KR20090098647A - A thermosetting resin composition for sealing - Google Patents

Abstract

A thermosetting resin composition for sealing, and a method for sealing a device by using the composition are provided to lower viscosity, to allow the coating amount to be controlled easily, to improve coating velocity, to reduce curing time and to enhance optical transmittance. A thermosetting resin composition(5) for sealing an electric or optical device comprises an epoxy resin 25-90 parts by weight; a thermosetting material 9-70 parts by weight; and a curing accelerator 0.1-5 parts by weight, wherein the composition has a viscosity of 10-3000 cps at 25 °C. The composition comprises further a coupling agent 0.001~5 parts by weight or an antioxidant 0.001~0.5 parts by weight. The epoxy resin is selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a hydrogenated bisphenol type epoxy resin, an alicyclic epoxy resin, an aromatic epoxy resin, a novolac and dicyclopentadiene type epoxy resin and their mixture.

Description

 Thermosetting resin composition for sealing {A THERMOSETTING RESIN COMPOSITION FOR SEALING}

The present invention relates to a thermosetting resin composition for sealing, and more particularly to a thermosetting resin composition for sealing of an electrical or optical element.

In general, the manufacture of electrical or optical devices such as OLEDs, LEDs, or dye-sensitized solar cells (DSSC) includes a sealing process for sealing the upper sealing member and the lower sealing member. OLED, which is one of the electric devices, can manufacture panels with a thinner thickness than existing display panels, and has excellent process ease in manufacturing panels, and due to the process suitability of the next-generation display flexible display, Be in the spotlight. In addition, OLED displays are very bright, have excellent color contrast and wide viewing angle, and have many advantages such as high brightness, light weight, and low driving voltage.

However, OLED devices are extremely weak in moisture, and the interface between the metal electrode and the organic EL layer is easily peeled off due to the influence of moisture, or the metal electrode is likely to deteriorate due to reaction with oxygen and moisture, resulting in dark spots and pixel shrinkage. This occurs and has a disadvantage that the yield is lowered.

In order to solve such a problem, a method of manufacturing a device by applying a resin composition in the form of a frame along the outside of the device and placing a getter composition on the upper surface of the device as a sealing method during device manufacturing has been invented. However, when fabricating a device by applying a resin composition to the outside of the device in the form of a frame, gas generated during the curing reaction flows into the panel and a perfect seal is not formed, resulting in dark spots, pixel shirinkage, and the like. Top emission method was not available unless getter material was developed.

In addition, OLED devices manufactured using three light emitting materials, red, green, and blue, have a lower lifespan than red and green, so that afterimages are deteriorated due to deterioration of the blue pixels as the use time of the display increases. The remaining phenomenon can be observed.

To solve this problem, three light emitting materials are formed in three layers, or three light emitting materials are dissolved in a solvent to make a device to emit white light, and a color filter is used to realize red, green, and blue colors. Invented. However, when the device is manufactured in this way, the photocurable resin composition which is used in general is applied to the composition through the color filter, so that the composition could not absorb UV and thus could not be applied.

In this respect, there is still a great need for a technique that can effectively seal various electrical or optical devices.

Therefore, the object of the present invention is that the viscosity is low, it is possible to apply the ODF (One Drop Fill) process, easy to control the coating amount, and has a process advantage that has a fast coating speed, the cost of the process is small, and the curing time is reduced It can be shortened, and it has excellent light transmittance characteristics, so it can be applied to top emission display, it blocks gas and moisture flowing into the panel when sealing, and can be applied to panels using color filters. It is possible to manufacture the device without deterioration, and it is possible to effectively protect the material that is weak against heat due to the low curing temperature, and at the same time, it is possible to realize the characteristics such as sufficient adhesive strength and prevention of coloring, and the manufacturing cost is low. It is an object to provide a composition.

The present invention to achieve the above object,

In the resin composition for sealing electric or optical elements,

a) 25-90 parts by weight of epoxy resin;

b) 9-70 parts by weight of a thermosetting agent; And

c) 0.1-5 parts by weight of curing accelerator

It includes, and provides a sealing thermosetting resin composition, characterized in that the viscosity is 10-3000 cps (at 25 ℃).

In addition, the present invention

In the method of sealing a device by bonding the lower sealing member and the upper sealing member, there is provided a sealing method of the device, characterized in that for using the sealing thermosetting resin composition.

The thermosetting resin composition for sealing according to the present invention has a low viscosity, so that the ODF (One Drop Fill) process can be applied, the coating amount can be easily controlled, and the coating speed is also high. It can shorten the time, and it has excellent light transmittance characteristics, so it can be applied to the top emission type display, it blocks gas and moisture flowing into the panel during sealing, and it can be applied to the panel that adopts color filter. It is possible to manufacture the device without deterioration of the device, and it is possible to effectively protect the material that is weak against heat due to the low curing temperature, and at the same time, it is possible to realize the characteristics such as sufficient adhesive strength and color prevention, and it is economical because of low manufacturing cost. Both the upper sealing member and the lower sealing member are elements of glass, and each of the members has a form for adhesively filling the members, or Effective for sealing optical elements.

The thermosetting resin composition for sealing of the present invention comprises a) 25-90 parts by weight of an epoxy resin; b) 9-70 parts by weight of a thermosetting agent; And c) 0.1-5 parts by weight of a curing accelerator, characterized in that the viscosity is 10-3000 cps (at 25 ℃). Preferably, it is preferable that both the upper sealing member and the lower sealing member to be sealed by the device are glass, more preferably the device is an OLED, LED or dye-sensitized solar cell.

 In addition, the sealing thermosetting resin composition of the present invention is a low viscosity resin composition in which a thermosetting agent and a curing accelerator are dispersed together with an epoxy resin, and may further include a coupling agent or an antioxidant.

Thermosetting resin composition for sealing of the present invention has a viscosity of 10-3000 cps at 25 ℃, preferably 100-2,000 cps. More preferably, by having a viscosity of 100-1,000 cps, the ODF (One Drop Fill) process is possible when applying to the sealing member of the thermosetting resin composition for sealing, so that the coating amount can be easily controlled, and the application speed is also high. The cost for the process is small and the curing time can be shortened.

The components used for the sealing thermosetting resin composition of this invention are demonstrated in detail.

a) epoxy resin

The epoxy resin applied to the sealing thermosetting resin composition of the present invention is bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol type epoxy resin, alicyclic epoxy resin, aromatic epoxy resin, novolac type, dicyclopentadiene type Epoxy resin etc. are mentioned, The compound which has these epoxy groups can be used individually or in mixture.

Moreover, it is preferable that the viscosity of the compound of the said epoxy group single or mixed type is 100-1000 cps.

b) thermosetting agents

Usually, as long as it can be used for thermosetting an epoxy resin, it can use, and it is not specifically limited. Specific examples include polyamine curing agents such as diethylenetriamine, triethylenetetramine, N-aminoethyl piperazine, diaminodiphenylmethane and dihydric acid dihydrazide; Acid anhydride curing agents such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methylnadic acid anhydride; Phenol novolak-type hardening | curing agent; Polymercaptan hardening | curing agents, such as a trioxane tristyrene mercaptan; Tertiary amine compounds such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; Imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-methylimidazole can be used. Moreover, the latent hardener of a solid dispersion type, the latent hardener encapsulated in a microcapsule, etc. can also be used.

c) curing accelerator

As the curing accelerator, quaternary ammonium salts, quaternary sulfonium salts, various metal salts, imidazoles, tertiary amines and the like can be used. Specific examples of the quaternary ammonium salts include tetramethyl ammonium bromide, tetrabutylammonium bromide, quaternary sulfonium salts such as tetra phenyl phosphonium bromide, tetrabutylphosphonium bromide, and metal salts such as octylate and tin octylate. As tertiary amines, such as 1-benzyl-2-methyl imidazole, 1-benzyl-2-phenyl imidazole, and 2-ethyl-4-methyl imidazole, benzyl dimethyl amine etc. are mentioned.

d) coupling agent

As a coupling agent, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a silicone compound, etc. are mentioned, These coupling agents can be used individually or in mixture. When the coupling agent is included, the adhesiveness of the resin composition may be improved and the viscosity may be reduced. The sealing thermosetting resin composition of the present invention may be included in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight. .

e) antioxidant

Antioxidant can be added to the thermosetting resin composition for sealing of this invention in order to prevent the oxidative deterioration at the time of thermosetting, and to improve the heat resistance stability of hardened | cured material further. As said antioxidant, a phenol type, sulfur type, phosphorus antioxidant etc. can be used. Specific examples include phenolic antioxidants such as dibutyl hydroxy toluene, 2,6-di-tetra-butyl-p-cresol (hereinafter referred to as BHT), sulfur-based antioxidants such as mercapto propionic acid derivatives, and triphenyl phosphite , Phosphorus-based antioxidants such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter, HCA), and the like, and the antioxidants may be used alone or in combination of two or more thereof. It can be used, it is preferably included in the heat curable resin composition for sealing of the present invention 0.001 to 5 parts by weight, preferably 0.01 to 0.5 parts by weight.

In another aspect, the present invention provides a sealing method of the device, characterized in that the sealing thermosetting resin composition is used in the method of sealing the device by bonding the lower sealing member and the upper sealing member, preferably of the present invention The sealing method is a method of sealing a device by bonding the lower sealing member and the upper sealing member, the one-drop filling process of one surface of the sealing member or one surface of the lower sealing member of the sealing thermosetting resin composition By applying the entire surface, and bonding the upper sealing member and the lower sealing member. Heat is applied to the bonded upper sealing member and the lower sealing member to cure the sealing thermosetting resin composition.

As a specific example, the sealing method of the OLED device according to the present invention includes a step of applying the entire surface of the upper sealing member or the cathode surface of the lower sealing member with the thermosetting resin composition, preferably using an ODF process (process glass). If necessary, the one side edge of the upper sealing member, or the anode, light emitting layer and the negative electrode laminated surface edge of the lower sealing member is preferably a photocurable resin composition or glass using a screen printing process (precision and workability glass). Can be applied with frit.

The lower sealing member is an anode, a light emitting layer and a cathode are sequentially provided on the lower substrate, preferably a hole injection layer (HIL), a hole transport layer (HTL), an electron injection layer (EIL) or an electron transport layer (ETL) is added It can be included as. The formation of the anode, the light emitting layer, the cathode, the hole injection layer (HIL), the hole transport layer (HTL), the electron injection layer (EIL) or the electron transport layer (ETL) on the lower substrate can be carried out by conventional methods.

In addition, the negative electrode surface of the upper sealing application surface and the lower seal member of the members in the above, or attached to each other an upper sealing member and the lower sealing member is a surface and the application surface of the lower seal member of the upper sealing member so as to be in contact with each other is preferably in a nitrogen atmosphere for 10 ^- It can be carried out in a vacuum atmosphere of less than ⁶ torr, more preferably 10 ^-7 torr or less.

Further, the sealing method of the device of the present invention is preferably a heat curing temperature of 75 to 120 ℃ to heat the bonded upper sealing member and the lower sealing member to cure the thermosetting resin composition for sealing. When the photocurable resin composition is applied to the edge of the sealing member, the photocuring process may be performed simultaneously or sequentially with the thermosetting. Preferably, the photocuring resin is thermally cured. The light may use light capable of curing the photocurable resin composition, and may use ultraviolet light as a specific example. In addition, when the glass frit is applied to the edge of the sealing member, a laser can be used. Through the heating, the sealing thermosetting resin composition is cured to form a cured body, and an airtight filling adhesive is bonded between the upper sealing member and the lower sealing member with the cured body.

The electrical or optical element sealed with the thermosetting resin composition for sealing according to the present invention has an excellent sealing life of the upper sealing member and the lower sealing member filled with no empty space by the cured body of the thermosetting resin composition as shown in FIG. Can exhibit characteristics.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1-6 Preparation of Thermosetting Resin Composition

A thermosetting resin composition for sealing was prepared in the composition shown in Table 1 below.

TABLE 1

Composition of thermosetting resin composition (parts by weight) Epoxy resin Thermosetting agent Curing accelerator  100MF YL983U CELLOXIDE 2021P Epikote 152 MH-700 EMI-24 K61B Example 1 9 37 0 0 53 One 0 Example 2 9 37 0 0 52 2 0 Example 3 9 37 0 0 52 0 2 Example 4 0 38 10 0 50 2 0 Example 5 0 23 23 0 52 2 0 Example 6 0 0 19 29 50 2 0

EPOLIGHT 100MF: Aliphatic Glycidyl Ether Compound (KYOEISHA)

YL983U: Bisphenol F type epoxy resin (Japan Epoxy)

CELLOXIDE 2021P: Alicyclic Epoxy Resin (DICEL Chemical Industry Co., Ltd.)

Epikote 152: cresol-novolak type epoxy resin (Japan epoxy company)

RIKACID MH-700: Liquid Alicyclic Acid Anhydride Curing Agent

EMI-24: imidazole curing accelerator (air-product)

K61B: Amine curing accelerator (Air-product)

Light transmittance, adhesive strength, viscosity, and curability of each of the thermosetting resin compositions prepared in Examples 1-6 were measured and shown in Table 2, respectively.

1. Light Transmittance Measurement

The measurement of the light transmittance was performed by dispensing the thermosetting composition using a dispenser so that a thickness of about 20 μm was placed on a transparent glass substrate (Samsung Corning Precision Glass Co., Ltd., product name: Eagle 2000) of 50 mm × 50 mm × 0.7 mm. The coating was applied over the entire surface of the coating. After curing for 1 hour on a hot plate at 100 ℃, using a reference glass substrate (Samsung Corning Precision Glass, product name: Eagle 2000) was measured for the transmittance of light when passing through the substrate, as a measuring instrument Using the spectrum analyzer MCPD-3000, the transmittance of each point of the glass substrate coated with the thermosetting composition in the wavelength range of 380 to 780 nm was measured as an average value within the wavelength range obtained.

2. Measurement of adhesive strength

Drop the thermosetting resin composition to a size of 2 mm in diameter on a substrate with a glass plate of 50 mm × 50 mm × 1.1 mm, attach the upper and lower plates, and cure for 1 hour on a hot plate at 100 ° C. (Instron, product name: Stud set) was measured using an adhesive strength measuring instrument (Instron, product name: UTM-5566).

3. Measurement of viscosity

The viscosity measured the viscosity when 0.5 g of a thermosetting composition showed the torque of about 80% using the viscometer (brand name: Brook Field viscometer).

4. Curable

The case where the thermosetting composition was curable for 1 hour on a hot plate at 100 ° C. was referred to as Good, and the case where the curing was not sufficient under the above curing conditions was referred to as Not good.

TABLE 2

Light transmittance (%) Adhesive Strength (kgf / cm ² ) Viscosity (cps) Curable Example 1 98.85 97 372 Good Example 2 99.16 117 459 Good Example 3 99.24 115 332 Good Example 4 99.29 146 381 Good Example 5 99.27 110 225 Good Example 6 99.46 94 584 Good

From the results of the above 2, it can be confirmed that the thermosetting resin composition for sealing of Examples 1 to 6 of the present invention exhibits excellent physical properties while being suitable for sealing.

Example 7 Sealing of Display Elements

A lower sealing member and an upper sealing member including a lower substrate, and an anode, a light emitting layer (red, green, blue surface emitting light) and a cathode stacked thereon were prepared. The negative electrode front surface of the lower sealing member was applied to the thermosetting resin composition of Example 1 by using an ODF process. Separately, the edge of the upper sealing member was applied to the photocurable resin composition using a screen printing process. The upper sealing member and the lower sealing member were bonded in a vacuum atmosphere of 10 ^-7 torr in a nitrogen atmosphere so that the coating surface of the upper sealing member and the coating surface of the lower sealing member were in contact with each other. The cured photocurable resin composition was irradiated with UV of 6000 mJ / cm ² to the bonded upper and lower sealing members, and then heated to 80 ° C. to cure the thermosetting resin composition, thereby manufacturing a display device. 2, (1): anode deposition process, (2) light emitting material (Red, Green, Blue surface light emission), (3) cathode deposition process, (4): color filter deposition process, (5 ): Photocurable resin coating process, (6): sealing thermosetting resin coating process (ODF process: coating the entire surface of substrate), (7): thermosetting process after bonding, (a): dispenser, (b) : Thermosetting composition, (c): heating)).

Example 8 Sealing of Display Elements

Sealing was performed in the same manner except that the glass frit was used instead of the photocurable resin of Example 7, and a process diagram is shown in FIG. 3. (In Figure 3 (1): anode deposition process, (2): light emitting material (Red, Green, Blue surface light emission), (3): cathode deposition process, (4): glass frit coating and plasticity process, (5): Color filter film forming process, (6): thermosetting resin coating process (ODF process: coating the entire surface of substrate), (7): thermosetting process after bonding, (a): dispenser, (b): thermosetting composition, (c) heating)

The devices manufactured in Examples 7 and 8 have the structure as shown in FIG. 1, and are excellent in light transmittance, moisture transmittance, adhesive strength, and thermal stability, and the light emitting bodies of the upper sealing member and the lower sealing member are in contact with each other. Causes of damage are inherently prevented.

1 is a schematic diagram of a display device according to an embodiment of the present invention, Figures 2 and 3 is a process chart of a sealing method according to an embodiment of the present invention.

<Drawing symbol>

DESCRIPTION OF SYMBOLS 1 Lower glass substrate, 2 anode, 3 light emitting layer, 4 cathode, 5 thermosetting resin composition, 6 color filter, 7 glass frit or photocurable resin composition, 8 top glass substrate

(1): anode deposition process, (2): light emitting material (Red, Green, Blue surface light emission), (3): cathode deposition process, (4): color filter deposition process (FIG. 2) or glass frit coating and plasticity process (FIG. 3), (5): photocurable resin coating (FIG. 2) or color filter film forming process (FIG. 3), (6): thermosetting resin coating process (ODF process: coating a predetermined interval on the front of the substrate), (7 ): Thermosetting process after bonding, (a): dispenser, (b): thermosetting composition, (c): heating)

Claims (11)

In the resin composition for sealing electric or optical elements, a) 25-90 parts by weight of epoxy resin; b) 9-70 parts by weight of a thermosetting agent; And c) 0.1-5 parts by weight of curing accelerator It includes, the viscosity of the thermosetting resin composition for sealing, characterized in that 10-3000 cps (at 25 ℃). The method of claim 1, The thermosetting resin composition for sealing, characterized in that the thermosetting resin composition further comprises 0.001 to 5 parts by weight of coupling agent or 0.001 to 0.5 parts by weight of antioxidant. The method of claim 1, The epoxy resin is a group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol type epoxy resin, alicyclic epoxy resin, aromatic epoxy resin, novolac type and dicyclopentadiene type epoxy resin, and mixtures thereof Thermosetting resin composition for sealing, characterized in that it is selected from. The method of claim 1, The thermosetting resin composition for sealing, characterized in that the viscosity of the thermosetting resin composition is 100-1000 cps (at 25 ℃). The method of claim 1, The thermosetting agent is diethylenetriamine, triethylenetetramine, N-aminoethylpiperazine, diaminodiphenylmethane, adipic dihydrazide, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydro anhydride Phthalic acid, methylhexahydrophthalic anhydride, methylnadic acid anhydride, phenol novolak-type curing agent, trioxane tritylenmercaptan, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 2-methylimidazole , 2-ethyl-4-methylimidazole, and 1-benzyl-2-methylimidazole. The thermosetting resin composition for sealing, characterized in that at least one member is selected. The method of claim 1, The curing accelerator is tetramethylammonium bromide, tetrabutylammonium bromide, tetraphenylphosphonium bromide, tetrabutylphosphonium bromide, zinc octylate, octylic acid tin, 1-benzyl-2-methyl imidazole, 1-benzyl-2- Thermosetting resin composition for sealing, It is selected from the group which consists of phenyl imidazole, 2-ethyl-4-methyl imidazole, and benzyl dimethylamine. The method of claim 2, Said coupling agent is selected from the group which consists of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a silicone compound, The thermosetting resin composition for sealing characterized by the above-mentioned. The method of claim 2, The antioxidants include dibutyl hydroxy toluene, 2,6-di-tetra-butyl-p-cresol, mercaptopropionic acid derivatives, and triphenyl phosphite, 9,10-dihydro-9-oxa-10-phosphape Thermosetting resin composition for sealing, characterized in that at least one member is selected from the group consisting of n-styrene-10-oxide. The method of claim 1, The electrical or optical device is a sealing thermosetting resin composition, characterized in that both the lower sealing member and the upper sealing member to be glass. The method of claim 1, The electrical or optical device is a sealing thermosetting resin composition, characterized in that the OLED, LED, or dye-sensitized solar cell. A method of sealing an element by joining a lower sealing member and an upper sealing member, wherein the sealing thermosetting resin composition according to claim 1 is used.

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