JP2012006991A - Polymer, composition, cured product and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a polymer capable of forming a cured body with little residual or generation of volatile components when sealing a sealed electronic device with a sealant, a composition containing the polymer, and formed from the composition The cured body and an electronic device including the cured body are provided.
The composition according to the present invention comprises a polymer (A) containing repeating units represented by the following general formulas (1) and (2), a compound (B) having two or more unsaturated bonds, It is characterized by containing.
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Description

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

  Electronic devices that are damaged by moisture, such as organic EL elements and liquid crystal display devices, need to be sealed with a sealant to prevent moisture from entering the device.

  For example, a liquid crystal display (Liquid Crystal Display; hereinafter referred to as “LCD”), which is a typical sealed electronic device, is manufactured by a liquid crystal dropping method (hereinafter also referred to as “ODF method”). The In the ODF method, a rectangular seal pattern is formed on one of two transparent substrates with electrodes by screen printing or the like, and then liquid crystal microdrops are dropped and applied into the frame of the transparent substrate with the sealant uncured. After the other transparent substrate is overlaid, the sealant is cured to produce an LCD.

  Sealing agents used for producing such a sealed electronic device can be broadly classified into three types: an ultraviolet curable type, an ultraviolet-heat combined curable type, and a thermal effect curable type (for example, see Patent Documents 1 to 3). .

JP 2006-23580 A JP 2010-20286 A JP-A-2005-2015

  However, with UV curable and UV-thermosetting sealants containing a photopolymerization initiator, the photopolymerization initiator may remain after being cured, or new decomposition products may be generated by UV irradiation. was there. On the other hand, with a heat-curable sealing agent that does not require a photopolymerization initiator, it is difficult to precisely control the thermosetting reaction, and low molecular weight components may remain in the cured cured sealant. .

  In any case, after the sealant is cured, if the photopolymerization initiator, low molecular weight components, or newly generated decomposition products remaining in the cured product diffuse into the electronic device, the charge transport that constitutes the electronic device It may be absorbed by organic materials such as materials, organic light-emitting materials, and liquid crystal materials to adversely affect display characteristics. In particular, when the decomposition product or low molecular weight component remaining in the sealant is a volatile component, the volatile component may gasify and cause volume expansion. In such a case, the electronic device may be deformed to break the sealing, thereby promoting the ingress of moisture and shortening the life of the electronic device.

  Therefore, some aspects of the present invention can form a cured body with less residual and generation of volatile components when a sealed electronic device is sealed with a sealant by solving the above-described problems. The present invention provides a polymer, a composition containing the polymer, a cured product formed from the composition, and an electronic device including the cured product.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
The composition according to the present invention comprises:
A polymer (A) containing repeating units represented by the following general formulas (1) and (2);
A compound (B) having two or more unsaturated bonds;
It is characterized by containing.
(In the above formulas (1) and (2), R ¹ and R ³ are at least selected from hydrogen, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group and a group represented by R ⁴ O—. R ⁴ is at least one selected from a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cyclic alkyl group and aryl group, and R ² is a single bond or a divalent group. Represents a hydrocarbon group, Ar represents an aryl group.)

[Application Example 2]
In the composition of Application Example 1,
The compound (B) can be a compound represented by the following general formula (3).
(R ⁵ ) nM (3)
(In the above formula (3), R ⁵ is at least one selected from a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group and group represented by R ⁶ O—. ⁵ may be the same or different, but at least two of the plurality of R ⁵ are groups having one or more unsaturated bonds, R ⁶ is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl And at least one selected from a group, a cyclic alkyl group, and an aryl group, n is an integer of 2 to 4, and is equal to the valence of M. M is a divalent to tetravalent atom.)

[Application Example 3]
In the composition of Application Example 2,
M in the general formula (3) may be aluminum.

[Application Example 4]
In the composition of any one of Application Examples 1 to 3,
The polymer (A) may have a weight average molecular weight of 300 or more and 100,000 or less.

[Application Example 5]
In the composition of any one of Application Examples 1 to 4,
A catalyst (C) for promoting the hydrosilylation reaction of the polymer (A) and the compound (B) can be further contained.

[Application Example 6]
In the composition of any one of Application Examples 1 to 5,
Benzothiazole, tris (2,4-di-t-butylphenyl) phosphite, 1-ethynyl-1-cyclohexanol, diethyl malate, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidone and N-vinyl It may further contain at least one stabilizer selected from -ε-caprolactam.

[Application Example 7]
The cured body according to the present invention is formed using the composition described in any one of Application Examples 1 to 6.

[Application Example 8]
An electronic device according to the present invention includes the cured body described in Application Example 7.

[Application Example 9]
The polymer according to the present invention is characterized by containing repeating units represented by the following general formulas (1) and (2).
(In the above formulas (1) and (2), R ¹ and R ³ are at least selected from hydrogen, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group and a group represented by R ⁴ O—. R ⁴ is at least one selected from a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cyclic alkyl group and aryl group, and R ² is a single bond or a divalent group. Represents a hydrocarbon group, Ar represents an aryl group.)

  The composition according to the present invention can be used as a sealing agent when forming a sealed electronic device. According to the composition of the present invention, it is possible to form a cured body (such as a coating film or a film) that suppresses diffusion of volatile components into the electronic device and has excellent adhesion between members. Furthermore, the composition according to the present invention can take an embodiment that does not contain a solvent. According to this aspect, since the solvent does not remain in the cured body, it is possible to form a cured body in which diffusion of the volatile component into the electronic device is further suppressed.

It is sectional drawing which shows typically an example of the organic EL element which concerns on this Embodiment. ^{1 is} a ¹ H-NMR spectrum diagram of poly (hydromethylsiloxane-co-benzylmethylsiloxane). FIG. ^{1 is} a ¹ H-NMR spectrum diagram of tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum. FIG.

  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. Polymer The polymer according to the present invention is characterized by including repeating units represented by the following general formulas (1) and (2).

In formula (1), R ¹ represents at least one selected from hydrogen, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, and a group represented by R ⁴ O—. R ⁴ represents at least one selected from a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cyclic alkyl group and aryl group. R ² represents a single bond or a divalent hydrocarbon group. Ar represents an aryl group.

In Formula (2), R ³ represents at least one selected from hydrogen, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, and a group represented by R ⁴ O—. R ⁴ represents at least one selected from a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cyclic alkyl group and aryl group.

  Examples of the alkyl group include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, hexadecyl group, tetramethylhexadecyl group, octadecyl group, and the like, 3, 3, 3- Examples thereof include a fluorinated alkyl group such as a trifluoropropyl group.

  Examples of the alkenyl group include a vinyl group, an octenyl group, a dodecenyl group, an octadecenyl group, and an allyl group.

  Examples of the alkynyl group include an ethynyl group, a propynyl group, and a phenylethynyl group.

  Examples of the cyclic alkyl group include a cyclohexyl group.

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

  The polymer according to the present embodiment, for example, a compound having a repeating unit represented by the following general formula (4) can be synthesized by the following method.

  Styrene is made into the quantitative ratio used as 0.1-0.5 mol with respect to 1 mol of polyhydrogensiloxane shown by following General formula (5). A catalyst prepared by dissolving a platinum-cyclovinylmethylmethylsiloxane complex in styrene in an amount of 2 to 2.3% by mass with respect to styrene is prepared as a catalyst, and this is dissolved in polyhydrogensiloxane at a temperature of 20 to 50 ° C. Drip in small portions. After completion of the dropwise addition, the mixture is sufficiently stirred, and the reaction solution is heat-treated at a temperature of 70 to 120 ° C., so that the weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography) is 9,000 to 14,000. The compound which has a repeating unit shown by the said General formula (4) whose number average molecular weight (Mn) is 6,000-9,000 can be manufactured. In addition, the compound from which the addition amount of styrene differs can be synthesize | combined by changing suitably the quantity of styrene with respect to polyhydrogensiloxane.

2. Composition The composition according to the present embodiment includes the above-described polymer (hereinafter also simply referred to as “polymer (A)”) and a compound (B) having two or more unsaturated bonds (hereinafter simply referred to as “compound”). (B) "). Hereinafter, each component constituting the composition according to the present embodiment will be described.

2.1. Polymer (A)
Since a polymer (A) is as having mentioned above, detailed description is abbreviate | omitted.

  The Si—H bond present in the polymer (A) can undergo an addition reaction (so-called hydrosilylation reaction) with the unsaturated bond present in the compound (B) described later. The composition according to the present embodiment can be cured by heating because the addition reaction can be promoted by heating to be crosslinked. In addition, since the composition according to the present embodiment can be thermally cured, it does not require a photopolymerization initiator necessary for ultraviolet curing, and does not generate decomposition products due to ultraviolet irradiation or the like. Moreover, since the composition according to the present embodiment can rapidly advance the addition reaction by heating, the possibility that a low molecular weight component remains in the cured body is low.

  The weight average molecular weight of the polymer (A) according to the present embodiment is preferably 300 or more and 100,000 or less, more preferably 500 or more and 50,000 or less. In the present invention, “weight average molecular weight” means a weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography). When the weight average molecular weight of the polymer (A) is in the above range, an appropriate viscosity can be imparted to the composition. Thereby, workability | operativity, such as application | coating and film-forming of the composition concerning this Embodiment, can be improved.

  The content of the polymer (A) in the composition according to the present embodiment is preferably 20% by mass to 90% by mass, more preferably 30%, when the total mass of the composition is 100% by mass. The mass is 80% by mass or more. When the content of the polymer (A) is in the above range, the composition can be imparted with an appropriate viscosity as described later, and workability such as coating and film formation when forming a cured product is good. Become.

2.2. Compound (B)
The composition according to the present embodiment contains a compound (B) having two or more unsaturated bonds. The Si—H bond present in the polymer (A) can undergo an addition reaction (so-called hydrosilylation reaction) to the unsaturated bond present in the compound (B). Then, when the two or more unsaturated bonds undergo the addition reaction, the polymer (A) can be cross-linked with the compound (B) and cured. The unsaturated bond present in the compound (B) may be a double bond or a triple bond, preferably a carbon-carbon unsaturated bond, more preferably a carbon-carbon double bond.

  The compound (B) is preferably a compound represented by the following general formula (3).

(R ⁵ ) nM (3)

In formula (3), R ⁵ is at least one selected from a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, and group represented by R ⁶ O—. R ⁶ is at least one selected from a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cyclic alkyl group and aryl group. Among these, R ⁵ is preferably a group represented by R ⁶ O—.

R ⁵ and R ⁶ may be linear or cyclic, and may have a branched chain. In the case where R ⁵ or R ⁶ is an alkenyl group or an alkynyl group, the position and number of double bonds and triple bonds are not particularly limited.

In the general formula (3), n is an integer of 2 to 4, and is equal to the valence of M. Accordingly, there are a plurality of R ⁵ . Here, a plurality of R ⁵ may be the same or different, but at least two of the plurality of R ⁵ have one or more unsaturated bonds. The position and number of unsaturated bonds in R ⁵ are not particularly limited. When the unsaturated bond is present in the R ^5, Si-H bonds present in the polymer (A) is capable of addition reaction to unsaturated bonds present in the R ⁵ (so-called hydrosilylation reaction). If at least two of the plurality of R ⁵ have one or more unsaturated bonds, the polymer (A) can be crosslinked by the compound (B) and cured by the addition reaction.

The carbon number of R ⁵ is not particularly limited, but is preferably 6-30, more preferably 10-20, and particularly preferably 12-20.

  Examples of the alkyl group include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, hexadecyl group, tetramethylhexadecyl group, octadecyl group and the like.

  Examples of the alkenyl group include octenyl group, dodecenyl group, octadecenyl group, allyl group and the like.

  Examples of the alkynyl group include an ethynyl group, a propynyl group, and a phenylethynyl group.

  Examples of the cyclic alkyl group include a cyclohexyl group.

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

  In the general formula (3), M is a divalent to tetravalent atom. Examples of such atoms include Group 2 elements, Group 4 elements, Group 12 elements, Group 13 elements, and Group 14 elements in the IUPAC periodic table. Specifically, Al, B, Mg, Zn, Ti, Zr, C, Si, Sn, Pb, etc. are mentioned.

  Specific examples of the compound represented by the general formula (3) include, for example, tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum, tri (2-dodecenoxy) aluminum, tri (vinyl carboxy). ) Aluminum, tri (dimethanolcyclohexanemonovinyl) aluminum, tri (β-citronelloxy) aluminum, tri (2,4-decadienoxy) aluminum, tri (13-docosenoxy) aluminum, tri (farnesyloxy) aluminum, tri (geranioxy) Aluminum, tri (nerol) aluminum, tri (oleyloxy) aluminum and the like can be mentioned.

Note that when M is a metal atom, the R ⁵ —M bond present in the compound (B) may have a function of trapping moisture by reacting with moisture. In such a case, the composition according to the present embodiment is more preferable because it can provide not only a sealing function for sealing but also a moisture absorption function capable of preventing moisture from entering the inside of the electronic device.

  When M is a metal atom, tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum is more preferable. Tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum has a structure represented by the following formula (6). Tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum is an alcohol that has a boiling point of 258 ° C. under 1 atm and is less likely to volatilize in the environment of use because it reacts with moisture. Is generated.

  The content of the compound (B) in the composition according to the present embodiment is preferably 10% by mass or more and 80% by mass or less, more preferably 20% by mass when the total mass of the composition is 100% by mass. % To 70% by mass. When the content of the compound (B) is within the above range, an appropriate viscosity as described later can be imparted to the composition, and workability such as coating and film formation when forming a cured product is good. Become.

2.3. Content ratio (W _A / W _B )
In the composition according to the present embodiment, the content of the polymer _{(A) (W} A) and the compound content of _{(B) (W} B) content ratio of _(W A / W _B) is preferably Is 0.25 or more and 9 or less, more preferably 0.4 or more and 5 or less, and particularly preferably 0.4 or more and 4 or less. When the content ratio (W _A / W _B ) is within the above range, the curability becomes good, and a cured product with more excellent mechanical strength can be obtained.

2.4. Other Additives To the composition according to the present embodiment, a catalyst (C) may be further added in order to promote the hydrosilylation reaction between the polymer (A) and the compound (B). The catalyst (C) is preferably a platinum complex or a rhodium complex. Examples of the platinum complex include a carbonylcyclovinylmethylsiloxane platinum complex, a platinum-octal / octanol complex, a cyclovinylmethylsiloxane platinum complex, a carbonyldivinylmethylplatinum complex, a divinyltetramethyldisiloxane platinum complex, and the like. Examples of the rhodium complex include tris (dibutyl sulfide) rhodium trichloride. As mentioned above, the illustrated catalyst (C) may be used alone or in combination of two or more.

  The content of the catalyst (C) in the composition according to the present embodiment is preferably 0.0001% by mass or more and 1% by mass or less, more preferably 100% by mass when the total mass of the composition is 100% by mass. It is 0.001 mass% or more and 0.1 mass% or less. When the content of the catalyst (C) is within the above range, not only the hydrosilylation reaction between the polymer (A) and the compound (B) can be promoted, but also the cured product obtained by curing the composition. This is preferable in that basic performance such as hygroscopicity and transparency is not impaired.

  A stabilizer may be further added to the composition according to the present embodiment. By further adding a stabilizer to the composition according to the present embodiment, gelation can be suppressed and storage stability is improved. Examples of the stabilizer include sulfur compounds, phosphorus compounds, alkyne compounds, maleic acid derivatives, nitrogen-containing compounds, and the like. Specifically, benzothiazole, tris (2,4-di-t-butylphenyl) phosphite, 1-ethynyl-1-cyclohexanol, diethyl malate, N-methylpyrrolidone, 1,3-dimethyl-2- Examples include imidazolidone and N-vinyl-ε-caprolactam (all available from Tokyo Chemical Industry Co., Ltd.). These stabilizers may be used alone or in combination of two or more. By using these stabilizers, the gelation time can be freely controlled, so that a composition having excellent storage stability can be easily obtained, and a good cured product is produced. be able to.

  The content of the stabilizer is preferably 0.01 parts by weight or more and 5 parts by weight or less, more preferably 0.05 parts by weight or more when the total weight of the composition excluding the stabilizer is 100 parts by weight. It is 0.05 parts by mass or less and particularly preferably 1 part by mass or less. When the content of the stabilizer is in the above range, the storage stability of the composition is improved, so that a sufficient pot life can be obtained and the curability of the composition is not impaired.

  Since it is desirable that the composition according to the present embodiment does not leave volatile components in the cured body to be formed, it is preferable not to add an organic solvent as much as possible. From the viewpoint of improving processability such as, an organic solvent can be added. 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.

2.5. Production method of composition The production method of the composition according to the present embodiment is not particularly limited, and the polymer (A) and the compound (B), and if necessary, the catalyst (C) and other additives are mixed. Can be manufactured. The method of mixing these components is not particularly limited, but polymer (A) is added little by little while stirring compound (B) (added with catalyst (C) and other additives as necessary). Then, the composition according to the present embodiment can be obtained by dissolving.

2.6. Physical Properties and Use of Composition The composition according to the present embodiment preferably has a viscosity at 20 ° C. of 20 to 500,000 cP. When the viscosity is within the above range, the composition can be directly applied to the element substrate by the ODF method or the dispensing method, and can be cured. This eliminates the need to prepare the composition according to the present embodiment in the form of a film-like molded body in advance and incorporate it into the device, 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 is possible. In addition, the said viscosity shows the value measured by the falling needle method.

  Since the composition according to the present embodiment can form a cured product containing the compound (B), when the compound (B) has a moisture trapping ability, it should be used for the purpose of trapping moisture. You can also. In such a case, the composition according to the present embodiment can be used as a moisture scavenger for organic EL elements, organic TFTs, organic solar cells, organic CMOS sensors, and the like, and particularly preferably used as a moisture scavenger for organic EL elements. It is done.

3. Cured body In the present invention, the “cured body” refers to a film whose viscosity or hardness has increased from that of the original composition by forming or molding the composition into a shape suitable for use and further heat-treating it. .

  The cured body according to the present embodiment can be obtained, for example, by applying the composition onto a substrate such as a glass substrate to form a film, and then heating and curing the composition.

  Examples of the coating method include known methods such as a spin coater, a roll coater, a spray coater, a dispenser, and a method using an inkjet apparatus.

  Although the temperature in the case of hardening is not restrict | limited in particular, For example, it is 50 to 150 degreeC.

  Although the shape of the obtained hardening body is not restrict | limited in particular, For example, it has a film shape. When this hardening body has a film shape, the film thickness is 5-100 micrometers, for example.

  The content of the polymer (A) in the cured product according to the present embodiment is preferably 20% by mass or more and 90% by mass or less, more preferably 30% by mass when the total mass of the cured product is 100% by mass. More than 80 mass%. It is preferable for the content of the polymer (A) to be within the above range since the mechanical strength of the cured product is increased.

4). Electronic Device The electronic device according to the present embodiment includes the cured body inside and / or the inner periphery of the electronic device. The cured body can be mounted on any electronic device as long as it is a sealed electronic device that dislikes the entry of moisture or the like. 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, an organic EL element 100 includes an organic EL layer 10, a structure 20 that houses the organic EL layer 10 and shields it from the outside air, and a sealing agent layer 30 formed in the structure 20. And consist 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 sealing agent layer 30 is a cured body of the composition. As shown in FIG. 1, the sealing agent layer 30 is preferably formed so as to be in close contact with the organic EL layer 10. Since the sealing agent layer 30 is a cured body in which volatile components remain and are not generated, the display characteristics of the organic EL layer 10 are not impaired. Moreover, the sealing agent layer 30 can protect the organic EL layer 10 while preventing moisture from entering 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 adhesive 26 is not particularly limited, but a cured product of the composition may be used. The structure of the structure 20 is not particularly limited as long as the organic EL layer 10 can be accommodated.

5). Example 5.1. Synthesis of Polymer (A) Poly (hydromethylsiloxane-co-benzylmethylsiloxane) (hereinafter also referred to as “ST-PMHS”) was synthesized as follows.

  A thermometer, a dropping funnel and a three-way cock are placed in a 1 L three-necked flask, and 600 g of methyl hydrogen silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KF-99”) is flown through the flask with dry nitrogen. Equivalent to 0.0 mmol). On the other hand, 208 g (corresponding to 2.00 mmol) of styrene (Mitsubishi Chemical Corporation) in which 2 to 2.3 wt% platinum-cyclovinylmethylmethylsiloxane complex (808 μL, 4.02 mmol) was dissolved was added to the dropping funnel and reacted. The solution was added dropwise little by little so that the liquid temperature did not exceed 80 ° C. It stirred for 30 minutes after completion | finish of dripping. The reaction solution was decompressed to 5 mmHg and treated at a bath temperature of 100 ° C. (solution solution temperature of 70 to 80 ° C.) for 1 hour. Thus, ST25-PMHS (808 g, 100%) to which 25% styrene was added was obtained as a colorless transparent liquid.

FIG. 2 is a ¹ H-NMR spectrum of the resulting poly (hydromethylsiloxane-co-benzylmethylsiloxane). ^{In 1} H-NMR measurement, toluene-d8 (near peak δ2.1) was used as an internal standard substance. FIG. 2 shows that the obtained compound is a polymer represented by the following general formula (4).

  Further, using the same method as described above, ST10-PMHS, ST30-PMHS, and ST50-PMHS having different styrene addition amounts were synthesized by appropriately changing the amount of styrene with respect to polyhydrogensiloxane. In addition, the number after ST shows the addition amount of styrene. The ST-PMHS thus obtained was used as the polymer (A) in the following examples and comparative examples.

5.2. Synthesis of Compound (B) Tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum was synthesized as follows.

  In a 500 mL three-necked flask, 162.0 g [756 mmol] of trimethylolpropane diallyl ether (manufactured by Daiso Corporation, trade name “Neoallyl T-20”) was charged, and 50.0 g [252.7 mmol of triisobutylaluminum was added little by little with stirring. ] Was dropped in the glow box. After stirring for 1 hour, the mixture was stirred at 120 ° C. for 90 minutes. While maintaining the temperature at 120 ° C., the unreacted raw material was distilled off while reducing the pressure with a vacuum pump, and the mixture was cooled to room temperature to obtain 164.0 g of tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum. Obtained as a colorless transparent oil. The yield was quantitative.

FIG. 3 is a ¹ H-NMR spectrum of the resulting tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum. ^{In 1} H-NMR measurement, toluene-d8 (near peak δ2.1) was used as an internal standard substance. FIG. 3 showed that the obtained compound had a chemical structure represented by the following formula (6).

  The tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum thus obtained was used as compound (B) in the following examples and comparative examples.

5.3. Production of Film Films to be evaluated in Examples 1 to 5 and Comparative Examples 1 to 3 were produced as follows.

  First, in a glove box with a dew point of −60 ° C. or less and an oxygen of 5 ppm or less, a predetermined amount of the compound (B) and the polymer (A) are mixed so as to have the composition shown in Table 1, and sufficiently stirred to be uniform. Solution. A predetermined amount of stabilizer was added thereto and further stirred until a uniform solution was obtained. Thereafter, a predetermined amount of catalyst (C) was added to obtain compositions A to G described in Table 1.

  Subsequently, the obtained composition was apply | coated on the glass substrate, it was made to thermoset by heating at the temperature of 80 degreeC for 60 minutes, and the film was shape | molded. The compositions of compositions A to G are shown in Table 1.

In addition, the abbreviation of the component in Table 1 represents the following component, respectively.
"ST-PMHS"; poly (hydromethylsiloxane-co-benzylmethylsiloxane)
“PMHS”; polymethylhydrogensiloxane “TMDE-3”; tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum “TMPDE”; trimethylolpropane diallyl ether “VC”; N-vinyl-ε-caprolactam

5.4. Evaluation method About each film obtained by said "5.3. Production of a film", the weight reduction rate at the time of hardening, fluidity | liquidity, and glass adhesiveness were evaluated by the following method. The thermal fluidity was evaluated by separately preparing a film by the following method. The results are shown in Table 1.

(1) Weight reduction rate (%)
1.00 g of each of the solutions of Examples and Comparative Examples was applied to a glass petri dish having an inner diameter of 5 cm and baked at 80 ° C. for 60 minutes. The film weight (W [anneal] g) after firing was measured, and the weight reduction rate relative to the coating weight (1.00 g) was calculated from the following formula (7). The results are also shown in Table 1.
Weight reduction rate (%) = {(1.00−W [anneal]) / 1.00} × 100 (7)

(2) Thermal fluidity (heat resistance)
First, an appropriate amount of any one of Compositions A to G was put in a sample tube and heated at 80 ° C. for 60 minutes to produce a film having a thickness of 2 mm on 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) Glass Adhesiveness Regarding the film obtained in “5.3. Production of Film”, the film that did not peel from the glass in the atmosphere was “◯”, and the film that peeled was “x”. In addition, when applying to uses, such as a display material in which the adhesiveness to a glass substrate is requested | required, a thing with favorable glass adhesiveness is preferable.

5.5. Evaluation results From the results in Table 1, according to the films formed from the compositions of Examples 1 to 5, since any composition contains the polymer (A) and the compound (B), the weight reduction rate. It has been found that a film having a low heat resistance and excellent glass adhesion can be obtained.

  Moreover, in the film formed from the composition of Comparative Example 1 containing a polymer having a structure not containing the repeating unit represented by the general formulas (1) and (2), under curing conditions of 80 ° C. for 60 minutes, A 9-10% weight loss was seen, suggesting the generation of volatile components.

  In addition, in the film formed from the composition of Comparative Examples 2-3 containing only any one of a polymer (A) and a compound (B), the bridge | crosslinking at the time of hardening becomes inadequate, and heat resistance and glass adhesion It turned out to be inferior.

  From the above results, it was found that the film formed from the composition containing the polymer (A) and the compound (B) had a low weight loss rate and was excellent in heat resistance and glass adhesion. Such a film is particularly useful in applications as a sealant in sealing a sealed electronic device.

  The present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

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

Claims (9)

A polymer (A) containing repeating units represented by the following general formulas (1) and (2);
A compound (B) having two or more unsaturated bonds;
A composition comprising:
(In the above formulas (1) and (2), R ¹ and R ³ are at least selected from hydrogen, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group and a group represented by R ⁴ O—. R ⁴ is at least one selected from a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cyclic alkyl group and aryl group, and R ² is a single bond or a divalent group. Represents a hydrocarbon group, Ar represents an aryl group.) In claim 1,
The compound (B) is a composition represented by the following general formula (3).
(R ⁵ ) nM (3)
(In the above formula (3), R ⁵ is at least one selected from a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group and group represented by R ⁶ O—. ⁵ may be the same or different, but at least two of the plurality of R ⁵ are groups having one or more unsaturated bonds, R ⁶ is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl And at least one selected from a group, a cyclic alkyl group, and an aryl group, n is an integer of 2 to 4, and is equal to the valence of M. M is a divalent to tetravalent atom.) In claim 2,
The composition in which M in the general formula (3) is aluminum. In any one of Claims 1 to 3,
The polymer (A) has a weight average molecular weight of 300 or more and 100,000 or less. In any one of Claims 1 thru | or 4,
A composition further comprising a catalyst (C) for promoting a hydrosilylation reaction between the polymer (A) and the compound (B). In any one of Claims 1 thru | or 5,
Benzothiazole, tris (2,4-di-t-butylphenyl) phosphite, 1-ethynyl-1-cyclohexanol, diethyl malate, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidone and N-vinyl A composition further comprising at least one stabilizer selected from ε-caprolactam.   A cured body formed using the composition according to any one of claims 1 to 6.   An electronic device comprising the cured body according to claim 7. The polymer containing the repeating unit shown by the following general formula (1) and (2).
(In the above formulas (1) and (2), R ¹ and R ³ are at least selected from hydrogen, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group and a group represented by R ⁴ O—. R ⁴ is at least one selected from a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cyclic alkyl group and aryl group, and R ² is a single bond or a divalent group. Represents a hydrocarbon group, Ar represents an aryl group.)