KR101623670B1 - Composition, display device end-face sealing agent comprising composition, and display device and method for manufacturing same - Google Patents

Abstract

A composition having a low viscosity, a high viscosity stability, and a cured product capable of preventing deterioration of the display element. (3) a microcapsule containing a secondary amine or a tertiary amine or a secondary amine or a tertiary amine which is solid at 23 DEG C; and (4) an epoxy resin which is liquid at 23 DEG C, Wherein the content of the component (4) is 50 to 300 parts by weight based on 100 parts by weight of the total of the components (1) and (3) Wherein the composition has a viscosity of 0.5 to 50 Pa · s.

Description

TECHNICAL FIELD [0001] The present invention relates to a display device, a display device, and a method for manufacturing the display device,

 TECHNICAL FIELD [0001] The present invention relates to a composition, a display device end face sealer made of the composition, a display device, and a manufacturing method thereof.

2. Description of the Related Art Recently, display devices for various electronic apparatuses include liquid crystal display type devices, organic EL type devices, and electrophoretic type devices. These display devices are generally a laminate having a display element such as a liquid crystal element and a pair of substrates sandwiching the display element. The display element has a structure in which a peripheral portion of the display element is sealed with a seal member. However, the sealing method of the seal member differs depending on the device.

For example, a liquid crystal display device can be manufactured by: 1) applying a liquid crystal sealant on a transparent substrate to form a rim for filling the liquid crystal, 2) dropping a minute liquid crystal in the rim, 3) (4) a method of curing the liquid crystal sealant (ODF method), or the like. That is, a sealing agent is disposed on one side of the substrate holding the display element, and thereafter the substrate on which the sealing agent is not disposed and the substrate on which the sealing agent is disposed are bonded through a sealing material.

As such a liquid crystal sealant, for example, a liquid crystal sealant comprising an epoxy resin having low solubility in liquid crystal and an epoxy resin curing agent has been proposed (for example, Patent Document 1).

On the other hand, a display device of an electrophoretic method or an electric flow method, such as a display device having a microcup structure (for example, Patent Document 2), has the following advantages: 1) a laminate having a display element and a pair of substrates , 2) sealing a gap (hereinafter also referred to as a cross section) between the substrates formed on the periphery of the laminate with a seal member. That is, it is known that after the display element is sandwiched between two substrates, the sealing material is infiltrated into the gap between the two substrates, and then the sealing agent is hardened.

Japanese Patent Application Laid-Open No. 2005-018022 Japanese Patent Publication No. 2004-536332

As described above, when a display device such as an electrophoresis method or an electric flow method is manufactured, a display device is manufactured by assembling a laminate sandwiched between a pair of substrates, and thereafter forming a minute gap ), And sealing is performed. Therefore, a sealant having a viscosity lower than that of the liquid crystal sealant used in a liquid crystal display device manufactured by the ODF method and capable of intruding into a minute gap is also desired.

On the other hand, a cured product of a sealant is required to have a high humidity resistance in order to prevent the display element from being damaged by external moisture or the like. Further, it is considered that it is necessary to prevent deterioration of the display element from occurring due to no occurrence of a component that deteriorates the display element from the sealant itself.

The present invention has been made in view of the above circumstances and provides a curable composition having a viscosity low enough to fill a minute gap and capable of preventing deterioration of a display element by a cured product. It is also an object of the present invention to provide a display device end seal member made of a composition, a display device using the same, and a manufacturing method thereof.

The present invention provides a composition having a viscosity low enough to fill a minute gap. (1) a liquid epoxy resin; (3) a microcapsule containing a secondary amine or a tertiary amine or a secondary amine or a tertiary amine which is solid at 23 DEG C; and (4) , The content of the filler (4) relative to the total amount of (1) liquid epoxy resin and (3) microcapsule was adjusted. It has been found that with such a composition, both the low point of the composition and the high device deterioration inhibition of the cured product of the composition can be achieved.

The first aspect of the present invention relates to the composition shown below.

 (3) a microcapsule containing a secondary amine or a tertiary amine or a secondary amine or a tertiary amine which is solid at 23 DEG C; and (4) an epoxy resin which is liquid at 23 DEG C, ≪ / RTI >

Wherein the content of the component (4) is 50 to 300 parts by weight based on 100 parts by weight of the total of the components (1) and (3), and the composition Wherein the viscosity of the composition is 0.5 to 50 Pa · s.

[2] The composition according to [1], wherein the content of the alkoxyl group per g of the composition is 5.4 × 10 ^-4 mol or less.

[3] The composition according to [2], wherein the content of the alkoxyl group per g of the composition is more than 1.3 × 10 ^-4 mol.

[4] The composition according to any one of [1] to [3], wherein the component (4) has a mass average particle diameter d50 of 0.05 to 30 μm.

[5] The composition according to [4], wherein the component (4) has a mass average particle diameter d50 of more than 1.0 μm.

[6] The composition according to any one of [1] to [5], wherein the water content is 0.9% by weight or less.

[7] The display device according to any one of [1] to [5], wherein the display element is sealed between a pair of substrates formed on a periphery of a pair of substrates sandwiching the electrophoretic display element, 6]. ≪ / RTI >

A second aspect of the present invention relates to a sealing agent described below.

[8] A display device end seal member comprising the composition according to any one of [1] to [6].

[9] The liquid crystal composition according to any one of [1] to [6], further comprising (2) an epoxy resin curing agent which is liquid at 23 ° C. selected from the group consisting of an acid anhydride and a thiol compound having two or more mercapto groups in the molecule By weight based on the total weight of the composition.

[10] A sealant comprising the composition according to any one of [1] to [6], wherein the moisture content of the composition is 0.5% by weight or less.

[11] The sealant according to any one of [1] to [6], wherein the filler comprises an inorganic filler and an organic filler.

[12] The secondary amine or tertiary amine which is solid at 23 [deg.] C is a fine particle selected from the group consisting of an imidazole compound and a modified polyamine having a melting point of 60 to 180 [deg.] C and has an average particle diameter of 0.1 to 10 [ A sealant comprising the composition according to any one of [1] to [6].

[13] The microcapsule may contain a core comprising at least one secondary amine or tertiary amine selected from the group consisting of an imidazole compound and a modified polyamine, a secondary amine or a tertiary amine, a melting point of 60 to 180 Lt; RTI ID = 0.0 > g /

The sealing agent according to any one of [1] to [6], wherein the microcapsules have an average particle diameter of 0.1 to 10 μm.

The organic filler may be at least one kind of fine particles selected from the group consisting of silicon fine particles, acrylic fine particles, styrene fine particles and polyolefin fine particles having a melting point or softening point of 60 to 120 ° C or a fine particle of carnauba wax, microcrystalline wax, Wherein the wax is one or more waxes selected from the group consisting of modified microcrystalline wax, Fischer-Tropsch wax and modified Fischer-Tropsch wax.

[15] A film having a thickness of 100 μm obtained by thermally curing the composition at 80 ° C. for 60 minutes, wherein the glass transition temperature Tg measured by a DMS at a heating rate of 5 ° C./min is from 30 to 110 ° C. [ 6]. ≪ / RTI >

[16] A film having a thickness of 100 μm obtained by thermally curing the above composition at 80 ° C. for 60 minutes, wherein the glass transition temperature Tg measured by a DMS at a heating rate of 5 ° C./min is 10 ° C. to 40 ° C. [ 6]. ≪ / RTI >

[17] The sealant according to [8], wherein the display device is a device for displaying information by an electrophoretic method.

[18] A sealing agent according to [8], wherein the display device is an electronic paper.

A third aspect of the present invention relates to a display device and a manufacturing method thereof.

[19] A sealant cured product according to [8], wherein a gap between the display element, a pair of substrates sandwiching the display element, and the pair of substrates formed on the periphery of the pair of substrates is sealed. Lt; / RTI >

[20] The pair of substrates is a glass substrate on one side and a resin sheet on the other, and the cured product has a glass transition temperature measured at a heating rate of 5 ° C / minute by DMS at a thickness of 100 μm And the Tg is 30 to 110 占 폚.

[21] A display device according to [19] or [20], wherein the gap between the pair of substrates is 20 to 500 μm.

[22] A method of manufacturing a display device, comprising the steps of: obtaining a laminate having a display element and a pair of substrates sandwiching the display element; A step of applying or dropping the sealing agent described in any one of the first and second embodiments, and a step of curing the coated or sealed display device end sealing agent in this order.

According to the present invention, there is provided a composition having a viscosity enough to fill a minute gap, and the cured product thereof can prevent deterioration of the display element. In addition, by using the composition of the present invention as a sealing agent for the end face of a display device, a display device with little deterioration of the display element can be manufactured.

1 is a schematic diagram showing an embodiment of a display device of the present invention.

1. Composition

The composition of the present invention comprises: (1) an epoxy resin which is liquid at 23 DEG C; (3) microcapsules containing a secondary amine or tertiary amine or a secondary amine or tertiary amine which is solid at 23 DEG C; 4) A resin composition comprising a filler, wherein the content of the component (4) is 50 to 300 parts by weight based on 100 parts by weight of the total of the component (1) and the component (3). The viscosity of the composition at 25 ° C and 2.5 rpm as measured by an E-type viscometer is 0.5 to 50 Pa · s.

In the composition of the first embodiment, the content of the alkoxyl group per 1 g of the composition is 5.4 x 10 < ^-4 > mol or less.

In the composition of the second embodiment, the mass average particle diameter d50 of the component (4) is 0.05 to 30 탆.

The composition of the third embodiment has a water content of 0.9 wt% or less.

(2) an epoxy resin curing agent which is liquid at 23 DEG C and is selected from the group consisting of an acid anhydride and a thiol compound having two or more mercapto groups in the molecule, (5) an epoxy resin curing agent having an alkoxyl group A compound, specifically, a silane coupling agent, and the like.

Hereinafter, the components (1) to (7) will be described. In the present specification, the numerical range defined by "~" includes the boundary value of the numerical range. For example, "10 to 100" means 10 or more and 100 or less.

(1) Liquid epoxy resin

The liquid epoxy resin is an epoxy resin which is liquid at 23 占 폚. The liquid epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule and is an epoxy resin that is liquid at room temperature (23 DEG C). Examples of the liquid epoxy resin include bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol E type, bisphenol S type, bisphenol AD type and hydrogenated bisphenol A type; Diphenylether epoxy resins; Novolak type epoxy resins such as phenol novolak type, cresol novolak type, biphenyl novolak type, bisphenol novolac type, naphthol novolak type, trisphenol novolak type and dicyclopentadien novolac type; Biphenyl-type epoxy resins; Naphthyl type epoxy resin; Triphenolalkene-type epoxy resins such as triphenol methane type, triphenol ethane type, and triphenol propane type; Alicyclic epoxy resins; Aliphatic epoxy resins; Polysulfide modified epoxy resins; Resole type epoxy resin; Glycidylamine type epoxy resins, and the like. In the resin having these structures, a resin containing an alkoxyl group as the functional group may be used.

Examples of the glycidylamine type epoxy resin include an epoxy resin having an N-glycidyl group represented by the following formula in the molecule.

The glycidylamine type epoxy resin preferably has at least two glycidyl groups in the molecule and at least one benzene nucleus. Such a compound is obtained by reacting an amino group of an aromatic amine compound with one or two epihalohydrins, and is a compound having a monoglycidylamino group or a diglycidylamino group. Specific examples of the glycidylamine type epoxy resin include N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) methyl aniline, N, N, N ' Glycidyl-4,4'-diaminodiphenylmethane, and the like.

Among these epoxy resins, bifunctional epoxy resins are preferable, and bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol E epoxy resins, bisphenol E epoxy resins, and bisphenol E epoxy resins are preferred from the viewpoints of relatively low crystallinity, good applicability, And polysulfide-modified epoxy resins are more preferable.

The weight average molecular weight (Mw) of the liquid epoxy resin is preferably 200 to 700, more preferably 300 to 500. The weight average molecular weight of the epoxy resin can be measured by gel permeation chromatography (GPC) using polystyrene as a standard.

The liquid epoxy resin may be used alone, or two or more kinds of epoxy resins different in kind or molecular weight may be used in combination.

The content of the liquid epoxy resin is preferably 5 to 50 wt%, more preferably 10 to 45 wt%, and even more preferably 10 to 30 wt% with respect to the total composition.

(2) Liquid epoxy resin curing agent

The liquid epoxy resin curing agent is a liquid curing agent at room temperature (23 캜) and does not rapidly cure the epoxy resin under ordinary storage conditions (room temperature, visible light), but is a thermosetting agent that cures the epoxy resin upon application of heat desirable. These thermosetting agents are incorporated as cross-linking agents in the resin after curing. Among them, a thermosetting agent for curing the epoxy resin at a relatively low temperature of about 80 占 폚 is preferable, and specific examples are acid anhydrides and thiol compounds having two or more mercapto groups in the molecule.

Examples of the acid anhydride include aromatic acid anhydrides such as phthalic anhydride; 2.2.1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, methylcyclohexyl phthalic anhydride, tetrahydrophthalic anhydride, Alicyclic acid anhydrides such as dicarboxylic acid anhydride; And aliphatic acid anhydrides such as succinic anhydride and the like. These may be used alone or in combination of two or more. Above all, alicyclic acid anhydride is preferable because it is a liquid having a low viscosity at room temperature.

Examples of the thiol compound having two or more mercapto groups in the molecule include an ester compound obtained by reacting a mercapto group-containing carboxylic acid with a polyhydric alcohol. Examples of the mercapto group-containing carboxylic acid include mercapto group-containing aliphatic carboxylic acids such as 2-mercaptopropionic acid, 2-mercaptoisobutyric acid and 3-mercaptoisobutyric acid.

Examples of polyhydric alcohols include aliphatic alcohols having 2 to 20 carbon atoms such as ethylene glycol, trimethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 2,3-butanediol, tetramethylene glycol and tetraethylene glycol; Diethylene glycol, glycerin, dipropylene glycol, trimethylol propane, ditrimethylol propane, pentaerythritol, dipentaerythritol, 1,3,5-tris (2-hydroxystearate, Hydroxyethyl) isocyanuric acid and the like, and preferably trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol and 1,3,5-tris (2-hydroxy Ethyl) isocyanuric acid, and the like.

A thiol compound having two or more mercapto groups in the molecule can be easily obtained as a commercial product. Examples of commercially available thiol compounds include 1,4-bis (3-mercaptobutyryloxy) butane (Carlens MT BD1, manufactured by Showa Denko K.K.), pentaerythritol tetrakis (3- (Manufactured by Showa Denko K.K.), pentaerythritol tetrakis (3-mercaptopropionate) (PEMP, manufactured by SC Organic Chemicals Co., Ltd.), trimethylol propane (3-mercaptopropionate) (DPMP, manufactured by SC Organic Chemical Co., Ltd.), dipentaerythritol hexaquis (3-mercaptopropionate) (QX-11, manufactured by Mitsubishi Chemical Corporation), tris- [(3-mercaptopropionyloxy) -ethyl] -isocyanurate (TEMPIC, manufactured by SC Organic Chemistry), bisphenol A- (2-mercaptoethylthio) -3-mercaptopropane (manufactured by Mitsui Chemicals, Inc.), tetraethylene glycol bis (3-mercaptopropionate) Manufactured by Kagaku Kogyo Co., Ltd.), thiol group-containing polyether polymer (cap (3-mercaptopropyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 3H) 5H) -thione (car lens MT NR1, manufactured by Showa Denko K.K.), and the like.

The liquid epoxy resin curing agent preferably has a number average molecular weight of 200 to 800 from the viewpoint of realizing an appropriate viscosity of the composition. When the number average molecular weight is within the range of 200 to 800, the viscosity of the composition tends to be suitable for coating property and filling property in the gap, and when the composition is used as a sealant, the shape of the seal can be stably maintained. The number average molecular weight of the liquid epoxy resin curing agent can be measured by GPC analysis or the like.

The content of the liquid epoxy resin curing agent is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, based on the entire composition. When the content of the liquid epoxy resin curing agent is within the above range, not only the viscosity of the composition can be lowered but also the cured product has appropriate flexibility.

The total content of (1) the liquid epoxy resin and (2) the liquid epoxy resin curing agent is preferably 10 to 90% by weight, more preferably 20 to 60% by weight based on the total composition. If the content is within the above range, the viscosity of the composition tends to be easy to handle when used as a sealant and the reaction between the liquid epoxy resin and the liquid epoxy resin curing agent contained in the composition hardly occurs even at room temperature, The stability is easily maintained.

(3) a microcapsule containing a secondary or tertiary amine or a secondary or tertiary amine which is solid at 23 DEG C

The microcapsules containing a secondary or tertiary amine or a secondary or tertiary amine which is solid at 23 占 폚 function as a curing agent or curing accelerator for the liquid epoxy resin. Examples of secondary or tertiary amines which are solid at 23 占 폚 include modified polyamines, imidazole compounds, polyamide amine compounds, polyamino urea compounds, organic acid hydrazide compounds and organic acid dihydrazide compounds.

The modified polyamine is a compound having a polymer structure obtained by reacting a polyamine with an epoxy resin. The polyamine in the modified polyamine is not particularly limited and includes primary, secondary and tertiary amines, preferably an imidazole compound.

Examples of the modified polyamines include Fujicure FXR-1081 manufactured by Fuji Kasei Kogyo Co., Ltd., ADEKA HARDNER EH4339S (softening point 120 to 130 DEG C) manufactured by ADEKA, ADEKA HARDNER EH4342 manufactured by ADEKA, Hardener EH4357S (softening point 73 to 83 DEG C) and the like.

Examples of imidazole compounds include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2 Phenylimidazole, 2-phenyl-4-methylimidazole, 2-aminopropylimidazole, and the like.

The polyamide amine compound is obtained by a dehydration condensation reaction between a dicarboxylic acid and a polyamine. Specific examples of the polyamide amine compound include imidazoline obtained by subjecting a dicarboxylic acid and an ethylenediamine to a dehydration condensation reaction followed by cyclization.

A polyamino urea compound is a compound obtained by thermally curing an amine and a urea. Examples of the polyamino urea compound include Fujikyure FXR-1081 (melting point 121 占 폚) and Fuji Cure FXR-1020 (melting point 124 占 폚).

Examples of the organic acid hydrazide compound include p-hydroxybenzoic acid hydrazide (PHBH, manufactured by Nippon Pharmk Co., melting point 264 ° C) and the like. Examples of the organic acid dihydrazide compound include adipic acid dihydrazide (melting point 181 캜), 1,3-bis (hydrazinocarbonyl) -5-isopropyl hydantoin (melting point 120 캜), 7 (Melting point: 160 占 폚), dodecane dianhydride dihydrazide (melting point: 190 占 폚), sebacic acid dihydrazide (melting point: 189 占 폚), and the like .

The melting point of the secondary or tertiary amine which is solid at 23 DEG C is preferably in the vicinity of the thermosetting temperature at the time of thermosetting the composition and is preferably 60 to 180 DEG C. [ If the melting point of the secondary amine or tertiary amine which is solid at 23 占 폚 is too low, the curing reaction of the liquid epoxy resin tends to occur at room temperature and the storage stability of the composition is lowered. If the melting point of a secondary amine or tertiary amine which is solid at 23 占 폚 is too high, the function as a curing agent or curing accelerator may not be obtained at the above-mentioned thermosetting temperature.

The average particle diameter of the secondary or tertiary amine which is solid at 23 占 폚 is preferably 0.1 to 10 占 퐉, for example, and preferably 0.1 to 0.5 占 퐉 in order to fill the gap between the minute substrates as described later Is more preferable.

The content of the secondary amine or tertiary amine which is solid at 23 占 폚 is preferably 2 to 20% by weight, more preferably 5 to 15% by weight based on the whole composition. If the content of the secondary amine or tertiary amine which is solid at 23 占 폚 is too small, the effect of increasing the curing rate of the epoxy resin may not be sufficiently obtained. On the other hand, if the content of the secondary amine or tertiary amine which is solid at 23 占 폚 is too large, the viscosity of the composition tends to increase.

(3) a secondary or tertiary amine which is solid at 23 占 폚 and (2) a liquid epoxy resin curing agent (component (3) / component (2)) is preferably 0.1 to 1.2. If the content ratio is too low, the liquid epoxy resin curing agent contained in the composition becomes relatively large, so that the viscosity of the liquid epoxy resin may be lowered by reacting with the liquid epoxy resin even at room temperature. On the other hand, if the content ratio is too high, the viscosity of the composition tends to increase.

The microcapsule containing the secondary or tertiary amine has a core composed of a secondary or tertiary amine and a capsule wall containing the core. The secondary or tertiary amine serving as the core is not particularly limited and may be in a liquid or solid state at 23 占 폚. Examples of the secondary or tertiary amine serving as the core include the same modified polyamines and imidazole compounds as described above. The material of the capsule wall is not particularly limited, but is preferably a polymer compound from the viewpoint of stability of the composition at the time of storage and balance of activity by heating. For example, a polymer compound obtained from a polyurethane compound, a polyurethane urea compound, a polyurea compound, a polyvinyl compound, a melamine compound, an epoxy resin, a phenol resin or the like. The melting point of the capsule wall is preferably 60 to 180 DEG C in order to make the microcapsule function as a curing agent or a curing accelerator at the thermosetting temperature of the composition. Examples of commercially available products of such microcapsules include imidazole-modified microcapsules (Novacure HX-3722, manufactured by Asahi Chemical Industry Co., Ltd.).

The average primary particle diameter of the microcapsules is preferably 0.1 to 10 mu m, more preferably 0.5 to 5 mu m, as described above. The content of the microcapsules may be adjusted so that the content of the secondary or tertiary amine in the composition is in the above-mentioned range. Such a composition comprising a secondary amine or a tertiary amine, or a microcapsule containing a secondary or tertiary amine which is solid at 23 DEG C, has low storage stability at room temperature because of low reactivity with liquid epoxy resin at room temperature high. Also, a composition comprising a secondary amine or a tertiary amine has a high curing rate.

(4) Fillers

The filler can adjust moisture resistance and linear expansion of the cured product of the composition. The filler is an inorganic filler or an organic filler, or a mixture thereof, preferably a mixture of an inorganic filler and an organic filler.

The inorganic filler is not particularly limited and examples thereof include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, Potassium, kaolin, talc, glass beads, cericite activated clay, bentonite, aluminum nitride, silicon nitride and the like, preferably silicon dioxide and talc.

The organic filler is not particularly limited, but preferably has a melting point or a softening point of 60 to 120 캜 from the viewpoint of preventing liquid leakage due to melting at a temperature near the thermosetting temperature. Examples of such an organic filler include fine particles selected from the group consisting of styrene fine particles and polyolefin fine particles such as silicon fine particles, acrylic fine particles and styrene / divinylbenzene copolymer; And waxes selected from the group consisting of carnauba wax, microcrystalline wax, modified microcrystalline wax, Fischer-Tropsch wax, and modified Fischer-Tropsch wax.

The shape of the filler is not particularly limited and may be either a regular shape such as a spherical shape, a plate shape, a needle shape, or an irregular shape. However, from the viewpoint of enhancing the filling property in a minute gap, the shape is preferably spherical.

The average primary particle diameter of the filler is preferably 0.1 to 20 占 퐉, more preferably 0.1 to 10 占 퐉, and still more preferably 0.5 to 5 占 퐉. The average primary particle diameter of the filler can be measured by the laser diffraction method described in JIS Z8825-1.

The mass average particle diameter d50 of the filler is preferably 0.05 to 30 mu m, more preferably less than 25 mu m. When the mass average particle diameter d50 of the filler is in the above range, the viscosity stability of the composition is enhanced. From the viewpoint of increasing the moisture permeability, the filler preferably has a mass average particle diameter d50 of 0.05 mu m or more, more preferably 0.1 mu m or more, more preferably 0.2 mu m or more, and more preferably 1.0 mu m or more. If the mass average particle diameter d50 is small, the viscosity of the composition becomes large, and the composition tends to be poorly filled in a small gap (cross section referred to herein). Further, it is presumed that the specific surface area of the filler becomes large, and water or the like becomes easy to permeate through the surface of the filler.

The mass average particle diameter d50 of the filler is a particle diameter expressed by a 50 mass% value on a mass curve obtained by a laser method particle size meter in accordance with JIS Z8825-1. The particle measuring apparatus can be measured using MT-3300 EX2 (laser wavelength: 780 nm) manufactured by Microtrac, a laser diffraction / scattering type particle size distribution measuring apparatus.

The average particle diameter of the filler by wet method can be measured by dispersing 0.1 g of the filler in 40 mL of ethanol and dispersing the dispersion liquid at an output of 25 W for 20 minutes by an ultrasonic homogenizer at room temperature using the above- have. Further, it can be measured using LS-230 (laser wavelength: 750 nm) manufactured by Beckman Coulter, LA-750 (laser wavelength: 632.8 nm) manufactured by Horiba Manufacturing Co.,

In terms of viscosity stability of the composition, the specific surface area of the filler is preferably not less than 0.7m ² / g and, more preferably 1.0m or more ² / g. When the filler having the same mass average particle diameter d50 and different specific surface area is compared, the filler having a large specific surface area means that the arithmetic standard deviation of the particle size distribution is larger and the particle size distribution is larger. The particle size distribution can be measured by using, for example, MT-3300 EX2 manufactured by Microtrac, a laser diffraction / scattering type particle size distribution measuring apparatus. The specific surface area can be measured by a gas adsorption method (BET method) in accordance with JIS Z8830.

True density (眞密度) of the filler, 0.5~4.0g / cm ³ is preferable, and more preferably 0.8~3.0g / cm ^3.

From the viewpoint of enhancing the filling property in a minute gap, the filler is preferably a broad dispersion rather than a single dispersion. A composition containing a filler having a high degree of dispersibility tends to have a high viscosity, so that the filling property with respect to a minute gap tends to decrease.

In order to suppress the viscosity increase of the composition due to agglomeration of the filler, the filler may be subjected to surface treatment. Specifically, since the aggregation of the filler tends to occur due to the mutual action of the fillers, it is preferable that a treatment for deactivating (non-polarizing) the filler surface is performed in order to prevent the fillers from interacting with each other.

Examples of the treatment for deactivating (non-polarizing) the surface of the filler may be a method capable of introducing a hydrophobic group into the surface of the filler, and may be a cyclic siloxane, a silane coupling agent, a titanate coupling agent, And the like.

The content of the filler is preferably 50 to 300 parts by weight, more preferably 70 to 200 parts by weight, and most preferably 75 to 200 parts by weight per 100 parts by weight of the total amount of (1) the liquid epoxy resin and (3) the secondary or tertiary amine. To 200 parts by weight. The amount is preferably 50 to 150 parts by weight, more preferably 75 to 125 parts by weight per 100 parts by weight of the total amount of (1) the liquid epoxy resin, (2) the liquid epoxy resin curing agent, and (3) the secondary or tertiary amine desirable. When the composition contains both inorganic filler and organic filler, the content of filler means the total content of inorganic filler and organic filler. As described above, the composition in which the content of the filler is adjusted maintains an appropriate viscosity, and is easy to penetrate into the narrow gap between the substrates that sandwich the display element, and the cured product of such a composition absorbs moisture Since it is difficult, reliability of moisture-proof adhesion is high.

(5) a compound having an alkoxy group

The composition of the present invention may contain a compound (5) having an alkoxyl group other than the above-mentioned components (1) to (4). (5) When a compound having an alkoxyl group is added, the substrate to be contacted when the composition of the present invention is cured, specifically, the composition of the present invention is used as a sealing device for the end face of a display device, The alkoxyl groups react and crosslink with respect to the resin subjected to polarization treatment by vapor deposition or the like, so that the adhesion strength between the cured product of the sealant and the substrate can be increased.

Examples of the compound (5) having an alkoxy group other than the components (1) to (4) include, but are not limited to, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) But are not limited to, ethyl trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-glycidoxypropyl Silane coupling agents such as triethoxysilane and 3-mercaptopropylmethyldimethoxysilane, and silane coupling agents such as 2,2-bis (4 - ((meth) acryloxypolyethoxypolypropoxy) ≪ / RTI >

As described above, it is generally considered to be preferable to add a large amount of an alkoxy group-containing compound in order to increase the bonding strength between the substrate and the cured product of the composition of the present invention. However, the content of the alkoxy group in the composition is preferably 5.4 x 10 < ^-4 > mol or less with respect to 1 g of the composition. When the content of the alkoxy group is too large, there is a fear that the alcohol generated by decomposition of the alkoxy group when the composition is cured by heating tends to deteriorate the display element. The content of the alkoxy group in the composition is preferably more than 1.3 x 10 < ^-4 > mol per 1 g of the composition.

The mechanism for deteriorating the device is not clear, but is presumed as follows. Since the compound having an alkoxy group has a high polarity, when the sealant is brought into contact with the substrate of the glass or the resin whose surface has been polarized, the alkoxy group-containing compound is localized on the substrate. Therefore, it is considered that the alcohol formed by decomposition of the alkoxyl group is entangled between the sealant and the substrate to form a hydrophilic fine gap. As a result, when a display device is made using a composition having an excessively large alkoxy group content, it is presumed that moisture and the like easily pass between the substrate and the cured product of the sealant, and the deterioration of the display element can not be suppressed efficiently.

(6) Solid epoxy resin

The composition of the present invention may further contain other curable resin within the range not impairing the effect of the present invention. Examples of other curable resins include solid epoxy resins and the like from the viewpoint of enhancing heat resistance of the composition and the like. Examples of the solid epoxy resin include a solid bisphenol A epoxy resin.

(7) Other components

The composition of the present invention may further contain additives such as a rubber agent, an ion trap agent, an ion exchanger, a leveling agent, a pigment, a dye, a plasticizer, a defoaming agent, and the like insofar as the effect of the present invention is not impaired. These additives may be used singly or in combination of plural kinds. Among them, it is preferable that the composition of the present invention further comprises a rubber agent in order to increase the impact resistance of the end face of the display device or to improve the adhesion with the substrate as described later. Examples of the rubber include silicone rubber, acrylic rubber, olefin rubber, polyester rubber, and urethane rubber.

The water content of the composition of the present invention is preferably 0.9% by weight or less, more preferably 0.5% by weight or less, more preferably 0.29% by weight or less, or 0.2% by weight or less. The water content is the weight part (% by weight) of the water contained in the composition when the total weight of the composition is 100. The composition of the present invention is preferably used as a seal member for the end face of a display device, as described later. When the moisture content in the sealant is large, moisture tends to invade from the sealant into the device sealed by the sealant, which may affect the display device. Particularly, devices displaying information by electrophoresis are susceptible to polar molecules such as water.

If the moisture content in the composition is large, the viscosity stability of the composition may be impaired. Particularly, when the composition is used as the end face sealant for a display device, the viscosity of the sealant needs to be kept low in order to uniformly penetrate the end face with the sealant. In particular, as described in 8) viscosity stability test to be described later, it is necessary to maintain a low viscosity in the case of being stored as a sealant.

When the moisture content of the composition is increased, the effect of impairing the viscosity stability is not clear. However, the composition of the present invention contains a large amount of filler and is adjusted to a low point as compared with an adhesive composition containing an ordinary epoxy resin Therefore, when the polymerizable component such as an epoxy resin contained in the composition of the present invention slightly reacts with moisture to increase the molecular weight, the fluidity of the filler is lowered, and the viscosity of the composition largely fluctuates.

The moisture content in the composition can be measured by the Karl Fischer method. In order to set the water content in the composition to the above-mentioned range, a raw material having a low water content is selected and the composition is prepared under a condition of low water content. It is also preferable to dewater each raw material before preparing the composition.

The viscosity of the composition of the present invention measured by an E-type viscometer at 25 DEG C and 2.5 rpm is preferably 0.5 to 50 Pas, and more preferably 1 to 20 Pas. When the viscosity of the composition is less than 0.5 Pa · s, it is difficult to maintain the shape of the seal pattern when the sealant is used, and liquid leakage is likely to occur. On the other hand, if the viscosity of the composition is more than 50 Pa · s, it can not be filled in a minute gap, and the sealing property tends to be lowered. The viscosity of the composition can be adjusted by the content of (1) the liquid epoxy resin, (2) the liquid epoxy resin curing agent, (4) the shape of the filler and the average primary particle diameter, as described above.

The composition of the present invention is preferably used in the form of a thixotropy which exhibits a viscosity measured at a relatively low shear rate and a viscosity ratio measured at a relatively high shear rate (low shear viscosity / high shear viscosity) it is preferable that the thixotropy index (TI value) is close to 1. The thixotropic index can be adjusted, for example, by the average primary particle diameter of the filler (4) contained in the composition or the mass average particle diameter d50 of the filler.

It is preferable that the cured product of the composition of the present invention has a heat resistance higher than a certain level in order to maintain the bonding strength with the substrate at a high temperature when the composition is used as a sealing agent of a display device. The preferable heat resistance is determined depending on the type of the substrate of the display device. For example, in a display device in which a display element is sandwiched between a glass substrate and a resin sheet having a coefficient of linear expansion close to the linear expansion coefficient of the composition, the composition of the present invention is used as a sealant for sealing the gap between a pair of substrates , The glass transition temperature (Tg) of the cured product obtained by heating and curing the composition at 80 ° C for 60 minutes is preferably 30 to 110 ° C. If the glass transition temperature of the cured product of the composition is in the above range, there is little possibility that interface peeling between each substrate and the sealant occurs, and a highly reliable display device can be obtained.

In the case where the composition of the present invention is used as a sealing agent for sealing the gap between a pair of substrates in a display device sandwiching the display element between two resin sheets or two glass substrates, (Tg) of the cured product obtained by heating and curing the composition at 80 캜 for 60 minutes is preferably 10 to 40 캜. When two resin sheets are used as a pair of substrates, the display device may be required to have flexibility. Thus, in this case, it is desirable to have seal system flexibility, and it is preferable to set the glass transition temperature of the cured product of the composition within the above range. Further, when two glass substrates are used as a pair of substrates, there is a possibility that peeling may occur at the interface between the glass substrate and the sealant due to the difference in linear expansion coefficient between the glass substrate and the sealant. Thus, by setting the glass transition temperature of the cured product within the above range, it is possible to make the interface detachment less likely to occur.

On the other hand, the resin sheet referred to herein is preferably composed of a resin having high transparency, and specifically, it is preferable that the resin sheet is made of a resin such as polyethylene terephthalate, polymethyl methacrylate, polycarbonate, cyclic polyolefin (COC), polypropylene, polystyrene, , Transparent ABS resin, transparent nylon, transparent polyimide, polyvinyl alcohol, and the like.

The glass transition temperature of the cured product is determined by measuring the glass transition temperature of a 100 탆 thick film obtained by thermally curing the composition of the present invention at 80 캜 for 60 minutes at a temperature raising rate of 5 캜 / minute by DMS .

The method for preparing the composition of the present invention is not particularly limited. For example, the composition of the present invention can be prepared by mixing the respective components described above. The means for mixing the respective components is not particularly limited and includes, for example, a twin-arm type stirrer, a roll kneader, a twin screw extruder, a ball mill kneader and a planetary stirrer. The composition of the present invention can be obtained by mixing the above-mentioned components and then filtering them with a filter to remove impurities and further performing a vacuum degassing treatment. The obtained composition of the present invention is stored in a sealed container filled with a glass bottle or a poly container. As described above, the composition preferably has a low water content. Therefore, it is preferable to store in a container having low water permeability.

The composition of the present invention is preferably used as a sealing device for end faces of various display devices, particularly for sealing a cross section in which a gap between two substrates sandwiching the display device is previously formed.

Since the composition of the present invention has a suitably low viscosity, the coating property (also referred to as penetration property or permeability) of the gap between the substrates, which sandwich the display element, is high, and the moisture resistance of the cured product is high. Therefore, a sealing agent for various display devices having a liquid crystal element, an EL element, an LED element, an electrophoretic display element, or the like; It is preferably used as a sealing agent for sealing the end face of a display device having a display element such as an electrophoresis system or an electric flow system which needs to apply a sealant to a gap between two substrates sandwiching the display element. Examples of electrophoretic display devices include electronic paper and the like.

2. Display device and its manufacturing method

The display device of the present invention has a display element such as an electrophoresis method and a pair of substrates sandwiching the display element and has a structure in which the sealing member encapsulates the gap between the substrates formed on the periphery of the pair of substrates . The seal member may be a cured product of the display device end seal of the present invention.

1 is a schematic diagram showing an embodiment of a display device of the present invention. The display device 10 has an electrophoretic display device 12 and a pair of substrates 14 and 16 for holding the display device 12. The display device 12 has a pair of substrates 14 and 16, And the gap 18 formed between the sealing member 20 and the sealing member 20 is sealed.

The display element 12 has an electrophoretic display layer 12A and transparent electrodes 12B and 12C for driving the display layer 12A.

The substrates 14 and 16 may be a glass plate, a resin sheet or the like, but it is preferable that at least a display surface of the substrates 14 and 16 is a transparent glass plate or a resin sheet. Examples of the transparent resin sheet include polyester resins such as polyethylene terephthalate; Acrylic resin; And a sheet composed of a polycarbonate resin or the like. The thickness of the substrates 14 and 16 depends on the application, but may be about 0.1 to 3 mm, preferably 0.5 to 1.5 mm.

The gaps (gaps) 18 between the substrates 14 and 16 depend on the application, but are, for example, 20 to 500 mu m, and more preferably 300 mu m or less in the case of electronic paper and the like.

The display device of the present invention can be manufactured, for example, as follows. The display device includes: 1) obtaining a laminate having a display element such as an electrophoresis method and a pair of substrates sandwiching the display element; 2) applying or dropping a sealant composed of the composition of the present invention to a gap between a pair of substrates formed on the periphery of the laminate to penetrate the gap; And 3) curing the sealant.

The means for applying or dropping the sealing agent for the end face of the display device on the periphery of the laminate is not particularly limited and may be dispenser, screen printing or the like.

The curing of the display device single-sided sealant may be either thermosetting or photo-curing, but thermosetting is preferable in view of suppressing deterioration of the display element. If the display device end seal agent is irradiated with ultraviolet light and photo-cured, the display element may be deteriorated by ultraviolet irradiation. This is because, if light is irradiated only to the sealant on the end face of the display device without light irradiation, the manufacturing efficiency is also poor.

The heat curing temperature is preferably 60 to 80 占 폚, more preferably 60 to 70 占 폚, from the viewpoint of reducing the damage to the display element. The heat curing time depends on the heat curing temperature and the amount of the sealant, but can be, for example, about 30 to 90 minutes.

As described above, in the method of manufacturing a display device of the present invention, after a laminate having a display element and a pair of substrates sandwiching the display element is assembled, the gap between the pair of substrates formed on the periphery of the laminate is sealed with a sealant . As described above, since the sealing agent of the present invention has a low viscosity appropriately despite the fact that it contains a large amount of filler, the sealing agent of the present invention can be embedded in a minute gap formed at the periphery of the pair of substrates with high precision. Further, since the sealant of the present invention has high moisture resistance, the resulting display device can maintain a high adhesive strength even under high temperature and high humidity.

Example

The components used in Examples and Comparative Examples are shown below.

(1) Liquid epoxy resin (component having a water content of 0.2 wt% or less was used)

A: bisphenol A type epoxy resin

  (JER828, epoxy equivalent 184-194 g / eq, manufactured by Mitsubishi Chemical Corporation)

B: Bisphenol F type epoxy resin

  (Epiclon 830S, epoxy equivalent 165 to 177 g / eq, manufactured by DIC)

C: Bisphenol E type epoxy resin

  (R710, epoxy equivalent: 160 to 180 g / eq, manufactured by PRINTECH CORPORATION)

D: p-Aminophenol type epoxy resin

  (ELM-100 manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent: 90 to 100 g / eq)

(2) Liquid epoxy resin curing agent (component having a water content of 100 ppm by weight or less was used)

A: A mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride

  (Rikacid MH-700, manufactured by Shin-Etsu Chemical Co., Ltd.)

B: 3-dodecene aniline anhydride

  (Rikacid DDSA, manufactured by Shin-Etsu Chemical Co., Ltd.)

C: Pentaerythritol tetrakis (3-mercaptopropionate)

D: Trimethylol propane tris (3-mercaptopropionate)

(3) Secondary amine or tertiary amine (component having a water content of 0.1% by weight or less was used)

A: Imidazole-modified microcapsule

  (Nova Cure HX-3722, manufactured by Asahi Chemical Industry Co., Ltd.)

B: Modified polyamine

  (Fuji Cure FXR-1081, melting point: 121 占 폚 manufactured by Fuji Kasei Kogyo Co., Ltd.)

C: 2-Phenylimidazole

  (Manufactured by Shikoku Chemical Co., Ltd .: 2PZ, melting point: 142 占 폚)

(4) filler (a component having a moisture content of 1% by weight or less was used)

Inorganic filler

A: Silicon dioxide

Average primary particle diameter d50: 15 mu m, specific surface area: 2.2 m < ² > / g, spherical shape)

B: Silicon dioxide

(Mass average particle diameter d50: 7 mu m, specific surface area: 1.6 m < ² > / g, spherical shape)

C: Silicon dioxide

(Crystalite 占 A-1, mass average particle diameter d50: 11 占 퐉, specific surface area: 1.1 m ² / g, spherical shape)

D: Silicon dioxide

(Mass average particle diameter d50: 25 mu m, specific surface area: 0.8 m < ² > / g, spherical shape)

E: silicon dioxide

(Mass-average particle diameter d50: 0.4 mu m, specific surface area: 6 m < ² > / g, spherical shape)

F: Silicon dioxide

(Mass average particle diameter d50: 36 mu m, specific surface area: 0.6 m < ² > / g, spherical shape)

G: Silicon dioxide

(Mass average particle diameter d50: 0.03 mu m, specific surface area: 50 m < ² > / g, spherical shape) manufactured by Nippon Aerosil Co.,

Organic filler:

A: Acrylic fine particles

  (Average primary particle diameter 0.5 mu m, mass average particle diameter d50: 0.5 mu m, spherical shape) manufactured by GANZ CHEMICAL Co., Ltd., F325G)

B: Acrylic fine particles

  (Average primary particle diameter 0.3 mu m, mass average particle diameter d50: 0.3 mu m, spherical shape) manufactured by GANZ CHEMICAL Co., Ltd., F351G)

(5) Silane coupling agent (a component having a water content of 0.1% by weight or less was used)

A: 3-glycidoxypropyltrimethoxysilane

  (KBM403, Shin-Etsu Chemical Co., Ltd., the number of alkoxy groups per molecule: 3, the molecular weight: 236.3, the alkoxyl group content (mol / g): 0.0127)

B: 2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane

  (KBM303 manufactured by Shin-Etsu Chemical Co., Ltd., the number of alkoxy groups per molecule: 3, the molecular weight: 246.4, the content of alkoxyl groups (mol / g): 0.0122)

C: 3-glycidoxypropylmethyl dimethoxysilane

  (KBM402 manufactured by Shin-Etsu Chemical Co., Ltd., the number of alkoxy groups per molecule: 2, the molecular weight: 220.3, the alkoxyl group content (mol / g): 0.0091)

D: 3-mercaptopropyltrimethoxysilane

  (KBM803 manufactured by Shin-Etsu Chemical Co., Ltd., the number of alkoxy groups per molecule: 2, the molecular weight: 196.4, the content of alkoxyl groups (mol / g): 0.0153)

(6) Others (a component having a moisture content of 0.1% by weight or less was used)

Solid epoxy resin: Bisphenol A type epoxy resin

  (JER1001, epoxy equivalents: 450 to 500 g / eq, softening point: 64 DEG C, manufactured by Mitsubishi Chemical Corporation)

(Example 1-1)

(1) 22 parts by weight of a bisphenol A epoxy resin (JER828, manufactured by Mitsubishi Chemical Corporation) as a liquid epoxy resin, (2) a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride as a liquid epoxy resin curing agent (Novacure HX-3722, manufactured by Asahi Chemical Industry Co., Ltd.) as an amine, 12 parts by weight of an imidazole-modified microcapsule (Nova Cure HX-3722, manufactured by Asahi Chemical Industry Co., 4) 45 parts by weight of silicon dioxide (Datsumori Co., Ltd.: RD-8) as an inorganic filler and 2 parts by weight of acrylic fine particles (F325G made by Gansu Kasei KK) as an organic filler were kneaded with a three-roll mill . Thereafter, the kneaded product was filtered with a filter and subjected to a vacuum degassing treatment to obtain a composition (hereinafter referred to as " sealing agent "). The preparation of the sealant was carried out under a low humidity such that the moisture content of the raw material such as liquid epoxy resin did not increase. The water content of the obtained composition was measured by Karl Fischer's method and found to be 0.1 wt%.

(Examples 1-2 to 1-44, Comparative Examples 1-1 to 1-11)

A sealant was obtained in the same manner as in Example 1 except that the composition of the composition was changed as shown in Tables 1 to 5. The alkoxy group concentration of the composition was calculated from the content of the alkoxy group-containing compound in the composition. For example, in Example 2, since 1 part by weight of the silane coupling agent A is added to 100 parts by weight of the composition, (1/100) * 0.0127 (mol / g) = 1.3 10 ^-4 (mol / do.

(Example 2-1)

(1) 22 parts by weight of a bisphenol A epoxy resin (JER828, manufactured by Mitsubishi Chemical Corporation) as a liquid epoxy resin, (2) a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride as a liquid epoxy resin curing agent (Novacure HX-3722, manufactured by Asahi Chemical Industry Co., Ltd.) as an amine, 12 parts by weight of an imidazole-modified microcapsule (Nova Cure HX-3722, manufactured by Asahi Chemical Industry Co., 4) 45 parts by weight of silicon dioxide (Datsumori Co., Ltd.: RD-8) as an inorganic filler and 2 parts by weight of acrylic fine particles (F325G made by Gansu Kasei KK) as an organic filler were kneaded with a three-roll mill . Thereafter, the kneaded product was filtered with a filter and subjected to a vacuum degassing treatment to obtain a composition (hereinafter referred to as " sealing agent "). The preparation of the sealant was carried out under a low humidity such that the moisture content of the raw material such as liquid epoxy resin did not increase. The water content of the obtained composition was measured by Karl Fischer's method and found to be 0.1 wt%.

(Examples 2-2 to 2-50, Comparative Examples 2-1 to 2-10)

A sealant was obtained in the same manner as in Example 1 except that the composition of the composition was changed as shown in Tables 6 to 11.

(Example 3-1)

(1) 22 parts by weight of a bisphenol A epoxy resin (JER828, manufactured by Mitsubishi Chemical Corporation) as a liquid epoxy resin, (2) a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride as a liquid epoxy resin curing agent (Novacure HX-3722, manufactured by Asahi Chemical Industry Co., Ltd.) as an amine, 12 parts by weight of an imidazole-modified microcapsule (Nova Cure HX-3722, manufactured by Asahi Chemical Industry Co., 4) 45 parts by weight of silicon dioxide (Datsumori Co., Ltd.: RD-8) as an inorganic filler and 2 parts by weight of acrylic fine particles (F325G made by Gansu Kasei KK) as an organic filler were kneaded with a three-roll mill . Thereafter, the kneaded product was filtered with a filter and subjected to a vacuum degassing treatment to obtain a composition (hereinafter referred to as " sealing agent "). The preparation of the sealant was carried out under a low humidity such that the moisture content of the raw material such as liquid epoxy resin did not increase. The water content of the obtained composition was measured by Karl Fischer's method and found to be 0.1 wt%.

(Examples 3-2 to 3-39, Comparative Examples 3-1 to 3-13)

A sealant was obtained in the same manner as in Example 1 except that the composition of the composition was changed as shown in Tables 12 to 15.

Examples 3-2, 3-3, 3-5, 3-6, 3-8, 3-9, 3-11, 3-12, 3-14, 3-15, 3-17, 3- 18, 3-20, 3-21, 3-23, 3-24, 3-26, 3-27, 3-29, 3-30, 3-32, 3-33, 3-35, 3-36, 3-38 and 3-39 and Comparative Examples 3-1 to 3-13, a sealant was prepared in an atmosphere of 35 DEG C and 95RH%, and when the moisture content (wt%) shown in Tables 12 to 15 was reached , And then evaluated in the manner described below.

(Example 3-40)

The column was charged with the molecular sieve 5A heated at 400 DEG C for 3 hours under reduced pressure with a vacuum pump and bisphenol A type epoxy resin (JER828 manufactured by Mitsubishi Chemical Corporation), 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride (Rikacid MH-700, manufactured by Shin-Etsu Chemical Co., Ltd.) was poured into the autoclave and dehydrated. Further, silicon dioxide (RD-8, manufactured by Tatsumori Co., Ltd.) was heated at 200 DEG C for 3 hours while being depressurized by a vacuum pump, and dehydrated. 22 parts by weight of a bisphenol A type epoxy resin (JER828, manufactured by Mitsubishi Chemical Corporation) as a liquid epoxy resin subjected to dehydration treatment, (2) 4 parts by weight of 4-methylhexahydrophthalic anhydride as a liquid epoxy resin curing agent, (Novacure HX-3722, manufactured by Asahi Chemical Industry Co., Ltd.) as an amine, and (3) 30 parts by weight of a mixture of anhydrous phthalic acid (RICACIDE MH-700, manufactured by Shin-Etsu Chemical Co., , 45 parts by weight of silicon dioxide (Datsumori: RD-8) as an inorganic filler and 4 parts by weight of acrylic fine particles (F325G manufactured by Ganutsu K.K.) as an organic filler By weight, and 3-roll mill. Thereafter, the kneaded product was filtered with a filter and subjected to a vacuum degassing treatment to obtain a composition (hereinafter referred to as " sealing agent "). The preparation of the sealant was carried out under a low humidity such that the moisture content of the raw material such as liquid epoxy resin did not increase. The water content of the obtained composition was measured by Karl Fischer's method and found to be 0.01 wt%.

The viscosity, bonding strength, cell deformation, high temperature and high humidity reliability, glass transition temperature (Tg), element deterioration test, permeation humidity resistance and viscosity stability of the sealant obtained in each of Examples and Comparative Examples were evaluated as follows.

1) Viscosity

The viscosity of the obtained sealant was measured by an E-type viscometer at 25 DEG C and 2.5 rpm.

2) Adhesive strength

To the obtained sealing agent, 1% of spherical silica having an average particle diameter of 50 탆 as a spacer was added, and mixed and defoamed. The sealant containing the spacer was drawn through a screen plate to form a circular seal pattern having a diameter of 1 mm on a 25 mm x 45 mm x 0.7 mm thick non-alkali glass.

The pair of alkali glasses were superimposed and fixed on the alkali-free glass painted with the seal pattern, and then heated at 80 占 폚 for 60 minutes to join. Two glass plates thus bonded (hereinafter referred to as " test pieces ") were stored in a thermostatic chamber at 25 ° C and a humidity of 50% for 24 hours. Thereafter, the plane tensile strength of the test piece taken out from the thermostat was measured at a tensile speed of 2 mm / min by a tensile tester (manufactured by Intesco Corporation).

3) Cell deformation test

A spherical spacer having an average particle diameter of 50 mu m was dispersed (placed) on alkali-free glass of 50 mm x 50 mm x 0.7 mm thick. A pair of 40 mm x 40 mm glass substrates were superimposed on the substrate, and then the sealant obtained was applied to the gap (50 mu m) between the substrates formed on the periphery by the dispenser. Thereafter, the sealant was heated at 80 캜 for 60 minutes and cured to prepare a cell. Whether a Newton ring occurred at the center of the obtained cell was observed to evaluate the presence or absence of deformation.

Newton ring not visible in center of cell: No deformation (○)

One Newton ring occurs in the center of the cell: with strain (△)

Two or more Newton rings occur in the center of the cell: with deformation (x)

4) High temperature and high humidity reliability test

10 mg of dried calcium carbonate fine powder was placed on a 50 mm x 50 mm x 0.7 mm thick alkali-free glass. On the substrate, a pair of 40 mm x 40 mm glass substrates were superimposed, and a sealant was applied to the gap (100 m) between the substrates formed on the periphery thereof with a dispenser. Thereafter, the sealant was heated at 80 캜 for 60 minutes and cured to prepare a cell.

The cell weighed before and after being allowed to stand when (1) the cell obtained was allowed to stand at 60 DEG C and 95% RH for 1000 hours and (2) at 85 DEG C and 85% RH for 1000 hours, respectively. The smaller the change in the cell weight before and after leaving, the higher the humidity resistance.

100% or more and 102% or less of the weight of the cell after being left untreated:

The weight of the cell after being left over is more than 102% of the weight of the cell before being left 105% or less:

The weight of the cell after being left is more than 105% of the weight of the cell before being left: X

5) Glass transition temperature (Tg)

The sealant containing the spacer prepared in 1) above was applied on a releasing paper with a thickness of 100 mu m by using an applicator. The release paper on which the coating film with the sealant was formed was held in a hot-air drying oven at 80 캜 for 60 minutes and taken out and cooled. Thereafter, the coating film was peeled from the release paper to obtain a film having a thickness of 100 mu m. The glass transition temperature (Tg) of the obtained film was measured at a heating rate of 5 占 폚 / min using a DMS-6100 manufactured by Seiko Instruments Inc.

6) Device Degradation Test

Three pieces of dryness test paper (12 mm x 40 mm) manufactured by Advantech Co. were placed on a 50 mm x 50 mm x 0.7 mm thick alkali-free glass. A pair of 45 mm x 45 mm glass substrates were superimposed on the substrate, and then a sealant was applied to the gap (gap distance: 100 m) between the substrates formed on the periphery thereof with a dispenser. Thereafter, the sealant was heated at 80 캜 for 60 minutes and cured to prepare a cell. The degree of discoloration of the test paper after left standing at 60 ° C and 80% RH for 500 hours was evaluated on the basis of a standard discoloration chart (moisture content of 1.0 to 10.0 displayed) of the test paper of the degree of drying test made by Advantech Co., Ltd.

Drying degree of the cross-sectional area of the cell after being left standing The color of the test paper corresponds to a moisture content of 1.0 to 3.0:

The dryness of the cell edge portion after being left standing The color of the test paper corresponds to a water content of 4.0 to 5.0:

Drying degree of the cell end face after leaving the test paper The color of the test paper corresponds to the moisture content 5.5 to 10.0:

7) Measurement of the amount of moisture permeation by the moisture-permeation cup method (according to JIS: Z0208)

An aluminum cup was produced by a method according to JIS: Z0208 using a 100 탆 film obtained in the item 6), and the weight was measured from the weight before and after standing for 24 hours in a high temperature and high humidity vessel at 60 캜 and 80% Respectively.

(G / m ² · 100 μm · 24 h) = [Weight of aluminum cup after leaving for 24 hours (g) - Weight of aluminum cup before leaving (g)] / Film area (m ² )

8) Viscosity stability

The viscosity measuring sealant was taken out with a plastic syringe and stored in a state in which the longitudinal axis of the syringe was vertical so that the viscosity stability of the composition of the present invention was evaluated in a state close to the storage state of the sealant on the end face of the display device . In the item 1), when the viscosity of the sealant measured at 25 ° C. and 2.5 rpm by the E-type viscometer is defined as A and the viscosity of the sealant measured after storage at 23 ° C. for 24 hours is represented by B, And calculated by a calculation formula.

Viscosity increase rate (%) = B / A x 100

The closer to 100% the increase rate of the viscosity before and after standing, the higher the viscosity stability.

Viscosity increase rate less than 120%: ○

Viscosity increase rate exceeding 120% and below 150%: △

Viscosity increase rate exceeding 150%: x

The viscosity of the sealant measured after storage at 23 DEG C for 48 hours was taken as C and the viscosity increase rate after storage for 48 hours was calculated by the following equation.

Viscosity increase rate (%) = C / A x 100

The closer to 100% the increase rate of the viscosity before and after standing, the higher the viscosity stability.

Viscosity increase rate less than 120%: ○

Viscosity increase rate exceeding 120% and below 150%: △

Viscosity increase rate exceeding 150%: x

The evaluation results of Examples 1-1 to 1-11 are shown in Table 1, the evaluation results of Examples 1-12 to 1-22 are shown in Table 2, the evaluation results of Examples 1-23 to 1-33 are shown in Table 3 , Evaluation results of Examples 1-34 to 1-44 are shown in Table 4, and evaluation results of Comparative Examples 1-1 to 1-11 are shown in Table 5, respectively. On the other hand, the numerical values of the numerical values of the egg in the compositions of Tables 1 to 5 are " parts by weight ". The "filler content ratio *" represents the ratio (parts by weight) of the component (4) (filler) to the total of 100 parts by weight of the components (1) and (3) (Parts by weight) of component (4) (filler) relative to 100 parts by weight of the total of components (1), (2) and (3).

As shown in Tables 1 to 4, all of the compositions of Examples 1-1 to 1-44 show that the viscosity is as low as 15 Pa · s or less even though the content ratio of the filler is high. Therefore, it can be seen that the compositions of Examples 1-1 to 1-44 have high reliability under high temperature and high humidity, because the gaps between the substrates can be sufficiently filled and the bonding strength is high. It is also seen that the results of the element deterioration test are good.

On the other hand, as shown in Table 5, all of the compositions of Comparative Examples 1-1, 1-3, 1-5, 1-7, 1-9, 1-10 are low in viscosity, high in bonding strength, It can be seen that the performance of the device deterioration test is poor even though the permeation humidity of water is low. Therefore, it can be seen that the alcohol generated by the decomposition of the alkoxyl group contained in the composition largely contributes to the deterioration of the device.

The reason why the result of the element deterioration test is bad despite the low transmission humidity is presumed as follows. 7), the permeability of only the cured product of the composition of the present invention is measured. In the 6) element deterioration test, the sealability between the cured product of the composition of the present invention and the substrate is also evaluated have. When the composition contains a compound having an alkoxy group, the compound having an alkoxy group is localized on the surface of the substrate having a relatively high polarity because of high polarity. Therefore, when the alkoxy group is decomposed to generate an alcohol, a path for passing water or the like is formed between the substrate and the cured product of the composition. Therefore, if the content of the alkoxy group in the composition exceeds a certain value, And the result of the element deterioration test is assumed to be poor.

Further, in Comparative Example 1-11, the content of the filler was small, so that the reliability under high temperature and high humidity was low and the sealability was considered to be lowered.

The evaluation results of Examples 2-1 to 2-11 are shown in Table 6, the evaluation results of Examples 2-12 to 2-22 are shown in Table 7, the evaluation results of Examples 2-23 to 2-33 are shown in Table 8 , Evaluation results of Examples 2-34 to 2-44 are shown in Table 9, evaluation results of Examples 2-45 to 2-50 are shown in Table 10, and evaluation results of Comparative Examples 2-1 to 2-10 are shown in Table 11 Respectively. On the other hand, the numerical values of the numerical values of the egg in the composition of Tables 6 to 11 are all " parts by weight ". The "filler content ratio *" represents the ratio (parts by weight) of the filler to the total 100 parts by weight of the components (1) and (3) (Parts by weight) based on 100 parts by weight of the total of the components (1) and (3).

As shown in Tables 6 to 10, all of the compositions of Examples 2-1 to 2-50 show that the viscosity is as low as 15 Pa · s or less even though the content ratio of the filler is high. Thus, it can be seen that the compositions of Examples 2-1 to 2-50 have high reliability under high temperature and high humidity because the gaps between the substrates can be sufficiently filled and the bonding strength is high. It is also seen that the results of the element deterioration test are good. It is also understood that the compositions of Examples 2-1 to 2-50 have a high viscosity stability required when used as a sealant.

In particular, when the examples using the inorganic filler D (mass average particle diameter d50 = 25 占 퐉) such as Examples 2-5, 2-10 and 2-13 and the example using the inorganic filler having a d50 of 25 占 퐉 or less are compared, When the mass average particle diameter of the inorganic filler is less than 25 mu m, it is understood that the viscosity stability is higher.

On the other hand, as shown in Table 11, all of the compositions of Comparative Examples 2-1 to 2-7 using inorganic filler F having a d50 of 36 mu m were found to have low viscosity stability. In Comparative Example 2-10 using the inorganic filler G, since the mass average particle diameter d50 of the filler was too small, the reliability of high temperature and high humidity was low, and the result of the device deterioration test was poor. Further, in Comparative Examples 2-8 and 2-9, since the content ratio of the filler to the total of 100 parts by weight of the components (1) and (3) was as low as 43, which was less than 50, the viscosity stability was high. However, And the evaluation of the device deterioration test is bad.

The evaluation results of Examples 3-1 to 3-13 are shown in Table 12, the evaluation results of Examples 3-14 to 3-26 are shown in Table 13, the evaluation results of Examples 3-27 to 3-40 are shown in Table 14 , And the evaluation results of Comparative Examples 3-1 to 3-13 are shown in Table 15, respectively. On the other hand, the numerical values of the numerical values of the egg in the composition of Tables 12 to 15 are all " parts by weight ". The "filler content ratio *" represents the ratio (parts by weight) of the filler to the total 100 parts by weight of the components (1) and (3) (Parts by weight) based on 100 parts by weight of the total of the components (1) and (3).

As shown in Tables 12 to 14, it can be seen that the compositions of Examples 3-1 to 3-40 all have a viscosity as low as 15 Pa · s or less even though the content ratio of the filler is high. Therefore, it can be seen that the compositions of Examples 3-1 to 3-40 have high reliability under high temperature and high humidity because the gaps between the substrates can be sufficiently filled and the bonding strength is high. It is also seen that the results of the element deterioration test are good. It is also understood that the compositions of Examples 3-1 to 3-40 have a high viscosity stability required when used as a sealant.

On the other hand, as shown in Table 15, since the compositions of Comparative Examples 3-1 to 3-13 had a high moisture content of 1%, the viscosity stability and the reliability of high temperature and high humidity of the cured product were low, .

According to the present invention, it is possible to provide a composition capable of preventing deterioration of a display element by a cured product having a viscosity low enough to be embedded even in a small gap and having high viscosity stability.

10: Display device
12: Display element
12A: Display layer
12B, 12C: transparent electrodes
14, 16: substrate
18: gap (gap)
20: Seal member

Claims (22)

(1) an epoxy resin which is liquid at 23 DEG C,
(2) an epoxy resin curing agent which is liquid at 23 DEG C and contains a thiol compound having two or more mercapto groups in the molecule,
(3) microcapsules containing a secondary amine or a tertiary amine or a secondary amine or tertiary amine which is solid at 23 DEG C,
(4) a filler having a mass average particle diameter d50 of 0.05 to 30 m
≪ / RTI >
Wherein the content of the component (4) is 50 to 300 parts by weight based on 100 parts by weight of the total of the components (1) and (3), and the composition Has a viscosity of 0.5 to 50 Pa · s,
The content of the alkoxyl group per 1 g of the composition is 5.4 x 10 < ^-4 > mol or less,
And a moisture content of 0.9 wt% or less. delete The method according to claim 1,
Wherein the content of the alkoxyl group per 1 g of the composition is more than 1.3 x 10 < ^-4 > mol. delete The method according to claim 1,
Wherein the mass average particle diameter d50 of the component (4) is greater than 1.0 占 퐉. delete The method according to any one of claims 1, 3, and 5,
And sealing the display element between the pair of substrates by penetrating the gap between the pair of substrates formed on the periphery of the pair of substrates holding the electrophoretic display element. An end seal for a display device comprising the sealant according to any one of claims 1, 3 and 5. delete The method according to claim 1,
Wherein the moisture content of the composition is 0.5 wt% or less. The method according to claim 1,
(4) The sealant comprising an inorganic filler and an organic filler. The method according to claim 1,
The secondary amine or tertiary amine which is solid at 23 DEG C is a fine particle selected from the group consisting of an imidazole compound and a modified polyamine having a melting point of 60 to 180 DEG C and has an average particle diameter of 0.1 to 10 mu m. The method according to claim 1,
The microcapsules (3)
A core comprising at least one secondary amine selected from the group consisting of an imidazole compound and a modified polyamine or a tertiary amine,
Having a capsule wall containing the above-mentioned secondary amine or tertiary amine and having a melting point of 60 to 180 DEG C,
Wherein the microcapsules have an average particle diameter of 0.1 to 10 占 퐉. 12. The method of claim 11,
The organic filler,
One or more fine particles selected from the group consisting of silicon fine particles having a melting point or softening point of 60 to 120 캜, acrylic fine particles, styrene fine particles and polyolefin fine particles, or fine particles having a melting point or softening point of 60 to 120 캜, Wherein the wax is at least one selected from the group consisting of Tropsch wax and modified Fischer-Tropsch wax. The method according to claim 1,
Wherein the glass transition temperature Tg of the film having a thickness of 100 占 퐉 obtained by heating and curing the composition at 80 占 폚 for 60 minutes at a heating rate of 5 占 폚 / min by DMS is 30 to 110 占 폚. The method according to claim 1,
Wherein the composition has a glass transition temperature Tg of 10 to 40 DEG C measured by a DMS at a heating rate of 5 DEG C / minute in a film having a thickness of 100 mu m obtained by heat curing at 80 DEG C for 60 minutes. 9. The method of claim 8,
Wherein the display device is a device for displaying information by an electrophoresis method. 9. The method of claim 8,
Wherein the display device is an electronic paper. A display element,
A pair of substrates sandwiching the display element,
The display device according to claim 8, wherein the sealing material is sealed between the pair of substrates formed on the periphery of the pair of substrates. 20. The method of claim 19,
The pair of substrates may be a glass substrate on one side and a resin sheet on the other side,
Wherein the cured product has a glass transition temperature Tg of 30 to 110 DEG C measured by a DMS at a temperature raising rate of 5 DEG C / minute at a thickness of 100 mu m. 20. The method of claim 19,
And the gap between the pair of substrates is 20 to 500 mu m. A step of obtaining a laminate having a display element and a pair of substrates sandwiching the display element;
Applying or dropping the sealant according to claim 8 to a gap between the pair of substrates formed on the periphery of the laminate,
And a step of curing the coated or unloaded display device end seal agent in this order.

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