JP2012246264A - Adamantane derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cured material excellent in flexural strength and hardness, and an adamantane derivative which is a raw material of the same.SOLUTION: For example, this adamantane derivative can be synthesized by a reaction expressed by the chemical formula.

Description

  The present invention relates to an adamantane derivative, a method for producing the same, a resin composition containing the adamantane derivative, a cured product obtained by curing the resin composition, an optical adhesive and a hard coat agent using the cured product.

The curable composition has a property of being cured by heating or light irradiation, and is used in various fields.
For example, acrylate resins are used in various fields such as sealing resins, adhesive resins, various coating agents, and structural materials.
Epoxy acrylate resins are used in various coating agents, structural materials, solder resists for wiring boards, color filter protective films for liquid crystal displays and image sensors, color resists, and the like.

As for the solder resist, for example, Patent Document 1 discloses a bisphenol A type epoxy acrylate resin. Patent Document 2 discloses a cresol novolac epoxy acrylate resin as a photosensitive composition for a color filter.
Also in the epoxy resin, a thermosetting resin such as a conventional bisphenol A type epoxy resin is used as a sealant (Non-Patent Document 1).

On the other hand, adamantane has a structure in which four cyclohexane rings are condensed into a cage shape, is a highly symmetric and stable compound, and its derivative exhibits a unique function. It is useful as a raw material for industrial materials.
In Patent Document 3, an attempt is made to use adamantane esters as a resin material for a photoresist. Patent Document 4 discloses an adamantane derivative having improved heat resistance compared to a conventional resin (bisphenol A type).
However, these resins still have room for improvement in bending strength and hardness performance.

JP-A-8-286371 JP 2002-341533 A Japanese Patent Laid-Open No. 4-39665 JP 2007-070407 A

Published by Technical Information Association: Monthly “Material Stage” June 2003, pages 20-24

  The objective of this invention is providing the hardened | cured material which is excellent in bending strength and hardness, and its raw material adamantane derivative.

［式中、Ｒ_１〜Ｒ_３はそれぞれ水素原子又はメチル基であり、Ｚはイミノ基又は酸素原子であり、Ｘは下記式（１）で表わされる基であり、ｍは０〜１０の整数、ｎは１〜１０の整数、ｐは２〜４の整数、ａは１〜４の整数である。

（式中、Ｚはイミノ基又は酸素原子であり、Ｒ_１〜Ｒ_３はそれぞれ水素原子又はメチル基であり、ｎは１〜１０の整数である。）
同一分子中に、複数のＲ_１〜Ｒ_３、Ｘ又はＺが存在する場合、それらはそれぞれ同一でも異なっていてもよい。］
２．下記式（VI）で表わされる化合物とアダマンタン誘導体を反応させる１に記載のアダマンタン誘導体の製造方法。

（式中、Ｒ_１〜Ｒ_３はそれぞれ水素原子又はメチル基であり、ｎは１〜１０の整数である。ｎが２以上の場合、複数のＲ_１及びＲ_２はそれぞれ同一でも異なっていてもよい。）
３．下記式（VII）で表わされる化合物と下記式（VIII）で表わされる化合物を反応させる１に記載のアダマンタン誘導体の製造方法。

（式中、Ｒ_１〜Ｒ_３はそれぞれ水素原子又はメチル基であり、ｍは０〜１０の整数、ｐは２〜４の整数、ｎは１〜１０の整数である。ｍ、ｐ又はｎがそれぞれ２以上の場合、複数のＲ_１及びＲ_２はそれぞれ同一でも異なっていてもよい。）
４．１に記載のアダマンタン誘導体を含有する樹脂組成物。
５．４に記載の樹脂組成物を加熱又は光照射により硬化させてなる硬化物。
６．１に記載のアダマンタン誘導体又は４に記載の樹脂組成物を用いた光学接着剤。
７．１に記載のアダマンタン誘導体又は４に記載の樹脂組成物を用いたハードコート剤。 According to the present invention, the following adamantane derivatives and the like are provided.
1. An adamantane derivative represented by any of the following formulas (I) to (V).

[Wherein, R _{1 to} R ₃ are each a hydrogen atom or a methyl group, Z is an imino group or an oxygen atom, X is a group represented by the following formula (1), and m is an integer of 0 to 10] , N is an integer of 1 to 10, p is an integer of 2 to 4, and a is an integer of 1 to 4.

(In the formula, Z is an imino group or an oxygen atom, R _{1 to} R ₃ are each a hydrogen atom or a methyl group, and n is an integer of 1 to 10.)
When a plurality of R _{1 to} R ₃ , X or Z are present in the same molecule, they may be the same or different. ]
2. 2. The method for producing an adamantane derivative according to 1, wherein a compound represented by the following formula (VI) is reacted with an adamantane derivative.

(In the formula, R _{1 to} R ₃ are each a hydrogen atom or a methyl group, and n is an integer of 1 to 10. When n is 2 or more, a plurality of R ₁ and R ₂ are the same or different. May be good.)
3. 2. The method for producing an adamantane derivative according to 1, wherein a compound represented by the following formula (VII) and a compound represented by the following formula (VIII) are reacted.

_(Wherein, R 1 to R ₃ are each hydrogen atom or a methyl group, m is an integer of 0, p is an integer of 2 to 4, n represents an integer of 1 to 10 .m, p or n If is 2 or more, respectively, it may be different in each of a plurality of R ₁ and R ₂ are the same.)
The resin composition containing the adamantane derivative as described in 4.1.
A cured product obtained by curing the resin composition according to 5.4 by heating or light irradiation.
An optical adhesive using the adamantane derivative described in 6.1 or the resin composition described in 4.
A hard coat agent using the adamantane derivative described in 7.1 or the resin composition described in 4.

  ADVANTAGE OF THE INVENTION According to this invention, the hardened | cured material which is excellent in bending strength and hardness, and its raw material adamantane derivative can be provided.

［式中、Ｒ_１〜Ｒ_３はそれぞれ水素原子又はメチル基であり、Ｚはイミノ基又は酸素原子であり、Ｘは下記式（１）で表わされる基であり、ｍは０〜１０の整数、ｎは１〜１０の整数、ｐは２〜４の整数、ａは１〜４の整数である。

（式中、Ｚはイミノ基又は酸素原子であり、Ｒ_１〜Ｒ_３はそれぞれ水素原子又はメチル基であり、ｎは１〜１０の整数である。）］ The adamantane derivative of the present invention is represented by any of the following formulas (I) to (V).

[Wherein, R _{1 to} R ₃ are each a hydrogen atom or a methyl group, Z is an imino group or an oxygen atom, X is a group represented by the following formula (1), and m is an integer of 0 to 10] , N is an integer of 1 to 10, p is an integer of 2 to 4, and a is an integer of 1 to 4.

(In the formula, Z is an imino group or an oxygen atom, R _{1 to} R ₃ are each a hydrogen atom or a methyl group, and n is an integer of 1 to 10)]

In the above formulas (I) to (V), when a plurality of R _{1 to} R ₃ , X or Z are present in the same molecule, they may be the same or different. That is, when m or n is 2 or more, a plurality of R ₁ and R ₂ may be the same or different, and when p is 2 or more, a plurality of R _{1 to} R ₃ and Z are the same or different. Alternatively, when a is 2 or more, the plurality of X may be the same or different from each other. When p is 2 or more, the plurality of m and n may be the same or different.

  m is preferably an integer of 0 to 3, more preferably 0. p is preferably 2. n is preferably an integer of 1 to 6, more preferably 2. a is preferably 1-2.

  The adamantane derivative of the present invention can be produced, for example, by the following method for producing the first or second adamantane derivative of the present invention.

（式中、Ｒ_１〜Ｒ_３は上記と同じである。） In the method for producing a first adamantane derivative of the present invention, an isocyanate group-containing (meth) acrylate compound represented by the following formula (VI) is reacted with an adamantane derivative. In the present invention, (meth) acrylate refers to acrylate and / or acrylate having a substituent at the α-position carbon atom.

(Wherein R _{1 to} R ₃ are the same as above)

  Examples of the adamantane derivative as a raw material include 1,3-diaminoadamantane, 2,4-diaminoadamantane, 1,4-diaminoadamantane, 1,3,5-triaminoadamantane, 1,3-diaminomethyladamantane, 2,4 -Diaminomethyladamantane, 1,4-diaminomethyladamantane, 1,3,5-triaminomethyladamantane, 1,3-diaminoethyladamantane, 2,4-diaminoethyladamantane, 1,4-diaminoethyladamantane, 1, 3,5-triaminoethyladamantane, 1,3-diaminopropyladamantane, 2,4-diaminopropyladamantane, 1,4-diaminopropyladamantane, 1,3,5-triaminopropyladamantane;

4- (1-adamantyl) -1,3-benzenediol, 4- (1-adamantyl) -1,2-benzenediol, 3- (1-adamantyl) -1,2-benzenediol, 2- (1- Adamantyl) -1,4-benzenediol, 2- (1-adamantyl) -1,3-benzenediol, 4- (1-adamantyl) -1,2,3-benzenetriol, 5- (1-adamantyl)- 1,2,3-benzenetriol, 2- (1-adamantyl) -1,3,5-benzenetriol, 3- (1-adamantyl) -1,2,4-benzenetriol, 5- (1-adamantyl) -1,2,4-benzenetriol, 6- (1-adamantyl) -1,2,4-benzenetriol;

1,3-bis (2,4-dihydroxyphenyl) adamantane, 1,3-bis (3,4-dihydroxyphenyl) adamantane, 1,3-bis (2,5-dihydroxyphenyl) adamantane, 1,3-bis (2,6-dihydroxyphenyl) adamantane, 1,3-bis (2,3,4-trihydroxyphenyl) adamantane, 1,3-bis (2,4,5-trihydroxyphenyl) adamantane, 1,3- Bis (2,4,6-trihydroxyphenyl) adamantane, 1,3-bis (2,5,6-trihydroxyphenyl) adamantane, 1,3-bis (3,4,5-trihydroxyphenyl) adamantane;

2,2-bis (2,4-dihydroxyphenyl) adamantane, 2,2-bis (3,4-dihydroxyphenyl) adamantane, 2,2-bis (2,5-dihydroxyphenyl) adamantane, 2,2-bis (2,6-dihydroxyphenyl) adamantane, 2,2-bis (2,3,4-trihydroxyphenyl) adamantane, 2,2-bis (2,4,5-trihydroxyphenyl) adamantane, 2,2- Bis (2,4,6-trihydroxyphenyl) adamantane, 2,2-bis (2,5,6-trihydroxyphenyl) adamantane, 2,2-bis (3,4,5-trihydroxyphenyl) adamantane;

2,3-bis (1-adamantyl) phenol, 2,4-bis (1-adamantyl) phenol, 2,5-bis (1-adamantyl) phenol, 2,6-bis (1-adamantyl) phenol, 3, 5-bis (1-adamantyl) phenol;

2,4-bis (1-adamantyl) -1,3-benzenediol, 2,5-bis (1-adamantyl) -1,3-benzenediol, 4,6-bis (1-adamantyl) -1,3 Benzenediol, 4,5-bis (1-adamantyl) -1,3-benzenediol, 3,4-bis (1-adamantyl) -1,2-benzenediol, 3,5-bis (1-adamantyl) -1,2-benzenediol, 3,6-bis (1-adamantyl) -1,2-benzenediol, 4,5-bis (1-adamantyl) -1,2-benzenediol;

2,3-bis (1-adamantyl) -1,4-benzenediol, 2,5-bis (1-adamantyl) -1,4-benzenediol, 2,6-bis (1-adamantyl) -1,4 -Benzenediol

4,5-bis (1-adamantyl) -1,2,3-benzenetriol, 4,6-bis (1-adamantyl) -1,2,3-benzenetriol, 2,5-bis (1-adamantyl) -1,3,4-benzenetriol, 2,6-bis (1-adamantyl) -1,3,4-benzenetriol, 5,6-bis (1-adamantyl) -1,3,4-benzenetriol;

1,3-bis (4-hydroxybenzene) adamantane, 2,2-bis (4-hydroxybenzene) adamantane, 1,3-bis (2,3-dihydroxybenzene) adamantane, 2,2-bis (2,3 -Dihydroxybenzene) adamantane and the like.

  Examples of the compound represented by the formula (VI) include 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate.

  Examples of the catalyst used include sodium amide, triethylamine, tributylamine, trioctylamine, pyridine, lutidine, dimethylaminopyridine, N, N-dimethylaniline, 1,5-diazabicyclo [4,3,0] nonene- 5 (DBN), 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), tetramethylammonium chloride, tetraethylammonium chloride, sodium, potassium, cesium, sodium hydride, potassium hydride, sodium hydroxide Potassium hydroxide, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, cesium carbonate, silver oxide, sodium methoxide, potassium t-butoxide and the like. Preferable examples include dimethylaminopyridine, DBN, DBU, and tetraethylammonium bromide.

Further, an organometallic compound may be used as a catalyst. The organometallic compound is an organometallic compound having catalytic activity for the urethanization reaction. For example, an organocobalt compound such as cobalt naphthenate, tetra-n-butyltin, trimethyltin hydroxide, dimethyltin dichloride, di- Examples thereof include organotin compounds such as n-butyltin dilaurate and tin octoate.
The amount of the catalyst used is usually preferably about 0.01 to 10 mol, more preferably 0.01 to 5 mol, with respect to the adamantane derivative as the raw material. When the amount of the catalyst used is 0.01 mol or more, the reaction time is not excessively long and becomes appropriate. When the amount of the catalyst used is 5 mol or less, the balance between the obtained effect and the economical efficiency becomes good.

The reaction may be solventless, but a solvent can be used if necessary. As the solvent, a solvent having an adamantane solubility of preferably 0.5% by mass or more, more preferably 10% by mass or more can be used.
Specific examples include hexane, heptane, toluene, dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), ethyl acetate, diethyl ether, tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like. These solvents may be used alone or in combination. Among these, DMF and DMSO are preferable from the viewpoint of reaction time.
The amount of the solvent is such that the concentration of the adamantane is preferably 0.5% by mass or more, more preferably 10% by mass or more. At this time, the adamantane may be in a suspended state, but is preferably dissolved.

  The reaction temperature is preferably about 0 to 150 ° C, more preferably 20 to 100 ° C. If the temperature is too low, the reaction rate may decrease and the reaction time may be prolonged. If the reaction temperature is 0 ° C. or higher, the reaction rate does not decrease and the reaction time becomes appropriate, so the reaction time is shortened. . Moreover, since there exists a possibility that coloring of a product may become intense when reaction temperature is higher than 100 degreeC, if it is 100 degrees C or less, a product with little coloring can be obtained.

  The pressure during the reaction is preferably about 0.01 to 10 MPa in absolute pressure, more preferably normal pressure to 1 MPa. If the pressure is too high, there is a safety problem and a special device is required, which is not industrially useful. However, if the pressure is 10 MPa or less, the safety is ensured, so a special device is not required, and the industry It is useful above. The reaction time is usually preferably about 1 minute to 24 hours, more preferably 1 to 15 hours.

  The reaction product can be purified if necessary. As the purification method, distillation, crystallization, column separation and the like are possible, and can be selected depending on the properties of the product and the type of impurities.

（式中、Ｒ_１〜Ｒ_３、ｍ、ｐ、ｎは上記式（Ｉ）と同じである。） In the method for producing a second adamantane derivative of the present invention, a compound represented by the following formula (VII) is reacted with a compound represented by the following formula (VIII).

(In the formula, R _{1 to} R ₃ , m, p, and n are the same as those in the above formula (I).)

Examples of the raw material adamantane derivative represented by the formula (VII) include adamantyl-1,3-diisocyanate and adamantyl-1,3,5-triisocyanate.
Raw material adamantane derivatives (isocyanate compounds) are described in the literature Synthetic Communications, (2008), 38, 8 p. 1153-1158 can be synthesized.

  Examples of the compound represented by the formula (VIII) include aminomethyl acrylate, aminoethyl acrylate, aminomethyl methacrylate, aminoethyl methacrylate, and the like. Preferable examples include aminoethyl acrylate and aminoethyl methacrylate.

  Reaction conditions such as the catalyst, solvent, reaction temperature, reaction pressure, and purification method used in the method for producing the second adamantane derivative are the same as those for the method for producing the first adamantane derivative.

The adamantane derivative of the present invention can be used as a polymerizable monomer used in a curable resin composition.
Materials constituting the resin composition of the present invention, such as polymerization initiators and various additives, can be appropriately used depending on the application.
Hereinafter, the constituent materials of the resin composition will be described.

As the polymerization initiator, for example, a thermal polymerization initiator is used when cured by heating, and a photopolymerization initiator is used when cured by light.
Examples of the thermal polymerization initiator include organic peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, methyl isobutyl peroxide, cumene hydroperoxide and t-butyl hydroperoxide, and azo such as azobisisobutyronitrile. And system initiators.
Examples of the photopolymerization initiator include acetophenones, benzophenones, benzyls, benzoin ethers, benzyl diketals, thioxanthones, acylphosphine oxides, acylphosphinic acid esters, aromatic diazonium salts, and aromatics. Examples include sulfonium salts, aromatic iodonium salts, aromatic iodosyl salts, aromatic sulfochionium salts, and metallocene compounds.

  It is preferable that the usage-amount of a polymerization initiator is 0.01-4 mass parts normally with respect to 100 mass parts of said adamantane derivatives, More preferably, it is 0.5-2 mass parts. By setting the content of the polymerization initiator in the above range, good physical properties such as polymerization and optical characteristics can be expressed.

In addition, the resin composition of the present invention, if necessary, is conventionally used, for example, a curing accelerator, a deterioration inhibitor, a modifier, a silane coupling agent, a defoaming agent, an inorganic powder, a solvent, You may mix | blend well-known various additives, such as a leveling agent, a mold release agent, dye, and a pigment, suitably.
Specific examples of the additives such as the curing accelerator, the deterioration inhibitor, and the modifier include the same ones as described in JP-A-2008-133246.

  As a method for curing the composition, for example, various additives that can be used as needed are mixed, poured into a mold (resin mold) to be molded, or formed into a desired shape by coating, and then heated. Alternatively, a method of curing by light irradiation can be used.

In the case of heat curing by heating, the curing temperature is usually preferably about 50 to 200 ° C, more preferably 100 to 180 ° C. Setting it to 50 ° C. or higher does not cause curing failure, and setting it to 200 ° C. or less prevents coloring and the like. The curing time varies depending on the curing component, curing agent, accelerator and initiator used, but is preferably 0.5 to 6 hours.
In the case of curing by light irradiation, ultraviolet rays are used. Quantity of ultraviolet light is preferably normal 500~5000mJ / cm ² or so, more preferably from 1000~4000mJ / cm ^2.
Moreover, after-heating may be performed after ultraviolet irradiation, and it is preferable to carry out at 70-200 degreeC for 0.5 to 12 hours.

  The molding method is not particularly limited, such as injection molding, blow molding, press molding, and the like. Preferably, the molding can be performed by injection molding using a pellet-shaped composition in an injection molding machine.

  Since the cured product of the present invention has excellent properties such as heat resistance, transparency and adhesion, an optical semiconductor (LED, etc.), a flat panel display (organic EL element, etc.), an electronic circuit, and an optical circuit (optical waveguide) It can be suitably used for encapsulants and adhesives for use, optical electronic members such as lenses for optical communication and optical films, resists for making printed circuit boards, solder resists, and the like.

  Also, as semiconductor elements / integrated circuits (IC, etc.), individual semiconductors (diodes, transistors, thermistors, etc.), LEDs (LED lamps, chip LEDs, light receiving elements, optical semiconductor lenses, etc.), sensors (temperature sensors, optical sensors, Magnetic sensors, etc.), passive components (high-frequency devices, resistors, capacitors, etc.), mechanical components (connectors, switches, relays, etc.), automotive components (circuit systems, control systems, sensors, lamp seals, etc.), adhesives (optical) Parts, optical discs, pickup lenses, etc.) and optical films for surface coating.

As a sealant for optical semiconductors (LED, etc.), it can be applied to shell-type or surface-mount (SMT) type elements, and is in good contact with a semiconductor such as GaN formed on metal or polyamide, and further, YAG, etc. The fluorescent dye can be used even if dispersed. Furthermore, it can be used for a surface coating agent for a bullet type LED, a lens for an SMT type LED, and the like.
When applied to organic EL, an organic EL device having a structure in which an anode / hole injection layer / light emitting layer / electron injection layer / cathode are sequentially provided on a light-transmitting substrate such as general glass or transparent resin It is applicable to. As a sealing material for organic EL elements, a gas barrier property is applied to a curable composition containing an adhesive when covering a resin film coated with a metal can, a metal sheet, or SiN on the EL element, or the adamantane derivative of the present invention. It is also possible to directly seal the EL element by dispersing an inorganic filler or the like in order to impart the. As a display method, it can be applied to the mainstream bottom emission type at present, but by applying it to the top emission type which is expected in the light extraction efficiency and the like, the transparency of the cured product of the present invention can be improved. Take advantage of heat resistance.

When used in an optical circuit, it can also be applied to a single-mode or multi-mode thermo-optic switch, arrayed waveguide grating, multiplexer / demultiplexer, wavelength tunable filter, or optical fiber core material or cladding material. Further, the present invention can be applied to a microlens array for condensing light in a waveguide or a mirror of a MEMS type optical switch. Moreover, it is applicable also to the pigment | dye binder etc. of a photoelectric conversion element.
When used as an optical film, it can be applied to displays such as liquid crystal film substrates and organic EL film substrates, or to color conversion films by dispersing light diffusion films, antireflection films, fluorescent dyes, etc. is there.
As the color resist material, it can be applied as a main component or additive of resist such as RGB and black matrix constituting a color filter for liquid crystal display.

Further, the adamantane derivative of the present invention used for the cured product of the present invention is a compound containing one group selected from an acryloyloxy group and a methacryloyloxy group, and has excellent heat resistance and adhesion, and Since it also has etching resistance, it is useful as a semiconductor forming material such as a resist material for a semiconductor and a base film for a semiconductor.
Accordingly, the present invention provides a resist material for a semiconductor, a color resist material, an undercoat film for a semiconductor, an adhesive for an optical component, a resist for producing a printed circuit board, a solder resist, and a hard coat layer using the adamantane derivative or cured product described above. Also provide.

Example 1

Triethylamine [5.3 g, 0.053 mol], 4,6-bis (1-adamantyl) -1,3-benzene was added to a 500 ml four-necked flask equipped with a reflux condenser, thermometer, stirrer, and nitrogen inlet tube. Diol [10 g, 0.026 mol] and DMF [100 ml] were charged and heated to 60 ° C. with stirring.
Thereafter, Karenz AOI (manufactured by Showa Denko) (2-acryloyloxyethyl isocyanate) [7.5 g, 0.053 mol] was slowly added dropwise. After confirming disappearance of the raw material by GC, the reaction solution was cooled to room temperature. Thereafter, the precipitated solid was recrystallized with a mixed solvent of toluene and heptane to obtain the target product (white solid, yield 15 g, yield 86%).

About the said target object, the < ¹ > H-NMR spectrum and the < ¹³ > C-NMR spectrum were measured. The results are shown below.
Nuclear magnetic resonance spectrum (solvent: CDCl ₃ , JNM-ECA500 manufactured by JEOL Ltd.):
¹ H-NMR (500 MHz): 1.65 (12H), 1.84 to 1.86 (12H), 2.2 (6H), 3.6 (4H), 4.3 (4H), 5.8 (2H) 6.1 (2H), 6.44 (2H), 7.10 (1H), 7.25 (1H)
¹³ C-NMR (125 MHz): 21.5, 29.1, 37.1, 41.3, 63.5, 100, 125.9, 127.9, 128.1, 128.9, 131.6, 145, 154.5, 166.1, 166.5

Example 2

  A 500 ml four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen inlet tube was charged with 1,3-diaminoadamatane [10 g, 0.055 mol] and DMF [100 ml] and stirred at 60 ° C. Until heated. Thereafter, Karenz AOI (manufactured by Showa Denko) [15.5 g, 0.11 mol] was slowly added dropwise. After stirring for 4 hours, the reaction solution was returned to room temperature, stirred for 24 hours, and water and ethyl acetate were added. The ethyl acetate phase was washed with water and concentrated, and the precipitated solid was recrystallized with a mixed solvent of toluene and heptane to obtain the desired product (white solid, yield 20 g, yield 79%).

For the above object, a nuclear magnetic resonance spectrum was measured in the same manner as in Example 1.
The results are shown below.
¹ H-NMR (500 MHz): 1.56 (10H), 2.11 (2H), 2.18 (2H), 3.6 (4H), 4.3 (4H), 5.8 (2H), 6.1 (2H), 6.44 (2H)
¹³ C-NMR (125 MHz): 30.54, 34.91, 41.3, 45.01, 49.26, 54.88, 63.5, 127.9, 131.6, 154.5, 166. 1

還流冷却器、温度計、攪拌機、窒素導入管を取り付けた５００ｍｌの四つ口フラスコに、トリエチルアミン［８．６ｇ、０．０８５ｍｏｌ］、アダマンチルジイソシアネート［１０ｇ、０．０４３ｍｏｌ］、ＤＭＦ［１００ｍｌ］を仕込み、攪拌しながら６０℃まで加熱した。その後、アミノエチルアクリレート［９．８ｇ、０．０８５ｍｏｌ］をゆっくり滴下した。ＬＣで原料の消失を確認後、反応液を室温まで冷却した。その後、酢酸エチル、水を加え、酢酸エチル相を抽出、濃縮し、トルエン、ヘキサン混合溶媒で再結晶を行い、目的物を得た（白色固体、収量１０ｇ、収率５０．２％）。 Example 3

Triethylamine [8.6 g, 0.085 mol], adamantyl diisocyanate [10 g, 0.043 mol], and DMF [100 ml] are charged into a 500 ml four-necked flask equipped with a reflux condenser, thermometer, stirrer, and nitrogen inlet tube. The mixture was heated to 60 ° C. with stirring. Thereafter, aminoethyl acrylate [9.8 g, 0.085 mol] was slowly added dropwise. After confirming disappearance of the raw material by LC, the reaction solution was cooled to room temperature. Thereafter, ethyl acetate and water were added, and the ethyl acetate phase was extracted and concentrated, and recrystallized with a mixed solvent of toluene and hexane to obtain the desired product (white solid, yield 10 g, yield 50.2%).

For the above object, a nuclear magnetic resonance spectrum was measured in the same manner as in Example 1.
The results are shown below.
¹ H-NMR (500 MHz): 1.56 (10H), 2.11 (2H), 2.18 (2H), 3.5 (2H), 4.2 (4H), 5.8 (2H), 6.1 (2H), 6.43 (2H)
¹³ C-NMR (125 MHz): 30.54, 34.91, 41.3, 45.01, 49.26, 54.88, 63.6, 128, 131.3, 154, 166.1

Example 4
60 parts by mass of the adamantane derivative obtained in Example 1, 40 parts by mass of methyl methacrylate and 1 part by mass of benzoin butyl ether which is a polymerization initiator are added to obtain a curable composition, and ultraviolet rays are irradiated to this with a light amount of 2000 mJ / cm ^2. A cured product was obtained. The following physical properties (1) to (3) were evaluated for the obtained cured product. The results are shown in Table 1.
(1) Curing shrinkage (%)
It calculated from the specific gravity before hardening of a curable composition, and the specific gravity after hardening.
(2) Flexural strength and flexural modulus Measured according to A method of JISK7017.
(3) Hardness The Shore hardness D of the cured product for measuring physical properties (thickness 3 mm) was measured using a hardness meter (dual meter, type D).

Example 5
A cured product was produced and evaluated in the same manner as in Example 4 except that the adamantane derivative obtained in Example 2 was used instead of the adamantane derivative obtained in Example 1. The results are shown in Table 1.

Comparative Example 1
60 parts by mass of 1,3-adamantyl diacrylate, 40 parts by mass of methyl methacrylate, and 1 part by mass of benzoin butyl ether as a polymerization initiator are added to form a curable composition, which is cured by irradiating with ultraviolet light at a light amount of 2000 mJ / cm ^2. I let you. The obtained cured product was evaluated in the same manner as in Example 4. The results are shown in Table 1.

  The cured product of the present invention is a sealing agent or adhesive for optical semiconductors (LEDs, etc.), flat panel displays (organic EL elements, etc.), electronic circuits and optical circuits (optical waveguides), lenses for optical communication, and optics. It can be used for optical electronic members such as films, resists for making printed circuit boards, solder resists, and the like.

Claims (7)

An adamantane derivative represented by any of the following formulas (I) to (V).

[Wherein, R _{1 to} R ₃ are each a hydrogen atom or a methyl group, Z is an imino group or an oxygen atom, X is a group represented by the following formula (1), and m is an integer of 0 to 10] , N is an integer of 1 to 10, p is an integer of 2 to 4, and a is an integer of 1 to 4.

(In the formula, Z is an imino group or an oxygen atom, R _{1 to} R ₃ are each a hydrogen atom or a methyl group, and n is an integer of 1 to 10.)
When a plurality of R _{1 to} R ₃ , X or Z are present in the same molecule, they may be the same or different. ] The method for producing an adamantane derivative according to claim 1, wherein the compound represented by the following formula (VI) is reacted with an adamantane derivative.

(In the formula, R _{1 to} R ₃ are each a hydrogen atom or a methyl group, and n is an integer of 1 to 10. When n is 2 or more, a plurality of R ₁ and R ₂ are the same or different. May be good.) The method for producing an adamantane derivative according to claim 1, wherein a compound represented by the following formula (VII) is reacted with a compound represented by the following formula (VIII).

_(Wherein, R 1 to R ₃ are each hydrogen atom or a methyl group, m is an integer of 0, p is an integer of 2 to 4, n represents an integer of 1 to 10 .m, p or n If is 2 or more, respectively, it may be different in each of a plurality of R ₁ and R ₂ are the same.)   A resin composition containing the adamantane derivative according to claim 1.   Hardened | cured material formed by hardening the resin composition of Claim 4 by heating or light irradiation.   An optical adhesive using the adamantane derivative according to claim 1 or the resin composition according to claim 4.   A hard coat agent using the adamantane derivative according to claim 1 or the resin composition according to claim 4.