JP2015174886A - Pressure-sensitive adhesive film, production method of pressure-sensitive adhesive film, and production method of organic electroluminescent element using pressure-sensitive adhesive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive film which is used for producing an organic electroluminescent element for the purpose of removing moisture in the element, in an electronic device such as an organic EL element, a liquid crystal display element or the like, and to provide a production method of the pressure-sensitive adhesive film.SOLUTION: A pressure-sensitive adhesive film 230 is produced by applying a composition for forming a pressure-sensitive adhesive layer onto a film, and in which the composition for forming the pressure-sensitive adhesive layer includes components written below. (A) A compound having a hydrolyzable structure, and (B) at least one compound selected from an acid generator and a base generator. The composition for forming the pressure-sensitive adhesive layer further includes at least one of a polymerizable compound (C), and a solvent (D) or a leveling agent. The compound (A) and the compound (B) may be reworded as a moisture capture agent (A) and an acid-base generator (B).

Description

  The present invention relates to a pressure-sensitive adhesive film, a method for producing a pressure-sensitive adhesive film, and a method for producing an organic electroluminescence element using the pressure-sensitive adhesive film.

An organic electroluminescence (hereinafter sometimes referred to as “organic EL”) element has a structure in which a light-emitting layer containing a light-emitting compound is sandwiched between a cathode and an anode, and electrons and holes are injected into the light-emitting layer. It is an element that generates excitons (excitons) by recombination and emits light by using light emission (fluorescence, phosphorescence) when the excitons are deactivated, and has a voltage of several V to several tens V. It is capable of emitting light, and also has a wide viewing angle because it is self-luminous, has high visibility, and is a thin-film type completely solid element, so it attracts attention from the viewpoints of space saving and portability. Yes. And the organic EL panel which formed the said organic EL element on the board | substrate can be used as a display device, a display, and various light emission light sources.
At present, among organic EL panels, a flexible display that can be folded is attracting attention. In order to obtain a flexible display, it is necessary to use a substrate having flexibility as a substrate on which the organic EL element is formed. Furthermore, light emitting layers (organic light emitters) used in organic EL elements and organic solids such as electrons and hole transport materials are generally extremely unstable with respect to moisture and oxygen and are present in organic EL elements. In addition to the moisture and oxygen to be used, it is deteriorated by moisture and oxygen entering from the outside of the device, and there is a problem that the luminous efficiency is remarkably lowered in addition to so-called dark spot growth and light transmittance reduction. Therefore, the substrate is required to have a high gas barrier property.
Furthermore, organic EL elements are affected by moisture that has penetrated into the element as the driving period becomes longer, 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 dry material made of a specific organometallic compound is arranged in advance in an electronic device, and the inside of the electronic device is maintained in a low humidity environment by capturing moisture in the dry material (for example, Patent Documents). 1).

  However, since such a dry material has a specific organometallic compound as a main component, it is difficult to handle it in the air, so that it is necessary to handle it in a sealed space in which humidity and the like are strictly controlled. In addition, additives to be added to improve the processability of dry materials must be strictly controlled in moisture, and adding substances that are difficult to control moisture, such as solvents and leveling agents, may impair the drying function. .

  Thus, if the handling in air and the tolerance to moisture are improved, the processability of the dried material is improved. For example, by adding a drying material to the adhesive layer forming composition, it is possible to produce an adhesive layer forming composition having a drying function, and producing an adhesive layer forming composition having a drying function as an organic EL. If it becomes possible to apply | coat on the film used by (1), the adhesive film suitable for manufacture of an organic electroluminescent apparatus will be able to be manufactured simply.

Japanese Patent No. 3936151

  The present invention has been made in view of the above problems. The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a pressure-sensitive adhesive film and a method for manufacturing a pressure-sensitive adhesive film used for manufacturing an organic EL element for the purpose of removing moisture in the element in electronic devices such as organic EL elements and liquid crystal display elements. It is to provide.

The invention made to solve the above problems is
A pressure-sensitive adhesive film produced by applying a pressure-sensitive adhesive layer forming composition on a film, wherein the pressure-sensitive adhesive layer forming composition includes the following components.
(A) a compound having a hydrolyzable structure;
(B) At least one compound selected from an acid generator and a base generator Furthermore, it is manufactured by applying a composition for forming an adhesive layer containing at least one of (C) a solvent or (D) a leveling agent. It is achieved by an adhesive film characterized in that.
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 said compound (B) is manufactured by applying the composition for adhesion layer formation which is an acid generator, It achieves with the adhesion film as described in any one of Claims 1-3 characterized by the above-mentioned. Is done.

[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. An organic group of 1 to 18, R ³ , R ⁴ and R ⁷ may form a cyclic structure together with the carbon atom to which they are directly bonded, and n is an integer of 0 or 1 to 18 * Represents 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; is there. ]

[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 represents 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 formulas 6 to 14, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, or Be a mercapto group; p is an integer of Less than six; r is an integer of 0 to 2, s is an integer of 1 to 30. ]
Furthermore, it is achieved by a method for producing an adhesive film including (1) a step of applying a composition for forming an adhesive layer on a film, and (2) a heating method.

    The present invention has been made in view of the above problems. The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a pressure-sensitive adhesive film and a method for manufacturing a pressure-sensitive adhesive film used for manufacturing an organic EL element for the purpose of removing moisture in the element in electronic devices such as an organic EL element and a liquid crystal display element. It is to provide.

It is sectional drawing which shows the organic EL element of embodiment of this invention.

The pressure-sensitive adhesive film of the present invention, the pressure-sensitive adhesive layer forming composition used for manufacturing the pressure-sensitive adhesive film, and the organic electroluminescence element manufactured using the pressure-sensitive adhesive film will be described.

[Adhesive layer forming composition]
The composition for forming an adhesive layer of 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 for adhesion layer formation further contains a polymeric compound (C). Furthermore, it is preferably used because it contains a solvent, a leveling agent and the like, so that the coating property on the film is improved.

  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. In addition, the compound represented by formula (i) (i is a formula number) is also referred to as compound (i).

[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. R ³ , R ⁴ and R ⁷ may be combined with the carbon atom to which they are directly bonded to form a cyclic structure; n is 0 or an integer of 1 to 18; Yes; * indicates a bond position. In formula (A1-2), R1 is a hydrogen atom or an organic group having 1 to 18 carbon atoms; R8 is 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 g74, * 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, the group 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.

R ³ , R ⁴ and R ⁷ (when n = 0, R ³ and R ⁴ ) may be combined with the carbon atom to which they are directly bonded to form a cyclic structure. 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. R ³ , R ⁴ and R 7 may be combined with the carbon atom to which they are directly bonded to form a cyclic structure. R2 to R7 in the formula (a2-1) are synonymous with the same symbols in the formula (A1-1), and preferred examples are also the same as those described in the 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, R6 and R7 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 In the case where the orthoester (a1), the polyhydric alcohol (a2), and the hydroxyl group-containing compound (a3) are reacted to produce the water scavenger (A1), the orthoester (a1) The mixing ratio of the hydric alcohol (a2) and the hydroxyl group-containing compound (a3) is 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 compounds represented by the formula (A1-iii) are mentioned.

In formula (A1-i), Y1 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. is there. 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 the formula (A1-ii), Y2 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. Examples of (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 an “aromatic group directly Or a non-condensed polycyclic aromatic group interconnected 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 represents a tetravalent organic group, for example, an aliphatic group, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and “the aromatic group is directly Or a non-condensed polycyclic aromatic group interconnected 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-tricarboxycyclopentyl acetate Water, 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-fur Nyl) -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 5- (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 formula (T-1) and formula (T-2), respectively.

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 from each other.

  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′-Tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) dipheny Sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic 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 (triphenyl) Phthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), 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 (anhydro trimellitate), 2,3,4,5-pyridinetetracarboxylic dianhydride, 2,6- Examples thereof include bis (3,4-dicarboxyphenyl) pyridine and compounds represented by the following formulas (T-3-1) to (T-3-4).

Tracarboxylic 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 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 that may have a substituent, or 3 to 12 carbon atoms that may have a substituent. A cycloalkyl group, an optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, a (meth) acryloyloxy group, a glycidoxy group, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, or 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 -OR1, 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 bond 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 R1, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group , N-tridecyl group, n-tetradecyl group, n-hexadecyl group. Examples of the cycloalkyl group for R ² in formulas (A3-1) and (A3-2) include a cycloheptyl group and a cyclooctyl group.

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 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} 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 R2 exists in the same molecule, they may be the 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 formula (A3-i) and formula (A3-ii), as exemplified by the following formula, have a hydroxyl group and a polymerizable group (oxiranyl group, oxetanyl group, (meth) acryloyl group, etc.) on tetraethoxysilane. ) 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 formula (A3-iv), as shown by the following formula, has a hydroxyl group and a polymerizable group (oxiranyl group, oxetanyl group, (meth) acryloyl group) on a silane compound having a methoxy group. 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).

(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.
[Compound (B)]
The composition for forming an adhesive layer of 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 composition for forming an adhesive layer of the present invention contains an acid generator (B1), at least one selected from water trapping agents (A1) to (A3) is used as the water trapping agent (A). When the composition for forming an adhesive layer of the present invention contains a base generator (B2), at least one selected from moisture trapping agents (A2) to (A3) is used as the moisture trapping 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 composition for forming an adhesive layer of the present invention, the content when the component (B) is an acid generator (B1) is preferably 0.1 to 20 masses per 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 composition for forming an adhesive layer of 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) nF (}} 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 - (n is, for example, 1 An integer of ˜8), N (SO ₂ CF ₃ ) ₂ ^— , C (SO ₂ CF ₃ ) ₃ ^{— and the} like are 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, the anion is B (C ₆ F ₅ ) ₄ ⁻ , P (Rf) nF _(6-n) ⁻ , N (SO _{2 )} from the viewpoint of reactivity. 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.

<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.

[Solvent (C)]
It is preferable that the composition for forming an adhesive layer of the present invention further contains a solvent (C). A solvent can be used for viscosity adjustment of the composition for adhesion layer formation, and can improve the coating property to the film base material of the composition for adhesion layer formation at the time of adhesive film manufacture.
The method for coating the adhesive layer forming composition on the substrate is not particularly limited, and can be performed by a spin coating method, a roll coating method, a die coating method, a blade coating method, or the like. A coating film can be obtained by arranging the film forming material solution on the base material so that the resulting film has a desired film thickness by these methods and then drying the solution. Although a drying temperature can be suitably selected according to the kind of solvent etc., it is 40 degreeC or more and 250 degrees C or less normally, Preferably it can be 50 degreeC or more and 200 degrees C or less. Drying may be performed at a constant temperature or may be performed by increasing the temperature stepwise. The drying time is usually 10 seconds to 60 minutes, preferably 30 seconds to 30 minutes. If it is 30 seconds or less, a large amount of solvent may remain, causing a problem in product reliability. If it is 30 minutes or more, it is not suitable for industrial productivity.

  Therefore, the solvent type can be appropriately selected in consideration of coating properties and drying properties in accordance with the purpose of use of the adhesive film. Thus, the pressure-sensitive adhesive film in which the composition for forming the pressure-sensitive adhesive layer is coated on the film substrate is suitable for a process using a roll-to-roll plastic substrate, which is one of the techniques for efficiently mass-producing electronic devices. Can be used.

As such a solvent, as long as the performance of the component which comprises the composition for adhesion layer formation is not impaired, it can be especially used without a restriction | limiting. Specific examples of the solvent include, for example, toluene and xylene.
Aromatic solvents; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether Ether solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, N-methylpyrrolidone; methyl cellosolve, ethyl cellosolve , Cellosolve solvents such as butyl cellosolve Methanol, ethanol, alcohol solvents such as propanol; and the like; dichloromethane, halogenated solvents such as chloroform.

In order to suppress coating unevenness due to the drying property of the solvent, a high boiling point solvent as shown below can be suitably used. For example, propylene carbonate, ethylene carbonate, butylene carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyrolactone, dioxolane, 4-methyldioxolane, N, N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, 1 , 2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl butyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and the like.
These solvents may be used alone or in combination of two or more. Of these solvents, ester solvents, ether solvents, and ketone solvents are preferably used.
In the present invention, the adhesive layer forming composition (A) a compound having a hydrolyzable structure;
(B) Since it contains at least one compound selected from an acid generator and a base generator,
In particular, an aprotic solvent is preferably used.
Examples of aprotic organic solvents include aprotic polar solvents such as N, N-dimethylformamide (DMF), dimethyl sulfoxide, hexamethylphosphoric triamide; diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, methyl t -Ether solvents such as butyl ether, dimethoxyethane, ethylene glycol and dimethyl ether; aromatic hydrocarbon solvents such as benzene, toluene and xylene; hydrocarbon solvents such as n-pentane and n-hexane; nitriles such as acetonitrile and butyronitrile Examples of the solvent include ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone. Examples of the protic solvent include alcohol solvents such as methanol, ethanol, isopropanol, and butanol; water and the like. These may be used alone or in combination of two or more.

[Leveling agent (D)]
In order to prevent uneven coating (uniformization of the coated surface) of the adhesive layer forming composition coated on the film and to reduce unevenness during drying, improve the leveling property of the adhesive layer forming composition on the film. It is effective to add a leveling agent to the adhesive layer forming composition as one means for improving the leveling property.
When a leveling agent is added to the adhesive layer forming composition, the surface tension change during the coating film formation process is reduced or reduced to prevent thermal convection and improve the film uniformity (non-patent) See reference 1, latest technology of coating additives, supervised by Haruo Kiryu, CMC, 2001). Although the optimum leveling agent type varies depending on the compatibility with the solvent, resin, and various additives in the target coating composition, a non-reactive leveling agent or a reactive leveling agent can be used. The non-reactive leveling agent is not particularly limited, and examples thereof include a fluorine-based leveling agent and a silicone-based leveling agent. The reactive leveling agent is not particularly limited, and examples thereof include a leveling agent having a fluorine-based or silicone-based skeleton and having a reactive polymerizable group, for example.
In general, the fluorine-based leveling agent has the same fluoroaliphatic group as the philic group that contributes to affinity for various compositions such as coatings and molding materials when the activator is used as an additive. Such a compound is generally obtained by copolymerizing a monomer having a fluoroaliphatic group and a monomer having a philic group. For example, the fluoroaliphatic group-containing polymer described in Japanese Patent No. 4474114 can be preferably used in the composition for forming a high refractive index layer of the present invention as a leveling agent. As a difference in composition ratio of Japanese Patent No. 4474114, a fluoroaliphatic group-containing polymer having a ratio of fluoroaliphatic group-containing polymerization units in the range of 50 to 70% can also be used as a leveling agent. JP-A-5-5868, JP-A-2012-252275, JP-A-2013-101274, JP-A-2009-120711, JP-A-2012-120980, JP-A-2006-227353, The leveling agent described in International Publication No. WO2012 / 03959 can be used.

  The amount of the leveling agent (D) is, for example, in the range of 0.05 to 2 parts by mass with respect to 100 parts by mass of the compound (A). By setting the leveling agent in the above range, for example, the coating property of the adhesive layer forming composition on the film substrate can be improved. Preferably it is the range of 0.1-1.5 mass part, More preferably, it is the range of 0.5-1.25 mass part.

[About other additives]
It is preferable that the composition for forming an adhesive layer of the present invention further contains a polymerizable compound (E). When the composition for forming an adhesive layer of the present invention contains the polymerizable compound (E), for example, the crosslinking reactivity can be enhanced. And the intensity | strength of the adhesion layer forming composition layer and sealing material formed from this composition and adhesiveness with a board | substrate can be improved.

  A polymeric compound (E) may be used individually by 1 type, and may use 2 or more types together.

  Examples of the polymerizable compound (E) 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 composition for forming an adhesive layer of the present invention, the content when the polymerizable compound (E) 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 (E) into the said range, the adhesiveness to a board | substrate can be improved effectively.

  The composition for forming an adhesive layer of the present invention can further contain a radical polymerization initiator (F). The composition for forming an adhesive layer of the present invention contains an initiator (F), for example, an alcohol compound (iii-1-1) and metal water formed by the hydrolysis reaction shown in the above chemical reaction formula. It becomes easy for the oxide (iii-1-2) to be efficiently fixed and stay in the pressure-sensitive adhesive layer formed from the composition for forming a pressure-sensitive adhesive layer.

  An initiator (F) may be used individually by 1 type, and may use 2 or more types together.

  Examples of the initiator (F) 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 of the present invention, the content when the radical polymerization initiator (D) is used is preferably 0.05 to 5 parts by mass, and 0.1 to 2 parts by mass with respect to 100 parts by mass of the component (A). Is more preferable. By making content of an initiator (D) into the said range, the desired radical polymerization reaction can be advanced rapidly.

In addition, the adhesive layer forming composition may have curved surface adhesiveness, removability, dismantling properties, radiation curable properties, temperature sensitivity, buffering properties, high transparency, flame retardancy, antistatic properties, electrical conductivity. , Thermal conductivity, solder resistance, light shielding, low metal corrosivity, near infrared absorption, etc. are required.
These performances can be designed by adding a compound having the function to the adhesive layer forming composition of the present invention. Regarding compounds having such functions, non-patent literature “Monthly Display, November 2013, Trends in Functions / Performance Required for Adhesive Layer-Forming Compositions”, pages 60 to 64, (Techno Times Co., Ltd.) Examples of other additives include powders such as colorants, pigments, surfactants, plasticizers, tackifiers, low molecular weight polymers, surface smoothing agents, and leveling agents. Depending on the use, antioxidants, corrosion inhibitors, light stabilizers, UV absorbers, polymerization inhibitors, silane coupling agents, inorganic or organic fillers, metal powders, particles, foils, etc. It can be added as appropriate.

As a film substrate used for the adhesive film of the present invention,
Although not particularly limited, a polymer film having transparency and optical isotropy is preferable. Examples of such polymer films include polyolefins such as polyethylene and polypropylene, polyimide, polyamideimide, polyamide, polyetherimide, polyetheretherketone, polyetherketone, polyketonesulfide, polyethersulfone, polysulfone, polyphenylenesulfide, Polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose polymers, epoxy resin, phenol resin, norbornene resin, isobutene / N-methylmaleimide Films such as a mixture of polymer and styrene / acrylonitrile copolymer It can be mentioned. Among these, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, cellulose polymer, norbornene resin, a mixture of isobutene / N-methylmaleimide copolymer and styrene / acrylonitrile copolymer, and the like are particularly preferable. Moreover, what performed surface treatments, such as a hydrophilization process, a hydrophobization process, and the process which reduces the solubility of a base material, to these polymer films can also be used.
The thickness of the polymer film can usually be 1 μm or more and 200 μm or less, preferably 10 μm or more and 150 μm or less, and particularly preferably 20 μm or more and 100 μm or less. When the thickness is less than 1 μm, the strength of the film is weak, so that stretching or shrinkage may cause uneven stretching. In the case of 200 μm or more, the tension necessary for stretching becomes too large, which is not suitable for industrial production.

  Next, the manufacturing method of the composition for adhesion layer formation of this invention is demonstrated.

  The composition for forming an adhesive layer of the present invention comprises (A) a compound having a hydrolyzable structure, (B) at least one compound selected from an acid generator and a base generator, and (C) if necessary. A solvent, (D) leveling agent, etc. can be mixed in advance and then stirred. (B) The composition for forming an adhesive layer in which an acid generator and a base generator are mixed proceeds with a hydrolysis reaction of the component (A) by light irradiation, and therefore is stored in a dark place after the preparation of the composition for forming an adhesive layer. It is desirable to do.

   Since the adhesive layer forming composition obtained by the above method can form an adhesive layer without impairing the coating workability, it can be used for adhesive layers constituting various adhesive films.

  As said adhesive film, it can be used for the surface protection film for protecting the surface of optical members, such as a polarizing plate, an optical compensation film, a phase difference plate, a film for dicing, a back grind film, etc., for example. In particular, the surface protective film for the optical member is preferable because it has an adhesive layer that satisfies performance requirements from the industry.

  The adhesive film has an adhesive layer on one or both sides of a film or sheet made of plastic such as polyethylene terephthalate.

  Although there is no restriction | limiting in particular in the thickness of the adhesion layer of this adhesion film, 1-100 micrometers is preferable. When using as a surface protection film especially, 5-30 micrometers is preferable.

   When used in a surface protective film, since a higher level of antistatic property is required as the film, it is preferable to use a plastic substrate that has been subjected to antistatic treatment.

  Examples of the method for applying the adhesive layer forming composition of the present invention on one or both sides of the plastic substrate include a method using a roll coater, gravure coater, reverse coater, spray coater, air knife coater, die coater, etc. Can be mentioned.

  In addition, after applying the adhesive layer forming composition on the plastic substrate, the method for drying the adhesive layer forming composition may be a method of curing at room temperature for a certain period of time. It may be cured in the range of 30 ° C. to 50 ° C. from the viewpoint of promoting the heat treatment.

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.
Component (A) [Synthesis of Moisture Capture Agent (A1)]
[Synthesis Example 1] Synthesis of moisture trapping agent (A-1) In a reaction apparatus 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. . Then, it heated up to 175 degreeC over 2 hours, and 46.5 parts of methanol was collect | recovered, and the water | moisture-content capture agent (A-1) was obtained as a colorless, transparent and viscous polyorthoester.

(A-1)
A compound having the following structure was used as the moisture capturing agent (A-2).

OXT-191 (manufactured by Toagosei Co., Ltd.)
4-Methylcyclohexanedicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the moisture trapping agent (A-3).
For component (B), B-1: CPI-210S (manufactured by San Apro Co., Ltd.) was used.

(X = Special phosphorus anion)
A compound having the following structure was used as the polymerizable compound (E). (E-1).

[Example 1]
23 parts of (A-1) as the moisture scavenger (A), 2 parts of (B-1) as the acid generator (B1), 50 parts by weight of butyl acetate as the solvent (C), and (D) as the leveling agent (D) -1) Weigh 2 parts by weight (manufactured by Dainippon Ink and Chemicals, trade name “GRANDICPC-4100”) and 55 parts (E-1) as a polymerizable compound in a container, and stir in a planetary stirrer Taro, Shinky Co., Ltd.) was sufficiently mixed to prepare an adhesive layer forming composition.

[Examples 2-5 and Comparative Examples 1-2]
In Example 1, a composition for forming an adhesive layer was prepared in the same manner as in Example 1 except that the components and amounts shown in Table 1 were used.
Each component shown in Table 1 is the compound shown below.
Solvent (C) Component C-1: Butyl acetate C-2: Methyl ethyl ketone C-3: Propylene glycol monomethyl ether acetate leveling agent (D) Component D-1: Product name “GRANDICPC-4100” manufactured by Dainippon Ink & Chemicals, Inc. "
D-2: Fluorosurfactant Product name "Megafac F142D (above, Dainippon Ink and Chemicals)"
[Formation of adhesive film]
Using the bar coater “E-789” (Yoshimitsu Seiki Co., Ltd.) having a gap size of 135 μm, the above adhesive layer forming composition is a PET film “T100-50” (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) having a film thickness of 100 μm. The coating was carried out at a coating speed of 2 cm / sec to form a coating film having a thickness of 20 μm. The film thickness of the coating film was measured with a depth gauge 547-251 (manufactured by Mitutoyo Corporation). The obtained coating film was heated in a clean oven at 80 ° C. for 1 hour to form an adhesive layer on the PET film, thereby producing an adhesive film.

[Measurement method of adhesive strength]
A 180-degree peel strength was measured in accordance with JIS Z-0237 for the adhesive film prepared by the above method attached to a substrate. It is practically preferable that the peel strength is approximately 0.15 N / 25 mm or less.

[Coating workability evaluation method]
The composition for forming an adhesive layer of the present invention was applied at a rate of 30 m / min on a 25 μm-thick polyethylene terephthalate film subjected to a release treatment using a roll coater so that the thickness after drying was 20 μm. The smoothness of the coating film surface of the composition for forming an adhesive layer was visually evaluated.

○: Good (smooth coated surface)
△: Partially defective (coating surface with relatively poor viscosity during coating but relatively smooth)
×: Defective (viscosity is poor at the time of coating, streaks are observed and it cannot be said that the coated surface is smooth)
[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, LiF was deposited at a thickness of 10 nm and a deposition rate of 0.1 nm / sec at a deposition rate of 0.1 nm / sec under a pressure condition of 10-5 Pa, and Ca was deposited at a thickness of 20 nm. Then, 100 nm of Al was laminated to form a cathode.

  Next, a sealant 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.

Subsequently, the adhesive film which produced the adhesive film in the said Example on the organic EL layer formed on the glass substrate was bonded together.
[Moisture resistance test]
Proportion (%) of the dark spot generated when the organic EL element obtained in [Production of organic EL element] in B is energized for 500 hours under the conditions of 85 ° C. and 85 RH% on the surface area 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.

DESCRIPTION OF SYMBOLS 10 Organic EL layer 22 Substrate 24 Sealing member 26 Sealing material 230 Adhesive film 300 Organic EL element 231 232 Support material

Claims (8)

A pressure-sensitive adhesive film produced by applying a pressure-sensitive adhesive on a film, wherein the pressure-sensitive adhesive contains the following components.
(A) a compound having a hydrolyzable structure;
(B) At least one compound selected from an acid generator and a base generator Furthermore, the adhesive film of Claim 1 manufactured by applying the adhesive containing at least any one of (C) solvent or (D) leveling agent.   3. The pressure-sensitive adhesive film according to claim 2, which is produced by applying a pressure-sensitive adhesive, wherein the solvent (C) according to claim 2 is an aprotic solvent. 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 pressure-sensitive adhesive film according to any one of claims 1 to 3, wherein the compound (B) is produced by applying a pressure-sensitive adhesive that 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. An organic group of 1 to 18, R ³ , R ⁴ and R ⁷ may form a cyclic structure together with the carbon atom to which they are directly bonded, and n is an integer of 0 or 1 to 18 * Represents 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; is there. ]
[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 represents 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 formulas 6 to 14, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, or Be a mercapto group; p is an integer of Less than six; r is an integer of 0 to 2, s is an integer of 1 to 30. ] It is used for manufacture of an organic electroluminescent apparatus, The adhesive film as described in any one of Claims 1-4 characterized by the above-mentioned.   The adhesive used for manufacture of the adhesive film of Claim 5. Production method of pressure-sensitive adhesive film having the following steps (1) A step of coating a pressure-sensitive adhesive on the film,
(2) Heating process   The organic electroluminescent element manufactured using the adhesive film obtained by the manufacturing method of Claim 7