Tiled display device

Abstract

A tiled display device is provided. This tiled display device comprises modules that are tiled, each of the modules including, at least, a substrate, a light emitting element mounted on the substrate, and an electrode portion for applying a voltage to the light emitting element, wherein a seam portion between adjacent modules comprises a cured product of an adhesive composition containing the following (a) and (b): (a) an epoxy compound having two or more epoxy groups in one molecule, at least one of which is an alicyclic epoxy group, and having an epoxy equivalent of 135 g / eq or less; and (b) an organosiloxane oligomer.

Description

Tiling type display device

[0001] The present invention relates to a tiling-type display device.

[0002] Conventionally, a tiling type display device is known in which a plurality of unit modules, each having a display unit with a light-emitting element mounted on a substrate, are arranged in a regular tile shape and connected.

[0003] Tiling-type display devices are being widely considered as a super-large and scalable display technology, but the noticeable seams in the gaps between adjacent modules remain a major challenge.

[0004] Patent Document 1: Japanese Patent Publication No. 2004-231934

[0005] Patent Document 1 describes a transparent composite composition comprising a transparent resin (a) and a glass filler (b), wherein the Abbe number of the transparent resin (a) is 45 or higher. Patent Document 1 describes that the difference in refractive index between the transparent resin (a) and the glass filler (b) is preferably 0.01 or lower. Although the difference in refractive index between the transparent resin (a) and the glass filler (b) included in the transparent composite composition described in Patent Document 1 is 0.01 or lower and the Abbe number of the transparent resin (a) is 45 or higher, the transparency of the display is insufficient because the difference in refractive index increases with wavelength. Consequently, when viewed from an oblique direction, the refraction of transmitted light passing through the core or the scattering of external light incident on the core is visible, which may result in a problem where sufficient seamlessness cannot be secured. Furthermore, "seamlessness" refers to the characteristic where external light scattering due to scattering or reflection of transmitted light at the seams between modules does not occur, making the seams difficult to see.

[0006] The transparent composite composition described in Patent Document 1 is suitable for use in rigid bodies such as substrates or lenses, and the cured product has very hard and brittle characteristics. Therefore, when used in the butt joint (core) of a substrate of a tiling-type display device, there was a problem that it would be damaged by bending or deformation during handling or easily peel off over time.

[0007] The present invention has been made in consideration of the above-described circumstances and aims to provide a means to improve seamlessness in the core while simultaneously improving flexibility and durability (peel resistance) of the core.

[0008] The inventors have conducted extensive research to solve the above problem. As a result, as a means of solving the above problem, a tiling-type display device is provided, wherein the module comprising at least a substrate, a light-emitting element mounted on the substrate, and an electrode portion for applying voltage to the light-emitting element is tiled, and the core between adjacent modules comprises a cured product of an adhesive composition comprising the following (a) and (b):

[0009] (a) an epoxy compound having two or more epoxy groups in one molecule, at least one of the epoxy groups being a dicycloaliphatic epoxy group, and having an epoxy equivalent of 135 g / eq or less; and

[0010] (b) Organosiloxane oligomer.

[0011] According to one embodiment, a tiling type display device having at least a module comprising a substrate, a light-emitting element mounted on the substrate, and an electrode portion for applying voltage to the light-emitting element, wherein

[0012] The core between adjacent modules comprises (a) an epoxy compound having two or more epoxy groups in one molecule, at least one of the epoxy groups being a cycloaliphatic epoxy group, and having an epoxy equivalent of 135 g / eq or less; and (b) a cured product of an adhesive composition including an organosiloxane oligomer.

[0013] According to another embodiment, the adhesive composition may further contain (c) a monofunctional epoxy compound having two or more aromatic hydrocarbon groups in one molecule.

[0014] According to another embodiment, the difference (ΔRI) between the refractive index of the substrate and the refractive index of the cured material in the visible light region may be -0.01 ≤ ΔRI ≤ 0.01.

[0015] According to another embodiment, the yellowness (YI value) of the cured product may be 3.0 or less.

[0016] According to another embodiment, the content of component (a) in the adhesive composition may be 10 mass% or more and 85 mass% or less with respect to the total mass of the adhesive composition.

[0017] According to another embodiment, the epoxy equivalent of the above (a) component may be 75 to 130 g / eq.

[0018] According to another embodiment, the above (a) component comprises 1,2-epoxy-4-epoxyethylcyclohexane, 1-methyl-4-(2-methyloxirane-1-yl)-7-oxabisclo[4.1.0]heptane(limonene dioxide), (3,4,3',4'-diepoxy)bicyclohexyl, 2,3'-bi(7-oxabisclo[4.1.0]heptane), 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,3-dioxane, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, It may include 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylcarboxylate, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, ethylenebis(3,4-epoxycyclohexanecarboxylate), dicyclopentadiene diepoxide, methylenebis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, 3,4:7,8-diepoxybicyclo[4.3.0]nonane or a combination thereof.

[0019] According to another embodiment, the content of component (b) in the adhesive composition may be 3 mass% or more and 40 mass% or less with respect to the total mass of the adhesive composition.

[0020] According to another embodiment, the above (b) component comprises an alkoxy group and a functional group, and the functional group may comprise an epoxy group, an acryloyl group, a methacryloyl group, a vinyl group, a thiol group, or a combination thereof.

[0021] According to another embodiment, the above (b) component may include a repeating unit represented by the following chemical formula 1:

[0022] <Chemical Formula 1>

[0023]

[0024] In the above formula,

[0025] X b is a functional group, and

[0026] L b is a divalent connector, and

[0027] n b is 0 or 1, and

[0028] R b is an alkyl group having 1 to 10 carbon atoms, and

[0029] Z b is an oxygen atom or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms.

[0030] According to another embodiment, the above component (b) may have an epoxy group.

[0031] According to another embodiment, the weight average molecular weight of the above (b) component may be, for example, 500 daltons or more and 30,000 daltons or less.

[0032] According to another embodiment, the content of the above (c) component may be 0.5 mass% or more and 30 mass% or less with respect to the total mass of the adhesive composition.

[0033] According to another embodiment, the above (c) component may include 2-phenylphenolglycidyl ether, 4-phenylphenolglycidyl ether, monostyrene phenolglycidyl ether, 4-cyano-4-hydroxybiphenylglycidyl ether, 4,4'-biphenol monoglycidyl ether, bisphenol A monoglycidyl ether, bisphenol F monoglycidyl ether, or a combination thereof.

[0034] According to another embodiment, the adhesive composition further comprises another epoxy compound distinct from the component (a), and

[0035] The above other epoxy compounds may include an aliphatic epoxy compound, a cycloaliphatic epoxy compound other than component (a), an aromatic epoxy compound other than component (c), or a combination thereof.

[0036] According to another embodiment, the silane coupling agent content may be 8 mass% or more and 65 mass% or less with respect to the total mass of the adhesive composition.

[0037] According to another embodiment, the adhesive composition further comprises a silane coupling agent distinct from the component (b), wherein the silane coupling agent comprises an epoxy-based silane coupling agent, a vinyl-based silane coupling agent, a (meth)acrylic-based silane coupling agent, an amino-based silane coupling agent, a uride-based silane coupling agent, a thiol-based silane coupling agent, an isocyanate-based silane coupling agent, or a combination thereof, a tiling-type display device.

[0038] According to another embodiment, the silane coupling agent content may be 0.25 mass% or more and 5 mass% or less with respect to the total mass of the adhesive composition.

[0039] According to another embodiment, the viscosity of the adhesive composition at 25°C may be 230 mPa·s or less.

[0040] According to another embodiment, the tiling type display device may be a transparent type device.

[0041] According to the present invention, by including a cured product of an adhesive composition comprising (a) an epoxy compound having two or more epoxy groups in one molecule, at least one of the epoxy groups being a cycloaliphatic epoxy group and having an epoxy equivalent of 135 g / eq or less, and (b) an organosiloxane oligomer, seamlessness in the core can be improved, and at the same time, flexibility and durability (peel resistance) of the core can be improved.

[0042] FIG. 1 is a drawing of a tiling type display device according to a preferred embodiment of the present invention, wherein (A) is a schematic plan view, (B) is a schematic cross-sectional view cut along line AA, and (C) is a schematic cross-sectional view cut along line BB.

[0043] Various embodiments of the present disclosure and the terms used therein are not intended to limit the technical features described in the present disclosure to specific embodiments, and should be understood to include various modifications, equivalents, or substitutions of said embodiments.

[0044] In relation to the description of the drawings, similar reference numerals may be used for similar or related components.

[0045] The singular form of the noun corresponding to the item may include one or multiple items, unless the relevant context clearly indicates otherwise.

[0046] In the present disclosure, each of the phrases such as “A or B”, “at least one of A and B”, “at least one of A or B”, “A, B or C”, “at least one of A, B and C”, and “at least one of A, B, or C” may include any one of the items listed together in the corresponding phrase, or all possible combinations thereof.

[0047] The term "and / or" includes a combination of multiple related described components or any of the multiple related described components.

[0048] Terms such as "first," "second," or "first" or "second" may be used simply to distinguish a component from another component and do not limit the components in other aspects (e.g., importance or order).

[0049] Additionally, terms such as 'front,' 'rear,' 'top,' 'bottom,' 'side,' 'left,' 'right,' 'top,' and 'bottom' used in this disclosure are defined based on the drawings, and the shape and location of each component are not limited by these terms.

[0050] Terms such as "include" or "have" are intended to specify the existence of the features, numbers, steps, actions, components, parts, or combinations thereof described in this disclosure, and do not preclude the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0051] When it is said that a component is "connected," "combined," "supported," or "in contact" with another component, this includes not only cases where the components are directly connected, combined, supported, or in contact, but also cases where they are indirectly connected, combined, supported, or in contact through a third component.

[0052] When it is said that a component is located "on" another component, this includes not only cases where one component is in contact with the other, but also cases where another component exists between the two components.

[0053]

[0054] Hereinafter, embodiments for implementing the present invention will be described in detail with appropriate reference to the drawings. The embodiments shown herein are examples intended to embody the technical concept of the present invention and do not limit the present invention. Furthermore, other implementable forms, embodiments, and operational techniques conceivable by those skilled in the art, etc., within the scope of the essence of the present invention, are all included within the scope and essence of the present invention and are simultaneously included within the scope equivalent to the invention described in the patent claims.

[0055] Also, unless otherwise specified, operations and measurements of physical properties, etc. are carried out under conditions of room temperature (20°C or higher and 25°C or lower) and relative humidity of 40%RH or higher and 50%RH or lower.

[0056] One embodiment of the present invention is a tiling-type display device having at least a substrate, a light-emitting element mounted on the substrate, and an electrode portion for applying voltage to the light-emitting element, wherein the core portion between adjacent modules comprises a cured product of an adhesive composition comprising the following components (a) and (b):

[0057] (a) an epoxy compound having two or more epoxy groups in one molecule, at least one of the epoxy groups being a dicycloaliphatic epoxy group, and having an epoxy equivalent of 135 g / eq or less (hereinafter also simply referred to as "component (a)")

[0058] (b) Organosiloxane oligomer (hereinafter also simply referred to as "Component (b)").

[0059] The tiling display device of the present invention having such a configuration improves seamlessness in the seam portion, while simultaneously improving the flexibility and durability (peel resistance) of the seam portion.

[0060] Hereinafter, the configuration of an LED display using an LED element as a light-emitting element (20) will be described. However, the tiling type display device (100) of the present invention is not limited to an LED display as a display type, and can be applied to other types of display devices such as an OLED (Organic Light Emitting Diode) display and a liquid crystal display.

[0061] The configuration of a tiling-type display device (100) according to one embodiment of the present invention will be described with appropriate reference to FIG. 1. However, FIG. 1 relates to a tiling-type display device (100) according to one embodiment of the present invention, and the tiling-type display device (100) of this embodiment is not limited to the configuration described by FIG. 1.

[0062] FIG. 1 illustrates a plan view and a cross-sectional view of a tiling type display device (100) according to a preferred embodiment of the present invention. In FIG. 1, (A) is a plan view of the tiling type display device (100), (B) is a cross-sectional view cut along line AA of FIG. 1 (A), and (C) is a cross-sectional view cut along line BB of FIG. 1.

[0063] As shown in FIGS. 1(A) to (C), the tiling type display device (100) is configured such that modules (110), each having at least a substrate (10), a light-emitting element (20) mounted on the substrate surface (surface) of the substrate (10), and an electrode portion (30) for applying a voltage required to drive the light-emitting element (20), are arranged in a matrix-like regularity. Between adjacent modules (110), a core portion (60) that serves as a gap between substrates (10) is interposed. FIG. 1(A) shows a configuration in which the modules (110) are arranged in a 2x2 arrangement. Furthermore, the number of modules (110) of the tiling type display device (100) is not limited to FIG. 1(A) and can be any number.

[0064] A tiling-type display device (100) has a driving circuit (40) as shown in FIG. 1(A) and a flexible substrate (50) that connects the driving circuit (40) and the electrode portion (30). A predetermined driving voltage is applied to the electrode portion (30) through the flexible substrate (50) by driving the driving circuit (40) of the tiling-type display device (100). A predetermined voltage is applied to the light-emitting element (20) from the electrode portion (30) so that the light-emitting element (20) emits light and displays a predetermined display content.

[0065] The substrate (10) is composed of a material capable of mounting a light-emitting element (20), such as alkali-free glass, polyimide, PET, polyolefin, or silicon. As for the alkali-free glass, a glass substrate such as Eagle XG (registered trademark, hereinafter the same, manufactured by Corning Japan Co., Ltd.) may be preferably used. The substrate (10) is not limited to the aforementioned materials, and an appropriate material may be arbitrarily selected by considering the planar flatness of the mounting surface of the light-emitting element (20) or the heat resistance when mounting the light-emitting element (20).

[0066] The light-emitting element (20) is composed of surface-mount LED elements of each RGB color and is mounted on the substrate (10). The light-emitting element (20) forms three color elements within each pixel of the substrate (10) and emits light by the voltage applied from the electrode portion (30).

[0067] The electrode portion (30) is composed of various wiring or a TFT (Thin Film Transistor) that connects the light-emitting element (20) and the flexible substrate (50). The electrode portion (30) is connected to the driving circuit (40) through the flexible substrate (50) and applies a predetermined driving voltage to the light-emitting element (20) based on the control of the driving circuit (40).

[0068] [Deep]

[0069] In a tiling type display device (100) according to one embodiment of the present invention, seamlessness of the core (60) can be achieved while improving the seamlessness of the reflected light and transmitted light in the core (60). In addition, the flexibility and durability (peel resistance) of the core (60) can be improved so that damage caused by bending or deformation during handling can be prevented, and the core (60) can be prevented from peeling off over time.

[0070] The core (60) between adjacent modules (110) is filled with a cured material (61) of an adhesive composition. The difference (ΔRI, hereinafter simply referred to as "refractive index difference (ΔRI)") between the refractive index of the substrate (60) in the visible light region and the refractive index of the cured material (61) may be in the range of, for example, -0.01 ΔRI ≤ 0.01. If the refractive index difference (ΔRI) is in this range, the seamlessness of the core (60) is further improved. The difference (ΔRI, hereinafter simply referred to as "refractive index difference (ΔRI)") between the refractive index of the substrate (60) in the visible light region may be in the range of, for example, -0.007 ≤ ΔRI ≤ 0.007. In order to further improve the seamlessness of reflected and transmitted light in the core (60) or to make seamlessness of the core (60) easier to achieve, the difference in refractive index (RI) may be in the range of, for example, 0.005 ≤ ΔRI ≤ 0.005. The difference between the refractive index of the substrate (60) and the refractive index of the cured material (61) in the visible light region (ΔRI, hereinafter also simply referred to as "difference in refractive index (ΔRI)") may be in the range of, for example, -0.003 ≤ ΔRI ≤ 0.003. The difference between the refractive index of the substrate (60) and the refractive index of the cured material (61) in the visible light region (ΔRI, hereinafter also simply referred to as "difference in refractive index (ΔRI)") may be in the range of, for example, -0.001 ≤ ΔRI ≤ 0.001. In addition, the difference in refractive index (ΔRI) can be controlled by appropriately selecting, for example, the type or content of component (a) and component (b) included in the adhesive composition.

[0071] The difference in refractive index (ΔRI) can be obtained by measuring the refractive indices (nd, nf, and nc) of the substrate and resin for the wavelengths of the sodium D line (589 nm), hydrogen F line (486.13 nm), and hydrogen C line (656.27 nm) based on a test method in accordance with JIS K7142: 2014 using an Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.). More specifically, it can be obtained by the method described in the examples.

[0072] The YI value (yellowness) of the cured material (61) may be, for example, 3.0 or less, 2.0 or less, 1.5 or less, or 1.0 or less. If the YI value (yellowness) is within this range, the seamlessness of the core (60) may be further improved. In addition, the YI value (yellowness) of the cured material (61) can be measured by the method described in the example.

[0073] [Adhesive composition]

[0074] In a tiling-type display device according to one embodiment of the present invention, the core comprises a cured product of an adhesive composition. The adhesive composition according to the present invention comprises (a) an epoxy compound having two or more epoxy groups in one molecule, at least one of which is a cycloaliphatic epoxy group, and an epoxy equivalent of 135 g / eq or less, and (b) an organosiloxane oligomer. Hereinafter, other components such as component (a), component (b), and optionally component (c) included in the adhesive composition will be described. Also, hereinafter, the cured product of the adhesive composition is also simply referred to as "cured product."

[0075] <(a) component>

[0076] The adhesive composition according to the present invention comprises (a) a component, that is, an epoxy compound having two or more epoxy groups in one molecule, at least one of the epoxy groups being a cycloaliphatic epoxy group, and also having an epoxy equivalent of 135 g / eq or less.

[0077] (a) The component has excellent reactivity and curing (cationic polymerization) proceeds effectively, and the resulting cured product has excellent color resistance under high temperature conditions. In addition, as the crosslinking density of the cured product increases, the elastic modulus of the cured product also increases appropriately, thereby improving heat resistance. Since the component (a) has a relatively low viscosity, the fluidity of the adhesive composition increases, the adhesion of the core (60) to the substrate (10) becomes good, and the generation or incorporation of bubbles in the core (60) is suppressed, thereby improving the appearance quality and the durability (peel resistance, adhesion) of the core (60) can also be improved.

[0078] In the present disclosure, an aliphatic epoxy group is an aliphatic epoxy group in which two carbon atoms as adjacent ring constituent atoms are bonded through an oxygen atom. That is, an aliphatic epoxy group has an epoxy group comprising a three-membered ring consisting of two carbon atoms and one oxygen atom on an aliphatic ring.

[0079] (a) The epoxy equivalent of the component may be, for example, 135 g / eq or less or 130 g / eq or less. If only an epoxy compound having two or more epoxy groups in one molecule, at least one of which is a dicyclic epoxy group, and having an epoxy equivalent exceeding 135 g / eq is used, the crosslinking density of the cured product is lowered, and the heat resistance is reduced. (a) The epoxy equivalent of the component may be, for example, 75 g / eq or more and 130 g / eq or less, 80 g / eq or more and 130 g / eq or less, 85 g / eq or more and 130 g / eq or less, or 90 g / eq or more and 130 g / eq or less. The epoxy equivalent may be measured, for example, in accordance with the method described in JIS K7236: 2001.

[0080] (a) Specific examples of the components include, for example, 1,2-epoxy-4-epoxyethylcyclohexane, 1-methyl-4-(2-methyloxiran-1-yl)-7-oxabisclo[4.1.0]heptane(limonene dioxide), (3,4,3',4'-diepoxy)bicyclohexyl, 2,3'-bi(7-oxabisclo[4.1.0]heptane), 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,3-dioxane, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, Examples include 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylcarboxylate, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, ethylenebis(3,4-epoxycyclohexanecarboxylate), dicyclopentadiene diepoxide, methylenebis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, 3,4:7,8-diepoxybicyclo[4.3.0]nonane, etc. (a) The ingredients may be used as a single type or in combination of two or more types.

[0081] (a) Commercial products may be used for the ingredients. Examples of commercial products include TTA-20, TTA-22, TTA-28, TTA-800 (all manufactured by Tetra), ceroxide (registered trademark, hereinafter the same), 2021P, ceroxide 8010 (all manufactured by Daicel Co., Ltd.).

[0082] The content of component (a) in the adhesive composition may be, for example, 10 mass% or more, 12 mass% or more, 15 mass% or more, 20 mass% or more, or 30 mass% or more with respect to the total mass of the adhesive composition. The content of component (a) in the adhesive composition may be, for example, 85 mass% or less, 80 mass% or less, 75 mass% or less, or 70 mass% or less with respect to the total mass of the adhesive composition. The content of component (a) in the adhesive composition may be, for example, 10 mass% or more and 85 mass% or less, 12 mass% or more and 80 mass% or less, 15 mass% or more and 75 mass% or less, 20 mass% or more and 70 mass% or less, or 30 mass% or more and 70 mass% or less with respect to the total mass of the adhesive composition. The content of component (a) within the above ranges can more efficiently enhance the effects of the present invention. When the adhesive composition contains two or more (a) components, the content of the (a) components represents the total amount.

[0083] <(b) component>

[0084] The adhesive composition according to the present invention comprises (b) component: organosiloxane oligomer.

[0085] Organosiloxane oligomers typically have multiple repeating units containing both alkoxy groups and functional groups within the molecule. Component (b) has high adhesion to the substrate (especially a glass substrate), which can improve the flexibility of the cured product. This prevents the core from peeling off due to bending or deformation during handling, thereby improving durability (peel resistance). Because the molecular weight between the functional groups is large, it suppresses curing shrinkage during the curing of the adhesive composition and reduces internal stress, thereby improving durability (peel resistance).

[0086] The alkoxy groups contained in the organosiloxane oligomer may include, for example, methoxy groups, ethoxy groups, propoxy groups, etc. The alkoxy groups may be, for example, methoxy groups and ethoxy groups. The alkoxy groups may be, for example, methoxy groups.

[0087] The functional groups contained in the organosiloxane oligomer can typically form chemical bonds by reacting with suitable organic compounds, etc. Examples of such functional groups include epoxy groups, acryloyl groups, methacryloyl groups, vinyl groups, thiol groups, etc. There may be one type of functional group or two or more types. Among the functional groups, from the perspective of effectively increasing durability (peel resistance), specifically, at least one functional group selected from the group consisting of epoxy groups, acryloyl groups, and methacryloyl groups may be present. For example, the functional group may be an epoxy group.

[0088] Organosiloxane oligomers typically comprise repeating units containing a silicon atom, an alkoxy group directly bonded to the silicon atom, and a functional group bonded to the silicon atom either directly or through a linker. Typically, these repeating units are connected through bonding hands extending from the silicon atom. Examples of organosiloxane oligomers include, for instance, oligomers containing repeating units represented by the following chemical formula 1.

[0089] <Chemical Formula 1>

[0090]

[0091] Among the above formulas, X b is a functional group, and L b is a divalent connector, and n b is 0 or 1, and R b is an alkyl group, and Z b is an oxygen atom or a divalent aliphatic hydrocarbon group.

[0092] Among the above formulas, X b represents a functional group. The functional group is as described above.

[0093] Among the above formulas, L brepresents a divalent linker. Examples of divalent linkers include, for instance, alkylene groups such as methylene, propylene, and hexylene groups; alkyleneoxyalkylene groups such as methyleneoxymethylene, propyleneoxymethylene, and octyleneoxymethylene groups; etc. L b The number of carbon atoms can be, for example, 1 or more, 2 or more, L b The number of carbon atoms in L can be, for example, 10 or less, 8 or less, or 6 or less. b The number of carbon atoms of may be, for example, 1 or more and 10 or less, 1 or more and 8 or less, or 2 or more and 6 or less. b An alkylene group is preferred.

[0094] Among the above formulas, n b is 0 or 1.

[0095] Among the above formulas, R b represents an alkyl group. R b The number of carbon atoms is, for example, 1–10, 1–5, 1–2, or 1. R b Examples of such groups include methyl, ethyl, propyl, isopropyl, and butyl groups. R b can be, for example, a methyl group and an ethyl group. R b It can be, for example, a methyl group.

[0096] Among the above formulas, Z b represents an oxygen atom or a divalent aliphatic hydrocarbon group. The divalent aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The divalent aliphatic hydrocarbon group may be, for example, a saturated aliphatic hydrocarbon group. The number of carbon atoms in the divalent aliphatic hydrocarbon group may be, for example, 1 or more, 2 or more, or 3 or more. The number of carbon atoms in the divalent aliphatic hydrocarbon group may be, for example, 6 or fewer, 5 or fewer, or 4 or fewer. The divalent aliphatic hydrocarbon group may be an alkylene group, for example, a methylene group, an ethylene group, a propylene group, etc. Z bIt can be, for example, an oxygen atom.

[0097] The number of repeating units per molecule of the organosiloxane oligomer may be, for example, 3 or more, or 4 or more. The number of repeating units per molecule of the organosiloxane oligomer may be, for example, 20 or less, or 10 or less. The number of repeating units per molecule of the organosiloxane oligomer may be, for example, 3 or more and 20 or less, or 4 or more and 10 or less.

[0098] The weight-average molecular weight of the organosiloxane oligomer may be, for example, 500 daltons or more and 30,000 daltons or less, 600 daltons or more and 20,000 daltons or less, 700 daltons or more and 20,000 daltons or less, or 800 daltons or more and 10,000 daltons or less. The weight-average molecular weight of the organosiloxane oligomer can be measured, for example, by gel permeation chromatography (GPC) on a polystyrene standard sample.

[0099] (b) Commercially available products can be used for the ingredients. Examples of commercially available products include, for instance, "KR-513 (organosiloxane oligomer containing a methoxy group as an alkoxy group and an acrylyl group as a functional group), "KR-516 (organosiloxane oligomer containing a methoxy group as an alkoxy group and an epoxy group as a functional group), "KR-517 (organosiloxane oligomer containing methoxy and ethoxy groups as alkoxy groups and an epoxy group as a functional group), "X-24-9590 (organosiloxane oligomer containing a methoxy group as an alkoxy group and an epoxy group as a functional group), "X-40-9296 (organosiloxane oligomer containing a methoxy group as an alkoxy group and a methacryloyl group as a functional group), "KR-511 (organosiloxane oligomer containing a methoxy group as an alkoxy group and a vinyl group as a functional group)," and "KR-518 (containing a methoxy and ethoxy groups as alkoxy groups and a thiol group as a functional group) Organosiloxane oligomer), "KR-519" (organosiloxane oligomer containing a methoxy group as an alkoxy group and a thiol group as a functional group), "X-40-9318" (organosiloxane oligomer containing a methoxy group as an alkoxy group and an isocyanate group as a functional group), "X-12-981S" (organosiloxane oligomer containing an ethoxy group as an alkoxy group and an epoxy group as a functional group), "X-12-984S" (organosiloxane oligomer containing an ethoxy group as an alkoxy group and an epoxy group as a functional group), "X-12-1048" (organosiloxane oligomer containing a methoxy group as an alkoxy group and an acrylyl group as a functional group), "X-12-1050" (organosiloxane oligomer containing a methoxy group as an alkoxy group and an acrylyl group as a functional group), "X-12-1159L" (methoxy group as an alkoxy group, Examples include organosiloxane oligomers containing an acrylyl group as a functional group (Shin-Etsu Chemical Co., Ltd.). (b) The component may be used as a single type or in combination of two or more types.

[0100] The content of component (b) in the adhesive composition may be, for example, 0.5 mass% or more, 1 mass% or more, 1.5 mass% or more, or 2.5 mass% or more with respect to the total mass of the adhesive composition. The content of component (b) in the adhesive composition may be, for example, 40 mass% or less, 35 mass% or less, 30 mass% or less, or 25 mass% or less with respect to the total mass of the adhesive composition. The content of component (b) in the adhesive composition may be, for example, 0.5 mass% or more and 40 mass% or less, 1 mass% or more and 35 mass% or less, 1.5 mass% or more and 30 mass% or less, or 2.5 mass% or more and 25 mass% or less with respect to the total mass of the adhesive composition. When the content of component (b) is within the above range, the effects of the present invention may be further exhibited. In addition, if the adhesive composition contains two or more (b) components, the content of the (b) components represents the total amount.

[0101] ((c) component)

[0102] The adhesive composition according to the present invention may further include (c) a monofunctional epoxy compound having two or more aromatic hydrocarbon groups in one molecule (hereinafter also simply referred to as "component (c)") in addition to components (a) and (b).

[0103] (c) Since the component has a bulky structure, it can further suppress curing shrinkage during curing, thereby further reducing internal stress and further improving durability (peel resistance).

[0104] (c) Examples of components include 2-phenylphenolglycidyl ether, 4-phenylphenolglycidyl ether, monostyrene phenolglycidyl ether, 4-cyano-4-hydroxybiphenylglycidyl ether, 4,4'-biphenol monoglycidyl ether, bisphenol A monoglycidyl ether, bisphenol F monoglycidyl ether, etc. (c) Components may be used alone or in combination of two or more types.

[0105] (c) Commercially available products may be used for the ingredients. Examples of commercially available products include OPP-G (manufactured by Sanko Co., Ltd.), Denacol (registered trademark, hereinafter the same), EX-142-IM (manufactured by Nagase Chemtex Co., Ltd.), etc.

[0106] The content of component (c) in the adhesive composition may be, for example, 0.5 mass% or more, 1 mass% or more, 1.5 mass% or more, or 2 mass% or more with respect to the total mass of the adhesive composition. The content of component (c) in the adhesive composition may be, for example, 30 mass% or less, 25 mass% or less, 20 mass% or less, or 18 mass% or less with respect to the total mass of the adhesive composition. The content of component (c) in the adhesive composition may be, for example, 0.5 mass% or more and 30 mass% or less, 1 mass% or more and 25 mass% or less, 1.5 mass% or more and 20 mass% or less, or 2 mass% or more and 18 mass% or less with respect to the total mass of the adhesive composition. When the content of component (c) is within the above range, peel resistance (durability) can be improved more effectively. In addition, if the adhesive composition contains two or more (c) components, the content of the (c) components represents the total amount.

[0107] The adhesive composition according to the present invention may further include other components in addition to the above (a) to (c). Examples of such other components include, for instance, epoxy compounds other than components (a) and (c); and organosiloxanes other than component (b): photogenerators, photosensitizers, photosensitizers, polymerization promoters, ion trappers, antioxidants, light stabilizers, chain transfer agents, tackifiers, thermoplastic resins, fillers, flow modifiers, plasticizers, defoamers, antistatic agents, leveling agents, dyes, various pigments (such as carbon black), organic solvents, etc. Hereinafter, other epoxy compounds other than components (a) and (c), organosiloxanes other than component (b), and photogenerators will be described.

[0108] (Other epoxy compounds other than component (a) and component (c))

[0109] The adhesive composition according to the present invention may further include other epoxy compounds other than components (a) and (c) (hereinafter also simply referred to as "other epoxy compounds"). Specific examples of such other epoxy compounds include aliphatic epoxy compounds, alicyclic epoxy compounds other than component (a), and aromatic epoxy compounds other than component (c). Such other epoxy compounds may be used as a single type or in combination of two or more types.

[0110] Aliphatic epoxy compounds are chain-type epoxy compounds that do not contain aromatic groups or alicyclic groups. Specific examples of aliphatic epoxy compounds include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate, and copolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate with other vinyl monomers. Representative compounds include, for example, glycidyl ethers of polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, diglycidyl ether of trimethylolpropane, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, and diglycidyl ether of polypropylene glycol; polyglycidyl ethers of polyether polyols that can be obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerin; and diglycidyl esters of aliphatic long-chain dibasic acids. In addition, examples include monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of polyether alcohols that can be obtained by adding alkylene oxide to phenol, cresol, butylphenol, or the same, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, epoxidized polybutadiene, etc.

[0111] Commercially available aliphatic epoxy compounds are available. Examples of commercially available products include, for instance, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-212L, Denacol EX-214L, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931, Denacol EX-931L, Denacol EX-991L (all manufactured by Nagase Chemtex Co., Ltd.); Examples include Epolite (registered trademark, hereinafter the same), M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (all manufactured by Kyoeisha Chemical Co., Ltd.), Adecaglycirol ED-503, Adecaglycirol ED-503G, Adecaglycirol ED-506, Adecaglycirol ED-523 T, Adecaresin EP-4088 S, Adecaresin EP-4080E (all manufactured by ADEKA Co., Ltd.).

[0112] (a) Examples of alicyclic epoxy compounds other than the component include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic group; epoxy compounds having two or more epoxy groups in one molecule, at least one of which is an alicyclic epoxy group, and having an epoxy equivalent of more than 135 g / eq; and compounds in which an epoxy group is directly bonded to an alicyclic group by a single bond. More specifically, examples include hydrogenated bisphenol A diglycidyl ether, dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, 3,4-epoxycyclohexylmethylacrylate, 3,4-epoxycyclohexylmethylmethacrylate, and 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol.

[0113] Commercially available cycloaliphatic epoxy compounds are available. Examples of commercially available products include, for instance, UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200 (all manufactured by Union Carbide Co., Ltd.), Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 2000, Celoxide 3000, Cyclomer (registered trademark, hereinafter the same) A200, Cyclomer M100, Cyclomer M101, Epolid (registered trademark, hereinafter the same) GT-301, Epolid GT-302, Epolid 401, Epolid 403, ETHB, Epolid HD300, EHPE3150, EHPE3150CE (all manufactured by Daicel Co., Ltd.), Adeka Acruz KRM-2110, Adeka Acruz Examples include KRM-2199 (manufactured by ADEKA Co., Ltd.).

[0114] (c) As aromatic epoxy compounds other than the component, examples include mono / polyglycidyl etherides of phenols having one aromatic ring, such as phenol, cresol, butylphenol, or their alkylene oxide adducts, for example, diglycidyl etherides of bisphenol A, bisphenol F, or compounds to which alkylene oxide is further added, or epoxy novolak resins; polyglycidyl etherides of aromatic compounds having two or more phenolic hydroxyl groups, such as resorcinol, hydroquinone, or catechol; polyglycidyl etherides of aromatic compounds having two or more alcoholic hydroxyl groups, such as phenyldimethanol, phenyldiethanol, or phenyldibutanol; Examples include polyglycidyl esters of polybasic aromatic compounds having two or more carboxylic acids, such as phthalic acid, terephthalic acid, and trimeric acid; glycidyl esters of benzoic acid; and epoxides of styrene oxide or divinylbenzene.

[0115] Commercially available aromatic epoxy compounds may be used. Examples of commercially available products include, for instance, Denacol EX-141, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Oncoat (registered trademark, hereinafter the same) EX-1020, Oncoat EX-1030, Oncoat EX-1040, Oncoat EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, and Oncoat 1012 (all manufactured by Nagase Chemtex Co., Ltd.); Ogsol (registered trademark, hereinafter the same) PG-100, Ogsol EG-200, Ogsol EG-210, and Ogsol EG-250 (all manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (all manufactured by DIC Corporation); ESN-475V (manufactured by Nittetsu Chemical & Material Co., Ltd.); jER (registered trademark) YX8800 (manufactured by Mitsubishi Chemical Corporation); Maprup (registered trademark) G-0105SA, Maprup G-0130SP (all manufactured by Nichiyu Corporation); Epichron (registered trademark, hereinafter the same) N-665, Epichron HP-7200 (all manufactured by DIC Corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (all manufactured by Nippon Kagaku Co., Ltd.); Examples include Adecaresin (registered trademark, hereinafter the same) EP-4000, Adecaresin EP-4005, Adecaresin EP-4100, Adecaresin EP-4901 (all manufactured by ADEKA Co., Ltd.); etc.

[0116] In order to further demonstrate the effects of the present invention, the content of other epoxy compounds in the adhesive composition may be, for example, 8 mass% or more, 10 mass% or more, or 20 mass% or more with respect to the total mass of the adhesive composition. The content of other epoxy compounds in the adhesive composition may be, for example, 65 mass% or less, 60 mass% or less, or 50 mass% or less with respect to the total mass of the adhesive composition. The content of other epoxy compounds in the adhesive composition may be, for example, 8 mass% or more and 65 mass% or less, 10 mass% or more and 60 mass% or less, or 20 mass% or more and 50 mass% or less with respect to the total mass of the adhesive composition.

[0117] ((b) Organosiloxane other than the component)

[0118] The adhesive composition according to the present invention may further include a low molecular weight organosiloxane other than component (b), that is, a low molecular weight silane coupling agent (hereinafter also simply referred to as "silane coupling agent"). As such a silane coupling agent, a silane compound having at least one functional group selected from the group consisting of an alkoxysilyl group or a silanol group produced by the hydrolysis thereof, an epoxy group, a vinyl group, a (meth)acryloyl group, an amino group, a urea group, a thiol group, and an isocyanate group may preferably be used.

[0119] Specific examples of silane coupling agents include, for instance, epoxy-based silane coupling agents, vinyl-based silane coupling agents, (meth)acrylic-based silane coupling agents, amino-based silane coupling agents, uride-based silane coupling agents, thiol-based silane coupling agents, isocyanate-based silane coupling agents, etc.

[0120] Specific examples of epoxy-based silane coupling agents include, for instance, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0121] Specific examples of vinyl-based silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, etc.

[0122] Specific examples of (meth)acrylic silane coupling agents include, for instance, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, etc.

[0123] Specific examples of amino-based silane coupling agents include, for instance, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, etc.

[0124] Specific examples of ureid-based silane coupling agents include, for instance, 3-ureidpropyltriethoxysilane.

[0125] Specific examples of thiol-based silane coupling agents include, for instance, 3-(dimethoxymethylsilyl)-1-propanethiol (3-mercaptopropylmethyldimethoxysilane), 3-(trimethoxysilyl)propanethiol (3-mercaptopropyltrimethoxysilane), etc.

[0126] Specific examples of isocyanate-based silane coupling agents include, for instance, 3-isocyanatepropyltriethoxysilane.

[0127] These silane coupling agents may be used as a single type or in combination of two or more types.

[0128] Commercially available silane coupling agents may be used. Examples of commercially available silane coupling agents include KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1003, KBE-1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBE-585, KBM-802, KBM-803, and KBE-9007 (all manufactured by Shin-Etsu Chemical Co., Ltd.); Examples include Z-6043, Z-6040, Z-6519, Z-6300, Z-6030, Z-6011, Z-6094, Z-6062 (all manufactured by DuPont Toray Specialty Materials, Inc.).

[0129] The content of the silane coupling agent in the adhesive composition may be 0.25 mass% or more, 0.5 mass% or more, or 0.75 mass% or more with respect to the total mass of the adhesive composition. The content of the low molecular weight silane coupling agent in the adhesive composition may be, for example, 5.0 mass% or less, 4.0 mass% or less, or 3.0 mass% or less with respect to the total mass of the adhesive composition. The content of the low molecular weight silane coupling agent in the adhesive composition may be, for example, 0.25 mass% or more and 5.0 mass% or less, 0.5 mass% or more and 4.0 mass% or less, or 0.75 mass% or more and 3.0 mass% or less with respect to the total mass of the adhesive composition. In addition, if the adhesive composition includes two or more types of silane coupling agents, the content of the silane coupling agents represents the total amount.

[0130] (Mining agent)

[0131] The adhesive composition according to the present invention can be cured by ring-opening polymerization of the epoxy groups. The energy used for polymerization is not particularly limited, but examples include heat and active energy rays. That is, the adhesive composition may be heat-curable or active energy ray-curable. When the adhesive composition is cured by heat, the adhesive composition may contain a curing agent, a thermal acid generator, or a thermal base generator. When the adhesive composition is cured by active energy rays, the adhesive composition may contain a photopolymerization initiator, a photogenerative agent, or a thermal base generator.

[0132] The adhesive composition may be an active energy beam curing type adhesive composition in which an epoxy compound is polymerized and cured by irradiation with active energy beams, such as ultraviolet rays, visible light, X-rays, or electron beams. The adhesive composition may be a UV-curing type adhesive composition that is cured by irradiation with ultraviolet rays, for example.

[0133] If the adhesive composition is of the UV-curing type, the integrated amount of UV light during curing is, for example, 100 mJ / cm² 2 Above, 1000 mJ / cm² 2 It may be higher. The accumulated amount of ultraviolet light during curing is, for example, 10,000 mJ / cm² 2 Less than, or 8000 mJ / cm² 2 The wavelength may be less than or equal to the following. The ultraviolet light irradiated onto the adhesive composition may be, for example, UVA (wavelength 320 nm or more and 400 nm or less), UVB (wavelength 280 nm or more and 320 nm or less), or UVC (wavelength 200 nm or more and 280 nm or less).

[0134] The adhesive composition may include, for example, a photogenerator. By including a photogenerator, the epoxy compound included in the adhesive composition can be cured by cationic polymerization to form a cured product of the adhesive composition. A photogenerator is a catalyst that generates cationic species or Lewis acids upon irradiation with active energy rays to initiate the polymerization reaction of the epoxy compound. Since the photogenerator acts as a photocatalyst, it exhibits excellent storage stability and workability even when mixed with the epoxy compound. Examples of photogenerators include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; and iron-arene complexes.

[0135] As aromatic diazonium salts, for example,

[0136] Benzenediazonium hexafluoroantimonate,

[0137] Benzenediazonium hexafluorophosphate,

[0138] Benzenediazonium hexafluoroborate,

[0139] You can lift the back.

[0140] As aromatic iodine salts, for example

[0141] Diphenyliodonium tetrakis(pentafluorophenyl)borate,

[0142] Diphenyliodonium hexafluorophosphate,

[0143] Diphenyliodonium hexafluoroantimonate,

[0144] Di(4-nonylphenyl)iodonium hexafluorophosphate,

[0145] You can lift the back.

[0146] As for aromatic sulfonium salts, for example

[0147] Triphenylsulfonium hexafluorophosphate,

[0148] Triphenylsulfonium hexafluoroantimonate,

[0149] Triphenylsulfonium tetrakis(pentafluorophenyl)borate,

[0150] Diphenyl(4-(phenylthio)phenyl)sulfonium hexafluorophosphate,

[0151] 4,4'-Bis(diphenylsulfonium)diphenylsulfide bishexafluorophosphate,

[0152] 4,4'-Bis[di(β-hydroxyethoxy)phenylsulfonium]diphenylsulfide bishexafluoroantimonate,

[0153] 4,4'-Bis[di(β-hydroxyethoxy)phenylsulfonium]diphenylsulfide bishexafluorophosphate,

[0154] 7-[di(p-tolyl)sulfonium]-2-isopropylthioxantone hexafluoroantimonate,

[0155] 7-[di(p-tolyl)sulfonium]-2-isopropylthioxantone tetrakis(pentafluorophenyl)borate,

[0156] 4-phenylcarbonyl-4'-diphenylsulfonium diphenylsulfide hexafluorophosphate,

[0157] 4-(p-tert-butylphenylcarbonyl)-4'-diphenylsulfonium diphenylsulfide hexafluoroantimonate,

[0158] 4-(p-tert-butylphenylcarbonyl)-4'-di(p-tolyl)sulfonium diphenylsulfide tetrakis(pentafluorophenyl)borate

[0159] You can lift the back.

[0160] As for iron-arenae complexes, for example

[0161] silene-cyclopentadienyl iron(II) hexafluoroantimonate,

[0162] Cumene-cyclopentadienyl iron(II) hexafluorophosphate,

[0163] xylene-cyclopentadienyl iron(II) tris(trifluoromethylsulfonyl)methanide

[0164] You can lift the back.

[0165] Photogenerators can be used as a single type or in combination of two or more types. Among the above photogenerators, aromatic sulfonium salts are particularly used because they have excellent curing properties due to their ultraviolet absorption characteristics even in the wavelength range of around 300 nm.

[0166] Aromatic sulfonium salts can be synthetic or commercially available. Examples of commercially available aromatic sulfonium salts include, for instance, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638 (all manufactured by Fujifilm Wako Junkak Co., Ltd.), CPI (registered trademark, hereinafter the same)-100P, CPI-101A, CPI-200K, CPI-210S (all manufactured by San Apro Co., Ltd.), Adeka Acruze (registered trademark, hereinafter the same) SP-056, Adeka Acruze SP-066, Adeka Acruze SP-130, Adeka Acruze SP-140, Adeka Acruze SP-082, Adeka Acruze SP-103, Adeka Acruze SP-601, Adeka Acruze SP-606, Adeka Acruze SP-701, Adeka Acruze SP-150, Examples include ADEKA Acruze SP-170 (manufactured by ADEKA Co., Ltd.).

[0167] The content (solid content) of the photocatalyst in the adhesive composition may be, for example, 0.25 mass% or more, 0.5 mass% or more, or 0.75 mass% or more with respect to the total mass of the adhesive composition. The content (solid content) of the photocatalyst in the adhesive composition may be, for example, 5.0 mass% or less, 4.0 mass% or less, or 3.0 mass% or less with respect to the total mass of the adhesive composition. The content (solid content) of the low molecular weight silane coupling agent in the adhesive composition may be, for example, 0.25 mass% or more and 5.0 mass% or less, 0.5 mass% or more and 4.0 mass% or less, or 0.75 mass% or more and 3.0 mass% or less with respect to the total mass of the adhesive composition. If the adhesive composition includes two or more types of silane coupling agents, the content of the photocatalyst represents the total amount.

[0168] The method of preparing the adhesive composition is not particularly limited and can be obtained by stirring and mixing each component included in the adhesive composition. The temperature or time during mixing is not particularly limited. There are also no particular restrictions on the order of mixing, and methods such as mixing each component all at once or mixing each component sequentially may be employed.

[0169] In one embodiment of the present invention, the cured product (61) may be colored with a predetermined color. The colored cured product may be close to the color tone of the electrode part (30) in terms of visibility. For example, pigments or dyes may be mixed into the colored cured product to become a color of a color family such as black, brown, or yellow, matching the color of the electrode part (30).

[0170] Although the method of connecting the seams is not particularly limited, for example, the seams can be obtained by dropping an adhesive composition onto the cut portions (connected portions) of cut glass substrates that are butted together, and then curing the adhesive composition.

[0171] The adhesive composition according to the present invention has low viscosity and excellent adhesion or filling properties to the cut portion (connection portion). Specifically, the viscosity of the adhesive composition at 25°C may be, for example, 230 mPa·s or less, 200 mPa·s or less, 150 mPa·s or less, 100 mPa·s or less, 90 mPa·s or less, 80 mPa·s or less, 60 mPa·s or less, 50 mPa·s or less, 30 mPa·s or less, or 20 mPa·s or less. In addition, the viscosity of the adhesive composition at 25°C is, for example, 5 mPa·s or more. Specifically, such viscosity can be measured by the method described in the examples. Such viscosity can be controlled by appropriately selecting the type or content of component (a) and component (b) included in the adhesive composition.

[0172] The adhesive composition according to the present invention may not include, for example, an oxetane compound.

[0173] In a tiling-type display device (100), a molding layer (70) having a thickness of less than half that of the substrate (10) can be formed to cover a light-emitting element (20). The molding layer (70) is composed of a resin such as silicone resin or epoxy resin, and silicone resin is preferred from the perspective of heat resistance.

[0174] The method of forming a layered member to constitute at least a portion of the molding layer (70) is not particularly limited and can be formed by known methods including, for example, solution spreading method, melt spreading method, coating method, sputtering method, deposition method, ion plating method, chemical vapor deposition method (CVD method), etc.

[0175] Although not shown in FIG. 1, the tiling-type display device may have a protective layer on one or both sides of the substrate for the purpose of improving strength, such as impact resistance. The protective layer may be composed of glass or an organic resin film. For example, a resin film that can be used as an optical film may be applied as the organic resin film, and the materials may include, for example, polyester (PET) such as polyethylene terephthalate (PET), triacetylcellulose (TAC), polymethyl methacrylate (PMMA), polycarbonate (PC), etc. An adhesive layer may be provided to adhere the protective layer to the substrate (10), and the adhesive layer may include a resin selected from the group consisting of acrylic resin, urethane resin, epoxy resin, silicone resin, and combinations thereof.

[0176] Although not illustrated in FIG. 1, the tiling type display device may form a low-reflection portion on at least one of the surface of the protective layer and the surface of the core. The low-reflection portion may have a composition consisting of a film formed of a low-reflection material (e.g., a black matrix resin containing a black material) and a composition having a predetermined surface treatment to make it low-reflection (e.g., AR (Anti-Reflection) treatment, LR (Low Reflection) treatment, AG (Anti-Glare) treatment, or a combination of these treatments).

[0177] The tiling display device of the present invention having the above configuration can suppress the deterioration of seamlessness caused by external light reflection and the refraction and scattering of transmitted light in the core. Since the core (60) can be made seamless, in addition to seamlessness from the front, improvement in seamlessness from the inclined direction can also be expected. Therefore, the tiling display device of the present invention can display an appearance similar to a single glass module, and can be widely used in transparent devices ranging from small displays to large displays. Furthermore, the tiling display device of the present invention has improved flexibility and durability (peel resistance) in the core, so that breakage or peeling does not easily occur even if bending or deformation occurs during handling.

[0178] Although embodiments of the present invention have been described in detail, it is clear that this is illustrative and exemplary and is not limiting, and that the scope of the present invention should be interpreted by the appended claims.

[0179] Hereinafter, we will examine the definitions of substituents used in this specification.

[0180] As used in this specification, the term "aliphatic" refers to a structure in which carbon atoms are connected in a chain or ring form and do not have a conjugated system.

[0181] As used in this specification, the term "alicyclic" refers to a structure in which carbon atoms are connected in a ring form and do not have a conjugated system.

[0182] As used in this specification, the term "aromatic hydrocarbon ring" refers to a structure in which carbon atoms are connected in a ring form, and said ring form has a conjugated system.

[0183] As used herein, the term "alkyl" refers to a fully saturated branched or unbranched (or straight-chain or linear) hydrocarbon.

[0184] Non-limiting examples of the above "alkyl" include methyl, ethyl, i-propyl, isopropyl, i-butyl, isobutyl, sec-butyl, i-pentyl, isopentyl, neopentyl, i-hexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, i-heptyl, etc.

[0185] As used in this specification, the term "alkoxy" refers to alkyl-O-, and said alkyl is as described above. Non-limiting examples of said alkoxy include methoxy, ethoxy, propoxy, 2-propoxy, butoxy, tert-butoxy, pentyloxy, hexyloxy, cyclopropoxy, cyclohexyloxy, etc. One or more hydrogen atoms of said alkoxy groups may be substituted with the same substituents as in the case of the said alkyl groups.

[0186] As used in this specification, the term "alkylene" group refers to a bivalent aromatic hydrocarbon corresponding to an "alkyl" group.

[0187] The effects of the present invention will be explained in more detail using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples.

[0188] (Example 1: Preparation of adhesive composition 1)

[0189] A homogeneous solution was prepared by mixing 40g of TTA-22 (1,2-epoxy-4-epoxyethylcyclohexane, manufactured by Tetra, epoxy equivalent: 75g / eq.) as a component, 5g of KR-516 (epoxy group-containing oligomer, manufactured by Shin-Etsu Chemical Co., Ltd.) as a component, and 15g of Denacol EX-141 (phenylglycidyl ether, manufactured by Nagase Chemtex Co., Ltd., epoxy equivalent: 151g / eq.), 10g of Denacol EX-214L (1,4-butanediol diglycidyl ether, manufactured by Nagase Chemtex Co., Ltd., epoxy equivalent: 115g / eq.), and 5g of Denacol Ex-931 (polypropylene glycol diglycidyl ether, manufactured by Nagase Chemtex Co., Ltd., epoxy equivalent: 471g / eq.) as other components. Next, 1 g of the silane coupling agent KBM-303 (2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and 2 g of the photocatalytic agent CPI-100P (manufactured by San Apro Co., Ltd.) were mixed to produce adhesive composition 1 in solution form.

[0190] (Examples 2 to 18: Preparation of adhesive compositions 2 to 18)

[0191] Adhesive compositions 2 to 18 were prepared in the same manner as Example 1 above, except that the composition was changed to the composition shown in Table 1 below.

[0192] In addition to the above components, the details of each component shown in Table 1 below are as follows. A blank space in the composition of Table 1 below indicates that the component is not included.

[0193] -(a) component

[0194] TTA-20: (1-methyl-4-(2-methyloxirane-1-yl)-7-oxabisclo[4.1.0]heptane, manufactured by Tetra, epoxy equivalent: 90 g / eq.)

[0195] TTA-800: ((3,4,3',4'-diepoxy)bicyclohexyl, manufactured by Tetra, epoxy equivalent: 105 g / eq.)

[0196] 8010: Celoxide 8010 (Daicel Co., Ltd., Epoxy equivalent: 100g / eq.)

[0197] 2021P: Celoxide 2021P (3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, Daicel Co., Ltd., epoxy equivalent: 130g / eq.).

[0198] -(c) component

[0199] OPP-G: OPP-G (2-phenylphenolglycidyl ether, manufactured by Sanko Co., Ltd., epoxy equivalent: 227 g / eq).

[0200] - Other ingredients

[0201] EX-212L: Denacol EX-212L (1,6-Hexanediol Diglycidyl Ether, manufactured by Nagase Chemtex Co., Ltd., Epoxy Equivalent: 135g / eq.)

[0202] EX-991L: Denacol EX-991L (Epoxy compound, manufactured by Nagase Chemtex Co., Ltd., Epoxy equivalent: 450g / eq.)

[0203] EHPE3150: EHPE3150CE (1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, manufactured by Daicel Corp., epoxy equivalent: 177 g / eq.)

[0204] 2081: Celoxide 2081 (Alicyclic epoxy resin, manufactured by Daicel Co., Ltd., Epoxy equivalent: 200g / eq.)

[0205] GT401: Epolid GT401 (tetrafunctional alicyclic epoxy resin, manufactured by Daicel Co., Ltd., epoxy equivalent: 220 g / eq.).

[0206] (Comparative Examples 1 to 13: Preparation of adhesive compositions Comparatives 1 to 13)

[0207] Adhesive compositions Comparisons 1 to 13 were prepared in the same manner as Example 1 above, except that the compositions were changed to those shown in Table 2 below. In addition, blank spaces in the compositions in Table 2 below indicate that the component is not included.

[0208] [Production of Evaluation Samples]

[0209] Two types of samples (Sample A, Sample B) used for various evaluations were prepared by following the process using the adhesive compositions 1 to 18 and adhesive composition comparisons 1 to 13 obtained above.

[0210] [Sample for Refractive Index and Flexibility Testing: Preparation of Sample A]

[0211] Process 1: A 0.7mm thick polypropylene (PP) plate was cut to a size of 50mm x 50mm, and a U-shaped spacer was produced by cutting the center to a size of 45mm x 40mm.

[0212] Process 2: Two sheets of Eagle XG measuring 50mm x 50mm x 0.5mm were prepared, and a non-adhesive sheet was bonded to one side of each of the two Eagle XG sheets using a transparent adhesive (hereinafter referred to as XG with a non-adhesive layer).

[0213] Process 3: In order to form a layer configuration of "XG with non-adhesive layer - spacer of Process 1 - XG with non-adhesive layer," one XG with a non-adhesive layer was offset by a few mm so that the non-adhesive layer surfaces faced each other, creating a gap, and the ends were secured with clips.

[0214] Process 4: The gap created in Process 3 was filled with an adhesive composition.

[0215] Process 5: The adhesive composition was cured by irradiating ultraviolet light using a black light (black light blue fluorescent lamp, manufactured by Sankyo Electric Co., Ltd.). The accumulated light intensity at this time was 6,000 mJ / cm². 2 (The illuminance meter used was the main body UVPF-A1 and the light receiving unit PD-365 (both manufactured by iGraphics Co., Ltd.)). After irradiation, it was stored at room temperature (25 ℃) for at least one night.

[0216] Process 6: XG with an unadhesive layer was peeled off to extract a cured layer of the adhesive composition with a thickness of 0.7 mm. An appropriate amount was cut from this cured layer and used as Sample A.

[0217] [Sample for Heat Resistance Test: Preparation of Sample B]

[0218] Process 1: A 0.7mm thick polypropylene (PP) plate was cut to a size of 50mm x 50mm, and a U-shaped spacer was produced by cutting the center to a size of 45mm x 40mm.

[0219] Process 2: Two sheets of Eagle XG measuring 50mm x 50mm x 0.5mm were prepared. One set of Eagle XG was offset by a few millimeters to create a gap so that the layers formed "Eagle XG - Spacer of Process 1 - Eagle XG," and the ends were secured with clips.

[0220] Process 3: The gap created in Process 2 was filled with an adhesive composition.

[0221] Process 4: The adhesive composition was cured by irradiating ultraviolet light using a black light (black light blue fluorescent lamp, manufactured by Sankyo Electric Co., Ltd.). The accumulated light intensity at this time was 6,000 mJ / cm². 2 (The illuminance meter used was the main body UVPF-A1 and the light receiving unit PD-365 (both manufactured by iGraphics Co., Ltd.)). Sample B was obtained by storing at room temperature (25 ℃) for at least one night after irradiation.

[0222] [Evaluation: Color (YI value)]

[0223] For the sample of evaluation configuration A obtained above, the YI value was measured using a spectrophotometer (CM-5, manufactured by Konica Minolta Corporation).

[0224] [Evaluation: Measurement of Refractive Index Difference (ΔRI)]

[0225] Sample A obtained above was measured at 25°C using an Abbe refractive index meter (DR-M2: manufactured by Atago Corporation) to determine the refractive index (nf) at a wavelength of 486 nm, the refractive index (nd) at a wavelength of 589 nm, and the refractive index (nc) at a wavelength of 656 nm, respectively. For the measured refractive indices, the difference in refractive index for each wavelength of Eagle XG used as a glass substrate (refractive index of the cured material - refractive index of the glass substrate, Δnf, Δnd, Δnc) was calculated, and the average value of the difference in refractive index (ΔRI) was further calculated from the obtained difference in refractive index.

[0226] [Evaluation: Vocal Quality]

[0227] An evaluation sample measuring 5mm x 40mm was cut from the cured layer obtained from the production of Sample A, and the flexibility or fracture state of the cured material was observed by bending it along a 40mm edge. It was evaluated as "present" if it could be bent to the point where the 5mm short edges came into contact, "brittle even if present" if the short edges could come into contact but cracked over time, and "no" if splitting or breakage of the cured material occurred.

[0228] [Evaluation: Viscosity Measurement]

[0229] Using Type E clay-based TVE-25L (manufactured by Toki Industry Co., Ltd.), measurements were taken at 25°C by appropriately adjusting the measurement mode and the rotation speed of the cone plate to achieve an appropriate range for viscosity measurement.

[0230] [Evaluation: Heat Resistance (Peeling Resistance)]

[0231] Sample B obtained above was stored in an 85°C constant temperature bath for 500 hours, and the peeling state of the cured material of Sample B after storage was observed and evaluated according to the following evaluation criteria:

[0232] ○ Same condition before and after storage

[0233] ○△: 1mm at the contact point between the cured material and the spacer, or at the interface between the cured material and Eagle XG. 2 Less than peeling

[0234] △: 1mm at the contact point between the cured material and the spacer, or at the interface between the cured material and Eagle XG. 2 More than 10mm 2 Less than peeling

[0235] ×: 10mm at the contact point between the cured material and the spacer or at the interface between the cured material and Eagle XG 2 Occurrence of peeling above.

[0236] The above evaluation results are shown in Table 1 and Table 2 below.

[0237] [Table 1-1]

[0238]

[0239] [Table 1-2]

[0240]

[0241] [Table 2-1]

[0242]

[0243] [Table 2-2]

[0244]

[0245] [result]

[0246] As can be seen from Tables 1 and 2 above, the cured products of Examples 1 to 18 obtained using adhesive compositions 1 to 18 have flexibility, and the peel resistance after the heat resistance test was also good. The difference in refractive index (ΔRI) between the cured product and the substrate in the visible light region is in the range of -0.01 ≤ ΔRI ≤ 0.01, and the YI value is also low, so the core is barely visible or faintly visible, indicating that seamlessness of the core has been achieved. The viscosity of adhesive compositions 1 to 18 at 25 is 230 mPa·s or less, and it was found that the adhesion and filling properties at the cut portion (connection portion) are excellent.

[0247] Meanwhile, the cured products of Comparative Examples 1 to 13 obtained using adhesive compositions Comparatives 1 to 13 showed peeling after the heat resistance test, resulting in inferior peel resistance. The cured products of Comparative Examples 1, 3 to 4, and 6 to 9 showed high YI values, resulting in inferior seamlessness. The cured product of Comparative Example 10 had a refractive index difference (ΔRI) with the substrate of 0.046, and in the sensory test of visibility, the core was clearly visible, indicating that seamlessness was not achieved. The cured products of Comparative Examples 7 and 13 lacked flexibility, resulting in inferior flexibility. The viscosity of adhesive compositions Comparatives 7 and 13 at 25°C exceeded 230 mPa·s, indicating inferior adhesion and filling properties at the cut portion (connection portion).

[0248] According to the present invention, by including a cured product of an adhesive composition comprising (a) an epoxy compound having two or more epoxy groups in one molecule, at least one of the epoxy groups being a cycloaliphatic epoxy group and having an epoxy equivalent of 135 g / eq or less, and (b) an organosiloxane oligomer, seamlessness in the core can be improved, and at the same time, flexibility and durability (peel resistance) of the core can be improved.

[0249] [Explanation of the symbol]

[0250] 10 substrate 20 light-emitting element

[0251] 30 Electrode section 40 Driving circuit

[0252] 50 flexible substrate 60 core

[0253] 61 Cured product of the adhesive composition 70 Molding layer

[0254] 100 tiling display units 110 modules

Claims

1. A module comprising a substrate, a light-emitting element mounted on the substrate, and an electrode portion for applying voltage to the light-emitting element, and A tiling-type display device comprising a seam between adjacent modules containing a cured product of an adhesive composition including the following (a) and (b): (a) an epoxy compound having two or more epoxy groups in one molecule, at least one of the epoxy groups being a dicycloaliphatic epoxy group, and having an epoxy equivalent of 135 g / eq or less; and (b) Organosiloxane oligomer.

2. In Paragraph 1, A tiling type display device, wherein the adhesive composition further comprises (c) a monofunctional epoxy compound having two or more aromatic hydrocarbon groups in one molecule.

3. In Paragraph 1, A tiling type display device in which the difference (ΔRI) between the refractive index of the substrate and the refractive index of the cured material in the visible light region is -0.01 ≤ ΔRI ≤ 0.

01.

4. In Paragraph 1, A tiling-type display device having a yellowness (YI value) of the above-mentioned cured product of 3.0 or less.

5. In Paragraph 1, A tiling-type display device in which the content of the above (a) component in the above adhesive composition is 10 mass% or more and 85 mass% or less with respect to the total mass of the above adhesive composition.

6. In Paragraph 1, A tiling type display device having an epoxy equivalent of the above (a) component of 75 to 130 g / eq.

7. In Paragraph 1, The above (a) component is 1,2-epoxy-4-epoxyethylcyclohexane, 1-methyl-4-(2-methyloxirane-1-yl)-7-oxabisclo[4.1.0]heptane(limonene dioxide), (3,4,3',4'-diepoxy)bicyclohexyl, 2,3'-bi(7-oxabisclo[4.1.0]heptane), 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,3-dioxane, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, A tiling display device comprising 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexane carboxylate, 3,4-epoxy-6-methylcyclohexyl carboxylate, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexane carboxylate, ethylenebis(3,4-epoxycyclohexane carboxylate), dicyclopentadiene diepoxide, methylenebis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, 3,4:7,8-diepoxybicyclo[4.3.0]nonane or a combination thereof.

8. In Paragraph 1, A tiling-type display device in which the content of the above-mentioned component (b) in the above-mentioned adhesive composition is 0.5 mass% or more and 40 mass% or less with respect to the total mass of the above-mentioned adhesive composition.

9. In Paragraph 1, The above (b) component includes an alkoxy group and a functional group, and A tiling type display device in which the above functional group comprises an epoxy group, an acryloyl group, a methacryloyl group, a vinyl group, a thiol group, or a combination thereof.

10. In Paragraph 1, A tiling display device comprising the above (b) component, which includes a repeating unit represented by the following chemical formula 1: <Chemical Formula 1> In the above formula, X b is a functional group, and L b is a divalent connector, and n b is 0 or 1, and R b is an alkyl group having 1 to 10 carbon atoms, and Z b is an oxygen atom or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms.

11. In Paragraph 1, The above component (b) is a tiling type display device having an epoxy group.

12. In Paragraph 1, A tiling type display device in which the weight average molecular weight of the above (b) component is, for example, 500 Dalton or more and 30,000 Dalton or less.

13. In Paragraph 2, A tiling-type display device in which the content of the above (c) component is 0.5 mass% or more and 30 mass% or less with respect to the total mass of the adhesive composition.

14. In Paragraph 2, A tiling type display device wherein the above (c) component comprises 2-phenylphenolglycidyl ether, 4-phenylphenolglycidyl ether, monostyrene phenolglycidyl ether, 4-cyano-4-hydroxybiphenylglycidyl ether, 4,4'-biphenol monoglycidyl ether, bisphenol A monoglycidyl ether, bisphenol F monoglycidyl ether, or a combination thereof.

15. In Paragraph 1, The adhesive composition further comprises another epoxy compound distinct from the component (a), and A tiling type display device wherein the other epoxy compound comprises an aliphatic epoxy compound, a dicycloidal epoxy compound other than component (a), an aromatic epoxy compound other than component (c), or a combination thereof.

16. In Paragraph 15, A tiling-type display device having a silane coupling agent content of 8 mass% or more and 65 mass% or less with respect to the total mass of the adhesive composition.

17. In Paragraph 1, The adhesive composition further comprises a silane coupling agent distinct from the component (b), and A tiling type display device comprising the above silane coupling agent being an epoxy-based silane coupling agent, a vinyl-based silane coupling agent, a (meth)acrylic-based silane coupling agent, an amino-based silane coupling agent, a uride-based silane coupling agent, a thiol-based silane coupling agent, an isocyanate-based silane coupling agent, or a combination thereof.

18. In Paragraph 17, A tiling-type display device having a silane coupling agent content of 0.25 mass% or more and 5 mass% or less with respect to the total mass of the adhesive composition.

19. In Paragraph 1, A tiling-type display device having a viscosity of 230 mPa·s or less at 25 ℃ of the above adhesive composition.

20. In any one of paragraphs 1 through 19, A tiling display device that is a transparent device.

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