JP2010001424A - Epoxy compound and cured epoxy product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy compound excellent in cation curability, heat resistance, the resistance to yellowing, and so on. <P>SOLUTION: This epoxy compound is represented by general formula (1) (wherein, R<SP>1</SP>is -H or a group represented by formula (2), R<SP>2</SP>is -CH<SB>2</SB>- or -CO-, and R<SP>3</SP>is a 2C-6C alkylene). A cured product from the epoxy compound is also disclosed. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel epoxy compound that gives excellent cured properties such as heat resistance and yellowing resistance and has little toxicity, and an epoxy cured product obtained by curing the epoxy compound.

Epoxy resins have excellent adhesion, electrical insulation, heat resistance, etc., so electrical / electronic materials, printed circuits, molding materials, optical material laminates, paints, adhesives, various composite materials, civil engineering and building materials, etc. Is used in various fields.
The bisphenol A diglycidyl ether type epoxy resin, which is a general-purpose epoxy resin, has a problem that it is slightly inferior in heat resistance, inferior in weather resistance because the main skeleton has a benzene ring, and particularly severe in light deterioration. As heat-resistant epoxy resins, there are phenol novolac epoxy resins and cresol novolac epoxy resins. Like bisphenol A diglycidyl ether type resins, these have a phenyl ether bond in the structure, and the main skeleton has a benzene ring. Therefore, there is still a problem in weather resistance.

On the other hand, an epoxy compound having a structure having an isocyanuric ring as the main skeleton, for example, a resin obtained by curing triglycidyl isocyanurate has a high glass transition temperature (Tg) because it has a rigid isocyanuric skeleton in the molecule. Therefore, the temperature at which heat is deformed becomes high, and when the epoxy resin is cured, it has high heat resistance. In addition, since the main skeleton is an isocyanuric ring, the binding energy is large, and the ratio of ultraviolet absorption is low, so the weather resistance is good.
However, since the crystallinity is high, there is a problem of crystal precipitation of triglycidyl isocyanurate when liquid compounded with liquid acid anhydride.

As means for solving the above problem, Patent Document 1 describes an example using tri (carboxyalkyl) isocyanurate triglycidyl ester. Unlike triglycidyl isocyanurate, it does not crystallize at room temperature and has low workability due to its low viscosity when heated.
However, the compound described in Patent Document 1 has a tendency to be slightly inferior in cationic curability because the reactive group is glycidyl ether. There is also a report that the glycidyl ether group has a slightly high mutagenicity.

Japanese Patent Laid-Open No. 08-08461

  The problem to be solved by the present invention is to provide a novel epoxy compound which is excellent in cationic curability and gives excellent cured properties such as heat resistance and yellowing resistance.

  The inventors of the present invention have a liquid epoxy epoxy compound having an alicyclic epoxy group on the isocyanuric ring, and have excellent cationic curability. A cured product obtained by curing the epoxy compound has excellent heat resistance, weather resistance, and the like. The problem was solved by finding that the cured product had good physical properties.

  That is, this invention provides the epoxy compound represented by General formula (1).

(In Formula (1), R ¹ is -H, or or Formula (2)

（２）

(2)

R ² represents —CH ₂ — or —CO—, and R ³ represents an alkylene chain having 2 to 6 carbon atoms. )

  Moreover, this invention provides the epoxy hardened | cured material obtained by hardening | curing the said epoxy compound.

According to the present invention, a poxy compound that is liquid and excellent in cationic curability is obtained, and a cured product obtained by curing the epoxy compound gives excellent cured properties such as heat resistance and weather resistance.
Moreover, since it does not have a glycidyl ether group, it has low mutagenicity and can be used safely.

(Compound represented by the general formula (1))
In the compound represented by the general formula (1), each R ¹ may be both —H, or one of R ¹ may be —H and the other may be a group represented by the formula (2). It does not matter if both R ¹ are groups represented by the formula (2). When there are two or more alicyclic epoxy groups in one molecule, the cation curability is excellent. Each R ² represents —CH ₂ — or —CO—.
Each R ³ independently represents an alkylene group having 2 to 6 carbon atoms such as an ethylene group, a propylene group, a butylene group, a pentylene group, or a hexylene group. Among these, an ethylene group, a butylene group, and a hexylene group are preferable because the raw materials are inexpensive.

Specific examples of the compound represented by the general formula (1) are shown in the formulas (3) to (6).

式（３）

Formula (3)

式（４）

Formula (4)

式（５）

Formula (5)

式（６）

Formula (6)

The compound represented by the general formula (1) of the present invention can be obtained by a known production method. For example, the compound in which R ² is —CH ₂ —, such as the compounds represented by the above formulas (3) and (5), is obtained by using 3-cyclohexene-1-methanol and tris (hydroxyethyl) isocyanurate as so-called William. It is obtained by etherification by Son synthesis and epoxidizing the resulting olefin.
The olefin epoxidation can be carried out by a conventional method. For example, a method using a peracid such as peracetic acid or metachloroperbenzoic acid, or a method using hydrogen peroxide using sodium tungstate as a catalyst can be applied.

In addition, the compound in which R ² is —CO—, such as the compounds represented by the formulas (4) and (6), is tris (hydroxyethyl) isocyanurate and 3-cyclohexene-1-carboxylic acid. It can be obtained by adding a methyl ester by transesterification and epoxidizing the resulting olefin.
It can also be obtained by adding 1,3-butadiene to Tris (2-acryloyloxyethyl) isocyanurate by Diels-Alder reaction and epoxidizing the resulting olefin.
The olefin epoxidation can be carried out by a conventional method. For example, a method using a peracid such as peracetic acid or metachloroperbenzoic acid, or a method using hydrogen peroxide using sodium tungstate as a catalyst can be applied.

Moreover, the compound represented by the general formula (1) of the present invention in which R ³ is a propylene group can be obtained by using tris (hydroxypropyl) isocyanurate. A compound in which R ³ is a butylene group can be obtained by using tris (hydroxybutyl) isocyanurate. A compound in which R ³ is a pentylene group can be obtained by using tris (hydroxypentyl) isocyanurate. A compound in which R ³ is a hexylene group can be obtained by using tris (hydroxyhexyl) isocyanurate. These tris (hydroxyalkyl) isocyanurates can be obtained by adding cyanuric acid and haloalkylol using sodium hydride or lithium hydroxide.

The epoxy compound represented by the general formula (1) of the present invention can be cured, that is, polymerized to obtain a cured epoxy resin having excellent heat resistance and weather resistance.
For example, when cured by heat, amines such as diaminodiphenylmethane and diaminodiphenylsulfone, acid anhydrides such as methyl nadic acid anhydride, methyl hymic acid anhydride, hexahydrophthalic acid anhydride, and tetrahydrophthalic acid anhydride Or a curing agent such as polyamide resin, polysulfide resin, boron trifluoride and amine complex, dicyandiamide, etc., and the epoxy compound represented by the general formula (1) may be cured alone, or other epoxy group The cured epoxy resin of the present invention can also be obtained by using a compound or resin having a bisphenol A diglycidyl ether type resin, a phenol novolac epoxy resin, or the like in combination.

It is also possible to cure by cationic polymerization using a thermal cationic polymerization initiator. In this case, an initiator such as an onium salt of nitrogen, sulfur, phosphorus, or iodine containing SbF ₆ ⁻ , SbF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ or the like as an anion component is used. The epoxy compound shown may be cured alone or may be cured in combination with other cationically polymerizable compounds. Examples of the cationic polymerizable compound include an epoxy compound, an oxetane compound, and a vinyl compound. Epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexyl) adipate, bisphenol A diglycidyl ether, diglycidyl ether condensate of bisphenol A, novolak Examples thereof include an epichlorohydrin-modified product of a resin or a cresol resin. As the oxetane compound, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (chloromethyl) oxetane, 1,4-bis And [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3-oxetanyl)] methyl} ether, and the like. Examples of the vinyl compound include 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, cyclohexane dimethanol divinyl ether, propylene carbonate propenyl ether, vinyl carbazole, vinyl pyrrolidone, and the like.

Moreover, when making it harden | cure by light, it is possible to make it react using a photocationic polymerization initiator. In this case, the cation moiety is aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, thioxanthonium, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene]- An iron cation, and thianthrenium, wherein the anion moiety is BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , [BX ₄ ] ⁻ (wherein X represents two or more hydrogen atoms of the phenyl group, An aromatic sulfonium salt, an aromatic iodonium salt, an aromatic diazonium salt, an aromatic ammonium salt, a thioxanthonium salt, and a functional group substituted with a fluorine atom or a trifluoromethyl group. 4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron salt, etc. The above can be used together. Examples of the aromatic sulfonium salt include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (Phenylthio) phenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluorophosphate, etc. Can be used. Examples of the aromatic iodonium salt include diphenyliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, and the like. be able to. Examples of the aromatic diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium tetrakis (pentafluorophenyl) borate, and the like. As the aromatic ammonium salt, 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, or the like can be used. Moreover, S-biphenyl 2-isopropyl thioxanthonium hexafluorophosphate etc. can be used as said thioxanthonium salt. The (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron salt includes (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene. ] -Iron (II) hexafluorophosphate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron (II) hexafluoroantimonate, and the like can be used.

  Examples of the photo cationic polymerization initiator include CPI-100P, CPI-101A (manufactured by San Apro Co., Ltd.), Syracure photocuring initiator UVI-6990, Syracure photocuring initiator UVI-6922, and Cyracure photocuring initiation. Agent UVI-6976 (above, manufactured by Dow Chemical Japan Co., Ltd.), Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172 (Asahi Denka Kogyo) CI-5102, CI-2855 (above, Nippon Soda Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-110L, Sun-Aid SI-180L, Sun-Aid SI-110, Sun-Aid SI-145, Sun-Aid SI-1 0, Sun-Aid SI-160, Sun-Aid SI-180 (manufactured by Sanshin Chemical Industry Co., Ltd.), Esacure 1064, Esacure 1187 (manufactured by Lamberti), Omnicat 432, Omnicat 440, Omnicat 445, Omni-Cat 550, Omni-Cat 650, Omni-Cat BL-550 (manufactured by IG Resin), Irgacure 250 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Rhodosil Photo Initiator 2074 (RHODORSIL PHOTOINITITOR 2074 (Rhodia Japan Co., Ltd.) ) And the like are commercially available.

These cationic polymerization initiators may be used alone or in combination. Although the usage-amount of a cationic polymerization initiator does not have limitation in particular, Usually, it is 0.1-15 mass% with respect to solid content, Preferably it is 0.5-8 mass%.
When the polymerization is carried out with heat, a known heat source such as hot air or near-infrared rays can be applied.
Moreover, when superposing | polymerizing by light irradiation, it is preferable to use visible light or an ultraviolet-ray normally. In particular, ultraviolet rays are suitable. As the ultraviolet light source, sunlight, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like is used.

  In addition, various additives such as fillers such as silica, alumina, talc and calcium carbonate, phosphorus-based flame retardants such as red phosphorus and phosphate esters, halogen-based flame retardants such as chlorinated paraffin, tertiary amine, fourth Curing accelerators such as quaternary ammonium salts, tertiary phosphines, and quaternary phosphonium salts, or toughness modifiers such as rubber particles can be blended. These types, blending amounts and the like are not particularly limited, and can be blended as appropriate according to desired physical properties.

Example 1 Method for Producing Compound Represented by Formula (4) Tris (hydroxyethyl) isocyanurate 5.0 g (19.14 mmol) was converted to 40.24 g (287 mmol) of 3-cyclohexene-1-carboxylic acid methyl ester. After dispersion, 0.226 g of Neostan-U300 (manufactured by Nitto Kasei Co., Ltd.) was added as a transesterification catalyst, and the mixture was heated and stirred at 120 ° C. for 6 hours while removing methanol under reduced pressure. Excess 3-cyclohexene-1-carboxylic acid methyl ester was removed from the reaction mixture under reduced pressure and dissolved in 100 ml of ethyl acetate. The extract was washed twice with 100 ml of distilled water, dried over anhydrous magnesium sulfate, and the solvent was removed to obtain a yellow transparent liquid. Further, this was passed through a silica gel column (hexane / ethyl acetate = 8/2) to remove the coloring component, and 10.41 g of an olefin compound represented by the formula (7) was obtained. The yield was 92.9%.

式（７）

Formula (7)

A solution of 16.32 g (61.47 mmol) of 65% metachloroperbenzoic acid in 160 ml of dichloromethane was cooled to 10 ° C., and 10.0 g (17.08 mmol) of the olefin represented by the above formula (7) was slowly added while stirring. After stirring for 3 hours, the mixture was allowed to stand at 6 ° C. for 24 hours. The precipitate was filtered off, and the solution was washed once with 200 ml of 10% aqueous sodium thiosulfate solution, twice with 100 ml of saturated aqueous sodium hydrogen carbonate solution, twice with 100 ml of distilled water, dried over magnesium sulfate, and desolvated. It passed through a silica gel column (hexane / ethyl acetate = 5/5) to obtain 9.10 g of a colorless transparent viscous liquid.
^{From 1} H NMR, ¹³ C NMR, and FT-IR spectrum analysis, it was confirmed that this compound had a structure represented by the formula (4).
The yield was 84.1%, the refractive index _D ²⁵ = 1.5142, and the Abbe number _D = 57.

¹ H NMR spectral value: 4.30 (t, J = 3.6 Hz, 6H), 4.16 (t, J = 4.8 Hz, 6H), 3.22 ppm (s, 2H), 3.12 ppm (s 4H), 2.46-1.26 ppm (m, 21H)
¹³ C NMR spectral values: 175.2 ppm, 174.4 ppm, 148.8 ppm, 61.1 ppm, 61.0 ppm, 52.1 ppm, 51.5 ppm, 51.2 ppm, 50.5 ppm, 41.9 ppm, 37.5 ppm, 35.6ppm, 27.0ppm, 26.0ppm, 23.6ppm, 22.7ppm, 20.7ppm

The result of measuring the infrared absorption (IR) of the obtained product is shown below.
IR spectral ^{values: 2958cm -1, 1735cm -1, 1701cm} -1, 1465cm -1, 1398cm -1, 1369cm -1, 1311cm -1, 1259cm -1, 1234cm -1, 1182cm -1, 1058cm -1, 1001cm - ^{1, 937cm -1, 908cm -1,} 862cm -1, 837cm -1, 800cm -1, 765cm -1, 630cm -1, 541cm -1, 478cm -1

(Example 2) Production method of the compound represented by the formula (6) 20.0 g (76.56 mmol) of tris (hydroxyethyl) isocyanurate was converted to 80.48 g (572 mmol) of 3-cyclohexene-1-carboxylic acid methyl ester. After dispersion, 0.60 g of Neostan-U300 (manufactured by Nitto Kasei Co., Ltd.) was added as a transesterification catalyst, and the mixture was heated and stirred at 120 ° C. for 4 hours while removing methanol under reduced pressure. Excess 3-cyclohexene-1-carboxylic acid methyl ester was removed from the reaction mixture under reduced pressure and dissolved in 100 ml of ethyl acetate. The extract was washed twice with 100 ml of distilled water, dried over anhydrous magnesium sulfate, and the solvent was removed to obtain a yellow transparent liquid. Further, this was passed through a silica gel column (using a solvent of hexane / ethyl acetate = 7/3) to remove the coloring component, and 10.2 g of an olefin represented by the formula (8) was obtained. The yield was 27.9%.

式（８）

Formula (8)

A solution of 12.00 g (45.2 mmol) of 65% metachloroperbenzoic acid in 160 ml of dichloromethane was cooled to 10 ° C., and 10.0 g (21.0 mmol) of the olefin compound represented by the formula (4) was slowly added while stirring. The mixture was added and stirred for 3 hours, and then allowed to stand at 6 ° C. for 24 hours. The precipitate was filtered off, and the solution was washed once with 200 ml of 10% aqueous sodium thiosulfate solution, twice with 100 ml of saturated aqueous sodium hydrogen carbonate solution, twice with 100 ml of distilled water, dried over magnesium sulfate, and desolvated. It passed through a silica gel column (hexane / ethyl acetate = 7/3) to obtain 9.18 g of a colorless transparent viscous liquid. ^{From 1} H NMR, ¹³ C NMR, and FT-IR spectrum analysis, it was confirmed that this compound had a structure represented by the formula (6). The yield was 91.8%, the refractive index _D ²⁵ = 1.5144, and the Abbe number _D = 53.

¹ H NMR spectral values: 4.33 (s, 4H), 4.18 (dd, J = 5.4, 4.3 Hz, 4H), 4.11 (t, J = 5.4 Hz, 2H), 3 .85 (dd, J = 9.3, 4.7 Hz, 2H), 3.22 ppm (s, 2H), 3.14 ppm (s, 2H), 2.57-1.26 ppm (m, 14H)
¹³ C NMR spectral value: 175.3 ppm, 174.6 ppm, 149.27 ppm, 149.26 ppm, 148.84 ppm, 148.80 ppm, 61.0 ppm, 59.9 ppm, 52.1 ppm, 51.6 ppm, 51.2 ppm, 50.7 ppm, 45.0 ppm, 41.9 ppm, 37.4 ppm, 35.6 ppm, 27.0 ppm, 25.09 ppm, 23.4 ppm, 22.7 ppm, 20.6 ppm

The result of measuring the infrared absorption (IR) of the obtained product is shown below.
IR spectral values: 3545 cm ⁻¹ , 2968 cm ⁻¹ , 1734 cm ⁻¹ , 1699 cm ⁻¹ , 1463 cm ⁻¹ , 1367 cm ⁻¹ , 1313 cm ⁻¹ , 1257 cm ⁻¹ , 1234 cm ⁻¹ , 1170 cm ⁻¹ , 1060 cm ⁻¹ , 1001 cm ^{− 1, 937cm -1, 860cm -1,} 800cm -1, 761cm -1, 634cm -1, 543cm -1

Example 3 Photocuring of Compound Represented by Formula (4) 0.04 part of Irgacure 250, a cationic photopolymerization initiator, was added to 1 part of the compound represented by Formula (4), 4 parts of 2 -Formulation diluted with methoxyethanol was prepared. It apply | coated to the glass substrate with the spin coater, and it dried for 5 minutes on a 100 degreeC hotplate. After irradiating a 120 W / cm high-pressure mercury lamp with a predetermined exposure amount and post-baking on a hot plate at 100 ° C. for 5 minutes, the solvent resistance is evaluated with an acetone wipe. Suppose that solvent is expressed.
It was confirmed that this formulation exhibited solvent resistance at an exposure amount of 120 mJ / cm ² .

Example 4 Mutagenicity Test of Compound Represented by Formula (4) Ames test was performed on the compound represented by Formula (4), and the mutagenic expression level of Salmonella was determined. It was 5 mg / plate (+ s9).
Note that bisphenol A glycidyl ether, which is a representative epoxy compound, is reported as mmo-sat 33 μg / plate (+ s9), and triglycidyl isocyanurate is reported as mmo-sat 333 μg / plate (+ s9). Was weak.

(Example 5) Thermoset of compound represented by formula (4) 24.5 parts of compound represented by formula (4) 24.5 parts of Celoxide 2021P (manufactured by Daicel Cytec), 51 parts of Epicron B650 (manufactured by DIC Corporation) and 5 parts of Hishicolin PX-4MP (manufactured by Nippon Chemical Industry Co., Ltd.) were added to prepare a thermosetting compound. It apply | coated to the glass substrate with the spin coater, and it heated at 150 degreeC for 2 hours, and obtained the thin film hardened | cured material with a film thickness of 10 micrometers.

(Evaluation of refractive index, heat resistance and light resistance of resin thin film)
The heat resistance of the resin thin film produced in Example 5 was evaluated by measuring the yellowness (YI value) after heating at 150 ° C. for 500 hours using a thermostat (manufactured by Isuzu Seisakusho). The light resistance test was evaluated by measuring the yellowness (YI value) after irradiating light for 100 hours or 500 hours with a sun tester (Sun tester CPS + manufactured by Atlas, xenon lamp, 550 W / m ² ). Yellowness (YI value) was measured according to JIS8722 with a colorimetric color difference meter (ZE2000 manufactured by Nippon Denshoku Industries Co., Ltd.).
As a result, the YI value after 500 hours of the heat resistance test and after 500 hours of the light resistance test was 1 or less, and the heat resistance and light resistance were excellent.

(Reference Example 1)
Solvent resistance in the same manner as in Example 3 except that liquid glycidyl TEPIC-PAS (manufactured by Nissan Chemical Co., Ltd.) having a triazine ring as a central skeleton was used instead of the compound represented by formula (4) in Example 3. The exposure amount expressing the sex was determined.
In this formulation, solvent resistance did not develop even at 2000 mJ / cm ² .

  The polymerizable alicyclic compound and the polymer thereof according to the present invention are materials such as light emitting diodes, plastic lenses, prisms, optical fibers, substrates for information recording media, optical components such as filters, specifically 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), passive components ( High-frequency devices, resistors, capacitors, etc.), mechanical parts (connectors, switches, relays, etc.), automotive parts (circuit systems, control systems, sensors, lamp seals, etc.), adhesives (optical parts, optical discs, pickup lenses, etc.) ), And is useful as a surface coating agent for optical films.

Claims (2)

An epoxy compound represented by the general formula (1).

(In Formula (1), R ¹ is -H, or or Formula (2)

(2)
R ² represents —CH ₂ — or —CO—, and R ³ represents an alkylene chain having 2 to 6 carbon atoms. ) An epoxy cured product obtained by curing the epoxy compound according to claim 1.