JP2007284472A - End sealing material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an end sealing material having excellent reliability for preventing mixing of water in the interior of a medium-/a large-sized panel of a liquid crystal, an organic EL (electroluminescent) display, etc. <P>SOLUTION: The end sealing material comprises (A) a liquid epoxy resin, (B) a curing agent, (C) an inorganic filler and (D) a hygroscopic inorganic filler. (C) The inorganic filler has the surface treated with an un-reactive organosilicon compound and 0.01-0.3 μm average particle diameter. (D) The hygroscopic inorganic filler has ≥1 to <25 μm average particle diameter and ≥100 to ≤400 m<SP>2</SP>/g BET specific surface area and is contained in an amount of ≥20 to ≤65 mass% based on the whole components. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an end seal material for preventing deterioration of thin panels, particularly medium- and large-sized panels such as liquid crystals and organic EL displays due to moisture.

  In recent years, there has been a remarkable improvement in the technology of thin displays, but in particular, it has become difficult to ensure the reliability of liquid crystal and organic EL panels in response to demands for their medium and large size. Moisture, which is the cause, is a problem because it causes contamination of the liquid crystal or deterioration of the organic EL element.

On the other hand, in order to prevent the deterioration of the liquid crystal and the organic EL element, a structural sealing material (UV curing type or UV + thermosetting type) is used.
However, it has become difficult to ensure the reliability of medium and large panels as described above with only this sealing material.

  On the other hand, as an example of applying a hygroscopic inorganic material, Japanese Patent No. 2774626 (Patent Document 1) has been proposed, but it is applied as the above-mentioned sealing material and sufficiently exhibits a hygroscopic function. It's hard to say. There is also a proposal in which a hygroscopic inorganic material is added to the CCD package.

Japanese Patent No. 2746826

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a highly reliable end seal material that prevents moisture from being mixed into the inside of a medium- or large-sized panel such as a liquid crystal or an organic EL display.

As a result of intensive studies to achieve the above object, the present inventor has obtained an average particle diameter that has been surface-treated with (A) a liquid epoxy resin, (B) a curing agent, and (C) a non-reactive organosilicon compound. Containing an inorganic filler having an average particle size of 1 μm or more and less than 25 μm and a BET specific surface area of 100 m ² / g or more and 400 m ² / g or less. A liquid epoxy resin composition comprising (D) a composition comprising 20% by mass or more and 65% by mass or less of a hygroscopic inorganic filler in a medium or large panel such as a liquid crystal or an organic EL display When used as an end seal material, it was possible to prevent moisture from entering the panel, and the end seal material was found to be excellent in reliability, leading to the present invention.

Therefore, the present invention
(A) Liquid epoxy resin,
(B) a curing agent,
(C) an inorganic filler that is surface-treated with a non-reactive organosilicon compound and has an average particle size of 0.01 to 0.3 μm;
(D) Hygroscopic inorganic filler having an average particle diameter of 1 μm or more and less than 25 μm and a BET specific surface area of 100 m ² / g or more and 400 m ² / g or less: comprising 20% by mass to 65% by mass of all components Provide end seal material.

  ADVANTAGE OF THE INVENTION According to this invention, the reliable end-seal material which prevents a water | moisture content mixing in the inside of medium / large sized panels, such as a liquid crystal and an organic electroluminescent display, is obtained.

The end seal material of the present invention is
(A) Liquid epoxy resin,
(B) a curing agent,
(C) an inorganic filler that is surface-treated with a non-reactive organosilicon compound and has an average particle size of 0.01 to 0.3 μm;
(D) A liquid epoxy resin composition comprising a hygroscopic inorganic filler having an average particle diameter of 1 μm or more and less than 25 μm and a BET specific surface area of 100 m ² / g or more and 400 m ² / g or less.

[Liquid epoxy resin composition]
[(A) Liquid epoxy resin]
The liquid epoxy resin (A) used in the liquid epoxy resin composition of the present invention is a component that imparts curability to the end seal material, and has two or more epoxy groups in one molecule. The molecular structure, molecular weight, and the like are not particularly limited as long as they satisfy the condition that they are liquid at room temperature, and all known epoxy resins can be used.

  Examples of the component (A) include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins; alicyclic epoxy resins; phenol novolac type epoxy resins and novolak type epoxy resins such as cresol novolak type epoxy resins. Resin; Triphenolalkane type epoxy resin such as triphenolmethane type epoxy resin and triphenolpropane type epoxy resin; Phenol aralkyl type epoxy resin, Biphenyl aralkyl type epoxy resin, Stilbene type epoxy resin, Naphthalene type epoxy resin, Biphenyl type epoxy resin And cyclopentadiene type epoxy resin. These liquid epoxy resins can be used singly or in combination of two or more.

  Among these, bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin are particularly preferable. Furthermore, an epoxy resin represented by the following structure can also be preferably used.

  Further, the total chlorine content contained in the liquid epoxy resin of the component (A) is preferably 1,500 ppm or less, particularly 1,000 ppm or less. Moreover, it is desirable that the amount of chlorine ions extracted under conditions of 100 ° C. × 20 hours in water containing 50% by mass of a liquid epoxy resin is 10 ppm or less. If the total chlorine content and the amount of extracted chlorine ions are not more than the upper limit, the moisture resistance is good and the reliability is not impaired.

[(B) Curing agent]
The component (B) used in the liquid epoxy resin composition of the present invention is a component for curing the liquid epoxy resin as the component (A). As the component (B), two or more functional groups capable of reacting with the epoxy group in the component (A), for example, a monovalent group such as a phenolic hydroxyl group and an amino group, As long as it is a substantially divalent group such as an acid anhydride group, it may be a compound having one or more thereof, and the molecular structure, molecular weight, etc. are not particularly limited, and all known epoxy resin curing agents are used. be able to.

  Examples of the component (B) include phenol resins having at least two phenolic hydroxyl groups in one molecule. More specifically, novolak type phenol resins such as phenol novolak resin and cresol novolak resin; paraxylylene Modified novolak resins, metaxylylene modified novolak resins, orthoxylylene modified novolak resins and other xylylene modified novolak resins; bisphenol A type resins, bisphenol F type resins and other bisphenol type phenol resins; biphenyl type phenol resins, resol type phenol resins, phenol aralkyls Type resins, biphenyl aralkyl type resins and other phenol resins; triphenol methane type resins, triphenol alkane type resins such as triphenol propane type resins, and their polymers Lumpur resin; naphthalene ring-containing phenolic resins, dicyclopentadiene-modified phenolic resin and the like are both available.

  As the case where the component (B) is an amine, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis ( Aliphatic amines such as aminomethyl) cyclohexane; metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4, And aromatic amines such as 4′-diaminodiphenylmethane.

  Examples of the case where the component (B) is an acid anhydride include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, 3,4- Dimethyl-6- (2-methyl-1-propenyl) -4-cyclohexane-1,2-dicarboxylic anhydride, 1-methyl-4- (1-methylethyl) -bicyclo [2.2.2] oct- 5-ene-2,3-dicarboxylic anhydride, benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether Dianhydrides, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, etc. Or having one or two aliphatic rings or aromatic rings in the molecule and one or two acid anhydride groups (that is, —CO—O—CO— groups) having 4 to 4 carbon atoms. 25, preferably about 8 to 20 acid anhydrides are suitable.

As the component (B), carboxylic acid hydrazides such as dicyandiamide, adipic acid hydrazide, and isophthalic acid hydrazide can also be used.
The curing agent for component (B) can be used singly or in combination of two or more.

  The amount of component (B) used is an amount that can sufficiently cure the liquid epoxy resin composition used as the end seal material of the present invention to a desired degree under normal curing conditions. If the conditions such that the cured product becomes brittle due to curing, the functional group derived from the curing agent does not remain after curing and the properties such as glass transition point, sealing property or adhesion of the cured product are not impaired are particularly limited. Is not to be done. For example, the amount of a functional group such as phenolic hydroxyl group, amino group, acid anhydride group, etc. contained in the curing agent with respect to 1 mol of the epoxy group in the component (A) (in the case of a polyvalent functional group) Is converted as having a plurality of monovalent groups), but it is usually preferable to use a curing agent in an amount of about 0.8 to 1.2 mol, preferably about 0.9 to 1.1 mol.

[Curing accelerator]
In the liquid epoxy resin composition of the present invention, a curing accelerator can be used in combination with the curing agent of the component (B) as necessary. The curing accelerator is not particularly limited as long as it accelerates the curing reaction, and all known ones can be used. Examples thereof include imidazole compounds, tertiary amine compounds, and organic phosphorus compounds. Can do.

  Examples of the imidazole compound include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 1,2-diethylimidazole. 2-phenyl-4-methylimidazole, 2,4,5-triphenylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methyl Imidazole, 1-cyanoethyl-2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-allyl-4,5-diphenylimidazole, 2-phenyl-4- Methyl-5-hy B carboxymethyl and imidazole.

  Among these, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethylimidazole, 1 , 2-dimethylimidazole, 1,2-diethylimidazole, 2,4-dimethylimidazole and 2-phenyl-4-methylimidazole are preferred.

  Examples of the tertiary amine compound include amine compounds having an alkyl group or an aralkyl group as a substituent bonded to a nitrogen atom such as triethylamine, benzyldimethylamine, benzyltrimethylamine, and α-methylbenzyldimethylamine; 1,8 -Diazabicyclo [5.4.0] undecene-7 and cycloamidine compounds such as phenol salts, octylates and oleates thereof, and salts thereof with organic acids; cycloamidine compounds such as compounds represented by the following structural formula And a salt or complex salt of quaternary boron compound.

Examples of organic phosphorus compounds include tributylphosphine, triphenylphosphine, tri (methylphenyl) phosphine, tri (nonylphenyl) phosphine, tri (methoxyphenyl) phosphine, diphenyltolylphosphine, triphenylphosphine / triphenylborane. And quaternary phosphonium salts such as tetraphenylphosphonium and tetraphenylborate.
These curing accelerators can be used singly or in combination of two or more.

  In addition, when using a hardening accelerator, a hardening acceleration effect is exhibited and from a viewpoint that the storage stability of a liquid epoxy resin composition is not impaired, 100 parts by weight of the liquid epoxy resin of the component (A) On the other hand, the amount is usually 10 parts by mass or less, preferably 0.01 to 10 parts by mass, particularly 0.5 to 5 parts by mass.

[(C) Inorganic filler surface-treated with non-reactive organosilicon compound]
The inorganic filler surface-treated with the non-reactive organosilicon compound (C) used in the liquid epoxy resin composition of the present invention is uniformly dispersed in the matrix of the liquid epoxy resin composition and has thixotropy. It is a component blended for imparting. In general, the end seal material is often applied to the end surfaces of two sheets of glass, and if the sagging of the seal material after application is large, the thickness of the end seal material becomes non-uniform and it is impossible to block moisture. Therefore, by imparting thixotropy and maintaining the shape, non-uniform thickness after coating can be prevented. The non-reactive organosilicon compound means a compound that does not have a functional group involved in the curing reaction.

  In addition, the component (C) has an inorganic filler whose average particle diameter is 0.01 to 0.3 μm, preferably 0.01 to 0.2 μm, and is surface-treated with a non-reactive organosilicon compound. It must be a thing. When the average particle size of the inorganic filler is less than 0.01 μm, the viscosity of the epoxy resin composition increases, and a liquid product cannot be obtained or the liquid state cannot be maintained. On the other hand, if it exceeds 0.3 μm, the shape cannot be maintained.

  Examples of the inorganic filler having an average particle diameter of 0.01 to 0.3 μm include fumed silica such as Aerosil 130, Aerosil 200, Aerosil 300 (trade name, manufactured by Nippon Aerosil Co., Ltd.); Nipsil VN-3-LP Silica such as wet silica such as (trade name, manufactured by Nippon Silica Kogyo Co., Ltd.) is preferably used. The average particle size is as described in the following component (D).

The surface treatment is performed in order to improve dispersibility. Non-reactive organosilicon compounds used for the surface treatment include, for example, CH ₃ Si (OCH ₃ ) ₃ , (CH ₃ ) ₃ SiOCH ₃ , PhSi (OCH ₃ ) ₃ , PhSiCH ₃ (OCH ₃ ) ₂ , {(CH ₃ ) ₃ Si} ₂ NH, CH ₃ CH ₂ Si (OCH ₃ ) _{3 and the} like (wherein “Ph” means a phenyl group).

  In addition, as a surface treatment method of the inorganic filler, the inorganic filler may be previously treated with the non-reactive organosilicon compound, and when the liquid epoxy resin composition of the present invention is prepared, The surface treatment may be performed by an integral blend method in which a nonreactive organosilicon compound is added and blended, but the former method is preferred from the viewpoint of suppressing the amount of the nonreactive organosilicon compound used.

  The amount of component (C) used is usually 1 to 5% by mass, preferably 2 to 3% by mass, based on the total amount of the liquid epoxy resin composition of the present invention. If the amount used is too small, it may be difficult to impart thixotropy, and conversely if too much, the thixotropy becomes too high and it is difficult to obtain a substantially liquid epoxy resin composition. There is a risk.

[(D) Hygroscopic inorganic filler]
The hygroscopic inorganic filler of component (D) used in the liquid epoxy resin composition of the present invention is a component blended to impart hygroscopic properties of the resulting cured product. As the component (D), various conventionally known inorganic fillers may be used as long as the hygroscopic inorganic filler has an average particle size of 1 μm or more and less than 25 μm and a BET specific surface area of 100 m ² / g or more and 400 m ² / g or less. Examples thereof include fused silica, crystalline silica, alumina, boron nitride, aluminum nitride, silicon nitride, magnesia, magnesium silicate, and the like. These can be used singly or in combination of two or more.

In the present invention, the average particle diameter of the component (D) is required to be 1 μm or more and less than 25 μm, and preferably 1 to 10 μm. When the average particle size is 25 μm or more, the number of coarse particles increases. When the average particle size is less than 1 μm, the viscosity of the epoxy resin composition increases and the fluidity decreases. And when apply | coating an end seal material using a syringe etc., since it becomes inferior to dispensing property, there exists a possibility of causing trouble on operation | work.
In the present invention, the average particle size and the particle size can be measured by, for example, particle size distribution measurement by a laser light diffraction method. Moreover, an average particle diameter can be calculated | required as a median diameter.

Further, the component (D) needs to have a BET specific surface area of 100 m ² / g or more and 400 m ² / g or less, and preferably 130 m ² / g or more and 300 m ² / g or less. When the specific surface area is less than 100 m ² / g, the moisture absorption function is lowered, and water is inevitably mixed into the panel. If it exceeds 400 m ² / g, the viscosity may be increased, which may hinder work during dispensing.

  As a method for producing the component (D), for example, in the case of silica, it can be prepared by preparing spherical silica gel particles that are excellent in surface smoothness and calcined under predetermined conditions. Preparation of spherical silica gel particles having excellent properties can be obtained by various liquid phase reactions, and spherical silica gel obtained by reaction of alkali silicate and mineral acid aqueous solution is particularly preferable. 2005-54129, JP-A-2005-54130, JP-A-2005-54131, and the like.

  Moreover, a commercial item can also be used for (D) component, As a commercial item, porous silica and porous inorganic substances, such as SS-150, SS-200 (made by MRC Unitech Co., Ltd.), a silica gel, etc. are mentioned, for example. be able to.

  The amount of component (D) used is 20% by mass or more and 65% by mass or less, preferably 30 to 60% by mass, based on the total amount of the liquid epoxy resin composition of the present invention. If the amount used is too small, the moisture absorption function of the resulting cured product is greatly reduced, and moisture is mixed into the panel. On the other hand, when the amount used is too large, the viscosity becomes too high, and it becomes difficult to obtain a liquid epoxy resin composition.

[Other ingredients]
In addition to each said component, the liquid epoxy resin composition of this invention can mix | blend another component as needed. However, the obtained epoxy resin composition needs to be in a liquid state, and must not impair the effects of the present invention.

For example, silicone rubber, silicone oil, liquid polybutadiene rubber or the like may be blended in order to relieve the stress of the obtained cured product.
Further, a surface treatment agent, a silane coupling agent for improving adhesion, a pigment such as carbon black, a dye, an antioxidant, and other additives can be blended. Examples of the surface treatment agent include hexamethyldisilazane, tetraethoxysilane, and the like. The surface treatment agent hydrophobizes the surface of the inorganic filler component and exhibits an effect of improving wettability with the resin component. Moreover, as said silane coupling agent, a well-known thing can be used, For example, KBM403 (brand name, the Shin-Etsu Chemical Co., Ltd. make) etc. are mentioned.

[Preparation of liquid epoxy resin composition]
The liquid epoxy resin composition of the present invention is agitated, dissolved, mixed, dispersed, etc. while the above components are simultaneously or sequentially introduced into the apparatus and a cooling treatment in the range of 15 to 25 ° C. is performed as necessary. It can prepare by performing operation of. The apparatus used for operations such as stirring, dissolution, mixing, and dispersion is not particularly limited. For example, a laika machine equipped with a stirring and heating device, a three-roll mill, a ball mill, a planetary mixer, and the like can be used. Further, a plurality of the devices may be combined as appropriate. However, when an acid anhydride is used as a curing agent, the adhesive property of the end seal material obtained tends to be reduced when the temperature is high, so the liquid of the present invention is used at a temperature of 10 to 25 ° C. It is preferable to prepare an epoxy resin composition.

  The liquid epoxy resin composition thus obtained is a thin panel, particularly a medium / large panel such as a liquid crystal or an organic EL display (the medium / large panel means a thing of 10 cm or more × 10 cm or more). Used as an end seal material. In this sealing process, the end seal material is accommodated in a dispenser such as a syringe, and after supplying a required amount of the end seal material from the dispenser to the sealed portion, a heat curing treatment is performed. Can be rubbed. The conditions for the heat curing treatment are usually 80 to 200 ° C., particularly 100 to 150 ° C., and 1 to 2 hours.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, wt% means mass%, and the average particle diameter is a value measured by a laser diffraction scattering method (Cilas Alcatel: Cirrus Laser HR850).

The materials used in the following examples and comparative examples are as follows.
(A) Liquid epoxy resin: bisphenol A type epoxy resin (RE310, manufactured by Nippon Kayaku Co., Ltd.)
(B) Curing agent: acid anhydride (MH700, manufactured by Shin Nippon Chemical Co., Ltd.)
Curing accelerator: Microencapsulated imidazole (HX-3741, manufactured by Asahi Kasei Kogyo Co., Ltd.)
(C) Surface-treated inorganic filler: fumed silica (Aerosil 130, Nippon Aerosil Co., Ltd., average particle size: 0.15 μm) surface-treated with hexamethyldisilazane (SE31, manufactured by Shin-Etsu Chemical Co., Ltd.)
(D) Inorganic filler: as described in the following table (Incidentally, the average particle diameter of silica used in each Example and Comparative Example, BET specific surface area, its product name, and product name are also as described in the following table. Is)
(E) Others: Silane coupling agent (γ-glycidoxypropyltrimethoxysilane, KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.)

[Examples 1 to 3, Comparative Examples 1 to 7]
The said component was mix | blended with the composition and compounding quantity shown to the following Tables 1-3, and the epoxy resin composition was obtained by knead | mixing uniformly.

<Various performance evaluation>
-Viscosity The viscosity (Pa * s) in 25 degreeC of each obtained epoxy resin composition was measured using the Brookfield E-type viscosity meter. The measurement results are shown in Tables 1-3.

-Presence or absence of sagging of the composition Each epoxy resin composition obtained was drawn on a glass plate using a syringe equipped with a nozzle having an inner diameter of 2 mm, and then cured at 100 ° C / 1 hour by standing the glass plate vertically. The presence or absence of sagging of the coated product was confirmed. The results are shown in Tables 1-3.

-Hygroscopicity of hardened | cured material The prism sample was produced by hardening | curing each obtained epoxy resin composition on 150 degreeC * 2 hours conditions in the type | mold of a shape of 4 mm x 10 mm x 100 mm.
Using each sample, the moisture absorption after 24 hours was measured at 121 ° C./2 atm using PCT (Pressure Cooker TEST), and the amount of drainage after 100 ° C./3 hours was measured using the sample after moisture absorption. The measurement results are shown in Tables 1-3.

（注）＊１：液状ではない

(Note) * 1: Not liquid

（注）＊１：液状ではない

(Note) * 1: Not liquid

Claims (2)

(A) Liquid epoxy resin,
(B) a curing agent,
(C) an inorganic filler that is surface-treated with a non-reactive organosilicon compound and has an average particle size of 0.01 to 0.3 μm;
(D) Hygroscopic inorganic filler having an average particle diameter of 1 μm or more and less than 25 μm and a BET specific surface area of 100 m ² / g or more and 400 m ² / g or less: comprising 20% by mass to 65% by mass of all components End seal material.   2. The end seal material according to claim 1, which is used for sealing a medium or large panel of a liquid crystal or organic EL display.