WO2011152251A1

WO2011152251A1 - Alicyclic monoallyl ether-monoglycidyl ether compound

Info

Publication number: WO2011152251A1
Application number: PCT/JP2011/061898
Authority: WO
Inventors: 博内田; 真尚原
Original assignee: 昭和電工株式会社
Priority date: 2010-06-03
Filing date: 2011-05-24
Publication date: 2011-12-08
Also published as: TW201202211A; JP2014024753A; TWI444372B

Abstract

Provided is a compound that is useful as a raw material for a thermosetting resin composition for an LED encapsulant, said compound being a hardened material with high hardness, lacking stickiness on the surface, and having excellent transparency, heat resistance, UV resistance, and strength. The compound is an alicyclic monoallyl ether-monoglycidyl ether compound represented by general formula (1) below {in the formula, R represents a divalent hydrocarbon group with 4 to 20 carbons containing an alicyclic structure}. Also provided is a thermosetting resin composition containing: an alicyclic trialkoxysilyl-monoglycidyl ether compound obtained by forcing said alicyclic monoallyl ether-monoglycidyl ether compound to undergo a hydrosilylation reaction with a trialkoxysilane; and an epoxy silicone compound obtained by applying the sol-gel process to said alicyclic trialkoxysilyl-monoglycidyl ether compound.

Description

Alicyclic monoallyl ether monoglycidyl ether compound

The present invention relates to an alicyclic monoallyl ether monoglycidyl ether compound, an alicyclic trialkoxysilyl monoglycidyl ether compound, and a curable resin composition containing the compound. More specifically, the present invention is excellent in optical properties, hardness, strength, and heat resistance, and particularly includes an alicyclic skeleton that is a raw material of a curable resin composition suitable for the field of electronic materials and light-emitting diode (LED) sealing. The present invention relates to an alicyclic monoallyl ether monoglycidyl ether compound, an alicyclic trialkoxysilyl monoglycidyl ether compound derived therefrom, and a curable resin composition containing the compound.

Epoxy resins are excellent in electrical properties, adhesiveness, heat resistance, etc., and are used in many applications such as the paint field, civil engineering field, and electrical field. In particular, aromatic epoxy resins such as bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, phenol novolac type epoxy resin, and cresol novolac type epoxy resin are water resistant, adhesive, mechanical properties, heat resistant, and electrical insulating properties. It is widely used in combination with various curing agents because of its excellent economic efficiency.

However, since these resins contain an aromatic ring, they are easily deteriorated by ultraviolet rays or the like, and there are restrictions in use in fields where weather resistance and light resistance are required. For example, in the field of blue and white LED devices, when an epoxy resin composition containing an aromatic is used as a sealing material, the resin deteriorates due to the light emitted from the LED element or the heat generated by the LED element, and the yellowing over time occurs. There is a problem that the luminance decreases.

Patent Document 1 below discloses a hydrogenated epoxy resin obtained by hydrogenating an aromatic epoxy resin, and an epoxy resin composition for electric / electronic materials containing a curing agent.
Moreover, the following patent document 2 discloses an epoxy resin composition in which an alicyclic epoxy resin obtained by oxidizing a cyclic olefin or an epoxy resin having a nitrogen atom therein is blended.
On the other hand, the following Patent Document 3 discloses a resin composition using an epoxy resin having a silicone structure with excellent weather resistance in the main chain.
Further, in Patent Document 4 and Non-Patent Document 1 below, a linear or cyclic siloxane bond and an alicyclic epoxy group (two adjacent carbon atoms forming an alicyclic skeleton and an oxygen atom, a three-membered ether (oxirane) A silicone hybrid epoxy resin having the structure) is disclosed.
Furthermore, Patent Document 5 discloses an epoxy silicone resin having a linear siloxane structure in the main chain and an isocyanuric group in the side chain or terminal.

Japanese Patent No. 3537119 JP 2000-196151 A JP 2005-263869 A JP 2006-290998 A JP 2004-99751 A

Epoxy resin compositions are widely used in low-power white LED sealing applications because of the high hardness of the cured product and excellent handling properties and necessary durability.
However, high-power LEDs have the disadvantages that discoloration is likely to occur due to an increase in light emission and heat generation, and it is difficult to obtain a sufficient life. In order to prevent discoloration due to an increase in calorific value, an epoxy resin that exhibits a high glass transition temperature is used, but such an epoxy resin is highly elastic and has lower strength and deflection than a normal epoxy resin and is lit off. There is also a problem that the sealing material is easily cracked due to a sudden temperature change due to. In addition, due to the recent shortening of the light emission wavelength of LEDs, there is a problem that the light emission output is likely to be lowered due to discoloration when continuously used. For this reason, the sealing material is required to have high strength as well as further improvement in heat resistance and light resistance.

Recently, LED encapsulants based on silicone resins with excellent weather resistance have been developed in place of epoxy resins. Resin compositions by addition reaction of hydrosilyl groups and olefins, and silicone resins having epoxy groups There have been reports of resin compositions obtained by curing a resin using a curing agent. However, many of the epoxy resins having a silicone resin or silicone skeleton in the main chain have high flexibility derived from the silicone skeleton, but the hardness of the cured product is low and the surface tends to be sticky, and the strength is high. It has the disadvantage of being low. For example, a compound having a carbon-carbon double bond capable of reacting with a hydrosilyl group and an epoxy group is industrially represented by the following formula (a):

Or formula (b):

A compound having a structure represented by is used.

Since the compound represented by the formula (a) is an aliphatic glycidyl ether, the hardness is low and stickiness cannot be eliminated.
In addition, the compound represented by the formula (b) can improve the hardness and the like to some extent, but since it is a cyclohexene oxide skeleton epoxy resin, it has poor adhesion to the LED chip or package to be sealed. There is a problem.

Thus, even if it is based on a silicone resin having excellent weather resistance, it has not yet been obtained that completely satisfies the physical properties required for the LED sealing material, sufficient hardness, strength, There is a demand for a material having flexibility, excellent heat resistance and UV (ultraviolet) resistance, and mass production and handling properties similar to those of epoxy resins.

Under such circumstances, the problem to be solved by the present invention is that the cured product has high hardness, has no stickiness on the surface, and has excellent transparency, heat resistance, UV resistance, and thermosetting for LED encapsulant. A compound useful as a raw material of a resin composition, and a curable resin composition containing a derivative of the compound.

As a result of intensive studies to solve the above-mentioned problems and repeated experiments, the present inventors have found that monoallyl ether compounds having an alicyclic skeleton in the molecule in order to develop hardness, heat resistance, UV resistance and strength. A curable resin composition containing a reaction product of a compound having a glycidyl ether structure and a silicone compound having a hydrosilyl group is suitable for LED sealing applications, and other electronic material applications such as semiconductor sealing materials and printed wiring boards. It was also found useful, and the present invention was completed.

That is, the present invention is as follows.
[1] The following general formula (1):

{Wherein R represents a C 4-20 divalent hydrocarbon group containing an alicyclic skeleton. } The alicyclic monoallyl ether monoglycidyl ether compound represented by these.

[2] In the formula, R represents an alicyclic monoallyl ether monoglycidyl ether compound according to the above [1] having a C 4-8 cycloalkane skeleton.

[3] The alicyclic monoallyl ether monoglycidyl ether compound according to [1] or [2], which has a molecular weight of 150 to 400.

[4] The compound represented by the general formula (1) is represented by the following formula (2):

The following equation (3):

Or the following formula (4):

The alicyclic monoallyl ether monoglycidyl ether compound according to any one of [1] to [3], which is represented by any one of:

[5] The following general formula (6):

{In the formula, R represents a divalent hydrocarbon group containing an alicyclic hydrocarbon having 4 to 20 carbon atoms, and R 'represents a hydrocarbon group having 1 to 4 carbon atoms. } The alicyclic trialkoxysilyl monoglycidyl ether compound represented by this.

[6] A curable resin composition containing an epoxy silicone compound obtained by sol-gelating an alicyclic trialkoxysilyl monoglycidyl ether compound represented by the general formula (6) described in [5].

The curable resin composition containing the alicyclic trialkoxysilyl monoglycidyl ether compound obtained by reacting the alicyclic monoallyl ether monoglycidyl ether compound and trialkoxysilane of the present invention has a hardened cured product. , There is little cure shrinkage, no stickiness on the surface of the cured product, excellent strength and transparency, excellent heat resistance and light resistance. Therefore, the curable resin composition of the present invention is useful in the fields of electronic materials such as paints, coating agents, printing inks, resist inks, adhesives, semiconductor encapsulants, molding materials, casting materials, and electrical insulating materials. It is. The curable resin composition of the present invention is particularly useful in the LED field, and is excellent as a thermosetting resin composition for LED sealing.

FIG. 1 is a diagram showing a general change over time of an epoxidation reaction in which diallyl ether is oxidized using an oxidizing agent. FIG. 2 shows the ¹ H-NMR measurement results of the alicyclic monoallyl ether monoglycidyl ether compound obtained in Example 1. FIG. 3 shows the results of ¹³ C-NMR measurement of the alicyclic monoallyl ether monoglycidyl ether compound obtained in Example 1. FIG. 4 shows the ¹ H-NMR measurement results of the alicyclic trialkoxysilyl monoglycidyl ether compound obtained in Example 2. FIG. 5 shows the results of ¹³ C-NMR measurement of the alicyclic trialkoxysilyl monoglycidyl ether compound obtained in Example 2. FIG. 6 shows the ¹ H-NMR measurement results of the epoxysilicone compound obtained in Example 3. FIG. 7 shows the results of ¹³ C-NMR measurement of the epoxysilicone compound obtained in Example 3. FIG. 8 shows the ¹ H-NMR measurement results of the alicyclic monoallyl ether monoglycidyl ether compound obtained in Example 4. FIG. 9 shows the results of ¹³ C-NMR measurement of the alicyclic monoallyl ether monoglycidyl ether compound obtained in Example 4. FIG. 10 shows the ¹ H-NMR measurement results of the alicyclic trialkoxysilyl monoglycidyl ether compound obtained in Example 5. FIG. 11 shows the results of ¹³ C-NMR measurement of the alicyclic trialkoxysilyl monoglycidyl ether compound obtained in Example 5. FIG. 12 shows the ¹ H-NMR measurement results of the epoxysilicone compound obtained in Example 6. FIG. 13 shows the results of ¹³ C-NMR measurement of the epoxysilicone compound obtained in Example 6.

Hereinafter, the present invention will be described in detail.
The alicyclic monoallyl ether monoglycidyl ether compound according to the present invention has the following general formula (1):

{Wherein R represents a C 4-20 divalent hydrocarbon group containing an alicyclic skeleton. }.
Such alicyclic monoallyl ether monoglycidyl ether compounds include, for example:
(1) A method of partially epoxidizing the corresponding diallyl ether with hydrogen peroxide, peracid or the like, or (2) a method of etherifying the corresponding diol with allyl chloride and further glycidyl ether using epichlorohydrin,
However, it is more preferable to use the method (1) in which no chlorine compound is mixed as an impurity.

The method of (1) is the following general formula (5):

{In the formula, R represents a divalent hydrocarbon group having 4 to 20 carbon atoms including an alicyclic skeleton having 4 to 20 carbon atoms. }
A method of oxidizing an alicyclic diallyl ether compound corresponding to the alicyclic monoallyl ether monoglycidyl ether compound represented by the above general formula (1), specifically, :
(A) a method of epoxidation with hydrogen peroxide in an acetonitrile-alcohol solvent,
(B) a method of epoxidation with a tungstic acid catalyst, or (C) a method of epoxidation with peracetic acid,
However, in the method (C), a peracid that tends to explode is used, and in the method (B), the epoxy group may be hydrolyzed. Therefore, the method (A) is more preferable.

As the method (A), 0.5 to 10-fold mol of acetonitrile is used with respect to the corresponding diallyl ether compound, an alcohol solvent is added to a concentration of 10 to 80% by mass, and the pH is adjusted with alkali. While controlling in the range of 7.5 to 13, by dropping 0.5 to 2 times mole hydrogen peroxide to the diallyl ether compound at a temperature of 0 to 80 ° C., the desired alicyclic ring A formula monoallyl ether monoglycidyl ether compound can be obtained.

The alicyclic monoallyl ether monoglycidyl ether compound preferably has at least a cycloalkane skeleton composed of a 4- to 8-membered ring, more preferably a 5- to 6-membered ring, in order to ensure adhesion to an LED chip or a package. Contains one.
Moreover, from the viewpoint of ensuring heat resistance, the molecular weight of the alicyclic monoallyl ether monoglycidyl ether compound is preferably 400 or less, more preferably 350 or less. On the other hand, if the molecular weight is too small, the shrinkage rate is increased at the time of curing and distortion tends to occur. Therefore, the molecular weight is preferably 150 or more, more preferably 220 or more.

Examples of such alicyclic monoallyl ether monoglycidyl ether compounds include the following formula (2):

Formula (3):

Or formula (4):

And a compound having a structure represented by:

In the method (A), when the amount of acetonitrile used is small, the yield of the target epoxy compound is low. On the other hand, when it is excessive, the amount of by-products increases and the utilization efficiency of hydrogen peroxide deteriorates. . Therefore, the amount of acetonitrile used is preferably 0.5 to 10-fold mol, and more preferably 1 to 6-fold mol based on the corresponding diallyl ether compound.

Acetonitrile reacts with hydrogen peroxide to produce a peroxide, which is said to oxidize allyl ether to give glycidyl ether, and at that time, equimolar acetamide is by-produced. . Therefore, it is necessary to remove acetamide after completion of the reaction, but this can be removed, for example, by adding a solvent such as toluene to the reaction solution and washing with water.

In the method (A), the epoxidation can be carried out with a solvent of acetonitrile alone, but the presence of alcohol is preferable because the selectivity of epoxidation is increased. The alcohol is preferably a saturated alcohol having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and isobutanol. In consideration of solubility in water, methanol, ethanol N-propanol and isopropanol are preferable, and methanol is particularly preferable in consideration of azeotropy with acetonitrile.

If the amount of alcohol solvent used is small, the effect of using it will not be obtained. Therefore, the amount of the alcohol solvent used is preferably 10 to 80% by mass, more preferably 20 to 70% by mass with respect to the concentration of the reaction solution before hydrogen peroxide is added (dropped as an aqueous hydrogen peroxide solution). .

In the method (A), if the amount of hydrogen peroxide used is small, the target monoallyl ether monoglycidyl ether cannot be obtained. On the other hand, if it is large, the target monoallyl ether monoglycidyl ether is converted to diglycidyl ether. It is not preferable because it is oxidized to the point. Therefore, the hydrogen peroxide is preferably used in an amount of 0.5 to 2 moles, more preferably 0.75 to 1.5 or 1.75 moles per mole of the diallyl ether compound. Regarding hydrogen peroxide, although depending on the pH of the reaction solution described later, there is a concern that when the required amount is charged into the reaction system from the beginning, the reaction rate is high and the reaction may run out of control. A method of dropping the reaction solution as a hydrogen oxide aqueous solution is desirable. At this time, in order to avoid accumulation of hydrogen peroxide in the reaction system, the hydrogen peroxide concentration of the reaction solution should be controlled to be 10% by mass or more, preferably 5% by mass or more. The concentration of the aqueous hydrogen peroxide solution used is preferably 5% by mass to 60% by mass, more preferably 15% by mass to 45% by mass because the higher the concentration, the higher the productivity, but the greater the safety risk. % Range.

Also, since the epoxidation reaction described above is affected by pH, it is necessary to perform the reaction on the alkali side. When the pH is close to neutral, the reaction rate is slow, and when it is too biased toward the alkali side, side reactions increase, which is not preferable. Therefore, the pH of the reaction solution is preferably 7.5 to 13, more preferably 8 to 12. Further, as the aqueous hydrogen peroxide solution is dropped, the pH moves to the neutral side, so it is more preferable to add an alkali compound and keep it constant. More preferably, the pH range is controlled within 10 to 11 from the start to the end of the reaction.

Examples of the alkali compound for adjusting the pH include alkali metal or alkaline earth metal hydroxides, carbonates, bicarbonates, and organic amine compounds. In consideration of adding alkali in the middle of the reaction, it is preferable to use an aqueous solution of sodium hydroxide, potassium hydroxide, potassium carbonate, methanol solution, or ethanol solution.

When the reaction temperature is high, side reactions increase and the utilization efficiency of hydrogen peroxide is deteriorated. When the reaction temperature is low, the reaction rate is slow. Therefore, the reaction is preferably performed at 0 to 80 ° C., more preferably 20 to 60 ° C.

In the method (A), after the epoxidation reaction, the treatment can be performed by an industrially practiced treatment method. For example, a solvent such as toluene or cyclohexane is added to separate an aqueous layer and an organic layer to separate excess hydrogen peroxide. After this, after washing with water to remove acetamide if necessary, the organic layer is treated with a reducing agent such as sulfite, bisulfite, and thiosulfate, and further if necessary. The crude product can be obtained by washing with water and distilling off the solvent.

Here, the time course of the epoxidation reaction generally follows the course as shown in FIG. In order to efficiently obtain monoallyl ether monoglycidyl ether, it is preferable to stop the reaction when the yield reaches about 40% and perform the above-described reaction termination operation.
Monoallyl ether monoglycidyl ether can be obtained by purifying and separating the obtained crude product by a method such as column chromatography. Further, it is possible to carry out the hydrosilylation reaction described later as it is, using a crude reaction solution containing 10% by mass or more, preferably 20% by mass or more of monoallyl ether monoglycidyl ether, and industrially. Rather, it may be preferable because it saves the labor of separation.

The alicyclic trialkoxysilyl monoglycidyl ether compound according to the present invention has the following general formula (6):

{In the formula, R represents a divalent hydrocarbon group containing an alicyclic hydrocarbon having 4 to 20 carbon atoms, and R 'represents a hydrocarbon group having 1 to 4 carbon atoms. }.

The alicyclic trialkoxysilyl monoglycidyl ether compound represented by the general formula (6) is obtained by replacing the alicyclic monoallyl ether monoglycidyl ether compound represented by the general formula (1) with trialkoxysilane and hydrosilyl. It can be obtained by a chemical reaction. Specifically, a trialkoxysilane such as trimethoxysilane, triethoxysilane, tri-n-propoxysilane, triisopropoxysilane, tri-n-butoxysilane, tri-tert-butoxysilane, or the like is used as the above crude product solution. The reaction is carried out with the isolated monoallyl ether monoglycidyl ether or the crude product liquid as it is in the presence of a noble metal catalyst. The amount of trialkoxysilane used is preferably 1 to 5 times mol and more preferably 1.5 to 4 times mol based on the alicyclic monoallyl ether monoglycidyl ether compound. As the catalyst, various known noble metals or complex compounds thereof can be used.

Examples of the noble metal catalyst include platinum, rhodium, palladium, ruthenium, iridium and the like. However, the noble metal catalyst is not limited to these, and two or more of them may be used as necessary. Moreover, you may use what fixed these metals to particulate carrier materials, for example, carbon, activated carbon, aluminum oxide, silica, etc.

Examples of noble metal complex compounds include platinum halogen compounds (PtCl ₄ , H ₂ PtCl ₆ · 6H ₂ O, Na ₂ PtCl ₆ · 4H ₂ O, etc.), platinum-olefin complexes, platinum-alcohol complexes, platinum-alcolate complexes, platinum -Ether complexes, platinum-carbonyl complexes, platinum-ketone complexes, platinum-vinylsiloxane complexes such as platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane, bis (γ-picoline) -platinum Dichloride, trimethylenedipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride, cyclopentadiene-platinum dichloride, bis (alkynyl) bis (triphenylphosphine) platinum complex, bis (alkynyl) (cycloocta Diene) platinum complex, lodge chloride Arm, tris (triphenylphosphine) rhodium chloride, although such tetrakis ammonium over rhodium chloride complexes include, not particularly limited, may be used two or more kinds as necessary.

The above precious metal catalysts may be dissolved alone or in advance in a solvent to be dissolved, and then charged into the reaction system. The use ratio of the noble metal catalyst is not particularly limited, but is in the range of 0.1 ppm to 100,000 ppm, preferably in the range of 1 ppm to 10,000 ppm, based on the mass of the isolated monoallyl ether monoglycidyl ether or crude product liquid usually used in the reaction. .

The hydrosilylation reaction can proceed without a solvent, but the reaction system may be diluted with an organic solvent if necessary, and the organic solvent to be used is not particularly limited as long as it does not adversely affect the reaction. Not. Examples of the organic solvent used as necessary include halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane, and fats such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone. Aromatic ketones such as benzene, toluene, ortho-xylene, meta-xylene, para-xylene, chlorobenzene and dichlorobenzene, ethers such as diethylene glycol dimethyl ether and triethylene glycol dimethyl ether, esters such as ethyl acetate and n-butyl acetate Kind. Two or more of these organic solvents may be selected and used as a mixed solvent.

The temperature conditions for the hydrosilylation reaction are not particularly limited, but are usually 0 ° C. to 200 ° C., preferably 30 ° C. to 180 ° C. If it is less than 0 ° C., it takes time for the reaction to proceed and it is not economical. On the other hand, if it exceeds 200 ° C., the addition reaction between the epoxy group and the hydrosilyl moiety proceeds, making it difficult to control the reaction.

In addition, as long as the functional expression of the curable resin composition according to the present invention is not impaired, hydrosilylation reaction is performed by using at least one carbon-carbon double bond and another compound containing an epoxy group in one molecule. The obtained resin may be used as a curable resin composition. Examples of other compounds containing at least one carbon-carbon double bond and an epoxy group in one molecule include allyl glycidyl ether, 4-vinylcyclohexene oxide, limonene oxide, and the like. Two or more kinds may be used in combination. Although the usage-amount of this compound is not specifically limited, From a viewpoint of function expression of the curable resin composition which concerns on this invention, with respect to 100 mass parts of isolated monoallyl ether monoglycidyl ether or crude product liquid used for reaction. 50 parts by mass or less is preferable.

The hydrosilylation product thus obtained, that is, the alicyclic trialkoxysilyl monoglycidyl ether compound according to the present invention is subjected to a sol-gelation reaction by a known method, whereby another aspect of the present invention is achieved. A curable resin composition containing an epoxy silicone compound can be obtained. As a general sol-gel reaction, a method of hydrolytic condensation in the presence of an acidic catalyst or a basic catalyst is used.

The hydrolysis condensation catalyst used in the sol-gelation reaction is not particularly limited, and a known acidic catalyst or basic catalyst can be used. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, toluenesulfonic acid, acetic acid, phosphoric acid, oxalic acid, and citric acid. Examples of the basic catalyst include sodium hydroxide, potassium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide.

In the sol-gelation reaction, the amount of the catalyst added is not particularly limited, but is represented by the general formula (6) in order to have sufficient reactivity and to keep the ring opening and gelation of the epoxy ring low. The range of 0.001 to 0.2 mol is preferable and the range of 0.005 to 0.1 mol is more preferable with respect to a total of 1 mol of hydrolyzable groups in the hydrosilylation product.

The reaction temperature in the sol-gelation reaction is not particularly limited because it varies depending on the reactivity of the hydrosilylation product represented by the general formula (6) as a raw material, the solvent used, etc., but the reaction rate becomes sufficiently high, and In order to suppress undesired side reactions, the range of 0 ° C. to 100 ° C. is preferable, and the range of 10 ° C. to 80 ° C. is more preferable. If the reaction temperature is too low, the reaction does not proceed efficiently, and if it is too high, side reactions such as opening of the epoxy ring may proceed.

In the sol-gelation reaction, it is preferable to use a solvent. The solvent to be used is not particularly limited as long as the raw material alkoxysilane and water are uniformly dissolved. For example, alcohols such as methanol, ethanol, 2-propanol, n-butanol, isobutanol, and t-butanol are used. Examples of the solvent include ketone solvents such as acetone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents may be used alone or in combination of two or more.

The reaction time of the sol-gelation reaction is not particularly limited because it varies depending on the reactivity, reaction temperature, etc. of the hydrosilylation product represented by the general formula (6) as a raw material, but in order to sufficiently increase the molecular weight of the product Is preferably in the range of 1 to 40 hours. When the reaction time is less than 1 hour, unreacted raw materials and low molecular weight oligomers may remain. On the other hand, even if the reaction is continued for more than 40 hours, the condensation reaction often does not proceed further.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples.

[Example 1: Synthesis of alicyclic monoallyl ether monoglycidyl ether compound]
First, 1,4-cyclohexanedimethanol diallyl ether as a raw material was synthesized as follows based on Williamson synthesis.
Into a 2 liter three-necked flask equipped with a stirrer and a thermometer, 144.2 g (1.00 mol) of 1,4-cyclohexanedimethanol (manufactured by Shin Nippon Rika Co., Ltd.) was added, and the inside of the reactor system was purged with nitrogen, and hydroxylated. Sodium aqueous solution (50 mass%) 480.0g (6.0mol) was added, it heated to 40 degreeC, and tetrabutyl ammonium bromide (made by Wako Pure Chemical Industries Ltd.) 3.224g (0.01 mol) was added. While keeping the inside of the reaction system at about 40 ° C., 168.3 g (2.20 mol) of allyl chloride (manufactured by Kashima Chemical Co., Ltd.) was added dropwise, and after 2 hours, 72.11 g (0. 50 mol) and 84.17 g (1.10 mol) of allyl chloride were added. Thereafter, the reaction was continued while gradually raising the reaction temperature, and 25.25 g (0.33 mol) of allyl chloride was added while watching the progress of the reaction to complete the reaction. After completion of the reaction, 33.7 g of toluene was added to carry out a liquid separation treatment, and the organic layer was washed with pure water 200 mL / times until neutral, and after the liquid separation, the organic layer was distilled off the solvent, allyl chloride, and the like by an evaporator. . After the solvent was distilled off, 1,4-cyclohexanedimethanol diallyl ether was obtained by precision distillation (distillation temperature: 63.9 to 67.7 ° C. (11 Pa)).
150 g (0.67 mol) of cyclohexanedimethanol diallyl ether obtained by the above synthesis, 109.7 g (2.67 mol) of acetonitrile, and 200 g of methanol were charged into a 1-liter three-necked flask, and a 10 mass% potassium hydroxide-methanol solution 0 was added. .13 g was added to adjust the pH in the reaction solution to about 10.5, and then 83.1 g (1.1 mol) of a 45 mass% hydrogen peroxide aqueous solution at an internal temperature of 35 ° C. The solution was added dropwise over 6 hours. In addition, since the pH decreases when hydrogen peroxide is added, a 10% by mass potassium hydroxide-methanol solution is also added dropwise so that the pH is maintained at 10.5 (the total added amount after 10 hours is 10.14 g). there were). After completion of the dropwise addition, the mixture was stirred for 2 hours while heating in a water bath so that the internal temperature was 35 to 40 ° C. After completion of the stirring, 200 g of toluene was added, washed once with 100 g of a 0.1% by mass aqueous phosphoric acid solution three times with 100 g of a 5% by mass aqueous sodium sulfite solution and twice with 100 g of pure water, and then the solvent was distilled off to react. A mixture was obtained. The resulting reaction mixture was purified by column chromatography using silica gel (developing solvent: hexane and ethyl acetate 4: 1 (volume ratio) mixed solution) to obtain monoallyl ether monoglycidyl ether. The ¹ H-NMR and ¹³ C-NMR of the purified product are shown in FIGS. 2 and 3, respectively.

[Example 2: Synthesis of alicyclic trialkoxysilyl monoglycidyl ether compound]
To a 200 mL three-necked flask equipped with a dropping funnel, a reflux tube, and a ball stopper, 13.7 g (83.2 mmol) of triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 15 g of toluene were placed, and the inside of the three-necked flask was purged with nitrogen. . To the dropping funnel, 10 g of the reaction mixture containing monoallyl ether monoglycidyl ether obtained in Example 1, 3% by weight IPA solution of Pt (dvs) (3% PT-VTS-IPA solution manufactured by N.E. Chemcat) (Divinyltetramethyldisiloxane platinum complex isopropyl alcohol solution)) 5 mg and 10 g of toluene were added and dropped into a three-necked flask at 60 ° C. over 1 hour. After completion of the dropping, stirring was further continued at 60 ° C. for 5 hours. The obtained reaction liquid was evaporated to obtain a mixture containing a trialkoxysilyl monoglycidyl ether compound as a main component. ¹ H-NMR and ¹³ C-NMR of the mixture are shown in FIGS. 4 and 5, respectively.

[Example 3: Synthesis of epoxy silicone compound]
A 100 mL eggplant flask equipped with a dropping funnel was charged with 10 g of 2-propanol, 1.87 g of distilled water, and 0.19 g of a 25% aqueous solution of tetramethylammonium hydroxide (manufactured by Showa Denko KK) and mixed uniformly. The temperature rose. The dropping funnel was charged with 7 g of the mixture containing the trialkoxysilyl monoglycidyl ether compound obtained in Example 2 as the main component and 10 g of 2-propanol, and dropped into the eggplant flask at 50 ° C. over 10 minutes. After completion of dropping, the mixture was further stirred at 50 ° C. for 5 hours and allowed to stand for 14 hours. To the obtained reaction solution, 10 g of toluene, 10 g of distilled water and 6 g of 0.5 mass% acetic acid aqueous solution were added, and 2-propanol was distilled off. The liquid in the flask was extracted with 20 g of toluene. The obtained organic layer was washed with water and dried using anhydrous sodium sulfate. The inorganic salt was filtered and the solvent was distilled off, followed by drying using a vacuum pump to obtain an epoxy silicone compound as a colorless transparent liquid. ¹ H-NMR and ¹³ C-NMR of the obtained reaction mixture are shown in FIGS. 6 and 7, respectively.

[Example 4: Synthesis of tricyclodecane dimethanol monoallyl monoglycidyl ether]
In a 500 mL three-diameter eggplant type flask equipped with a magnetic stirrer, 100.0 g (0.36 mol) of tricyclodecane dimethanol diallyl ether (Asahi Chemical Industry Co., Ltd.), 59.4 g of acetonitrile (manufactured by Junsei Chemical Co., Ltd.) (1.45 mol) and 92.3 g (2.88 mol) of methanol (manufactured by Junsei Chemical Co., Ltd.) were weighed. The temperature in the system was heated to 35 ° C. using a water bath, and the pH was reached to 10.5 with a saturated aqueous potassium hydroxide solution (KOH / H ₂ O = 110 g / 100 mL). Until the end of the reaction, a saturated aqueous potassium hydroxide solution was added as needed so that the reaction temperature did not exceed 40 ° C., and the pH was controlled in the range of 10.75 to 10.25. 44.7 g (0.59 mol) of 45% aqueous hydrogen peroxide solution (manufactured by Nippon Peroxide Co., Ltd.) was added dropwise with a 100 mL dropping funnel over 12 hours, and then stirred for 6 hours to complete the reaction. The resulting reaction solution was purified by column chromatography using silica gel to obtain tricyclodecane dimethanol monoallyl ether monoglycidyl ether. ¹ H-NMR and ¹³ C-NMR of the purified product are shown in FIGS. 8 and 9, respectively.

[Example 5: Synthesis of trialkoxysilyl monoglycidyl ether compound of tricyclodecane dimethanol]
8.4 g (51 mmol) of triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 15 g of toluene were placed in a 200 mL three-necked flask equipped with a dropping funnel, a reflux tube and a ball stopper, and the inside of the three-necked flask was purged with nitrogen. To the dropping funnel, 10 g of the epoxidation reaction mixture obtained in Example 4, 3% IPA solution of Pt (dvs) (3% PT-VTS-IPA solution (divinyltetramethyldisiloxane platinum complex manufactured by N.E. Chemcat) 5 mg of isopropyl alcohol solution)) and 10 g of toluene were added and dropped into a three-necked flask at 60 ° C. over 1 hour. After completion of the dropping, stirring was further continued at 60 ° C. for 5 hours. The obtained reaction liquid was evaporated to obtain a mixture containing a trialkoxysilyl monoglycidyl ether compound as a main component. ¹ H-NMR and ¹³ C-NMR of the mixture are shown in FIGS. 10 and 11, respectively.

[Example 6: Synthesis of epoxy silicone compound]
A 100 mL eggplant flask equipped with a dropping funnel was charged with 5 g of 2-propanol, 0.20 g of distilled water, and 0.08 g of a 25% aqueous solution of tetramethylammonium hydroxide (manufactured by Showa Denko KK) and mixed uniformly. The temperature rose. The dropping funnel was charged with 1 g of a mixture containing the trialkoxysilyl monoglycidyl ether compound obtained in Example 5 as a main component and 5 g of 2-propanol, and dropped into the eggplant flask at 50 ° C. over 10 minutes. After completion of dropping, the mixture was further stirred at 50 ° C. for 5 hours. After adding 5 g of toluene, 5 g of distilled water, and 2.4 g of 0.5% acetic acid aqueous solution to the obtained reaction solution, 2-propanol was distilled off. The liquid in the flask was extracted with 10 g of toluene. The obtained organic layer was washed with water and dried using anhydrous sodium sulfate. The inorganic salt was filtered and the solvent was distilled off, followed by drying using a vacuum pump to obtain an epoxy silicone compound as a colorless transparent liquid. ¹ H-NMR and ¹³ C-NMR of the reaction mixture are shown in FIGS. 12 and 13, respectively.

The curable resin composition containing the alicyclic trialkoxysilyl monoglycidyl ether compound obtained by reacting the alicyclic monoallyl ether monoglycidyl ether compound and trialkoxysilane according to the present invention has a hardened product. In addition, there is little cure shrinkage, no stickiness on the surface of the cured product, excellent strength and transparency, and excellent heat resistance and light resistance. Therefore, the curable resin composition according to the present invention is used in the fields of electronic materials such as paints, coating agents, printing inks, resist inks, adhesives, semiconductor encapsulants, molding materials, casting materials, and electrical insulating materials. Useful. The curable resin composition of the present invention is particularly useful in the LED field, and is excellent as a thermosetting resin composition for LED sealing.

Claims

The following general formula (1):

{Wherein R represents a C 4-20 divalent hydrocarbon group containing an alicyclic skeleton. } The alicyclic monoallyl ether monoglycidyl ether compound represented by these.
The alicyclic monoallyl ether monoglycidyl ether compound according to claim 1, wherein R has a cycloalkane skeleton having 4 to 8 carbon atoms.
The alicyclic monoallyl ether monoglycidyl ether compound according to claim 1 or 2, having a molecular weight of 150 to 400.
The compound represented by the general formula (1) is represented by the following formula (2):

The following equation (3):

Or the following formula (4):

The alicyclic monoallyl ether monoglycidyl ether compound according to any one of claims 1 to 3, represented by any one of:
The following general formula (6):

{In the formula, R represents a divalent hydrocarbon group containing an alicyclic hydrocarbon having 4 to 20 carbon atoms, and R 'represents a hydrocarbon group having 1 to 4 carbon atoms. } The alicyclic trialkoxysilyl monoglycidyl ether compound represented by this.
A curable resin composition comprising an epoxy silicone compound obtained by sol-gelating an alicyclic trialkoxysilyl monoglycidyl ether compound represented by the general formula (6) according to claim 5.