JP2016084412A - Resin composition excellent in heat resistance and high temperature stability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent curable resin composition excellent in heat resistance and stability at high temperature and having balance of hardness and flexibility and a cured article thereof.SOLUTION: There is provided a transparent resin cured article obtained from a curable resin composition containing a curable compound (A) represented by the formula (1) and a curable compound (B) of dimethacrylate having viscosity at 25°C or 10 mPa s or less with a mass ratio of (A) and (B) of 10/90 to 40/60. (1), where R is H or a C1 to C5 alkyl group, a ring Z is a single ring or a 2 to 5 polycyclic alicyclic hydrocarbon ring, n is 1 or 2, X is each independently H or a methyl group.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition having excellent stability at high temperatures, which is used for display applications such as LCD and organic EL, optical applications such as image sensors and optical pickups, and electronic material applications such as semiconductors.

  In recent years, digital products and mobile terminals have been improved in performance and cost. As a result, there is a demand for a material that can withstand extremely severe reliability tests, such as heat cycles and high-temperature and high-humidity tests, and manufacturing processes involving severe temperature conditions such as wire bonding processes and reflow processes.

As such a material, in addition to heat resistance that does not cause decomposition at a high temperature, a material that exhibits little change in physical properties even when the temperature is changed is suitable. By increasing the cross-link density of the cured product, a cured product with little change in physical properties with respect to temperature change can be obtained, but the stress at the time of curing remains strong and the material becomes brittle. I can not use it. In addition, when an aromatic curing compound such as bisphenol or novolac is used, a cured product having high heat resistance and little change in physical properties even at high temperatures can be obtained. However, a resin containing an aromatic ring is easily colored and used in optical applications. There is a drawback that light resistance is inferior due to light absorption. On the other hand, a transparent resin cured product having a Tg of 250 ° C. or more can be obtained by using a thermosetting resin such as an epoxy resin or a curable (meth) acrylate resin (for example, Patent Document 1, Patent Document 2, Patent Document 3). ). However, since the resin is exposed to a temperature of 260 ° C. or higher in the reflow process, these resins are insufficient in heat resistance.

Japanese Patent Publication No. 7-45555 JP 2002-356666 A JP 2005-154543 A

An object of the present invention is to provide a transparent curable resin composition and a cured product thereof, which have solved the above problems, have excellent heat resistance and stability at high temperature, and have a balance between hardness and flexibility. .

（式中、Ｒは水素原子又は炭素数１〜５のアルキル基、環Ｚは単環又は２〜５の多環式脂環族炭化水素環、ｎは１又は２を示す。Ｘは同一又は異なってよい、水素原子又はメチル基を示す。）
［２］（Ａ）と（Ｂ）の質量比が１０／９０〜４０／６０である［１］に記載の硬化性樹脂組成物。
［３］硬化性化合物（Ａ）が式（２）で示される化合物である［１］又は［２］に記載の硬化性樹脂組成物。

（式中、Ｒは水素原子又は炭素数１〜５のアルキル基を示す。Ｘは同一又は異なってよい、水素原子又はメチル基を示す。）
［４］
硬化促進剤（Ｃ）を硬化性化合物の合計量１００質量部に対して、０．００１〜１質量部含む請求項［１］〜［３］のいずれか１に記載の硬化性樹脂組成物。
［５］
［１］〜［４］のいずれか１に記載の硬化性樹脂組成物を硬化させることによって得られた硬化物。 As a result of intensive studies on the above problems, the present inventors have found that the cured resin obtained by curing the following composition is excellent in heat resistance, transparency, and stability at high temperatures. The headline and the present invention were completed.
For example, the present invention is as follows.
[1]
A curable resin composition containing a curable compound (A) represented by the formula (1) and a curable compound (B) which is dimethacrylate having a viscosity at 25 ° C. of 10 mPa · s or less.

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, ring Z represents a monocyclic or 2 to 5 polycyclic alicyclic hydrocarbon ring, and n represents 1 or 2. X is the same or A hydrogen atom or a methyl group, which may be different.
[2] The curable resin composition according to [1], wherein the mass ratio of (A) and (B) is 10/90 to 40/60.
[3] The curable resin composition according to [1] or [2], wherein the curable compound (A) is a compound represented by the formula (2).

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. X represents a hydrogen atom or a methyl group which may be the same or different.)
[4]
The curable resin composition according to any one of claims [1] to [3], comprising 0.001 to 1 part by mass of the curing accelerator (C) with respect to 100 parts by mass of the total amount of the curable compound.
[5]
[1] A cured product obtained by curing the curable resin composition according to any one of [4].

According to the present invention, a transparent cured resin product having heat resistance and stability at high temperatures and a curable resin composition for producing the same are obtained. Since the cured resin has high heat resistance and high stability at high temperatures, it requires extremely strict reliability tests, such as heat cycles and high temperature and high humidity tests, and severe temperatures such as wire bonding and reflow processes. It can be suitably used as a resin cured product for display applications such as LCD and organic EL, which require manufacturing processes with conditions, optical applications such as image sensors and optical pickups, and electronic material applications such as semiconductors.

  The present invention relates to a curable resin composition comprising a curable compound (A) represented by the formula (1) and a curable compound (B) which is a dimethacrylate having a viscosity at 25 ° C. of 10 mPa · s or less, and this It is a transparent resin cured product obtained by curing.

First, the curable compound (A) will be described.
Examples of the ring Z in the formula (1) include a monocyclic alicyclic hydrocarbon ring such as cyclopentane, cyclohexane, and cycloheptane. In addition, a polycyclic alicyclic hydrocarbon ring such as a decalin ring, an adamantane ring, a tricyclo [5.2.1.0 ^2,6 ] decane ring, a pentacyclo [9.2.1.1 ^3,9 . 0 ^2,10 . 0 ^4,8 ] pentadecane ring and the like. Among these, a compound having an adamantane ring represented by the formula (2) is particularly preferable from the viewpoint of heat resistance and stability at high temperature.

  Examples of the synthesis method of the curable compound include an esterification reaction between a corresponding alcohol compound and a (meth) acrylic acid compound. For example, alcohol compounds corresponding to the curable compound represented by the formula (2) include 1,3,5-trihydroxyadamantane, 7-methyl-1,3,5-trihydroxyadamantane, 7-ethyl-1,3. , 5-trihydroxyadamantane. These can be synthesized according to a known method such as the method described in JP-A No. 2001-335519, Japanese Patent No. 4010078 and 4508670.

Specific examples of the (meth) acrylic acid compound include (meth) acrylic acid, (meth) acrylic acid halide, (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid t-butyl ( Examples include (meth) acrylic acid esters, (meth) acrylic acid salts such as sodium (meth) acrylate, and anhydrous (meth) acrylic acid.
Alternatively, the esterification reaction may be carried out after the hydroxyl group of the alcohol compound is converted to an alcoholate state with an alkali metal such as lithium or sodium, an alkyl lithium such as butyl lithium, or a Grignard reagent such as ethyl magnesium bromide. That is, an OH group that is a hydroxyl group may be converted to an OX group (X is Li, Na, MgBr, MgCl, etc.) and then used for esterification.

  The reaction time for esterification of the corresponding alcohol compound and (meth) acrylic acid compound is 0.5 to 100 hours, preferably 1 to 10 hours. The reaction time depends on the reaction temperature, the esterification method, etc., and is determined according to the desired yield, and is not limited to the above range.

In the esterification reaction between the alcohol compound and the (meth) acrylic acid compound, the amount of the (meth) acrylic acid compound used is 1 to 100 equivalents, preferably 1 to 10 equivalents, based on 1 equivalent of the hydroxyl group of the alcohol compound used. is there. If it is less than that, the yield decreases, and if it is more than that, it is not economical. In the esterification reaction, a solvent, a catalyst, and an additive can be used, and can be appropriately selected and used depending on the type of the (meth) acrylic acid compound. Hereinafter, the reaction conditions depending on the type of (meth) acrylic acid compound to be used will be specifically described.

[When (meth) acrylic acid halide is used as the (meth) acrylic acid compound]
In order to react with the alcohol compound quickly and in high yield, a base compound is preferably present as an additive. This is because when the base compound is present, the concentration of by-produced hydrogen halide does not increase and the reaction proceeds rapidly, and the target substance can be obtained in high yield. Examples of the base compound include organic bases, specifically, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, diisopropylamine, tri-n-propylamine. , N-butylamine, di-n-butylamine, diisobutylamine, tri-n-butylamine, diphenylamine, 1,5-diazabicyclo [4.3.0] nonene-5, 1,5-diazabicyclo [5.4.0] Amines such as undecene-5 and diazabicyclo [2.2.2] octane, and anilines such as aniline, methylaniline, dimethylaniline, toluidine, anisidine, chloroaniline, bromoaniline, nitroaniline and aminobenzoic acid, which are also organic amines. Kind, Lysine, pyridine such as dimethylamino pyridine, pyrroles, quinolines, nitrogen-containing heterocyclic compounds such as piperidines, and the like.

Also, metal alkoxides such as sodium methoxide, lithium methoxide, quaternary ammonium hydroxides such as tetramethylammonium hydroxide, trimethyl-n-propylammonium hydroxide, ethylammonium sulfate, trimethylammonium nitrate, anilinium chloride, etc. An inorganic base such as sodium hydrogen carbonate such as amine sulfate, nitrate and chloride, and a Grignard reagent such as ethylmagnesium bromide may be present in the reaction solution.
When using these additives, the usage-amount is 0.1-10 equivalent with respect to an alcohol compound, and 0.2-5 equivalent is preferable. Even if it exceeds 10 equivalents, there is no yield improvement effect. There is no restriction | limiting in particular in the addition method of a base compound. It may be charged in advance before adding the methacrylic acid compound, may be added after the methacrylic acid compound is charged, or may be added dropwise simultaneously with the methacrylic acid compound. At that time, it is preferable to control the addition rate so that the reaction temperature does not rise abnormally because the progress of the side reaction can be suppressed.

In the case of using a solvent, it is preferable that the raw material and the target substance have high solubility. Examples of such solvents include halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, ether compounds such as tetrahydrofuran, dioxane, diethyl ether, diisopropyl ether and methyl t-butyl ether, hexane, heptane, octane, nonane, Aliphatic hydrocarbons having 6 to 10 carbon atoms such as decane, cycloaliphatic hydrocarbons having 6 to 10 carbon atoms such as cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane, benzene, toluene, xylene, trialkylbenzene, ethylbenzene, cumene The reaction temperature is -70 to 200 ° C, preferably -50 to 80 ° C. This is because if it is lower than −70 ° C., the reaction rate is lowered, and if it is higher than 200 ° C., it becomes difficult to control the reaction or a side reaction proceeds to lower the yield.

[When methacrylic acid or methacrylic anhydride is used as the methacrylic acid compound]
It is preferable to use an acid catalyst and remove water by-produced during the reaction by azeotropic or dehydrating agent. For example, a Dean-Stark water separator can be used for azeotropic water removal.
Also when using methacrylic anhydride, it is preferable to make it react in presence of an acid catalyst.

  Examples of the acid catalyst include sulfuric acid as the inorganic acid, and examples of the organic acid include benzenesulfonic acid and p-toluenesulfonic acid, and sulfuric acid is particularly preferable because it is inexpensive. A well-known thing can be utilized as a dehydrating agent. Examples include concentrated sulfuric acid, boron trifluoride etherate, trifluoroacetic anhydride, dicyclohexylcarbodiimide, 2-halobenzothiazolium fluoroborate, 2-halogenated pyridinium salt, triphenylphosphine, thionyl chloride / base compound, and the like.

In the case of using a solvent, when water to be generated is removed by azeotropy, a solvent having low compatibility with water and high solubility of the target substance and further inert to the reaction of the present invention is selected. .
Moreover, since it becomes easy to remove water produced as a by-product during the reaction, it is preferable to use a solvent azeotropic with water. Examples of such organic solvents include, for example, aliphatic hydrocarbons having 6 to 10 carbon atoms such as hexane, heptane, octane, nonane, decane, and the like and 6 to 6 carbon atoms such as cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane. 10 aromatic hydrocarbons such as alicyclic hydrocarbon, benzene, toluene, xylene, ethylbenzene, cumene, trialkylbenzene and the like, and toluene having a particularly high boiling point is preferable from the viewpoint of reaction temperature.

  Solvents that can be used when a dehydrating agent is used include nitriles such as acetonitrile and benzonitrile, amides such as formamide, acetamide, dimethylformamide, and dimethylacetamide, and carbon atoms such as hexane, heptane, octane, nonane, and decane. -10 aliphatic hydrocarbons, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane and other C6-C10 alicyclic hydrocarbons, halogenated hydrocarbons, nitro compounds, esters such as ethyl acetate, tetrahydrofuran, diethyl And ethers such as ether, diisopropyl ether and dioxane.

These solvents can be used alone or in a system in which two or more solvents are mixed. The solvent is used in a proportion of 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass with respect to 1 part by mass of the alcohol.
The reaction temperature is the azeotropic temperature of the organic solvent used and water in the case of azeotropic dehydration. When (anhydrous) methacrylic acid is used or when a dehydrating agent is used, the reaction temperature is 0 to 150 ° C, preferably 20 to 120 ° C. When the reaction temperature is lower than 0 ° C., the reaction rate is remarkably reduced. When the reaction temperature is higher than 150 ° C., the selectivity of the target substance is reduced.

[When (meth) acrylic acid esters are used as the (meth) acrylic acid compound]
The alcohol by-produced by the transesterification reaction is removed from the reaction system by a known method such as distillation to obtain the target substance.
In this reaction, a metal and a derivative thereof can be used as a catalyst. Examples of the catalyst include metals such as tin, titanium, germanium, zinc, lead, cobalt, iron, zirconium, manganese, antimony, and potassium, and derivatives thereof. Derivatives include halogen compounds, oxides, carbonates, metal alkoxides, carboxylates and the like.

The reaction temperature is 0 to 150 ° C, preferably 50 to 100 ° C. When the temperature is lower than 0 ° C., the reaction rate decreases, and when the temperature is higher than 150 ° C., the side reaction proceeds and the yield decreases.
When removing the by-produced alcohol out of the reaction system by distillation, a method of reacting near the boiling point of the by-produced alcohol can be mentioned.
When a solvent is used, it is preferable that the raw material and the target substance have high solubility and are inert to the reaction. As such, halogen compounds such as dichloromethane, chloroform and 1,2-dichloroethane, ether compounds such as tetrahydrofuran, diethyl ether and methyl t-butyl ether, hydrocarbon compounds such as benzene, toluene, hexane and heptane, acetonitrile and the like A nitrile compound is mentioned.

Hereinafter, common items in the esterification step described above will be described.
A polymerization inhibitor may be added during the esterification reaction. The polymerization inhibitor is not particularly limited as long as it is a general one. 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl, N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxyl Amine aluminum salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, N-nitrosodiphenylamine, N-nitroso-N-methylaniline, nitrosonaphthol, p-nitrosophenol, N, N'-dimethyl-p Nitroso compounds such as nitrosoaniline, sulfur-containing compounds such as phenothiazine, methylene blue, 2-mercaptobenzimidazole, N, N′-diphenyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, 4 -Hydroxy Amines such as phenylamine and aminophenol, quinones such as hydroxyquinoline, hydroquinone, methylhydroquinone, p-benzoquinone and hydroquinone monomethyl ether, methoxyphenol, 2,4-dimethyl-6-t-butylphenol, catechol, 3-s -Phenols such as butylcatechol and 2,2-methylenebis- (6-t-butyl-4-methylphenol), imides such as N-hydroxyphthalimide, oximes such as cyclohexane oxime and p-quinone dioxime, di Examples thereof include alkylthiodipropinates.
The addition amount is 0.001 to 10% by mass, preferably 0.01 to 1% by mass, based on the methacrylic acid compound.

After completion of the esterification reaction, it can be easily performed by a conventional method such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, purification using activated carbon, or a combination of these. Can be separated and purified. For example, an excess (meth) acrylic acid compound, an additive such as an acid or a base, a catalyst, or the like can be removed by washing the reaction solution with water. At this time, the washing water may contain an appropriate inorganic salt such as sodium chloride or sodium bicarbonate.
Moreover, in order to remove an unreacted (meth) acrylic acid compound, alkali washing | cleaning can also be used together. Examples of the alkali cleaning include an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous sodium carbonate solution, an aqueous sodium hydrogen carbonate solution, and aqueous ammonia, but there are no particular restrictions on the alkaline component used. In addition, acid cleaning may be performed to remove metal impurities. Examples of the acid cleaning include inorganic acids such as hydrochloric acid aqueous solution, sulfuric acid aqueous solution, and phosphoric acid aqueous solution, and organic acids such as oxalic acid aqueous solution. In the cleaning, an organic solvent may be added to the cleaning liquid according to the physical properties of the alcohol compound as the raw material and the curable compounds represented by the formulas (1) and (2) as the products. The organic solvent to be added may be the same as that used in the reaction or may be different, but it is usually preferable to use a solvent with a small polarity that is easily separated from water.

  The esterification reaction step in the present invention can be performed under normal pressure, reduced pressure or increased pressure. The reaction can be carried out by a conventional method such as batch, semi-batch or continuous.

Next, dimethacrylate (B) will be described.
Among the curable compounds of the present invention, dimethacrylate (B) having a viscosity at 25 ° C. of 10 mPa · s or less is an E-type viscometer, B-type viscometer, or vibration among compounds having two methacrylic groups. The viscosity at 25 ° C. measured with a mold viscometer is 10 mPa · s or less.

  Specific examples of dimethacrylate (B) include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylenediol dimethacrylate, neopentyl glycol dimethacrylate, 1, Examples include 6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, propion glycol dimethacrylate, and dipropylene glycol dimethacrylate.

Next, the curable resin composition will be described.
In the present invention, the mass ratio of (A) and (B) in the curable resin composition is 10/90 to 40/60. When the content of (A) is 10% by mass or less, heat resistance and stability at high temperature are insufficient, and when the content of (A) exceeds 40% by mass, a large amount of expensive (A) is added. It becomes economically disadvantageous.

  In the present invention, a curing accelerator (C) can be used. The curing accelerator is a compound that generates radicals or acids / alkalis by heat or active energy rays, and a thermal curing accelerator and a photocuring accelerator can be used.

  A generally known curing accelerator (C) can be used. For example, Irgacure 184, Irgacure 651, Irgacure 127, Irgacure 907, Irgacure 369, Darocure 1173, Irgacure 819, Lucyrin TPO (above) , Manufactured by BASF), azo compounds such as azoisobutyronitrile as thermosetting accelerators, commercially available V-70, V-65, V-601, V-59, V-40, VF-096 , V-30, VAm-110, VAm-111 (manufactured by Wako Pure Chemical Industries, Ltd.), Nyper BW, Nyper BMT, Parroyl TCP, Parroyl L, Parroyl 355, Parroyl SA, Parhexa HC, Perbutyl 355, Perbutyl D, Perbutyl L, perbutyl ND, perocta O, perhexyl D Perhexyl O, Perhexyl PV (above, manufactured by NOF Corporation), Trigonox 36-C75, Laurox, Parkadox L-W75, Parkadox CH-50L, Trigonox TMBH, Kayacumen H, Kayabutyl H-70, Parkadox BC-FF, Kayahexa AD, Parkadox 14, Kayabutyl C, Kayabutyl D, Parkadox 12-XL25, Trigonox 22-N70 (22-70E), Trigonox D-T50, Trigonox 423-C70, Kaya Esters CND-C70, Trigonox 23-C70, Trigonox 257-C70, Kaya ester P-70, Kaya ester TMPO-70, Trigonox 121, Kaya ester O, Kaya ester HTP-65W, Kaya ester AN, Trigonox 42 Trigonox F-C50, Kayabutyl B, Kaya-Carbon EH, Kaya-Carbon I-20, Kaya-Carbon BIC-75, Trigonox 117, Kayalen 6-70 (manufactured by Kayaku Akzo Co., Ltd.), and the like, are not limited thereto. Absent. These curing accelerators can be used alone or in combination.

  Content when using a hardening accelerator (C) is 0.001 mass part-5 mass parts with respect to 100 mass parts of total amounts of a sclerosing | hardenable compound (A) and (B), Preferably it is 0.01 mass. Part to 5 parts by mass, more preferably 0.1 to 1 part by mass. Use in this range is preferable because the crosslinking density increases.

  The curable resin composition of this invention can also contain another curable compound in the range which does not impair the effect of this application. Examples of other curable compounds include known acrylic acid compounds. For example, trimethylolpropane tri (meth) acrylate, ethoxylated bisphenol A (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, glycerin di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo Pentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, benzyl (meth) acrylate, methyl (Meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n Lauryl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , Glycidyl (meth) acrylate, (meth) acrylic acid, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like, but are not limited thereto.

  Furthermore, when producing the curable resin composition of the present invention, if necessary, a thermoplastic resin, a color pigment, an antifoaming agent, a surface conditioner, a flame retardant, an ultraviolet absorber, an antioxidant, a flow conditioner. A known additive such as can be added.

  The curable resin composition of this invention can be prepared by mixing each compound used as a raw material by a well-known method. In particular, the curable resin composition of the present invention is prepared by mixing (A), (B), and other components as necessary, and filtering and degassing the resulting mixture. Is preferred.

The curable resin composition of the present invention can be made into a resin cured product by being poured into a mold or a glass mold and cured by heating only, light irradiation only, or a combination of light irradiation and heating. The cured resin can be obtained by melting the curable resin composition or dissolving it in a solvent, then pouring it into a mold, suitably removing low-boiling components such as a solvent, and curing under normal conditions.

When it hardens only by heating, it hardens | cures in the temperature range of 30 to 300 degreeC, Preferably it is 50 to 260 degreeC. If the curing temperature is too low, the degree of curing of the cured resin will be low, and if it is too high, cracks and coloring will occur. The curing time is 1 to 100 hours, preferably 2 to 50 hours. If the curing time is too short, insufficient curing or cracks will occur. If it is too long, the productivity will be lowered, which is not preferable.

In the case of photocuring, in addition to sunlight, a general light source such as a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a light emitting diode, and a laser, an electron beam, and radiation can be used. The irradiation amount is 1 to 100,000 mJ / cm ² , preferably 50 to 20000 mJ / cm ² . If the irradiation amount is too small, curing is insufficient, and if it is too large, productivity is lowered.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

7.5 g of 1,6-hexanediol dimethacrylate (HxDM, viscosity 6 mPa · s at 25 ° C.), 2.5 g of 5-hydroxy-1,3-adamantane dimethacrylate (HAADDM), Irgacure 184 (IRG184) 0.05 g was weighed and mixed to dissolve uniformly, and then degassed with a vacuum pump to prepare a curable resin composition. A viton O-ring (Viton: Trademark of DuPont) having a thickness of 1.0 mm was sandwiched between two glass plates having a thickness of 3 mm, and the curable resin composition was injected between the glass plates using a syringe. After irradiating 10.5 J / cm ² of the curable resin composition from both sides of the glass with an eye graphic irradiator Icure Light (metal halide lamp 1.5 kW), it was placed in an oven and heated at 190 ° C. for 24 hours. A cured product 1 was obtained.

Comparative Example 1

A cured product 2 was obtained in the same manner as in Example 1 except that 5-hydroxy-1,3-adamantane dimethacrylate (HAADDM) was changed to 1,3-adamantane dimethacrylate (ADDM). It was.

Comparative Example 2

The same procedure as in Example 1 was performed except that 5-hydroxy-1,3-adamantane dimethacrylate (HAADDM) was changed to tricyclodecane dimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., Ltd.). A cured product 3 was obtained.

Comparative Example 3

8 g of PEG # 200 dimethacrylate (4EG, manufactured by Kyoeisha, viscosity 14 mPa · s at 25 ° C.), 2 g of 5-hydroxy-1,3-adamantane dimethacrylate (HAADDM), 0.05 g of Irgacure 184 (IRG184) A curable resin composition was prepared by weighing and mixing to dissolve uniformly and then degassing with a vacuum pump. Using this composition, the same operation as in Example 1 was performed to obtain a cured product 4.

Comparative Example 4

  Weighed 10 g of 1,6-hexanediol dimethacrylate (HxDM) and 0.05 g of Irgacure 184 (IRG184), mixed and dissolved uniformly, and then deaerated with a vacuum pump to prepare a curable resin composition. . Using this composition, the same operation as in Example 1 was performed to obtain a cured product 5.

Comparative Example 5

A homogeneous solution was prepared by weighing and mixing 5 g of 1,6-hexanediol dimethacrylate (HxDM), 5 g of 5-hydroxy-1,3-adamantane dimethacrylate (HAADDM), and 0.05 g of Irgacure 184 (IRG184). Was not obtained.
The evaluation results of Examples and Comparative Examples are summarized in Table 1.

<Evaluation of storage modulus>
Measuring device: Dynamic viscoelastic device DMS6100 (manufactured by Seiko Instruments Inc.)
Measuring method: bending mode, frequency 10 Hz, heating rate 2 ° C./min
The change rate of the storage elastic modulus was obtained from the following formula.
Change rate of storage elastic modulus (%) = {[“30 ° C. storage elastic modulus” − “180 ° C. storage elastic modulus”] / “30 ° C. storage elastic modulus”} × 100
A change rate of less than 60% was indicated by ◯, a change rate of 60% or more and less than 70% by Δ, and a change rate of 70% or more by ×.
<Evaluation of 1% weight loss temperature>
Measuring device: TG / DTA6200 (manufactured by Seiko Instruments Inc.)
Measurement method: Measure the temperature at which the respective weight loss is shown by raising the temperature at 10 ° C./min in a nitrogen atmosphere.
The 1% weight loss was rated as ◯ when the temperature was 260 ° C. or higher, and x when it was lower than 250 ° C.

  It can be said that the resin composition of Example 1 is excellent in heat resistance and stability at high temperatures because the change rate of the storage elastic modulus is small and the thermal decomposition temperature is high.

  According to the present invention, it is possible to obtain a curable resin composition excellent in heat resistance and stability at high temperatures and a cured product thereof.

Claims (5)

A curable resin composition comprising a curable compound (A) represented by the formula (1) and a curable compound (B) which is a dimethacrylate having a viscosity at 25 ° C. of 10 mPa · s or less.

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, ring Z represents a monocyclic or 2 to 5 polycyclic alicyclic hydrocarbon ring, and n represents 1 or 2. X is the same or A hydrogen atom or a methyl group, which may be different. The curable resin composition according to claim 1, wherein the mass ratio of (A) to (B) is 10/90 to 40/60. The curable resin composition according to claim 1 or 2, wherein the curable compound (A) is a compound represented by the formula (2).

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. X represents a hydrogen atom or a methyl group which may be the same or different.) The curable resin composition according to any one of claims 1 to 3, comprising 0.001 to 1 part by mass of the curing accelerator (C) with respect to 100 parts by mass of the total amount of the curable compound.   Hardened | cured material obtained by hardening the curable resin composition of any one of Claims 1-4.