KR100722464B1 - Getter for packaging, highly active calcium oxide, and method for preparing highly active calcium oxide - Google Patents

Abstract

The present invention relates to a packaging getter, a high active calcium oxide contained in the getter, and a method for preparing the high active calcium oxide, more specifically, a first organopolysiloxane compound represented by the following Chemical Formula 1, and the following Chemical Formula 2 A getter for packaging comprising a getter binder prepared from a binder composition comprising a second organopolysiloxane compound, and an active material for adsorption, a highly active calcium oxide contained in the getter, and the preparation of the highly active calcium oxide. It is about a method.

[Formula 1]

[Formula 2]

Where

R ¹ to R ¹⁵ are each independently a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a vinyl group and 6 to 6 carbon atoms. Any one selected from the group consisting of an aromatic group having 14 and a heteroaromatic group having 4 to 16 carbon atoms,

In the examples of R ¹ to R ¹⁵ , the aromatic group and heteroaromatic group are each independently a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a vinyl group, C1-C20 alkoxy group, halogen group, cyano group, nitro group, aldehyde group, C2-C20 acyl group, C2-C20 ester group, C1-C20 amide group, amino group (NR ¹⁶ R ¹⁷ ) It may or may not include one or more substituents selected from the group consisting of a silyl group (SiR ¹⁸ R ¹⁹ R ²⁰ ), and a germanyl group (GeR ²¹ R ²² R ²³ ),

R ¹⁶ to R ²³ of the amino group, the silyl group, and the germanyl group are each independently hydrogen, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 3 to C 23 carbon atoms. It is any substituent selected from the group which consists of a 12 cyclic alkyl group, a C6-C14 aromatic group, and a C4-C16 hetero aromatic group,

N is an integer of 10 to 10,000,

A is an integer of 0 to 9,999,

B is an integer of 1 to 10,000,

1 ≦ a + b ≦ 10,000.

The packaging getter of the present invention exhibits excellent thin film properties, including a binder having excellent gas permeability and durability, and the highly active calcium oxide most suitable for the getter exhibits excellent moisture or oxygen adsorption properties.

Initial absorption rate, high specific surface area, calcium oxide, getter, binder, silicone resin, moisture, adsorption, thin film, organic electroluminescent device

Description

GETTER FOR PACKAGING, HIGH ACTIVE CALCIUM OXIDE, AND METHOD FOR PREPARING HIGHLY ACTIVE CALCIUM OXIDE}

Figure 1 shows a quantitative moisture absorption graph of the highly active calcium oxide and commercially available calcium oxide prepared according to Examples 1 to 3 of the present invention.

Figure 2 shows a quantitative moisture absorption graph of the packaging getter prepared according to Examples 5 to 7 and Comparative Examples 1 to 3 of the present invention.

3 is a sectional view of a green light organic EL device manufactured according to Embodiment 8 of the present invention.

4 is an optical micrograph showing the results of a 500-hour acceleration condition test of the organic EL device prepared according to Example 8 and Comparative Example 4 of the present invention.

 <Explanation of symbols for the main parts of the drawings>

1 ... organic EL element 11 ... transparent glass substrate

12 ... anode 13 ... hole injection layer

14 ... hole transport layer 15 ... light emitting layer and electron transport layer

16 ... electron injection layer 17 ... cathode

21 ... metal cans 22 ... getter

23 ... sealing material

[Industrial use]

The present invention relates to a method for manufacturing a getter for packaging, a highly active calcium oxide, and a highly active calcium oxide of a display device, and having excellent gas permeability and durability, and excellent ability to adsorb moisture or oxygen. It relates to a getter, and a highly active calcium oxide used therein, and a method for preparing the same.

[Private Technology]

Flat panel or thin display such as plasma display panel (PDP), liquid crystal display (LCD), inorganic light emitting diode (Inorganic LED), field emission display (FED: field emission display), and organic electronic electroluminescent device (Organic LED). In particular, since OLEDs) deteriorate device characteristics due to moisture penetrating from the outside, a desiccant for eliminating this phenomenon must be mounted inside the device.

Such desiccants are commonly referred to as getters or getters for packaging.

Drying agents for absorbing moisture include hygroscopic powdery inorganic fillers such as calcium oxide (CaO), barium oxide (BaO), calcium chloride (CaCl ₂ ), phosphorus pentoxide (P ₂ O ₅ ), molecular sieves, etc. (inorganic filler) is put into the main body for sealing and then used by attaching an adhesive film to prevent it from being separated, a method of putting the filler in a moisture-permeable bag and adhering to the main body, compressing the powder and using it in the form of pellets Method, or a method in which the powder phase is mixed with a polymer binder to form a film and used.

The method using the adhesive film has a disadvantage in that productivity is low due to the complicated process configuration, and the defect rate of the bag is high, and the method of using the filler in the moisture-permeable bag is thicker than the film form, and the bag is expanded at high temperature. (swelling) phenomenon and the disadvantage that the filler powder is separated, the manufacturing method of the pellet form is difficult to manufacture a thin film, there is a disadvantage that the solids fall off.

The additive in the form of a film prepared by mixing an inorganic filler and a polymer binder is simple in composition and can be manufactured in a thin film of several hundred micrometers or less, and thus is applicable to an electronic and electrical device which is continuously changing to a thin and thin form. .

Conventional polymer binders used in film-type packaging getters include fluorinated resins, polyethylene resins, polyamide resins, polyester resins, and polyolefin resins having hydrophilic groups. resins, polyacrylic resins, polyacrylonitrile resins, epoxy resins, and the like.

The film additive is simple in composition and can be manufactured to several hundred micrometers or less, but conventional polymers used as binders have a low polymer binder when mixed with fillers added at a certain weight percent (wt%) of the film. The gas permeability prevents the inorganic filler itself from fully exerting the water absorption. In addition, in order to make use of the properties of the filler, the secondary processing to stretch the polymer is being performed.

As such, the polymer material used as a getter binder is i) poor in gas permeability, thereby lowering the water absorption activity of the active material for adsorption, and ii) even when the polymer support having good moisture permeability is compatible with the active material for adsorption. It is not good, the solid content is separated, iii) the processability when forming a thin film to a few hundred micro or less, iv) it is difficult to control the water absorption activity.

In addition, the general calcium oxide used as a conventional getter adsorption material has a problem that it is difficult to remove moisture and oxygen at a high rate because the initial absorption rate is not good.

The present invention has been made to solve the above problems, an object of the present invention is excellent high-permeability calcium oxide and gas permeability excellent in the initial moisture absorption rate, excellent thin film properties and durability and very miscible with the hygroscopic material It is to provide a packaging getter comprising an excellent getter binder.

Another object of the present invention is to provide a method for producing a highly active calcium oxide used in the packaging getter.

In order to achieve the above object, the present invention provides a binder for a getter prepared from a binder composition comprising a first organopolysiloxane compound represented by Chemical Formula 1, and a second organopolysiloxane compound represented by Chemical Formula 2, and a specific surface area. Provided is a packaging getter comprising the active material for adsorption which is 10 to 100 m ² / g.

[Formula 1]

[Formula 2]

Where

R ¹ to R ¹⁵ are each independently a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a vinyl group and 6 to 6 carbon atoms. Any one selected from the group consisting of an aromatic group having 14 and a heteroaromatic group having 4 to 16 carbon atoms,

In the examples of R ¹ to R ¹⁵ , the aromatic group and heteroaromatic group are each independently a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a vinyl group, C1-C20 alkoxy group, halogen group, cyano group, nitro group, aldehyde group, C2-C20 acyl group, C2-C20 ester group, C1-C20 amide group, amino group (NR ¹⁶ R ¹⁷ ) It may or may not include one or more substituents selected from the group consisting of a silyl group (SiR ¹⁸ R ¹⁹ R ²⁰ ), and a germanyl group (GeR ²¹ R ²² R ²³ ),

R ¹⁶ to R ²³ of the amino group, the silyl group, and the germanyl group are each independently hydrogen, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 3 to C 23 carbon atoms. It is any substituent selected from the group which consists of a 12 cyclic alkyl group, a C6-C14 aromatic group, and a C4-C16 hetero aromatic group,

N is an integer of 10 to 10,000,

A is an integer of 0 to 9,999,

B is an integer of 1 to 10,000,

1 ≦ a + b ≦ 10,000.

The present invention also provides a highly active calcium oxide for getters having a specific surface area of 40 to 100 m ² / g and a moisture absorption rate (%) defined by the following formula 1 having a moisture absorption amount of 70 to 99% by weight.

[Calculation 1]

% Moisture absorption = (actual moisture absorption over 1 hour) / (theoretical moisture absorption) × 100

The present invention also provides a method for producing highly active calcium oxide comprising hydrating the calcium oxide with water in the presence of a surfactant to produce calcium hydroxide particles, and sintering and reducing the calcium hydroxide particles in the presence of hydrogen gas. do.

Hereinafter, the present invention will be described in more detail.

The packaging getter of the present invention comprises a binder prepared from a binder composition comprising a first organopolysiloxane compound containing a vinyl group as a base polymer and a second organopolysiloxane compound which is a hydrogensiloxane compound as a curing agent.

More specifically, the first organopolysiloxane compound may be represented by Formula 1, and the second organopolysiloxane compound may be represented by Formula 2.

In addition, the weight ratio of the first organopolysiloxane compound and the second organopolysiloxane compound is preferably 25:75 to 95: 5.

In the getter of the present invention, in order for the binder to exhibit more excellent properties and to improve workability and economical efficiency in manufacturing the getter, the first organopolysiloxane compound is most preferably polydimethylsiloxane represented by the following formula (3), and the second Most preferably, the organopolysiloxane compound is a polymethylhydrogen siloxane represented by the following formula (4).

[Formula 3]

[Formula 4]

Where

n is an integer from 10 to 10,000,

a is an integer from 0 to 9,999,

b is an integer from 1 to 10,000,

1 ≦ a + b ≦ 10,000.

The binder composition used to manufacture the binder may further include a catalyst for crosslinking reaction. The catalyst may use any kind of organic or inorganic catalyst capable of causing a crosslinking reaction, and preferably a transition metal catalyst comprising at least one transition metal selected from the group consisting of platinum, palladium, and rhodium. Can be.

The concentration of the catalyst included in the composition for the binder can be appropriately adjusted within a conventional range, preferably can be used in a concentration of 1 to 500 ppm relative to the total composition weight.

In addition, the binder composition is selected from the group consisting of tetrakistrialkylsiloxysilane of Formula 5 and tetraalkyl-tetravinyl-cyclo tetrasiloxane of Formula 6 to improve curing of the binder and film properties of the getter. It may further comprise one or more additives.

[Formula 5]

[Formula 6]

Where

R ²⁴ to R ³¹ are each independently a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a vinyl group and 6 to 6 carbon atoms. Any one selected from the group consisting of an aromatic group having 14 and a heteroaromatic group having 4 to 16 carbon atoms,

In the examples of R ²⁴ to R ³¹ , the aromatic group and the heteroaromatic group are each independently a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a vinyl group, C1-C20 alkoxy group, halogen group, cyano group, nitro group, aldehyde group, C2-C20 acyl group, C2-C20 ester group, C1-C20 amide group, amino group (NR ¹⁶ R ¹⁷ ) It may or may not include one or more substituents selected from the group consisting of a silyl group (SiR ¹⁸ R ¹⁹ R ²⁰ ), and a germanyl group (GeR ²¹ R ²² R ²³ ),

R ¹⁶ to R ²³ of the amino group, the silyl group, and the germanyl group are each independently hydrogen, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 3 to C 23 carbon atoms. It is any substituent chosen from the group which consists of a cyclic alkyl group of 12, a C6-C14 aromatic group, and a C4-C16 hetero aromatic group.

As such, when the composition for the binder of the present invention further includes the additives of Chemical Formulas 5 to 6, the first organopolysiloxane compound represented by Chemical Formula 1 is 30 to 70% by weight, and the second organic polysiloxane compound represented by Chemical Formula 2 is To 40% by weight, tetrakistrialkylsiloxysilane represented by the formula (5) 0 to 10% by weight, and tetraalkyl-tetravinyl-cyclotetra siloxane represented by the formula (6) preferably comprises 0 to 10% by weight Do. However, the content range is merely an example of limiting the range in which the composition for preparing a binder of the present invention can better exhibit excellent properties, but the content of the present invention is not limited only to the above range.

The binder composition used for preparing the getter of the present invention is in a liquid state having a suitable viscosity and fluidity at room temperature, has good miscibility with the active material for adsorption even when a separate organic solvent is not used, and workability for forming a thin film. Has an excellent advantage.

The binder composition forms a binder by an addition reaction, and an example of the addition reaction may be represented as in Scheme 1 below.

Scheme 1

As shown in Scheme 1, the binder of the present invention has an advantage of low impurities because no by-products are generated in the manufacturing process. In addition, the binder prepared as in Scheme 1 includes a silicon-ethylene bond, excellent permeability to moisture and oxygen, good miscibility with the active material for adsorption, film processability such as winding (winding) It is very suitable to be used as a binder for getters.

The packaging getter of the present invention includes an active material for adsorption together with the binder, wherein the active material for adsorption is preferably included in an amount of 1% by weight or more based on the total getter weight to obtain excellent adsorption capacity. It is more preferably included in the wt% or more, it is preferably included in 90% by weight or less for the thin film properties and excellent durability of the getter.

The active material for adsorption may be used as long as the active material for adsorption excellent in water adsorption performance, but is preferably an active material for adsorption having a specific surface area of 10 to 100 m ² / g, specific surface area 40 to 100 m It is more preferable that it is an active material for adsorption of ² / g. The larger the specific surface area of the adsorption active material, the better the ability to adsorb moisture, but it is preferable to satisfy the range of the specific surface area for proper mechanical properties and adsorptivity.

Examples of the active material for adsorption include one or more selected from the group consisting of inorganic phosphorus compounds, metal oxides, metal halides, inorganic acid salts of metals, organic acid salts, and porous inorganic compounds, preferably phosphorus pentoxide (phosphorous pentaoxide, P ₂ O ₅ ), barium oxide (BaO), magnesium oxide (MgO), calcium oxide (CaO), strontium oxide (SrO), silica gel (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), Calcium chloride (CaCl ₂ ), potassium carbonate (K ₂ CO ₃ ), calcium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH), lithium sulfate (Li ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ) , Calcium sulfate (CaSO ₄ ), magnesium sulfate (MgSO ₄ ), cobalt sulfate (CoSO ₄ ), gallium sulfate (Ga ₂ (SO ₄ ) ₃ ), titanium sulfate (Ti (SO ₄ ) ₂ ), nickel sulfate (NiSO ₄ ), Zeolite, and molecular sieve of 3 to 4 mm 3.

In addition, in order to maximize the moisture and oxygen adsorption capacity of the getter of the present invention, it is preferable to include a highly active adsorbent material having improved hygroscopic performance, and most preferably, the specific surface area is 40 to 100 m ² / g, and the following Equation 1 A moisture absorption rate (%) defined as may include 70 to 99% by weight of highly active calcium oxide.

[Calculation 1]

% Moisture absorption = (actual moisture absorption over 1 hour) / (theoretical moisture absorption) × 100

The high activity calcium oxide is a step of hydrating the calcium oxide with water in the presence of a surfactant in order to increase the hygroscopic performance of conventional calcium oxide to prepare calcium hydroxide particles; And sintering and reducing the calcium hydroxide in the presence of hydrogen gas. The manufacturing process of the high active calcium oxide is shown in Scheme 2 below.

Scheme 2

Calcium oxide used for the production of the highly active calcium oxide may be used commercially available general calcium oxide, but is not particularly limited to any kind, the higher the purity is better.

In the hydration reaction, to prepare calcium hydroxide having a large specific surface area, i) 100 parts by weight of water, ii) 30-100 parts by weight of one or more alcohols selected from the group consisting of methanol, ethanol, and isopropyl alcohol, iii) Tween 1 to 30 parts by weight of one or more nonionic surfactants selected from the group consisting of series (e.g., Tween-20, 40, 60, 80, 85, etc.), glycerin, ethylene glycol, diethylene glycol, and Triton-X iv) at least one member selected from the group consisting of oxalic acid, tartaric acid, lactic acid, citric acid, glyceric acid, and sulfonic acid After mixing 1 to 30 parts by weight of the hydrating retardant, and 10 to 50 parts by weight of calcium oxide, the mixture was filtered by reaction for 6 to 24 hours at a speed of 100 to 300 rpm, then sufficiently washed with water and dried under vacuum. The calcium hydroxide thus prepared preferably has a specific surface area of 10 to 60 m ² / g.

The calcium hydroxide produced by the above method is heat-treated in a sintering furnace which can use vacuum and carrier gas, thereby making it possible to produce highly active calcium oxide having excellent hygroscopicity.

Grind the sufficiently dried calcium hydroxide finely, put it in a sintering furnace so that the carrier gas can be evenly contacted, and reduced the pressure to 0.01 to 1 torr vacuum, and then slowly increase the temperature from room temperature to 400 to 600 ℃ over 1 to 6 hours

Temperature 400-600 When the temperature is reached, the vacuum is released and the carrier gas containing hydrogen is flowed at 400 to 600 ° C. at a rate of 50 to 300 mL / min for 0.5 to 5 hours. At this time, the carrier gas is more preferably a mixed gas containing hydrogen and nitrogen or argon, more preferably the content of hydrogen gas is 10 to 99% by volume.

Subsequently, the supply of the carrier gas containing hydrogen gas was stopped, and the pressure was reduced to 0.01 to 1 torr vacuum again, and the temperature was lowered to 200 to 250 ° C. over 1 to 3 hours. When the temperature is completed, the vacuum is released and the calcium oxide is collected and sealed-packed at 200 to 250 ° C.

Calcium oxide prepared by the above method has a high specific surface area of 40 to 100 m ² / g and has a very small particle size, which has excellent compatibility with polymer binders and excellent reactivity with moisture, and thus has excellent initial moisture absorption rate. do.

In particular, the high active calcium oxide exhibits a moisture absorption rate 1.5 times faster than commercially available high purity calcium oxide, and exhibits a moisture absorption of 70 to 99% compared to the theoretical moisture absorption.

Packaging getter of the present invention comprising the binder and the hygroscopic active material as described above preferably has a thickness of less than 1000 ㎛ in order to reduce the volume of the device, in order to ensure excellent moisture removal properties and properties of the film-type getter It is preferable that it is 10 micrometers or more, and it is more preferable that it is a thin film which has a thickness of 40 micrometers or more.

The packaging getter may be prepared by uniformly mixing the composition for preparing a binder of the present invention and the active material for adsorption in an appropriate ratio to prepare a getter slurry, and then molding the slurry into an appropriate form and then thermosetting it. have.

The slurry may be formed into a thin film using a method such as injection molding, compression molding, injection molding, extrusion molding, silkscreen, or doctor blade. You can choose freely.

The thermosetting conditions for the getter slurry can be adjusted differently according to the components of the composition for preparing the binder, the choice of catalyst, and the content of each component, but it is most appropriate to thermoset at 50 to 200 ° C. for 1 to 20 minutes.

The thermosetting method is not particularly limited, but heat is preferably applied by exposing the applied slurry to hot air or by thermal contact with a heater. More specifically, the slurry is formed into a thin film and then heated sufficiently to completely cure the slurry. Alternatively, it may be appropriately heated to semi-curing, and then molded by an appropriate molding method and heated again to complete the curing process.

The thin film getter manufactured as described above has excellent gas and moisture permeability, uniform thin film properties, and excellent durability. It also has moderate elasticity and good dimensional stability, thus facilitating subsequent work to manufacture display devices.

Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

EXAMPLE

Example 1

Hydration of Calcium Oxide

Into a mixed solution of 150 g of distilled water and 150 g of isopropyl alcohol (IPA), add 1.8 g of citric acid hydrate (Citric acid monohydrate, Aldrich) and 3.6 g of a nonionic surfactant, Tween-20 (Aldrich), and stir for 10 minutes. Melted.

60 g of CaO powder (99.9%, Aldrich) was added at 10 ° C., stirred at 200 rpm for 2 hours, and then hydrated at 25 ° C. for 22 hours.

After the reaction, the precipitate was filtered, washed sufficiently with distilled water, and dried under reduced pressure under vacuum.

The yield of calcium hydroxide obtained at this time was 78g (98 weight%), the property was white powder, and the specific surface area measured by BET method was 21.6 m <^2> / g.

(Sintering and reduction reaction)

8 g of the obtained calcium hydroxide powder was placed in a quartz vessel having a diameter of 2 cm and a length of 10 cm, placed in a sintering furnace, and then heated at room temperature under vacuum, and heated to 600 ° C. within 3 hours.

Subsequently, hydrogen gas (99% by volume) was flowed through the sintering furnace at a rate of 180 mL / min at 600 ° C. for 2 hours, and the sintering furnace was cooled to 250 ° C. for 1.5 hours under vacuum.

After cooling the sintering furnace, the vacuum was released, and the highly active CaO contained in the container was recovered. At this time, the yield was 5.9 g (98 wt%), the appearance was an off-white powder, and the specific surface area measured by the BET method was 61.7 m ² / g.

Example 2

Hydration of Calcium Oxide

Glycerine (60 g) was added to 240 g of distilled water, and the solution was stirred for 10 minutes to completely dissolve.

60 g of CaO powder (99.9%, Aldrich) was added at 10 ° C., stirred at 200 rpm for 2 hours, and then hydrated at 25 ° C. for 22 hours.

After the reaction, the precipitate was filtered, washed sufficiently with distilled water, and dried under reduced pressure under vacuum.

The yield of calcium hydroxide obtained at this time was 77 g (97 weight%), the property was white powder, and the specific surface area measured by BET method was 53.8 m <^2> / g.

(Sintering and reduction reaction)

8 g of the obtained calcium hydroxide powder was treated in the same manner as in the sintering and reduction step of Example 1 to recover high activity CaO. At this time, the yield was 5.8 g (96 wt%), the appearance was an off-white powder, and the specific surface area measured by the BET method was 88.4 m ² / g.

Example 3

8 g of CaO powder (99.9%, Aldrich) was placed in a quartz vessel of 2 cm in diameter and 10 cm in length, placed in a sintering furnace and started heating at room temperature under vacuum. It heated up.

Subsequently, hydrogen gas (99% by volume) was flowed through the sintering furnace at a rate of 180 mL / min at 600 ° C. for 2 hours, and the sintering furnace was cooled to 250 ° C. for 1.5 hours under vacuum.

After cooling the sintering furnace, the vacuum was released, and CaO contained in the container was recovered. The yield was then 7.9 g (99% by weight).

Example 4

(Production of the composition for the binder)

8.0 g of polydimethylsiloxane (Aldrich), 1.0 g of polydimethylsiloxane-co-methylhydrosiloxane (Aldrich), 1.0 mg of chloroplatinic acid, 0.5 g of tetrakistrimethylsiloxysilane (Aldrich) in a 500 ml round bottom flask, and 0.5 g of 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl cyclotetrasiloxane (Aldrich) was added and stirred at room temperature (25 ° C.) for 30 minutes to prepare a binder composition. It was.

After stirring the mixture, bubbles were sufficiently removed and stored in a glove box at room temperature in anhydrous nitrogen atmosphere.

Example 5

(Manufacture of thin film getter)

In a high purity nitrogen (99.9999%) in anhydrous atmosphere, 1.0 g of highly active calcium oxide prepared according to Example 2, 1.0 g of the binder composition prepared according to Example 4, and 0.03 g of carbon were added in 20 ml volumes. A slurry for getters in which solids were completely dispersed was prepared by stirring in a vial for 1 hour or more.

After forming the thin film using the screen printer coating method (Screen printer) coating method was hot air cured at 100 ℃ for 15 minutes to prepare a getter of a thin film form having a thickness of 120 ㎛, the getter thin film 1 cm × 1 cm Samples were prepared by cutting to the size of.

Example 6

(Manufacture of thin film getter)

Thin film form in the same manner as in Example 5 except that 1.0 g of the highly active calcium oxide of Example 2, 1.0 g of the binder preparation prepared according to Example 4, and 0.03 g of carbon, 0.5 g of toluene Getters and samples were prepared.

Example 7

(Manufacture of thin film getter)

Thin film form in the same manner as in Example 5, except that 1 g of commercially available calcium oxide powder (99.9%, Aldrich), 1.0 g of a binder preparation prepared according to Example 4, and 0.03 g of carbon were used. Getters and samples were prepared.

Comparative Example 1

(Production of getter using epoxy binder)

1 g of the epoxy resin and 1 g of the highly active calcium oxide of Example 2 were mixed for 1 hour using a stirrer under anhydrous high purity nitrogen (99.9999%), and the thickness was 120 μm using the mixed slurry. A getter thin film was prepared, and a sample was prepared by cutting the getter thin film into a size of 1 cmⅹ1 cm.

Comparative Example 2

(Production of getter using PAN binder)

1 g of polyacrylonitrile resin and 1 g of the highly active calcium oxide of Example 2 were prepared in the same manner according to Comparative Example 1 to obtain a getter thin film having a thickness of 120 μm, the getter thin film having a size of 1 cm ⅹ 1 cm. The sample was prepared by cutting.

Comparative Example 3

(Manufacture of getter using PAN binder and general Ca0)

A getter thin film having a thickness of 120 μm was prepared by using 1 g of polyacrylonitrile resin and 1 g of Aldrich's commercially available calcium oxide (99.9%) in the same manner as in Comparative Example 1, wherein the getter thin film was 1 cm × 1 cm. Samples were prepared by cutting to size.

[Water Adsorption Test of Getter]

The water adsorption amount of the calcium oxide prepared according to Examples 1 to 3 and commercially available Aldrich's calcium oxide (99.9%), Examples 5 to 7, and getter samples prepared according to Comparative Examples 1 and 2 were SMS (Surface). Measurement was performed using a Dynamic Vapor Sorption (DVS) (Model name Advantage 1) measuring instrument.

The ratio of the actual moisture absorption to the theoretical moisture absorption of calcium oxide is summarized in Table 1 by calculating the moisture absorption rate, specifically, the calcium oxide prepared according to Examples 1 to 3 and commercially available calcium oxide (99.9%) A quantitative moisture absorption graph is shown in FIG. 1 together.

 TABLE 1

CaO CaO weight (mg) Actual moisture absorption amount (mg) Theoretical moisture absorption (mg) Hygroscopicity (%) Aldrich CaO 5.21 0.99 1.67 59 Example 1 5.11 1.53 1.64 93 Example 2 5.15 1.62 1.65 98 Example 3 5.28 1.35 1.70 79

Since the moisture absorption mechanism of calcium oxide is 1: 1 equivalent of calcium oxide and water molecules, as shown in Scheme 3, the theoretical moisture absorption of calcium oxide contained in the getter may be calculated by multiplying the number of moles by the molecular weight of water.

Scheme 3

In the results of Table 1, in the case of the moisture absorption rate (%) representing the actual moisture absorption amount compared to the theoretical moisture absorption amount within the measurement time for 1 hour, Examples 1 and 2 of the present invention show an excellent moisture absorption rate of 90% or more, Example 3 exhibited a moisture absorption rate of 70% or more, whereas commercially available Aldrich calcium oxide showed a moisture absorption activity of 60% or less within the measurement time.

In addition, the ratio of the moisture absorption amount of the getter to the theoretical moisture absorption amount of calcium oxide with respect to the getters of Examples 5 to 7 and the getters of Comparative Examples 1 to 3 is summarized in Table 2 below by calculating the moisture absorption rate. Figure 2 shows a graph of quantitative moisture absorption of the getters of the 7 to 7 and the getter according to Comparative Examples 1 to 3.

TABLE 2

Getter bookbinder Hygroscopic substance Total weight (mg) CaO weight (mg) Actual moisture absorption amount (mg) Theoretical moisture absorption (mg) Hygroscopicity (%) Example 5 Siloxane Example 2 11.58 5.79 1.75 1.86 94.02 Example 6 Siloxane Example 2 11.43 5.66 1.68 1.82 92.31 Example 7 Siloxane General CaO 11.69 5.84 0.942 1.88 50.11 Comparative Example 1 Epoxy Example 2 11.55 5.78 0.72 1.92 37.50 Comparative Example 2 PAN Example 2 11.97 5.98 0.71 1.86 38.17 Comparative Example 3 PAN General CaO 11.89 5.91 0.585 1.90 30.79

In the results of Table 2, in the case of the moisture absorption rate (%) representing the actual moisture absorption amount of the getter to the theoretical moisture absorption amount of calcium oxide within the measurement time for 1 hour, the moisture absorption rate of 90% or more in all of Examples 5 to 6 In the case of Example 7 using general CaO, it can be seen that the moisture absorption rate is superior to that of Comparative Examples 1 to 3.

Therefore, it can be seen that the binder resin included in the getter of the present invention does not inhibit the activity of the hygroscopic active substance, and in particular, when a high active calcium oxide is used, excellent hygroscopic performance can be maintained.

Example 8

(Organic EL device fabrication comprising getter of Example 5)

In Table 2, the getter of Example 7 having the best hygroscopicity was used as a getter of the organic EL device to check device characteristics.

The cross section of the said organic electroluminescent element is as FIG. Referring to FIG. 3, the organic EL device will be described. A 1800 In thick Indium Tin Oxide (ITO) electrode is formed on the transparent glass substrate 11 as the anode 12 by the sputtering method, and then the photolithography method is used. To pattern the anode to the desired shape.

Subsequently, 4,4 ′, 4 ″ -tris (N-3-methylphenyl-N-phenyl-amino) -triphenylamine (m-MTDATA) was injected into the hole injection layer on the anode 12 under vacuum at 10 ⁻⁶ torr. 600 kV, N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) benzidine (NPB) to the hole transport layer 14 as 150 kV, the light emitting layer and the electron transport layer 15 Tris- (8-hydroxy-quinolinolato) -aluminum (Alq3) was formed to 600 mm thick.

Subsequently, 10 Å of lithium fluoride (LiF) was deposited on the electron injection layer 16 and 2,000 Å of aluminum was deposited on the cathode 17 to provide an organic EL device having a light emitting area of 2 mmⅹ3 mm.

The stainless metal can 21 to which the getter 22 manufactured according to Example 8 was bonded to the organic EL device substrate was sealed with an epoxy resin 23 using an ultraviolet curing method in a dry atmosphere filled with nitrogen, The organic EL device 1 equipped with a getter was completed.

Comparative Example 4

(Manufacture of Organic EL Device Comprising Getter of Comparative Example 1)

An organic EL device was manufactured in the same manner as in Example 8, except that the getter of Comparative Example 1 was used.

[Measurement of High Temperature and High Humidity of Organic EL Devices]

The organic EL device manufactured according to Example 8 and Comparative Example 4 was allowed to stand at 500 ° C. under accelerated conditions of 60 ° C. and 85% humidity. 500 hours in the acceleration condition experiment corresponds to tens of thousands of hours at room temperature, humidity.

The non-light-emitting portion (hereinafter referred to as "dark spot") generated by the trace amount of water under the acceleration conditions under the acceleration condition was confirmed by an optical microscope having a magnification of 50 times, and the results are shown in FIG. 4. It was.

As shown in FIG. 4, the organic EL device manufactured according to Example 8 did not change the light emitting part until 500 hours had elapsed. This result means that the getter of the present invention has excellent hygroscopic activity.

On the other hand, the light emitting part of the organic EL device according to Comparative Example 4 was observed for 200 hours after the minute change occurs in the light emitting part, that is, the generation of dark spots due to moisture penetration was observed, the dark spots and The growth was further intensified, and when it reached 500 hours, dark spots were formed throughout the light emitting portion, and it was confirmed that they were grown. The generation and growth of such dark spots causes the device life to be greatly reduced.

The packaging getter of the present invention has excellent thin film properties, excellent gas permeability, and excellent moisture absorption activity for water, which is very suitable for use in getters for electronic materials.

Claims (13)

A getter binder prepared from a binder composition comprising a first organopolysiloxane compound represented by Formula 1 below, and a second organopolysiloxane compound represented by Formula 2 below; And Active material for adsorption with specific surface area of 10 to 100 m ² / g Packaging getters, including: [Formula 1]

[Formula 2]

Where R ¹ to R ¹⁵ are each independently a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a vinyl group and 6 to 6 carbon atoms. Any one selected from the group consisting of an aromatic group having 14 and a heteroaromatic group having 4 to 16 carbon atoms, In the examples of R ¹ to R ¹⁵ , the aromatic group and heteroaromatic group are each independently a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a vinyl group, C1-C20 alkoxy group, halogen group, cyano group, nitro group, aldehyde group, C2-C20 acyl group, C2-C20 ester group, C1-C20 amide group, amino group (NR ¹⁶ R ¹⁷ ) It may or may not include one or more substituents selected from the group consisting of a silyl group (SiR ¹⁸ R ¹⁹ R ²⁰ ), and a germanyl group (GeR ²¹ R ²² R ²³ ), R ¹⁶ to R ²³ of the amino group, the silyl group, and the germanyl group are each independently hydrogen, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 3 to C 23 carbon atoms. It is any substituent selected from the group which consists of a 12 cyclic alkyl group, a C6-C14 aromatic group, and a C4-C16 hetero aromatic group, N is an integer of 10 to 10,000, A is an integer of 0 to 9,999, B is an integer of 1 to 10,000, 1 ≦ a + b ≦ 10,000. The method of claim 1, The binder composition is a getter for packaging comprising the first organopolysiloxane compound and the second organopolysiloxane compound in a weight ratio of 25:75 to 95: 5. The method of claim 1, The binder composition further comprises at least one additive selected from the group consisting of tetrakistrialkylsiloxysilane represented by the following Chemical Formula 5, and tetraalkyl-tetravinyl-cyclotetrasiloxane represented by the following Chemical Formula 6. Getters for in-packaging: [Formula 5]

[Formula 6]

Where R ²⁴ to R ³¹ are each independently a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a vinyl group and 6 to 6 carbon atoms. Any one selected from the group consisting of an aromatic group having 14 and a heteroaromatic group having 4 to 16 carbon atoms, In the examples of R ²⁴ to R ³¹ , the aromatic group and the heteroaromatic group are each independently a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a vinyl group, C1-C20 alkoxy group, halogen group, cyano group, nitro group, aldehyde group, C2-C20 acyl group, C2-C20 ester group, C1-C20 amide group, amino group (NR ¹⁶ R ¹⁷ ) It may or may not include one or more substituents selected from the group consisting of a silyl group (SiR ¹⁸ R ¹⁹ R ²⁰ ), and a germanyl group (GeR ²¹ R ²² R ²³ ), R ¹⁶ to R ²³ of the amino group, the silyl group, and the germanyl group are each independently hydrogen, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 3 to C 23 carbon atoms. It is any substituent chosen from the group which consists of a cyclic alkyl group of 12, a C6-C14 aromatic group, and a C4-C16 hetero aromatic group. The method of claim 3, The binder composition is 30 to 70 wt% of the first organopolysiloxane compound, 5 to 50% by weight of the second organopolysiloxane compound, 0-10% by weight of said tetrakistrialkylsiloxysilane, and 0-10% by weight of said tetraalkyl-tetravinyl-cyclotetra siloxane Packaging getter comprising a. The method of claim 1, The adsorption active material is packaging getter that is contained in 10 to 90% by weight relative to the total getter weight. The method of claim 1, The adsorption active material is Phosphorous pentoxide (P ₂ O ₅ ), barium oxide (BaO), magnesium oxide (MgO), calcium oxide (CaO), strontium oxide (SrO), silica gel (SiO ₂ ), aluminum oxide (Al ₂ O ₃₎ ), Calcium chloride (CaCl ₂ ), potassium carbonate (K ₂ CO ₃ ), potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH), lithium sulfate (Li ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ), Calcium sulfate (CaSO ₄ ), magnesium sulfate (MgSO ₄ ), cobalt sulfate (CoSO ₄ ), gallium sulfate (Ga ₂ (SO ₄ ) ₃ ), titanium sulfate (Ti (SO ₄ ) ₂ ), nickel sulfate (NiSO ₄ ), a getter for packaging, which is at least one member selected from the group consisting of a zeolite, and a molecular sieve of 3 to 4 mm 3. The method of claim 6, The adsorption active material has a specific surface area of 40 to 100 m ² / g, the getter for packaging is a highly active calcium oxide having a moisture absorption rate (%) defined by the following formula (1) is 70 to 99% by weight: [Calculation 1] % Moisture absorption = (actual moisture absorption over 1 hour) / (theoretical moisture absorption) × 100 The method of claim 7, wherein The calcium oxide is prepared by hydrating the calcium oxide with water in the presence of a surfactant to prepare calcium hydroxide particles; And Packaging getter prepared according to the manufacturing method of high active calcium oxide comprising the step of sintering and reducing the calcium hydroxide in the presence of hydrogen gas. The method of claim 1, The packaging getter is a packaging getter that is a thin film having a thickness of 10 to 1000 ㎛. Highly active calcium oxide having a specific surface area of 40 to 100 m ² / g, and a moisture absorption rate (%) defined by the following formula 1 is 70 to 99% by weight: [Calculation 1] % Moisture absorption = (actual moisture absorption over 1 hour) / (theoretical moisture absorption) × 100 Hydrating the calcium oxide with water in the presence of a surfactant to produce calcium hydroxide particles; And And sintering the calcium hydroxide particles in the presence of hydrogen gas to reduce the calcium hydroxide particles. The method of claim 11, The hydration reaction is i) 100 parts by weight of water, ii) 30 to 100 parts by weight of one or more alcohols selected from the group consisting of methanol, ethanol, and isopropyl alcohol, iii) 1 to 30 parts by weight of at least one nonionic surfactant selected from the group consisting of Tween series, glycerin, ethylene glycol, diethylene glycol, and Triton-X, iv) 1 to 30 parts by weight of one or more hydrating retardants selected from the group consisting of oxalic acid, tartaric acid, lactic acid, citric acid, glyceric acid, and sulfonic acid, and v) 10 to 50 parts by weight of calcium oxide After mixing, to produce a calcium hydroxide having a specific surface area of 10 to 60 m ² / g by reacting for 6 to 24 hours at a speed of 100 to 300 rpm. The method of claim 11, The sintering and reducing step Gradually heating the calcium hydroxide for 1 to 6 hours to 400 to 600 ° C. in a vacuum of 0.01 to 1 torr; Releasing the vacuum state and flowing a carrier gas having a hydrogen gas content of 10 to 99% by volume at 400 to 600 ° C. at a rate of 50 to 300 mL / min for 0.5 to 5 hours; And Stopping supply of the carrier gas, reducing the pressure to a vacuum of 0.01 to 1 torr, lowering the temperature to 200 to 250 ° C. over 1 to 3 hours, and then releasing the vacuum; Method for producing a high activity calcium oxide comprising a.

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