JP2011026556A - Composition, cured product, and electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition capable of forming a cured product excellent in at least water-absorbing properties, oxygen-absorbing properties, and heat resistance; a cured product formed from the composition; and an electronic device including the cured product. <P>SOLUTION: The composition contains: (A) an organometallic compound represented by general formula (1): (R<SP>1</SP>)nM; and (B) a polymer including a repeating unit represented by general formula (2) and having a weight-average molecular weight (Mw) of 10,000-1,000,000. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a composition, a cured body formed from the composition, and an electronic device including the cured body.

  Electronic devices that are damaged by the ingress of moisture or oxygen, such as capacitors and organic EL elements, need to be sealed and used. However, it is very difficult to seal in a state where moisture is sufficiently removed. Moreover, the function of an electronic device will fall gradually unless the water | moisture content which approachs into a device gradually is removed during use.

  For example, an organic EL element that is a typical sealed electronic device has a luminance that is caused by the electrode being oxidized by moisture or oxygen that has entered the organic EL element as the driving period becomes longer, and further the organic matter is denatured. In addition, there is a problem that the light emission characteristics such as the light emission efficiency are remarkably deteriorated.

  As one method for protecting an organic EL element from moisture or oxygen, a technique of arranging a desiccant in the element and keeping the inside of the element in a low humidity and low oxygen environment has been studied (for example, Patent Documents 1 to 6). reference).

Japanese Patent Laid-Open No. 9-148066 JP 2003-142256 A JP 2003-338366 A JP-A-2005-230818 JP 2006-68729 A JP 2006-59571 A

  However, the moisture or oxygen scavengers described in Patent Documents 1 to 6 have insufficient moisture absorption and oxygen absorption capacity in consideration of long-term use, and further, volume expansion and opaqueness associated with moisture absorption and oxygen absorption. There was a problem of expansion and the like due to generation of volatile components. In particular, in a top emission type organic EL element, since it is necessary to form a capturing agent layer between the light emitting layer and the display surface, the capturing agent is required to be transparent.

  In addition, since the above-mentioned moisture or oxygen scavenger alone is difficult to arrange in an electronic device, a technique for mixing a moisture or oxygen scavenger and a polymer binder to form a sheet has been proposed (for example, Patent Document 2). However, such sheet-shaped scavengers have insufficient heat resistance, and some of them are heat-fluidized and deformed in a high temperature use environment. Furthermore, components generated by decomposition due to moisture absorption may act as a binder plasticizer, which may adversely affect the maintenance of the device structure.

  Since the sheet-like capturing agent as described above is applied and formed at a predetermined position of the organic EL element, it has an appropriate viscosity, and defects such as cracks occur after the formation of the capturing agent layer. It is required to be difficult. In addition, good compatibility between the moisture or oxygen scavenger and the binder is also required.

  The present invention has been made to solve at least a part of the above-described problems, and is realized as the following aspect or application example to form a cured body excellent in water absorption, oxygen absorption, and heat resistance. The present invention provides a moisture or oxygen scavenging composition that can be used, a cured body formed from the composition, and an electronic device including the cured body.

[Application Example 1]
One aspect of the composition according to the present invention is:
(A) a compound represented by the following general formula (1);
(B) a polymer containing a repeating unit represented by the following general formula (2) and having a weight average molecular weight (Mw) of 10,000 or more and 1,000,000 or less;
Containing.

(R ¹ ) nM (1)
(In Formula (1), R ¹ is ^one selected from a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cyclic alkyl group, an aryl group, an alkoxyl group, a carboxyl group, and an amino group, R ¹ present may be the same or different, n is 2 or 3, and is equal to the valence of M. M is a divalent or trivalent atom, and the compound represented by formula (1) is , Having at least one CM bond.)

（式（２）中、Ｒ^２、Ｒ^３は、水素原子、アルキル基、アルケニル基、アルキニル基、環式アルキル基、アリール基、アルコキシル基、カルボキシル基、およびアミノ基から選択される１種である。）

(In formula (2), R ² and R ³ are one selected from a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cyclic alkyl group, an aryl group, an alkoxyl group, a carboxyl group, and an amino group. is there.)

[Application Example 2]
In application example 1,
The M may be aluminum.

[Application Example 3]
In application example 1 or application example 2,
The compound (A) is at least one selected from tridodecyl aluminum, trihexadecyl aluminum, tristetramethylhexadecyl aluminum, tri (1-phytyl) aluminum, and tri (3-cyclododecylpropyl) aluminum. be able to.

[Application Example 4]
In any one of Application Examples 1 to 3,
The polymer (B) may be poly (meth) acrylic acid or poly (meth) acrylic ester.

[Application Example 5]
The composition described in any one of Application Examples 1 to 4 can be used for the purpose of capturing moisture or oxygen.

[Application Example 6]
One aspect of the cured body according to the present invention is formed using the composition described in any one of Application Examples 1 to 5.

[Application Example 7]
One aspect of the electronic device according to the present invention is characterized in that the cured body described in Application Example 6 is provided inside.

  Since the composition according to the present invention contains a specific compound capable of trapping moisture or oxygen and a specific polymer as a matrix, the composition has excellent moisture absorption, oxygen absorption and heat resistance. A body (a coating film, a film, etc.) can be formed. For example, the cured body is not deformed by heat flow even under a use environment exceeding 80 ° C.

  The cured body is suitable for applications such as a sealing material for electronic devices such as organic EL elements, and when it is excellent in transparency, it can be used for, for example, a top emission type organic EL element.

It is sectional drawing which shows typically an example of the organic EL element concerning this Embodiment. It is IR spectrum figure of the film which consists of polymethyl methacrylate. FIG. 6 is an IR spectrum diagram of the film produced in Example 10.

  Hereinafter, preferred embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, Various modifications implemented in the range which does not change the summary of this invention are also included.

1. Composition The composition concerning this Embodiment is
(A) a compound represented by the following general formula (1) (hereinafter, also simply referred to as “component (A)”) and (B) a repeating unit represented by the following general formula (2), Mw) is a polymer having a molecular weight of 10,000 or more and 1,000,000 or less (hereinafter also simply referred to as “component (B)”).

(R ¹ ) nM (1)
(In Formula (1), R ¹ is ^one selected from a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cyclic alkyl group, an aryl group, an alkoxyl group, a carboxyl group, and an amino group, R ¹ present may be the same or different, n is 2 or 3, and is equal to the valence of M. M is a divalent or trivalent atom, and the compound represented by formula (1) is , Having at least one CM bond.)

（式（２）中、Ｒ^２、Ｒ^３は、水素原子、アルキル基、アルケニル基、アルキニル基、環式アルキル基、アリール基、アルコキシル基、カルボキシル基、およびアミノ基から選択される１種である。）

(In formula (2), R ² and R ³ are one selected from a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cyclic alkyl group, an aryl group, an alkoxyl group, a carboxyl group, and an amino group. is there.)

  Hereinafter, each component which comprises the composition concerning this Embodiment is demonstrated.

1.1. (A) component The composition concerning this Embodiment contains the compound shown by (A) following General formula (1).

(R ¹ ) nM (1)
(In Formula (1), R ¹ is ^one selected from a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cyclic alkyl group, an aryl group, an alkoxyl group, a carboxyl group, and an amino group, R ¹ present may be the same or different, n is 2 or 3, and is equal to the valence of M. M is a divalent or trivalent metal atom, and the compound represented by the formula (1) Have at least one CM bond.)

  As one of the functions of the component (A), the CM bond (where C represents a carbon atom and M represents a divalent or trivalent atom) present in the component (A) is moisture or Examples include capturing moisture or oxygen by reacting with oxygen. By using such a compound, a cured product excellent in hygroscopicity and oxygen absorption can be obtained.

In the general formula (1), R ¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cyclic alkyl group, an aryl group, a carboxyl group, or an amino group.

  As the alkyl group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, hexadecyl group, tetramethylhexadecyl group And octadecyl group.

  Examples of the alkenyl group include a propenyl group, a butenyl group, an octenyl group, a dodecenyl group, and an octadecenyl group.

  Examples of the alkynyl group include a propynyl group and a phenylethynyl group.

  Examples of the cyclic alkyl group include a cyclopropyl group and a cyclohexyl group.

  Examples of the aryl group include a phenyl group and a benzyl group.

  Examples of the alkoxyl group include an ethoxy group, a propoxy group, and a butoxy group.

  These alkyl group, alkenyl group and alkynyl group may be linear or branched.

The number of carbon atoms of ^{R 1} is preferably 1 to 30, more preferably 6 to 25, particularly preferably 12 to 20. In particular, when the carbon number of R ¹ is 6 to 25, when the component derived from R ¹ is liberated by hydrolysis, it is difficult to form an outgas component, and it is preferable to form a uniform mixture with the component (B). .

  In the general formula (1), M is a divalent or trivalent atom. Examples of such atoms include Group 2 elements, Group 4 elements, Group 12 elements and Group 13 elements in the IUPAC periodic table. Specifically, Al, B, Mg, Zn, Ti, Zr etc. can be illustrated. Among these, Al or B is preferable from the viewpoint of excellent hygroscopicity and oxygen absorption, and Al is more preferable from the viewpoint of maintaining transparency without being colored after being decomposed by trapping moisture and oxygen.

  Specific examples of the compound represented by the general formula (1) include triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tricyclopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t. -Butylaluminum, tri-2-methylbutylaluminum, tri-n-hexylaluminum, tricyclohexylaluminum, tri (2-ethylhexyl) aluminum, tri-n-octylaluminum, tri-n-decylaluminum, trihexadecylaluminum, Tristetramethylhexadecylaluminum, triphenylaluminum, tribenzylaluminum, dimethylphenylaluminum, dibutylphenylaluminum, diisobutylphenol Le aluminum, methyldiphenyl aluminum, ethoxy diethyl aluminum, Etokishiji -n- octyl aluminum, triethyl borane, tributyl borane, tri -n- octyl borane, tri -n- dodecyl borane, triphenyl borane, and the like.

Among the compounds represented by the general formula (1), compounds in which R ¹ is a group having 6 or more carbon atoms, such as tri-n-hexyl aluminum, tri-n-octyl aluminum, tri-n-dodecyl aluminum, trihexa Compounds such as decylaluminum and tristetramethylhexadecylaluminum are preferred, and R ¹ is a group having 12 or more carbon atoms, such as tridodecylaluminum, tri (3-cyclododecylpropyl) aluminum (compound represented by the following formula (3) ), Trihexadecylaluminum, tristetramethylhexadecylaluminum, tris (3,7,11,15-tetramethylhexadecyl) aluminum (hereinafter also referred to as tri (1-phytyl) aluminum, represented by the following formula (4). And the like are particularly preferred. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the component (A) in the composition according to the present embodiment is such that the content of the component (A) in the composition is 10% by mass when the total mass of the resulting composition is 100% by mass. Although it will not specifically limit if it can set so that it may become 80 mass% or less above, It is preferable that it is 10 mass% or more and 50 mass% or less. It is preferable for the content of the component (A) to be in the above-mentioned range since the action of capturing moisture and oxygen can be effectively expressed in the cured body. Furthermore, when the content of the component (A) is within the above range, an appropriate viscosity as described later can be imparted to the composition, and workability (applicability, etc.) when forming a cured product is good. It becomes.

1.2. (B) Component The composition according to the present embodiment includes (B) a repeating unit represented by the following general formula (2), and a weight average molecular weight (Mw) of 10,000 or more and 1,000,000 or less. Contains a polymer.

（式（２）中、Ｒ^２、Ｒ^３は、水素原子、アルキル基、アルケニル基、アルキニル基、環式アルキル基、アリール基、アルコキシル基、カルボキシル基、およびアミノ基から選択される１種である。）

(In formula (2), R ² and R ³ are one selected from a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cyclic alkyl group, an aryl group, an alkoxyl group, a carboxyl group, and an amino group. is there.)

  The function of the component (B) in the present embodiment will be described below.

  (1) It functions as a binder (matrix) and can improve the applicability of the component (A). Since the component (A) is solid or liquid at room temperature, it is difficult for the component (A) alone to be applied or formed into a film inside an electronic device or the like. Therefore, by mixing the component (A) with the component (B) and, if necessary, an additive such as an organic solvent, and having an appropriate viscosity, the applicability of the component (A) The film formability can be remarkably improved.

  (2) The heat resistance of the cured product obtained by curing the composition can be increased.

  (3) In general, a compound having high hygroscopicity is a substance that is difficult to handle, such as reacting with a compound having a polar functional group such as a ketone or spontaneous ignition in air. Therefore, even when a cured product in which a highly hygroscopic compound is fixed with a binder is produced, the storage stability of the cured product may not be maintained. However, the storage stability of the component (A) can be ensured by forming a cured body in which the component (A) having high hygroscopicity is fixed using the component (B) as a binder. Thereby, the hardening body which has the stable quality can be produced.

(4) By mounting a cured body formed from the composition according to this embodiment inside a sealed electronic device such as an organic EL element, moisture and oxygen entering from the outside of the electronic device are captured, and the electronic device Can be protected from moisture and oxygen. Such trapping of moisture and oxygen is achieved mainly by decomposing or oxidizing the component (A). When the component (A) is decomposed, an organic component such as an alkane derived from the group represented by R ¹ in the general formula (1) is generated. Such organic components generally have high volatility and may have a function as a binder plasticizer, which may cause aging deterioration of electrical elements and the like mounted inside the electronic device. However, when a polymer containing the repeating unit represented by the general formula (2) is present, the repeating unit interacts as a polar group, so that the effect of the generated organic component as a plasticizer can be suppressed. It is speculated that the deterioration over time can be suppressed.

  (5) The component (B) is excellent in compatibility with the component (A). Therefore, depending on the compatibility between the component (A) and the component (B), the transparency of the cured product obtained by curing the composition may be ensured.

  The weight average molecular weight (Mw) of the polymer as the component (B) is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) using tetrahydrofuran as an eluent. The polymer as the component (B) has a weight average molecular weight (Mw) of 10,000 to 1,000,000, preferably 20,000 to 500,000. When the weight average molecular weight is within the above range, an appropriate viscosity as described later can be imparted to the composition, and workability (applicability, etc.) when forming a cured product is improved. On the other hand, when the weight average molecular weight is less than the above range, the film formability is deteriorated and the adhesion to the substrate is lowered, and the compatibility with the component (A) is deteriorated and the transparency is impaired. This is not preferable. If the weight average molecular weight exceeds the above range, the viscosity increases and the workability (formability, etc.) in forming a cured product becomes poor, and the component (A) and / or the component (A) are moisture. Or when the compatibility with components generated by trapping oxygen deteriorates and the transparency is impaired, or when these components bleed on the surface of the film and the adhesion to the substrate decreases This is not preferable.

  Although it does not specifically limit as a manufacturing method of the said (B) component, The predetermined amount of a monomer, a polymerization initiator, and the organic solvent as needed are prepared, and it mixes at predetermined temperature under nitrogen atmosphere, and is made to carry out radical polymerization reaction Is mentioned.

  Examples of the monomer include (meth) acrylic acid, methyl methacrylate (MMA), ethyl methacrylate (EMA), propyl methacrylate (PMA), butyl methacrylate (BMA), ethyl hexyl methacrylate (EHMA), glycidyl methacrylate ( GMA), trimethoxysilylpropyl methacrylate (TMSPMA), tertiary butyl methacrylate (t-BMA), hydrogenated polybutadiene methacrylate (for example, “L1253” manufactured by Kuraray Co., Ltd.), ethylene glycol dimethacrylate (EGDMA), acrylic Examples include methyl acid, ethyl acrylate, and benzyl acrylate. Among these, (meth) acrylic acid, methyl methacrylate (MMA), butyl methacrylate (BMA), and ethylhexyl methacrylate (EHMA) are preferable. Moreover, these monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the polymerization initiator include azobisisobutyronitrile (AIBN) and azobiscyclohexanecarbonitrile.

  Examples of the organic solvent include toluene, xylene, cyclohexane and the like.

  Moreover, in this invention, when the repeating unit of the said polymer makes the total mass of a polymer 100 mass%, it is preferable that 10-100 mass% of repeating units derived from the said General formula (2) are included. In addition, “100% by mass of the repeating unit derived from the general formula (2)” means that the component (B) is substantially composed only of the repeating unit derived from the general formula (2). This includes the case where the terminal is not a repeating unit derived from the above general formula (2).

  The content of the component (B) in the composition according to the present embodiment is preferably 10% by mass or more and 70% by mass or less when the total mass of the composition is 100% by mass. It is preferable that the content of the component (B) is within the above range because a function of capturing moisture and oxygen can be sufficiently obtained, and the component (B) can sufficiently function as a polymer matrix.

1.3. Other additive The composition concerning this Embodiment can contain various additives as needed. Examples of various additives include organic solvents, softeners, compatibilizers, and the like. For example, when processing such as coating, it can be used by uniformly dissolving in an organic solvent that does not react with the component (A). Examples of such organic solvents include aromatic organic solvents such as toluene and xylene; aliphatic organic solvents such as paraffin, liquid paraffin, and decalin; ether-based organic solvents such as diglyme. The content of the organic solvent is not particularly limited, but is preferably an amount in which the component (A) and the component (B) are uniformly dissolved.

1.4. Manufacturing method of composition The composition concerning this Embodiment can be manufactured by mixing (A) component, (B) component, and another additive as needed.

  The method of mixing these components is not particularly limited, but a method of homogenizing the component (A) alone or a solution obtained by dissolving the component (A) in a solvent while mixing and stirring the component (B) solution. Is mentioned.

1.5. Physical Properties and Use of Composition The composition according to the present embodiment preferably has a viscosity of 50 to 20,000 cP. When the viscosity is within the above range, the composition can be directly applied to the element substrate by the ODF method and cured. This eliminates the need to prepare the composition according to the present embodiment in the form of a film or the like in advance and incorporate it into the element, thereby simplifying the process. Further, if a photoacid generator or the like is added to the composition according to the present embodiment to impart photosensitivity, fine patterning becomes possible.

  In addition, the said viscosity shows the value measured by the falling needle method. Furthermore, when the composition is used after being diluted with a solvent or the like, it means the viscosity in the composition state at the time of coating.

  Since the composition concerning this Embodiment can form the hardening body containing (A) component, it can be used for the use which capture | acquires a water | moisture content or oxygen. The composition concerning this Embodiment can be used for sealing materials, such as an organic EL element, an organic TFT, an organic solar cell, and an organic CMOS sensor, and is used suitably especially for the sealing material of an organic EL element.

2. Cured body In the present invention, the “cured body” refers to a material having a viscosity higher than that of the original composition by forming or forming the composition into a shape suitable for use and further drying or firing. .

  The cured body according to the present embodiment can be obtained, for example, by applying the above composition on a substrate to form a coating film, and then drying the coating film to remove the solvent.

  Examples of the coating method include a spin coater, a roll coater, a spray coater, a dispenser, and a method using an ink jet apparatus.

  Although the temperature in the case of drying is not specifically limited, For example, it is 5 to 100 degreeC.

  Although the shape of the obtained hardening body is not specifically limited, For example, it has a film shape. When this hardening body has a film shape, the film thickness is 0.1-1.0 mm, for example.

  The content of the component (A) in the cured product according to the present embodiment is preferably 10% by mass or more and 80% by mass or less, more preferably 10% by mass or more, when the total mass of the cured product is 100% by mass. It is 50 mass% or less, Most preferably, it is 40 mass% or more and 50 mass% or less. It is preferable for the content of the component (A) to be within the above range because the function of capturing moisture and oxygen can be sufficiently expressed. Furthermore, it is preferable that the content of the component (A) is in the above-mentioned range because the film formability is improved and the cured body is easily imparted with transparency.

  In addition, it is estimated that the hardening body concerning this Embodiment may contain the polymer which consists of a repeating unit shown by following General formula (5).

（式（５）中、Ｒ^１、Ｒ^２、Ｒ^３は、水素原子、アルキル基、アルケニル基、アルキニル基、環式アルキル基、アリール基、アルコキシル基、カルボキシル基およびアミノ基から選択される１種であって、複数存在するＲ^１は同一または異なってもよい。ｎは２または３であり、Ｍの原子価に等しい。Ｍは２価または３価の原子である。また、式（５）で示される化合物は、少なくとも１つのＣ−Ｍ結合を有する。）

(In the formula (5), R ¹ , R ² and R ³ are selected from a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cyclic alkyl group, an aryl group, an alkoxyl group, a carboxyl group and an amino group. A plurality of R ¹ may be the same or different, n is 2 or 3, and is equal to the valence of M. M is a divalent or trivalent atom, and the formula (5 ) Has at least one CM bond.)

  The reason for this can be considered from the IR spectrum chart shown in “4. Examples” below. FIG. 2 is a chart obtained by measuring the IR spectrum of the polymer B9, that is, a film of polymethyl methacrylate (hereinafter also referred to as “PMMA”). FIG. 3 is a chart obtained by measuring an IR spectrum of a film formed from a composition of PMMA and tridodecyl aluminum.

As shown in FIG. 2, in the PMMA film, stretching vibration based on the carbonyl group of methyl ester is observed as one absorption band at 1751 cm ⁻¹ . On the other hand, as shown in FIG. 3, in the film formed from the composition of PMMA and tridodecylaluminum, stretching vibrations based on the carbonyl group of the methyl ester have two absorption bands at 1751 cm ⁻¹ and 1672 cm ^−1. As observed. Further, the absorption band observed at 1672cm ^-1, the film is lost As the moisture absorption, be a single absorption band of which is observed at the same 1751Cm ^-1 the film of PMMA only have been identified.

  From the above, the cured product according to the present embodiment includes a polymer composed of the repeating unit represented by the general formula (5) in which the component (A) is coordinated to the carbonyl group of the component (B). It is estimated that there is.

3. Electronic Device The electronic device according to the present embodiment includes the cured body inside the electronic device. The cured body can be mounted on any electronic device as long as it is an electronic device that dislikes moisture and oxygen. Hereinafter, an example of an organic EL element, which is a typical sealed electronic device, will be described with reference to the drawings.

  FIG. 1 is a cross-sectional view schematically showing an example of the organic EL element according to the present embodiment.

  As shown in FIG. 1, the organic EL element 100 includes an organic EL layer 10, a structure 20 that houses the organic EL layer and blocks it from the outside air, and a trapping agent layer 30 formed in the structure 20. It consists of.

  The organic EL layer 10 may have a structure in which an organic light emitting material layer made of an organic material is sandwiched between a pair of electrodes facing each other. For example, anode / charge (hole) transport agent / light emitting layer / cathode A known structure such as the above can be adopted.

  The scavenger layer 30 is a cured product of the above composition. As shown in FIG. 1, the scavenger layer 30 may be formed away from the organic EL layer 10 or may be formed so as to cover the organic EL layer 10.

  In FIG. 1, the structure 20 includes a substrate 22, a sealing cap 24, and an adhesive 26. Examples of the substrate 22 include a glass substrate, and examples of the sealing cap 24 include a structure made of glass. The structure of the structure 20 is not particularly limited as long as the organic EL layer 10 can be accommodated.

4). Examples Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The composition was prepared in a dry nitrogen atmosphere having a dew point of −60 ° C.

4.1. Synthesis of compound (A) 4.1.1. Synthesis of tri (1-phytyl) aluminum A 200 mL three-necked flask was charged with 2.32 g (11.7 mmol) of triisobutylaluminum, 10.0 g (35.6 mmol) of 1-phytene, and 15 mL of heptane in a glove box. Refluxed overnight. Thereafter, the mixture was cooled to 55 ° C., and the solvent was distilled off under reduced pressure with a vacuum pump at this temperature, followed by cooling to room temperature to obtain 10.4 g of tri (1-phytyl) aluminum as a colorless transparent oil. The yield was quantitative.

4.1.2. Synthesis of tri (3-cyclododecylpropyl) aluminum 15.5 g (0.637 mol) of shaved magnesium and 600 mL of anhydrous tetrahydrofuran were placed in a 1,000 mL reaction vessel, and 30 g of 150 g (0.607 mol) of bromocyclododecane was added dropwise. did. This was heated to 50 ° C., and when the reaction started, the remaining bromocyclododecane was added dropwise while maintaining a state where it was removed from the bath and weakly refluxed. After completion of the dropwise addition, the mixture was refluxed for 2 hours and cooled to room temperature. This was cooled in an ice-water bath, 57.8 mL (0.668 mol) of 3-bromo-1-propene was added dropwise at an internal temperature of 30 ° C., and the mixture was refluxed overnight after completion of the addition. After cooling to room temperature, 1N aqueous hydrogen chloride was added dropwise in an ice-water bath to separate the organic layer, and the organic layer was washed 3 times with 200 mL of water. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated sequentially. The obtained residue was subjected to distillation, and 43 g of the target compound, 3-cyclododecyl-1-propene, was obtained as a colorless and transparent liquid from a fraction obtained under conditions of 109 to 110 ° C./3.2 mmHg. The yield was 34%.

  Next, 10 g (50.4 mmol) of triisobutylaluminum, 31.9 g (153 mmol) of 3-cyclododecyl-1-propene, and 50 mL of heptane were charged into a 200 mL three-necked flask in a glove box and refluxed overnight. Thereafter, the mixture was cooled to 55 ° C., and the solvent was distilled off while reducing the pressure with a vacuum pump at this temperature, followed by cooling to room temperature to obtain a syrupy colorless transparent oil. This was left in the glove box for several days to obtain 33 g of tri (3-cyclododecylpropyl) aluminum white solid. The yield was quantitative.

4.2. Polymer synthesis [B1 synthesis]
A 200 mL three-necked flask equipped with a thermometer, three-way cock, and nitrogen introduction tube was charged with 22.5 g (0.157 mol) of butyl methacrylate, 75 mL of toluene, and 0.26 g (1.58 mmol) of AIBN, and nitrogen was introduced into this solution for 10 minutes. did. The temperature was raised in an oil bath, and the mixture was stirred at 70 ° C. for 4 hours. After cooling, purification by the reprecipitation method was performed 3 times with 1 L of methanol and dried with a vacuum pump. 13.5 g (60%) of the target polybutyl methacrylate was obtained as a white solid.

  As a result of measuring the obtained copolymer by gel permeation chromatography (manufactured by Tosoh Corporation, apparatus model number “HLC-8220”, column model number “TSK-GEL Super H4000 and H2000”, eluent is tetrahydrofuran), polystyrene was obtained. The converted weight average molecular weight (Mw) was 63,600.

[Synthesis of B2 to B10]
By performing the same operations as described above at the charging ratios and reaction conditions described in Table 1, B2 to B10 polymers having the weight average molecular weight described in Table 1 were obtained. In bulk polymerization with a solvent / substrate ratio of 0, toluene was added to the solidified polymer to dissolve it, and purification was performed in the same manner.

In addition, the abbreviation of the component in Table 1 represents the following component, respectively.
"MMA"; methyl methacrylate; "BMA"; butyl methacrylate; "EHMA"; ethylhexyl methacrylate; "EGDMA"; ethylene glycol dimethacrylate

4.3. Example 4.3.1. Production of Film Films to be evaluated in Examples 1 to 10 and Comparative Examples 1 to 5 were produced as follows.

  First, the polymer described in Table 2 or 3 was dissolved in toluene to prepare a toluene solution so that the concentration of the polymer was 20 to 25% by mass. Next, the compound (A) described in Table 2 or Table 3 is added to a toluene solution containing a polymer in a glove box having a dew point of −60 ° C. or less and an oxygen of 1 ppm or less, and the compound is added to the whole solution after the addition. A coating solution was prepared by adjusting the concentration so that (A) was 20% by mass and stirring sufficiently. This coating solution was applied on a glass substrate and dried at 100 ° C. for 20 minutes to obtain a film.

In addition, the abbreviation of the component in Table 2 or Table 3 represents the following component, respectively.
・ "L12": Tridodecyl aluminum (trade name "TDDA", manufactured by Chemtura)
"B20"; tri (1-phytyl) aluminum (synthesized in the above "4.1. Synthesis of Compound (A)")
"C15"; tri (3-cyclododecylpropyl) aluminum (synthesized in the above "4.1. Synthesis of compound (A)")
・ "Zeonor"; cycloolefin polymer (trade name "Zeonor 1420R", manufactured by Nippon Zeon)
・ "PC": Polycarbonate (trade name "Panlite AD-5503, manufactured by Teijin Chemicals Ltd.")

4.3.2. Evaluation method About the film obtained by said "4.3.1. Production of a film", hygroscopicity, transparency, film-forming property, and glass adhesiveness were evaluated by the following method. Further, the thermal fluidity was evaluated by separately preparing a film by the following method. The results are shown in Tables 2 and 3. Since oxygen absorption is known to have a correlation with hygroscopicity, evaluation was omitted.

(1) Hygroscopicity To a glass petri dish having an inner diameter of 3 cm, a film having a thickness of 0.6 mm is prepared for each film of Examples and Comparative Examples, and a vacuum desiccator with an internal volume of 800 cm ³ equipped with a hygrometer and a thermometer. The previously produced film was put together with the glass petri dish, and the changes in humidity and temperature inside the vacuum desiccator were measured. The absolute humidity (Ha,%) was determined from the relative humidity (Hr,%), the temperature in degrees Celsius (Tc, ° C) obtained by the measurement, and the following formula (6). Then, the absolute humidity Ha (0h) at the start of measurement is assumed to be 100%, and the reduction rate of the absolute humidity Ha (2h) after 2 hours is calculated by the following formula (7) and evaluated by making the water absorption rate. did.

Ha = 4.0 × 10 ⁻³ {exp (6.4 × 10 ⁻² · Tc)} Hr (6)

Water absorption rate (%) = 100 × (Ha (0h) −Ha (2h)) / Ha (0h) (7)
The water absorption (%) is preferably 35% or more, and more preferably 38% or more.

(2) Thermal fluidity (heat resistance)
First, an appropriate amount of the above toluene solution was put in a sample tube and heat-treated at 100 ° C. for 60 minutes to produce a film having a thickness of 2 mm at the bottom of the sample tube. Next, after sufficiently absorbing the film in the atmosphere, the lid is further closed and sealed, and the sample tube is placed in an environment of 85 ° C. with the bottom of the sample tube being fixed (the film formation surface is upward). Left to stand. Thereafter, the state of the film when 336 hours passed was observed. The evaluation criteria for heat fluidity were “◯” when no change was observed in the film, and “X” when the film was slid downward and deformation was observed.

(3) Transparency Regarding the film obtained in the above “4.3.1. Production of film”, “○” indicates that no white turbidity is observed by visual observation. What became cloudy was set as "(triangle | delta)", and what became cloudy immediately after heat processing was set as "x". In addition, when applying to uses, such as organic EL in which transparency is requested | required, a thing with favorable transparency is more preferable.

(4) Film-forming property About the film obtained by said "4.3.1. Production of film", when a crack or an unevenness | corrugation has not generate | occur | produced in the film visually, it is "(circle)", and a crack or an unevenness | corrugation is slightly in a film. “Δ” was recognized, and “x” was assigned when many cracks or irregularities were observed on the film. In addition, when applying to uses, such as organic EL by which transparency is requested | required, what can suppress generation | occurrence | production of a crack and an unevenness | corrugation is more preferable.

(5) Glass adhesion For the film obtained in the above “4.3.1. Production of film”, “◯” indicates that the film does not peel from the glass in the atmosphere, and “△” indicates that the film peels only at the edge. The thing was made into "x". In addition, when applying to uses, such as a display material in which the adhesiveness to a glass substrate is requested | required, what has favorable glass adhesiveness is more preferable.

4.3.3. Evaluation results From the results of Tables 2 and 3, it was found that according to the compositions of Examples 1 to 10, films excellent in hygroscopicity and heat resistance were obtained. Regarding the evaluation items of transparency, film formability, and glass adhesion, it was found that the results were different depending on the combination of the compound (A) and the polymer (B).

  On the other hand, the film formed from the composition of Comparative Example 1 or Comparative Example 2 showed good heat resistance, but was not excellent in hygroscopicity. Moreover, the film formed from the composition of Comparative Example 1 or Comparative Example 2 was not excellent in transparency, film forming property, and glass adhesion.

  The composition of Comparative Example 3 is obtained by mixing calcium oxide generally used as a hygroscopic agent with B1 of the polymer (B). Calcium oxide did not dissolve at all in B1, but was dispersed in B1. The film formed from the composition of Comparative Example 3 showed good heat resistance but was not excellent in hygroscopicity. Moreover, the film formed from the composition of Comparative Example 3 was not excellent in transparency because calcium oxide was dispersed in the film.

  The film formed from the composition of Comparative Example 4 showed good heat resistance, hygroscopicity, transparency, and glass adhesion, but was not excellent in film formability.

  The film formed from the composition of Comparative Example 5 showed good heat resistance, hygroscopicity, and transparency, but was not excellent in film formability and glass adhesion.

  Here, IR spectrum was measured about the film formed from the composition of Example 10, and the structural state of this film was analyzed. FIG. 2 is a chart obtained by measuring an IR spectrum of a polymer B9 (PMMA) film. FIG. 3 is a chart obtained by measuring IR spectrum of a film formed from the composition of Example 10.

As shown in FIG. 2, in the PMMA film, stretching vibration based on the carbonyl group of methyl ester is observed as one absorption band at 1751 cm ⁻¹ . On the other hand, as shown in FIG. 3, in the film formed from the composition of PMMA and tridodecylaluminum, stretching vibrations based on the carbonyl group of the methyl ester have two absorption bands at 1751 cm ⁻¹ and 1672 cm ^−1. As observed. Further, the absorption band observed at 1672cm ^-1, the film is lost As the moisture absorption, be a single absorption band of which is observed at the same 1751Cm ^-1 the film of PMMA only have been identified.

  From the above, the composition according to the present embodiment is estimated to include a polymer composed of the repeating unit represented by the general formula (5) in which the compound (A) is coordinated to the carbonyl group of the polymer B9. can do. In addition, it is presumed that moisture is absorbed by the decomposition of the structure in which the compound (A) is coordinated to the carbonyl group of the polymer B9 represented by the general formula (5).

DESCRIPTION OF SYMBOLS 10 ... Organic EL layer, 20 ... Structure, 22 ... Substrate, 24 ... Sealing cap, 26 ... Adhesive, 30 ... Capture agent layer, 100 ... Organic EL element

Claims (7)

(A) a compound represented by the following general formula (1);
(B) a polymer containing a repeating unit represented by the following general formula (2) and having a weight average molecular weight (Mw) of 10,000 or more and 1,000,000 or less;
A composition comprising:
(R ¹ ) nM (1)
(In Formula (1), R ¹ is ^one selected from a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cyclic alkyl group, an aryl group, an alkoxyl group, a carboxyl group, and an amino group, R ¹ present may be the same or different, n is 2 or 3, and is equal to the valence of M. M is a divalent or trivalent atom, and the compound represented by formula (1) is , Having at least one CM bond.)

(In formula (2), R ² and R ³ are one selected from a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cyclic alkyl group, an aryl group, an alkoxyl group, a carboxyl group, and an amino group. is there.) In claim 1,
The composition wherein M is aluminum. In claim 1 or claim 2,
The compound (A) is at least one selected from tridodecyl aluminum, trihexadecyl aluminum, tristetramethylhexadecyl aluminum, tri (1-phytyl) aluminum, and tri (3-cyclododecylpropyl) aluminum. ,Composition. In any one of Claims 1 to 3,
The polymer (B) is a composition that is poly (meth) acrylic acid or poly (meth) acrylic acid ester.   The water or oxygen scavenging composition according to any one of claims 1 to 4.   A cured product formed using the composition according to claim 1.   The electronic device which equipped the inside with the hardening body of Claim 6.

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