embodiment 19, wherein the siloxane oligomer includes at least one of the following:

[0609] (i) Chemical Structure 2

[0610]

[0611] wherein

[0612] R1 andR2 are each selected from Ci-Cio alkyl and C5-C20 aryl;

[0613] X is selected from C1-C10 alkyl; and

[0614] R3 is H or Me; and

[0615] (ii) Chemical Structure 4

[0618] R1 andR2 are each selected from C1-C10 alkyl and C5-C20 aryl;

[0619] XI is selected from C1-C10 alkyl;

[0620] X2 is methylene or a direct bond; and

[0621] R3 is H or Me.

[0622] Embodiment 22: The photocurable ink composition of Embodiment 21, wherein the siloxane oligomer includes Chemical Formula 2 or Chemical Formula 4 alone.

[0623] Embodiment 23: The photocurable ink composition of Embodiment 21, wherein the siloxane oligomer includes both Chemical Formulas 2 and 4, and wherein a weight ratio of Chemical Formula 2:Chemical Formula 4 is 30:70 to 70:30.

[0624] Embodiment 24: The photocurable ink composition of Embodiment 19, wherein in the siloxane oligomer, the content of impurities including cyclic siloxanes D4 to D10 is 50 ppm or less.

[0625] Embodiment 25: The photocurable ink composition of Embodiment 19, wherein based on the total weight of the photocurable ink composition,

[0626] the content of the polyorganosiloxane is 9 wt% to 90 wt%,

[0627] the content of at least one siloxane oligomer is 9 wt% to 90 wt%, and

[0628] the content of at least one photoinitiator is 0.1 wt% to 6 wt%.

[0629] Embodiment 26: The photocurable ink composition of Embodiment 22, wherein based on the total weight of the photocurable ink composition,

[0630] the content of the polyorganosiloxane is 49 wt% to 90 wt%,

[0631] the content of the siloxane oligomer including Chemical Formula 2 or 4 is 9 wt% to 50 wt%, and

[0632] the content of at least one photoinitiator is 0.1 wt% to 6 wt%.

[0633] Embodiment 27: The photocurable ink composition of Embodiment 23, wherein the siloxane oligomer includes both Chemical Formulas 2 and 4, and

[0634] based on the total weight of the photocurable ink composition,

[0635] the content of the polyorganosiloxane is 10 wt% to 90 wt%,

[0636] the content of the siloxane oligomer including Chemical Formula 2 is 4 wt% to 50 wt%,

[0637] the content of the siloxane oligomer including Chemical Formula 4 is 4 wt% to 50 wt%, and

[0638] the content of at least one photoinitiator is 0.1 wt% to 6 wt%.

[0639] Embodiment 28: The photocurable ink composition of Embodiment 19, wherein a contact angle of the photocurable ink composition to a glass substrate is 23° or less.

[0640] Embodiment 29: A cured product manufactured by curing the photocurable ink composition of any one of Embodiments 19-28.

[0641] Embodiment 30: The cured product of Embodiment 29, wherein a storage modulus of the cured product is from 0.1 GPa to 10 GPa.

[0642] Embodiment 31 : An image display device comprising the cured product of Embodiment 30.

Claims

CLAIMS1. A silicone compound represented by Chemical Structure 1 :whereinR1 and R2 are each selected from C1-C10 alkyl and C5-C20 aryl;X is selected from C1-C10 alkyl, optionally substituted with O, N, or a halogen;Q is selected from:XI is methylene or a direct bond; andR3 is H or Me.

2. The silicone compound of claim 1, represented by Chemical Structure 2whereinR1 andR2 are each selected from Ci-Cio alkyl and C5-C20 aryl;X is selected from C1-C10 alkyl; andR3 is H or Me.

3. The silicone compound of claim 1, represented by Chemical Structure 3whereinR1 and R2 are each selected from C1-C10 alkyl and C5-C20 aryl;X is selected from C1-C10 alkyl; andR3 is H or Me.

4. The silicone compound of claim 1, represented by Chemical Structure 4whereinR1 andR2 are each selected from C1-C10 alkyl and C5-C20 aryl;XI is selected from C1-C10 alkyl;X2 is methylene or a direct bond; andR3 is H or Me.

5. The silicone compound of claim 1, represented by Chemical Structure 5whereinR1 and R2 are each selected from C1-C10 alkyl and C5-C20 aryl;XI is selected from C1-C10 alkyl; andR3 is H or Me.

6. The silicone compound of claim 1, represented by Chemical Structure 6whereinR1 and R2 are each selected from C1-C10 alkyl and C5-C20 aryl;X is selected from C1-C10 alkyl; andR3 is H or Me.

7. The silicone compound of claim 1, represented by Chemical Structure 7whereinR1 andR2 are each selected from Ci-Cio alkyl and C5-C20 aryl;X is selected from C1-C10 alkyl; andR3 is H or Me.

8. A process of preparing the silicone compound of claim 2 or claim 3, comprising:(i) reacting a pentasiloxane dihydride of Chemical Structure 8with methacrylate of Chemical Structure 9in presence of a platinum catalyst; whereinR1 andR2 are each selected from Ci-Cio alkyl and C5-C20 aryl;X is O or N;R3 is H or Me; and(ii) purifying compound obtained from step (i) by air purging at 80-90°C for 2 hours in vacuum.

9. A process of preparing the silicone compound of claim 2 or claim 3, comprising:(i) reacting a pentasiloxane dihydride of Chemical Structure 8with allyloxyethanol in presence of a platinum catalyst to produce a compound ofChemical Structure 10whereinR1 andR2 are each selected from C1-C10 alkyl and C5-C20 aryl;(ii) reacting compound of Chemical Structure 10 with methacrylic anhydride or methacrylic acid in presence of a catalyst; and(iii) purifying compound obtained from step (ii) by air purging at 85 °C for 2 hours under vacuum.

10. A process of preparing the silicone compound of claim 4, comprising:(i) reacting a pentasiloxane dihydride of Chemical Structure 8with compound in presence of a platinum catalyst; to produce a compound of Chemical Structure 11whereinR1 andR2 are each selected from Ci-Cio alkyl and C5-C20 aryl;(ii) reacting the compound of Chemical Structure 11 with methacrylic acid anhydride in presence of a catalyst; and(iii) purifying the compound obtained from step (ii) by air purging at 85 °C for 2 hours in vacuum.

11. A process of preparing the silicone compound of claim 4, comprising:(i) reacting a pentasiloxane dihydride of Chemical Structure 8Chemical Structure 8 whereinR1 and R2 are each selected from C1-C10 alkyl and C5-C20 aryl; andR3 is H or Me,with compound in presence of a platinum catalyst; and(ii) purifying the compound obtained from step (i) by air purging at 85-90 °C for 2 hours in vacuum.

12. A process of preparing the silicone compound of claim 5, comprising(i) reacting a pentasiloxane dihydride of Chemical Structure 8with compoundpresence of a platinum catalyst; to produce a compound of Chemical Structure 12wherein R1 and R2 are each selected from C1-C10 alkyl and C5-C20 aryl; and R3 is H or Me;(ii) reacting the compound of Chemical Structure 12 with methacrylic anhydride in the presence of a catalyst; and(iii) purifying the compound obtained from step (ii) by air purging at 85-90 °C for 2 hours in vacuum.

13. A process of preparing the silicone compound of claim 5, comprising:(i) reacting a pentasiloxane dihydride of Chemical Structure 8with a compound in presence of a platinum catalyst; wherein R1 and R2 are each selected from C1-C10 alkyl and C5-C20 aryl; and R3 is H or Me.

14. A process of preparing the silicone compound of claim 6 by(i) reacting a pentasiloxane dihydride of Chemical Structure 8with compound in presence of a platinum catalyst; wherein R1 and R2 are each selected from C1-C10 alkyl and C5-C20 aryl; and R3 is H or Me.

15. A process of preparing the silicone compound of claim 6, comprising:(i) reacting a pentasiloxane dihydride of Chemical Structure 8with compound in presence of a platinum catalyst; whereinR1 and R2 are each selected from C1-C10 alkyl and C5-C20 aryl; andR3 is H or Me.

16. The process of any one of claims 8, 9, 11, or 14, wherein the catalyst is selected from dimethyl amino pyridine, 1 -methyl imidazole, tri-ethyl amine, and aluminum tritiate.

17. The silicone compound of any one of claims 1 to 7, having a viscosity in the range of 5 to 200 centipoise.

18. The silicone compound of any one of claims 1 to 7, having a residual cyclosiloxanes (D4- D10) content less than 50 ppm.

19. A photocurable ink composition comprising: a polyorganosiloxane including a trifunctional silicone unit (T unit) bound with a (meth)acrylate group; at least one siloxane oligomer including (meth)acrylate groups at both terminals; and at least one photoinitiator; wherein the photocurable ink has a viscosity 10 cP to 30 cP at 25 °C.

20. The photocurable ink composition of claim 19, wherein the polyorganosiloxane is represented by the following Chemical Structure 12:wherein:RIA, R2A, R3A, R4A, and R5A are the same as or different from each other, and are each independently an alkyl group having 1 to 10 carbon atoms;R6A is an acrylate group or a methacrylate group; and ml and nl are each independently 1 to 200.

21. The photocurable ink composition of claim 19, wherein the siloxane oligomer includes at least one of the following:(i) Chemical Structure 2whereinR1 andR2 are each selected from Ci-Cio alkyl and C5-C20 aryl;X is selected from C1-C10 alkyl; andR3 is H or Me; and(ii) Chemical Structure 4whereinR1 andR2 are each selected from C1-C10 alkyl and C5-C20 aryl;XI is selected from C1-C10 alkyl;X2 is methylene or a direct bond; and R3 is H or Me.

22. The photocurable ink composition of claim 21, wherein the siloxane oligomer includes Chemical Formula 2 or Chemical Formula 4 alone.

23. The photocurable ink composition of claim 21, wherein the siloxane oligomer includes both Chemical Formulas 2 and 4, and wherein a weight ratio of Chemical Formula 2: Chemical Formula 4 is 30:70 to 70:30.

24. The photocurable ink composition of claim 19, wherein in the siloxane oligomer, the content of impurities including cyclic siloxanes D4 to DIO is 50 ppm or less.

25. The photocurable ink composition of claim 19, wherein based on the total weight of the photocurable ink composition, the content of the polyorganosiloxane is 9 wt% to 90 wt%, the content of at least one siloxane oligomer is 9 wt% to 90 wt%, and the content of at least one photoinitiator is 0.1 wt% to 6 wt%.

26. The photocurable ink composition of claim 22, wherein based on the total weight of the photocurable ink composition, the content of the polyorganosiloxane is 49 wt% to 90 wt%, the content of the siloxane oligomer including Chemical Formula 2 or 4 is 9 wt% to 50 wt%, and the content of at least one photoinitiator is 0.1 wt% to 6 wt%.

27. The photocurable ink composition of claim 23, wherein the siloxane oligomer includes both Chemical Formulas 2 and 4, and based on the total weight of the photocurable ink composition, the content of the polyorganosiloxane is 10 wt% to 90 wt%, the content of the siloxane oligomer including Chemical Formula 2 is 4 wt% to 50 wt%, the content of the siloxane oligomer including Chemical Formula 4 is 4 wt% to 50 wt%, and the content of at least one photoinitiator is 0.1 wt% to 6 wt%.

28. The photocurable ink composition of claim 19, wherein a contact angle of the photocurable ink composition to a glass substrate is 23° or less.

29. A cured product manufactured by curing the photocurable ink composition of any one of claims 19-28.

30. The cured product of claim 29, wherein a storage modulus of the cured product is from 0.1 GPa to 10 GPa.

31. An image display device comprising the cured product of claim 30.

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