阅读说明：本技术 脂环式环氧化合物制品 (Alicyclic epoxy compound product ) 是由 井上宽子 谷川博人 于 2020-04-10 设计创作，主要内容包括：本发明提供用于形成透明性及耐热性优异的固化物的用途的脂环式环氧化合物制品。在本申请的脂环式环氧化合物制品中,下述式(1)表示的化合物的纯度为85重量％以上,下述式(a)表示的化合物和下述式(b)表示的化合物的合计含量为0.5重量％以下。其中,式中的X表示单键或连结基团。本申请的脂环式环氧化合物制品可以经过使下述式(1”)表示的化合物进行脱水反应而得到下述式(1’)表示的化合物、并使得到的下述式(1’)表示的化合物与有机过氧酸反应的工序来制造。(The invention provides for formingAn alicyclic epoxy compound product which is excellent in transparency and heat resistance and is useful as a cured product. In the alicyclic epoxy compound product of the present application, the purity of the compound represented by the following formula (1) is 85% by weight or more, and the total content of the compound represented by the following formula (a) and the compound represented by the following formula (b) is 0.5% by weight or less. Wherein X in the formula represents a single bond or a linking group. The alicyclic epoxy compound product of the present application can be produced through a step of obtaining a compound represented by the following formula (1') by subjecting a compound represented by the following formula (1 ") to a dehydration reaction, and reacting the obtained compound represented by the following formula (1') with an organic peroxyacid.)

1. An alicyclic epoxy compound product, wherein,

the purity of the compound represented by the following formula (1) is 85% by weight or more,

the total content of the compound represented by the formula (a) and the compound represented by the formula (b) is 0.5% by weight or less,

wherein X represents a single bond or a linking group.

2. The alicyclic epoxy compound article according to claim 1, wherein,

the total content of the compound represented by the following formula (c) and the compound represented by the following formula (d) is 10% by weight or less,

wherein X represents a single bond or a linking group.

3. The alicyclic epoxy compound article according to claim 1 or 2, wherein,

the content of the compound represented by the following formula (x) is 1000ppm or less,

wherein X represents a single bond or a linking group.

4. The alicyclic epoxy compound article according to any one of claims 1 to 3, wherein,

the thermal gelation time determined by the following measurement method was 400 seconds or less,

method for measuring gelation time:

a curable composition prepared by adding 0.6 part by weight of SAN-AID SI-100L, manufactured by shin-Kogyo Kagaku K.K., to 100 parts by weight of an alicyclic epoxy compound product was subjected to dynamic viscoelasticity measurement under conditions of a frequency of 1Hz, a strain of 5%, a gap of 0.2mm and a temperature of 80 ℃ and the thermal gelation time was defined as the intersection of the storage modulus (G ') and the loss modulus (G').

5. The alicyclic epoxy compound article according to any one of claims 1 to 4, wherein,

the UV gelation time determined by the following measurement method was 45 seconds or less,

method for measuring gelation time:

a curable composition comprising 100 parts by weight of an alicyclic epoxy compound product and 1.0 part by weight of CPI-101A manufactured by San-apro corporation was compounded at a frequency of 10Hz, a strain of 5%, a gap of 0.1mm and a temperature of 25 ℃ in an amount of 10mW/cm²After 10 seconds of UV irradiation, dynamic viscoelasticity was measured, and the intersection point of the storage modulus (G ') and the loss modulus (G') was defined as the UV gelation time.

6. A method of making an alicyclic epoxy compound article, the method comprising: the alicyclic epoxy compound product according to any one of claims 1 to 5 is obtained by subjecting the product to the following steps,

step 1: a compound represented by the following formula (1') is subjected to a dehydration reaction to obtain a compound represented by the following formula (1'),

wherein X represents a single bond or a linking group;

and a step 2: reacting a compound represented by the formula (1') with an organic peroxy acid to obtain a reaction product containing a compound represented by the following formula (1),

wherein X is as defined above;

step 3: fractionating the reaction product by using a rectifying tower with 1-20 actual tower plates under the following conditions,

the temperature of the tower bottom is 100-250 DEG C

The temperature of the top of the tower is 80-200 DEG C

Overhead pressure of 0.1-50 mmHg

The pressure at the bottom of the tower is 1-200 mmHg.

7. The method for producing an alicyclic epoxy compound product according to claim 6, wherein,

the compound represented by the following formula (a) and the compound represented by the following formula (b) are removed by fractional distillation in step 3,

wherein X represents a single bond or a linking group.

8. A curable composition comprising the alicyclic epoxy compound product according to any one of claims 1 to 5.

9. The curable composition according to claim 8, further comprising a curing agent (B) and a curing accelerator (C).

10. The curable composition according to claim 8, further comprising a curing catalyst (D).

11. A cured product of the curing composition according to any one of claims 8 to 10.

12. The cured product according to claim 11, wherein the light transmittance at a wavelength of 400nm is 50% or more.

13. A sealant comprising the cured composition of any one of claims 8 to 10.

14. An adhesive comprising the cured composition according to any one of claims 8 to 10.

15. A coating agent comprising the cured composition according to any one of claims 8 to 10.

16. An optical member comprising the cured product according to claim 11 or 12.

Technical Field

The present invention relates to a high purity alicyclic epoxy compound product. The present application claims priority based on Japanese patent application No. 2019-080264 filed on the date 19/4/2019, the contents of which are incorporated herein by reference.

Background

Optical semiconductor devices using optical semiconductor elements such as LEDs as light sources have been used in various applications such as various indoor or outdoor display panels, light sources for image reading, traffic signals, and large display units. Such an optical semiconductor device generally has a structure in which an optical semiconductor element is sealed with a resin (sealing resin). The sealing resin serves to protect the optical semiconductor element from damage such as moisture and impact.

In recent years, such optical semiconductor devices have been developed to have higher output and shorter wavelength, and for example, in blue/white light semiconductor devices, yellowing of the thermally conductive sealing resin emitted from the optical semiconductor element has been a problem. The sealing resin thus yellowed absorbs light emitted from the optical semiconductor element, and therefore the light intensity of light output from the optical semiconductor device decreases with time. Therefore, a resin excellent in transparency and heat resistance is required.

Patent document 1 describes a curable epoxy resin composition. The curable epoxy resin composition is described as being capable of forming a cured product having excellent transparency. However, a composition capable of forming a cured product having higher transparency is required. In addition, it is also required to shorten the gelling time of the composition, that is, to improve curability.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2013-18921

Disclosure of Invention

Problems to be solved by the invention

Accordingly, an object of the present invention is to provide an alicyclic epoxy compound product for use in forming a cured product having excellent transparency.

Another object of the present invention is to provide an alicyclic epoxy compound product for use in forming a cured product having excellent curability and excellent transparency and heat resistance.

Another object of the present invention is to provide a method for producing the above alicyclic epoxy compound product.

Another object of the present invention is to provide a curable composition capable of forming a cured product having excellent curability and excellent transparency and heat resistance.

Another object of the present invention is to provide a sealing agent, an adhesive, or a coating agent that can form a cured product having excellent curability and excellent transparency and heat resistance.

Another object of the present invention is to provide an optical member having a cured product excellent in transparency and heat resistance.

In the present specification, the term "product" refers to a material that can be industrially produced and distributed on the market, and does not mean a chemical substance itself. In its meaning, is a composition containing an object as a main component (in other words, containing approximately 100% by weight of the object).

Means for solving the problems

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an alicyclic epoxy compound product containing a compound represented by the formula (1) as a main component contains a transition hydride and an isomer in a specific ratio. Further, it has been found that excessive hydride or isomer is incorporated into the product, which results in lowering of curability of the product and lowering of transparency of the obtained cured product.

In addition, conventionally, as a method for producing a compound represented by formula (1), a method of subjecting a reaction product of a compound represented by formula (1') and an organic peroxyacid to a solvent removal treatment and a high boiling point removal treatment has been known, but it has been found that: in the above method, it is difficult to remove excessive hydride, isomers having a boiling point very close to that of the compound represented by formula (1); if the reaction product is introduced into a rectifying column and fractionated under specific distillation conditions, excessive hydrides and isomers can be removed with good efficiency. The present invention has been completed based on these findings.

That is, the present invention provides an alicyclic epoxy compound product in which,

the purity of the compound represented by the following formula (1) is 85% by weight or more, and the total content of the compound represented by the following formula (a) and the compound represented by the following formula (b) is 0.5% by weight or less.

[ chemical formula 1]

(wherein X represents a single bond or a linking group)

Further, the present invention provides the above alicyclic epoxy compound product, wherein,

the total content of the compound represented by the following formula (c) and the compound represented by the following formula (d) is 10% by weight or less.

[ chemical formula 2]

(wherein X represents a single bond or a linking group)

Further, the present invention provides the above alicyclic epoxy compound product, wherein,

the content of the compound represented by the following formula (x) is 1000ppm or less.

[ chemical formula 3]

(wherein X represents a single bond or a linking group)

Further, the present invention provides the above alicyclic epoxy compound product, wherein,

the thermal gelation time determined by the following measurement method was 400 seconds or less.

Method for measuring gelation time:

a curable composition prepared by blending 100 parts by weight of an alicyclic epoxy compound product with 0.6 part by weight of SAN-AID SI-100L (manufactured by shin-Etsu chemical Co., Ltd.) was subjected to dynamic viscoelasticity measurement under conditions of a frequency of 1Hz, a strain of 5%, a gap of 0.2mm and a temperature of 80 ℃ and the intersection of the storage modulus (G ') and the loss modulus (G') was defined as a thermal gelation time.

Further, the present invention provides the above alicyclic epoxy compound product, wherein,

the UV gelation time determined by the following measurement method was 45 seconds or less.

Method for measuring gelation time:

100 parts by weight of an alicyclic epoxy compound product and 1.0 part by weight of CPI-101A (manufactured by San-apro Co., Ltd.) were subjected to UV irradiation (at 10 mW/cm) at a frequency of 10Hz, a strain of 5%, a gap of 0.1mm and a temperature of 25 ℃²Irradiation for 10 seconds), and the intersection of the storage modulus (G') and the loss modulus (G ″) was defined as the UV gelation time.

Further, the present invention provides a method for producing an alicyclic epoxy compound product, comprising: the alicyclic epoxy compound product was obtained through the following steps.

Step 1: a compound represented by the following formula (1') is obtained by subjecting a compound represented by the following formula (1') to a dehydration reaction.

[ chemical formula 4]

(wherein X represents a single bond or a linking group)

And a step 2: the compound represented by the formula (1') is reacted with an organic peroxy acid to obtain a reaction product containing the compound represented by the following formula (1).

[ chemical formula 5]

(wherein X is as defined above)

Step 3: fractionating the reaction product using a rectifying column having 1 to 20 stages of actual plate number under the following conditions.

The temperature of the tower bottom is 100-250 DEG C

The temperature of the top of the tower is 80-200 DEG C

Overhead pressure of 0.1-50 mmHg

The pressure at the bottom of the tower is 1-200 mmHg

The present invention also provides a method for producing the alicyclic epoxy compound product, wherein the compound represented by the following formula (a) and the compound represented by the following formula (b) are removed by fractional distillation in step 3.

[ chemical formula 6]

(wherein X represents a single bond or a linking group)

The present invention also provides a curable composition containing the alicyclic epoxy compound product.

The present invention also provides the curable composition, which further contains a curing agent (B) and a curing accelerator (C).

The present invention also provides the above curable composition, which further contains a curing catalyst (D).

The present invention also provides a cured product of the above-mentioned curing composition.

The present invention also provides the cured product, wherein the light transmittance at a wavelength of 400nm is 50% or more.

In addition, the present invention provides a sealant comprising the above-mentioned cured composition.

The present invention also provides an adhesive comprising the cured composition.

Further, the present invention provides a coating agent comprising the above-mentioned curing composition.

The present invention also provides an optical member comprising the cured product.

ADVANTAGEOUS EFFECTS OF INVENTION

The alicyclic epoxy compound product of the present application is high in purity and the content of specific impurities (e.g., excessive hydride, preferably excessive hydride and isomers) is extremely low. Therefore, the curable composition obtained by adding a curing agent or a curing catalyst to the alicyclic epoxy compound product of the present application has extremely excellent curability, and the obtained cured product has excellent transparency and heat resistance. Therefore, the alicyclic epoxy compound product of the present application can be suitably used for industrial applications (for example, a sealant, an adhesive, a coating agent, or a raw material thereof).

Drawings

Fig. 1 is a graph showing the results of gas chromatography measurement of the alicyclic epoxy compound product (6) obtained in example 1.

Fig. 2 is a graph showing the results of gas chromatography measurement of the alicyclic epoxy compound product (7) obtained in comparative example 1.

Detailed Description

[ alicyclic epoxy Compound product ]

The alicyclic epoxy compound product of the present application contains a compound represented by the following formula (1) and has a purity (or content) of 85% by weight or more. The purity (or content) of the compound represented by the above formula (1) is preferably 90% by weight or more, and particularly preferably 95% by weight or more, from the viewpoint of obtaining a cured product having excellent curability and excellent transparency and heat resistance.

[ chemical formula 7]

In the formula (1), X represents a single bond or a linking group (a divalent group having 1 or more atoms). Examples of the linking group include: divalent hydrocarbon groups, alkenylene groups in which part or all of the carbon-carbon double bonds have been epoxidized, ether bonds, and groups in which a plurality of these groups are linked together. The epoxycyclohexyl group in the formula (1) may have a substituent (e.g., C) bonded thereto_1-3Alkyl groups, etc.).

As representative examples of the compound represented by the above formula (1), there can be mentioned: (3,4,3 ', 4' -diepoxy) bicyclohexane, bis (3, 4-epoxycyclohexylmethyl) ether, 1, 2-epoxy-1, 2-bis (3, 4-epoxycyclohexan-1-yl) ethane, 2-bis (3, 4-epoxycyclohexan-1-yl) propane, 1, 2-bis (3, 4-epoxycyclohexan-1-yl) ethane, and the like.

In the alicyclic epoxy compound product, the total content of the compound represented by the following formula (a) and the compound represented by the following formula (b) is 0.5% by weight or less, preferably 0.1% by weight or less, and particularly preferably less than 0.05% by weight. The lower limit of the total content of the compound represented by the following formula (a) and the compound represented by the following formula (b) is, for example, 0.01% by weight. In the following formula, X is the same as defined above.

[ chemical formula 8]

Further, in the alicyclic epoxy compound product, the total content of the compound represented by the following formula (c) and the compound represented by the following formula (d) is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 3% by weight or less. In the following formula, X is the same as defined above.

[ chemical formula 9]

The alicyclic epoxy compound product contains the compound represented by the formula (1) in high purity as described above, and the content of each of the compounds represented by the formulae (a) to (d) is extremely low.

Therefore, the alicyclic epoxy compound product has excellent curability, and the thermal gelation time determined by the following measurement method is, for example, 400 seconds or less, preferably 350 seconds or less, particularly preferably 300 seconds or less, and most preferably 250 seconds or less.

Method for measuring gelation time:

a thermosetting composition prepared by blending 100 parts by weight of an alicyclic epoxy compound product with 0.6 part by weight of SAN-AID SI-100L (manufactured by shin chemical Co., Ltd.) was subjected to dynamic viscoelasticity measurement under conditions of a frequency of 1Hz, a strain of 5%, a gap of 0.2mm and a temperature of 80 ℃ and the intersection of the storage modulus (G ') and the loss modulus (G') was defined as a thermal gelation time.

The alicyclic epoxy compound product has excellent curability, and the UV gelation time determined by the following measurement method is, for example, 45 seconds or less, preferably 40 seconds or less, more preferably 35 seconds or less, particularly preferably 30 seconds or less, most preferably 25 seconds or less, and particularly preferably 20 seconds or less.

Method for measuring gelation time:

UV irradiation (at 10 mW/cm) was performed on 100 parts by weight of an alicyclic epoxy compound product and 1.0 part by weight of CPI-101A (manufactured by San-apro Co., Ltd.) under conditions of a frequency of 10Hz, a strain of 5%, a gap of 0.1mm and a temperature of 25 ℃²Irradiation for 10 seconds), and the intersection of the storage modulus (G') and the loss modulus (G ″) was defined as the UV gelation time.

Therefore, the above alicyclic epoxy compound product can be suitably used, for example, as: a sealing agent, an adhesive, a coating agent, an electrically insulating material, a laminate, an ink, a sealant, a resist, a composite material, a transparent base material, a transparent sheet, a transparent film, an optical element, an optical lens, a photo-molding, electronic paper, a touch panel, a solar cell substrate, an optical waveguide, a light guide plate, a holographic memory, and the like.

(method for producing alicyclic epoxy Compound product)

The alicyclic epoxy compound product of the present application can be produced through the following steps.

Step 1: the compound represented by the formula (1 ") is subjected to a dehydration reaction to obtain a compound represented by the formula (1') (dehydration step).

And a step 2: the compound represented by the formula (1') is reacted with an organic peroxy acid to obtain a reaction product containing the compound represented by the formula (1') (epoxidation step).

Step 3: the reaction product was fractionated using a rectifying column (fractionation step).

In the method for producing the alicyclic epoxy compound product, other steps may be provided in addition to the steps 1 to 3. Examples of other steps include: the following steps 2-1, 2-2, 2-3, etc. These steps are preferably provided between step 2 and step 3 (after step 2 and before step 3), and in these steps, step 2-1 is preferably provided first. The step subsequent to the step 2-1 may be any of the steps 2-2 and 2-3.

Step 2-1: a step of washing the obtained reaction product with water to remove the organic peroxy acid used in the reaction and its decomposition product (washing step)

Step 2-2: a step of subjecting the reaction product to a solvent removal treatment (solvent removal step)

Step 2-3: a step of subjecting the reaction product to high-boiling removal treatment (high-boiling removal step)

Among the above methods for producing an alicyclic epoxy compound product, it is preferable to perform the steps of step 1 (dehydration step), step 2 (epoxidation step), step 2-1 (water washing step), step 2-2 (desolvation step), step 2-3 (high boiling removal step), and step 3 (fractionation step) in order to obtain an alicyclic epoxy compound product that can form a cured product having particularly excellent curability and excellent transparency and heat resistance.

(dehydration step)

The dehydration step is a step of obtaining a compound represented by the following formula (1') by a method (method 1) of intramolecular dehydration of a compound represented by the following formula (1 ") using the compound represented by the following formula (1") as a raw material. In the following formula, X is the same as defined above.

[ chemical formula 10]

The intramolecular dehydration reaction of the compound represented by the formula (1 ") can be carried out by, for example, subjecting the compound to a heat treatment at 100 to 200 ℃ in the presence of an acid catalyst such as concentrated sulfuric acid.

The compound represented by the above formula (1') can also be produced by diels-alder reaction represented by the following formula (method 2). In the following formulae, X represents a single bond or a linking group.

[ chemical formula 11]

However, the reaction product obtained by using the compound represented by the formula (1') obtained by the method 2 inevitably contains the compound represented by the formula (x) as well as the compound represented by the formula (1). Further, the compound represented by the following formula (x) is not preferable because it is difficult to remove the compound by washing with water, distillation, or the like, and therefore, it is included in the alicyclic epoxy compound product as a final product, and if the compound represented by the formula (x) is included in the alicyclic epoxy compound product, the reactivity tends to be lowered. In the following formula, X is the same as defined above.

[ chemical formula 12]

(wherein X represents a single bond or a linking group)

On the other hand, when the compound represented by the formula (1') obtained by the above method 1 is reacted with an organic peroxyacid, the compound represented by the above formula (x) is not by-produced.

In the present invention, since the method 1 is employed, the content of the compound represented by the formula (x) in the alicyclic epoxy compound product can be suppressed to, for example, 1000ppm or less (preferably 500ppm or less, particularly preferably 100ppm or less, and most preferably 50ppm or less), and an alicyclic epoxy compound product having good reactivity can be obtained.

(epoxidation step)

The epoxidation step is a step of reacting the compound represented by the formula (1') obtained through the dehydration step with an organic peroxy acid to obtain a reaction product. Through this step, a reaction product containing a compound represented by the following formula (1) can be obtained. In the following formula, X is the same as defined above.

[ chemical formula 13]

The organic peroxy acid is preferably at least one selected from the group consisting of peroxyformic acid, peroxyacetic acid, peroxypropionic acid, m-chloroperoxybenzoic acid, trifluoroperoxyacetic acid, peroxybenzoic acid, and the like.

The amount of the organic peroxy acid used is, for example, 0.5 to 3 moles per 1 mole of the compound represented by formula (1).

The epoxidation reaction may be carried out in the presence of a solvent. Examples of the solvent include: aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, diethylbenzene, and p-cymene; alicyclic hydrocarbons such as cyclohexane and decalin; aliphatic hydrocarbons such as n-hexane, heptane, octane, nonane, and decane; alcohols such as cyclohexanol, hexanol, heptanol, octanol, nonanol, furfuryl alcohol and the like; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; esters such as ethyl acetate, n-pentyl acetate, cyclohexyl acetate, isoamyl propionate, and methyl benzoate; polyhydric alcohols such as ethylene glycol, propylene glycol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and derivatives thereof; halogen compounds such as chloroform, dimethyl chloride, carbon tetrachloride and chlorobenzene; and ethers such as 1, 2-dimethoxyethane. These solvents may be used alone or in combination of two or more.

The amount of the solvent used is, for example, about 0.2 to 10 times by weight of the compound represented by the formula (1).

If necessary, a stabilizer for organic peroxy acids (e.g., ammonium hydrogen phosphate, potassium pyrophosphate, 2-ethylhexyl tripolyphosphate, etc.), a polymerization inhibitor (e.g., hydroquinone, piperidine, ethanolamine, phenothiazine, etc.), and the like may be used in the epoxidation reaction.

The reaction temperature of the epoxidation reaction is, for example, 0to 70 ℃. The reaction gas atmosphere is not particularly limited as long as the reaction is not inhibited, and may be any gas atmosphere, such as an air atmosphere, a nitrogen atmosphere, or an argon atmosphere.

(washing step)

The washing step is a step of removing the organic peroxy acid contained in the reaction product obtained through the epoxidation step and the organic acid as a decomposition product thereof by washing with water.

The amount of water used is, for example, about 0.1 to 3 times (v/v) the amount of the reaction product. The water washing may be carried out using an equilibrium type extractor of a mixed settling type or the like, an extraction column, a centrifugal extractor, or the like.

(desolvation step)

The solvent removal step is a step of distilling off components (for example, a solvent, moisture, and the like) having a lower boiling point than the compound represented by formula (1) contained in the reaction product. By performing this step, the content of the compound having a lower molecular weight than the compound represented by formula (1) mixed into the alicyclic epoxy compound product can be reduced, and the purity of the compound represented by formula (1) can be improved.

In the solvent removal step, a thin film evaporator or a distillation column may be used. The distillation is preferably carried out at a heating temperature of 50 to 200 ℃ and a pressure of 1 to 760 mmHg.

In the solvent removal step, a component having a lower boiling point than that of the compound represented by the formula (1) is evaporated from the reaction product, whereby a mixture of the compound represented by the formula (1) and a component having a higher boiling point than that of the compound can be obtained as a bottom residue.

(high boiling removal step)

The high boiling point removal step is a step of distilling the compound represented by formula (1) from a mixture of the compound represented by formula (1) and a component having a higher boiling point than the compound, which is a bottom residue obtained through the solvent removal step. By performing this step, the content of the compound having a higher molecular weight than the compound represented by formula (1) mixed into the alicyclic epoxy compound product can be reduced, and the purity of the compound represented by formula (1) can be improved.

In the high-boiling-point removal step, a thin film evaporator or a distillation column may be used. The distillation is preferably carried out at a heating temperature of 100 to 200 ℃ and a pressure of 0.01 to 100 mmHg.

Preferably, the bottom residue is introduced into a distillation column, the compound represented by the formula (1) is recovered as a column top distillate, and a column bottom liquid containing a high boiling point component is discharged to the outside of the system.

(fractionation step)

The fractionation step is a step of separating and removing impurities [ particularly, components having a lower boiling point than the compound represented by formula (1) (for example, compounds represented by formulae (a) and (b)) which are by-produced in the dehydration step from the compound represented by formula (1) which is a main component.

For example, in the case of method 1 being employed in the dehydration step, the compounds represented by formulae (a) to (d) are mixed as by-products, but by this step, the above-mentioned by-products (in particular, the compounds represented by formulae (a) and (b) (perhydroxide)) can be separated and removed from the compound represented by formula (1), and an alicyclic epoxy compound product containing the compound represented by formula (1) at high purity and having a suppressed content of the above-mentioned by-products (in particular, perhydroxide) can be obtained.

In order to improve the separation efficiency of the by-product (particularly, the excessive hydride) and further to separate and remove the compound represented by the formula (c) or (d) (isomer) and further to improve the purity of the product, it is preferable to use a rectifying column having an actual number of plates of, for example, 1 to 20 layers (preferably 5 to 15 layers, particularly preferably 8 to 12 layers) in the fractionation step.

The temperature of the column bottom is, for example, 100 to 250 ℃ and preferably 130 to 170 ℃.

The temperature at the top of the column is, for example, 80 to 200 ℃ and preferably 100 to 120 ℃.

The overhead pressure is, for example, 0.1 to 50mmHg, preferably 0.1 to 1 mmHg.

The pressure at the bottom of the column is, for example, 1 to 200mmHg, preferably 1 to 5 mmHg.

The reflux ratio is preferably in the range of, for example, 0.5 to 5. When the reflux ratio is higher than the above range, energy cost tends to be high, and on the contrary, when the reflux ratio is lower than the above range, removal efficiency of the compounds represented by the formulae (a) to (d) tends to be low, and the compounds tend to be easily mixed into products.

Further, the alicyclic epoxy compound product in which the content of the by-product (particularly, excessive hydride) is suppressed can be obtained by the fractionation step. As a method for recovering the product, for example, in the case of performing a batch fractionation operation, a fraction may be separated into a plurality of fractions and recovered, and a fraction having a low content of the by-product (particularly, excessive hydride) may be used as the product. The content of the excessive hydride and the isomer in the fraction can be measured by gas chromatography or the like. In the case of performing the continuous fractionation operation, the low boiling point component may be removed from the top of the column, and the bottom residue obtained from the bottom of the column may be recovered and used as a product, or the low boiling point component may be removed from the top of the column, and the high boiling point component may be removed from the bottom of the column, and the product may be recovered from the side stream.

[ curable composition ]

The curable composition of the present application contains the above-described alicyclic epoxy compound product.

The curable composition contains the above-mentioned alicyclic epoxy compound product as the curable compound (a), but may contain one or two or more other curable compounds in addition to the above-mentioned curable compound (a). Examples of other curable compounds include: a cationic polymerizable compound such as an epoxy compound other than the compound represented by formula (1) (═ other epoxy compound), an oxetane compound, and a vinyl ether compound.

The proportion of the compound represented by formula (1) contained in the curable composition in the total amount (100% by weight) of the curable compounds (a) is, for example, 50% by weight or more (for example, 50 to 100% by weight), preferably 60% by weight or more, particularly preferably 70% by weight or more, and most preferably 80% by weight or more.

The curable composition preferably contains a curable compound (a), a curing agent (B) and a curing accelerator (C), or a curing catalyst (D).

The total content of the curable compound (a), the curing agent (B), and the curing accelerator (C) is, for example, 60% by weight or more, preferably 70% by weight or more, particularly preferably 80% by weight or more, most preferably 90% by weight or more, and particularly preferably 95% by weight or more of the total amount of the curable composition.

The total content of the curable compound (a) and the curing catalyst (D) is, for example, 60% by weight or more, preferably 70% by weight or more, particularly preferably 80% by weight or more, most preferably 90% by weight or more, and particularly preferably 95% by weight or more of the total amount of the curable composition.

Therefore, the content of the compound other than the curable compound (a), the curing agent (B), the curing accelerator (C) and the curing catalyst (D) in the total amount of the curable composition is, for example, 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less, particularly preferably 20% by weight or less, most preferably 10% by weight or less, and particularly preferably 5% by weight or less.

(curing agent (B))

As the curing agent (B), for example: acid anhydrides (acid anhydride curing agents), amines (amine curing agents), polyamide resins, imidazoles (imidazole curing agents), polythiols (polythiol curing agents), phenols (phenol curing agents), polycarboxylic acids, dicyandiamide, organic hydrazides, and the like are known or commonly used as curing agents for epoxy resins. These may be used alone or in combination of two or more.

Examples of the acid anhydrides include: methyltetrahydrophthalic anhydride (4-methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, etc.), dodecenylsuccinic anhydride, methylendomethyltetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, nadic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexene tetracarboxylic anhydride, maleic anhydride, sebacic anhydride, dodecanedioic anhydride, and the like, Vinyl ether-maleic anhydride copolymers, alkylstyrene-maleic anhydride copolymers, and the like. Among them, from the viewpoint of handling properties, acid anhydrides which are liquid at 25 ℃ [ for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, methylendomethyltetrahydrophthalic anhydride, etc. ], are preferable.

Examples of the amines include: aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylpentamine, dipropylenediamine, diethylaminopropylamine, and polypropylenetriamine;alkanediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3, 9-bis (3-aminopropyl) -3,4,8, 10-tetraoxaspiro [5, 5]]Alicyclic polyamines such as undecane; mononuclear polyamines such as m-phenylenediamine, p-phenylenediamine, toluene-2, 4-diamine, toluene-2, 6-diamine, mesitylene-2, 4-diamine, 3, 5-diethyltoluene-2, 4-diamine, and 3, 5-diethyltoluene-2, 6-diamine; biphenyldiamine, 4-diaminodiphenylmethane, 2, 5-naphthalenediamineAnd aromatic polyamines such as 2, 6-naphthalenediamine.

Examples of the polyamide resin include: and polyamide resins having either or both of a primary amino group and a secondary amino group in the molecule.

Examples of the imidazoles include: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazoleTrimellitic acid salt, 1-cyanoethyl-2-phenylimidazoleTrimellitic acid salt, 2-methylimidazoleIsocyanurates, 2-phenylimidazoleIsocyanurate, 2, 4-diamino-6- [ 2-methylimidazolyl- (1)]-ethyl-s-triazine, 2, 4-diamino-6- [ 2-ethyl-4-methylimidazolyl- (1)]-ethyl-s-triazine and the like.

Examples of the polythiols include: liquid polythiols, polysulfide resins, and the like.

Examples of the phenols include: aralkyl resins such as novolak-type phenol resins, novolak-type cresol resins, p-xylylene-modified phenol resins, p-xylylene/m-xylylene-modified phenol resins, terpene-modified phenol resins, dicyclopentadiene-modified phenol resins, triphenol propane, and the like.

Examples of the polycarboxylic acids include: adipic acid, sebacic acid, terephthalic acid, trimellitic acid, carboxyl group-containing polyester, and the like.

Among the curing agents (B), acid anhydrides (acid anhydride curing agents) are preferable from the viewpoint of heat resistance and transparency of the resulting cured product, and for example: commercially available products such as "RIKACID MH-700", "RIKACID MH-700F" (manufactured by Nippon chemical and physical Co., Ltd.), and "HN-5500" (manufactured by Hitachi chemical Co., Ltd.).

The content (blending amount) of the curing agent (B) is preferably 50 to 200 parts by weight, more preferably 80 to 150 parts by weight, based on 100 parts by weight of the total amount of the compounds having epoxy groups contained in the curable composition. More specifically, when an acid anhydride is used as the curing agent (B), it is preferably used in a ratio of 0.5 to 1.5 equivalents to 1 equivalent of an epoxy group contained in the curable composition of the present application. By setting the content of the curing agent (B) to 50 parts by weight or more, curing can be sufficiently advanced, and the toughness of the obtained cured product tends to be improved. On the other hand, when the content of the curing agent (B) is 200 parts by weight or less, a cured product having excellent transparency with suppressed coloration tends to be obtained.

(curing Accelerator (C))

When the curable composition of the present application contains the curing agent (B), it preferably further contains a curing accelerator (C). When a compound having an epoxy group (oxirane group) is reacted with the curing agent (B), the curing accelerator (C) has an effect of accelerating the reaction rate.

Examples of the curing accelerator (C) include: 1, 8-diazabicyclo [5.4.0]]Undecene-7 (DBU) or a salt thereof (e.g., phenoxide, octanoate, p-toluenesulfonate, formate, tetraphenylborate, etc.), 1, 5-diazabicyclo [4.3.0 ]]Nonene-5 (DBN) or a salt thereof (e.g., phenoxide, octoate, p-toluenesulfonate, formate, tetraphenylborate, etc.); tertiary amines such as benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and N, N-dimethylcyclohexylamine; imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; a phosphate ester; phosphines such as triphenylphosphine and tris (dimethoxy) phosphine; tetraphenyl radicalTetra (p-tolyl) boronic acidSalt, etcA compound; organic metal salts such as zinc octoate, tin octoate and zinc stearate; metal chelates such as aluminum acetylacetonate complexes, and the like. These may be used alone or in combination of two or more.

As the curing accelerator (C), for example: trade names "U-CAT SA 506", "U-CAT SA 102", "U-CAT 5003", "U-CAT 18X" and "U-CAT 12 XD" (products of the above, manufactured by San-apro Co., Ltd.); trade names "TPP-K" and "TPP-MK" (manufactured by Beixinghua chemical industry Co., Ltd.); commercially available products such as "PX-4 ET" (manufactured by Nippon chemical industries, Ltd.).

The content (blending amount) of the curing accelerator (C) is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, and still more preferably 0.03 to 3 parts by weight, based on 100 parts by weight of the curing agent (B). When the content of the curing accelerator (C) is 0.01 part by weight or more, a more effective curing acceleration effect tends to be obtained. On the other hand, when the content of the curing accelerator (C) is 5 parts by weight or less, a cured product having excellent transparency with suppressed coloring tends to be obtained.

(curing catalyst (D))

The curable composition of the present application may contain a curing catalyst (D) in place of the curing agent (B). The curing catalyst (D) has an action of initiating and/or accelerating a curing reaction (polymerization reaction) of a cationic curable compound such as the compound represented by the formula (1) to cure the curable composition. Examples of the curing catalyst (D) include: cationic polymerization initiators (photo-cationic polymerization initiators, thermal cationic polymerization initiators, etc.), lewis acid catalysts, protonic acid salts, imidazoles, etc., which generate cationic species to initiate polymerization by light irradiation, heat treatment, etc. These may be used alone or in combination of two or more.

Examples of the photo cation polymerization initiator include: hexafluoroantimonate, pentafluoro hydroxy antimonate, hexafluorophosphoric acidSalts, hexafluoroarsenate, and the like, and more specifically, for example: sulfonium salts (particularly triarylsulfonium salts) such as triarylsulfonium hexafluorophosphate (e.g., p-phenylthiophenyldiphenylsulfonium hexafluorophosphate), triarylsulfonium hexafluoroantimonate, and the like; diaryl iodidesHexafluorophosphate, diaryl iodideHexafluoroantimonate, bis (dodecylphenyl) iodideTetrakis (pentafluorophenyl) borate, iodine[4- (4-Methylphenyl-2-methylpropyl) phenyl group]Iodine such as hexafluorophosphateSalt; tetrafluoro compoundHexafluorophosphates and the likeSalt; n-hexyl pyridinePyridine such as tetrafluoroborateSalts and the like. In addition, as the photo cation polymerization initiator, for example: the trade name "UVACURE 1590" (manufactured by Daicel Cytec Co., Ltd.); the trade names "CD-1010", "CD-1011", "CD-1012" (manufactured by Sartomer, USA); trade name "Irgacure 264" (manufactured by BASF corporation); commercially available products such as "CIT-1682" (manufactured by Nippon Caoda corporation) are available.

As the above-mentioned thermal cationic polymerExamples of the initiator include: aryl diazonium salt and aryl iodineAs the onium salt, arylsulfonium salt, allene-ion complex, and the like, those having the trade names "PP-33", "CP-66" and "CP-77" (manufactured by ADEKA Co., Ltd.); trade name "FC-509" (manufactured by 3M); trade name "UVE 1014" (manufactured by G.E.); trade names "SAN-AID SI-60L", "SAN-AID SI-80L", "SAN-AID SI-100L", "SAN-AID SI-110L" and "SAN-AID SI-150L" (manufactured by Sanxin chemical industries, Ltd.); commercially available products such as "CG-24-61" (manufactured by BASF corporation).

Examples of the lewis acid catalyst include: BF (BF) generator₃N-hexylamine, BF₃-monoethylamine, BF₃-benzylamine, BF₃-diethylamine, BF₃-piperidine, BF₃-triethylamine, BF₃-aniline, BF₄N-hexylamine, BF₄-monoethylamine, BF₄-benzylamine, BF₄-diethylamine, BF₄-piperidine, BF₄-triethylamine, BF₄-aniline, PF₅-ethylamine, PF₅-isopropylamine, PF₅-butylamine, PF₅Laurylamine, PF₅-benzylamine, AsF₅Laurylamine and the like.

Examples of the protonic acid salts include: aliphatic sulfonium salt, aromatic sulfonium salt, and iodineSalt,Salts and the like.

Examples of the imidazoles include: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazoleTrimellitic acid salt, 1-cyanoethyl-2-phenylimidazoleTrimellitic acid salt, 2-methylimidazoleIsocyanurates, 2-phenylimidazoleIsocyanurate, 2, 4-diamino-6- [ 2-methylimidazolyl- (1)]-ethyl-s-triazine, 2, 4-diamino-6- [ 2-ethyl-4-methylimidazolyl- (1)]-ethyl-s-triazine and the like.

The content (blending amount) of the curing catalyst (D) is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 4 parts by weight, and still more preferably 0.03 to 3 parts by weight, based on 100 parts by weight of the cationically curable compound contained in the curable composition. When the curing catalyst (D) is used in the above range, the curing rate of the curable composition tends to be improved, and the heat resistance and transparency of the cured product tend to be well balanced.

The curable composition of the present application may contain one or two or more additives, if necessary, in addition to the above. Examples of the additives include: polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin; defoaming agents, leveling agents, silane coupling agents, surfactants, inorganic fillers, flame retardants, colorants, ion absorbers, pigments, phosphors, mold release agents, and the like.

The curable composition can be prepared by stirring and mixing the above components in a heated state as necessary. The stirring/mixing may use, for example: various mixers such as dissolvers and homogenizers, kneaders, roll mills, bead mills, and autorotation stirring devices. In addition, defoaming may be performed under vacuum after stirring/mixing.

The curable composition is excellent in curability because it contains the alicyclic epoxy compound product.

When the curable composition contains the curing agent (B) or the thermal cationic polymerization initiator as the curing catalyst (D), a cured product can be formed by performing heat treatment.

The heating temperature is, for example, 80 to 180 ℃. The heating time is, for example, 30 to 600 minutes. The heating time can be appropriately adjusted by shortening the heating time when the heating temperature is increased, or by increasing the heating time when the heating temperature is decreased.

On the other hand, when the curable composition contains a photo cationic polymerization initiator as the curing catalyst (D), a cured product can be formed by performing a photo irradiation treatment.

Ultraviolet rays are preferably used for light irradiation. The wavelength of the ultraviolet ray used is preferably 200 to 400 nm. The preferable irradiation condition is illumination intensity of 5-300 mW/cm²The irradiation amount is 50 to 18000mJ/cm²。

[ cured product ]

The cured product of the present application can be obtained by curing the above-described curable composition.

The cured product has excellent transparency, and the cured product (thickness: 3mm) has a light transmittance at a wavelength of 400nm of, for example, 50% or more, preferably 55% or more. The light transmittance at a wavelength of 450nm is, for example, 75% or more. The light transmittance at a wavelength of 550nm is, for example, 85% or more.

The cured product is excellent in heat resistance, and has a glass transition temperature (Tg) of, for example, 300 ℃ or higher, preferably 340 ℃ or higher. The linear expansion coefficient (. alpha.1: ppm/. degree. C.) at a temperature not higher than the glass transition temperature is, for example, not higher than 65 (for example, 50 to 65), preferably not higher than 60 (for example, 50 to 60). The linear expansion coefficient (. alpha.2: ppm/. degree. C.) at a temperature not lower than the glass transition temperature is, for example, not higher than 150 (e.g., 110 to 150), and preferably not higher than 140 (e.g., 110 to 140). The Tg, α 1, and α 2 can be measured by the methods of examples.

The curable composition of the present application can be used, for example, for: various applications such as sealants, adhesives, coating agents, electrical insulating materials, laminates, inks, sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optical lenses, optical moldings, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, and holographic memories.

Since the curable composition can form a cured product having excellent transparency as described above, when the curable composition is used as a sealant for an optical semiconductor element in an optical semiconductor device, a die attach paste (die attach paste), or the like, the light intensity emitted from the optical semiconductor device tends to be further improved.

< sealing agent >

The sealant of the present application contains the curable composition. The sealant can be preferably used for sealing an optical semiconductor (optical semiconductor element) in an optical semiconductor device. When the above-mentioned sealing agent is used, the optical semiconductor element can be sealed with a cured product (i.e., a sealing material) having excellent transparency and heat resistance.

The content of the curable composition in the total amount of the sealant is, for example, 50% by weight or more, preferably 60% by weight or more, and particularly preferably 70% by weight or more. The sealant may be composed of only the curable composition.

< adhesive agent >

The adhesive of the present application contains the curable composition. The adhesive can be used for bonding and fixing a member or the like to an adherend, and specifically, can be used for: a die bonding paste for bonding and fixing an optical semiconductor element to a metal electrode in an optical semiconductor device; an adhesive for lenses for fixing a lens of a camera or the like to an adherend or bonding the lenses to each other; and various applications requiring transparency and heat resistance, such as an adhesive for optical films for fixing optical films (e.g., polarizers, polarizer protective films, retardation films, etc.) to an adherend or bonding optical films to each other or to another film.

The above adhesive can be particularly preferably used as a die attach paste (or die bonding agent). By using the above adhesive as a die-bonding paste, an optical semiconductor device can be obtained in which an optical semiconductor element is bonded to an electrode by a cured product excellent in transparency and heat resistance.

The content of the curable composition in the total amount of the adhesive is, for example, 50 wt% or more, preferably 60 wt% or more, and particularly preferably 70 wt% or more. The adhesive may be composed of only the curable composition.

< coating agent >

The coating agent of the present application contains the curable composition. The coating agent can be used for various applications particularly requiring transparency and heat resistance.

The content of the curable composition is, for example, 50% by weight or more, preferably 60% by weight or more, and particularly preferably 70% by weight or more, based on the total amount of the coating agent of the present application. The coating agent may be composed of only the curable composition.

< optical Member >

The optical member of the present application includes a cured product of the curable composition. Examples of the optical member include: an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable composition; an optical semiconductor device in which an optical semiconductor element is bonded to an electrode by a cured product of the curable composition; and an optical semiconductor device in which an optical semiconductor element is bonded to an electrode by a cured product of the curable composition and the optical semiconductor element is sealed by a cured product of the curable composition.

The optical member has a structure in which the optical member is sealed and bonded by a cured product of the curable composition, and therefore, has excellent heat resistance and high light extraction efficiency.

The above-described configurations of the present invention, combinations thereof, and the like are examples, and additions, omissions, substitutions, and changes in the configurations may be appropriately made without departing from the spirit of the present invention. The present invention is not limited to the embodiments, but is limited only by the scope of the claims.

Examples

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.

Example 1

(dehydration step)

1000g of 4, 4' -dihydroxybicyclohexane, 125g of a dehydration catalyst [ a dehydration catalyst prepared by stirring and mixing 95% by weight of sulfuric acid (70g) and 1, 8-diazabicyclo [5.4.0] undecene-7 (55g) ], 1500g of pseudocumene were charged into a 3L jacketed glass flask, and the flask was heated. When the internal temperature exceeded 115 ℃, the formation of water began to be confirmed. Then, the temperature is increased continuously to the boiling point of pseudocumene (internal temperature 162 to 170 ℃), and the dehydration reaction is carried out under normal pressure. The by-produced water was distilled off and discharged to the outside of the system through a dehydration tube. The dehydration catalyst is liquid under the reaction conditions and is finely dispersed in the reaction solution. After 3 hours, roughly the theoretical amount of water (180g) had distilled off, so the reaction was considered to be complete. After pseudocumene was distilled off from the reaction-completed solution by using a 10-layer Oldershaw type distillation column, the reaction solution was distilled under an internal pressure of 10Torr (1.33kPa) and an internal temperature of 137 to 140 ℃ to obtain 731g of 3,4,3 ', 4' -bicyclohexene.

(epoxidation step)

To a 1L jacketed glass flask, 100g of 3,4,3 ', 4' -bicyclohexene and 300g of ethyl acetate were charged, and while blowing nitrogen gas into the gas phase portion, 307.2g of an ethyl acetate solution of peroxyacetic acid (peroxyacetic acid concentration: 29.2%, moisture content: 0.31%) was added dropwise over about 2 hours so that the temperature in the reaction system reached 30 ℃. After the addition of the peroxyacetic acid was completed, the reaction was terminated by aging at 30 ℃ for 3 hours.

(washing step, solvent removal step, and high boiling removal step)

The obtained reaction-terminated liquid was washed with water at 30 ℃ and desolvated by a WFE type thin film evaporator at 70 ℃/20mmHg, and then high-boiling was carried out at the same heating temperature of 180 ℃ and under a pressure of 4mmHg to obtain 71.2g of a mixture (1) containing (3,4,3 ', 4' -diepoxy) bicyclohexane represented by the following formula (1-1), a perhydride represented by the following formula (a-1) and/or the following formula (b-1), and an isomer represented by the following formula (c-1) and/or the following formula (d-1).

[ chemical formula 14]

[ chemical formula 15]

(fractionation step)

524g of the obtained mixture (1) was fed to a glass batch packed column having 10 theoretical plates, and a fractionation operation was performed under the following conditions to separate and extract about 50g of distillate each time, and the fractions were set to 1 to 6 in the order of distillation. These were used as alicyclic epoxy compound products (1) to (6).

< fractionation Condition >

Heating temperature: 160 ℃ and 175 DEG C

Temperature at the bottom of the column: 136- & lt152- & gt

The tower top temperature: 117 ℃ C. and 118 ℃ C

Bottom pressure: 1.8-2.3mmHg

Pressure at the top of the column: 0.6-0.7mmHg

Comparative example 1

The procedure was carried out in the same manner as in example 1 except that the distillation (fractionation step) was not carried out. That is, the mixture (1) obtained through the water washing step, the solvent removal step, and the high boiling point removal step is directly used as the product (7) of the alicyclic epoxy compound.

The alicyclic epoxy compound products obtained in examples and comparative examples were subjected to gas chromatography measurement. Fig. 1 shows the measurement results of the alicyclic epoxy compound product (6), and fig. 2 shows the measurement results of the alicyclic epoxy compound product (7).

As is clear from fig. 1 and 2, the fraction having a boiling point very close to that of (3,4,3 ', 4' -diepoxy) bicyclohexane can be efficiently removed by the fractional distillation operation. It is also found that the alicyclic epoxy compound product obtained by the fractionation operation contains the compound represented by formula (1) in high purity, and the contents of the compound represented by formula (a) and the compound represented by formula (b) are suppressed to an extremely low level.

The gas chromatography measurement of the alicyclic epoxy compound product was performed under the following conditions.

< measurement Condition >

A measuring device: trade name "HP-5", manufactured by Agilent

Chromatographic column packing agent: (5% phenyl) methylsiloxane

Column size: a length of 30m, an inner diameter of 0.32mm, a diameter of 0.25 μm, and a film thickness of 0.25 μm

Column temperature: 60 ℃→ (warming at 10 ℃/min) → 300 ℃ (5 minutes)

A detector: FID

From the results of the gas chromatography measurement, the content (═ purity) of the main component ((3,4,3 ', 4' -diepoxy) bicyclohexane) in the alicyclic epoxy compound preparation, the content of the transition hydride (including the compound represented by formula (a-1) and the compound represented by formula (b-1)), and the content of the isomer (including the compound represented by formula (c-1) and the compound represented by formula (d-1)) were determined by calculating the area% of the peak of each compound.

The retention time of the main component was 16.566 minutes, the retention time of the transition hydride was 13.891 minutes, and the retention times of the isomers were 16.029 minutes, 6.124 minutes, and 16.236 minutes.

According to the results of the gas chromatography measurement, the compounds represented by the following formula (x-1) were not detected from the alicyclic epoxy compound products (1) to (7).

[ chemical formula 16]

The results of composition analysis of the alicyclic epoxy compound products obtained in example 1 and comparative example 1 are summarized in the following table.

[ Table 1]

The lower limit value of the color of the red mud is less than 0.05 percent

Example 2

To 100 parts by weight of the alicyclic epoxy compound product (2) obtained in example 1, 0.6 part by weight of a product having a trade name of "SAN-AID SI-100L" (manufactured by shin-chemie corporation) as a thermal cationic polymerization initiator was added, and the resultant mixture was uniformly mixed and defoamed using a rotary mixer (trade name of "Awatori Rentaro AR-250", manufactured by THINKY, ltd.) to obtain a thermosetting composition.

Examples 3 and 4, and comparative example 2

A thermosetting composition was obtained in the same manner as in example 2, except that the formulation was changed as shown in table 2 below.

The curability of the thermosetting compositions obtained in examples 2 to 4 and comparative example 2 was evaluated in accordance with the following method.

[ method for evaluating curability ]

The heat-curable composition was heated from 25 ℃ to 80 ℃ at a heating rate of 5 ℃ per minute, and held at 80 ℃ for 50 minutes, and the loss modulus and the storage modulus were measured under conditions of a gap of 0.2mm, a strain control of 5%, and a frequency of 1Hz using a rheometer (MCR302, manufactured by Anton-Paar). Then, the time from the time when 80 ℃ was reached to the intersection of the loss modulus and the storage modulus was defined as the thermal gelation time. The curing property is excellent when the thermal gelation time is short.

The evaluation results are summarized in the following table.

[ Table 2]

As can be seen from table 2, curability improved as the content of excessive hydride and isomer in the thermosetting composition decreased.

Examples 5 to 9 and comparative example 3

A thermosetting composition was obtained in the same manner as in example 2, except that the formulation was changed as shown in table 3 below. With respect to the obtained thermosetting composition, a cured product was obtained in accordance with the following method, and the heat resistance, mechanical properties, and transparency of the obtained cured product were evaluated in accordance with the following method.

[ curing method ]

The thermosetting composition was injection-molded into a molding machine and heated under curing conditions of 45 ℃ for 6.5 hours and then 150 ℃ for 2 hours to obtain a cured product.

[ method for evaluating Heat resistance ]

The cured product was heated from 30 ℃ to 300 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere by using a TMA measuring apparatus ("TMA/SS 100", manufactured by SII Nano Technology corporation) according to the method according to JIS K7197, and after measuring the thermal expansion coefficient in the above temperature range, the lines were drawn to the low temperature region and the high temperature region of the TMA spectrum, which were compared with the glass transition temperature, and the glass transition temperature (Tg) was determined from the intersection points of the lines.

From the TMA spectrum, the linear expansion coefficient α 1 (ppm/. degree. C.) of the cured product at a temperature not higher than the glass transition temperature and the linear expansion coefficient α 2 (ppm/. degree. C.) at a temperature not lower than the glass transition temperature were obtained. When the values of α 1 and α 2 are small, the dimensional stability of the cured product is good.

[ method for evaluating mechanical Properties ]

The flexural strength (MPa) and flexural modulus (MPa) of the cured product were measured by subjecting the cured product (4 mm in thickness, 10mm in width, 80mm in length) to a 3-point bending test using a Tensilon Universal tester (manufactured by Orient Tech Co., Ltd.) under conditions of a side span of 67mm and a bending speed of 2 mm/min.

[ method for evaluating transparency ]

The light transmittance (%) at a wavelength of 400nm of the cured product (thickness: 3mm) was measured using a spectrophotometer (trade name: UV-2450, manufactured by Shimadzu corporation).

The evaluation results are summarized in the following table.

[ Table 3]

As can be seen from table 3, regardless of the content of the isomer in the thermosetting composition, when the content of the excessive hydride is decreased, the heat resistance, mechanical properties, and transparency of the obtained cured product are improved.

Example 10

To 100 parts by weight of the alicyclic epoxy compound product (2) obtained in example 1, 1 part by weight of a product having a trade name of "CPI-101A" (manufactured by San-apro Co., Ltd.) as a photo cation polymerization initiator was added, and the mixture was homogenized by using a rotary stirring apparatus (trade name of "Awatorei Rentaro AR-250" and manufactured by THINKY Co., Ltd.) and defoamed to obtain a photocurable composition.

Examples 11 to 13 and comparative example 4

A photocurable composition was obtained in the same manner as in example 10, except that the formulation was changed as described in table 4 below. The curability of the obtained photocurable composition was evaluated in accordance with the following method.

[ method for evaluating curability ]

UV irradiation (at 10 mW/cm) at 25 ℃ to the photocurable composition²Irradiation for 10 seconds), the resulting material was measured for loss modulus and storage modulus using a rheometer (MCR302, manufactured by Anton-Paar, Ltd.) at 25 ℃, a gap of 0.1mm, a strain control of 5%, and a frequency of 10 Hz. Further, the time taken until the intersection of the loss modulus and the storage modulus was defined as the UV gelation time. The curing property is excellent when the UV gelation time is short.

The evaluation results are summarized in the following table.

[ Table 4]

As can be seen from table 4, curability improved as the content of excessive hydride and isomer in the photocurable composition decreased.

As a summary of the above, the aspects of the present invention and modifications thereof are described below.

[1] An alicyclic epoxy compound product, wherein,

the purity of the compound represented by the formula (1) is 85% by weight or more,

the total content of the compound represented by the formula (a) and the compound represented by the formula (b) is 0.5% by weight or less.

[2] The alicyclic epoxy compound product according to [1], wherein,

the total content of the compound represented by the formula (c) and the compound represented by the formula (d) is 10% by weight or less.

[3] The alicyclic epoxy compound product according to [1] or [2], wherein,

the content of the compound represented by the formula (x) is 1000ppm or less.

[4] The alicyclic epoxy compound product according to any one of [1] to [3], wherein,

the thermal gelation time determined by the following measurement method was 400 seconds or less,

method for measuring gelation time:

a curable composition prepared by blending 100 parts by weight of an alicyclic epoxy compound product with 0.6 part by weight of SAN-AID SI-100L (manufactured by shin-Etsu chemical Co., Ltd.) was subjected to dynamic viscoelasticity measurement under conditions of a frequency of 1Hz, a strain of 5%, a gap of 0.2mm and a temperature of 80 ℃ and the intersection of the storage modulus (G ') and the loss modulus (G') was defined as a thermal gelation time.

[5] The alicyclic epoxy compound product according to any one of [1] to [4], wherein,

the UV gelation time determined by the following measurement method was 45 seconds or less,

method for measuring gelation time:

at a frequency of 10Hz, a strain of 5% and a clearance of 0.1mm100 parts by weight of an alicyclic epoxy compound product and 1.0 part by weight of CPI-101A (manufactured by San-apro Co., Ltd.) were subjected to UV irradiation (at 10 mW/cm) at 25 ℃²Irradiation for 10 seconds), and the intersection of the storage modulus (G') and the loss modulus (G ″) was defined as the UV gelation time.

[6] A method of making an alicyclic epoxy compound article, the method comprising: an alicyclic epoxy compound product according to any one of [1] to [5] obtained by subjecting the product to the following steps,

step 1: subjecting the compound represented by the formula (1 ") to a dehydration reaction to obtain a compound represented by the formula (1');

and a step 2: reacting a compound represented by formula (1') with an organic peroxyacid to obtain a reaction product containing the compound represented by formula (1);

step 3: fractionating the reaction product by using a rectifying tower with 1-20 actual tower plates under the following conditions,

the temperature of the tower bottom is 100-250 DEG C

The temperature of the top of the tower is 80-200 DEG C

Overhead pressure of 0.1-50 mmHg

The pressure at the bottom of the tower is 1-200 mmHg.

[7] The process for producing an alicyclic epoxy compound product according to [6], wherein,

the compound represented by the formula (a) and the compound represented by the formula (b) are removed by fractional distillation in step 3.

[8] The method for producing an alicyclic epoxy compound product according to [6] or [7], further comprising:

and a step of distilling the reaction product at a temperature of 50 to 200 ℃ and a pressure of 1 to 760mmHg to remove a compound having a lower molecular weight than the compound represented by the formula (1).

[9] The method for producing an alicyclic epoxy compound product according to any one of [6] to [8], further comprising:

distilling the reaction product at a temperature of 100 to 200 ℃ and a pressure of 0.01 to 100mmHg to evaporate and recover the compound represented by the formula (1), and removing a component having a boiling point higher than that of the compound represented by the formula (1).

[10] A curable composition comprising the alicyclic epoxy compound product according to any one of [1] to [5 ].

[11] The curable composition according to [10], further comprising a curing agent (B) and a curing accelerator (C).

[12] The curable composition according to [10], which further comprises a curing catalyst (D).

[13] A cured product of the cured composition according to any one of [10] to [12 ].

[14] The cured product according to [13], which has a light transmittance of 50% or more at a wavelength of 400 nm.

[15] A sealant comprising the cured composition according to any one of [10] to [12 ].

[16] An adhesive comprising the cured composition according to any one of [10] to [12 ].

[17] A coating agent comprising the cured composition according to any one of [10] to [12 ].

[18] An optical member comprising the cured product according to [13] or [14 ].

[19] A method for producing a sealant using a curable composition containing the alicyclic epoxy compound product according to any one of [1] to [5 ].

[20] A method for producing an adhesive using a curable composition containing the alicyclic epoxy compound product according to any one of [1] to [5 ].

[21] A method for producing a coating agent using a curable composition containing the alicyclic epoxy compound product according to any one of [1] to [5 ].

[22] Use of a curable composition comprising the alicyclic epoxy compound product according to any one of [1] to [5] as a sealant.

[23] Use of a curable composition comprising the alicyclic epoxy compound product according to any one of [1] to [5] as an adhesive.

[24] Use of a curable composition comprising the alicyclic epoxy compound product according to any one of [1] to [5] as a coating agent.