Compositions and packaging structures

Abstract

This invention discloses a composition and encapsulation structure. The composition comprises a first oligomer, a second oligomer, and a core-shell hardener. The core-shell hardener comprises a core and a shell, wherein the core is a compound having an imidazolyl group, a compound having an imidazolinyl group, or a combination thereof, and the shell comprises polycaprolactone, wherein the polycaprolactone has a weight average molecular weight of 70,000 g / mol to 90,000 g / mol.

Description

Technical Field

[0001] This invention designs a composition and its packaging structure. Background Technology

[0002] With the trend towards larger LCD screen sizes, liquid crystal injection and panel encapsulation technologies have also changed accordingly. Currently, the liquid crystal droplet-injection (ODF) process has replaced the traditional, time-consuming siphon method. Simply put, this involves directly coating the aligned glass substrate with encapsulating adhesive, then dropping a precisely measured amount of liquid crystal into it, followed by alignment and bonding with the substrate, and finally assembling the panel. The encapsulating adhesive is then cured. This method significantly shortens the liquid crystal injection time and saves liquid crystal materials, thus improving production efficiency and the utilization rate of liquid crystal materials, giving it a clear advantage in the production of ultra-large-size panels.

[0003] The main functions of encapsulating adhesives are to bond two substrates together, prevent external contamination of the liquid crystal, avoid liquid crystal exposure, and prevent the entry of external moisture and oxygen. However, traditional encapsulating adhesives have a short shelf life at room temperature, and the viscosity of common adhesives slowly increases over time, which is not conducive to long-term continuous operation. Therefore, the long-term room temperature storage stability of encapsulating adhesives is a primary issue to be addressed.

[0004] On the other hand, considering that panel manufacturers expect panel thermosetting processes to reduce curing temperature and shorten curing time in order to save energy and maintain liquid crystal activity, most encapsulants currently use low-temperature, highly reactive curing agents. However, such low-temperature, highly reactive curing agents can also affect the room temperature storage stability of encapsulants.

[0005] Therefore, a novel encapsulating adhesive composition is needed to address the problems faced by existing technologies. Summary of the Invention

[0006] According to embodiments of the present invention, a composition is provided. The composition comprises 100 parts by weight of a first oligomer, 40 to 60 parts by weight of a second oligomer, and 0.5 to 10 parts by weight of a core-shell hardener. The first oligomer may be a reaction product of reactant (a) and reactant (b), wherein reactant (a) may be a compound having an acrylic group, and reactant (b) may be a liquid aromatic epoxy resin. The second oligomer may be a reaction product of reactant (b) and reactant (c), or the second oligomer may be a reaction product of reactant (b), reactant (c), and reactant (d), wherein reactant (c) has the structure shown in formula (I) or formula (II), and reactant (d) is a liquid aliphatic epoxy resin.

[0007] Where X is O 、 And, R1 It can be independently H, F, -CH3, or CF3. The core-shell hardener comprises a core and a shell, wherein the core is a compound having an imidazolyl group, a compound having an imidazolinyl group, or a combination thereof. The shell may partially or completely encapsulate the core. The shell comprises polycaprolactone, wherein the polycaprolactone has a weight-average molecular weight of 70,000 g / mol to 90,000 g / mol.

[0008] According to an embodiment of the present invention, the present invention also provides a packaging structure comprising a substrate and a sealing layer disposed on the substrate, wherein the sealing layer is a cured product of the composition described in the present invention. Attached Figure Description

[0009] Figure 1 This is a schematic cross-sectional view of the core-shell hardener described in an embodiment of the present invention;

[0010] Figure 2 This is a cross-sectional schematic diagram of the packaging structure described in an embodiment of the present invention;

[0011] Figure 3 An optical microscope image of the core-shell hardener dispersed in water as described in Example 1.

[0012] Symbol Explanation

[0013] 10. Core-shell hardener;

[0014] 20 cores;

[0015] 30. Shell;

[0016] 100 package structure;

[0017] 110 First substrate;

[0018] 120 Second substrate;

[0019] 130 Sealing layer;

[0020] 140 cavity; and

[0021] 150 Optoelectronic components. Detailed Implementation

[0022] The following provides a detailed description of the composition and packaging structure described in this invention. It should be understood that the following description provides many different embodiments for implementing different variations of the invention. The specific elements and arrangements described below are merely illustrative of the invention. Of course, these are only examples and not limitations of the invention. In this invention, the term "about" means that the specified amount can be increased or decreased by an amount that is generally and reasonably understood by those skilled in the art.

[0023] The use of ordinal numbers such as "first," "second," "third," etc., in the specification and claims to modify elements of the claims does not in itself imply or represent any prior ordinal number of the claimed element, nor does it represent the order of one claimed element with another, or the order of manufacturing process. The use of these ordinal numbers is only to enable a claim element with a certain name to be clearly distinguished from another claim element with the same name.

[0024] In the accompanying drawings, the shape or thickness of the embodiments may be enlarged and indicated in a simplified or convenient manner. Furthermore, portions of the various elements in the drawings will be described separately. It is worth noting that elements not shown or described in the drawings are those known to those skilled in the art. Moreover, specific embodiments are merely to illustrate particular ways of using the invention and are not intended to limit the invention. Unless otherwise defined, all terms used in this invention (including technical and scientific terms) have the same meaning as commonly understood by those skilled in the art to which this invention pertains. It will be further understood that terms defined in common dictionaries should be interpreted as having the same meaning as their application in the relevant art and the content of this invention, and unless explicitly defined herein, will not be interpreted in an idealized or overly formal sense.

[0025] This invention provides a composition, for example, an encapsulating adhesive composition for use in optoelectronic devices. By incorporating an encapsulating thermosetting agent and combining it with specific components, the composition of this invention maintains high adhesion, rapid curing, and laser-removable properties while simultaneously exhibiting excellent processability and storage stability (viscosity increase of less than or equal to 20% after 72 hours of storage at room temperature), making it highly suitable for applications in the display or semiconductor industries. Furthermore, when the composition of this invention is used as an encapsulating adhesive material in liquid crystal display manufacturing processes, no leachates diffuse into the liquid crystal after ultraviolet (UV) light and thermosetting processes.

[0026] According to embodiments of the present invention, the composition comprises 100 parts by weight of a first oligomer, 40 to 60 parts by weight (e.g., 45, 50, or 55 parts by weight) of a second oligomer, and 0.5 to 10 parts by weight (e.g., 1, 2, 3, 5, or 8 parts by weight) of a core-shell curing agent. According to embodiments of the present invention, the first oligomer may be a reaction product of reactant (a) and reactant (b). The second oligomer may be a reaction product of reactant (b) and reactant (c), or the second oligomer may be a reaction product of reactant (b), reactant (c), and reactant (d). According to embodiments of the present invention, the weight ratio of the second oligomer to the first oligomer may be about 4:10 to 6:10. If the amount of the first oligomer is too low, the UV conversion rate will be insufficient during UV curing of the composition. If the amount of the first oligomer is too high, the composition is not conducive to the disassembly and manufacturing process of liquid crystal displays.

[0027] According to embodiments of the present invention, the composition described herein can be used not only as an encapsulating adhesive composition for liquid crystal displays, but also as an encapsulating adhesive composition for other displays (such as quantum dot light-emitting diode displays, organic light-emitting diode displays, or other suitable displays) or solar cells, because it has high adhesion strength to the substrate.

[0028] According to embodiments of the present invention, reactant (a) may be a compound having an acrylic group; reactant (b) may be a liquid aromatic epoxy resin; reactant (c) has a structure shown in formula (I) or formula (II).

[0029]

[0030]

[0031] Where X is O, And, R 1 It is independently H, F, -CH3, or CF3; and the reactant (d) is a liquid aliphatic epoxy resin.

[0032] According to embodiments of the present invention, the chemical structure of the compound having an acrylic group can be as follows: Where R 2It can be hydrogen or a C1-C8 alkyl group. According to embodiments of the present invention, the alkyl group can be a linear or branched alkyl group. For example, C1-C8 alkyl groups can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or isomers thereof. For example, the compound having an acrylic group can be acrylic acid, methacrylic acid, or a combination thereof.

[0033] According to embodiments of the present invention, the liquid aromatic epoxy resin is liquid at room temperature (e.g., about 18°C ​​to 35°C). For example, the liquid aromatic epoxy resin of the present invention includes bisphenol A epoxy resin, bisphenol F epoxy resin, or a combination thereof. The structure of bisphenol A epoxy resin is as follows: The structure of bisphenol F epoxy resin is as follows:

[0034]

[0035] According to embodiments of the present invention, the liquid aliphatic epoxy resin is liquid at room temperature (e.g., about 18°C ​​to 35°C). According to embodiments of the present invention, the liquid aliphatic epoxy resin may be a compound having the structure shown in formula (III).

[0036]

[0037] A 1It is a C2-C10 alkylene group or a C2-C10 alkoxyalkylene group. The alkylene group described in this invention can be a linear or branched alkylene group. For example, the C2-C10 alkylene group can be ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, or its isomers. The alkoxyalkylene group described in this invention can be a linear or branched alkylene group. According to embodiments of the present invention, the liquid aliphatic epoxy resin may be 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neoopentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, or a combination thereof.

[0038] According to embodiments of the present invention, the molar ratio of reactant (a) to reactant (b) used to prepare the first oligomer can be from 1:1.05 to 1:1.5 (e.g., 1:1.1, 1:1.2, 1:1.3, or 1:1.4). If the amount of reactant (b) is too low, the reactivity of the first oligomer with the second oligomer will be reduced during thermosetting of the composition. If the amount of reactant (b) is too high, the UV conversion rate will be insufficient during UV curing of the composition.

[0039] According to embodiments of the present invention, the second oligomer may be the reaction product of reactant (b) (i.e., liquid aromatic epoxy resin) and reactant (c), wherein the molar ratio of reactant (b) to reactant (c) is 4:1 to 8:1 (e.g., 5:1, 6:1, or 7:1). If the amount of reactant (b) is too low, reactant (c) will not easily form a homogeneous phase with reactant (b). If the amount of reactant (b) is too high, the viscosity of the resulting second oligomer will be too high and unsuitable for encapsulating adhesive compositions.

[0040] According to embodiments of the present invention, the second oligomer may be a reaction product of reactant (b) (i.e., liquid aromatic epoxy resin), reactant (c), and reactant (d) (i.e., liquid aliphatic epoxy resin), wherein the molar ratio of reactant (b) to reactant (d) may be 1:9 to 9:1 (e.g., 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, or 8:2). If the amount of reactant (b) is too high, the viscosity of the resulting second oligomer will be too high and unsuitable for encapsulating adhesive compositions. If the amount of reactant (d) is too high, it is not conducive to application in laser disassembly manufacturing processes. Furthermore, the ratio of the molar number of reactant (c) to the total molar number of reactants (b) and reactant (d) may be 1:3 to 1:12 (e.g., 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, or 1:11). If the amount of reactant (c) is too low, the viscosity of the resulting second oligomer will be too high to be suitable for the encapsulating adhesive composition. If the amount of reactant (c) is too high, reactant (c) will not easily form a homogeneous phase with reactants (b) and (d).

[0041] According to embodiments of the present invention, the weight-average molecular weight of the first oligomer can be from 1,000 g / mol to 4,500 g / mol (e.g., 1,500 g / mol to 3,800 g / mol or 2,000 g / mol to 3,300 g / mol). If the weight-average molecular weight of the first oligomer is too small, it may result in poor mechanical properties of the cured composition. If the weight-average molecular weight of the first oligomer is too large, it may result in the oligomer of the resulting composition being difficult to process. In some embodiments, the first oligomer has epoxy groups at both ends. According to embodiments of the present invention, the second oligomer can be from 3,000 g / mol to 20,000 g / mol (e.g., 3,500 g / mol to 18,000 g / mol or 4,000 to 15,000 g / mol). If the weight-average molecular weight of the second oligomer is too small, it may result in poor mechanical properties of the cured composition. If the weight-average molecular weight of the second oligomer is too large, it may result in the oligomer of the resulting composition being difficult to process. In some embodiments, both ends of the second oligomer are epoxy groups.

[0042] According to an embodiment of the present invention, the core-shell hardener comprises a core and a shell. The shell may be disposed on the surface of the core to partially or completely cover the surface of the core. Here, partial coverage of the core surface by the shell means that 30% to 99.99% (e.g., 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, or 99%) of the core surface is covered by the shell. According to one embodiment of the present invention, such as Figure 1As shown, the core-shell hardener 10 of this embodiment of the invention has a core 20 and a shell 30 covering the core 20. According to embodiments of the invention, the core may be a compound having an imidazolyl group, a compound having an imidazolinyl group, or a combination thereof. For example, the core having an imidazolyl group... The compounds in group () may be imidazole, 2-phenylimidazole, 2-methylimidazole, 2-undecylimidazole, 2-undecyl-4,5-diformylimidazole, 2-heptadecylimidazole, 2-n-butyl-4,5-diformylimidazole, 2-phenyl-4-thiocarbamoylimidazole, 2-ethylimidazole, etc. The compounds containing the imidazolinyl group are 2-methylimidazoline, 2-n-propylimidazoline, 2-n-butylimidazoline, 2-ethyl-4-methylimidazoline, 1-methylimidazoline, 1-methyl-2-ethylimidazoline, 1-benzylimidazoline, 1-benzyl-2-methylimidazoline, 1-benzyl-2-phenylimidazoline, or combinations thereof. According to embodiments of the present invention, the compound having the imidazolinyl group is 2-methylimidazoline, 2-phenylimidazoline, or combinations thereof.

[0043] According to an embodiment of the present invention, the shell layer comprises polycaprolactone (PCL), wherein the weight average molecular weight of the polycaprolactone may be from 70,000 g / mol to 90,000 g / mol (e.g., 71,000 g / mol, 72,000 g / mol, 73,000 g / mol, 74,000 g / mol, 75,000 g / mol, 76,000 g / mol, 7...). (7,000 g / mol, 78,000 g / mol, 79,000 g / mol, 80,000 g / mol, 81,000 g / mol, 82,000 g / mol, 83,000 g / mol, 84,000 g / mol, 85,000 g / mol, 86,000 g / mol, 87,000 g / mol, 88,000 g / mol, or 89,000 g / mol). According to embodiments of the present invention, if the weight average molecular weight of the polycaprolactone is too low or too high, the resulting core-shell hardener will have a large particle size or will not be able to be successfully coated, resulting in poor room temperature storage stability of the composition. According to embodiments of the present invention, the particle size of the core-shell hardener of the present invention can be from 1 μm to 30 μm, for example 5 μm, 10 μm, 15 μm, 20 μm, or 25 μm. For example, the weight ratio of the core to the shell can be approximately 1:9 to 9:1 (e.g., 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, or 8:2). This results in a composition with high adhesion and storage safety. The weight-average molecular weight (Mw) of the oligomer or polycaprolactone described in this invention can be determined by gel permeation chromatography (GPC) (using polystyrene as a standard to create a calibration curve).

[0044] According to an embodiment of the present invention, the core-shell hardener is composed of a core and a shell; the core may be composed of a compound having an imidazolyl group, a compound having an imidazolinyl group, or a combination thereof; and the shell may be composed of polycaprolactone (PCL).

[0045] According to embodiments of the present invention, the composition may further comprise 0.1 to 10 parts by weight (e.g., 1 part by weight, 2 parts by weight, 3 parts by weight, 5 parts by weight, or 8 parts by weight) of a crosslinking agent. According to embodiments of the present invention, the crosslinking agent may be a polyfunctional acrylate crosslinking agent. For example, the multifunctional acrylate crosslinking agent can be dipentaerythritol hexaacrylate (DPHA), 1,6-hexanediol diacrylate (HDDA), polyethylene glycol (200) diacrylate (PEG200DA), tetraethylene glycol diacrylate (TTEGDA), triethylene glycol diacrylate (TIEGDA), pentaerythritol tetraacrylate (PETTA), tripropylene glycol diacrylate (TPGDA), polybutadiene diacrylate (PBDDA), or 3-methyl-1,5-pentanediol diacrylate (3-methyl-1,5-pentanediol diacrylate).5-pentanediol diacrylate (MPDA), polyethylene glycol (400) diacrylate (PEG400DA), ethoxylated 3bisphenol A diacrylate (BPA3EODA), trimethylolpropane triacrylate (TMPTA), di-trimethylolpropane tetraacrylate (Di-TMPTTA), tris(2-hydroxyethyl)isocyanurate triacrylate (THEICTA), dipentaerythritol pentaacrylate (DPPA), ethoxylated (20)trimethylolpropane triacrylate (TMP20EOTA), pentaerythritol triacrylate (pentaerythritol) triacrylate (PETIA), ethoxylated (3)trimethylolpropane triacrylate (TMP3EOTA), propoxylated (3)trimethylolpropane triacrylate (TMP3POTA), ethoxylated (4)pentaerythritol tetraacrylate, ethoxylated (6)trimethylolpropane triacrylate (TMP6EOTA), ethoxylated (9)trimethylolpropane triacrylate (TMP9EOTA), dipropylene glycol diacrylate (DPGDA), 1,10-decanediol diacrylate (1,10decanediol diacrylate (DDDA), ethoxylated (4)bisphenol A diacrylate (BPA4EODA), ethoxylated (10)bisphenol A diacrylate (BPA10E0DA), esterdiol diacrylate (EDDA), polyethylene glycol (600) diacrylate (PEG600DA), alkoxylated diacrylate (alkoxylated diacrylate), tricyclodecanedimethanol diacrylate (TCDDMDA), propoxylated (2)neopentyl glycol diacrylate (PONPGDA), propoxylated (3)glyceryl triacrylate (propoxylated (3)glyceryl triacrylate) Triacrylate (GPTA), ethoxylated (15)trimethylolpropane triacrylate (TMP15EOTA), ethoxylated (12)glyceryl triacrylate (G12EOTA), or combinations thereof.

[0046] According to embodiments of the present invention, the composition of the present invention may further comprise 0.1 to 40 parts by weight (e.g., 1 part by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, or 35 parts by weight) of inorganic filler. According to embodiments of the present invention, the inorganic filler may be silicon dioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, sodium carbonate, titanium dioxide, zinc oxide, zirconium oxide, quartz, graphite, magnesium carbonate, potassium titanate, mica, calcium phosphate, talc, silicon nitride, kaolin, barium sulfate, silsesquioxane, or a combination thereof.

[0047] According to embodiments of the present invention, the composition may further comprise 0.1 to 5 parts by weight (e.g., 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, or 4 parts by weight) of an initiator, such as a photoinitiator. The photoinitiator may be a benzoin-based compound, an acetophenone-based compound, a thioxanthone-based compound, a ketal compound, a benzophenone-based compound, an α-aminoacetophenone compound, an acylphosphine oxide compound, a biimidazole-based compound, a triazine-based compound, or a combination thereof.

[0048] According to embodiments of the present invention, the acetophenone compounds may be photoinitiators manufactured by Ciba Geigy and with trade numbers Irgacure 2959, Irgacure 184, Irgacure 500, Irgacure 651, Irgacure 369, Irgacure 379, Irgacure 907, or Darocur 1173.

[0049] According to embodiments of the present invention, the initiator may be a photoinitiator with trade numbers IRGACURE 819, IRGACURE 1800, Lucirin TPO, or Lucirin TPO-L. According to embodiments of the present invention, the initiator may also be a photoinitiator manufactured by Lambson with trade numbers Esacure 1001M, Esacure KIP150, Speedcure BEM, Speedcure EHA, Speedcure BMS, Speedcure MBP, Speedcure PBZ, Speedcure ITX, Speedcure DETX, Speedcure EBD, Speedcure MBB, Speedcure BP, or a photoinitiator manufactured by CibaGeigy with trade numbers Irgacure 2100, Irgacure 250, or Irgacure 784.

[0050] According to an embodiment of the present invention, the present invention also provides a packaging structure 100, comprising a first substrate 110, a second substrate 120, a sealing layer 130 fixing the second substrate 120 onto the first substrate 110 to form a cavity 140, and a photoelectric element 150 disposed in the cavity 140. Please refer to... Figure 2 The sealing layer 130 is a cured product obtained by a curing process of the above-mentioned compound. The substrate 10 may be a glass substrate, a plastic substrate, a semiconductor substrate, or a combination thereof. The optoelectronic element 150 may be a liquid crystal display element, a quantum dot light-emitting element, an organic light-emitting element, or a solar energy element, but is not limited thereto.

[0051] To make the above-mentioned and other objects, features and advantages of the present invention more apparent and understandable, preferred embodiments are described below in detail with reference to the accompanying drawings.

[0052] Table 1 lists the reagents involved in the preparation examples and embodiments of the present invention:

[0053] Table 1

[0054]

[0055]

[0056]

[0057]

[0058] Preparation Example 1

[0059] Two moles of 4-aminobenzoic acid, one mole of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propanedianhydride (BPADA) (1 mole), and one mole of isoquinoline (catalyst amount) were added to γ-butyrolactone (GBL) (as solvent) to obtain a mixture. The mixture was heated to 200°C and reacted for 4 hours to obtain monomer (1). The structure of monomer (1) is as follows:

[0060]

[0061] Preparation Example 2: First Oligomer (1)

[0062] Acrylic acid (AA) (manufactured by TCI) (0.45 mol), bisphenol A epoxy resin (trade name YL983U, sold by Mitsubishi Chemical) (0.475 mol), triphenylphosphine (TPP) (catalyst amount), and hydroquinone monomethyl ether (MEHQ) (as a heat inhibitor) (0.0006 mol) were added to a reaction flask. The reaction flask was then heated to 110°C and reacted for 4 hours to obtain the first oligomer (1) (weight average molecular weight approximately 2,782 g / mol).

[0063] Preparation Example 3: Second Oligomer (1)

[0064] The monomer (1) obtained in Preparation Example 1 (0.02 moles), bisphenol F epoxy resin (trade name YL983U, sold by Mitsubishi Chemical) (0.09 moles), and 1,6-hexanediol diglycidyl ether (HDGE) (0.07 equivalent moles) were added to a reaction flask. The reaction flask was then heated to 150°C and reacted for 5 hours to obtain the second oligomer (2) (weight average molecular weight approximately 7488 g / mol).

[0065] Preparation Example 4: Core-shell hardener (1)

[0066] First, 1 g of 2-phenyl imidazole (as a hardener) was dissolved in 30 mL of dichloromethane and stirred thoroughly to obtain a first solution. Next, 0.2 g of polycaprolactone (PCL) (weight average molecular weight approximately 80,000 g / mol) was dissolved in 40 mL of dichloromethane and stirred thoroughly to obtain a second solution. Then, the first solution was added dropwise to the second solution over 10 to 20 minutes at room temperature to obtain a third solution. Next, 120 mL of an aqueous solution of polyvinyl alcohol (PVA) (trade name BP-05, sold by Changchun Petrochemical) (concentration 1 wt%) (as a stabilizer, which was then removed) was added dropwise to the third solution over 30 to 60 minutes to obtain a fourth solution (containing the hardener). Next, the fourth solution was stirred at room temperature for 8 to 16 hours to allow the dichloromethane to be slowly removed through evaporation. The resulting product was then observed using an optical microscope (OM), and the results are as follows: Figure 3 As shown. By Figure 3 It was found that microcells (i.e., the core-shell hardener obtained through subsequent separation and preparation processes) formed in the solution at this time, and the particle size of the microcells was approximately 15 μm to 30 μm. Next, the solid was collected by centrifugation (centrifuge speed approximately 2,000 rpm). Then, the obtained solid was washed with water (ethyl acetate) to remove residual polyvinyl alcohol. Finally, the product was dried under vacuum at 35°C to obtain the core-shell hardener (1).

[0067] Preparation Example 5: Core-shell hardener (2)

[0068] Preparation Example 5 was carried out according to the preparation method of the core-shell hardener (1) described in Preparation Example 4, except that the amount of polycaprolactone was increased from 0.2 g to 1 g, and a core-shell hardener (2) was obtained.

[0069] Preparation Example 6: Core-shell hardener (3)

[0070] Preparation Example 6 was carried out according to the preparation method of the core-shell hardener (1) described in Preparation Example 4, except that the polycaprolactone with a weight average molecular weight of about 80,000 g / mol was replaced with polycaprolactone with a weight average molecular weight of about 10,000 g / mol, to obtain the core-shell hardener (3).

[0071] Preparation Example 7: Core-shell hardener (4)

[0072] Preparation Example 7 was carried out according to the preparation method of the core-shell hardener (1) described in Preparation Example 4, except that the polycaprolactone with a weight average molecular weight of about 80,000 g / mol was replaced with polycaprolactone with a weight average molecular weight of about 10,000 g / mol, and the amount of polycaprolactone was increased from 0.2 g to 1 g, to obtain the core-shell hardener (4).

[0073] Preparation Example 8: Core-shell hardener (5)

[0074] First, imidazole (IM) (0.6 g) (as a hardener) was dissolved in dichloromethane (10 mL) and stirred thoroughly to obtain a first solution. Next, polycaprolactone (PCL) (weight average molecular weight approximately 80,000 g / mol) (0.6 g) was dissolved in dichloromethane (40 mL) and stirred thoroughly to obtain a second solution. Then, the first solution was added dropwise to the second solution over 10 to 20 minutes at room temperature to obtain a third solution. Next, a 1 wt% aqueous solution of polyvinyl alcohol (PVA) (trade name BP-05, sold by Changchun Petrochemical) (120 mL) (as a stabilizer, which was then removed) was added dropwise to the third solution over 30 to 60 minutes to obtain a fourth solution. Finally, the fourth solution was stirred at room temperature for 8 to 16 hours to allow the dichloromethane to be slowly removed through evaporation. Next, the obtained solution was observed using an optical microscope (OM). At this point, microcells (i.e., the core-shell hardener obtained through subsequent separation and preparation processes) were formed in the solution, and the particle size of the microcells was approximately 10 to 20 μm. The solid was then collected by centrifugation (centrifuge speed approximately 2,000 rpm). The obtained solid was then washed with water (ethyl acetate) to remove residual polyvinyl alcohol. Finally, the product was dried under vacuum at 35°C to obtain the core-shell hardener (5).

[0075] Preparation Example 9: Core-shell hardener (6)

[0076] Preparation Example 9 was carried out according to the preparation method of the core-shell hardener (1) described in Preparation Example 8, except that the amount of polycaprolactone was increased from 0.6 g to 1 g, and a core-shell hardener (6) was obtained.

[0077] Preparation Example 10: Core-shell hardener (7)

[0078] Preparation Example 10 was carried out according to the preparation method of the core-shell hardener (5) described in Preparation Example 8, except that the amount of imidazole (IM) added was reduced from 0.6 g to 0.2 g, and 0.6 g of 2-phenylimidazole was added to obtain the core-shell hardener (7).

[0079] Preparation Example 11: Core-shell hardener (8)

[0080] Preparation Example 11 was carried out according to the preparation method of the core-shell hardener (5) described in Preparation Example 8, except that 0.3 g of 2-phenyl imidazole and 0.6 g of imidazole (IM) were added as hardeners to obtain the core-shell hardener (8).

[0081] Preparation Example 12: Core-shell hardener (9)

[0082] Preparation Example 12 was carried out according to the preparation method of the core-shell hardener (5) described in Preparation Example 8, except that the polycaprolactone with a weight average molecular weight of about 80,000 g / mol was replaced with polycaprolactone with a weight average molecular weight of about 10,000 g / mol, to obtain the core-shell hardener (3).

[0083] Preparation Example 13: Core-shell hardener (10)

[0084] Preparation Example 13 was carried out according to the preparation method of the core-shell hardener (5) described in Preparation Example 8, except that the polycaprolactone with a weight average molecular weight of about 80,000 g / mol was replaced with polycaprolactone with a weight average molecular weight of about 10,000 g / mol, and the amount of polycaprolactone was increased from 0.6 g to 1 g, to obtain the core-shell hardener (10).

[0085] Preparation Example 14: Core-shell hardener (11)

[0086] First, 1 g of 2-undecylimidazole (2UZ) (as a hardener) was dissolved in 10 mL of dichloromethane and stirred thoroughly to obtain a first solution. Next, 1 g of polycaprolactone (PCL) (weight average molecular weight approximately 80,000 g / mol) was dissolved in 40 mL of dichloromethane and stirred thoroughly to obtain a second solution. Then, the first solution was added dropwise to the second solution over 10 to 20 minutes at room temperature to obtain a third solution. Next, 120 mL of an aqueous solution of polyvinyl alcohol (PVA) (trade name BP-05, sold by Changchun Petrochemical) (concentration 1 wt%) (as a stabilizer, which was then removed) was added dropwise to the third solution over 30 to 60 minutes to obtain a fourth solution. Next, the fourth solution was stirred at room temperature for 8 to 16 hours to allow the dichloromethane in the fourth solution to be slowly removed by evaporation. The resulting solution was then observed using an optical microscope (OM), at which point microcells (i.e., the core-shell hardener obtained through subsequent separation processes) formed in the solution, with a particle size of approximately 15 to 25 μm. The solid was then collected by centrifugation (centrifuge speed approximately 2,000 rpm). The solid was then washed with water (ethyl acetate) to remove residual polyvinyl alcohol. Finally, the product was dried under vacuum at 35°C to obtain the core-shell hardener (11).

[0087] Preparation Example 15: Core-shell hardener (12)

[0088] Preparation Example 15 was carried out according to the preparation method of the core-shell hardener (11) described in Preparation Example 14, except that the polycaprolactone with a weight average molecular weight of about 80,000 g / mol was replaced with polycaprolactone with a weight average molecular weight of about 10,000 g / mol, to obtain the core-shell hardener (12).

[0089] Preparation Example 16: Core-shell hardener (13)

[0090] Preparation Example 16 was carried out according to the preparation method of the core-shell hardener (2) described in Preparation Example 5, except that the polycaprolactone with a weight average molecular weight of about 80,000 g / mol was replaced with polycaprolactone with a weight average molecular weight of about 45,000 g / mol, to obtain the core-shell hardener (13).

[0091] Table 2 lists the amount and type of hardener used to prepare core-shell hardeners (1) to (13), the amount and weight-average molecular weight of polycaprolactone, and the particle size of core-shell hardeners (1) to (13).

[0092] Table 2

[0093]

[0094]

[0095] As shown in Table 2, when the weight average molecular weight of polycaprolactone used to form the core-shell hardener is 10,000 g / mol, the hardener is more likely to aggregate, resulting in a larger particle size of the obtained core-shell hardener.

[0096] Preparation of encapsulation composition

[0097] Example 1

[0098] 30 g of the first oligomer (1), 20 g of the second oligomer (1), 1.88 g of dipentaerythritol hexaacrylate (DPHA) (as a multifunctional monomer), 5.33 g of polymethylsilsesquioxane particles (trade name MSP-N080, sold by Nikko Rika Co., Ltd.) (particle size range of approximately 2 μm to 5 μm), 0.65 g of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (trade name IRGACURE 819, sold by BASF) (as a photoinitiator), and core-shell hardener (1) (containing 1 g of 2-phenyl imidazole) were placed in a stirrer (AR310, manufactured by Thinky Co., Ltd.) and mixed and degassed at room temperature (speed approximately 2,000 rpm) for 3 to 5 minutes. Next, the obtained material was dispersed using a three-roller grinder (80S, manufactured by EXAKT) at a speed of approximately 110 rpm. After mixing and degassing again using a stirrer for 2 minutes, the encapsulation composition (1) was obtained.

[0099] Example 2

[0100] Example 2 was prepared according to the method of preparing the encapsulation composition (1) described in Example 1, except that the core-shell hardener (1) was replaced with the core-shell hardener (2) to obtain the encapsulation composition (2).

[0101] Comparative Example 1

[0102] Comparative Example 2 was prepared according to the method of preparing the encapsulation composition (1) described in Example 1, except that the core-shell hardener (1) was replaced with the core-shell hardener (3) to obtain the encapsulation composition (3).

[0103] Comparative Example 2

[0104] Comparative Example 2 was prepared according to the method of preparing the encapsulation composition (1) described in Example 1, except that the core-shell hardener (1) was replaced with the core-shell hardener (4) to obtain the encapsulation composition (4).

[0105] Comparative Example 3

[0106] Comparative Example 3 was prepared according to the method of encapsulation composition (1) described in Example 1, except that the core-shell hardener (1) was replaced with 1 gram of 2-phenyl imidazole, to obtain encapsulation composition (5).

[0107] Next, the storage stability of encapsulation compositions (1) to (5) was evaluated as follows. First, the viscosity (V1) of the encapsulation composition at 25°C was measured. Then, after the encapsulation composition (1) was placed at 25°C for 72 hours, its viscosity (V2) was measured again, and the viscosity increase of the encapsulation composition (1) was calculated ([(V2-V1) / V1]x100%). If the viscosity increase after 72 hours of storage at room temperature was less than or equal to 20%, it was considered to have passed the storage stability test and was recorded as O; otherwise, it was recorded as X. The results are shown in Table 3. The viscosity was measured using a high shear rate viscometer (CAP2000 H, Brookfield).

[0108] Next, the adhesion of encapsulation compositions (1) to (5) was evaluated. The adhesion was evaluated as follows. Encapsulation compositions (1) to (5) were coated onto indium tin oxide (ITO) glass substrates (3cm × 8cm) to form a coating with a diameter of 6mm. Next, another indium tin oxide glass substrate was provided, and the two glass substrates were aligned and pressed together to obtain a test piece. Next, the test piece was irradiated with ultraviolet light (wavelength 365nm, energy 1,500mJ / cm²) using a mercury lamp. 2 The specimens were then baked at 120°C for 30 minutes to harden. Next, the resulting specimens were tested for tensile shear strength using a QC Teck tensile testing machine (tensile rate 20 mm / min). When the tensile shear strength of the specimen exceeded 2.4 kgf / mm², the test was considered successful. 2 If the result is positive, it is considered to have passed the adhesion test and recorded as O; otherwise, it is recorded as X. The results are shown in Table 3.

[0109] Table 3

[0110]

[0111]

[0112] As shown in Table 3, compared to Comparative Example 3, the encapsulation compositions of Examples 1 and 2, by replacing 2-phenylimidazole (which was not coated with polycaprolactone) with a core-shell hardener (2-phenylimidazole coated with polycaprolactone at a weight average molecular weight of 80,000 g / mol), can pass the storage stability test while maintaining high adhesion. Consequently, the viscosity of the encapsulation compositions of Examples 1 and 2 does not increase significantly after storage at room temperature for 72 hours, thus ensuring their usability in product manufacturing processes. Furthermore, the core-shell hardener used in Comparative Examples 1 and 2 is obtained by coating 2-phenylimidazole with 10,000 g / mol polycaprolactone. Compared to the encapsulation compositions of Examples 1 and 2, the encapsulation compositions of Comparative Examples 1 and 2 fail the storage stability test.

[0113] Example 3

[0114] 30 g of the first oligomer (1), 20 g of the second oligomer (1), 1.88 g of dipentaerythritol hexaacrylate (DPHA) (as a multifunctional monomer), 5.33 g of polymethylsilsesquioxane particles (trade name MSP-N080, sold by Nikko Rika Co., Ltd.) (particle size range of approximately 2 μm to 5 μm), 0.65 g of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (trade name IRGACURE 819, sold by BASF) (as a free radical photoinitiator), and core-shell hardener (5) (containing 0.6 g of imidazole) were placed in a stirrer (AR310, manufactured by Thinky Co., Ltd.) and mixed and degassed at room temperature (speed approximately 2,000 rpm) for 3 to 5 minutes. Next, the obtained material was dispersed using a three-roller grinder (80S, manufactured by EXAKT) at a speed of approximately 110 rpm. After mixing and degassing again using a stirrer for 2 minutes, the encapsulation composition (6) was obtained.

[0115] Example 4

[0116] Example 4 was prepared according to the method of preparing the encapsulation composition (6) described in Example 3, except that the core-shell hardener (5) was replaced with the core-shell hardener (6) to obtain the encapsulation composition (7).

[0117] Example 5

[0118] Example 5 was prepared according to the method of preparation of the encapsulation composition (6) described in Example 3, except that the core-shell hardener (5) was replaced with a core-shell hardener (7) (containing 0.6 g of 2-phenylimidazole and 0.2 g of imidazole) to obtain the encapsulation composition (8).

[0119] Example 6

[0120] Example 6 was prepared according to the method of preparation of the encapsulation composition (6) described in Example 3, except that the core-shell hardener (5) was replaced with the core-shell hardener (8) (containing 0.3 g of 2-phenylimidazole and 0.6 g of imidazole) to obtain the encapsulation composition (9).

[0121] Comparative Example 4

[0122] Comparative Example 4 was prepared according to the method of preparing the encapsulation composition (6) described in Example 3, except that the core-shell hardener (5) was replaced with the core-shell hardener (9) to obtain the encapsulation composition (10).

[0123] Comparative Example 5

[0124] Comparative Example 5 was prepared according to the method of preparing the encapsulation composition (6) described in Example 3, except that the core-shell hardener (5) was replaced with the core-shell hardener (10) to obtain the encapsulation composition (11).

[0125] Comparative Example 6

[0126] Comparative Example 6 was prepared according to the method of preparation of the encapsulation composition (6) described in Example 3, except that the core-shell hardener (5) was replaced with 0.6 g of imidazole, to obtain the encapsulation composition (12).

[0127] Next, the storage stability of the encapsulation compositions (6) to (12) was evaluated as described above, and the results are shown in Table 4. Also, the adhesion of the encapsulation compositions (6) to (12) was evaluated as described above, and the results are shown in Table 4.

[0128] Table 4

[0129]

[0130]

[0131] As shown in Table 4, compared to Comparative Example 6, the encapsulation compositions of Examples 3 and 4, by replacing imidazole (which was not coated with polycaprolactone) with a core-shell hardener (imidazolium coated with polycaprolactone at a weight average molecular weight of 80,000 g / mol), passed the storage stability test while maintaining high adhesion. Examples 5 and 6 further used a core-shell hardener containing both imidazole and 2-phenylimidazolium, and the resulting encapsulation compositions passed the storage stability test. Furthermore, the core-shell hardener used in Comparative Examples 4 and 5 was obtained by coating imidazole with 10,000 g / mol polycaprolactone. Compared to the encapsulation compositions of Examples 3 and 4, the encapsulation compositions of Comparative Examples 1 and 2 failed the storage stability test.

[0132] Example 7

[0133] 30 g of the first oligomer (1), 20 g of the second oligomer (1), 1.88 g of dipentaerythritol hexaacrylate (DPHA) (as a multifunctional monomer), 5.33 g of polymethylsilsesquioxane particles (trade name MSP-N080, sold by Nikko Rika Co., Ltd.) (particle size range of approximately 2 μm to 5 μm), 0.65 g of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (trade name IRGACURE 819, sold by BASF) (as a free radical photoinitiator), and core-shell hardener (11) (containing 1 g of 2-undecylimidazole) were placed in a stirrer (AR310, manufactured by Thinky Co., Ltd.) and mixed and degassed at room temperature (speed approximately 2,000 rpm) for 3 to 5 minutes. Next, the obtained material was dispersed using a three-roller grinder (80S, manufactured by EXAKT) at a speed of approximately 110 rpm. After mixing and degassing again using a stirrer for 2 minutes, the encapsulation composition (13) was obtained.

[0134] Comparative Example 7

[0135] Comparative Example 7 was prepared according to the method of preparing the encapsulation composition (13) described in Example 7, except that the core-shell hardener (11) was replaced with the core-shell hardener (12) to obtain the encapsulation composition (14).

[0136] Comparative Example 8

[0137] Comparative Example 8 was prepared according to the method of preparing the encapsulation composition (13) described in Example 7, except that the core-shell hardener (11) was replaced with 1 gram of 2-undecylimidazole, to obtain the encapsulation composition (15).

[0138] Comparative Example 9

[0139] Comparative Example 9 was prepared according to the method of preparing the encapsulation composition (13) described in Example 7, except that the core-shell hardener (11) was replaced with the core-shell hardener (13) to obtain the encapsulation composition (16).

[0140] Next, the storage stability of the encapsulation compositions (13) to (16) was evaluated as described above, and the results are shown in Table 5. Also, the adhesion of the encapsulation compositions (13) to (16) was evaluated as described above, and the results are shown in Table 5.

[0141] Table 5

[0142]

[0143]

[0144] As shown in Table 5, compared to Comparative Example 8, the encapsulation composition of Example 7, by replacing 2-undecylimidazole (which was not coated with polycaprolactone) with a core-shell hardener (2-undecylimidazole coated with polycaprolactone at a weight average molecular weight of 80,000 g / mol), passed the storage stability test while maintaining high adhesion. Furthermore, the core-shell hardener used in Comparative Example 7 was obtained by coating 2-undecylimidazole with 10,000 g / mol polycaprolactone. Compared to the encapsulation composition of Example 7, the encapsulation composition of Comparative Example 7 failed the storage stability test.

[0145] In summary, by introducing a coating thermosetting agent and combining it with specific first and second oligomers, the composition of the present invention can maintain high adhesion, rapid curing, and laser decomposability while also exhibiting excellent processability and storage stability (viscosity increase of less than or equal to 20% after 72 hours of storage at room temperature), making it very suitable for applications in the display or semiconductor industries.

[0146] Although the present invention has been disclosed above with reference to several embodiments, it is not intended to limit the present invention. Any person skilled in the art can make any modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be defined by the appended claims.

Claims

1. A composition comprising: 100 parts by weight of a first oligomer, wherein the first oligomer is a reaction product of reactant (a) and reactant (b), wherein reactant (a) is a compound having an acrylic group, and reactant (b) is a liquid aromatic epoxy resin; 40 to 60 parts by weight of a second oligomer, wherein the second oligomer is a reaction product of reactant (b) and reactant (c), or a reaction product of reactant (b), reactant (c), and a reactant (d), wherein reactant (c) has the structure shown in formula (I) or formula (II), and reactant (d) is a liquid aliphatic epoxy resin. Where X is O, or And, R 1 It can be independently H, F, -CH3, or CF3; and 0.5 to 10 parts by weight of a core-shell hardener, wherein the core-shell hardener comprises a core and a shell, wherein the core is a compound having an imidazole group, a compound having an imidazole group, or a combination thereof, and the shell comprises polycaprolactone, wherein the polycaprolactone has a weight average molecular weight of 70,000 g / mol to 90,000 g / mol.

2. The composition of claim 1, wherein the molar ratio of reactant (a) to reactant (b) used to prepare the first oligomer is from 1:1.05 to 1:1.

5.

3. The composition of claim 1, wherein the second oligomer is the reaction product of reactant (b) and reactant (c), wherein the molar ratio of reactant (b) to reactant (c) is 4:1 to 8:

1.

4. The composition of claim 1, wherein the second oligomer is the reaction product of reactant (b), reactant (c), and reactant (d), wherein the molar ratio of reactant (b) to reactant (d) is 1:9 to 9:1; and the ratio of the number of moles of reactant (c) to the total number of moles of reactant (b) and reactant (d) is 1:3 to 1:

12.

5. The composition of claim 1, wherein the liquid aromatic epoxy resin is bisphenol A epoxy resin, bisphenol F epoxy resin, or a combination thereof.

6. The composition of claim 1, wherein the liquid aliphatic epoxy resin is a compound having the structure shown in formula (III). Where A1 is a C2-C10 alkylene group or a C2-C10 alkoxyalkylene group.

7. The composition of claim 1, wherein the compound having an imidazole group is imidazole, 2-phenylimidazolium, 2-methylimidazolium, 2-undecylimidazolium, 2-undecyl-4,5-di(aldehyde)imidazolium, 2-heptadecylimidazolium, 2-n-butyl-4,5-di(aldehyde)imidazolium, 2-phenyl-4-aminothiocarbonylimidazolium, 2-ethylimidazolium, 2-n-propylimidazolium, 2-n-butylimidazolium, 2-ethyl-4-methylimidazolium, 1-methylimidazolium, 1-methyl-2-ethylimidazolium, 1-benzylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, or a combination thereof.

8. The composition of claim 1, wherein the compound having an imidazoline group is 2-methylimidazoline, 2-phenylimidazoline, or a combination thereof.

9. The composition of claim 1, wherein the particle size of the core-shell hardener is from 1 μm to 30 μm.

10. A packaging structure comprising: Substrate; and A sealing layer disposed on the substrate, wherein the sealing layer is a cured product of the composition according to any one of claims 1 to 9.

Images