WO2022102624A1

WO2022102624A1 - Curable composition and cured product thereof

Info

Publication number: WO2022102624A1
Application number: PCT/JP2021/041220
Authority: WO
Inventors: 彰治森山; 雄介山本; 和義保坂; 和輝江口
Original assignee: 日産化学株式会社
Priority date: 2020-11-11
Filing date: 2021-11-09
Publication date: 2022-05-19
Also published as: JPWO2022102624A1; CN116391001A; KR20230104893A; TW202225354A

Abstract

This curable composition contains the following components (A) and (B).　Component (A): a monofunctional radical-polymerizable compound containing a compound represented by formula [1] Component (B): a radical initiator (In formula [1], X¹ represents a structure selected from among formulae [1-a] to [1-g].　X² represents a linear C2-14 alkylene group. The alkylene group may be subjected to specific substitution.　X³ represents -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, or-NH-.　X⁴ represents a linear or branched C12-40 alkyl group.) (T^A represents a hydrogen atom or a benzene ring. * indicates a bond.)

Description

Curable composition and its cured product

The present invention relates to a curable composition and a cured product thereof.

In display elements and semiconductor elements, various adhesives have been conventionally used for the purpose of attaching various members inside the element. The properties required for an adhesive are not only the adhesion between the base material and the member, but also its workability and reliability.

Further, the adherend to be adhered includes an organic base material such as a printed wiring board and a transparent polyimide film, and an inorganic base material such as glass, aluminum, ITO (Indium Tin Oxide), and SiN (Silicon Nitride). Therefore, the adhesive needs to be designed according to each target adherend.

So far, epoxy curable resin components using highly reliable epoxy group compounds and radical curable resin components using radically polymerizable compounds have been used as adhesives for display elements and semiconductor elements. (For example, Patent Document 1 and Patent Document 2).

The epoxy curing system includes a compound having an epoxy group, an epoxy resin, and a resin component including a curing catalyst in which a cationic catalyst is generated by heat or light. On the other hand, the radical curing system is generally a resin component containing a compound having an acrylate group or the like that undergoes radical polymerization, a resin thereof, and a radical initiator that generates a radical by irradiation with heat or ultraviolet rays.

Japanese Unexamined Patent Publication No. 2010-229172 Japanese Unexamined Patent Publication No. 2002-203427

As the optical element becomes thinner, it is required to reduce the film thickness of the adhesive layer (also referred to as an adhesive layer) used for the optical element. In order to reduce the film thickness of the adhesive layer, it is necessary to reduce the film thickness of the curable composition to be applied to the substrate. However, many of the conventional curable compositions using a compound having an epoxy group have a high viscosity, and when it is applied with a thin film thickness, repelling and coating unevenness are likely to occur.

In addition, in the radical curable composition, the radicals are susceptible to oxygen inhibition, so that the curability of the adhesive layer is low. Further, since the curing shrinkage at the time of curing is larger than that using an epoxy group, strain and voids are generated at the interface between the base material and the adhesive layer, and the adhesive strength (also referred to as adhesion) to the base material is generated. There is a problem that the

From the above points, it is an object of the present invention to provide a radical curable curable composition having a low viscosity, a small curing shrinkage, and a high adhesiveness.

As a result of diligent research to achieve the above object, the present inventor has completed the present invention having the following gist.
That is, it is a curable composition containing the following components (A) and (B).
Component (A): Monofunctional radically polymerizable compound containing a compound represented by the following formula [1] (also referred to as a specific compound) Component (B): Radical initiator

(In the formula [1], X ¹ indicates a structure selected from the following formulas [1-a] to [1-g].
X ² represents a linear alkylene group having 2 to 14 carbon atoms. However, the alkylene group may be substituted with at least one of the following (i) and (ii).
(I): Any -CH _2- , -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-,-, which is not adjacent to X ¹ or X ³ of the above alkylene group. Substitution with NH-, benzene ring or cyclohexane ring (ii) Substitution of any -CH _2- for the above alkylene group with -CH (CH ₃ )-X ³ is -O-, -CO-, -COO- , -OCO-, -CONH-, -NHCO- or -NH-.
X4 represents a linear or branched alkyl group having 12 to ⁴⁰ carbon atoms. )

( ^TA indicates a hydrogen atom or a benzene ring. * Indicates a bond.)

Since the curable composition of the present invention has a low viscosity, it can be applied to various coating methods and can be uniformly coated without uneven film thickness. Further, when the curable composition of the present invention is used as an adhesive for a display element or a semiconductor element, the curing shrinkage is small and the adhesiveness is high. It is possible to suppress the generation and obtain a highly reliable element.
The mechanism by which the curable composition having the above-mentioned excellent properties is obtained by the present invention is not necessarily clear, but it is presumed as follows.
A radically curable polymerizable compound that reacts with a radical is used as the curable composition. Therefore, since the viscosity is lower than that of the compound having an epoxy group, the viscosity of the curable composition using the compound is low.
Further, the structure of X4 in the above formula [ ¹ ] in the specific compound is a long-chain alkyl group in which the Tg of the cured product is low. Therefore, the curable composition containing the specific compound is cured while maintaining its viscosity, so that the adhesion to the base material and the member is improved. Further, since the structure of ^X4 has a large exclusion volume between molecules, it is possible to reduce the curing shrinkage.

It is the schematic which looked at the test cell used for the adhesion evaluation from the top surface. It is the schematic which looked at the test cell used for the adhesion evaluation from the side. It is a schematic diagram of the U-shaped upper jig used for the adhesion evaluation. It is a schematic diagram of the U-shaped lower jig used for the adhesion evaluation. It is the schematic which looked at the test cell from the top view explaining the area where the test cell and a U-shaped jig come into contact at the time of adhesion evaluation.

Hereinafter, the present invention will be specifically described.
The curable composition of the present invention contains the following components (A) and (B).
(A) Component: Monofunctional radically polymerizable compound containing the compound represented by the above formula [1] (B) Component: Radical initiator Further, another aspect of the present invention is represented by the above formula [1]. It is a compound.

<Ingredient (A)>
The component (A) is a monofunctional radically polymerizable compound containing a compound represented by the above formula [1] (also referred to as a specific compound) as an essential component. Here, the monofunctional radically polymerizable compound is a compound having one functional group that reacts with a radical in the molecule.
In the formula [1], X ¹ , X ² , X ³ and X ⁴ are as defined above, but the following are preferable.
From the viewpoint of enhancing the reactivity of the radical reaction, X ¹ preferably has a structure represented by the above formula [1-a], formula [1-b], formula [1-c] or formula [1-d].
X ² preferably has a structure represented by the following formula [X1a].

(In the formula [X1a], M ¹ and M ² independently represent -CH ₂ -CH _2- , -CH (CH ₃ ) -CH _2- or -CH ₂ -CH (CH ₃ )-. Z ¹ indicates -O-, -CO-, -COO- or -OCO-. N indicates an integer of 0 to 4. When n is an integer of 2 or more, n Z ¹ and M ² are respectively. It has the above definition independently. * 1 indicates the bond position with X ¹ and * 2 indicates the bond position with X ^3. )

X ³ is preferably -O-, -CO-, -COO- or -OCO-.
X4 is preferably a branched alkyl group having 12 to ⁴⁰ carbon atoms from the viewpoint of lowering the Tg of the cured product and increasing the intramolecular exclusion volume.

Among these, the specific compound is more preferably a compound represented by the following formula [1a].

(In the formula [1a], R ¹ represents a hydrogen atom or a methyl group. L ¹ and L ² are independently -CH ₂ -CH _2- , -CH (CH ₃ ) -CH _2- or -CH, respectively. ₂ -CH (CH ₃ )-indicates. Y ¹ indicates -O-, -CO-, -COO- or -OCO-. N indicates an integer of 0 to 4. When n is an integer of 2 or more. , N Y ¹ and L ² have the above definitions independently. Y ² indicates -COO- or -OCO-. L ³ is a single bond or a linear or branched form having 1 to 4 carbon atoms. R ² and R ³ independently represent a linear or branched alkyl group having 4 to 18 carbon atoms, respectively. R ⁴ is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms. When L ^{3 represents a group other than a single bond, the total number of carbon atoms of L 3} ^and R ² to R ⁴ is 11 to 39, and L ³ represents a single bond. , The total number of carbon atoms of ^R2 to ^R4 is 11 to 39.)

Specific specific compounds include compounds represented by the following formulas [A1] to [A5], and it is preferable to use these.

Further, from the viewpoint of adjusting the liquid properties of the curable composition and the film properties of the cured product, the component (A) may contain a monofunctional radically polymerizable compound other than the specific compound.

Examples of the monofunctional radically polymerizable compound other than the specific compound include 2-ethylhexyl acrylate, 1-butylethyl acrylate, 2-butoxyethyl acrylate, 2-cyanoethyl acrylate, benzyl acrylate, cyclohexyl acrylate, and 2-hydroxypropyl acrylate, 2 -Ethoxyethyl acrylate, N, N-diethyl-2-aminoethyl acrylate, N, N-dimethyl-2-aminoethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, isobol Nyl acrylate, isodecyl acrylate, lauryl acrylate, 4-acryloyl morpholine, 2-phenoxyethyl acrylate, diethylene glycol acrylate phenyl ether, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl Acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, 2-ethylhexyl methacrylate, 1-butylethyl methacrylate, 2-butoxyethyl methacrylate, 2 -Cyanoethyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethoxyethyl acrylate, N, N-diethyl-2-aminoethyl methacrylate, N, N-dimethyl-2-aminoethyl methacrylate, dicyclopentanyl Methacrylate, dicyclopentenyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, isodecyl methacrylate, lauryl methacrylate, 4-methacryloylmorpholine, 2-phenoxyethyl methacrylate, diethylene glycol methacrylate phenyl ether, 2,2,2-tri Examples thereof include fluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, nonylphenol EO modified acrylate, and nonylphenol EO modified methacrylate.

More specifically, NK Ester A-LEN-10, AM-90G, AM-130G, AMP-20GY, A-SA, S-1800A, CB-1, M-90G, M-230G, PHE-1G, Examples thereof include S, SA (above, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Aronix M-111, M-120, M-140 (above, manufactured by Toagosei Co., Ltd.) and the like.

As the monofunctional radically polymerizable compound other than the above, monofunctional aromatic urethane acrylate or aliphatic urethane acrylate may be contained from the viewpoint of curability and curing shrinkage of the adhesive layer.

Further, as a monofunctional radically polymerizable compound other than the above, a compound having a thiol group in the molecule may be contained from the viewpoint of enhancing the adhesion between the adhesive layer and the substrate. Specific examples thereof include 1-decanethiol, 1-dodecanethiol, 1-hexadecanethiol, 1-octanethiol, 1-octadecanethiol and the like.

Further, as the monofunctional radically polymerizable compound other than the above, it is preferable to contain a compound having a phosphoric acid group in the molecule for the purpose of enhancing the adhesion between the adhesive layer and the substrate. Specific examples of the monofunctional radically polymerizable compound having a phosphoric acid group in the molecule include Hosmer M, PE, PP (all manufactured by Unichemical Co., Ltd.), light acrylate P-1A (N), and light ester P-1M. (The above is manufactured by Kyoeisha Chemical Co., Ltd.).

As the component (A), only a specific compound can be used, or two or more specific compounds can be mixed and used. It is also possible to mix and use one or more specific compounds and a monofunctional radically polymerizable compound other than one or more specific compounds. The ratio of the specific compound to the monofunctional radically polymerizable compound other than the specific compound among the components (A) is preferably 10 parts by mass or more when the component (A) is 100 parts by mass.

<Ingredient (B)>
As the component (B), a thermal radical initiator that generates radicals by heat and a photoradical initiator that generates radicals by ultraviolet rays can be used. These are appropriately selected depending on the curing step of the curable composition.

Thermal radical initiators that generate radicals by heat include ketone peroxide structures, peroxyketal structures, hydroperoxide structures, dialkyl peroxide structures, diacyl peroxide structures, peroxyester structures, peroxydicarbonate structures, or Examples thereof include compounds having an azo-based structure. If a thermal radical initiator that generates gas when radicals are generated may generate voids, the thermal radical initiators include ketone peroxide structure, peroxyketal structure, hydroperoxide structure, and dialkyl peroxide. Compounds having a structure, a diacyl peroxide structure, a peroxy ester structure or a peroxy dicarbonate structure are preferable.

Specifically, diisobutyryl peroxide, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3. 3-Tetramethylbutyl peroxyneodecanate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, tert-hexylperoxyneodecanoate, tert-butylper Oxyneodecanoate, tert-butylperoxyneoheptanoate, tert-hexylperoxypivalate, tert-butylperoxypivalate, bis (3,5,5-trimethylhexanoyl) peroxide, dilaurylper Oxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, dissuccinic acid peroxide, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, tert-Hexylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, tert-butylperoxy-2-ethylhexanoate, dibenzoyl peroxide, 1,1-bis (t-butyl) Peroxy) -2-methylcyclohexane, 1,1-bis (tert-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-hexylperoxy) cyclohexane, 1,1-bis (Tert-Butylperoxy) cyclohexane, 2,2-bis (4,4-di- (tert-butylperoxy) cyclohexyl) propane, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxymaleic acid, tert -Butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexylmonocarbonate, tert-hexylperoxy Benzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, tert-butylperoxyacetate, 2,2-bis (tert-butylperoxy) butane, tert-butylperoxybenzoate, n- Butyl-4,4-bis (tert-butylperoxy) ballere , 1,4-bis (tert-butylperoxyisopropyl) benzene, dicumyl peroxide, di-tert-hexyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane , Tert-Butyl cumyl peroxide, di-tert-butyl peroxide, p-menthan hydroperoxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) -3-hexine, diisopropylbenzenehydroper Examples include oxides, 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, tert-butylhydroperoxide and the like.

More specifically, parloyl IB, park mill ND, parloyl NPP, parloyl IPP, parloyl SBP, perocta ND, parloyl TCP, parloyl OPP, perhexyl ND, perbutyl ND, perbutyl NHP, perhexyl PV, perbutyl PV, perloyl 355, parloyl L. , Perocta O, Perloyl SA, Perhexa 25O, Perhexil O, Niper PMB, Perbutyl O, Niper BMT, Niper BW, Perhexa MC, Perhexa TMH, Perhexa HC, Perhexa C, Pertetra A, Perhexyl I, Perbutyl MA, Perbutyl 355, Perbutyl L, Perbutyl I, Perbutyl E, Perhexyl Z, Perhexa 25Z, Perbutyl A, Perhexa 22, Perbutyl Z, Perhexa V, Perbutyl P, Park Mill D, Perhexil D, Perhexil 25B, Perbutyl C, Perbutyl D, Permenta H, Perhexin 25B, Examples thereof include Park Mill P, Per Octa H, Park Mill H, Perbutyl H, and Novmer BC (all manufactured by NOF CORPORATION).

Among them, bis (4-tert-butylcyclohexyl) peroxydicarbonate (parloyl TCP / manufactured by Nichiyu Co., Ltd.) and tert-butylperoxypivalate (perbutyl PV / Nichiyu Co., Ltd.) are particularly important in terms of reactivity and reaction start temperature. , 1,1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate (PeroctaO / manufactured by Nichiyu Co., Ltd.), 1,1-bis (tert-hexylperoxy) cyclohexane (Perhexa HC /) (Nippon Oil Co., Ltd.), 2,5-dimethyl-2,5-di (benzoylperoxy) hexane (Perhexa 25Z / Nichiyu Co., Ltd.), tert-butyl peroxybenzoate (Perbutyl Z / Nichiyu Co., Ltd.) and 1 , 4-Bis (tert-butylperoxyisopropyl) benzene (Perbutyl P / manufactured by Nichiyu Co., Ltd.) is preferably used.

The ratio of the thermal radical initiator used is 0.01 to 10% by mass with respect to 100 parts by mass of all the radically polymerizable compounds including the component (A) from the viewpoint of storage stability and curability of the curable composition. It is preferably a radical. More preferred is 0.05 to 5 parts by mass. Further, these thermal radical initiators may be used alone or in combination of two or more, depending on the above-mentioned characteristics.

Examples of photoradical initiators that generate radicals with ultraviolet rays include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenylketone, and 2-hydroxy-2-methyl-1-phenylpropane-. 1-on, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-) Methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2- (dimethylamino) -2- [(4-Methylphenyl) Methyl] -1- [4- (4-morphonyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyldiphenylphosphinoxide, bis (2,4,6-trimethylbenzoyl) ) Phenylphosphine oxide, 1- [4- (phenylthio) phenyl] octane-1,2-dione = 2- (O-benzoyloxime)], 1- [9-ethyl-6- (2-methylbenzoyl)- 9H-Carbazole-3-yl] -etanone = 1- (O-acetyloxime), methylbenzoylformate, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] ethyl ester and oxyphenyl Examples thereof include a mixture of acetic-2- [2-hydroxy-ethoxy] ethyl ester, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, and the like.

More specifically, Omnirad1173, 184, 127, 2959, 369, 379, 389, 907, 4265, 1000, 651, TPO-H, TPO-L, 819, 819DW, 2022, 2100, 754, OXE-01, Examples thereof include OXE-02, OXE-03, OXE-04, BPFlakes, 4MBZFlakes, OMBB, 1601, BMS, ITX, DETX, BBF, EMK, EscaleKIP150, KIP100F, TZT and the like (above, manufactured by IGM Resins).

Among them, 1-hydroxycyclohexylphenyl ketone (Omnirad 184 / IGM Resins), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Omnirad 1173 / IGM Resins) from the viewpoint of reactivity and wavelength selectivity. , 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone (Omnirad369 / IGM Resins), 2-methyl-1- (4-methylthiophenyl) )-2-Morphorinopropan-1-one (Omnirad907 / IGM Resins), Bis (2,4,6-trimethylbenzoyl) Phenylphosphinoxide (Omnirad819 / IGM Resins), 2,4,6- Trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO-H / IGM Resins), Omnirad TPO-L / IGM Resins, 1- [4- (Phenylthio) phenyl] octane-1,2-dione = 2- (O-) (Benzoyl oxime)] (O-acetyl oxime) (OmniradOXE01 / IGM Resins), and 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -etanone = 2,1 -(O-Acetyloxym) (OmniradOXE02 / IGM Resins) is preferably used.

The ratio of the photoradical initiator used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of all the radically polymerizable compounds including the component (A) from the viewpoint of curability of the adhesive layer. .. More preferred is 0.05 to 5 parts by mass. Further, these photoradical initiators can be used alone or in combination of two or more depending on the wavelength of the light source used in the curing treatment and the curability of the adhesive layer.

<Ingredient (C)>
In the present invention, from the viewpoint of curability and film strength of the adhesive layer, a bifunctional or more radically polymerizable compound having two or more radical-reacting functional groups in the molecule as the component (C) (hereinafter, many). It is also preferable to use (referred to as a functional radically polymerizable compound).

Specific examples thereof include the following polyfunctional radically polymerizable compounds.
For example, 4,4'-biphenyldiacrylate, diethylstillbestrol diacrylate, 1,4-bisacryloyloxybenzene, 4,4'-bisacryloyloxydiphenyl ether, 4,4'-bisacryloyloxydiphenylmethane, 3,9 -[1,1-dimethyl-2-acryloyloxyethyl] -2,4,8,10-tetraspiro [5,5] undecane, α, α'-bis [4-acryloyloxyphenyl] -1,4-diisopropyl Benzene, 1,4-bisacryloyloxytetrafluorobenzene, 4,4'-bisacryloyloxyoctafluorobiphenyl, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, glycerol diacrylate , 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol diacrylate, trimethylol propanetriacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ditrimethylolpropanetetraacrylate, dipentaerythritol hexaacrylate, Dipentaerythritol monohydroxypentaacrylate, 4,4'-diacryloyloxystylben, 4,4'-diacryloyloxydimethylstylben, 4,4'-diacryloyloxydiethylsylben, 4,4'-diacryloyloxydipropyl Stillben, 4,4'-diacryloyloxydibutylstilben, 4,4'-diacryloyloxydipentylstylben, 4,4'-diacryloyloxydihexylstilben, 4,4'-diacryloyloxydifluorostilben, 2,2 3,3,4,4-hexafluoropentanediol-1,5-diacrylate, 1,1,2,2,3,3-hexafluoropropyl-1,3-diacrylate, diethylene glycol dimethacrylate, 1,4 -Butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropanetrimethacrylate, pentaerythritol tetramethacrylate, pentaerythritoltri Methacrylate, Ditrimethylol Propa Ntetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxypentamethacrylate, 2,2,3,3,4,4-hexafluoropentanediol-1,5-dimethacrylate, tricyclodecanedimethanol diacrylate, Tricyclodecanedimethanol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 700 diacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, polypropylene glycol # 400 Dimethacrylate, Polypropylene Glycol # 700 Dimethacrylate, Polyethylene Glycol # 200 Diacrylate, Polyethylene Glycol # 400 Diacrylate, Polyethylene Glycol # 600 Diacrylate, Polyethylene Glycol # 200 Dimethacrylate, Polyethylene Glycol # 400 Dimethacrylate, Polyethylene Glycol # 600 Dimethacrylate Examples include monomers such as methacrylate, ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, propoxyylated bisphenol A dimethacrylate, or ethoxylated pentaerythritol tetraacrylate, and oligomers.

More specifically, NK Ester 701A, A-200, A-400, A-600, A-1000, AB1206PE, ABE-300, A-BPE-10, A-BPE-20, A-BPE- 30, A-BPE-4, A-BPEF, A-BPP-3, A-DCP, A-DOD-N, A-HD-N, A-NOD-N, APG-100, APG-200, APG- 400, APG-700, A-PTMG-65, A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM- 3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, BPE-1300N, DCP, DOD-N, HD-N, NOD-N, NPG, 1206PE, 701, 9PG, TMPT (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), KAYARADFM-400, HX-220, HX-620, R-712 (all manufactured by Nippon Kayaku Co., Ltd.), Blemmer PDE-100, PDE-200, PDE-400, PDP-400N, ADE-200, ADE-300, Examples thereof include ADE-400A or ADP-400 (all manufactured by NOF CORPORATION).

Among them, tricyclodecanedimethanol diacrylate, tricyclodecanedimethanol dimethacrylate, polyethylene glycol # 200 diacrylate, polyethylene glycol # 400 diacrylate, and polyethylene glycol # 600 diacrylate from the viewpoint of film strength and curing shrinkage of the adhesive layer. Acrylic, Polyethylene Glycol # 200 Dimethacrylate, Polyethylene Glycol # 400 Dimethacrylate, Polyethylene Glycol # 600 Dimethacrylate, Tripropylene Glycol Diacrylate, Polypropylene Glycol # 400 Diacrylate, Polypropylene Glycol # 700 Diacrylate, Tripropylene Glycol Dimethacrylate, Polypropylene Glycol # 400 dimethacrylate, polypropylene glycol # 700 dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, KAYARADFM-400, HX-220, and HX-620 (all manufactured by Nippon Kayaku Co., Ltd.) are preferable. ..

The component (C) preferably contains an aromatic urethane polyfunctional acrylate or an aliphatic urethane polyfunctional acrylate from the viewpoint of curability and curing shrinkage of the adhesive layer. Specifically, EBECRYL210, 220, 230, 270, 4858, 8402, 8804, 8807, 9270, 4513, 4738, 4740, 8311, 9260, 8701, 4265, 4587, 4666, 8210, 1290, 5129, 8301R, 4501. , 2221, 1271, 4859, 8409, 8465, 8809, 8810, 8811, 4101, 4201, 8209, 1291, 8602, 225, KRM8911, 8667, 8296, 8200, 8904, or 8452 (all manufactured by Daisel Ornex). And so on.

Among them, from the viewpoint of the transparency of the adhesive layer, it is preferable to include the aliphatic urethane polyfunctional acrylates EBECRYL230, 4858, 8402, 8804, 8807, 4859, 8465, 8809 and 8811 (all manufactured by Dycel Ornex). ..

Further, the component (C) preferably contains a polyfunctional radically polymerizable compound having a thiol group in the molecule from the viewpoint of enhancing the adhesion between the adhesive layer and the substrate. Specifically, trimethylolpropanetris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isosyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol. Bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), trimethylolpropanetris (3-mercaptobutyrate), trimethylol ethanetris (3-mercaptobutyrate), penta Elythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trion , Neopentanetetrathiol, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and the like. More specifically, Karenz MTPE1, BD1, NR1, and TPMB (all manufactured by Showa Denko KK) can be mentioned. Among them, it is preferable to include Calends MTPE1, BD1 and NR1 (all manufactured by Showa Denko KK).
The blending ratio of the polyfunctional radically polymerizable compound having a thiol group in the molecule is preferably 0.05 to 10 parts by mass, preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total of the components (A) and (C). 5 parts by mass is more preferable.
The compound having a thiol group acts as a chain transfer agent for radical polymerization. The residue of the compound having one thiol group in the molecule is usually present at the end of the polymerized chain like the initiator. However, when a compound having two or more thiol groups in the molecule is used, the residue of the compound is polymerized as a result of not only acting as a chain transfer agent but also a growth reaction occurring from two or more thiol groups in the molecule. It exists in the middle of the chain. Furthermore, when a compound having 3 or more thiol groups in the molecule is used, a growth reaction occurs from the 3 or more thiol groups in the molecule, and as a result, the residue of the compound can also be a cross-linking point of the polymer chain. Therefore, in the present invention, the compound having two or more thiol groups in the molecule is included in the polyfunctional radically polymerizable compound.

Further, a polyfunctional radically polymerizable compound having a phosphoric acid group in the molecule may be used for the purpose of enhancing the adhesion between the adhesive layer and the substrate. Specific examples thereof include KAYAMER PM-2 or PM-21 (all manufactured by Nippon Kayaku Co., Ltd.).
The blending ratio of the polyfunctional radically polymerizable compound containing a phosphoric acid group in the molecule is preferably 0.01 to 3 parts by mass, preferably 0.05 with respect to 100 parts by mass of the total of the components (A) and (C). ~ 2 parts by mass is more preferable.

One or more of these polyfunctional radically polymerizable compounds can be used as the component (C).

<Curable composition>
The curable composition contains the component (A) and the component (B). At that time, the component (C) may be contained from the viewpoint of curability and film strength of the adhesive layer.

When the component (A) and the component (C) are contained, the blending ratio of the component (A) is preferably 10 to 99 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (C). Of these, 20 to 95 parts by mass is more preferable, and 40 to 90 parts by mass is even more preferable. Further, it is preferable that the component (C) is contained in an amount of 1 part by mass or more with respect to a total of 100 parts by mass of the component (A) and the component (C). Among them, 5 parts by mass or more is more preferable, and 10 parts by mass or more is more preferable. Further, when the component (A) and the component (C) are contained, the blending ratio of the component (C) is 90 parts by mass or less with respect to a total of 100 parts by mass of the component (A) and the component (C). It is preferably 80 parts by mass or less, more preferably 60 parts by mass or less.
Further, the compounding ratio of the compound represented by the above formula [1] when the component (A) and the component (C) are contained is based on 100 parts by mass of the total of the component (A) and the component (C). 10 to 99 parts by mass is preferable. Of these, 20 to 95 parts by mass is more preferable, and 40 to 90 parts by mass is even more preferable.

It is preferable to adjust the blending ratio of the component (A), the component (B) and the component (C) so that the curable composition has a viscosity at 25 ° C. of 1 to 10000 mPa · s. In addition, in order to apply to various coating methods shown below, it is preferable that the viscosity at 25 ° C. is 1 to 500 mPa · s. Among them, 1 to 300 mPa · s is more preferable, and 1 to 100 mPa · s is more preferable, from the viewpoint of maintaining dimensional control and reducing unevenness generated when the curable composition is applied or cured.
As a method for preparing the curable composition, a method of mixing the component (A), the component (B) and the component (C) together, or a method in which the component (A) and the component (C) are mixed in advance may be used. (B) A method of mixing the components can be mentioned.

The curable composition can be used as a varnish by adding a solvent. As a result, the applicability to the base material can be improved and the processability can be improved. The solvent at that time is not particularly limited as long as the component (A), the component (B) and the component (C) are uniformly dissolved, and known solvents can be used. Specifically, methanol, ethanol, isopropyl alcohol, acetone, toluene, tetrahydrofuran, hexane, ethyl acetate, 1-butanol, 2-methoxyethanol, 2-ethoxyethanol, cyclohexanone, propylene glycol monomethyl ether acetate, N-methyl-2. -Pyrrolidone, γ-butyrolactone and the like can be mentioned. These can be used alone or in admixture of two or more. However, when it is necessary to reduce the generation of gas derived from the solvent, it is preferable not to add the solvent.

The curable composition may contain an inorganic filler or an organic filler. Above all, it is preferable to use an inorganic filler from the viewpoint of increasing the heat resistance of the adhesive layer. Examples of the inorganic filler include known ones, and examples thereof include aluminum hydroxide, magnesium hydroxide, boron nitride, crystalline silica, and amorphous silica. These can be used alone or in admixture of two or more.

A spacer for controlling the gap (also referred to as a gap) of the adhesive layer can be introduced into the curable composition.

The curable composition can be used, for example, as an adhesive.
The cured product of the present invention is obtained from the curable composition or adhesive of the present invention. The cured product is obtained, for example, by a curing treatment of a curable composition described later.

<Method of manufacturing the adhesive layer>
The curable composition can be used as an adhesive for adhering a base material to a base material, attaching a member to the base material, or attaching a liquid crystal display element or an organic EL element to each other. Examples of the bonding method include a step of applying the curable composition to the adhesive surface of one adherend (base material), and the other adherend (base material or member) to the adhesive surface of the adherend. A method including a step of pasting the adhesive and a step of curing the curable composition can be mentioned. When the curable composition of the present invention is used as an adhesive, the adhesive may be a solvent-free adhesive that does not substantially contain a solvent from the viewpoints of environment, safety and health. Here, "substantially free" means that the total amount of the curable composition is 100 parts by mass, and 0 to 0.5 parts by mass, preferably 0 to 0.2 parts by mass of the solvent is contained. Further, the curable composition of the present invention can also be used as a cured film such as an insulating film by applying the curable composition and curing it.

The methods for applying the curable composition to the substrate include spin coating method, slit coating method, roll coating method, inkjet method, screen printing method, bar coating method, flexographic printing method, gravure printing method, die coating method, and dispense. The law etc. can be mentioned. These are appropriately selected according to the type of the base material and the thickness of the target adhesive layer. The curable composition of the present invention has a low viscosity and is therefore most suitable for application by inkjet.

The curing treatment of the curable composition is appropriately selected depending on the type of radical initiator.

In the case of a curable composition using a thermal radical initiator, the following methods can be mentioned. The curable composition is applied by the above method, and the base material is bonded to the base material, or the member is attached to the base material, and then heat treatment is performed. Examples of the heating device used at that time include a hot plate, a heat circulation type oven, an IR (infrared) type oven, etc. Since curing inhibition occurs in the presence of oxygen, oxygen is removed in a nitrogen atmosphere or under vacuum. It is preferably in a state. Further, in the heat treatment, it is preferable to press the base materials against each other or between the base material and the member.

In the case of a curable composition using a photoradical initiator, the following methods can be mentioned. After applying the curable composition by the above method, there is a method of laminating the other base material or pasting a member and irradiating with ultraviolet rays. At that time, similarly to the above, it is preferable to have a nitrogen atmosphere or a vacuum. Further, in order to improve the accuracy of bonding or bonding, as a temporary curing step, after applying the curable composition, the layer of the cured composition after coating is irradiated with ultraviolet rays, and the other substrate is bonded. Alternatively, there is a method of pasting a member to perform the main curing treatment. Irradiation of ultraviolet rays in the temporary curing step is preferably performed in the atmosphere. In addition, examples of the main curing treatment include irradiation with ultraviolet rays or heat treatment. The irradiation amount of ultraviolet rays and the temperature of the heat treatment are appropriately selected depending on the type of the substrate and the type of the radical initiator. It is preferable that the ultraviolet irradiation and the heat treatment are performed in a nitrogen atmosphere. The oxygen concentration may be controlled to less than 100 mg / L.

The lower the curing shrinkage rate after curing of the curable composition of the present invention, the more preferably 9.0% or less, and more preferably 8.5% or less in the present embodiment.
The curing shrinkage rate can be determined by the method described in "Evaluation of curing shrinkage rate" described later.

Examples of the light source of the ultraviolet irradiation device used for irradiating ultraviolet rays include a metal halide lamp, a high-pressure mercury lamp, and an LED light source. At that time, the wavelength of ultraviolet rays is preferably 250 to 450 nm. Of these, 310 to 400 nm is more preferable.
The illuminance of ultraviolet rays is preferably in the range of 1 to 50 mW / cm ² from the viewpoint of improving productivity. The irradiation amount of ultraviolet rays is preferably in the range of 50 mJ / cm ² to 30,000 mJ / cm ² from the viewpoint of sufficient curing.

As the base material of the adherend, oxides / nitrides (for example, quartz, glass, silica, titania, alumina, sapphire, aluminosilicate glass, borosilicate glass, silicon nitride, SiON, ITO, IZO, IGZO, etc.) , Plastics (eg, polymethylmethacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ABS, polycarbonate, polystyrene, epoxy, unsaturated polyester, melamine, diallyl phthalate, polyimide, urethane, nylon, polyethylene, polypropylene, cycloolefin polymer , Polyvinyl chloride, fluororesin (polytetrafluoroethylene resin, polychlorotrifluoroethylene resin, polyfluorovinylidene resin, polyvinylfluorovinyl resin, perfluoroalkoxyfluororesin, tetrafluoroethylene / hexafluoropropylene copolymer resin, Ethylene / tetrafluoroethylene copolymer resin, ethylene / chlorotrifluoroethylene copolymer resin, etc.), polybutadiene, polyisoprene, SBR, nitrile rubber, EPM, EPDM, epichlorohydrin rubber, neoprene rubber, porsulfide, butyl rubber, Examples include substrates of metals (eg, iron, aluminum, stainless steel, titanium, gold, silver, copper, zinc, molybdenum, and alloys thereof), sheet films, etc. (such as cellulose, cellulose derivatives, and cellulose analogs).

Among them, glass, silica, alumina, aluminosilicate glass, borosilicate glass, silicon nitride, SiON, and ITO are preferable for the oxide / nitride for optical element applications. The plastic is preferably polymethylmethacrylate, polyethylene terephthalate, polycarbonate, and polyimide. Aluminum, silver, copper, molybdenum, and alloys thereof are preferable as the metal.

The optical element of the present invention is obtained by using the curable composition of the present invention.
Further, the optical element of the present invention can be obtained by using the adhesive of the present invention.

The curable composition can also be suitably used as a sealing material for electronic devices. Examples of the electronic device include an organic EL element, an organic thin-film solar cell, and a light emitting diode element. As a method for sealing the electronic device, a known method can be used. Specifically, the curable composition can be applied onto a base material or a member by a spin coating method or an inkjet method, and then heat-treated or irradiated with ultraviolet rays to cure the electronic device. ..
Further, the curable composition can also be used as an adhesive for attaching a plastic plate such as an acrylic plate or a transparent polyimide resin or a touch panel sensor to a liquid crystal display element, an organic EL display, a quantum dot display or the like. At that time, it can also be used when bonding display elements such as a liquid crystal display element, an organic EL display, and a quantum dot display.

The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

[Synthesis of specific compound]
A1 to A5 are novel compounds that have not been published in the literature, and the synthetic method will be described in detail below.

The products (A1 to A5) described in Examples 1 to 5 below were identified by ¹ H-NMR analysis (analytical conditions are as follows).
Equipment: BRUKER ADVANCE III-500MHz
Measuring solvent: DMSO-d ₆ , CDCl ₃
Reference substance: Tetramethylsilane (TMS) (δ0.0 ppm for ¹ H)

The abbreviations in the present invention have the following meanings.
EDC ・ HCl: 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride DMAP: 4-dimethylaminopyridine

2-Hydroxyethyl methacrylate (13.0 g, 99.9 mmol), 2,2,4,8,10,10-hexamethylundecane-5-carboxylic acid (30.0 g, 105 mmol), methylene chloride (78 g) , EDC.HCl (23.0 g, 120 mmol), and DMAP (1.22 g, 9.99 mmol) were charged and stirred at 25 ° C. for 20 hours. After completion of the reaction, stirring was stopped, water (80 g) was added and washed separately, washed with saturated aqueous sodium hydrogen carbonate solution (80 g), and washed with water (80 g). The organic layer was concentrated to give a pale yellow oil. Purification was performed by column chromatography (developing solvent: heptane / ethyl acetate = 4/1 (volume ratio)), and the solvent was removed to obtain a specific compound (A1) (yield: 37 g, 93.3 mmol, Yield: 98%).
^{1 1} H-NMR (500 MHz / DMSO-d ₆ ): δ (ppm) = 6.03 (s, 1H), 5.69 (s, 1H), 4.35-4.20 (m, 4H), 2 .18-2.11 (m, 1H), 1.87 (s, 3H), 1.79-0.72 (m, 34H).

2,2,4,8,10,10-hexamethylundecane-5-carboxylic acid with respect to polyethylene glycol monomethacrylate (trade name: Blemmer PE-90, manufactured by NOF CORPORATION) (16.0 g, 91.8 mmol). (26.4 g, 92.8 mmol), methylene chloride (96 g), EDC / HCl (26.4 g, 138 mmol), and DMAP (1.12 g, 9.17 mmol) were charged and stirred at 25 ° C. for 10 days. After completion of the reaction, stirring was stopped, water (96 g) was added and washed separately, washed with saturated aqueous sodium hydrogen carbonate solution (96 g), and washed with water (96 g). The organic layer was concentrated to give a pale yellow oil. Purification was performed by column chromatography (developing solvent: ethyl acetate), and the solvent was removed to obtain the specific compound (A2) (yield: 35 g, 79.4 mmol, yield: 87%).
^{1 1} H-NMR (500 MHz / DMSO-d ₆ ): δ (ppm) = 6.03 (s, 1H), 5.69 (m, 1H), 4.39-4.05 (m, 4H), 3 .70-3.45 (m, 4H), 2.30-2.09 (m, 2H), 1.88 (s, 3H), 1.80-0.72 (m, 33H).

2- (4,4-dimethyl-2-pentanyl) -5,7,7-trimethyl-1-octanol (40.0 g, 148 mmol), succinic anhydride (30.0 g, 300 mmol), ethyl acetate ( 240 g), pyridine (26.0 g, 325 mmol), and DMAP (1.80 g, 14.8 mmol) were charged and stirred at 90 ° C. for 5 hours. After stopping stirring and cooling to 25 ° C., the mixture was washed three times with water (120 g) to concentrate the organic layer, and an oil and a partially precipitated white crystal mixture were obtained. Heptane (230 g) is added thereto, and the mixture is stirred at 25 ° C. for 30 minutes and filtered to remove white crystals. The filtrate is washed twice with 1N hydrochloric acid (230 g), and the organic layer is concentrated and dried. , Compound (1) was obtained (yield: 54 g, 146 mmol, yield: 99%).
^{1 1} H-NMR (500 MHz / DMSO-d ₆ ): δ (ppm) = 12.2 (s, 1H), 4.00-3.83 (m, 2H), 2.53-2.53 (m, 4H), 1.62-1.73 (m, 1H), 1.49-0.72 (m, 34H).

Next, for compound (1) (54.0 g, 146 mmol), 2-hydroxyethyl methacrylate (19.3 g, 148 mmol), methylene chloride (326 g), EDC / HCl (33.7 g, 176 mmol), and DMAP ( 1.80 g, 14.7 mmol) was charged, and the mixture was stirred at 25 ° C. for 21 hours. After completion of the reaction, stirring is stopped, water (326 g) and saturated brine (54 g) are added for separate liquid washing, and saturated aqueous sodium hydrogen carbonate solution (272 g) and saturated brine (109 g) are used for separate liquid washing. Then, the organic layer (including a part of the aqueous layer) was concentrated. Heptane (320 g) was added and the liquid was separated and extracted, and the organic layer was concentrated again. Purification was performed by column chromatography (developing solvent: heptane / ethyl acetate = 4/1 (volume ratio)), and the solvent was removed to obtain the specific compound (A3) (yield: 57 g, 118 mmol, yield). : 80%).
^{1 1} H-NMR (500 MHz / DMSO-d ₆ ): δ (ppm) = 6.03 (s, 1H), 5.67 (s, 1H), 4.27 (s, 4H), 3.97-3 .85 (m, 2H), 2.56-2.54 (m, 4H), 1.87 (s, 3H), 1.70-1.60 (m, 1H), 1.49-0.72 (M, 34H).

2-Hydroxyethyl methacrylate (16.9 g, 130 mmol) vs. 2-hexyldecanoic acid (40.0 g, 156 mmol), methylene chloride (240 g), EDC / HCl (29.9 g, 156 mmol), and DMAP (1.59 g). , 13.0 mmol) was charged, and the mixture was stirred at 25 ° C. for 4 days. After completion of the reaction, stirring was stopped, water (80 g) was added, and the liquid was separated and washed to concentrate the organic layer. Heptane (240 g) was added, and the mixture was washed separately with saturated aqueous sodium hydrogen carbonate solution (240 g), dimethyl sulfoxide (240 g), and water (240 g) to concentrate the organic layer. The obtained oil was purified by column chromatography (developing solvent: heptane / ethyl acetate = 4/1 (volume ratio)) and the solvent was removed to obtain a specific compound (A4) (yield). : 46 g, 124 mmol, yield: 95%).
^{1 1} H-NMR (500 MHz / CDCl ₃ ): δ (ppm) = 6.13 (s, 1H), 5.58 (s, 1H), 4.34-4.32 (m, 4H), 2.39 -2.32 (m, 1H), 1.94 (s, 3H), 1.65-1.57 (m, 2H), 1.45-1.43 (m, 2H), 1.31-1 .09 (m, 20H), 0.88-0.87 (m, 6H).

Mixture of 2-octyldecanoic acid and 2-hexyldodecanoic acid (trade name: Isostearic acid T, manufactured by Nissan Chemical Industries, Ltd.) (40.0 g, 141 mmol), chloride with respect to 2-hydroxyethyl methacrylate (15.2 g, 117 mmol). Methylene (240 g), EDC / HCl (27.0 g, 141 mmol), and DMAP (1.43 g, 11.7 mmol) were charged and stirred at 25 ° C. for 24 hours. After completion of the reaction, stirring was stopped, water (240 g) was added, and the liquid was separated and washed to concentrate the organic layer. Heptane (240 g) was added, and the saturated aqueous sodium hydrogen carbonate solution (240 g), dimethyl sulfoxide (240 g), and water (240 g) were separated and washed in this order to concentrate the organic layer. The obtained oil was purified by column chromatography (developing solvent: heptane / ethyl acetate = 4/1) and the solvent was removed to obtain a mixture (A5) of a specific compound (yield: 42 g). , 106 mmol, yield: 91%).
^{1 1} H-NMR (500MHz / CDCl ₃ ): δ (ppm) = 6.12 (s, 1H), 5.58 (s, 1H), 4.35-4.34 (m, 4H), 2.39 -2.32 (m, 1H), 1.95 (s, 3H), 1.67-1.57 (m, 2H), 1.45-1.43 (m, 2H), 1.31-1 .11 (m, 24H), 0.89-0.86 (m, 6H).

[Compounds used for preparation of curable composition]
<Specific compound>
A1 to A5: Compounds and mixtures obtained in the above Examples, respectively <monofunctional radically polymerizable compounds other than specific compounds>
A6: Aronix M-111 (nonylphenol EO-modified acrylate) (manufactured by Toagosei Co., Ltd.)
<Radical initiator>
B1: Perhexa 25Z (manufactured by NOF Corporation) / Thermal radical initiator B2: OmniradTPO-H (manufactured by IGM Resins) / Photo-radical initiator B3: OmniradOXE01 (manufactured by IGM Resins) / Photo-radical initiator <2 functional or higher Radical polymerizable compound>
C1: Blemmer PDE-200 (polyethylene glycol # 200 dimethacrylate) (manufactured by NOF CORPORATION)
C2: NK ester DCP (tricyclodecanedimethanol dimethacrylate) (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
C3: EBECRYL230 (manufactured by Daicel Ornex) / Urethane acrylate C4: EBECRYL9270 (manufactured by Daicel Ornex) / Urethane acrylate C5: Karenz MTBD1 (manufactured by Showa Denko) / Polymerizable compound having a thiol group C6: Karenz MTPE1 (Showa) Denko Co., Ltd.) / Polymerizable compound having a thiol group C7: KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.) / Polymerizable compound having a phosphate group

[Preparation of curable composition]
<Comparative Examples 1 and 2 and Examples 6 and 24>
By mixing each component in the blending ratio (mass ratio) shown in Table 1 below, curable compositions (1) to (21) of Comparative Examples 1 and 2 and Examples 6 to 24 were obtained. In Table 1, the numerical values represent the mixing ratio (parts by mass) of each compound with respect to 100 parts by mass of the curable composition.

In Table 1, "Other" refers to a monofunctional radically polymerizable compound other than the specific compound.

Using the curable composition obtained above, the viscosity of the curable composition was measured, the adhesion was evaluated, and the curing shrinkage rate was evaluated by the following method. In the evaluation of the adhesion and the curing shrinkage rate, a curable composition that was pressure-filtered with a membrane filter having a pore diameter of 1 μm was used.

[Measurement of viscosity of curable composition]
For the viscosity of the curable composition, an E-type viscometer TVE-25L (manufactured by Toki Sangyo Co., Ltd.) was used, the sample volume was 1.1 mL, the cone rotor TE-1 (1 ° 34', R24), and the number of rotations at the time of measurement. It was measured at 10 rpm and a temperature of 25 ° C.

[Evaluation of adhesion]
<Method for producing test cell (curable composition using thermal radical initiator)>
Test cells were prepared by the following methods using the curable compositions (1) and (3) to (9) containing the thermal radical initiator, respectively.
Two glass substrates (length: 15 mm, width: 55 mm, thickness: 1.1 mm) washed with pure water, acetone and IPA (isopropyl alcohol) were prepared. A 4 μm bead spacer was added in an amount of 0.5% by mass to the curable composition obtained above, and then spin-coated on one glass substrate (lower glass substrate 1) to form an uncured curable composition layer. (Hereinafter, also referred to as a glass substrate with an uncured curable composition layer) was obtained. Then, as shown in FIG. 1A, the other glass substrate (upper glass substrate 2) is brought into close contact with the glass substrate with the uncured curable composition layer so that the center points intersect in a direction orthogonal to the above-mentioned uncured curable composition layer, and a clip is used. The two substrates were crimped to obtain a crimp cell. After removing the unnecessary curable composition adhering to the crimping cell, the mixture was placed in a heat circulation type oven and heat-treated at 140 ° C. for 1 hour. After the treatment, the substrate was deheated and the clip was removed to obtain a test cell for adhesion evaluation (including a cured product obtained from a curable composition using a thermal radical initiator). By adding the bead spacer to the curable composition, as shown in FIG. 1B, the cured product obtained from the curable composition is sandwiched between the lower glass substrate 1 and the upper glass substrate 2 of the obtained test cell. The adhesive layer region 3 is formed.

<Method for producing test cell (curable composition using photo-radical initiator)>
In Comparative Example 2 and Examples 13 to 22 (curable compositions (2), (10) to (19)), the coating film surface of the glass substrate with the uncured curable composition layer produced by the same method as described above. In the atmosphere, ultraviolet rays were irradiated using an ultraviolet light emitting diode. Specifically, the wavelength of the light source of the ultraviolet light emitting diode was 365 nm, the illuminance of ultraviolet rays was 6.6 mW / cm ² , and the irradiation time was 30 seconds (corresponding to a total irradiation amount of 198 mJ / cm ² ). .. After that, the other glass substrate (upper glass substrate 2) is brought into close contact with the glass substrate with the curable composition layer irradiated with ultraviolet rays so that the center points intersect in a direction orthogonal to the above-mentioned ultraviolet rays, and the two substrates are used with clips. Was crimped to obtain a crimp cell. After removing the unnecessary curable composition adhering to the crimping cell, the mixture was placed in a heat circulation type oven and heat-treated at 140 ° C. for 1 hour. After the treatment, the substrate was deheated and the clip was removed to obtain a test cell for adhesion evaluation (including a cured product obtained from a curable composition using a photoradical initiator).
In Examples 23 and 24 (curable compositions (20) and (21)), a glass substrate with an uncured curable composition layer prepared by the same method as described above was prepared, and the other glass was prepared. The substrate (upper glass substrate 2) is brought into close contact with the glass substrate with the uncured curable composition layer so that the center points intersect in an orthogonal direction, and the two substrates are crimped using a clip to form a crimp cell. Obtained. The crimping cell is irradiated with ultraviolet rays under the conditions that the wavelength of the light source of the ultraviolet light emitting diode is 365 nm, the illuminance of the ultraviolet rays is 6.6 mW / cm ² , and the irradiation time is 220 seconds (total irradiation amount of 1452 mJ / cm ² ). A test cell for evaluation of adhesion (including a cured product obtained from a curable composition using a photoradical initiator) was obtained.

<Evaluation method of adhesion>
The adhesion was evaluated using the universal testing machine EZ-SX100N (Shimadzu Corporation) and the U-shaped jigs (upper jig 4 and lower jig 5) shown in FIGS. 2A and 2B. Specifically, the lower end portion 7 (the area in contact with the lower jig 5) of the upper glass substrate 2 of the test cell shown in FIG. 3 is in contact with the lower jig 5 of the testing machine. It was set so as to be in contact with the part 6 (the part in contact with the test cell). After that, the upper jig 4 of the testing machine is moved downward at a speed of 5 mm per second, and the upper jig 4 is brought into contact with the upper end 8 (the region in contact with the upper jig 4) of the lower glass substrate 1 of the test cell. The test cell consisting of two substrates was vertically peeled off from the surface of the adhesive layer (cured product obtained from the curable composition). The adhesion was calculated by dividing the maximum value of the force applied at this time by the area of the adhesive layer region 3. The higher the value, the better the adhesion.

"Evaluation of curing shrinkage rate"
The curing shrinkage was calculated by a density method using the density of the curable composition and the cured product thereof.
The cured product of the curable composition using the thermal radical initiator was prepared by heat-treating at 140 ° C. for 1 hour in a heat circulation type oven under a nitrogen atmosphere. The cured product of the curable composition using the photoradical initiator uses an ultraviolet light emitting diode having a wavelength of a light source of 365 nm under a nitrogen atmosphere, an ultraviolet illuminance of 6.6 mW / cm ² , and an irradiation time of 220 seconds. It was produced by performing the ultraviolet treatment (corresponding to a total irradiation amount of 1452 mJ / cm ² ).
A drywall densitometer Accupic II (Shimadzu Corporation) was used to measure the density.
The curing shrinkage rate was calculated by the following formula.
Curing shrinkage rate (%) = ((d ₁ / d ₀ ) -1) × 100
In the above formula, d ₀ is the density of the curable composition before curing, and d ₁ is the density of the curable composition after curing.
The lower the value of the curing shrinkage rate, the smaller the curing shrinkage, that is, the better the curing shrinkage.

Table 2 shows the evaluation results of the curable composition using the thermal radical initiator, and Table 3 shows the evaluation results of the curable composition using the photoradical initiator.

As shown in Tables 2 to 3, the curable composition containing the specific compound obtained in Examples 6 to 24 has a curable composition as compared with the curable composition of Comparative Example in which the specific compound is not used. The viscosity of the compound was low, the adhesion when the cured film was produced was high, and the curing shrinkage was small. Specifically, in the comparison under the same conditions, it is a comparison between Comparative Example 1 and Example 7, and a comparison between Comparative Example 2 and Example 14.
Furthermore, when a compound having a thiol group was used as the radically polymerizable compound, the adhesion was higher than when it was not used. Specifically, it is a comparison between Example 14 and Example 15 in the comparison under the same conditions.
In addition, when a compound having a phosphoric acid group was used as the radically polymerizable compound, the adhesion was higher than that when it was not used. Specifically, it is a comparison between Example 17 and Example 18 in the comparison under the same conditions.
Further, when the aliphatic urethane acrylate was used as the radically polymerizable compound, the curing shrinkage was smaller than that when it was not used. Specifically, it is a comparison between Example 7 and Example 8 in the comparison under the same conditions. Furthermore, when a polymerizable compound having a thiol group and a polymerizable compound having a phosphoric acid group are used in combination, by using an aliphatic urethane acrylate as the polymerizable compound, the curing shrinkage is reduced and the adhesion is also improved. rice field. Specifically, it is a comparison between Example 18 and Example 19 in the comparison under the same conditions.

By using a curable composition containing a compound having a specific structure, a radical curable composition having a low viscosity, a small curing shrinkage, and a high adhesion can be obtained. Therefore, the display element and the semiconductor element obtained by using the curable composition of the present invention as an adhesive are excellent in reliability.

1 Lower glass substrate 2 Upper glass substrate 3 Adhesive layer area 4 Upper jig 5 Lower jig 6 Contact part 7 Lower end 8 Upper end

Claims

A curable composition containing the following components (A) and (B).
(A) Component: Monofunctional radically polymerizable compound containing a compound represented by the following formula [1] (B) Component: Radical initiator

(In the formula [1], X 1 indicates a structure selected from the following formulas [1-a] to [1-g].
X 2 represents a linear alkylene group having 2 to 14 carbon atoms. However, the alkylene group may be substituted with at least one of the following (i) and (ii).
(I): Any -CH 2- , -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-,-, which is not adjacent to X 1 or X 3 of the alkylene group. Substitution with NH-, benzene ring or cyclohexane ring (ii) Substitution of any -CH 2- for the above alkylene group with -CH (CH 3 )-X 3 is -O-, -CO-, -COO- , -OCO-, -CONH-, -NHCO- or -NH-.
X4 represents a linear or branched alkyl group having 12 to 40 carbon atoms. )

( TA indicates a hydrogen atom or a benzene ring. * Indicates a bond.)
X 1 in the formula [1] indicates a structure selected from the formulas [1-a] to [1-d], X 2 is a structure represented by the following formula [X1a], and X 3 is −. The curable composition according to claim 1, wherein the curable composition represents O-, -CO-, -COO- or -OCO-, and X4 represents a branched alkyl group having 12 to 40 carbon atoms.

(In the formula [X1a], M 1 and M 2 independently represent -CH 2 -CH 2- , -CH (CH 3 ) -CH 2- or -CH 2 -CH (CH 3 )-. Z 1 indicates -O-, -CO-, -COO- or -OCO-. N indicates an integer of 0 to 4. When n is an integer of 2 or more, n Z 1 and M 2 are respectively. It has the above definition independently. * 1 indicates the bond position with X 1 and * 2 indicates the bond position with X 3. )
The curable composition according to claim 1 or 2, wherein the compound represented by the formula [1] is a compound represented by the following formula [1a].

(In the formula [1a], R 1 represents a hydrogen atom or a methyl group. L 1 and L 2 are independently -CH 2 -CH 2- , -CH (CH 3 ) -CH 2- or -CH, respectively. 2 -CH (CH 3 )-indicates. Y 1 indicates -O-, -CO-, -COO- or -OCO-. N indicates an integer of 0 to 4. When n is an integer of 2 or more. , N Y 1 and L 2 have the above definitions independently. Y 2 indicates -COO- or -OCO-. L 3 is a single bond or a linear or branched form having 1 to 4 carbon atoms. R 2 and R 3 independently represent a linear or branched alkyl group having 4 to 18 carbon atoms, respectively. R 4 is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms. When L 3 represents a group other than a single bond, the total number of carbon atoms of L 3 and R 2 to R 4 is 11 to 39, and L 3 represents a single bond. , The total number of carbon atoms of R2 to R4 is 11 to 39.)
The curable composition according to any one of claims 1 to 3, which contains a bifunctional or higher functional radical polymerizable compound as a component (C).
The curable composition according to claim 4, wherein the radically polymerizable compound of the component (C) contains a compound having a thiol group in the molecule.
The curable composition according to any one of claims 1 to 5, wherein the component (A) further contains a monofunctional radically polymerizable compound having a thiol group in the molecule.
The curable composition according to claim 4, wherein the radically polymerizable compound of the component (C) contains a compound having a phosphoric acid group in the molecule.
The curable composition according to any one of claims 1 to 7, wherein the component (A) further contains a monofunctional radically polymerizable compound having a phosphoric acid group in the molecule.
The item according to any one of claims 4 to 8, wherein the blending ratio of the component (A) is 10 to 99 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (C). The curable composition according to description.
The curable composition according to any one of claims 1 to 9, wherein the radical initiator is a thermal radical initiator that generates radicals by heat.
The curable composition according to any one of claims 1 to 9, wherein the radical initiator is a photoradical initiator that generates radicals with ultraviolet rays.
An optical element obtained by using the curable composition according to any one of claims 1 to 11.
An adhesive containing the curable composition according to any one of claims 1 to 11.
The adhesive according to claim 13, wherein the adhesive is a solvent-free adhesive.
An optical element obtained by using the adhesive according to claim 13 or 14.
A cured product obtained from the curable composition according to any one of claims 1 to 11.
A cured product obtained by irradiating the curable composition according to claim 11 with ultraviolet rays and then heat-treating it.
A compound represented by the following formula [1].

(In the formula [1], X 1 indicates a structure selected from the following formulas [1-a] to [1-g].
X 2 represents a linear alkylene group having 2 to 14 carbon atoms. However, the alkylene group may be substituted with at least one of the following (i) and (ii).
(I): Any -CH 2- , -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-,-, which is not adjacent to X 1 or X 3 of the alkylene group. Substitution with NH-, benzene ring or cyclohexane ring (ii) Substitution of any -CH 2- for the above alkylene group with -CH (CH 3 )-X 3 is -O-, -CO-, -COO- , -OCO-, -CONH-, -NHCO- or -NH-.
X4 represents a linear or branched alkyl group having 12 to 40 carbon atoms. )

( TA indicates a hydrogen atom or a benzene ring. * Indicates a bond.)
In the formula [1], X 1 indicates a structure selected from the formulas [1-a] to [1-d], X 2 indicates a structure represented by the following formula [X1a], and X 3 is −. The compound according to claim 18, wherein it is O-, -CO-, -COO- or -OCO-, and X4 represents a branched alkyl group having 12 to 40 carbon atoms.

(In the formula [X1a], M 1 and M 2 independently represent -CH 2 -CH 2- , -CH (CH 3 ) -CH 2- or -CH 2 -CH (CH 3 )-. Z 1 indicates -O-, -CO-, -COO- or -OCO-. N indicates an integer of 0 to 4. When n is an integer of 2 or more, n Z 1 and M 2 are respectively. It has the above definition independently. * 1 indicates the bond position with X 1 and * 2 indicates the bond position with X 3. )
The compound according to claim 18 or 19, wherein the compound represented by the formula [1] is a compound represented by the following formula [1a].

(In the formula [1a], R 1 represents a hydrogen atom or a methyl group. L 1 and L 2 are independently -CH 2 -CH 2- , -CH (CH 3 ) -CH 2- or -CH, respectively. 2 -CH (CH 3 )-indicates. Y 1 indicates -O-, -CO-, -COO- or -OCO-. N indicates an integer of 0 to 4. When n is an integer of 2 or more. , N Y 1 and L 2 have the above definitions independently. Y 2 indicates -COO- or -OCO-. L 3 is a single bond or a linear or branched form having 1 to 4 carbon atoms. R 2 and R 3 independently represent a linear or branched alkyl group having 4 to 18 carbon atoms, respectively. R 4 is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms. When L 3 represents a group other than a single bond, the total number of carbon atoms of L 3 and R 2 to R 4 is 11 to 39, and L 3 represents a single bond. , The total number of carbon atoms of R2 to R4 is 11 to 39.)