JP6596223B2 - Adhesive composition, laminate, and method for producing laminate - Google Patents

Description

  The present invention relates to an adhesive composition useful for an organic light emitting diode, a laminate, and a method for producing the laminate.

  In recent years, organic light emitting diodes (OLEDs) having high brightness, wide color gamut, low power consumption, and long life have been widely used in the fields of displays and lighting. When manufacturing OLEDs, for example, an adhesive is used for the purpose of adhesion between the substrate and the support, etc. The adhesive for OLED not only has high transparency, but also reduces the protrusion of the adhesive at the edge, after curing Adhesion performance such as reduction of void (void) generation and uniformity during coating is also required.

  For example, in Patent Document 1, as a composition for an LED sealing material, 80 parts of a component made of an alicyclic epoxy compound and 20 parts of a component made of a polyfunctional hydrogenated epoxy compound and / or a polyfunctional alicyclic epoxy compound The composition for sealing materials to be included is specifically disclosed.

JP 2012-62438 A

  However, since the composition for an LED sealing material described in Patent Document 1 is intended for sealing, sticking performance required for an adhesive such as reduction of protrusion, reduction of voids, coating uniformity, etc. There was still room for improvement.

  This invention is made | formed in view of the said situation, Comprising: It aims at providing the manufacturing method of the adhesive composition which can be used suitably for an OLED use, a laminated body, and a laminated body.

In order to solve the above problems, the present invention employs the following configuration.
That is, the first aspect of the present invention includes an alicyclic epoxy compound (A1) represented by the following formula (A1) and a polyfunctional alicyclic epoxy compound that does not correspond to the alicyclic epoxy compound (A1) ( A2) and an acid generator (B), wherein the mass proportion of the alicyclic epoxy compound (A1) and the polyfunctional alicyclic epoxy compound (A2) is The adhesive composition is characterized in that (A1) / (A2) = 70/30 to 51/49.

［式中、Ｒ^１、Ｒ^２はそれぞれ独立に、脂環式エポキシ基を有していてもよい有機基であって、少なくともＲ^１、Ｒ^２のいずれか一方は脂環式エポキシ基を有するものであり、Ｙ^１、Ｙ^２はそれぞれ独立に、単結合又は２価の連結基である。］

[Wherein R ¹ and R ² are each independently an organic group optionally having an alicyclic epoxy group, and at least ^one of R ¹ and R ² has an alicyclic epoxy group. Y ¹ and Y ² are each independently a single bond or a divalent linking group. ]

A second aspect of the present invention is a laminate formed by bonding a substrate and a support through an adhesive layer containing the adhesive composition of the first aspect.
3rd aspect of this invention is a manufacturing method of a laminated body which bonds a board | substrate and a support body through the contact bonding layer containing the adhesive composition of said 1st aspect.

  The adhesive composition of the present invention reduces not only the performance required for general OLED adhesives such as heat resistance, moisture resistance, heat cycle characteristics, applicability, and transparency, but also reduction of protrusion of the adhesive at the edge portion. Since the bonding performance such as reduction in void (void) generation after curing and uniformity during coating is also good, a good adhesive layer for OLED can be formed.

In the present specification and claims, “aliphatic” is a relative concept with respect to aromatics, and means a group having no aromaticity, a compound having no aromaticity, and the like. Define.
Unless otherwise specified, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
The “alkylene group” includes linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified.
The “halogenated alkyl group” is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
“Fluorinated alkyl group” or “fluorinated alkylene group” refers to a group in which part or all of the hydrogen atoms of an alkyl group or alkylene group are substituted with fluorine atoms.
“Structural unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When it is described as “may have a substituent”, when a hydrogen atom (—H) is substituted with a monovalent group, and when a methylene group (—CH ₂ —) is substituted with a divalent group And both.
“Exposure” is a concept including general irradiation of radiation.

≪Adhesive composition≫
The adhesive composition of the first aspect of the present embodiment includes an alicyclic epoxy compound (A1), a polyfunctional alicyclic epoxy compound (A2) not corresponding to the alicyclic epoxy compound (A1), and an acid. And a generator (B).
In the present embodiment, the “alicyclic epoxy compound” is a compound having an alicyclic epoxy group. The “alicyclic epoxy group” refers to a group having an oxacyclopropane structure which is a three-membered ring ether and an alicyclic group.
The alicyclic group serving as the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. Moreover, the hydrogen atom of these alicyclic groups may be substituted with an alkyl group, an alkoxy group, a hydroxyl group or the like.

<Alicyclic epoxy compound (A1)>
In the present embodiment, the alicyclic epoxy compound (A1) (hereinafter sometimes referred to as “component (A1)”) is represented by the following formula (A1).

［式中、Ｒ^１、Ｒ^２はそれぞれ独立に、脂環式エポキシ基を有していてもよい有機基であって、少なくともＲ^１、Ｒ^２のいずれか一方は脂環式エポキシ基を有するものであり、Ｙ^１、Ｙ^２はそれぞれ独立に、単結合又は２価の連結基である。］

[Wherein R ¹ and R ² are each independently an organic group optionally having an alicyclic epoxy group, and at least ^one of R ¹ and R ² has an alicyclic epoxy group. Y ¹ and Y ² are each independently a single bond or a divalent linking group. ]

In formula (A1), R ¹ and R ² are each independently an organic group optionally having an alicyclic epoxy group, and at least ^one of R ¹ and R ² is an alicyclic epoxy group. Have In the present embodiment, the “organic group optionally having an alicyclic epoxy group” means not only a combination of an alicyclic epoxy group and an organic group, but also a group consisting of only an alicyclic epoxy group (organic Group).

  Examples of the organic group include a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, and a hetero which may have a substituent. Examples thereof include an aryl group, an aralkyl group which may have a substituent, and a heteroaralkyl group which may have a substituent.

The organic group of R ¹ and R ² may have an alicyclic epoxy group, and at least ^one of R ¹ and R ² has an alicyclic epoxy group.
The organic groups that may have an alicyclic epoxy group of R ¹ and R ² may be different or the same.
R ¹ and R ² are preferably both organic groups having an alicyclic epoxy group, more preferably both are groups composed of an alicyclic epoxy group, and both are 1,2-epoxycyclohexyl. Particularly preferred is a group.

In formula (A1), Y ¹ and Y ² are each independently a single bond or a divalent linking group.
Although it does not specifically limit as a bivalent coupling group, The aliphatic hydrocarbon group which contains a ring in a linear or branched chain structure, or an aromatic hydrocarbon group is mentioned.
The aliphatic hydrocarbon group or aromatic hydrocarbon group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group.
In the aliphatic hydrocarbon group or the aromatic hydrocarbon group, a part of carbon atoms and hydrogen atoms constituting the structure may be substituted with a substituent containing a hetero atom. Examples of the substituent containing a hetero atom include —O—, —C (═O) —O—, —C (═O) —, —O—C (═O) —O—; —C (═O) —. NH—, —NH—, —NH—C (═O) —O—, —NH—C (═NH) — (H may be substituted with a substituent such as an alkyl group or an acyl group); _{-S -, - S (= O} ) 2 -, - S (= O) 2 -O-, the formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 -C (= O) —O—, —C (═O) —O—Y ²¹ , — [Y ²¹ —C (═O) —O] _{m ″} —Y ²² — or —Y ²¹ —O—C (═O) — A group represented by Y ²² — wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, and is a linear or branched alkylene In the formula, O is an oxygen atom m "is an integer of 0 to 3. ] Etc. are mentioned.

Y ¹ and Y ² may be different or the same.
When Y ¹ and Y ² are a divalent linking group, the divalent linking group may be a linear or branched chain which may have a substituent, or an aliphatic carbon containing a ring in the structure. A hydrogen group is preferable, a linear or branched aliphatic hydrocarbon group which may have a substituent is more preferable, and a linear or branched alkylene group which may have a substituent Is more preferable. 1-30 are preferable, as for carbon number of an aliphatic hydrocarbon group and an alkylene group, 1-10 are more preferable, and 1-3 are more preferable.
Y ¹ and Y ² are preferably a single bond, a methylene group, an ethylene group or a propylene group, more preferably a single bond or a methylene group, particularly preferably Y ¹ is a single bond and Y ² is a methylene group.

  Preferred examples of the component (A1) include compounds represented by the following formulas (A1-1) to (A1-2).

［式中、Ｒ^１、Ｒ^２は前記同様であり、Ｙ^０２は単結合又は２価の連結基であり、ｎ^１、ｎ^４はそれぞれ独立に０〜３の整数であり、ｎ^２は０〜１０の整数であり、ｎ^３は０又は１である。］

[Wherein, R ¹ and R ² are the same as above, Y ⁰² is a single bond or a divalent linking group, n ¹ and n ⁴ are each independently an integer of 0 to 3, and n ² is 0. is an integer from to 10, ^{n 3} is 0 or 1. ]

In formulas (A1-1) to (A1-2), R ¹ and R ² are the same as described above, and both are preferably organic groups having an alicyclic epoxy group, and both are alicyclic epoxy groups. It is more preferable that
Wherein ^{(A1-1) ~ (A1-2),} Y 02 is a single bond or a divalent linking group, the divalent linking group include the same groups as above ^Y 1, ^{Y 2.} Among these, a single bond or a linear or branched chain which may have a substituent or an aliphatic hydrocarbon group containing a ring in the structure is preferable.
In formulas (A1-1) to (A1-2), n ¹ and n ⁴ are each independently an integer of 0 to 3, and 0 or 1 is preferable.
In formulas (A1-1) to (A1-2), n ² is an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably 0.
In formulas (A1-1) to (A1-2), n ³ is 0 or 1, and 0 is preferable.

Specific examples of the component (A1) are listed below. In the following formula, n ²¹ is an integer of 1 to 10.

  Preferred examples of commercially available alicyclic epoxy compounds include Celoxide 2021, 2021P, 2081, 2083, 2085 (manufactured by Daicel Chemical Industries).

<Polyfunctional alicyclic epoxy compound (A2)>
In the present embodiment, the polyfunctional alicyclic epoxy compound (A2) (hereinafter sometimes referred to as “component (A2)”) is a compound that does not correspond to the component (A1). The component (A2) may be a low molecular compound or a polymer compound, but is preferably a polymer compound.
The component (A2) is a bifunctional or higher polyfunctional epoxy compound, and is preferably a trifunctional or higher functional epoxy compound.
As the component (A2), a compound represented by the following formula (A2-1) is preferable because of excellent chemical resistance and light resistance.

［式中、Ｒ^１１はｑ個の活性水素基を有する有機化合物中の活性水素基を除いた残基である。ｎ^１１、ｎ^１２、・・・、ｎ^ｑはそれぞれ独立に０〜１００の整数を示し、その和は１〜１００である。ｑは１〜１００の整数を示す。Ａは、置換基Ｒ^１２を含有するオキシシクロヘキサン骨格、又は置換基Ｒ^１２を含有するオキシノルボルネン骨格を有し、且つ下記式（ａ１）又は（ａ２）で表される。］

[Wherein R ¹¹ is a residue obtained by removing an active hydrogen group in an organic compound having q active hydrogen groups. n ¹¹ , n ¹² ,..., n ^q each independently represents an integer of 0 to 100, and the sum thereof is 1 to 100. q shows the integer of 1-100. A is represented by the oxycyclohexane skeleton containing substituents ^{R 12,} or having a oxy norbornene skeleton containing substituents ^{R 12,} and the following formula (a1) or (a2). ]

［式中、Ｒ^１２はそれぞれ独立に下記式（ａ１１）〜（ａ１３）で表される基であって、式（Ａ２−１）で表される化合物は、（ａ１１）で表される基を１個以上含む。式（ａ１）、（ａ２）で表される基は、波線の結合手において式（Ａ２−１）で表される化合物中のＲ^１１に結合し、＊印の結合手において式（Ａ２−１）で表される化合物中の水素原子（Ｈ）に結合する。］

[Wherein, R ¹² is a group represented by the following formulas (a11) to (a13) independently, and the compound represented by the formula (A2-1) is a group represented by (a11). Contains one or more. The groups represented by the formulas (a1) and (a2) are bonded to R ¹¹ in the compound represented by the formula (A2-1) at the wavy bond, and the formula (A2-1) is bonded to the bond at the * mark. ) To a hydrogen atom (H) in the compound represented by ]

［Ｒ^１３はアルキル基、アルキルカルボニル基、又はアリールカルボニル基を示す。式（ａ１１）〜（ａ１３）で表される基は、波線の結合手において、式（ａ１）、（ａ２）で表される基に結合する。］

[R ¹³ is an alkyl group, an alkylcarbonyl group, or an arylcarbonyl group. The groups represented by the formulas (a11) to (a13) are bonded to the groups represented by the formulas (a1) and (a2) at the wavy bond. ]

In the above formula (A2-1), R ¹¹ is a residue obtained by removing an active hydrogen group in an organic compound having an active hydrogen group, but as an “organic compound having an active hydrogen group” as a precursor thereof, , Alcohols, phenols, carboxylic acids, amines, thiols and the like.

The alcohols may be monohydric alcohols or polyhydric alcohols. Specifically, aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol; aromatic alcohols such as benzyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene Glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, cyclohexanedimethanol, glycerin, diglycerin, polyglycerin, Examples thereof include polyhydric alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol and dipentaerythritol.
Examples of the phenols include phenol, cresol, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4′-dihydroxybenzophenone, bisphenol S, a phenol resin, and a cresol novolac resin.
The above carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids of animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecanedioic acid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic acid And terephthalic acid. Moreover, the compound which has both a hydroxyl group and a carboxyl group, such as lactic acid, a citric acid, and oxycaproic acid, is also mentioned.
Examples of the amines include monomethylamine, dimethylamine, monoethylamine, diethylamine, propylamine, monobutylamine, dibutylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, dodecylamine, 4,4'-diaminodiphenylmethane, isophorone. Examples include diamine, toluene diamine, hexamethylene diamine, xylene diamine, diethylenetriamine, triethylenetetramine, and ethanolamine.
Examples of the thiols include mercaptos such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, phenyl mercaptan; ethylene glycol dimercaptopropionate, trimethylolpropane trimercaptopropionate, pentaerythritol tetramercaptopropionate, etc. And propionic acid or mercaptopropionic acid polyhydric alcohol ester.

  Further, organic compounds having active hydrogen groups include polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, acrylic polyol resin, styrene allyl alcohol copolymer resin, styrene. -Maleic acid copolymer resin, alkyd resin, polyester polyol resin, polyester carboxylic acid resin, polycaprolactone polyol resin, polypropylene polyol, polytetramethylene glycol and the like can also be mentioned.

The organic compound having an active hydrogen group may have an unsaturated double bond in its skeleton. Specific examples include allyl alcohol, acrylic acid, methacrylic acid, 3-cyclohexenemethanol, tetrahydrophthalic acid and the like.
The above organic compounds having an active hydrogen group may be used alone or in combination of two or more.

In the formula ^{(A2-1), n 11, n} 12, ···, n q are independently an integer of 0 to 100, the sum is 1-100. Moreover, q shows the integer of 1-100.
Of these ^{n 11, n 12, ···,} n q is preferably independently 2-10 integer, an integer of 3-6 is more preferable. ^Further, n ^11, n 12, · · ·, the sum of ^{n q} is preferably 4 to 30, more preferably 4 to 20. By setting the sum to 4 or more, the crosslinking density after curing can be increased and the hardness can be increased. Moreover, by making the said sum 30 or less, the solubility to a solvent can be improved and handling property can be improved.

In the formula (A2-1), A is represented by a oxy norbornene skeleton containing oxycyclohexane skeleton or substituents ^{R 12} contains a substituent ^{R 12,} and the above formula (a1) or (a2) The A is preferably represented by the above formula (a1). The q A's may be the same or different.

  It is essential that the epoxy compound represented by the above formula (A2-1) contains at least one group represented by the above formula (a11). On the other hand, the smaller the group represented by the formula (a13), the more preferable.

The epoxy compound represented by the above formula (A2-1) is prepared by using an organic compound having an active hydrogen group as an initiator, as described in Japanese Patent Publication No. 7-119270, or 4-vinylcyclohexene-1-oxide or Polyether resin obtained by ring-opening polymerization of a mixture of 5-vinylbicyclo [2.2.1] hept-2-ene-2-oxide and a compound having one epoxy group, that is, a vinyl group side chain And a polyether resin having a cyclohexane skeleton or a vinyl side chain and a norbornene skeleton is produced by epoxidation with peracetic acid or hydrogen peroxide.
Examples of commercially available products, manufactured by Daicel Chemical Industries, Ltd. of EHPE3150 ^(sum of ⁿ 11 ~n ^q is 15 on average), and as is preferred.

In this embodiment, the compounding ratio of the component (A1) and the component (A2) is (A1) / (A2) = 70/30 to 51/49 (mass ratio), and 70/30 to 60/40. (Mass ratio) is more preferable.
By setting the above blending ratio, the melt viscosity of the obtained adhesive layer is within a preferable range described later, so that the heat resistance is excellent, the protrusion of the adhesive at the edge portion is reduced, and voids (voids) are generated after curing. Can be obtained, and an adhesive layer excellent in adhesion such as uniformity during application can be obtained.

<Acid generator (B)>
In the present embodiment, the acid generator (B) (hereinafter sometimes referred to as “component (B)”) generates an acid by the action of light or heat, and cures the epoxy compound by the generated acid.
(B) It does not specifically limit as a component, What has been proposed as an acid generator of various uses until now can be used.
The component (B) may be a photoacid generator that generates an acid upon exposure, or a thermal acid generator that generates an acid upon heating.

(Photoacid generator)
Examples of the photoacid generator include an anion moiety represented by the following general formula (an-1) or (an-2) and a cation represented by the following general formulas (ca-1) to (ca-4). Can be used.

［式中、Ｒｂ^０１〜Ｒｂ^０４は、それぞれ独立にフッ素原子、又は置換基を有していてもよいアリール基である。
Ｒｂ^０５は、フッ素原子、又は置換基を有していてもよいフッ素化アルキル基であって、複数のＲｂ^０５は同一であってもよく、それぞれ異なっていてもよい。］

[Wherein, Rb ^{01 to} Rb ⁰⁴ are each independently a fluorine atom or an aryl group which may have a substituent.
Rb ⁰⁵ is a fluorine atom or a fluorinated alkyl group which may have a substituent, and a plurality of Rb ⁰⁵ may be the same or different. ]

［式中、Ｒ^２０１〜Ｒ^２０７、およびＲ^２１１〜Ｒ^２１２は、それぞれ独立に置換基を有していてもよいアリール基、アルキル基又はアルケニル基を表し、
Ｒ^２０１〜Ｒ^２０３、Ｒ^２０６〜Ｒ^２０７、Ｒ^２１１〜Ｒ^２１２は、相互に結合して式中のイオウ原子と共に環を形成してもよい。
Ｒ^２０８〜Ｒ^２０９はそれぞれ独立に水素原子または炭素数１〜５のアルキル基を表し、
Ｒ^２１０は置換基を有していてもよいアリール基、アルキル基又はアルケニル基であり、
Ｌ^２０１は−Ｃ（＝Ｏ）−または−Ｃ（＝Ｏ）−Ｏ−を表し、
Ｙ^２０１は、それぞれ独立に、アリーレン基、アルキレン基又はアルケニレン基を表し、
ｘは１または２であり、
Ｗ^２０１は（ｘ＋１）価の連結基を表す。］

[Wherein, R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² each independently represents an aryl group, an alkyl group or an alkenyl group which may have a substituent,
R ^{201 to} R ²⁰³ , R ^{206 to} R ²⁰⁷ , and R ^{211 to} R ²¹² may be bonded to each other to form a ring together with the sulfur atom in the formula.
R ^{208 to} R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R ²¹⁰ is an aryl group, an alkyl group or an alkenyl group which may have a substituent,
L ²⁰¹ represents —C (═O) — or —C (═O) —O—,
Y ²⁰¹ each independently represents an arylene group, an alkylene group or an alkenylene group,
x is 1 or 2,
W ²⁰¹ represents a (x + 1) -valent linking group. ]

In formula (an-1), Rb ^{01 to} Rb ⁰⁴ are each independently a fluorine atom or an aryl group which may have a substituent.
The aryl group which may have a substituent of Rb ^{01 to} Rb ⁰⁴ preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. preferable. Specific examples include a naphthyl group, a phenyl group, and an anthracenyl group, and a phenyl group is preferable because it is easily available.
The aryl group may have a substituent. Although it does not specifically limit as a substituent, A halogen atom, a hydroxyl group, and a hydrocarbon group (a linear or branched alkyl group is preferable, and C1-C5 is preferable), a halogen atom or A halogenated alkyl group having 1 to 5 carbon atoms is more preferable, and a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is particularly preferable. When the aryl group has a fluorine atom, the polarity of the anion moiety is increased, and Rb ^{01 to} Rb ⁰⁴ are preferably perfluoroaryl groups.

Preferable specific examples of the anion moiety represented by the formula (an-1) include tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ); tetrakis [(trifluoromethyl) phenyl] borate ([B (C ₆ H ₄ CF ₃ ) ₄ ] ⁻ ); difluorobis (pentafluorophenyl) borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ⁻ ); trifluoro (pentafluorophenyl) borate ([( C ₆ F ₅ ) BF ₃ ] ⁻ ); tetrakis (difluorophenyl) borate ([B (C ₆ H ₃ F ₂ ) ₄ ] ⁻ ) and the like. Of these, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferable.

In the formula (an-2), Rb ⁰⁵ is a fluorine atom or a fluorinated alkyl group which may have a substituent, and a plurality of Rb ⁰⁵ may be the same or different. Good.
The fluorinated alkyl group which may have a substituent of Rb ⁰⁵ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 and even more preferably 1 to 5. Specifically, in the alkyl group having 1 to 5 carbon atoms, a group in which part or all of the hydrogen atoms are substituted with fluorine atoms can be used.
Among them, Rb ⁰⁵ is preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, a fluorine atom, a trifluoromethyl group or pentafluoro. More preferred is an ethyl group.

  As the anion moiety represented by the formula (an-2), an anion moiety represented by the following formula (an-21) is also preferable.

［式中、Ｒｂｆ^０５は置換基を有していてもよいフッ素化アルキル基であって、ｎｂ^１は１〜５の整数である。］

[Wherein, Rbf ⁰⁵ is a fluorinated alkyl group which may have a substituent, and nb ¹ is an integer of ¹ to 5. ]

In formula (an-21), the fluorinated alkyl group which may have a substituent for Rbf ⁰⁵ is the same as the fluorinated alkyl group which may have a substituent for Rb ^05. .
In formula (an-21), nb ¹ is preferably ¹ to 4, more preferably 2 to 4, and most preferably 3.

In formulas (ca-1) to (ca-4), examples of the aryl group in R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² include an unsubstituted aryl group having 6 to 20 carbon atoms, a phenyl group, A naphthyl group is preferred.
The alkyl group in R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² is a chain or cyclic alkyl group and preferably has 1 to 30 carbon atoms.
The alkenyl group in R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² preferably has 2 to 10 carbon atoms.
Examples of the substituent that R ^{201 to} R ²⁰⁷ and R ^{210 to} R ²¹² may have include, for example, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, And groups represented by formulas (ca-r-1) to (ca-r-9), respectively.

［式中、Ｒ’^２０１はそれぞれ独立に、水素原子、置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、又は置換基を有していてもよい鎖状のアルケニル基である。］

[Wherein, each R ′ ²⁰¹ independently has a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It may be a chain alkenyl group. ]

R ′ ²⁰¹ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. .

Cyclic group which may have a substituent:
The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

The aromatic hydrocarbon group for R ′ ²⁰¹ is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, further preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring of the aromatic hydrocarbon group in R ′ ²⁰¹ include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a part of carbon atoms constituting these aromatic rings substituted with a heteroatom. And aromatic heterocycles. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specific examples of the aromatic hydrocarbon group for R ′ ²⁰¹ include a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), and one of the hydrogen atoms of the aromatic ring. And a group substituted with an alkylene group (for example, an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.) and the like. . The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

Examples of the cyclic aliphatic hydrocarbon group for R ′ ²⁰¹ include an aliphatic hydrocarbon group containing a ring in the structure.
As the aliphatic hydrocarbon group containing a ring in this structure, an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), an alicyclic hydrocarbon group is linear or branched Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group in which one or more hydrogen atoms have been removed from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among these, the polycycloalkane includes polycycloalkanes having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane; condensed ring systems such as a cyclic group having a steroid skeleton A polycycloalkane having a polycyclic skeleton is more preferable.

Among them, the cyclic aliphatic hydrocarbon group for R ′ ²⁰¹ is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane or polycycloalkane, and a group obtained by removing one hydrogen atom from a polycycloalkane. More preferred are an adamantyl group and a norbornyl group, and most preferred is an adamantyl group.

The linear or branched aliphatic hydrocarbon group that may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 4 carbon atoms. Is more preferable, and 1-3 are most preferable.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [ — (CH ₂ ) ₃ —], tetramethylene group [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like can be mentioned.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH _{3) 2} -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) _{CH 2 CH 2 CH 2 -,} - CH 2 CH (CH 3) CH 2 CH 2 - And the like alkyl alkylene group such as an alkyl tetramethylene group of. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

A chain-like alkyl group which may have a substituent:
The chain alkyl group for R ′ ²⁰¹ may be either linear or branched.
The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specifically, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group Group, pentadecyl group, hexadecyl group, isohexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group and the like.
The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, Examples include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and the like.

A chain-like alkenyl group which may have a substituent:
The chain alkenyl group for R ′ ²⁰¹ may be either linear or branched, preferably has 2 to 10 carbon atoms, more preferably 2 to 5, more preferably 2 to 4, 3 is particularly preferred. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched alkenyl group include 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, 2-methylpropenyl group and the like.
Among the above, the chain alkenyl group is preferably a linear alkenyl group, more preferably a vinyl group or propenyl group, and particularly preferably a vinyl group.

Examples of the substituent in the chain alkyl group or alkenyl group of R ′ ²⁰¹ include, for example, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the cyclic group in R ′ ²⁰¹ above. Etc.

Among them, R ′ ²⁰¹ is preferably a cyclic group which may have a substituent, or a chain-like alkyl group which may have a substituent, and a cyclic group which may have a substituent. A group is more preferable, and an aromatic hydrocarbon group which may have a substituent is particularly preferable.

^{R 201 ~R 203, R 206 ~R} 207, R 211 ~R 212 , when bonded to each other to form a ring with the sulfur atom, a sulfur atom, an oxygen atom, or a hetero atom such as nitrogen atom, carbonyl _{group, -SO -, - SO 2 -} , - SO 3 -, - COO -, - CONH- , or -N _(R N) - (. the _{R N} is an alkyl group having 1 to 5 carbon atoms), etc. You may couple | bond through the functional group of. As the ring to be formed, one ring containing a sulfur atom in the ring skeleton in the formula is preferably a 3- to 10-membered ring, particularly a 5- to 7-membered ring, including the sulfur atom. preferable. Specific examples of the ring formed include, for example, thiophene ring, thiazole ring, benzothiophene ring, thianthrene ring, benzothiophene ring, dibenzothiophene ring, 9H-thioxanthene ring, thioxanthone ring, thianthrene ring, phenoxathiin ring, tetrahydro A thiophenium ring, a tetrahydrothiopyranium ring, etc. are mentioned.

In formula (ca-3), R ^{208 to} R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, In this case, they may be bonded to each other to form a ring.

In formula (ca-3), R ²¹⁰ represents an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. An —SO ₂ — containing cyclic group which may have a group.
The aryl group in R ^210, include unsubstituted aryl group having 6 to 20 carbon atoms, a phenyl group, a naphthyl group.
The alkyl group for R ²¹⁰ is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group for R ²¹⁰ preferably has 2 to 10 carbon atoms.
In R ^210, -SO which may have a substituent 2 _- containing cyclic group, -SO 2 _- within the ring skeleton thereof means a cyclic group containing a ring containing, in particular, A cyclic group in which the sulfur atom (S) in —SO ₂ — forms part of the cyclic skeleton of the cyclic group. The ring containing —SO ₂ — in the ring skeleton is counted as the first ring, and when it is only the ring, it is a monocyclic group, and when it has another ring structure, it is a polycyclic group regardless of the structure. Called. The —SO ₂ — containing cyclic group may be monocyclic or polycyclic, but is preferably a polycyclic group. Further, the ring -O-SO ₂ in the skeleton - cyclic group containing, i.e. -O-SO ₂ - ring -O-S- is medium containing sultone (sultone) ring forms part of the ring skeleton A formula group is preferred.

In formula (ca-4), Y ²⁰¹ each independently represents an arylene group, an alkylene group, or an alkenylene group.
Examples of the arylene group in Y ²⁰¹ include a group in which two hydrogen atoms have been removed from the aromatic ring exemplified in the description of the aromatic hydrocarbon group in R ^{201 ′} .
Examples of the alkylene group and alkenylene group for Y ²⁰¹ include a group obtained by removing one hydrogen atom from the groups exemplified as the chain alkyl group and the chain alkenyl group for R ^{201 ′} .

In the formula (ca-4), x is 1 or 2.
In formula (ca-4), W ²⁰¹ represents a (x + 1) -valent, that is, divalent or trivalent linking group.
As the divalent linking group in W ^{201, a} divalent hydrocarbon group which may have a substituent is preferable, and the divalent linking group exemplified for Y ¹ and Y ² in the above formula (A1) and The same group may be mentioned, which may be linear, branched or an aliphatic hydrocarbon group containing a ring in the structure or an aromatic hydrocarbon group, and an aliphatic hydrocarbon containing a ring in the structure It is preferably a group or an aromatic hydrocarbon group. Of these, a group in which two carbonyl groups are combined at both ends of an arylene group, or a group consisting of only an arylene group is preferable. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferable.
^Examples of the trivalent linking group in W ²⁰¹ include a group obtained by removing one hydrogen atom from the divalent linking group in W ²⁰¹ , a group in which the divalent linking group is further bonded to the divalent linking group, and the like. Can be mentioned. The trivalent linking group in W ²⁰¹ is preferably a group in which two carbonyl groups are bonded to an arylene group.

  Specific examples of suitable cations represented by formula (ca-1) include cations represented by the following formulas (ca-1-1) to (ca-1-18), respectively.

  Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation and bis (4-tert-butylphenyl) iodonium cation.

  Specific examples of suitable cations represented by the formula (ca-4) include cations represented by the following formulas (ca-4-1) to (ca-4-2).

  Among the above, the cation part is preferably a cation represented by the general formula (ca-1), and more preferably a cation represented by each of the formulas (ca-1-1) to (ca-1-18).

Examples of the photoacid generator include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone;
Benzophenones such as benzophenone, 2-chlorobenzophenone and p, p′-bisdimethylaminobenzophenone; benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
Sulfur compounds such as thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene; 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2, Anthraquinones such as 3-diphenylanthraquinone;
Organic peroxides such as benzoyl peroxide and cumene peroxide;
Thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; imidazolyl such as 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer Compound;
triazine compounds such as p-methoxytriazine;
2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl ] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-Diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (triazine compound having a 4-n-butoxyphenyl) -4,6-bis (halomethyl groups such as trichloromethyl) -s-triazine;
Aminoketone compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one;
Oxime ester compounds such as ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime);
α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2 -Chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, [alpha]-(ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, and oxime sulfonate compounds;
Bissulfonyldiazomethanes such as bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane; p-toluenesulfone Nitrobenzyl derivatives such as 2-nitrobenzyl acid, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate, dinitrobenzyl carbonate;
Pyrogallol trimesylate, pyrogallol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, N-methylsulfonyloxyphthalimide, etc. Kind;
Trifluoromethanesulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide;
Diphenyliodonium hexafluorophosphate, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenyl Onium salts such as sulfonium trifluoromethanesulfonate and (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate;
Benzoin tosylates such as benzoin tosylate and α-methylbenzoin tosylate;
Other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzyl carbonate, bisalkyl or bisarylsulfonyldiazomethanes, diazomethane acid generators such as poly (bissulfonyl) diazomethanes, and the like can also be used.

  IRGACURE PAG290 (manufactured by BASF Japan), CPI-210S (manufactured by San Apro), and the like can be used as commercial products of the photoacid generator.

(Thermal acid generator)
The thermal acid generator is preferably an acid generator that decomposes at about 100 ° C. to generate an acid. By using a thermal acid generator capable of generating an acid at about 100 ° C., it is suitably cured even when a member or device bonded using the adhesive composition of this embodiment is inferior in heat resistance. It can be performed. For example, also when using the adhesive composition of this embodiment for OLED use, an epoxy compound can be hardened reliably, suppressing the influence of the heat | fever to a LED element.
As such a thermal acid generator, for example, it has an anion moiety represented by the above general formula (an-1) or (an-2) and a cation moiety represented by the following general formula (ca-11). An onium salt compound can be used.

［式中、Ｒｂ^１１は水素原子又は炭素数１〜５のアルキル基を示し、Ｒｂ^１２〜Ｒｂ^１３は、それぞれ独立に置換基を有していてもよいアルキル基、アリール基、アリールアルキル基又はアルケニル基を表す。］

[Wherein, Rb ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Rb ^{12 to} Rb ¹³ each independently represents an alkyl group, an aryl group, an arylalkyl group, or Represents an alkenyl group. ]

In formula (ca-11), Rb ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
In formula (ca-11), the bonding position of the hydroxyl group (—OH) is not particularly limited, but the para position is preferable.

In formula (ca-11), Rb ^{12 to} Rb ¹³ each independently represent an alkyl group, an aryl group, or an alkenyl group that may have a substituent.
The alkyl group in Rb ^{12 to} Rb ¹³ is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The aryl group in Rb ¹² ~Rb ^13, include an unsubstituted aryl group having 6 to 20 carbon atoms, a phenyl group, a naphthyl group.
The arylalkyl group in Rb ^{12 to} Rb ¹³ is preferably a benzyl group or a phenethyl group.
The alkenyl group for Rb ^{12 to} Rb ¹³ preferably has 2 to 10 carbon atoms.
Examples of the substituent that Rb ^{12 to} Rb ¹³ may have include, for example, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and the formula (ca-r-1). ) To (ca-r-9), respectively.

A thermal acid generator using a quaternary ammonium cation instead of the cation moiety represented by the above formula (ca-11) is also preferable. The quaternary ammonium cation is represented by “N ⁺ -(Rb ¹⁵ ) ₄ ”, and Rb ¹⁵ is an alkyl group, an aryl group or an alkenyl group which may each independently have a substituent, and the above Rb ¹² ~Rb ¹³ is the same as that.

In addition, as the thermal acid generator, a cationic or protonic acid catalyst such as trifluoromethanesulfonate, boron trifluoride etherate, hexafluorophosphate, perfluorobutanesulfonate, boron trifluoride, etc. Etc. can also be used. Specific examples include diethylammonium trifluoromethanesulfonate, triethylammonium trifluoromethanesulfonate, diisopropylammonium trifluoromethanesulfonate, ethyl diisopropylammonium trifluoromethanesulfonate, and the like.
Among aromatic onium salts that are also used as acid generators, there are those that generate cationic species by heat, and these can also be used as thermal cationic polymerization initiators. Commercially available products include, for example, Sun-Aid SI-45, SI-47, SI-60, SI-60L, SI-80, SI-80L, SI-100, SI-100L, SI-110, SI-110L, SI-145, SI-150, SI-160, SI-180L, SI-B3, SI-B3A (manufactured by Sanshin Chemical Industry Co., Ltd.); CI-2921, CI-2920, CI-2946, CI-3128, CI-2624, CI- 2639, CI-2064 (manufactured by Nippon Soda Co., Ltd.); CP-66, CP-77 (manufactured by ADEKA); FC-520 (manufactured by 3M) K-PURE TAG-2396, TAG-2713S, TAG-2713, TAG- 2172, TAG-2179, TAG-2168E, TAG-2722, TAG-2507, TAG-2678, TAG-2681, TAG- 2679, TAG-2690, TAG-2700, TAG-2710, TAG-2100, CDX-3027, CXC-1615, CXC-1616, CXC-1750, CXC-1738, CXC-1614, CXC-1742, CXC-1743, CXC-1613, CXC-1739, CXC-1751, CXC-1766, CXC-1763, CXC-1736, CXC-1756, CXC-1821, CXC-1802-60 (manufactured by KING INDUSTRY) and the like.

As the component (B), the above-mentioned photoacid generator and thermal acid generator may be used singly or in combination of two or more.
As for content of (B) component in adhesive composition, 0.01-60 mass parts is preferable with respect to 100 mass parts of total amounts of (A1) component and (A2) component, 0.5-30 mass parts Is more preferable, and 1-10 mass parts is further more preferable.
By making content of (B) component more than the said lower limit, the (A1) component and (A2) component which are epoxy compounds can be hardened | cured favorably. Moreover, compatibility with another component can be made favorable by setting it as the said upper limit or less.

<Optional component>
[Surfactant (E)]
The adhesive composition in the present embodiment further contains a surfactant (E) (hereinafter also referred to as “component (E)”) in addition to the above components (A1), (A2) and (B). You may contain.
Examples of the component (E) include silicone surfactants and fluorine surfactants.
Specific examples of the silicone surfactant include BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, and BYK-322. BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341, BYK-344, BYK-345, BYK-346, BYK-348, BYK-354, BYK -355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390 (manufactured by BYK Chemie) or the like can be used.
Specific examples of the fluorosurfactant include F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, and F-445. F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F -484, F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130 TF-1116SF, TF-1131, TF-1132, TF-1027SF, TF-1441, TF-1442 (manufactured by DIC); Polyfox series PF- 36, PF-6320, PF-656, PF-6520 (manufactured by OMNOVA Solutions Inc.) may be used.

(E) A component may be used individually by 1 type and may use 2 or more types together.
The content of the component (E) is preferably 0.01 to 10 parts by mass, and 0.02 to 2 parts by mass with respect to 100 parts by mass in total of the components (A1) and (A2). More preferably, it is 0.0.3-1 mass part. By setting it as the said range, the adhesiveness of the contact bonding layer which consists of an adhesive composition, and a board | substrate or a support body can be made favorable.

[(S) component: organic solvent component]
The adhesive composition of this embodiment can be produced by dissolving it in an organic solvent (S) (hereinafter sometimes referred to as “component (S)”) for the purpose of improving applicability and adjusting viscosity.
As component (S), benzene, toluene, xylene, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 3-methoxybutyl acetate (MA), 3-methoxybutanol (BM) , 3-methyl- -Methoxybutyl acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate or a mixture thereof . Among these, it is preferable to use PGMEA, PGMEA, MA, a mixed solvent of PGME and PGMEA, a mixed solvent of MA and BM, and the like.

  Although the usage-amount of (S) component is not specifically limited, It is suitably set according to the film thickness of the contact bonding layer to form at the density | concentration which can be apply | coated to a board | substrate etc. Specifically, the solid content concentration of the adhesive composition is preferably in the range of 10 to 95% by mass, particularly 20 to 90% by mass.

  When the adhesive composition of this embodiment contains (S) component, it is preferable that the viscosity in 25 degreeC of an adhesive composition is 0.005-10 Pa.s, and is 0.01-1 Pa.s. It is more preferable. By forming the adhesive layer by applying the adhesive composition by setting the viscosity to the above lower limit value or more, a predetermined film thickness, for example, a film thickness of 1 to 20 μm, preferably 2 to 10 μm is secured. Can do.

The viscosity can be measured by a known method using a rotational viscometer or the like.
More specifically, in the case of using an E-type viscometer with a corn plate type thermostatic bath, the adhesive composition solution collected using a syringe is injected into a cup installed at the bottom of the corn plate, and 100 rpm The viscosity can be calculated by converting the resistivity applied to the cone plate when the cone plate is rotated for 3 minutes.

[Other additives]
The adhesive composition of the present embodiment may further contain other miscible materials as long as the properties are not impaired. For example, various commonly used additives such as additional resins, plasticizers, adhesion assistants, stabilizers, colorants, dyes and the like for improving the performance of the adhesive can be further used.

  The adhesive composition of the present embodiment described above contains (A1) component and (A2) component at a predetermined ratio, so that heat resistance, moisture resistance, heat cycle characteristics, applicability, transparency, etc. Not only the performance required for general OLED adhesives, but also adhesive performance such as reduction of adhesive protrusion at the edge portion, reduction of voids (voids) after curing, uniformity during application, and the like are improved. Therefore, the adhesive composition of the present embodiment is suitable for OLED applications, particularly for applications in which a substrate and a support are bonded.

≪Laminated body≫
The laminate which is the second aspect of the present invention is formed by bonding the substrate and the support through the adhesive layer containing the adhesive composition which is the first aspect of the present invention. is there.
The substrate is not particularly limited, and a conventionally known substrate can be used. Examples thereof include a substrate for electronic components and a substrate on which a predetermined wiring pattern is formed. More specifically, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. As a material for the wiring pattern, for example, copper, aluminum, nickel, gold or the like can be used.
The substrate may be one in which an inorganic and / or organic film is provided on the above-described substrate. An inorganic antireflection film (inorganic BARC) is an example of the inorganic film. Examples of the organic film include an organic antireflection film (organic BARC) and an organic film such as a lower organic film in a multilayer resist method.
The support is not particularly limited, and examples thereof include a support made of glass and a support made of a metal or an alloy.

The thickness of the adhesive layer is preferably 1 to 20 μm, and more preferably 2 to 10 μm.
Further, the melt viscosity at 25 ° C. of the formed adhesive layer is preferably 1.5 to 100 Pa · s, and more preferably 3 to 60 Pa · s. By setting the melt viscosity to be equal to or higher than the above lower limit, it is possible to reduce the protrusion when the adhesive composition is applied to form the adhesive layer. Moreover, generation | occurrence | production of the void at the time of forming an adhesive layer using an adhesive composition can be reduced by making a viscosity below the said upper limit.

The melt viscosity can be measured by a known method using a dynamic viscosity measuring device or the like.
More specifically, after the adhesive composition is applied onto a silicon wafer, it is baked on a hot plate at 100 ° C. for 5 minutes (when it contains a thermal acid generator as the component (B), it is heated at 80 ° C. for 10 minutes). An adhesive layer having a thickness of 100 μm is formed. The formed adhesive layer can be measured for melt viscosity at 25 ° C. (frequency: 10 Hz) using a dynamic viscosity measuring device (Reogel-E4000, manufactured by UBM Co., Ltd.).

  The method for producing the laminate of the second aspect is not particularly limited, and for example, it can be produced by the production method of the third aspect described later.

≪Laminated body manufacturing method≫
Although the manufacturing method of a laminated body is not specifically limited, For example, the adhesive composition which is the said 1st aspect of this invention is apply | coated on a board | substrate, a baking process is performed, and an adhesive layer is formed. A support body is arrange | positioned on the said contact bonding layer, and pressurization and temporary fixing are carried out as needed. Then, if the substrate-adhesive layer-photoacid generator is used, exposure is performed, and if the thermal acid generator is used, heating is performed to cure the adhesive layer, and then through the adhesive layer. A board | substrate and a support body can be bonded together.

Application of the adhesive composition can be performed using a general coating apparatus such as a spin coater, a roll coater, a spray coater, or a slit coater.
The baking treatment can be performed, for example, on a hot plate at a temperature of 80 to 150 ° C. for 0.5 to 60 minutes, preferably 1 to 30 minutes. Moreover, when using a thermal acid generator as (B) component which an adhesive composition contains, it is preferable to set baking temperature and time below the temperature which a thermal acid generator can generate | occur | produce an acid.
The bonding of the support and the substrate is preferably performed by applying a pressure of 30 to 5000 kgf under vacuum or a substantially vacuum condition. Moreover, you may heat at the time of bonding as needed. A general vacuum pressure bonding apparatus can be used for such bonding.

A low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like can be used as a radiation source at the time of exposure when a photoacid generator is used. The radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, γ rays, electron beams, proton beams, neutron beams, ion beams, and the like. The amount of radiation irradiation varies depending on the composition of the adhesive composition of the present embodiment, the film thickness of the adhesive layer, and the like, but is, for example, 100 to 10,000 mJ / cm ² when using an ultrahigh pressure mercury lamp. After the exposure, further baking treatment can be performed to promote the diffusion of the generated acid and the curing of the adhesive layer. The baking is performed, for example, at a temperature of 80 to 150 ° C. for 5 minutes to 120 minutes, preferably 30 minutes to 60 minutes.
When the thermal acid generator is used, the heating for curing the adhesive layer is performed at a temperature of 80 to 150 ° C., more preferably 90 to 110 ° C., for 5 to 120 minutes, preferably 30 to 60 minutes. Minutes are preferred.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.
In this example, the compound represented by the chemical formula (1) is referred to as “compound (1)”, and the same applies to compounds represented by other chemical formulas.

[Examples 1-7, Comparative Examples 1-4]
<Preparation of adhesive composition>
Each component shown in Table 1 was mixed and dissolved in PGEMA (propylene glycol monomethyl ether acetate) to prepare an adhesive composition used for manufacturing the laminates in each example (solid content concentration 70% by mass, viscosity 0) .05 Pa · s).

In Table 1, each abbreviation has the following meaning. The numerical value in [] is a compounding amount (part by mass).
(A) -1: The following compound (A) -1 (Celoxide 2021P (trade name), manufactured by Daicel Chemical Industries, Ltd.).
(A) -2: a polyfunctional alicyclic epoxy resin (EHPE3150 (trade name)) corresponding to the compound represented by the formula (A2-1) (having a group represented by the formula (a 1 )) Manufactured by Daicel Chemical Industries, Ltd.).
(A) -A: bisphenol A type epoxy resin (jER 827 (trade name), manufactured by Mitsubishi Chemical Corporation).
(A) -B: Hydrogenated bisphenol A type epoxy resin (jER YX8000 (trade name), manufactured by Mitsubishi Chemical Corporation).
(B) -1: The following compound (B) -1 (CPI-210S (trade name), manufactured by San Apro).
(B) -2: The following compound (B) -2 Tris (4- (4-acetylphenyl) thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate (Irgacure PAG290 (trade name), manufactured by BASF Japan Ltd.).
(B) -3: The following compound (B) -3 (Sun aid SI-B3 (trade name), manufactured by Sanshin Chemical Industry Co., Ltd.).
(B) -4: The following compound (B) -4 (Sun-Aid SI-110 (trade name), manufactured by Sanshin Chemical Industry Co., Ltd.).
(B) -5: Thermal acid generator K-PURE CXC-1821 (trade name; manufactured by KING INDUSTRY) .
(E) -1: The following compound (E) -1 (Polyfox PF-656 (trade name), manufactured by Omninova).

<Heat resistance evaluation>
The adhesive composition of each of the above examples was uniformly applied on a glass substrate using a spin coater, and baked at the temperature and time shown in Table 1, and the adhesive layer having the thickness shown in Table 1 was formed. Formed.
The glass substrate having the formed adhesive layer was heated at 85 ° C. for 1000 hours using an oven. The transmittance of the adhesive layer after heating was measured with a commercially available spectrophotometer, and those having a transmittance of 97.5% or more were evaluated as ◯ and those having a transmittance of less than 97.5% were evaluated as x. The results are shown in Table 2 as “heat resistance”.

<Moisture resistance evaluation>
The adhesive composition of each of the above examples was uniformly applied on a glass substrate using a spin coater, and baked at the temperature and time shown in Table 1, and the adhesive layer having the thickness shown in Table 1 was formed. Formed.
The glass substrate having the formed adhesive layer was allowed to stand for 1000 hours under conditions of 60 ° C. and 90% humidity. The transmittance of the adhesive layer after standing was measured with a commercially available spectrophotometer, and those having a transmittance of 97.5% or more were evaluated as ◯ and those having a transmittance of less than 97.5% were evaluated as x. The results are shown in Table 2 as “moisture resistance”.

<Heat cycle evaluation>
The adhesive composition of each of the above examples was uniformly applied on a glass substrate using a spin coater, and baked at the temperature and time shown in Table 1, and the adhesive layer having the thickness shown in Table 1 was formed. Formed.
The glass substrate having the formed adhesive layer is used as a sample and put into a thermal shock tester TSE-11-A (trade name; manufactured by ESPEC), and the sample is put into a -30 ° C constant temperature bath and 85 ° C respectively. It moved between thermostats. The holding time of the sample in each thermostat was 30 minutes, and it was set as 1 heat cycle in 1 hour in total. After carrying out the heat cycle test up to 100 cycles, the transmittance of the adhesive layer is measured using a commercially available spectrophotometer after the end of 100 cycles, and the transmittance is 97.5% or more. What was less than was evaluated as x. The results are shown in Table 2 as “heat cycle”.

(Melt viscosity)
The adhesive compositions of the above examples were uniformly applied onto an 8-inch silicon wafer using a spin coater, and baked at the temperatures and times shown in Table 1 to form an adhesive layer having a thickness of 100 μm. . About the formed contact bonding layer, the melt viscosity in 25 degreeC (frequency 10Hz) was measured with the dynamic viscosity measuring apparatus (Reogel-E4000, UBM Co., Ltd. make). The results are also shown in Table 1.

<Manufacture of laminates>
The adhesive composition of each of the above examples was uniformly applied onto an 8-inch silicon wafer using a spin coater and baked at the temperature and time shown in Table 1 to obtain the film thicknesses shown in Table 1. An adhesive layer was formed.
Next, a glass substrate (0.7 μm) was placed on the adhesive layer, and pasting was performed for 60 seconds under vacuum pressure conditions of 25 ° C., 100 kgf, and less than 20 Pa.
Thereafter, in Examples 1 to 3 and 7 and Comparative Examples 1 to 4, the entire surface exposure (1000 mJ / cm ² ) was performed using a high-pressure mercury lamp from the glass substrate, and then exposed at 100 ° C. for 60 minutes. Post-heating treatment was performed to cure the adhesive layer, and a laminate was obtained.
Moreover, in Examples 4-6, the heat processing for 60 minutes were performed at 100 degreeC, the adhesive bond layer was hardened, and the laminated body was obtained.

<Applicability evaluation>
In manufacturing the laminate as described above, the adhesive layer after the adhesive composition was applied on an 8-inch silicon wafer and baked was visually observed. The results of evaluation based on the following criteria are shown in Table 2 as “applicability”.
○: No striation is allowed.
X: A striation occurred.

<Paste performance evaluation>
Table 2 shows the results obtained by visually observing the laminate produced as described above, and evaluating it according to the following criteria as “sticking performance”.
TTV is a total thickness variation, and is an index of the accuracy of the thickness of the entire laminate. TTV was measured using C8870 manufactured by Hamamatsu Photonics. The smaller the TTV value, the higher the thickness accuracy.
○: The adhesive composition does not protrude from the edge portion, no void is generated, and the TTV is less than 2 μm.
X: The adhesive composition protrudes in the edge part and / or the void has generate | occur | produced and / or TTV is 2 micrometers or more.

From the results shown in Table 2, it was confirmed that Examples 1 to 7 showed heat resistance equivalent to that of Comparative Examples 1 to 4 or superior to that of Comparative Examples 1 to 4.
Moreover, it has confirmed that Examples 1-7 showed the sticking performance superior to Comparative Examples 1-4.

Claims (6)

An alicyclic epoxy compound (A1) represented by the following formula (A1) and a polyfunctional alicyclic epoxy compound represented by the following formula (A2-1) not corresponding to the alicyclic epoxy compound (A1) ( An adhesive composition containing A2) and an acid generator (B),
The mass ratio of the alicyclic epoxy compound (A1) and the polyfunctional alicyclic epoxy compound (A2) is (A1) / (A2) = 70/30 to 51/49. Agent composition.

[Wherein R ¹ and R ² are each independently an organic group optionally having an alicyclic epoxy group, and at least ^one of R ¹ and R ² has an alicyclic epoxy group. Y ¹ and Y ² are each independently a single bond or a divalent linking group. ]

[Wherein R ¹¹ is a residue obtained by removing an active hydrogen group in an organic compound having q active hydrogen groups. n ¹¹ , n ¹² ,..., n ^q each independently represents an integer of 0 to 100, and the sum thereof is 4 to 100. q shows the integer of 1-100. A is represented by the oxycyclohexane skeleton containing substituents ^{R 12,} or having a oxy norbornene skeleton containing substituents ^{R 12,} and the following formula (a1) or (a2). ]

[Wherein, R ¹² is independently a group represented by any one of the following formulas (a11) to (a13), and the compound represented by the formula (A2-1) is represented by (a11) One or more groups. The groups represented by the formulas (a1) and (a2) are bonded to R ¹¹ in the compound represented by the formula (A2-1) at the wavy bond, and the formula (A2-1) is bonded to the bond at the * mark. ) To a hydrogen atom (H) in the compound represented by ]

[Wherein, R ¹³ represents an alkyl group, an alkylcarbonyl group, or an arylcarbonyl group. The group represented by any one of the formulas (a11) to (a13) is bonded to the groups represented by the formulas (a1) and (a2) at the wavy bond. ]   The adhesive composition according to claim 1, further comprising an organic solvent and having a viscosity at 25 ° C of 0.005 to 10 Pa · s.   The adhesive composition of Claim 1 or 2 used in order to adhere | attach a board | substrate and a support body.   The laminated body formed by bonding a board | substrate and a support body through the contact bonding layer containing the adhesive composition as described in any one of Claims 1-3. The thickness of the adhesive layer is a 1 to 20 [mu] m, the melt viscosity at 25 ° C. of the adhesive layer is a 3~60Pa · s, laminate according to claim 4.   The manufacturing method of a laminated body which bonds a board | substrate and a support body through the contact bonding layer containing the adhesive composition as described in any one of Claims 1-3.