JP2015120880A - Electronic device, organic electroluminescence(el) element, and liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electronic device such as an organic EL element and a liquid crystal display element, which has an adhesive layer formed of an adhesive composition that removes moisture in the element and reduces intrusion of moisture into the element.SOLUTION: The electronic device has an adhesive layer 180 formed of an adhesive composition that comprises (A) a compound having a hydrolyzable structure and (B) at least one compound selected from an acid generator and a base generator.

Description

  The present invention relates to an electronic device, an organic EL element, and a liquid crystal display element.

  One of electronic devices that has been actively developed in recent years is an organic electroluminescence (EL) element. The organic EL element is a simple device having a laminated structure composed of an anode / organic light emitting layer / cathode as a basic structure, and is a light emitting element capable of obtaining bright light emission, but the problem that the organic light emitting layer is easily affected by moisture have.

  In other words, as the driving period becomes longer, the organic EL element is affected by moisture that has entered the element, and there is concern about the formation of so-called dark spots, and the light emission characteristics such as luminance and light emission efficiency gradually decrease. Have concerns. For this reason, in an organic EL element, it is necessary to remove moisture in the element and use it in a sealed state, but it is difficult to completely seal such an electronic device by sealing.

  Similarly to organic EL elements, liquid crystal display elements are known as electronic devices that are being actively developed. The liquid crystal display element has a configuration in which liquid crystal is sandwiched between a pair of substrates that are spaced apart. Since the liquid crystal display element may cause a display defect due to the influence of moisture on the liquid crystal between the substrates, it is used in a sealed state in which moisture is prevented from entering the element from the outside like the organic EL element. Is required.

  Therefore, a technique is known in which a moisture trapping agent made of a specific organometallic compound is placed in the electronic device in advance, and the moisture inside the electronic device is kept in a low humidity environment by trapping moisture in the moisture trapping agent (for example, Patent Document 1).

Japanese Patent No. 3936151

Electronic devices such as organic EL elements and liquid crystal display elements are required to be used in a sealed state in which moisture in the element is removed and moisture is prevented from entering the element from the outside.
For this reason, in an organic EL element and a liquid crystal display element, an adhesive composition that can seal the element and protect the organic light emitting layer and the liquid crystal from moisture entering from the outside is used. For example, in an organic EL element, a sealing material formed from an adhesive composition is disposed around an organic light emitting layer so as to protect the organic light emitting layer. Moreover, in the liquid crystal display element, a sealing material formed from an adhesive composition is disposed between substrates around the display portion.

  However, the conventional adhesive composition does not have a sufficient function of removing moisture in the element and a function of suppressing moisture from entering the element. For this reason, in an organic EL element and a liquid crystal display element, deterioration of the element due to moisture or generation of a defect may be a problem.

  The present invention has been made in view of the above problems. That is, an object of the present invention is to provide an adhesive layer formed from an adhesive composition that removes moisture in an element and reduces moisture intrusion into the element in electronic devices such as organic EL elements and liquid crystal display elements. It is providing the electronic device which has this.

The present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that the above problems can be solved by an adhesive composition having the following configuration, and have completed the present invention.
For example, the present invention relates to the following [1] to [7].

  [1] An adhesive layer formed from an adhesive composition containing (A) a compound having a hydrolyzable structure and (B) at least one compound selected from an acid generator and a base generator. Electronic device having.

  [2] The compound (A) is at least one compound (A1) selected from a compound having a structural moiety represented by the formula (A1-1) and a compound represented by the formula (A1-2), carvone At least selected from the group consisting of acid anhydride (A2), and at least one compound (A3) selected from the compound represented by formula (A3-1) and the compound represented by formula (A3-2) The electronic device according to [1], wherein the electronic device is one type and the compound (B) is an acid generator.

[In formula (A1-1), R ^{1 to} R ⁵ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group or a carbon number. 1 to 18 organic groups, and two or more groups selected from R ³ , R ⁴ and R ⁷ are bonded to each other to form a cyclic structure together with the carbon atoms to which they are directly bonded. N is 0 or an integer of 1 to 18, and * represents a bonding position; in formula (A1-2), R ¹ is a hydrogen atom or an organic group having 1 to 18 carbon atoms; Each ⁸ is independently an organic group having 3 to 10 carbon atoms. ]

[In the formulas (A3-1) and (A3-2), X represents a silicon atom, a titanium atom or a zirconium atom; R ¹ represents a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, a 3,4-epoxy. An organic group having at least one group selected from a cyclohexyl group, a mercapto group, and an isocyanate group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a benzyl group; R ² is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, and an optionally substituted carbon. Aromatic hydrocarbon group of number 6-14, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, or merca P is an integer of 0-6; r is an integer of 0-2; s is an integer of 1-30. ]

  [3] The compound (A) is at least one selected from the carboxylic acid anhydride (A2), the compound represented by the formula (A3-1), and the compound represented by the formula (A3-2). The electronic device according to [1], wherein the electronic device is at least one selected from the group consisting of the compound (A3), and the compound (B) is a base generator.

[4] The electronic device according to any one of [1] to [3], wherein the adhesive composition further contains (C) a polymerizable compound.
[5] The electronic device according to any one of [1] to [4], which is an organic EL element or a liquid crystal display element.

  [6] The electronic device is fixed to the substrate by the substrate, the organic EL layer provided on the substrate, the adhesive layer formed on at least the periphery of the organic EL layer on the substrate, and the adhesive layer. The electronic device according to [5], wherein the electronic device is an organic EL element comprising a substrate and a sealing substrate for housing the organic EL layer together with the adhesive layer and blocking from the outside air.

  [7] The electronic device according to [6], wherein a gas barrier film covering the entire surface of the organic EL layer is provided.

  According to the present invention, an electronic device such as an organic EL element and a liquid crystal display element has an adhesive layer formed of an adhesive composition that removes moisture in the element and reduces moisture intrusion into the element. An electronic device can be provided. The adhesive composition is a liquid crystal included in organic EL elements such as organic EL lighting and organic EL display elements that can suppress the generation of dark spots even when driven for a long time, TVs, portable information devices, and the like that require high reliability. It can be suitably used as a component of a display element.

FIG. 1 is a cross-sectional view schematically showing an example of the organic EL element of the present invention. FIG. 2 is a cross-sectional view schematically showing an example of the liquid crystal display element of the present invention.

  Adhesive composition used in the present invention, an adhesive layer such as a sealing material formed using the composition, and an electronic device such as an organic EL element and a liquid crystal display element having the adhesive layer such as the sealing material And will be described.

[Adhesive composition]
The adhesive composition used in the present invention contains a compound (A) having a hydrolyzable structure and at least one compound (B) selected from an acid generator and a base generator. Moreover, it is preferable that the said composition further contains a polymeric compound (C).

  In the following description, the compound (A) and the compound (B) are also referred to as a water trapping agent (A) and an acid / base generator (B), respectively, and the water trapping agent (A) and the acid / base generator (B). ) And the polymerizable compound (C) are also referred to as a component (A), a component (B), and a component (C), respectively. The same applies to other examples unless otherwise specified.

[Moisture capture agent (A)]
The moisture trapping agent (A) is a compound having a structure that can be hydrolyzed in the presence of an acid or a base, for example. As the moisture capturing agent (A), for example, at least one compound (A1) selected from a compound having a structural moiety represented by the formula (A1-1) and a compound represented by the formula (A1-2), Carboxylic anhydride (A2), and at least one compound (A3) selected from a compound represented by formula (A3-1) and a compound represented by formula (A3-2) can be mentioned. Each of these compounds (A1) to (A3) may be used alone or in combination of two or more. In the following description, the compounds (A1) to (A3) are also referred to as moisture trapping agents (A1) to (A3), respectively.

<Moisture capture agent (A1)>
The moisture capturing agent (A1) is at least one compound selected from a compound having a structural moiety represented by the formula (A1-1) and a compound represented by the formula (A1-2). The moisture trapping agent (A1) is stable with low reactivity with water under neutral and basic conditions, but easily causes hydrolysis reaction in the presence of an acid.

In formula (A1-1), R ^{1 to} R ⁵ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms; R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group or 1 carbon atom. -18 organic groups; two or more groups selected from R ³ , R ⁴ and R ⁷ are bonded together to form a cyclic structure together with the carbon atoms to which they are directly bonded. N is 0 or an integer of 1 to 18; * indicates a bonding position. In formula (A1-2), R ¹ is a hydrogen atom or an organic group having 1 to 18 carbon atoms; R ⁸ is each independently an organic group having 3 to 10 carbon atoms.

In addition, in description of each formula which concerns on a moisture capture agent (A1), unless otherwise mentioned,
Examples of the “organic group having 1 to 18 carbon atoms” include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, n-octyl, 2-ethylhexyl. , Decyl, dodecyl, octadecyl or the like linear or branched alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms; cycloalkyl having 3 to 12 carbon atoms such as cyclohexyl or methylcyclohexyl A cycloalkyl group-substituted alkyl group having 4 to 18 carbon atoms such as cyclohexylmethyl or cyclohexylethyl; a phenyl group; an aralkyl group having 7 to 18 carbon atoms such as a phenyl-substituted alkyl group (eg, benzyl group or phenethyl group); A group in which a part of these groups is substituted with an oxygen atom (hereinafter also referred to as “oxygen atom substituent”); ; Vinyl group, an allyl group, (meth) acryloyloxy group, oxiranyl group, oxetanyl group, a glycidyl group; include carboxyl group, also can be a group represented by the following formula G1 to G7;
Examples of the “organic group having 3 to 10 carbon atoms” include carbon atoms having at least one group selected from “vinyl group, allyl group, (meth) acryloyloxy group, oxiranyl group, oxetanyl group and glycidyl group”. The organic group of 3-10 is mentioned, Moreover, group represented by the following formula g1-g7 can also be mentioned.

In the above formulas g1 to g7, * represents a bonding position.

  Examples of the oxygen atom substituent include alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, propoxymethyl, and butoxymethyl; alkanoyloxyalkyl groups such as acetoxymethyl and acetoxyethyl; aryloxyalkyl groups such as phenoxymethyl and phenoxyethyl; An alkoxy group such as methoxy; an aryloxy group such as phenoxy; and a hydroxyalkyl group such as hydroxymethyl.

In formula (A1-1), the total number of carbon atoms of the groups represented by R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ (when n is 0, it is represented by R ^{2 to} R ⁵ . The total number of carbon atoms of the groups to be formed is preferably 0 to 18, more preferably 0 to 12, from the viewpoint of water absorption ability and solubility.

Further, two or more groups selected from R ³ , R ⁴ and R ⁷ (when n = 0, R ³ and R ⁴ ) are bonded to each other, together with the carbon atom to which they are directly bonded. The ring structure may be formed. Examples of the cyclic structure include a cyclohexane ring and a cyclopentane ring.

In formula (A1-1), R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom.
In formula (A1-1), R ^{2 to} R ⁵ each independently represent a hydrogen atom, the above-described alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a cyclohexane having 4 to 18 carbon atoms. It is preferably an alkyl group-substituted alkyl group, a phenyl group, an aralkyl group having 7 to 18 carbon atoms, or an oxygen atom substituent, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a hydrogen atom. It is more preferable.

In formula (A1-1), R ^{6 to} R ⁷ each independently represent a hydrogen atom, a hydroxyl group, the above-described alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or 4 to 18 carbon atoms. A cycloalkyl group-substituted alkyl group, a phenyl group, an aralkyl group having 7 to 18 carbon atoms, an oxygen atom substituent, a vinyl group, an allyl group, a (meth) acryloyloxy group, an oxiranyl group, an oxetanyl group, a glycidyl group, a carboxyl group, It is preferably a group represented by the above formulas g1 to g7, and more preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or a group represented by the above formulas g1 to g2.

R ^{1 to} R ⁷ are preferably the above atoms or groups from the viewpoint of water absorption ability as a moisture trapping agent and compatibility with other components.
In formula (A1-1), n is 0 or an integer of 1 to 18, preferably 0 or 1, and more preferably 1. When n is an integer of 2 or more, R ⁶ and R ⁷ may be the same or different.
In formula (A1-2), R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁸ is preferably independently a group represented by the above formulas g1 to g7.

<< Compound having a structural moiety represented by the formula (A1-1) >>
As a compound which has a structure part represented by a formula (A1-1), the compound represented by a following formula is mentioned, for example. Specific examples of this compound include compounds represented by the following formula (A1-i), formula (A1-ii), and formula (A1-iii).

In the formula, A is a structural moiety represented by the formula (A1-1); Y is a hydroxyl group-containing compound (a3) described later having p (p ≧ 2) hydroxyl groups in one molecule; Residues excluding m (2 ≦ m ≦ p) hydroxyl groups; m is an integer of 2 to p.

  Examples of the compound having a structural moiety represented by the formula (A1-1) are obtained by reacting an ortho ester (a1), a polyhydric alcohol (a2), and a hydroxyl group-containing compound (a3) described below. Compounds.

Orthoester (a1)
The ortho ester (a1) is a compound represented by the formula (a1).

In the formula (a1), R ¹ is a hydrogen atom or an organic group having 1 to 18 carbon atoms; each of three Ras is independently an organic group having 1 to 18 carbon atoms. The organic group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a substituted alkyl group having 4 to 18 carbon atoms. A linear or branched alkyl group having 1 to 6 carbon atoms is more preferable.

Examples of the orthoester (a1) include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, methyl orthoacetate, ethyl orthoacetate, methyl orthopropionate, ethyl orthopropionate, methyl orthobutyrate, orthobutyric acid. Ethyl is mentioned. Among these, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate are preferable.
Orthoester (a1) may be used individually by 1 type, and may use 2 or more types together.

Polyhydric alcohol (a2)
As a polyhydric alcohol (a2), the compound which has 2 or more of hydroxyl groups in 1 molecule is mentioned, for example, The compound represented by a formula (a2-1) is preferable. Specific examples include α-glycol having two hydroxyl groups in one molecule and a compound having two or more hydroxyl groups in one molecule other than α-glycol.

In formula (a2-1), R ^{2 to} R ⁵ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms. R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 18 carbon atoms. Two or more groups selected from R ³ , R ⁴ and R ⁷ may be bonded to each other to form a cyclic structure together with the carbon atom to which they are directly bonded. R ^{2 to} R ⁷ in formula (a2-1) have the same meanings as the same symbols in formula (A1-1), and preferred examples are also the same as those described in formula (A1-1).

In formula (a2-1), n is 0 or an integer of 1 to 18, preferably 0 or 1, and more preferably 1. When n is an integer of 2 or more, R ⁶ and R ⁷ may be the same or different.

  α-glycol in which n is 0 is preferred. α-Glycol has two adjacent hydroxyl groups. Therefore, the reaction between the ortho ester and α-glycol proceeds efficiently, which is suitable for the production of a moisture trapping agent.

  Examples of α-glycol include ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 1,2-hexanediol, 1,2-dodecanediol, 1,2- Hydrolyzate of dihydroxycyclohexane, pinacol, long chain alkyl monoepoxide; fatty acid monoglyceride (α form) such as glycerin monoacetate (α form), glycerin monostearate (α form); 3-ethoxypropane-1,2-diol , 3-phenoxypropane-1,2-diol. Among these, ethylene glycol, 1,2-propylene glycol, and 1,2-hexanediol are preferable.

  A compound in which n is 1 is particularly preferred. The said compound has two or three or more hydroxyl groups which adjoined like the alpha-glycol mentioned above. Therefore, the reaction between the ortho ester and the compound proceeds efficiently, which is suitable for the production of a moisture trapping agent.

  Examples of the compound in which n is 1 include neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 2- Ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3-propane Diol, (2-allyloxymethyl) -2-ethylpropane-1,3-diol, 2- (hydroxymethyl) -2-ethylpropane-1,3-diol, glycerin, 2-phenoxypropane-1,3-diol Diol, 2-methyl-2-phenylpropane-1,3-diol, 1,3-propylene glycol, 1,3-butylene glycol, dimethylolpropylene Acid, dimethylolbutanoic acid, 2-ethyl-1,3-octanediol, 1,3-dihydroxycyclohexane; fatty acid monoglycerides (β form) such as glycerin monoacetate (β form) and glycerin monostearate (β form) Is mentioned. Among these, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexane Diol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, (2-allyloxy Particularly preferred are methyl) -2-ethylpropane-1,3-diol, 2- (hydroxymethyl) -2-ethylpropane-1,3-diol, and glycerin.

Hydroxyl-containing compound (a3)
The hydroxyl group-containing compound (a3) is a compound having two or more hydroxyl groups in one molecule.
When the hydroxyl group-containing compound (a3) is a compound having two or more hydroxyl groups in one molecule, for example, from the polyhydric alcohol (a2) such as a compound represented by the formula (a2-1) A hydroxyl group-containing compound (a3) can also be selected and used. In that case, it is preferable that the compound selected as the hydroxyl group-containing compound (a3) is selected from compounds other than the compound selected as the polyhydric alcohol (a2).

  Examples of the hydroxyl group-containing compound (a3) include a compound having 2 hydroxyl groups in one molecule and a compound having 3 or more, preferably 3 to 40 hydroxyl groups in one molecule.

  Examples of the compound having two hydroxyl groups include 1,4-butanediol, 1,4-dihydroxycyclohexane, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, and 3-methyl. 1,5-pentanediol, 1,4-dimethylolcyclohexane, tricyclodecane dimethanol, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate [this is hydroxy Corresponds to an ester of pivalic acid and neopentyl glycol], bisphenol A, bisphenol F, bis (4-hydroxyhexyl) -2,2-propane, bis (4-hydroxyhexyl) methane, 3,9-bis (1 , 1-Dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxa Pyro [5,5] undecane, diethylene glycol, triethylene glycol, tetra or higher polyethylene glycol, dipropylene glycol, tripropylene glycol, tetra or higher polypropylene glycol, hydroxyl groups at both ends formed by copolymerization of ethylene oxide and propylene oxide A linear polyester having hydroxyl groups at both ends, such as a polycaprolactone diol, polycarbonate diol, and a diepoxide carboxylic acid adduct.

  Examples of the compound having three or more hydroxyl groups include glycerin, diglycerin, triglycerin, pentaerythritol, dipentaerythritol, sorbitol, mannitol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris (2-hydroxy). Ethyl) isocyanurate, gluconic acid, polymers containing 3 or more hydroxyl groups (polyesters containing 3 or more hydroxyl groups, polyethers, acrylic polymers, ketone resins, phenol resins, epoxy resins, urethane resins, polyvinyl acetates) Saponified polyvinyl alcohol, natural sugars such as glucose, etc.).

  As the hydroxyl group-containing compound (a3), a compound having a molecular weight in the range of 90 to 100,000, particularly 90 to 5,000 is preferable. The hydroxyl group-containing compound (a3) is preferably a compound having a hydroxyl value in the range of 20 to 1850 mgKOH / g, particularly 40 to 1650 mgKOH / g.

Reaction ratio Orthoester (a1), polyhydric alcohol (a2), and hydroxyl group-containing compound (a3) are reacted to produce a water scavenger (A1). In this case, orthoester (a1) and polyhydric alcohol (a2) are produced. ) And the hydroxyl group-containing compound (a3) are not particularly limited.

  For example, the amount of the ortho ester (a1) is 0.01 to 10 mol, preferably 0.05 to 5 mol, more preferably 0.1 to 2 with respect to 1 mol equivalent of the hydroxyl group in the hydroxyl group-containing compound (a3). The ratio of the polyhydric alcohol (a2) in the range of 0.01 to 10 mol, preferably 0.05 to 5 mol, more preferably 0.1 to 2 mol. It is appropriate to use it from the viewpoint of easy control of the molecular weight. When the hydroxyl group-containing compound (a3) is selected from the polyhydric alcohol (a2), the compound selected as the hydroxyl group-containing compound (a3) is a compound other than the compound selected as the polyhydric alcohol (a2). Selected.

  The moisture trapping agent (A1) can be obtained by subjecting three components of an ortho ester (a1), a polyhydric alcohol (a2), and a hydroxyl group-containing compound (a3) to a condensation reaction. For example, the above-mentioned three components are usually used in the presence of an organic solvent and an acid catalyst such as formic acid, usually at room temperature to 250 ° C., preferably 70 to 200 ° C. for 1 hour to 20 hours. It can manufacture suitably by carrying out a condensation reaction by heating to the extent. Moreover, you may convert the group which the compound obtained by the above method has into another group by a well-known method. For the synthesis method, for example, International Publication No. 01/021611 pamphlet can be referred to.

  In this way, the water scavenger having a structure in which the hydroxyl group in the hydroxyl group-containing compound (a3) is blocked by a 5-membered ring or a 6-membered ring formed from the ortho ester (a1) and the polyhydric alcohol (a2). (A1) can be obtained.

Specific examples of the compound having the structural moiety represented by the formula (A1-1) Specific examples of the compound having the structural moiety represented by the formula (A1-1) include, for example, the formula (A1-i), the formula ( A1-ii) and a compound represented by the formula (A1-iii) are mentioned.

In formula (A1-i), Y ¹ is an m-valent residue obtained by removing m (2 ≦ m ≦ p) hydroxyl groups from a compound having p (p = 2 to 6) hydroxyl groups in one molecule. It is. R ¹ to R ⁷ and n have the same meanings as R ¹ to R ⁷ and n in formula (A1-1). The above compound is synthesized by using, for example, an orthoester of formula (a1), a polyhydric alcohol of formula (a2-1), and a compound having 2 to 6 hydroxyl groups in one molecule as raw materials. Can do.

In formula (A1-ii), Y ² is a divalent residue obtained by removing two hydroxyl groups from a compound having two hydroxyl groups in one molecule. R ¹ to R ⁷ and n have the same meanings as R ¹ to R ⁷ and n in formula (A1-1). The above compound can be synthesized by using, for example, an ortho ester of the formula (a1), a polyhydric alcohol of the formula (a2-1), and a compound having two hydroxyl groups in one molecule as raw materials.

In formula (A1-iii), Y ³ is a tetravalent residue obtained by removing four hydroxyl groups from a compound having four hydroxyl groups in one molecule. R ¹ to R ⁷ and n have the same meanings as R ¹ to R ⁷ and n in formula (A1-1). The above compound can be synthesized by using, for example, an ortho ester of the formula (a1), a polyhydric alcohol of the formula (a2-1), and a compound having four hydroxyl groups in one molecule as raw materials.

Specific examples of the compound represented by the formula (A1-2) Specific examples of the compound represented by the formula (A1-2) include compounds represented by the following formula.

<Moisture capture agent (A2)>
The moisture trapping agent (A2) is a carboxylic acid anhydride, and examples thereof include monocarboxylic acid anhydrides, dicarboxylic acid anhydrides, and tetracarboxylic dianhydrides. The moisture scavenger (A2) is stable with low reactivity with water under neutral conditions, but easily causes a hydrolysis reaction in the presence of an acid or a base.

<Anhydride of monocarboxylic acid>
Examples of monocarboxylic acid anhydrides include trifluoroacetic anhydride, benzoic anhydride, isatoic anhydride, isopentanoic anhydride, isobutyric anhydride, n-valeric anhydride, crotonic anhydride, and the like. . The carbon number of the monocarboxylic acid anhydride is preferably 4 to 20, more preferably 4 to 14, from the viewpoint of the volatility of the carboxylic acid that can be generated by hydrolysis.

Monocarboxylic acid anhydrides may be used alone or in combination of two or more.
<Dicarboxylic anhydride>
As the dicarboxylic acid anhydride, a compound represented by the formula (A2-1) can be given.

In formula (A2-1), Ra is a divalent organic group such as an aliphatic group, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and a “aromatic group directly Or a non-condensed polycyclic aromatic group connected to each other by a bridging member (eg, —O—, —CO—, —S—, —SO ₂ —, an alkylene group, —C (CF ₃ ) ₂ —) ” A divalent group selected from: The carbon number of Ra is usually 1-30, but preferably 4-30, more preferably 6-18, from the viewpoint of the volatility of the dicarboxylic acid that can be generated by hydrolysis.

Examples of the dicarboxylic acid anhydride include aliphatic dicarboxylic acid anhydrides, alicyclic dicarboxylic acid anhydrides, and aromatic dicarboxylic acid anhydrides.
Aliphatic dicarboxylic acid anhydrides include, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and other aliphatic saturated dicarboxylic acid anhydrides; maleic acid, fumaric acid And anhydrides of aliphatic unsaturated dicarboxylic acids such as itaconic acid, mesaconic acid and citraconic acid.

  Examples of the alicyclic dicarboxylic acid anhydride include alicyclic dicarboxylic acid anhydrides such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and 4-methylcyclohexanedicarboxylic acid anhydride.

An aromatic dicarboxylic acid anhydride refers to a dicarboxylic acid anhydride of an organic compound in which at least two carboxyl groups are bonded to an aromatic ring. Examples of the aromatic dicarboxylic acid anhydride include phthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, 2,3-dicarboxyphenyl phenyl ether, 3,4-dicarboxyphenyl phenyl ether, 2,3-biphenyldicarboxylic acid, 3,4-biphenyldicarboxylic acid, 2,3-dicarboxyphenylphenylsulfone, 3,4-dicarboxyphenylphenylsulfone, 2,3-dicarboxyphenylphenylsulfide, 3,4- Dicarboxyphenyl phenyl sulfide, 1,2-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 1,2-anthracenedicarboxylic acid, 2,3-anthracenedicarboxylic acid, 1,9- Anthracene dicarboxylic acid, etc. Anhydrides of aromatic dicarboxylic acids.
A dicarboxylic acid anhydride may be used individually by 1 type, and may use 2 or more types together.

<< tetracarboxylic dianhydride >>
As the tetracarboxylic dianhydride, a compound represented by the formula (A2-2) can be given.

In the formula (A2-2), Rb is a tetravalent organic group such as an aliphatic group, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and a “aromatic group directly Or a non-condensed polycyclic aromatic group connected to each other by a bridging member (eg, —O—, —CO—, —S—, —SO ₂ —, an alkylene group, —C (CF ₃ ) ₂ —) ” A tetravalent group selected from The carbon number of Rb is usually 4 to 100, but preferably 4 to 30 and more preferably 4 to 18 from the viewpoint of the volatility of the tetracarboxylic acid that can be generated by hydrolysis.

Examples of tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides.
Examples of the aliphatic and alicyclic tetracarboxylic dianhydrides include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2 , 3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5 (Tetrahydro-2,5-dioxo-3-furani ) -Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-) 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, -(2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5 , 6-tetracarboxylic dianhydride, compounds represented by formulas (T-1) and (T-2).

In formula (T-1) and formula (T-2), R ¹ and R ³ are divalent organic groups having an aromatic ring; R ² and R ⁴ are a hydrogen atom or an alkyl group, R ² and R ⁴ present may be the same or different.

  An aromatic tetracarboxylic dianhydride refers to a tetracarboxylic anhydride of an organic compound in which at least four carboxyl groups are bonded to an aromatic ring. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, and 3,3 ′, 4,4′-diphenyl sulfone. Tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl Ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylmethane tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′ , 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide anhydrous 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4 , 4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (Triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol bis (anhydro trimellitate), propylene glycol bis (anhydro trimellitate) 1,4-butanediol-bis (anhydro trimellitate), 1,6-hexanediol-bis (anhydro trimellitate), 1,8-octanediol-bis (anhydro trimellitate) ), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), 2,3,4,5-pyridinetetracarboxylic dianhydride, 2,6-bis (3,4- Dicarboxyphenyl) pyridine, and compounds represented by the following formulas (T-3-1) to (T-3-4).

A tetracarboxylic dianhydride may be used individually by 1 type, and may use 2 or more types together.

<Moisture capture agent (A3)>
The moisture capturing agent (A3) is at least one selected from the compound represented by the formula (A3-1) and the compound represented by the formula (A3-2). The moisture trapping agent (A3) is stable with low reactivity with water under neutral conditions, but easily causes a hydrolysis reaction in the presence of an acid or a base.

In formulas (A3-1) and (A3-2), X represents a silicon atom, a titanium atom or a zirconium atom. Among these, a silicon atom is preferable.

In the formulas (A3-1) and (A3-2), R ¹ is at least 1 selected from “(meth) acryloyl group, oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, mercapto group and isocyanate group”. An organic group having one group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a benzyl group.

In formulas (A3-1) and (A3-2), R ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or 3 to 3 carbon atoms which may have a substituent. 12 cycloalkyl groups, optionally substituted aromatic hydrocarbon groups having 6 to 14 carbon atoms, (meth) acryloyloxy groups, glycidoxy groups, oxiranyl groups, oxetanyl groups, 3,4-epoxycyclohexyl groups, Or a mercapto group.

  In the formulas (A3-1) and (A3-2), r is an integer of 0 to 2; p is an integer of 0 to 6, preferably an integer of 0 to 3, more preferably 0 or 3. preferable. s is an integer of 1-30, the integer of 1-20 is preferable, and the integer of 1-10 is more preferable.

When there are a plurality of groups represented by — (CH ₂ ) _p —R ^2, they may be the same or different. When there are a plurality of groups represented by —OR ^1, they may be the same or different.

As said organic group in R < ¹ > in Formula (A3-1) and (A3-2), group represented by a following formula is mentioned, for example. In the following formula, * represents a bonding position, R ³ is a hydrogen atom or a methyl group, R ⁴ is an alkylene group having 1 to 3 carbon atoms, and n is an integer of 1 to 3.

The alkyl group for R ¹ in formulas (A3-1) and (A3-2) may be linear or branched, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl; and cycloalkyl groups include, for example, cyclohexyl.

The alkyl group for R ² in formulas (A3-1) and (A3-2) may be either linear or branched. Carbon number of the said alkyl group is 1-20, Preferably it is 1-10, More preferably, it is 1-6. Specifically, in addition to the alkyl group exemplified for R ¹ , n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group Group, n-tridecyl group, n-tetradecyl group, n-hexadecyl group. As a cycloalkyl group in R < ² > in Formula (A3-1) and (A3-2), a cycloheptyl group and a cyclooctyl group are mentioned, for example.

Examples of the aromatic hydrocarbon group for R ² in formulas (A3-1) and (A3-2) include monocyclic to tricyclic aromatic hydrocarbon groups, specifically, a phenyl group , Tolyl group, naphthyl group, anthryl group, and phenanthryl group. Among these, a phenyl group, a tolyl group, and a naphthyl group are preferable, and a phenyl group is more preferable.

The alkyl group, cycloalkyl group and aromatic hydrocarbon group in R ² in the formulas (A3-1) and (A3-2) may have a substituent, and examples of the substituent include a halogen atom, Examples include a hydroxyl group, a nitro group, a cyano group, and an alkoxy group having 1 to 6 carbon atoms. In addition, the position and number of substituents are arbitrary, and when it has two or more substituents, the substituents may be the same or different. Examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom and an iodine atom, and among these, a fluorine atom is preferable. The halogen atom can substitute a part or all of the hydrogen atoms of the alkyl group, cycloalkyl group and aromatic hydrocarbon group, but preferably all are substituted. Specific examples of the halogen-substituted alkyl group and the halogen-substituted cycloalkyl group include perfluoroalkyl groups such as trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorocyclopropyl group, and perfluoroalkyl groups. A cycloalkyl group is mentioned. Moreover, as a C1-C6 alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, and iso-propoxy group are mentioned, for example.

R ² in the formulas (A3-1) and (A3-2) is preferably an alkyl group having 1 to 6 carbon atoms, a halogen-substituted alkyl group, a phenyl group, a (meth) acryloyloxy group, or a glycidoxy group. In addition, when ^two or more R < ² > exists in the same molecule, they may be same or different.

Specific examples of the compound (A3) include silane compounds in which X is a silicon atom.
In compound (A3-1),
Examples of the silane compound in which r is 0 and s is 1 include alkoxysilane compounds having two alkyl groups having 1 to 20 carbon atoms such as dimethyldimethoxysilane and dibutyldimethoxysilane; and 6 to 6 carbon atoms such as diphenyldimethoxysilane. 14 alkoxysilane compounds having two aromatic hydrocarbon groups; 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxy An silane having a (meth) acryloyloxy group and an alkyl group having 1 to 20 carbon atoms, such as silane, 3-acryloyloxypropylethyldimethoxysilane, and 3-acryloyloxypropylmethyldiethoxysilane. Coxysilane compounds; (meth) acryloyloxy groups such as 3-methacryloyloxypropylphenyldimethoxysilane, 3-methacryloyloxypropylphenyldiethoxysilane, 3-acryloyloxypropylphenyldimethoxysilane, 3-acryloyloxypropylphenyldiethoxysilane, and carbon Alkoxysilane compounds having an aromatic hydrocarbon group of 6 to 14; 2 (meth) acryloyloxy groups such as 3,3′-dimethacryloyloxypropyldimethoxysilane and 3,3′-diaacryloyloxypropyldimethoxysilane One alkoxysilane compound; 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane Alkoxysilane compounds having a glycidoxy group such as 3-glycidoxypropylethyldiethoxysilane and an alkyl group having 1 to 20 carbon atoms; 3-glycidoxypropylphenyldimethoxysilane, 3-glycidoxypropylphenyldiethoxy Examples thereof include alkoxysilane compounds having a glycidoxy group such as silane and an aromatic hydrocarbon group having 6 to 14 carbon atoms.

  Examples of the silane compound in which r is 1 and s is 1, include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-iso-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri- alkoxysilane compounds having one alkyl group having 1 to 20 carbon atoms such as iso-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, and decyltrimethoxysilane; and 1 to 20 carbon atoms such as trifluoropropyltrimethoxysilane Alkoxysilane compounds having one halogen-substituted alkyl group, alkoxysilane compounds having one C6-C14 aromatic hydrocarbon group such as phenyltrimethoxysilane, phenyltriethoxysilane, etc .; 3-methacryloyloxy Propyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltripropoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltripropoxysilane And alkoxysilane compounds having one (meth) acryloyloxy group.

  Examples of the silane compound in which r is 2 and s is 1 include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetrabutoxysilane, tetraphenoxysilane, and tetrabenzyloxysilane. Is mentioned.

  As compound (A3-1), the compounds of formula (A3-i) and formula (A3-ii) shown below can be further exemplified. The compounds of the formula (A3-i) and the formula (A3-ii) are, as exemplified by the following formula, tetraethoxysilane, a hydroxyl group and a polymerizable group (oxiranyl group, oxetanyl group, (meth) acryloyl group, etc. ) Can be obtained by reacting in the presence of an alkali.

As compound (A3-1), the compounds of formula (A3-iii) and formula (A3-iv) shown below can be further exemplified. The compound of (A3-iii) and the formula (A3-iv) has a hydroxyl group and a polymerizable group (oxiranyl group, oxetanyl group, (meth) acryloyl group) as shown in the following formula. Etc.) can be obtained by reacting in the presence of an alkali.

Examples of the compound (A3-1) further include a compound represented by the formula (A3-v).

As the compound (A3-2),
3-methacryloyloxypropyldimethylmethoxysilane, 3-methacryloyloxypropyldiethylethoxysilane, 3-methacryloyloxypropyldimethylethoxysilane, 3-acryloyloxypropyldimethylmethoxysilane, 3-acryloyloxypropyldiethylmethoxysilane, 3-acryloyloxypropyl An alkoxysilane compound having one (meth) acryloyloxy group such as dimethylethoxysilane and two alkyl groups having 1 to 20 carbon atoms;
It has one (meth) acryloyloxy group such as 3-methacryloyloxypropyldiphenylmethoxysilane, 3-methacryloyloxypropyldiphenylethoxysilane, 3-acryloyloxypropyldiphenylmethoxysilane, 3-acryloyloxypropyldiphenylethoxysilane, and carbon. An alkoxysilane compound having two aromatic hydrocarbon groups of formula 6-14;
It has one glycidoxy group such as 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldiethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, and two alkyl groups having 1 to 20 carbon atoms. Having an alkoxysilane compound;
Examples thereof include silane compounds having one glycidoxy group such as 3-glycidoxypropyldiphenylmethoxysilane and 3-glycidoxypropyldiphenylethoxysilane and two aromatic hydrocarbon groups having 6 to 14 carbon atoms.
Moreover, as what can be purchased with the commercial item of a compound (A3), OXT-191 (made by Toagosei), X-22-3000T (made by Shin-Etsu Chemical Co., Ltd.), etc. are mentioned, for example.

<Description of effects>
The effects of the adhesive composition used in the present invention will be described below.
When the adhesive composition used in the present invention is heated and / or irradiated with light, an acid or a base is formed from the acid / base generator (B). This acid or base accelerates the hydrolysis reaction of the moisture scavenger (A) based on the water present in the system in which the composition is used, thereby consuming water present in the system with high efficiency. can do. In the present specification, “moisture capture” is used in this sense. The hydrolysis product of the moisture trapping agent (A) is less likely to degrade the performance of electronic devices such as organic EL elements and liquid crystal display elements as will be described later.

  For this reason, in this invention, when forming adhesive layers, such as a sealing material which the said electronic device has, using the said adhesive composition, the water | moisture content in an element can be removed efficiently. In addition, in the adhesive layer such as the sealing material formed from the adhesive composition used in the present invention, a part of the moisture trapping agent (A) or a structural part derived therefrom remains without being decomposed. it is conceivable that. For this reason, the moisture in the element can be absorbed for a long period of time after the formation, and the deterioration of the characteristics of the electronic device due to the moisture can be suppressed.

  In general, the decomposition product is dispersed in the organic EL element by volatilization or the like, and reaches the organic EL layer that becomes the light emitting layer of the organic EL element to be contaminated and generate a dark spot. There is a concern of degrading the performance of the EL element. However, in the present invention, the hydrolysis product generated from the moisture trapping agent (A) has an appropriate molecular weight, so that volatilization and the like are suppressed, and it remains in the adhesive layer such as a sealing material. it can. As the hydrolyzed product has a larger molecular size, it tends to stay in the moisture trapping body. Therefore, a compound having a relatively large molecular weight is preferable as the moisture trapping agent (A).

  The moisture trapping agent (A) used in the present invention hardly generates a highly volatile hydrolysis product such as a low molecular alcohol even when moisture is trapped. For example, adhesion of the hydrolysis product Thus, even when used in an organic EL element that easily generates dark spots, it is possible to suppress the generation of dark spots due to the adhesion of the decomposition products to the organic EL layer.

An example of the hydrolysis reaction of the moisture trapping agent (A) is shown below.
For example, the hydrolysis reaction of the water capturing agent having the structural site of formula (i-1) and the water capturing agent having the structural site of formula (i-2), which are examples of the water capturing agent (A1), is as follows. A chemical reaction formula can be shown. In the following formula, * represents a bonding position. It is considered that an alcohol compound is generated as a hydrolysis product. These alcohol compounds are less volatile and have an appropriate molecular weight.

For example, examples of the moisture scavenger (A2) are a monocarboxylic acid anhydride of formula (ii-1), a dicarboxylic acid anhydride of formula (ii-2), and a tetracarboxylic acid dianhydride of formula (ii-3) The following chemical reaction formula can be shown for the hydrolysis reaction of the product. It is considered that carboxylic acid compounds such as carboxylic acid (ii-1-1), dicarboxylic acid (ii-2-1) and tetracarboxylic acid (ii-3-1) are generated as hydrolysis products. These carboxylic acid compounds are difficult to volatilize and have an appropriate molecular weight.

For example, the following chemical reaction formula can be shown for the hydrolysis reaction of the compounds of formula (iii-1) and formula (iii-2), which is an example of the moisture trapping agent (A3). As a hydrolysis product, alcohol compound (iii-1-1) and metal hydroxide (iii-1-2), alcohol compound (iii-2-1) and metal hydroxide (iii-2-2) Generate. Unreacted R ¹ O in the metal hydroxide (iii-1-2) can react with water to further generate an alcohol compound (iii-1-1). Alcohol compounds (iii-1-1) and (iii-2-1) can react in the R ¹ group and remain in the adhesive. Metal hydroxides (iii-1-2) and (iii-2-2) can react at the R ² group and remain in the adhesive. Further, the metal hydroxides (iii-1-2) and (iii-2-2) are fixedly held in the adhesive by the R ² group and scattered in the adhesive, and the water is regenerated by the condensation reaction. Occurrence is prevented.

[Compound (B)]
The adhesive composition used in the present invention contains at least one compound (B) selected from an acid generator and a base generator. Hereinafter, the acid generator and the base generator are also referred to as “acid generator (B1)” and “base generator (B2)”, respectively.

  When the adhesive composition used in the present invention contains the acid generator (B1), at least one selected from the water trapping agents (A1) to (A3) is used as the water trapping agent (A). When the adhesive composition used by this invention contains a base generator (B2), at least 1 sort (s) chosen from a moisture capture agent (A2)-(A3) is used as a moisture capture agent (A).

  Examples of the acid generator (B1) include a radiation sensitive acid generator and a thermal acid generator, and a radiation sensitive acid generator is preferable. Examples of the base generator (B2) include a radiation sensitive base generator and a thermal base generator, and a radiation sensitive base generator is preferred.

  A radiation-sensitive acid generator and a radiation-sensitive base generator can be defined as compounds capable of releasing an acidic active substance and a basic active substance, respectively, by irradiating them with radiation. The acidic active substance to be released acts as a catalyst when the above-described water trapping agent (A) is subjected to a hydrolysis reaction, for example. The basic active substance to be released acts as a catalyst when the above-described water capturing agents (A2) and (A3) are subjected to a hydrolysis reaction, for example.

  Examples of the radiation irradiated to decompose the radiation-sensitive acid generator or the radiation-sensitive base generator and generate the cation of the acidic active substance or the anion of the basic active substance include, for example, visible light, ultraviolet light, far ultraviolet light, Examples include X-rays and charged particle beams. Among these radiations, it is preferable to use ultraviolet rays because they have a constant energy level, can achieve a high curing rate, and the irradiation device is relatively inexpensive and small.

  In the adhesive composition used in the present invention, the content when the component (B) is the acid generator (B1) is preferably 0.1 to 20 mass with respect to 100 mass parts of the component (A). Part, more preferably 0.5 to 10 parts by mass. By setting the content of component (B) within the above range, for example, a composition having excellent radiation sensitivity can be obtained.

In the adhesive composition used in the present invention, the content when the component (B) is a base generator (B2) is preferably 0.1 to 30 mass with respect to 100 mass parts of the component (A). Part, more preferably 1 to 10 parts by mass. By setting the content of component (B) within the above range, for example, a composition having excellent radiation sensitivity can be obtained.
Each of the components (B1) and (B2) may be used alone or in combination of two or more.

<Acid generator (B1)>
As the acid generator (B1), for example, light or thermal cation curing catalysts such as iodonium salts, sulfonium salts, phosphonium salts, and anion curing catalysts such as imidazoles and acid anhydrides can be used. In these, a cationic curing catalyst is preferable and a photocationic curing catalyst is more preferable. This is because the curing rate is high and the polymerization reaction does not start unless light is applied, so that the storage stability is good.

Specific examples of the cation curing catalyst include cations such as iodonium, sulfonium, and phosphonium substituted with an alkyl group or an aryl group, and SbF ₆ ⁻ , BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , and PF _{6. ^{-, P (Rf) n F}} (6-n) - (Rf is, for example, a perfluoroalkyl group having 1 to 8 carbon atoms; n is an integer of 1 to _{3), C n F 2n + 1} SO 3 - is (n For example, a salt composed of an anion such as 1 to 8), N (SO ₂ CF ₃ ) ₂ ⁻ , C (SO ₂ CF ₃ ) ₃ ⁻ or the like is used. Specifically, CPI-100P, CPI101A, CPI-200K, CPI-210S, etc. (above, manufactured by Sun Apro), Sun-Aid SI-150L, Sun-Aid SI-110L, Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L (Above, manufactured by Sanshin Chemical Industry Co., Ltd.), CI series such as PI-2074 manufactured by Rhodia, CI2920 manufactured by Nippon Soda Co., Ltd. Examples include WPAG series and WPI series.

Among these acid generators (B1), in the cationic curing catalyst, B (C ₆ F ₅ ) ₄ ⁻ , P (Rf) _n F _(6-n) ⁻ , N (SO ₂ CF ₃ ) ₂ ⁻ and C (SO ₂ CF ₃ ) ₃ ^— are preferable, and the cation is preferably a sulfonium cation substituted with an alkyl group or an aryl group from the viewpoint of storage stability.

  Moreover, as an acid generator (B1), Unexamined-Japanese-Patent No. 2006-096742, Unexamined-Japanese-Patent No. 2006-282633, Unexamined-Japanese-Patent No. 2010-241733, Unexamined-Japanese-Patent No. 2012-153642, Unexamined-Japanese-Patent No. 2012-201611 Further, thermal acid generators described in JP 2013-100300 A, JP 2013-058411 A, JP 5505656 A, and the like can be given.

<Base generator (B2)>
The base generator (B2) is preferably a radiation-sensitive base generator, and the radiation-sensitive base generator is not particularly limited as long as it is a compound that generates a base such as an amine upon irradiation with radiation. Examples of the radiation sensitive base generator include transition metal complexes such as cobalt, orthonitrobenzyl carbamates, acyloxyiminos, and α, α-dimethyl-3,5-dimethoxybenzyl carbamates.

  Transition metal complexes include, for example, bromopentammonium cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonia cobalt perchlorate, hexamethylamine cobalt perchlorate. Examples include chlorate and hexapropylamine cobalt perchlorate.

  Examples of orthonitrobenzyl carbamates include [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, [[(2-nitrobenzyl) oxy]. Carbonyl] hexylamine, [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy] carbonyl] aniline, [[(2-nitrobenzyl) oxy] carbonyl] piperidine, bis [ [(2-Nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] toluenediamine, bis [[ (2-Nitrobenzyl) oxy Carbonyl] diaminodiphenylmethane, bis [[(2-nitrobenzyl) oxy] carbonyl] piperazine, [[(2,6-dinitrobenzyl) oxy] carbonyl] methylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl ] Propylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2,6-dinitrobenzyl) oxy] Carbonyl] aniline, [[(2,6-dinitrobenzyl) oxy] carbonyl] piperidine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2,6-dinitrobenzyl) Oxy] carbonyl] phenylenediamine, bis [ (2,6-dinitrobenzyl) oxy] carbonyl] toluenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine Can be mentioned.

  Acyloxyiminos include, for example, propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl benzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, adipoyl benzophenone oxime, adipoyl Acetone oxime, acryloyl acetophenone oxime, acryloyl benzophenone oxime, acryloyl acetone oxime may be mentioned.

  As other examples of the radiation sensitive base generator, 2-nitrobenzylcyclohexyl carbamate, O-carbamoylhydroxyamide and O-carbamoylhydroxyamide are particularly preferable.

  Moreover, as a base generator (B2), international publication 2011/136704 pamphlet, Unexamined-Japanese-Patent No. 2012-193340, Unexamined-Japanese-Patent No. 2013-241548, Unexamined-Japanese-Patent No. 2013-241607, Unexamined-Japanese-Patent No. 2014-097930 Mention may also be made of thermal base generators described in Japanese Patent Publication No. 2012/026400 pamphlet, Japanese Patent No. 5406995.

[Polymerizable compound (C)]
The adhesive composition used in the present invention preferably further contains a polymerizable compound (C). When the adhesive composition used in the present invention contains the polymerizable compound (C), for example, the crosslinking reactivity can be increased. And the intensity | strength of the adhesive bond layer and sealing material formed from this composition and adhesiveness with a board | substrate can be improved.

The polymerizable compound (C) is a compound having a polymerizable group.
A polymeric compound (C) may be used individually by 1 type, and may use 2 or more types together.
Examples of the polymerizable compound (C) include compounds having a cyclic ether group such as a compound having an epoxy group and a compound having an oxetanyl group; and a compound having a polymerizable double bond.

As a compound having an epoxy group, for example,
As monofunctional epoxy compounds, glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, stearyl glycidyl ether, lauryl glycidyl ether, butoxy polyethylene glycol glycidyl ether, phenol polyethylene glycol glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, p-methyl Phenyl glycidyl ether, p-ethylphenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl and the like;
As a multifunctional epoxy compound,
Polyglycidyl ethers of bisphenols such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether Glycidyl ether;
Aliphatic polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3 , 4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxy Rate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4-epoxycyclohexanecarboxylate), lactone modified 3, 4-D Carboxymethyl epoxycyclohexylmethyl-3 ', compounds having a 4'-epoxycyclohexane carboxylate of the 3,4-epoxycyclohexyl group.

As a compound having an oxetanyl group, for example,
Monofunctional oxetane compounds include 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), 2-ethylhexyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (dode). Siloxymethyl) oxetane, 3-ethyl-3- (octadecyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3-hydroxymethyloxetane and the like;
As the polyfunctional oxetane compound, xylylene bisoxetane, 1-butoxy-2,2-bis [(3-ethyloxetane-3-yl) methoxymethyl] butane, 3-ethyl-3 {[(3-ethyloxetane-3 -Yl) methoxy] methyl} oxetane, 1,1,1-tris [(3-ethyloxetane-3-yl) methoxymethyl] propane and the like.

  Among these, from the viewpoint of enhancing the crosslinking reactivity, the compound having a cyclic ether group is preferably a compound having an epoxy group, more preferably a polyfunctional epoxy compound, a polyglycidyl ether of a polyhydric alcohol, 3,4- A compound having an epoxycyclohexyl group is more preferable, and polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate are particularly preferable.

  As the compound having a polymerizable double bond, a compound having an oxygen atom is preferable, and a (meth) acrylate compound is more preferable. As a (meth) acrylate compound, a monofunctional (meth) acrylate compound and a polyfunctional (meth) acrylate compound are mentioned, for example.

  Among these, the compound having a polymerizable double bond is preferably a polyfunctional (meth) acrylate compound, more preferably a polyfunctional methacrylate compound, polyethylene glycol dimethacrylate, polypropylene glycol diene, from the viewpoint of enhancing crosslinking reactivity. Methacrylate is more preferable, and polyethylene glycol # 400 dimethacrylate and polypropylene glycol # 400 dimethacrylate are particularly preferable.

  In the adhesive composition used in the present invention, the content when the polymerizable compound (C) is used is preferably 10 to 3000 parts by mass, and 50 to 2000 parts by mass with respect to 100 parts by mass of the component (A). Is more preferable. By making content of a polymeric compound (C) into the said range, the adhesiveness to the board | substrate of an adhesive bond layer and a sealing material can be improved effectively.

[Radical polymerization initiator (D)]
The adhesive composition used in the present invention can further contain a radical polymerization initiator (D). The adhesive composition used in the present invention contains the initiator (D), for example, the alcohol compound (iii-1-1) and metal water formed by the hydrolysis reaction shown in the above chemical reaction formula. The oxide (iii-1-2) is efficiently fixed and easily retained in the adhesive layer / sealant formed from the composition.

An initiator (D) may be used individually by 1 type, and may use 2 or more types together.
Examples of the initiator (D) include thermal radical polymerization initiators such as azo compounds and peroxides; thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salts. And photoradical polymerization initiators such as benzene compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, acylphosphine oxide compounds, and imide sulfonate compounds.

  In the adhesive composition used in the present invention, the content when the radical polymerization initiator (D) is used is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the component (A). 1-2 mass parts is more preferable. By making content of an initiator (D) into the said range, the desired radical polymerization reaction can be advanced rapidly.

[Other optional ingredients]
The adhesive composition used in the present invention can further contain other optional components. Examples of other optional components include silicone rubber, silicone oil, and diene polymer in order to relieve stress of the formed adhesive layer / sealant. Other examples include silane coupling agents, surfactants, pigments such as carbon black, dyes, antioxidants, stabilizers, heat transfer fillers, carbodiimide compounds, and other additives.

  Examples of the silane coupling agent include KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.), and also described in JP 2006-171670 A, JP 2006-184908 A, and JP 2011-007864 A. Mention may also be made of compounds. As surfactant, the compound described in Unexamined-Japanese-Patent No. 2012-226181 and Unexamined-Japanese-Patent No. 2013-23414 can be mentioned, for example.

  Examples of the diene polymer include styrene / butadiene copolymer and its hydride, styrene / isoprene copolymer and its hydride, styrene / butadiene / styrene block copolymer and its hydride, and styrene / isoprene. -Styrene block copolymers and hydrides thereof are mentioned. Also, WO 2004-055064 pamphlet, JP-A No. 04-224813, JP-A No. 09-095507, JP-A No. 2004-197107, Mention may also be made of the compounds described in Japanese Utility Model Publication No. 2007-254692.

  Examples of the carbodiimide compound include polycarbodiimide, and JP-A 05-178594, JP-A 09-124582, JP-A 10-067978, JP-A 2007-138080, International Publication No. The compounds described in the pamphlet of 2008-081230 and the pamphlet of international publication 2010-072111 can also be mentioned.

[Method for Preparing Adhesive Composition]
In the adhesive composition used in the present invention, the component (A) and the component (B) are mixed, and the component (C), the component (D), and other additives are mixed at a predetermined ratio as necessary. Can be prepared.

  The adhesive composition used in the present invention is preferably used as an adhesive for producing an electronic device in which moisture may deteriorate the characteristics, particularly as a sealing material constituting an organic EL element and a liquid crystal display element. Can do. For example, an electronic device is produced (for example, sealed) using the composition, and then the moisture capturing ability of the composition is expressed by irradiation and / or heating.

[Adhesive layer]
The adhesive layer used in the present invention is formed using the above-described adhesive composition.
As a manufacturing method of the said adhesive bond layer, the process 1 which forms a coating film on the board | substrates, such as a glass substrate, using the said adhesive composition, the said coating film is irradiated with radiation, heated, or radiation Step 2 is irradiation and heating.

  The adhesive composition is applied onto the substrate using, for example, a spin coater, roll coater, spray coater, bar coater, dispenser, or inkjet device. What is necessary is just to change suitably as an aspect of application | coating according to the formation location of an adhesive bond layer.

  The radiation in step 2 is not particularly limited as long as the hydrolysis reaction described above can proceed in the adhesive composition, and preferably the coating film can be cured, but ultraviolet light is preferable. When heating is performed in step 2, the heating temperature is preferably 30 to 200 ° C, more preferably 50 to 150 ° C; the heating time is preferably 1 minute to 24 hours, more preferably 10 minutes to 5 hours. .

The radiation of the composition in Step 2 can be carried out by a known method and conditions, and can be performed by, for example, using a high-pressure mercury lamp and irradiating with ultraviolet rays (eg, 500 to 15000 mJ / cm ² ).

  Although the film thickness of an adhesive bond layer is not specifically limited according to a use, For example, 1-500 micrometers, Preferably it is 5-200 micrometers, More preferably, it is 5-100 micrometers. The film thickness of the film can be measured, for example, with a depth gauge 547-251 (manufactured by Mitutoyo Corporation).

  Since the adhesive layer used in the present invention, for example, the sealing material is formed from the above-mentioned adhesive composition, at the time of formation, the adhesive layer is applied in an electronic device such as an organic EL element or a liquid crystal display element. Water can be efficiently removed and water in the electronic device can be consumed after the formation.

An example of sealing an element using the above sealing material is shown below. For example, the adhesive composition is accommodated in a dispenser such as a syringe, and after the required amount of the composition is supplied from the dispenser to the sealing portion, it is cured by irradiation with light such as ultraviolet rays and sealed. It can be performed. The adhesive composition can be cured by light irradiation using known methods and conditions. For example, a high-pressure mercury lamp can be used and ultraviolet light irradiation (eg, 500 to 15000 mJ / cm ² ) can be used.

  The sealing material formed from the said adhesive composition can be used for a thin panel, and can be used suitably especially as a sealing material for organic EL elements, and a sealing material for liquid crystal display elements.

[Electronic device]
The electronic device of the present invention includes an adhesive layer formed from the adhesive composition, for example, a sealing material. As the electronic device, any electronic device may be used as long as moisture may cause deterioration in characteristics, and examples thereof include an organic EL element and a liquid crystal display element. The organic EL element can constitute, for example, a highly reliable organic EL lighting device or an organic EL display element.

  When the electronic device of the present invention includes the adhesive layer, moisture in the electronic device can be efficiently removed when forming the adhesive layer. In addition, since the adhesive layer can absorb moisture in the electronic device for a long time after the adhesive layer is formed, deterioration of the electronic device due to moisture can be suppressed.

[Organic EL device]
The organic EL element of the present invention includes the above-described adhesive layer, for example, a sealing material. For example, the organic EL element of the present invention is fixed to the substrate by the substrate, the organic EL layer provided on the substrate, the adhesive layer formed on at least the periphery of the organic EL layer on the substrate, and the adhesive layer, An organic EL element comprising an organic EL layer together with a substrate and an adhesive layer, and a sealing substrate for shielding from the outside air, wherein the adhesive layer is formed from the above-described adhesive composition. .

Fig.1 (a) is sectional drawing which shows typically an example of the organic EL element of this invention.
An organic EL element 1 shown in FIG. 1A is formed in an organic EL layer 10, a structure 20 for housing the organic EL layer 10 and blocking it from the outside air, and the structure 20 as necessary. And a desiccant film 30.

  Although the details of the structure of the organic EL layer 10 are omitted, the organic EL layer 10 may have a structure in which an organic light emitting layer made of an organic material is sandwiched between a pair of electrodes facing each other, that is, an anode in which the organic light emitting layers face each other. Any structure may be used as long as it is sandwiched between a cathode and a cathode. For example, a known structure consisting of an anode / a charge (hole) transport layer / an organic light emitting layer / a cathode may be employed.

The organic light emitting layer contains a light emitting material that is an organic material, that is, an organic light emitting material. The organic light emitting material contained in the organic light emitting layer may be a low molecular organic light emitting material or a polymer organic light emitting material. For example, a material obtained by doping quinacridone or coumarin into a base material base such as Alq ₃ (tris (8-quinolinolato) aluminum), BeBq ₃ (bis (10-hydroxybenzo [h] quinolinate) beryllium) can be used. Moreover, when using the coating method of the organic luminescent material by the inkjet method, it is preferable that it is a polymeric organic luminescent material suitable for it. Examples of the polymer organic light emitting material include polyphenylene vinylene and derivatives thereof, polyacetylene and derivatives thereof, polyphenylene and derivatives thereof, polyparaphenylene ethylene and derivatives thereof, poly 3 -Hexylthiophene (Poly 3-hexyl thiophene (P3HT)) and its derivatives, polyfluorene (Poly fluorene (PF)), its derivatives, etc. can be selected and used.

The anode and cathode of the organic EL layer 10 are each made of a conductive material.
As the material of the anode of the organic EL layer 10, for example, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), tin oxide, or the like is selected.

  In the organic EL layer 10, a hole injection layer and / or an intermediate layer may be disposed between the anode and the organic light emitting layer. When the hole injection layer and the intermediate layer are disposed between the anode and the organic light emitting layer, the hole injection layer is disposed on the anode, the intermediate layer is disposed on the hole injection layer, and on the intermediate layer. An organic light emitting layer is disposed on the substrate. Further, the hole injection layer and the intermediate layer may be omitted as long as holes can be efficiently transported from the anode to the organic light emitting layer.

  As a material for the cathode of the organic EL layer 10, for example, ITO, IZO, tin oxide, or the like can be selected. Further, for example, barium (Ba), barium oxide (BaO), aluminum (Al), an alloy containing Al, or the like can be selected.

In the organic EL layer 10, an electron injection layer made of, for example, barium (Ba), lithium fluoride (LiF), or the like may be disposed between the cathode and the organic light emitting layer.
The structure 20 of the organic EL element 1 includes a substrate (element substrate) 22, a sealing material 26 formed on the periphery of the organic EL layer 10 in the substrate 22, and a sealing member fixed to the substrate 22 by the sealing material 26. And a stop substrate 24. The organic EL layer 10 is sealed with a substrate 22, a sealing substrate 26 and a sealing material 26. The inside of the organic EL element 1 has a hollow structure and may be filled with an inert gas so as not to deteriorate the organic EL layer 10.

The sealing material 26 is a sealing material formed from the above-described adhesive composition.
Examples of the substrate 22 of the organic EL element 1 include a glass substrate and a resin substrate. Examples of the material constituting the substrate include glass such as non-alkali glass; polyester (eg, polyethylene terephthalate, polyethylene naphthalate), and fluorene ring modification. Polyester, polyolefin (eg, polyethylene, polypropylene), alicyclic polyolefin, polystyrene, triacetyl cellulose, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, polyarylate, polyethersulfone, polysulfone, polyetheretherketone , Polycarbonate, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyurethane, (meth) acryloyl compounds, etc. Butter, and the like.

  Examples of the sealing substrate 24 include a structure made of glass, resin, or the like. Examples of the constituent material of the sealing substrate 24 include resins such as polyethylene terephthalate, polyethylene naphthalate, and polyimide, as well as the substrate 22, and other resins exemplified as the constituent materials of the substrate 22. The sealing substrate 24 is made of an inorganic material, for example, a substrate formed of an inorganic material such as a glass substrate such as a non-alkali glass substrate, or a material obtained by kneading an inorganic material and a resin. It is also possible to use a substrate in which an inorganic material is vapor-deposited or applied on a substrate formed from the above, a glass substrate, or a resin substrate.

  The sealing material 26 fixes the sealing substrate 24 to the substrate 22 and seals the organic EL layer 10 between the sealing substrate 24 and the substrate 22. The structure of the structure 20 is not particularly limited as long as the organic EL layer 10 can be accommodated and sealed using the sealing material 26.

  For example, when the organic EL element 1 is produced, after the substrate 22 and the sealing substrate 24 are adhered by the coating film made of the above-described adhesive composition, the coating film is formed by irradiation and / or heating. The sealing material 26 can be formed by curing, and moisture in the sealed space can be removed.

  The desiccant film 30 is a film containing a desiccant and is formed as necessary. For example, the desiccant film 30 can be formed using the technique described in Patent Document 1 described above. The desiccant film 30 can also be formed using the adhesive composition described above. The structure and arrangement of the desiccant film 30 are not particularly limited. For example, the desiccant film 30 is arranged on the sealing substrate 24 so as to be separated from the organic EL layer 10 like the organic EL element 1. Further, the desiccant film 30 may be disposed on the side surface of the organic EL layer 10 or the sealing material 26 in the sealed space. Further, the desiccant film 30 may be laminated on the organic EL layer so as to be in close contact with the organic EL layer 10, or may be disposed so as to fill the entire sealing space in the structure 20 without any gap. . In the present invention, since the sealing material 26 functions as a moisture trap, the desiccant film 30 may not be provided.

  The organic EL element 1 having the above structure includes the sealing material 26, so that moisture in the element can be removed and moisture can be prevented from entering. And the organic EL element 1 can suppress the fall of the light emission characteristics, such as a brightness | luminance and light emission efficiency resulting from a water | moisture content.

In the following drawings, the desiccant film 30 is omitted unless otherwise specified.
FIG.1 (b) is sectional drawing which shows typically an example of the organic EL element of this invention. In the organic EL element 2 shown in FIG. 1B, the sealing substrate 24 is fixed to the substrate 22 with a sealing material 26, where the sealing material 26 is interposed between the substrate 22 and the sealing substrate 24. It is provided throughout. The organic EL element 1 shown in FIG. 1A has a hollow structure, whereas the organic EL element 2 shown in FIG. 1B also has a sealing material 26 corresponding to the hollow structure of the organic EL element 1. It is comprised by. With such a structure, the sealing material 26 can protect the organic EL layer 10 formed on the substrate 22. As a result, the reliability performance of the organic EL element 2 can be improved.

  FIG.1 (c) is sectional drawing which shows typically an example of the organic EL element of this invention. The organic EL element 3 shown in FIG. 1C differs from the organic EL element 1 shown in FIG. 1A in that a gas barrier film 40 that covers the entire surface of the organic EL layer 10 is provided. The point is the same.

  FIG.1 (d) is sectional drawing which shows typically an example of the organic EL element of this invention. The organic EL element 4 shown in FIG. 1D differs from the organic EL element 2 shown in FIG. 1B in that a gas barrier film 40 that covers the entire surface of the organic EL layer 10 is provided. The point is the same.

  FIG.1 (e) is sectional drawing which shows typically an example of the organic EL element of this invention. The organic EL element 5 shown in FIG. 1 (e) has a desiccant film 30 formed from the adhesive composition on the organic EL layer 10 as compared with the organic EL element 4 shown in FIG. 1 (d). However, it is different in that a gas barrier film 40 covering the entire surface of the desiccant film 30 and the side surface of the organic EL layer 10 is provided, and the other points are the same.

  The gas barrier film 40 is provided to prevent moisture and oxygen from coming into contact with the organic EL layer 10. The gas barrier film 40 is not particularly limited and a conventionally known film can be used, and examples thereof include a film in which organic films and inorganic films are alternately laminated.

  Further, as the gas barrier film 40, US Patent Application Publication No. 2005/202646, US Patent Application Publication No. 2005/176181, US Patent Application Publication No. 2003/203210, US Patent Application Publication No. 2009. / 208754 specification, International Publication No. 2003/028903 pamphlet, International Publication No. 2008/094352 pamphlet, International Publication No. 2009/009306 pamphlet, International Publication No. 2010/077754 pamphlet, etc. You can also.

  Since the organic EL elements 3 and 4 include the gas barrier film 40 together with the sealing material 26, the moisture in the elements 3 and 4 is removed, and the contact of moisture with the organic EL layer 10 can be further reduced. .

[Liquid crystal display element]
The liquid crystal display element of the present invention includes the above-described adhesive layer, for example, a sealing material.
FIG. 2 is a cross-sectional view schematically showing an example of the liquid crystal display element of the present invention.

  A liquid crystal display element 101 shown in FIG. 2 is an example of the liquid crystal display element of the present invention, and is a color liquid crystal display element driven by a TFT. The liquid crystal display element 101 can be a color liquid crystal display element of a TN (Twisted Nematic) type liquid crystal mode.

  The liquid crystal display element 101 is disposed so as to face the color filter on array substrate 110, the counter substrate 120 on which a counter electrode (not shown) is formed, and the liquid crystal sealed between the substrate 110 and the substrate 120. Layer 130.

  In the liquid crystal display element 101, an alignment film (not shown) is formed on the surface of the substrate 110 and the counter substrate 120 that are in contact with the liquid crystal layer 130. Each alignment film is subjected to an alignment process such as a rubbing process, if necessary, so that a uniform alignment of the liquid crystal layer 130 can be realized.

  In the color filter on array 110, TFTs 112 as switching elements are formed at predetermined positions on the upper surface of a TFT substrate 111 which is a transparent substrate made of a glass substrate or the like. Since a known TFT can be used as the TFT, description of its structure is omitted here.

  On the TFT substrate 111 on the side where the TFT 112 is provided, a color filter layer 140 composed of a plurality of color filter portions 141, 142, 143... That transmits different color lights is formed. On the upper surface of the color filter layer 140, a transparent electrode layer 150 made of, for example, ITO is formed. A plurality of columnar spacers 160 are formed on the transparent electrode layer 150 to ensure a gap in a space in which liquid crystal is sealed.

  In the color filter layer 140, the color filter portions 141, 142, 143... Adjacent to each other are formed so as to be in direct contact with each other at the boundary. The plurality of color filter units include, for example, a red color filter unit 141, a green color filter unit 142, a blue color filter unit 143, and the like, but may include color filter units of other colors.

In the color filter-on-array substrate 110 and the counter substrate 120, polarizing plates 170 are disposed on the surface opposite to the liquid crystal layer 130, respectively.
The color filter on array substrate 110 and the counter substrate 120 are fixed to each other by a sealing material 180 provided on the periphery of the display portion of the substrate 110. The sealing material 180 is the sealing material described above. The sealing material 180 seals the liquid crystal layer 130 together with the substrate 110 and the substrate 120.

  In FIG. 2, reference numeral 200 denotes backlight light emitted from the backlight unit (not shown) toward the liquid crystal layer 130. As the backlight unit, for example, a structure in which a fluorescent tube such as a cold cathode fluorescent lamp (CCFL) and a scattering plate are combined can be used. A backlight unit using a white LED as a light source can also be used. As the white LED, for example, a white LED that obtains white light by mixing a red LED, a green LED, and a blue LED, and a white light that is obtained by mixing a blue LED, a red LED, and a green phosphor to emit white light. A white LED that obtains white light by mixing white LEDs, a blue LED, a red light emitting phosphor, and a green light emitting phosphor to obtain white light by mixing colors, a white LED that obtains white light by mixing colors with a YAG phosphor, A combination of a blue LED, an orange light emitting phosphor, and a green light emitting phosphor to obtain white light by mixing colors, a white LED, an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor And white LEDs that obtain white light by color mixing.

  The liquid crystal display element 101 having the above structure includes the sealing material 180, so that entry of moisture into the element can be reduced. In addition, the liquid crystal display element 101 can suppress display unevenness due to moisture intrusion and deterioration of the liquid crystal layer 130.

In the above description, the liquid crystal display element having a color filter on array substrate has been described as an example, but a liquid crystal display element having a color filter on a counter substrate may be used.
In addition to the above-described TN type, the liquid crystal display element according to the embodiment of the present invention may be an STN (Super Twisted Nematic) type, an IPS (In-Plane Switching) type, a VA (Vertical Aligned Bending) type, or an OCB (Optically Compensating Bench). It is also possible to use a liquid crystal mode such as a mold.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following description of Examples and the like, “part” means “part by mass” unless otherwise specified.

[ Measurement of ¹ H-NMR]
¹ H-NMR was measured at 25 ° C. using a nuclear magnetic resonance apparatus (“JNM-ECS400” (400 MHz) manufactured by JEOL Ltd.).

[Synthesis of Moisture Capture Agent (A1)]
[Synthesis Example 1] Synthesis of water trapping agent (AO-1) A reactor equipped with a stirrer, a cooler, a temperature control device, and a solvent recovery device, 53.0 parts of methyl orthoformate, 2-butyl-2-ethyl −1,3-propanediol 80.0 parts, pentaerythritol 17.0 parts and 90 wt% formic acid aqueous solution 0.5 part were charged, and maintained at about 85 ° C. for 1 hour while distilling off methanol produced by the alcohol exchange reaction. . Thereafter, the temperature was raised to 175 ° C. over 2 hours, and 46.5 parts of methanol was recovered to obtain a water capturing agent (AO-1) as a colorless, transparent, viscous polyorthoester.

When ¹ H-NMR of the moisture trapping agent (AO-1) was measured, it was as follows.
¹ H-NMR (CDCl ₃ ); δ 0.76 to 0.96 (24H, m), δ 1.20 to 1.40 (24H, m), δ 1.10 to 1.60 (32H, m), δ 3.. 34-4.10 (24H, m), δ 5.24 (4H, s).

[Synthesis Example 2] Synthesis of water trapping agent (AO-2) A reactor equipped with a stirrer, a cooler, a temperature control device and a solvent recovery device was added to 53.0 parts of methyl orthoformate, trimethylolpropane monoallyl ether 80. 0.0 parts, 17.0 parts of pentaerythritol and 0.5 parts of a 90 wt% formic acid aqueous solution were charged, and the mixture was kept at about 85 ° C. for 1 hour while distilling off the methanol produced by the alcohol exchange reaction. Then, it heated up to 175 degreeC over 2 hours, and 46.5 parts of methanol were collect | recovered, and the water | moisture-content capture agent (AO-2) was obtained as a colorless, transparent and viscous polyorthoester.

When ¹ H-NMR of the moisture trapping agent (AO-2) was measured, it was as follows.
¹ H-NMR (CDCl ₃ ); δ 0.83 (12H, m), δ 1.24 to 1.56 (8 H, m), δ 3.20 to 4.10 (40 H, d), δ 5.10 to 5. 36 (12H, m), δ 5.88 (4H, m).

[Synthesis Example 3] Synthesis of Water Capture Agent (AO-3) In a reactor equipped with a stirrer, cooler, temperature control device and solvent recovery device, 50.0 parts of water capture agent (AO-1), t- 3.0 parts of butoxypotassium was charged and stirred at 160 ° C. for 6 hours under a nitrogen atmosphere. Thereafter, 0.6 parts of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added as an alkali adsorbent and treated at 120 ° C. for 1 hour. A water scavenger (AO-3) was obtained as an ortho ester.

When ¹ H-NMR of the moisture trapping agent (AO-3) was measured, it was as follows.
¹ H-NMR (CDCl ₃ ); δ0.87 (12H, m), δ1.40 (8H, m), δ1.55 (12H, d), δ3.20 to 4.20 (24H, d), δ3 .25 to 4.10 (32H, m), δ 4.25 to 4.45 (4H, m), δ 5.10 to 5.40 (4H, m), δ 5.80 to 6.15 (4H, m) .

[Synthesis Example 4] Synthesis of water trapping agent (AO-4) A reactor equipped with a stirrer, a cooler, a temperature control device and a solvent recovery device, 63.0 parts of methyl orthoformate, 55.0 parts of glycerin, penta 20.0 parts of erythritol and 0.5 parts of a 90 wt% formic acid aqueous solution were charged, and the mixture was kept at about 85 ° C. for 1 hour while distilling off methanol produced by the alcohol exchange reaction. Then, it heated up to 175 degreeC over 2 hours, 57.0 parts methanol was collect | recovered, and also it concentrated on 175 degreeC and 300 Pa conditions, and removed the volatile component. A water scavenger (AO-4) was obtained as a polyorthoester having a colorless and transparent viscosity.

When ¹ H-NMR of the moisture trapping agent (AO-4) was measured, it was as follows.
¹ H-NMR (CDCl ₃ ); δ 3.20-4.20 (24H, m), δ 4.20-4.70 (4H, m), δ 5.60-6.10 (4H, m).

(Preparation of adhesive composition)
Moisture trapping agent (A) (component (A)), acid generator (B1) (component (B)), and polymerizable compound (C) (component (C) used in the preparation of the adhesive composition such as Preparation Examples )) Is shown below.

<Ingredient (A)>
AO-1: [Synthesis Example 1]
AO-2: [Synthesis Example 2]
AO-3: [Synthesis Example 3]
AO-4: [Synthesis Example 4]
AK-1: OXT-191 (manufactured by Toagosei Co., Ltd.)

AS-1: 4-methylcyclohexanedicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)
AS-2: 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride
(Manufactured by Tokyo Chemical Industry Co., Ltd.)
AC-1: Calcium oxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Component (B)>
B-1: CPI-210S (manufactured by Sun Apro Co., Ltd.)

(X = Special phosphorus anion)

<Ingredient (C)>
C-1: Celoxide 2021P (manufactured by Daicel Corporation; 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate)

[Preparation Example 1]
Weigh out 23 parts of (AO-1) as the moisture scavenger (A), 2 parts of (B-1) as the acid generator (B1), and 75 parts of (C-1) as the polymerizable compound (C), Thorough mixing was performed using a planetary stirrer (Awatori Nertaro, Shinky). Thereafter, defoaming was performed under vacuum to prepare an adhesive composition.

[Preparation Examples 2-8 and Comparative Preparation Examples 1-2]
In Preparation Example 1, an adhesive composition was prepared in the same manner as in Preparation Example 1 except that each component was changed to the types and amounts shown in Table 1.

[A. Formation of cured product]
Using the bar coater “E-789” (Yoshimitsu Seiki Co., Ltd.) having a gap size of 135 μm, the adhesive composition is applied onto a PET film “T100-50” (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) having a thickness of 100 μm. Coating was performed at a coating speed of 2 cm / sec to form a coating film having a thickness of 100 μm. The film thickness of the coating film was measured with a depth gauge 547-251 (manufactured by Mitutoyo Corporation). The resulting coating film was exposed using a PLA-501F exposure machine (extra-high pressure mercury lamp, manufactured by Canon Inc.) so that the integrated dose was 30000 J / m ^2, and then in a clean oven The cured product was formed on the PET film by heating at 80 ° C. for 1 hour.

[B. Manufacture of organic EL elements]
Poly (3,4) as a hole injection material on a glass substrate (manufactured by Asahi Glass Co., Ltd.) having an ITO film having a thickness of 15 nm formed on a glass plate having a length and width of 25 mm and a thickness of 0.7 mm and a pattern having a width of 2 mm. A coating solution for forming a hole injection layer containing ethylenedioxythiophene / polystyrene sulfonate (PEDOT / PSS) is spin-coated at 3000 rpm for 50 seconds to form a hole injection layer having a thickness of 50 nm, and then high purity. Heating and drying were performed at 200 ° C. for 10 minutes in nitrogen. Here, as the hole injection layer forming coating solution, a solution in which PEDOT / PSS was dissolved in pure water at a solid content of 0.1% by mass was used. On the hole injection layer, a 1.0 mass% solution of the light emitting material polyfluorene derivative was spin-coated at 2000 rpm for 50 seconds to form a light emitting layer having a thickness of 70 nm, and then baked at 60 ° C. for 10 minutes. On the light-emitting layer, 10 nm of LiF was deposited at a deposition rate of 0.1 nm / sec under a pressure condition of 10 ⁻⁵ Pa, and 20 nm of Ca was deposited at a deposition rate of 0.1 nm / sec, and 20 nm / sec was deposited thereon. A cathode was formed by laminating 100 nm of Al at a speed.

Next, the adhesive composition was applied to the peripheral edge of the obtained glass substrate with a film using a dispenser to form a coating film having a thickness of 100 μm. Next, using a vacuum laminating apparatus, a counter glass substrate having a length and width of 25 mm and a thickness of 0.7 mm is bonded to the film-formed glass substrate through the coating film, and an ultrahigh pressure mercury lamp (strength at 365 nm is 100 mW). After irradiating with ultraviolet light for 30 seconds, the coating film was cured by heating at 80 ° C. for 30 minutes to form a sealing material.
The organic EL element was produced as described above.

[Evaluation]
The following evaluation was performed about the said adhesive composition, hardened | cured material, and organic EL element.

<Moisture permeability>
With respect to the cured product having a film thickness of 100 μm obtained in A above, the temperature was changed to 60 ° C. and 80 ° C. under the condition of 95% humidity in accordance with JIS-K7129, and the moisture permeability was measured.

<Adhesiveness>
Two pieces of glass obtained by cutting a glass substrate having a thickness of 0.7 mm into 25 mm × 75 mm were prepared. The said adhesive composition was apply | coated to the center part of one glass piece, the coating film with a film thickness of 100 micrometers was formed, two glass pieces were made to cross | intersect a cross shape, and it was made to adhere | attach through the said coating film. Using a PLA-501F exposure machine (extra-high pressure mercury lamp, manufactured by Canon Inc.), the exposure is performed so that the integrated dose becomes 30000 J / m ^2, and then heated at 80 ° C. for 1 hour in a clean oven. By this, the said coating film was hardened. The glass substrate was peeled up and down under the condition of a peeling speed of 150 mm / min, and the maximum load was divided by the application area of the adhesive composition measured in advance to obtain an adhesive force (unit: MPa).

<Moisture resistance test>
The ratio (%) of the dark spot generated when the organic EL element obtained in B was energized for 500 hours under the conditions of 85 ° C. and 85 RH% to the surface area of the upper surface of the organic EL layer was measured. When this ratio was 5% or less, it was judged that the moisture resistance was good, that is, the occurrence of dark spots was suppressed.

1, 2, 3, 4, 5 Organic EL element 10 Organic EL layer 20 Structure 22 Substrate 24 Sealing substrate 26 Sealing material 30 Desiccant film 40 Gas barrier film 101 Liquid crystal display element 110 Color filter on array substrate 111 TFT substrate 112 TFT
DESCRIPTION OF SYMBOLS 120 Opposite substrate 130 Liquid crystal layer 140 Color filter layer 141,142,143 Color filter part 150 Transparent electrode layer 160 Columnar spacer 170 Polarizing plate 180 Sealing material 200 Backlight

Claims (7)

(A) a compound having a hydrolyzable structure;
(B) An electronic device having an adhesive layer formed from an adhesive composition containing at least one compound selected from an acid generator and a base generator. The compound (A) is at least one compound (A1) selected from a compound having a structural moiety represented by the formula (A1-1) and a compound represented by the formula (A1-2), a carboxylic acid anhydride (A2) and at least one selected from the group consisting of at least one compound (A3) selected from the compound represented by formula (A3-1) and the compound represented by formula (A3-2) Yes,
The electronic device according to claim 1, wherein the compound (B) is an acid generator.
[In formula (A1-1), R ^{1 to} R ⁵ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group or a carbon number. 1 to 18 organic groups, and two or more groups selected from R ³ , R ⁴ and R ⁷ are bonded to each other to form a cyclic structure together with the carbon atoms to which they are directly bonded. N is 0 or an integer of 1 to 18, and * represents a bonding position; in formula (A1-2), R ¹ is a hydrogen atom or an organic group having 1 to 18 carbon atoms; Each ⁸ is independently an organic group having 3 to 10 carbon atoms. ]
[In the formulas (A3-1) and (A3-2), X represents a silicon atom, a titanium atom or a zirconium atom; R ¹ represents a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, a 3,4-epoxy. An organic group having at least one group selected from a cyclohexyl group, a mercapto group, and an isocyanate group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a benzyl group; R ² is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, and an optionally substituted carbon. Aromatic hydrocarbon group of number 6-14, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, or merca A pto group;
p is an integer from 0 to 6;
r is an integer of 0 to 2, and s is an integer of 1 to 30. ] The compound (A) is at least one compound (A3) selected from the carboxylic acid anhydride (A2), the compound represented by the formula (A3-1), and the compound represented by the formula (A3-2). At least one selected from the group consisting of:
The electronic device according to claim 1, wherein the compound (B) is a base generator.
[In the formulas (A3-1) and (A3-2), X represents a silicon atom, a titanium atom or a zirconium atom; R ¹ represents a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, a 3,4-epoxy. An organic group having at least one group selected from a cyclohexyl group, a mercapto group, and an isocyanate group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a benzyl group; R ² is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, and an optionally substituted carbon. Aromatic hydrocarbon group of number 6-14, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, or merca A pto group;
p is an integer from 0 to 6;
r is an integer of 0 to 2, and s is an integer of 1 to 30. ] The adhesive composition is
(C) The electronic device according to any one of claims 1 to 3, further comprising a polymerizable compound. It is an organic EL element or a liquid crystal display element, The electronic device of any one of Claims 1-4. The electronic device is fixed to the substrate by the substrate, the organic EL layer provided on the substrate, the adhesive layer formed on at least the periphery of the organic EL layer on the substrate, and the substrate, The electronic device according to claim 5, wherein the electronic device is an organic EL element comprising an organic EL layer together with the adhesive layer and a sealing substrate for shielding from the outside air. The electronic device according to claim 6, wherein a gas barrier film covering the entire surface of the organic EL layer is provided.