JP2001181238A - Alicyclic group-containing ester compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aliphatic group-containing ester compound capable of being used as various cross-linking agents for giving cured materials excellent in weather resistance, heat resistance, waterproof property, etc., and as a stabi lizer of a resin having an organic phosphorus compound as a flame retardant agent, and having a new specific structure, and a method for producing the same compound. SOLUTION: This alicyclic group-containing ester compound is expressed by general formula (1) wherein, (y) is an integer selected from 1 or 2; (b) is 0 or 1; A, D and E are each independently H, a halogen atom, an alkyl group having a <=12C substituent or an alkoxyl; X, Y are each independently an unsaturated alicyclic ester expressed by general formula (2) [wherein (m) is an integer selected from 1 or 2] or an epoxydized alicyclic ester expressed by general formula (3) [wherein (n) is an integer selected from 1 or 2] ; B is H, a halogen atom, an alkyl allowed to have a <=12C substituent, alkoxyl, allyl ester or glycidyl}.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an alicyclic group-containing ester compound having an alicyclic reactive group. More specifically, various crosslinked structure-forming agents having an alicyclic reactive group having a specific structure via an ester bond, and giving a cured product excellent in weather resistance, water resistance, and heat resistance, and a resin stabilizer And a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a cross-linking structure forming agent used in electric insulating materials, adhesives, various cast molding materials, paints and the like,
Compounds having a reactive functional group that causes a cross-linking reaction by heat or light are widely used, and in recent years, their types and applications have been further expanding. In general, it is preferable that these crosslinking structure forming agents perform an addition reaction without by-products at the time of a crosslinking reaction with a reactive curing agent or the like, and a crosslinking structure forming agent having a certain storage stability before use is used. is needed. As these crosslinked structure forming agents, for example,
A compound having an epoxy group such as a glycidyl group or an allyl group as a reactive functional group involved in crosslinking is preferable,
In particular, compounds having an epoxy group such as a glycidyl group as a reactive functional group are widely used, and compounds having higher performance are desired in various fields.

For example, in the coatings field, there is a strong demand for a crosslinked structure-forming agent which forms a cured product having high weather resistance, and in the field of electric insulating materials, a curing agent having a high heat distortion temperature and a low water absorption is required. There is a need for a crosslinked structure forming agent that forms a product.

In recent years, compounds having an epoxy group such as a glycidyl group have been used in a thermoplastic resin containing an acid component or generating an acidic component at the time of molding, or a compound containing a compound having an acidic component. It has also been proposed as an additive for stabilizing a plastic resin. For example, an alloy of polycarbonate resin / ABS resin having flame retardancy, which is widely used in general, contains a flame retardant in order to impart flame retardancy. As the flame retardant, generally, an organic phosphorus compound formed by bonding a phenol compound is widely used. However, the organic phosphorus compound generally contains acidic components such as organic phosphoric acids and phenolic hydroxyl groups derived from phenolic compounds, and these acidic components are contained in the polycarbonate resin / AB.
For example, the alloy made of the S resin may be discolored during the molding process to cause deterioration of the appearance. When the acid component is contained in a molded article made of the above alloy, the impact resistance and the elongation at break tend to decrease when exposed to a high temperature and high humidity environment for a long time.

[0005] The use of a compound having an epoxy group such as a glycidyl group as an additive in the flame-retardant polycarbonate / ABS alloy can stabilize the acidic component. It is necessary that the compound has high weather resistance, heat resistance, and water resistance. Further, there is a strong demand for a compound containing an epoxy group, which has high compatibility with a flame-retardant polycarbonate / ABS alloy and gives a molded article long-term reliability under a high-temperature and high-humidity environment.

As a compound having an epoxy group such as a glycidyl group, for example, an epoxy compound having a glycidyl group derived from a phenol compound such as diglycidyl ether derived from bisphenol A is widely used. However, an epoxy resin derived from a phenolic compound such as bisphenol A has a low level of weather resistance, such as discoloration by ultraviolet rays, and has a limitation in outdoor use.

When a diglycidyl ether compound derived from an aliphatic compound is used as a crosslinking structure-forming agent, the resulting cured product generally has low heat resistance and water resistance. Further, the compatibility with the flame-retardant polycarbonate / ABS alloy tends to be low.

Further, as a compound having an epoxy group such as a glycidyl group which forms a cured product having high weather resistance,
For example, glycidyl compounds derived from substances other than phenolic compounds such as triglycidyl isocyanurate, diglycidyl terephthalate, and triglycidyl trimellitate have been proposed. These cured products have high weather resistance and are widely used in the paint field. However, for example, the water resistance is not sufficient, and the water absorption is not sufficient in the field of electric insulation.

The above-mentioned epoxy compound having a glycidyl group is generally produced using epichlorohydrin, and the resulting epoxy compound contains ionic chlorine, organically-bonded chlorine, and water having a chlorohydrin structure. Since it contains decomposable chlorine, there is a limitation when it is used, for example, in the field of electric insulating materials.

An alicyclic epoxy compound represented by the following formula (9) is generally used as a weather-resistant compound having an alicyclic epoxy group. However, when such a monoester compound is blended with polycarbonate or the like, there is a concern that the molecular weight may be reduced, and this may result in a decrease in mold deposit (MD) and mechanical properties during molding.

[0011]

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[0012] Further, Deposited Doc.
(1980), VINITI 1479-80, 13p
In p, an alicyclic group-containing epoxy compound derived from terephthalic acid represented by the following formula (10) is described:
The compound has high water resistance such as low water absorption as well as weather resistance and heat resistance.

[0013]

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However, since the compound is a crystalline solid and tends to have a high melting point, and has low solubility in a solvent, for example, when used as a casting or a solvent-based coating, the compound is not suitable for use. There is a limit.

[0015]

SUMMARY OF THE INVENTION The present invention provides weather resistance,
Heat resistance, and can be suitably used as a crosslinked structure forming agent that gives a cured product having water resistance, and has a low melting point or is liquid at room temperature, so that the compounding and molding properties with the curing agent are good, and A novel alicyclic group-containing epoxy compound having high compatibility with ester resins such as polycarbonate and useful as an additive for stabilizing the resin, and a method for producing the same.

[0016]

Means for Solving the Problems The present inventors have proposed weather resistance,
The present inventors focused on a compound containing an alicyclic group, which can impart heat resistance and water resistance, and further intensively studied an alicyclic group-containing ester compound for the purpose of enhancing the compatibility with an ester compound such as polycarbonate. As a result, the alicyclic group-containing ester compound having a specific structure is
It has been found that the contribution to the compatibility with the ABS alloy and the stabilization to the molded article is high. Further, the present inventors have found that the alicyclic group-containing ester compound having the specific structure is easy to mold when used as a crosslinked structure-forming agent, and has weather resistance, heat resistance, and water resistance. The present inventors have found that it can be applied to a cured product, and have reached the present invention.

That is, the present invention is as follows. 1. An alicyclic group-containing ester compound represented by the following general formula (1).

[0018]

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(Where y represents an integer selected from 1 or 2; b represents 0 or 1; and A, D and E
Are each independently a hydrogen atom, a halogen atom,
It represents an alkyl group or an alkoxyl group which may have the following substituents. X and Y each independently represent an unsaturated alicyclic ester group represented by the following general formula (2) or an epoxidized alicyclic ester group represented by (3).
B represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent having 12 or less carbon atoms, an alkoxyl group, an allyl ester group, or a glycidyl ester group. )

[0020]

Embedded image (In the formula, m represents an integer selected from 1 or 2.)

[0021]

Embedded image (In the formula, n represents an integer selected from 1 or 2.)

2. In the general formula (1), X and Y are each an unsaturated alicyclic ester group represented by the general formula (2), and B is a hydrogen atom, a halogen atom, and a carbon atom of 1;
1. The above-mentioned 1. which is an alkyl group, an alkoxyl group, or an allyl ester group which may have 2 or less substituents. The alicyclic group-containing ester compound according to the above.

3. In the general formula (1), X and Y are each an unsaturated alicyclic ester group represented by the general formula (2), and B is a hydrogen atom. The alicyclic group-containing ester compound according to the above.

4. In the general formula (1), X and Y are both epoxidized alicyclic ester groups represented by the general formula (3), and B has a hydrogen atom, a halogen atom, and a substituent having 12 or less carbon atoms. 1. The above-mentioned 1., which may be an alkyl group, an alkoxyl group or a glycidyl ester group.
The alicyclic group-containing ester compound according to the above.

[5] 2. The alicyclic group-containing ester compound according to the above 1, wherein X and Y in the general formula (1) are each an epoxidized alicyclic ester group represented by the general formula (3), and B is a hydrogen atom.

6. An alicyclic group-containing ester compound represented by the following general formula (4).

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(Wherein, R represents an aliphatic hydrocarbon group having 5 or more carbon atoms and 50 or less, or a naphthalene skeleton.
r, s, p, and q represent integers of 0 or more, and (r + s + p +
q) is 2 or more, and (r + s) is an integer of 1 or more. X1 represents an unsaturated alicyclic ester group represented by the following general formula (5).

[0028]

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(In the formula, m is an integer selected from 1 and 2.) X ₂ represents an epoxidized alicyclic ester group represented by the following general formula (6).

[0030]

Embedded image (In the formula, n is an integer selected from 1 and 2.)

7. 5. In the general formula (4), s = 0 and q = 0. The alicyclic group-containing ester compound according to the above.

8. 5. The general formula (4), wherein r = 0 and p = 0. The alicyclic group-containing ester compound according to the above.

9. 5. In the general formula (4), p = 0 and q = 0. The alicyclic group-containing ester compound according to the above.

10. In the general formula (4), s = 0, p
5. The above 6. wherein q = 0 and q = 0. The alicyclic group-containing ester compound according to the above.

11. In the general formula (4), r = 0, p
5. The above 6. wherein q = 0 and q = 0. The alicyclic group-containing ester compound according to the above.

12. 1. The transesterification reaction using an organic ester compound and an unsaturated alicyclic alcohol compound, or the unsaturated alicyclic alcohol compound and allyl alcohol. 3. , 7. Or 10. The production method of the alicyclic group-containing ester compound according to the above.

13. 2. The above-mentioned item 3, wherein a transesterification reaction between the organic ester compound and the unsaturated alicyclic alcohol compound is carried out. Or 10. The production method of the alicyclic group-containing ester compound according to the above.

14. 3. The alicyclic group-containing ester compound according to the above item 2, which is subjected to an epoxidation reaction using an oxidizing agent. Or 4. The production method of the alicyclic group-containing ester compound according to the above.

15. 3 above. 4. The epoxidation reaction of the alicyclic group-containing ester compound according to the above, using an oxidizing agent. The production method of the alicyclic group-containing ester compound according to the above.

16. 7 above. 5. The epoxidation reaction of the alicyclic group-containing ester compound according to the above, using an oxidizing agent. Or 8. The production method of the alicyclic group-containing ester compound according to the above.

17. 10 above. 9. The epoxidation reaction of the alicyclic group-containing ester compound according to the above, using an oxidizing agent. Or 11. The production method of the alicyclic group-containing ester compound according to the above.

18. A method for producing an alicyclic group-containing ester compound, comprising subjecting an alicyclic group-containing ester compound represented by the following general formula (7) to an epoxidation reaction using hydrogen peroxide.

[0043]

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(In the formula, R represents an aliphatic hydrocarbon group having 4 or more carbon atoms, and m and n each represent an integer selected from 1 and 2.)

19. 13. The above item 14. wherein the oxidizing agent is hydrogen peroxide. ~ 17. The production method according to any of the above.

20. 13. The above item 14. wherein the oxidizing agent is a percarboxylic compound. ~ 17. The production method according to any of the above.

21. 1 selected from organic ester compounds, unsaturated alicyclic alcohols and alicyclic epinol compounds
A transesterification reaction using at least one kind of alicyclic alcohol compound or at least one kind of compound selected from allyl alcohol and 2,3-epoxy-1-propanol with an alicyclic alcohol compound; The above 1. Or 6. The production method of the alicyclic group-containing ester compound according to the above.

22. An organic ester compound and an alicyclic epinol compound, or the alicyclic epinol compound and 2,
3. Transesterification using 3-epoxy-1-propanol. , 5. , 8. Or 11. The production method of the alicyclic group-containing ester compound according to the above.

23. A process for producing an alicyclic group-containing ester compound, comprising subjecting an alkyl ester compound represented by the following general formula (8) to transesterification with an alicyclic epinol.

[0050]

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(In the formula, R represents an aliphatic hydrocarbon group having 4 or more carbon atoms. R ₁ and R ₂ each represent an alkyl group having 1 to 12 carbon atoms.)

24. 4. The transesterification of an organic ester compound and an alicyclic epinol compound. Or 11. The production method of the alicyclic group-containing ester compound according to the above.

25. An organic carboxylic acid halide compound,
1. The method according to the above 2, wherein the unsaturated alicyclic alcohol compound or the unsaturated alicyclic alcohol compound is reacted with allyl alcohol. 3. , 7. Or 10. The production method of the alicyclic group-containing ester compound according to the above.

26. 2. The above-mentioned item 3, wherein the organic carboxylic acid halide compound is reacted with an unsaturated alicyclic alcohol compound. Or 10. The production method of the alicyclic group-containing ester compound according to the above.

27. 4. The method according to the above item 5, wherein the organic carboxylic acid halide is reacted with an alicyclic epinol compound.
Or 6. The method for producing the alicyclic ester compound according to the above.

28. The above 1. And 6. A composition comprising an alicyclic group-containing ester compound having a melting point of 160 ° C. or lower, which is a mixture comprising two or more alicyclic group-containing ester compounds as described in the above.

29. The above 1. And 6. A composition comprising at least one alicyclic group-containing ester compound according to claim 1 and another epoxy compound.

30. (A) Claim 1 and / or Claim 6
The alicyclic ester compound described above, (b) an organic phosphorus compound,
And (c) a thermoplastic resin.

Hereinafter, the present invention will be described in detail. A, D and E in the general formula (1) of the present invention are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent having 12 or less carbon atoms, or an alkoxyl group. Examples of the halogen include fluorine, chlorine, bromine, and iodine. When the alkyl group has more than 12 carbon atoms, the heat resistance of the cured product obtained when used as a crosslinking agent tends to decrease. Moreover, the substituent which the alkyl group may have is not particularly limited as long as it does not affect the weather resistance and water resistance of the obtained cured product or resin molded product, and for example, a nitrile group, a nitro group, Examples include an acetyl group and a halogen group. Further, as the alkoxyl group,
Usually, an alkoxyl group having 12 or less carbon atoms is desirable from the viewpoint of heat resistance, and examples thereof include a methoxy group and an ethoxy group. In the present invention, A, D and E are preferably hydrogen atoms in view of water resistance, moldability as a crosslinking structure forming agent, and compatibility with resins such as polycarbonate.

In the above general formula (1), X and Y are
Each is independently an unsaturated alicyclic ester group or an epoxidized alicyclic ester group represented by the general formula (2) or (3). M and n in the general formulas (2) and (3) are 1
Or, it is an integer selected from 2, and it is particularly preferable that both are 2 from the viewpoint of improving heat resistance and water resistance.

In the above general formula (1), y is 1 or 2
It is. When y is 1, the viscosity of the resulting alicyclic group-containing ester compound at the time of molding tends to be low, and when y is 2, the water resistance of the obtained cured product when used as a crosslinking agent and The heat resistance and further the mechanical strength tend to be improved.

B represented by the above general formula (1) is a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, an allyl ester group, or a glycidyl ester group which may have a substituent having 12 or less carbon atoms. Represents The number of bonds b of B is 0 or 1. The halogen is fluorine, iodine, bromine and chlorine. When the alkyl group has more than 12 carbon atoms, the heat resistance of the cured product obtained when used as a crosslinking agent tends to decrease. Moreover, the substituent which the alkyl group may have is not particularly limited as long as it does not affect the weather resistance and water resistance of the obtained cured product or resin molded product, and for example, a nitrile group, a nitro group, And a halogen group. As the alkoxyl group, an alkoxyl group having 12 or less carbon atoms is usually desirable in terms of heat resistance, and examples thereof include a methoxy group and an ethoxy group. In the present invention, B is preferably a hydrogen atom, an allyl ester group or a glycidyl ester group.

In the present invention, one preferred structure of the alicyclic group-containing ester compound represented by the general formula (1) is that X and Y are both the epoxidized alicyclic ester group, and A and B Is a halogen atom, an alkyl group which may have a substituent having 12 or less carbon atoms, an alkoxyl group,
And glycidyl ester groups. A more preferred structure is when X and Y are both the epoxidized alicyclic ester groups, and A and B are hydrogen atoms. These are cases where only epoxy groups are used as reactive functional groups.For example, when used as a cross-linking agent, the curing agent used at the same time should be cured with at least one substance that cleaves or bonds to the epoxy ring. Can be. Also,
When only the epoxidized alicyclic ester group is used as the reactive functional group, the heat resistance and water resistance of the obtained cured product are high, and when used as an additive of flame-retardant polycarbonate / ABS alloy, It has high compatibility and has a large effect of stabilizing acidic components. In addition, the compounds having these preferred structures are liquid at a temperature in the range of room temperature to 80 ° C., and thus are easy to handle. Preferred structures in the case of having only the epoxidized alicyclic ester group in the general formula (1) of the present invention are shown below.

[0064]

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Further, in the present invention, the above general formula (1)
Another preferred structure of the alicyclic group-containing ester compound represented by is a case where X and Y are both the above-mentioned unsaturated alicyclic ester groups, and B is a hydrogen atom or an allyl ester group. These compounds can obtain the above-mentioned epoxidized alicyclic group-containing ester compound by epoxidizing the unsaturated carbon-carbon double bond contained in the structure, and are useful raw materials for the epoxy compound. sell. Preferred structures in the present invention in the case where only the unsaturated alicyclic ester group in the general formula (1) is shown below.

[0066]

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The present inventors have also found that the alicyclic group-containing compound represented by the general formula (4) can solve the above problem.

R in the general formula (4) represents an aliphatic hydrocarbon group having 5 to 50 carbon atoms or a naphthalene skeleton. When the number of carbon atoms of the aliphatic hydrocarbon group is 5 or less, a mold deposit tends to be generated on the surface of a mold when injection molding is performed by blending the aliphatic hydrocarbon group with a flame retardant polycarbonate / ABS alloy. When the number of carbon atoms exceeds 50, the compatibility with the alloy tends to decrease. In the present invention, the number of carbon atoms is preferably 5 or more and 20 or less, more preferably 5 or more and 15 or less. Further, the aliphatic hydrocarbon group is an unsaturated double bond, a halogen group, a nitrile group, or the like, as long as the weather resistance, water resistance, and heat resistance of the cured product obtained when the crosslinked structure forming agent is used are not reduced. It may contain an alkoxyl group, an epoxy group or the like.

In the present invention, r, s, p, and q in the general formula (4) are positive integers including 0, and (r +
It is essential that (s + p + q) is 2 or more and (r + s) is an integer of 1 or more. In the present invention,
(R + s + p + q) is usually 2 to 12, more preferably 2 to 8. When (r + s + p + q) is less than 2,
When used as a crosslinked structure-forming agent, the crosslinked density tends to be low, and the resulting cured product tends to have low mechanical strength. Further, in the present invention, m and n represented in the general formulas (5) and (6) are integers selected from 0 or 1, and when both are 1, heat resistance and water resistance are increased. There is a tendency and is preferable.

In the general formula (4), p and q are 0 and only an alicyclic ester group is present as a reactive alicyclic group. This is preferable in that the water resistance and heat resistance of the product are improved.

In the present invention, as one preferred structure of the alicyclic group-containing ester compound represented by the general formula (4), X ₁ and X ₂ are both epoxidized represented by the general formula (6). An alicyclic ester group, wherein p is 0; A more preferred structure is where X ₁ and X ₂ are both epoxidized alicyclic ester groups represented by the general formula (6), and p and q are 0. These are cases having only an epoxy group as a reactive functional group. For example, when used as a crosslinked structure forming agent, a curing agent used simultaneously can be cured with at least one kind of substance as described above. When only an epoxidized alicyclic epoxy group is contained, the obtained cured product has high heat resistance and water resistance, and when used as an additive of flame-retardant polycarbonate / ABS alloy, compatibility is low. It is high and has a large stabilizing effect on acidic components. The following formula shows a preferable structure when only the epoxidized alicyclic ester group is used in the general formula (4) of the present invention.

[0072]

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[0073]

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In the present invention, the above-mentioned general formula (4)
As another preferred structure of the alicyclic group-containing ester-containing compound represented by the formula, X ₁ and X ₂ are both an unsaturated alicyclic ester group represented by the general formula (5), and q is 0. There are cases. As a more preferred structure, X ₁
And X ₂ are both unsaturated alicyclic ester groups represented by the general formula (5), and p and q are 0. These compounds have the structure of unsaturated carbon-
By epoxidizing the carbon double bond, the above-mentioned epoxidized alicyclic group-containing ester compound can be obtained, which is a useful raw material for the epoxy compound. In the formula below,
A preferable structure in the case of having only the unsaturated alicyclic ester group in the general formula (4) of the present invention is shown.

[0075]

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[0076]

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Hereinafter, a method for producing the alicyclic group-containing ester compound of the present invention will be described. First, a method for producing an alicyclic group-containing ester compound of the present invention having only a carbon-carbon unsaturated double bond will be described.

In the alicyclic group-containing ester compound of the present invention, the compound having only a carbon-carbon unsaturated double bond is
An organic ester compound and an unsaturated alicyclic alcohol compound,
Alternatively, it can be obtained by a transesterification reaction using the unsaturated alicyclic alcohol compound and allyl alcohol.

The unsaturated alicyclic alcohol referred to in the present invention means 3-hydroxycyclopentene and 3-hydroxycyclohexene represented by the following formula.

[0080]

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The organic ester compound referred to in the present invention is an organic compound having two or more alkyl ester groups, and is represented by the following general formulas (9) and (10). Means a compound.

[0082]

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(Where A ₁ is an alkyl ester group, A ₂ and A ₃ are each independently a hydrogen atom or an alkyl ester group, and A ₂ and A ₃ are not simultaneously hydrogen atoms. , D, and E represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent having 12 or less carbon atoms, or an alkoxyl group.)

[0084]

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(Wherein, R represents an aliphatic hydrocarbon group having 5 to 50 carbon atoms and a naphthalene skeleton. X represents an alkyl ester group, and x represents an integer of 2 or more.)

In the present invention, the alkyl moiety contained in the alkyl ester group in the general formulas (9) and (10) is preferably an alkyl group having 12 or less carbon atoms, more preferably 6 or less carbon atoms, and particularly preferably. Is an alkyl group having 4 or less carbon atoms. The alkyl moiety is transesterified with an unsaturated alicyclic alcohol to form an alkyl alcohol.If the number of carbon atoms is small, the generated alkyl alcohol tends to be easily removed to the outside of the reaction system. This is desirable because the yield of the contained ester compound tends to be improved.

The alkyl ester groups in the above general formulas (9) and (10) may have the same number of carbon atoms and different structures in the same molecule in the same molecule. . This is the case, for example, when a methyl ester group and an ethyl ester group are present simultaneously in the same molecule.

Examples of the organic ester compound represented by the general formula (9) and preferably used in the present invention include phthalic acid esters and isophthalic acid esters. Examples of the phthalic esters include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, and dioctyl phthalate. Examples of the isophthalic esters include dimethyl isophthalate, diethyl isophthalate, and dibutyl isophthalate.

R in the general formula (10) is an aliphatic hydrocarbon group having 5 to 50 carbon atoms or a naphthalene skeleton. The aliphatic hydrocarbon group may contain a carbon-carbon unsaturated double bond or an alicyclic group. These organic ester compounds suitably used in the present invention include, for example, dialkyl pimerate, dialkyl suberate, dialkyl azelate, dialkyl sebacate, dialkyl undecandioate, dialkyl dodecane diate, and homopin. Acid dialkyl ester, cyclopentane dicarboxylic acid dialkyl ester, cyclohexane dicarboxylic acid dialkyl ester, cyclohexane diacetate dialkyl ester, norbornene dicarboxylic acid dialkyl ester, bicyclo [2.2.2] octane dicarboxylic acid dialkyl ester, adamantane dicarboxylic acid dialkyl ester, spiro [3.3] Dialkyl heptane dicarboxylate, dialkyl tetrahydrophthalate, etc. Aliphatic dialkyl esters, aliphatic trialkyl esters such as cyclohexanetricarboxylic acid trialkyl esters, aliphatic tetraalkyl esters such as cyclohexanetetracarboxylic acid tetraalkyl esters, 2,6-naphthalenedicarboxylic acid dialkyl esters, 1,6 And dialkyl naphthalenedicarboxylic acids such as dialkyl naphthalenedicarboxylic acid.

In the method for producing the alicyclic group-containing ester compound of the present invention, the amount of the raw material alcohol such as unsaturated alicyclic alcohol or allyl alcohol used as the raw material may be, for example, When all of the alkyl ester groups are transesterified, the stoichiometric amount is equivalent to the ester groups. However, because the reaction is an equilibrium reaction and favors the production system, it is usually
The use amount of the raw material alcohols is desirably from equivalent to 100 equivalents, preferably from 1.1 equivalent to 20 equivalents, particularly preferably from 1.5 equivalent to 6 equivalents. When the alicyclic group-containing ester compound of the present invention simultaneously contains, for example, an allyl ester group and a cyclohexenyl ester group, allyl alcohol and 3-hydroxycyclohexenol are simultaneously added so as to have a desired ratio. Alternatively, it may be prepared by transesterifying only one raw material and transesterifying using the other raw material alcohol as a subsequent step. When the reaction is performed in two or more stages as described above, the amount of the above-mentioned raw material alcohols is not limited as long as the alicyclic group-containing ester compound of the present invention having a desired structure is obtained.

The organic ester compound represented by the general formulas (9) and (10) used as a raw material in the production method of the present invention preferably has an acid value of 0.05 equivalent / 100 g or less. More preferably 0.005 equivalents / 100 g or less, particularly preferably 0.001 equivalent / 10
0 g or less. In the present invention, the case where the acid value is 0 is most preferable. However, the compound represented by the above general formula (9) or (10) is usually used to prepare an unreacted residual carboxylic acid group or a carboxylic acid formed by hydrolysis. A compound containing an acid group, and further an acid component such as an acid catalyst used in synthesizing the raw material ester compound may be contained as an impurity,
In most cases, it has an acid value derived from the acidic component. If the acid value is as high as 0.05 equivalent / 100 g or more, 3-hydroxycyclohexenol or 3-hydroxycyclopentanol used as a raw material tends to cause a dehydration reaction, and the acid value of cyclohexadiene or the like is increased. Since alicyclic diene compounds and alicyclic ether compounds such as dicyclohexenyl ether condensed to each other via an ether bond tend to be formed, the selectivity of these raw materials to the alicyclic group-containing ester compound of the present invention is reduced. It tends to decrease.

The acid value in the present invention refers to the compound 100
g is the acid equivalent contained in g, and is determined by the method described in Part 1, Chapter 5 of "Actual Determination of Organic Compounds by Functional Group" (by Weiss, Akira Ejima, first edition of Hirokawa Shoten) . Specifically, the acid value used in the present invention is determined by using a phenolphthalein ethanol solution as an indicator, dissolving a sample Wg in 25 ml of 2-propanol, cooling with ice water, and determining the normality in advance. Sodium hydroxide alcoholic solution (volume of 2-propanol: volume of water =
The titration is carried out according to 1: 1), and from the titration amount Aml of the sodium hydroxide alcoholic solution at the end point, it is determined by the following formula. Acid value (equivalent / 100 g) = (A × N) / (10 × W))

In the method for producing an alicyclic group-containing ester compound of the present invention, a commonly used known transesterification catalyst can be suitably used.

Examples of such a catalyst include hydrides, oxides, hydroxides, alcoholates, amides and salts of alkali metals. Examples of the alkali metals include lithium, sodium, potassium, rubidium and cesium, and lithium, sodium and potassium are particularly preferably used. In the present invention, alcoholates of alcohols such as unsaturated alicyclic alcohols used for transesterification in the present invention may be used. Further, the salts of alkali metals are those of organic acids or inorganic acids, for example, acetate, propionate, benzoate, stearate, carbonate, hydrogencarbonate, phosphate, borate, C1-C4 stannates or antimonates, stannates and the like can be mentioned.
In the present invention, among these, hydroxides, oxides, alcoholates, carbonates, hydrogencarbonates of alkali metals can be particularly preferably used, and alcoholates and hydroxides are preferred. It can be more preferably used. In the present invention, these catalysts are usually used in the reaction mixture to be reacted.
0.0001-20% by weight, preferably 0.001-10
% By weight, particularly preferably from 0.005 to 5% by weight.

Further, a substance which forms a complex with an alkali metal compound such as crown ethers and polyethylene glycols may be used. Such a complexing agent can be used in a range of 0.1 to 200 mol% based on the alkali metal compound.

In the production method of the present invention, salts or complexes of titanium, tin or zirconium can be suitably used as a catalyst. Examples of such catalyst systems include titanium alkoxides, titanium acetate, titanium acetylacetonate, butylstannic acid, tin alkoxides,
Dimethyltin, dibutyltin oxide, dibutyltin dilaurate, tributyltin hydride, tributyltin chloride, zirconium alkoxides, zirconium (IV) halides,
Zirconium nitrates, zirconium acetylacetonate, and the like. These may be used alone or in combination of one or more. Examples of the above alkoxides include methoxide, ethoxide, propoxide, butoxide and the like. In the present invention,
Titanium alkoxides, tin alkoxides, dibutyltin oxide and zirconium alkoxide can be particularly preferably used, and titanium alkoxides and dibutyltin oxide can be more preferably used. In the present invention, the use amount of these catalysts is 0.0001 to 20% by weight based on the reaction mixture,
It is preferably in the range of 0.001 to 10% by weight.

As the catalyst that can be used in the production method of the present invention, nitrogen-containing salts as described in US Pat. No. 4,062,884 may be used. Examples of these are triethylamine, tributylamine, methylbenzylamine, dimethylcyclohexylamine and the like. These can be used in the present invention in the range of 0.0001 to 10% by weight based on the reaction mixture.

Further, as a catalyst that can be used in the production method of the present invention, thallium compounds such as oxides,
Hydroxides, carbonates, bromides, chlorides, fluorides, cyanates, phosphonates, acetates, nitrates, thallium methylate, thallium ethylate, and the like can be used. These amounts are generally from 0.0001 to 10% by weight, based on the reaction mixture.

Further, as a catalyst which can be used in the present invention,
Ion exchange resins having tertiary amines or quaternary ammonium groups as functional groups, antimony compounds such as antimony oxide, manganese compounds such as manganese acetate,
Phosphines such as tributylphosphine and triphenylphosphine; arsines such as trimethylarsine, tributylarsine and triphenylarsine; stibines such as triphenylstibine; sulfur compounds such as diphenylsulfide and diphenyldisulfide; and selenium such as diphenylselenide. Onium salts such as compounds, triphenylphosphonium halide (chlorine or bromine), tetraphenylphosphonium halide (chlorine, bromine, or iodine), and tetraphenylarsonium halide (chlorine, bromine, and iodine) are included.

In the process for producing an alicyclic group-containing ester compound according to the present invention, the transesterification temperature is usually 5
The range is 0 to 250 ° C. The preferred temperature range is 70-2
00 ° C, particularly preferably in the range of 80 to 180 ° C. When the temperature exceeds 250 ° C., a side reaction tends to occur and the yield decreases. At 50 ° C. or lower, the reaction rate is low, and the industrial productivity is low. The reaction temperature may be constant, or the temperature may be controlled in a stepwise or continuous manner.

The reaction system of the present invention may be a pressure system, a normal pressure system,
Or it is a decompression system. In particular, a preferable method of the present invention is a normal pressure or reduced pressure system. For example, by gradually reducing the pressure from normal pressure to removing the alkyl alcohols generated by transesterification from the reaction system, the equilibrium reaction is performed. Advantageous methods are desirable.

When the reaction is carried out in a normal pressure system, a known method such as bubbling an inert gas such as nitrogen into the reaction atmosphere or the reaction solution or increasing the liquid area with respect to the reaction atmosphere is used. It is desirable to remove the alkyl alcohols generated by transesterification from the reaction solution in order to improve the reaction generation rate and the yield. In the present invention, for example, the general formulas (11) and (1)
2) the conversion of the ester compound represented by 2) is 30% or more;
Further, a method may be employed in which the reaction is carried out at normal pressure to 50% or more, particularly 70% or more, and then the pressure is reduced to improve the conversion.

When the reaction is carried out under reduced pressure, if the alcohol compound used as a starting material tends to be removed from the reaction system at the same time as the alkyl alcohols resulting from the reaction, the starting alcohol compound may be contained in the reaction system. It is necessary not to run short.

The degree of vacuum at the time of pressure reduction depends on the vapor pressure of the alkyl alcohol produced by the transesterification, the alcohol compound used as a raw material, and the reaction temperature, but is usually in the range of 0.01 torr to normal pressure. In particular, 0.1 torr or more is preferable. The degree of vacuum may be changed stepwise or continuously, for example, by increasing the vacuum at the end of the reaction or after the end of the reaction, to improve the conversion of the raw material, and further used the raw material remaining in the reaction system. Excess alcohol compounds and alkyl alcohols resulting from transesterification may be removed from the reaction system.

In the present invention, a solvent may be used during the transesterification reaction as long as the reaction is not inhibited or the product is not affected. Examples of such a solvent include, but are not limited to, hydrocarbons such as toluene, xylene, and ethylbenzene, and halides thereof.

In the present invention, as long as the alicyclic group-containing ester compound of the present invention obtained in the above transesterification reaction does not adversely affect its use, the starting alcohol compound and the alkyl alcohol produced by transesterification, A catalyst or the like may remain. Further, the catalyst can be removed by a known method such as washing with various solvents such as water, a liquid-liquid extraction method, and in the case of a heterogeneous catalyst, a filtration method, an ion exchange resin method, an adsorption method using silica gel, or the like. . When removing these catalysts, the reaction product may be diluted with a solvent. The solvent is not particularly limited as long as it does not denature the product, and hydrocarbons such as hexane, toluene, and xylene; ketones such as acetone; esters such as ethyl acetate; and halogens such as methylene chloride and chloroform. Hydrocarbons and the like can be suitably used.

In the alicyclic group-containing ester compound of the present invention, the compound having only a carbon-carbon unsaturated double bond may be an organic carboxylic acid halide and the above unsaturated alicyclic alcohol compound or the unsaturated alicyclic alcohol compound. It can be obtained by reacting with an alcohol compound comprising a formula alcohol compound and allyl alcohol.

The organic carboxylic acid halide referred to in the present invention is an organic compound having two or more acid halide groups, and means compounds represented by the following general formulas (11) and (12). .

[0109]

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Wherein A ₁ is a halogen atom, A ₂ and A ₃ are each independently a hydrogen atom or an acid halogen group, and A ₂ and A ₃ are not simultaneously hydrogen atoms.
A, D, and E are a hydrogen atom, a halogen atom, and a carbon atom of 12;
It represents an alkyl group or an alkoxyl group which may have the following substituents. )

[0111]

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(In the formula, R is an aliphatic hydrocarbon group having 5 to 50 carbon atoms and a naphthalene skeleton. X is an acid halogen group, and x is an integer of 2 or more.)

In the above general formulas (11) and (12), halogen means chlorine, fluorine, bromine and iodine. In general, compounds that are chlorine are preferred because they are readily available.

In the above production method, the amount of the alcohol compound used as a raw material is, for example, when all the acid halide portions of the raw acid halide compound are esterified,
It is 1 equivalent to the acid halide portion. However, in order to complete the reaction sufficiently, the amount used is desirably 1
Not less than 100 equivalents, preferably not less than 1.1 equivalents 3
It is 0 equivalent or less.

In the present invention, it is desirable to use a solvent for the reaction using the above-mentioned acid halide, as long as the solvent does not react with the acid halide, the alcohol compound used as a raw material, and the produced ester compound. There are no particular restrictions. For example, hexane, toluene,
Examples thereof include, but are not limited to, hydrocarbons such as xylene, halides such as methylene chloride and chloroform, nitrogen-containing organic solvents such as dimethylformamide and N-methylpyrrolidone, and sulfur-containing organic solvents such as dimethylsulfoxide. The use amount of these solvents is not particularly limited, but is usually within a range from 0.1 to 200 parts by weight based on 1 part by weight of the compound represented by the general formula (4) used as a raw material.

When the halogen is chlorine, the reaction is a dehydrochlorination reaction, and it is desirable to coexist with a hydrochloric acid scavenger for the purpose of scavenging hydrochloric acid generated in the reaction system. As the hydrochloric acid scavenger, generally known compounds capable of forming a salt with hydrochloric acid, such as pyridine and triethylamine, which have the ability to scavenge hydrochloric acid, are suitably used. The use amount of these hydrochloric acid scavengers is usually equal to or more than the amount of hydrochloric acid generated in the reaction system.

In the above production method of the present invention, it is desirable to add a raw material alcohol compound to a system comprising the above organic carboxylic acid halide compound, a solvent and a hydrochloric acid scavenger. When two or more alcohol compounds used as raw materials are used, they may be added simultaneously as a mixture, or may be added separately in two or more stages.

During the reaction, the temperature may be controlled by cooling or heating within a range that does not affect the product. Further, the rate of addition of the alcohol compound may be controlled for the purpose of controlling heat generation due to the reaction or suppressing by-products. Also,
In order to increase the reaction rate, a method of cooling during the addition of the alcohol compound and heating after the addition is also effective. The reaction temperature carried out in the present invention is usually -10 to 200C,
Desirably, it is in the range of 10 to 150 ° C.

The above reaction may be carried out under pressure using an autoclave or the like, or may be carried out under normal pressure or further under reduced pressure.

After the completion of the reaction, the alcohol and the solvent used for the unreacted raw materials can be removed, for example, by reducing the pressure. Further, for example, by washing with water, the hydrochloride of the hydrochloric acid scavenger that has captured the hydrochloric acid can be removed.

The alicyclic group-containing ester compound of the present invention obtained by the above-described method is obtained by epoxidizing a carbon-carbon unsaturated double bond contained in the compound using an oxidizing agent. Among the alicyclic group-containing ester compounds, compounds containing an epoxidized alicyclic ester group or a glycidyl group can be obtained.

As the oxidizing agent used in the present invention, a carbon-carbon unsaturated double bond in an unsaturated alicyclic group or an allyl group contained in the alicyclic group-containing ester compound obtained above can be epoxidized. There is no particular limitation as long as it is a thing. Examples of these oxidizing agents include t-butyl hydroperoxide, cyclohexene hydroperoxide, organic peroxides such as cumene hydroperoxide, formic acid,
Examples include percarboxylic acids such as peracetic acid, perpropionic acid, trifluoroperacetic acid, and m-chloroperbenzoic acid, hydrogen peroxide, and molecular oxygen. Above all, reactivity, selectivity,
The oxidizing agent is preferably hydrogen peroxide or percarboxylic acids from the viewpoint of easy purification.

As another method for epoxidizing a carbon-carbon unsaturated double bond, for example, a halohydrin compound in which chlorohydrin or the like is added to the double bond is once formed, and then the epoxy is obtained by dehydrochlorinating with an alkali. The halohydrin method for obtaining compounds is generally known. However, in the case of the halohydrin method, for example, an unreacted halohydrin structure tends to remain in the obtained epoxy compound after the subsequent dehydrochlorination step, and the hydrolyzable halogen tends to remain in the product. In particular, when the alicyclic group-containing ester compound obtained in the present invention has a high boiling point and ordinary distillation operation is difficult, purification becomes difficult.

The case where the oxidizing agent is hydrogen peroxide will be described below. When the oxidizing agent is hydrogen peroxide, various epoxidation catalysts are usually used in combination. As the epoxidation catalyst, any known epoxidation catalyst can be used in the present invention as long as the epoxidation of the carbon-carbon unsaturated double bond proceeds sufficiently in the presence of hydrogen peroxide, and there is no particular limitation. . For example, titanium compounds such as titanosilicalite (for example, a commercial catalyst TS-1 in which titanium is supported on silica, which is well known to those skilled in the art), tungstic acid and salts thereof, phosphotungstic acid and salts thereof, and the like. Tungsten-containing compounds, molybdenum-containing compounds such as molybdic acid and its salts, phosphomolybdic acid and its salts, heteropoly acids, vanadium-containing compounds, rhenium-containing compounds, cobalt-containing compounds, arsenic-based compounds, boron-based compounds, antimony-based compounds, and transitions Metal porphyrin complexes and the like. These may be used alone or as a mixture of two or more kinds.When tungstic acid, molybdic acid or a salt thereof is used as an epoxidation catalyst, they may be used in combination with acids such as phosphoric acid. good.

The amount of these catalysts used is usually 0.001 to 30 parts by weight per 100 parts by weight of the alicyclic group-containing compound of the present invention.
It is suitable that the amount be in the range of 0.01 to 20 parts by weight, preferably 0.01 to 20 parts by weight.

In the present invention, when performing epoxidation using hydrogen peroxide and the above-mentioned catalyst, it is desirable to use a solvent in that the reaction speed is high and the handling of the reaction solution is easy. At this time, the solvent used is not particularly limited as long as it has a solubility of usually about 0.1% by weight or more in the alicyclic group-containing ester compound used as a raw material and the obtained epoxidized product and does not generate by-products. For example, aromatic hydrocarbon compounds such as benzene, toluene and xylene, aliphatic hydrocarbon compounds such as hexane and cyclohexane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, chloroform, methylene chloride, carbon tetrachloride, dichloroethane And halogenated hydrocarbon compounds such as tetrachloroethane, chlorobenzene and dichlorobenzene, acetates such as ethyl acetate, isopropyl acetate and butyl acetate, and ethers such as ethylene glycol dimethyl ether. The use amount of these solvents is not particularly limited, but is usually in the range of 0.1 to 200 ml per 1 g of the alicyclic group-containing compound of the present invention.

The hydrogen peroxide used has a concentration of 0.0
A solution in the state of 1 to 100% is suitably used. Usually, a solution in the form of an aqueous solution of 5 to 80%, preferably 25 to 70% can be easily obtained industrially, and special equipment and the like are required. It can be used most preferably because it is not required. The amount of the hydrogen peroxide to be used is theoretically one equivalent to the carbon-carbon double bond in the alicyclic group-containing ester compound used as a raw material, but is usually 1.01 to 1:10, preferably 1.0 to 1:10. 1:
It is used in the range of 1.01 to 1: 2.

The alicyclic group-containing ester compound of the present invention is obtained by carrying out an epoxidation reaction using the above-mentioned catalyst, solvent and aqueous solution of hydrogen peroxide.
Since the reaction is a two-phase reaction composed of an aqueous phase, the stirring efficiency greatly affects the epoxidation reaction rate. In the present invention, it is useful to increase the stirring efficiency or increase the epoxidation reaction rate by using a reactor with a baffle or the like to increase the stirring efficiency.

When a tungsten-containing compound such as phosphotungstic acid or sodium tungstate or a molybdenum-containing compound is used as the above catalyst, a phase transfer catalyst such as an onium salt is used for the purpose of increasing the epoxidation reaction rate. It is desirable to use them together. Examples of the onium salt include those represented by the general formula R ₁ R ₂ R ₃ R ₄ M ⁺ Q ⁻ (R _{1 to} R ₄ are alkyl groups having 1 to 50 carbon atoms which may have a hydroxyl group, and M represents nitrogen or phosphorus, and Q ⁻ represents a halogen ion or an inorganic anion.), And quaternary ammonium salts and quaternary phosphonium salts. Examples of the alkyl group in the onium salt include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a cyclohexyl group, and the like.
Examples of the halogen ion include chlorine ion, bromide ion and iodine ion, and examples of the inorganic ion include hydroxyl ion and sulfite ion. Specific examples of the quaternary ammonium salt include a cetylpyridinium salt, a trioctylmethylammonium salt, a tetrahexylammonium salt, a tetrapropylammonium salt, a tetrabutylammonium salt, an alkylpicoliniumammonium salt, an alkylimidazoline salt and the like. Also, 4
Specific examples of the secondary phosphonium salt include a tetrabutylphosphonium salt, a tetrapropylphosphonium salt, a trioctylmethylphosphonium salt, a trioctylethylphosphonium salt, and a tetrahexylphosphonium salt. These are used alone or in combination of two or more.
These onium salts, for the alicyclic group-containing compound used,
Usually 0.001 to 30% by weight, preferably 0.01 to 1%
Used at 5% by weight.

Further, the onium tungstate salt or the like is adjusted by mixing the epoxidation catalyst such as sodium tungstate or phosphotungstic acid with the phase transfer catalyst, and then added to the reaction system. You may.

When the epoxidation reaction is carried out in the above-described two-phase oil-water phase system, the pH of the aqueous phase containing hydrogen peroxide is 0.3 to 6, more preferably 0.5 to 5, especially 0.5 to 5. 1.
It is desirable to be in the range of 0-4. When the pH is 6 or more, the epoxidation reaction rate is low, and when the pH is 0.3 or less, the generated epoxy groups tend to be cleaved in the reaction system, which is not desirable. The pH of the aqueous phase can be adjusted with, for example, phosphoric acid or hydrochloric acid.

The reaction using hydrogen peroxide is not particularly limited as long as the temperature is within a temperature range in which the rate of self-decomposition of hydrogen peroxide can be kept low.
C, more preferably in the range of 15 to 70C. The reaction may be carried out at normal pressure, or may be carried out under pressure in an autoclave, for example. The reaction time depends on the reaction conditions such as the amount of the alicyclic compound of the present invention to be used, the amount of the catalyst, the concentration of hydrogen peroxide and the temperature.
Time, preferably in the range of 0.5 to 100 hours, is appropriate.

The reaction product obtained by the above-described synthesis method is filtered, solvent extracted, washed with water, washed with alkaline water, separated by a column using silica gel, etc., purified by an ion exchange resin, cooled and precipitated. , Etc., can be easily purified by combining generally known means, and the alicyclic group-containing ester compound having an epoxy group of the present invention can be obtained.

Hereinafter, a method for producing an alicyclic group-containing ester compound containing an epoxidized alicyclic ester group of the present invention will be described.
A production method using an alicyclic epinol will be described.

The alicyclic group-containing ester compound having an epoxidized alicyclic ester group of the present invention can be prepared by using an organic ester compound represented by the above general formula (9) or (10) and an alicyclic epinol compound. It can be obtained by transesterification. When the alicyclic group-containing ester compound of the present invention has an unsaturated alicyclic ester group and an epoxidized alicyclic ester group at the same time, using the unsaturated alicyclic alcohol and the alicyclic epinol compound, It can be obtained by transesterification with the organic ester compound. Further, when an allyl ester group or a glycidyl ester group is contained, the alicyclic group-containing ester compound of the present invention can be obtained by using allyl alcohol or 2,3-epoxypropanol together with the alicyclic epianol.

The alicyclic epinol compound referred to in the present invention is 2,3-epoxycyclopentane-formula represented by the following formula:
1-ol or 2,3-epoxycyclohexane-
It means 1-ol.

[0137]

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In the transesterification reaction using the alicyclic epinol compound, the amount of the alcohol compound containing an alicyclic epinol used as a raw material is stoichiometrically equivalent to the raw material organic ester compound. In order to make the equilibrium of the transesterification reaction advantageous to the production system, the equivalent is usually at least equivalent, more preferably at least 1.2 equivalent, particularly preferably at least 2 equivalent and not more than 20 equivalent. When an alicyclic group-containing ester compound of the present invention containing an unsaturated alicyclic ester group or a glycidyl ester group is also obtained by the above-mentioned transesterification method, the respective functional groups may have a desired ratio. Unsaturated alicyclic alcohol compounds and a few
-Epoxy propanol may be charged at the same time as the alicyclic epinol compound, or may be produced by transesterification with only one raw material and transesterifying with the other raw material as a subsequent step, In the case where the reaction is performed in two stages as described above, the amount of the alicyclic epinol compound used is not limited as long as an alicyclic epoxy compound having a desired structure is obtained.

Also, in the transesterification reaction using the alicyclic epinol compound of the present invention, the acid value of the compound represented by the above general formulas (9) and (10) used as a raw material is 0.05 equivalent /. 100 g or less, more preferably 0.005 equivalent / 100 g or less,
Particularly preferably, it is 0.001 equivalent / 100 g or less.
If the acid value is as high as 0.05 equivalent / 100 g or more, the epoxy ring of the alicyclic epinol compound used as a raw material is cleaved and further polymerized to form a high-boiling substance which is difficult to separate. There is a tendency.

In the transesterification reaction using an alicyclic epinol compound, the above-mentioned generally known transesterification catalyst can be suitably used. In particular, hydrides, oxides, hydroxides, alcoholates, amides or salts of alkali metals can be suitably used. Examples of the alkali metals include lithium, sodium, potassium, rubidium and cesium, and lithium, sodium and potassium are particularly preferably used. In the present invention, alcoholates of alicyclic epinol compounds used for transesterification in the present invention may be used.

In the above production method by transesterification, the reaction temperature is usually in the range of 50 to 200 ° C.
A preferred temperature range is 70-170 ° C., particularly preferably 80-170 ° C.
It is in the range of 150 ° C. When the temperature exceeds 200 ° C., side reactions such as cleavage of the epoxy ring of the alicyclic epinol compound tend to occur and the yield decreases. Also, 5
Below 0 ° C., the reaction rate is low and the industrial productivity is low. The reaction temperature may be constant, or the temperature may be controlled in a stepwise or continuous manner.

Further, the reaction system of the present invention may be a pressurized system, a normal pressure system,
Or it is a decompression system. In particular, a preferable method of the present invention is a normal pressure or reduced pressure system. For example, by gradually reducing the pressure from normal pressure to removing the alkyl alcohols generated by transesterification from the reaction system, the equilibrium reaction is performed. Advantageous methods are desirable.

When the reaction is carried out in a normal pressure system, known methods such as bubbling an inert gas such as nitrogen into the reaction atmosphere or the reaction solution, or increasing the liquid area with respect to the reaction atmosphere are used. It is desirable to remove the alkyl alcohols generated by transesterification from the reaction solution in order to improve the reaction generation rate and the yield.

When the reaction is carried out under reduced pressure, if the alcohol compound used as a starting material tends to be removed from the reaction system at the same time as the alkyl alcohols resulting from the reaction, the starting alicyclic compound may be contained in the reaction system. It is necessary to ensure that there is no shortage of epinol compounds.

The degree of vacuum at reduced pressure depends on the vapor pressure of the alkyl alcohol produced by the transesterification, the alicyclic epinol compound used as a raw material, and the reaction temperature, but is usually from 0.01 torr to normal pressure. , And more preferably 0.1 torr or more. The degree of vacuum may be changed stepwise or continuously, for example, by increasing the vacuum at the end of the reaction or after the end of the reaction, to improve the conversion of the raw material, and further used the raw material remaining in the reaction system. An excessive amount of an alcohol compound such as an alicyclic epinol compound or an alkyl alcohol produced as a result of transesterification may be removed from the reaction system.

In the present invention, a solvent may be used during the transesterification reaction as long as the reaction is not inhibited or the product is not affected. Examples of such a solvent include, but are not limited to, hydrocarbons such as toluene, xylene, and ethylbenzene, and halides thereof.

In the production method of the present invention using an alicyclic epinol, the starting alicyclic epinol compound may be used as long as the alicyclic group-containing ester compound of the present invention obtained in the above transesterification does not adversely affect its use. Alkyl alcohols generated by ester exchange and transesterification, used catalysts, and the like may remain. Further, the catalyst can be removed by a known method such as washing with various solvents such as water, a liquid-liquid extraction method, and in the case of a heterogeneous catalyst, a filtration method, an ion exchange resin method, an adsorption method using silica gel, or the like. . When removing these catalysts, the reaction product may be diluted with a solvent. The solvent is not particularly limited as long as it does not denature the product, and hydrocarbons such as hexane, toluene, and xylene; ketones such as acetone; esters such as ethyl acetate; and halogens such as methylene chloride and chloroform. Hydrocarbons and the like can be suitably used.

Further, the production method of the present invention by transesterification using an alicyclic epinol can be suitably used even in an aliphatic hydrocarbon group having 4 or more carbon atoms in the general formula (4).

Further, the alicyclic ester compound of the present invention having an epoxidized alicyclic ester group can be obtained by reacting the above-mentioned alicyclic epinol with the above-mentioned organic halide compound. This reaction can be carried out under the same conditions as in the reaction between the acid halide and the alcohol compound.

By the method described above, an alicyclic group-containing ester compound having a novel structure of the present invention can be obtained in high yield.

In the alicyclic group-containing ester compound of the present invention, as the compound having two or more epoxy groups, a curing agent used for a usual curing reaction of an epoxy compound can be suitably used. The curing agent is capable of forming a crosslinked structure by reacting with an epoxy group by light or heat, and is a compound containing a plurality of acidic or basic active hydrogens added to the epoxy group, or a catalyst having an epoxy group. It is an acidic or basic compound that is to be polymerized. Compounds used as these curing agents include acid or acid anhydride-based curing agents, amine-based curing agents, polyaminoamide-based curing agents obtained by reacting polycarboxylic acids with polyalkylene polyamines, imidazoles, and polymercaptan-based curing agents. It is a curing agent, a Lewis acid, a Bronsted acid, a phenolic compound or a mixture thereof.

Examples of the acid or acid anhydride-based curing agent include polyazeleic anhydride, polyadipic anhydride,
Aliphatic carboxylic anhydrides such as dodecenyl succinic anhydride, polysebacic anhydride, poly (phenylhexadecane diacid) anhydride, poly (ethyl octadecane diacid) anhydride and their carboxylic acids, methylcyclohexenedicarboxylic anhydride, Alicyclic carboxylic acid anhydrides such as alkyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride and the like, and their carboxylic acids and anhydrides Aromatic carboxylic anhydrides such as phthalic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate and their carboxylic acids, and carboxylic acid terminated Or in the chain Resins such as polyester or polyamide having, further include resins having a copolymer containing a (meth) acrylic acid.

Examples of the amine curing agent include, for example,
Ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tri (methylamino) hexane, methyliminobispropylamine, dipropylenediamine,
Aliphatic amines such as hexamethylenediamine and diethylaminopropylamine, cyclohexanediamine, isophoronediamine, mensendiamine, diaminodicyclohexylmethane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-bis (aminomethyl) cyclohexane A cyclic amine such as N-aminoethylpiperazine, monocyclic aromatic amine such as 2,4-diaminotoluene, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine;
Diaminodiphenylsulfones such as 4,4'-diaminodiphenylsulfone and 3,3'-dimethyl-4,4'-diaminodiphenylsulfone;4,4'-diaminodiphenylmethane;3,3'-dimethyl-4,4' -Diaminodiphenylmethane, 3,3'-diethyl-4,4'-
Aromatic amines such as diaminodiphenylmethanes such as diaminodiphenylmethane, dimethyldiphenylethers, diaminodiphenylketones and diaminodiphenylpropanes; or 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxa Spiro (5,5)
Spirocyclic amines such as undecane and the like, and mixtures thereof.

Examples of the compound containing a basic active hydrogen include organic acid dihydrazide compounds such as dicyandiamide and adipic dihydrazide.

Examples of imidazoles include 2-methylimidazole and 2-ethyl-4-methylimidazole.

Examples of the phenol compound include bisphenol A, bisphenol F, bisphenol AD, dihydroxybenzene, and phenol resin.

The above curing agents may be used alone or as a mixture in which two or more kinds are mixed in a desired ratio.

With respect to the alicyclic group-containing ester compound of the present invention, the above curing agent can be selected according to its use. For example, when flexibility is required, an aliphatic curing agent can be used, and when a high glass transition point is required, it is desirable to use an aromatic curing agent.

The amount of the curing agent to be used can be appropriately selected depending on the equivalent of the epoxy group of the alicyclic group-containing ester compound, the structure of the curing agent and the number of functional groups. For example, the equivalent ratio of the functional group of the curing agent to the epoxy group is 0.3 to 1.8,
Preferably it is in the range of 0.5 to 1.2. When the corresponding amount ratio is lower than 0.3 or higher than 1.8, the obtained cured product tends to contain a large amount of unreacted substances and low molecular weight oligomer substances, and mechanical properties deteriorate.

When the alicyclic group-containing ester compound of the present invention is used as an epoxy compound as various cross-linking structure forming agents or resin additives, it may be used alone or two or more of the alicyclic group-containing alicyclic group-containing compounds of the present invention. Ester compounds may be used as a mixture. When used as a mixture, the properties are 25
Desirably, it is an amorphous solid having a softening point of 120 ° C. or higher, and a crystalline solid having a melting point of 160 ° C. or lower. In particular, a liquid solid at 25 ° C. or a crystalline solid having a melting point of 160 ° C. or less is preferred in terms of easy handling. When the melting point exceeds 160 ° C., since the temperature is at or near the usual curing temperature, a cured product having a non-uniform curing state tends to be used. When it is crystalline, it generally has a low viscosity when dissolved, is easier to handle than amorphous solids, and is easier to knead with a curing agent, resin, or the like.

The alicyclic group-containing ester compound of the present invention may be used as a mixture with another epoxy compound. Here, other epoxy compounds, excluding the alicyclic group-containing ester compound of the present invention, mean compounds containing more than one epoxy group in the molecule on average, for example, those derived from alcohols and phenols. Glycidyl ether compounds, glycidylamine compounds derived from amines, glycidyl ester compounds derived from acids and acid anhydrides, and alicyclic epoxy resin compounds.

Examples of the alcohols include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclopentanediol, cyclohexanedimethanol, cyclododecanediol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol AD, glycerin, diethylene glycol, triethylene glycol, tetraethylene glycol and the like.

As phenols, hydroquinone,
Methylhydroquinone, trimethylhydroquinone, tetramethylhydroquinone, ethylhydroquinone, diethylhydroquinone, vinylhydroquinone, propylhydroquinone, butylhydroquinone, hexylhydroquinone, cyclohexylhydroquinone, octylhydroquinone, 4-
Phenylmethylhydroquinone, 4-methylpentylhydroquinone, nitrohydroquinone, resorcinol, methoxyresorcinol, dimethoxyresorcinol, ethoxyresorcinol, methylresorcinol, dimethylresorcinol, trimethylresorcinol, ethylresorcinol, diethylresorcinol, propylresorcinol, butylresorcinol, pentylresorcinol, pentylresorcinol, pentylresorcinol , Phenyl resorcinol, heptyl resorcinol, octyl resorcinol, nonyl resorcinol, ethyl methyl resorcinol, ethyl pentyl resorcinol, nitro resorcinol, dinitro resorcinol, catechol, methyl catechol, ethyl catechol, propyl catechol, butyl catechol, -(1,1-dimethylethyl) catechol, pentylcatechol, 4- (1,1-dimethylpropyl) catechol, hexylcatechol, cyclohexylcatechol, nonylcatechol, dimethylcatechol, nitrocatechol, dinitrylcatechol, methoxycatechol, propoxy Catechol, dimethyl catechol, dinitrocatechol, trimethoxycatechol, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, trihydroxydiphenyldimethylmethane, oxybisphenol, thiobisphenol, 4,4′-sulfinylbisphenol,
Examples thereof include 4,4′-isobitylidenebisphenol, methylidenebiscatechol, dihydroxydiphenyl, pyrogallol, fluoroglycine, salicylic acid, anacardic acid, novolak resin, cresol novolak resin, and the like, and halides thereof.

Examples of amines include allylamine, isopropylamine, 3,3′-iminobis (propylamine), methylamine, 2-ethylhexylamine,
-(2-ethylhexyloxy) propylamine, 3-
Ethoxypropylamine, dibutylaminopropylamine, butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, N-methyl-3,3′-iminobis (propylamine), 3-methoxypropylamine, isocyanurate, diethylenetriamine, Triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, bis (hexamethylene) triamine, 1,3,6-trisaminomethylhexane, trimethylhexamethylenediamine, diethyleneglycol / bispropylenediamine, diethylaminopropylamine, mensendiamine, Isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine, metaxylenediamine, metaf Enylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylmethane, 1,3-bisaminomethylcyclohexane, bismethylaminodiphenylamine, diaminodiphenylamine, diaminodibenzylamine, triaminotribenzylamine, diaminoxylene, xylylenediamine, diaminomesitylene, Tetrahydronaphthylenediamine, naphthylenediamine, methylbenzidine,
Diaminodibenzyl, diaminomethyldiphenylmethane, diaminodimethyldiphenyl, diaminofluorene, diaminostilbene, bisaminophenylacetylene, diaminoanthracene, diaminodinaphthyl, tetraphenyl-bisaminophenylxylol, ethylene glycol-bisaminophenylether, diaminodiphenylether, diamino Diphenyl sulfide, diamino diphenyl disulfide, hydroquinone-bisaminophenyl ether, diamino dibenzyl sulfide, diamino naphthol, oxybenzidine, diamino diphenyl carbinol, diamino triphenyl carbinol, diamino catechol, diamino dioxy phenanthrene, diamino pyrogallol, diamino fluorogluol Shin, etc. .

Further, polybasic acids and acid anhydrides are compounds having one or more acid anhydride rings or two or more carboxyl groups, for example, phthalic anhydride, maleic anhydride, phthalic acid, maleic acid, isophthalic acid. Acid, terephthalic acid, methyl terephthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 4,4'-carbonyldibenzoic acid, 4,4'-oxydibenzoic acid, 4,4'-sulfonyldibenzoic acid, phenylene dibenzoic acid Acid, succinic acid, fumaric acid, glutaric acid, cyclopropanedicarboxylic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid,
Cyclohexanedicarboxylic acid, 1,4- (2-norbornene) dicarboxylic acid, 2,3-bicyclo [2.2.2]
Octanedicarboxylic acid and its anhydride, cyclohexanediacetic acid and its anhydride, 1,3-adamantanedicarboxylic acid, adipic acid and the like can be mentioned.

In the present invention, an epoxy resin having a single composition selected from the above-mentioned alcohols, phenols, amines, polybasic acids, and acid anhydrides may be used, or two or more copolymers may be used. Or a mixture.

The alicyclic epoxy resin is a cycloaliphatic compound having an epoxycyclohexyl ring in the molecule, for example, bis (3,4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexyl Methyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) oxalate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3,4-epoxycyclohexylmethyl) pimelate , 6-methyl-
3,4-epoxycyclohexylmethyl-6-methyl-
3,4-epoxycyclohexanecarboxylate,
3,4-epoxy-1-methylcyclohexylmethyl-
3,4-epoxy-1-methylcyclohexanecarboxylate, 3,4-epoxy-5-methyl-cyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, vinylcyclohexene dioxide, dipentenedionoxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanemethane and the like.

The epoxy equivalent of the epoxy compound used in the present invention depends on its molecular weight.
Those having a weight of 80 to 10000 g / equivalent are suitably used.
The epoxy resin used in the present invention may be liquid or solid at room temperature (25 ° C.).

When the alicyclic group-containing ester compound of the present invention is used in combination with another epoxy resin, the mixing ratio of the two depends on the application field and the like. Ring group-containing compound: other epoxy resin) = (1
To 99:99 to 1).

The alicyclic group-containing ester compound of the present invention may contain, if necessary, a reaction accelerator, a reaction diluent, a filler or a reinforcing agent, a trioxide, or the like, in addition to the above-mentioned curing agents and other epoxy compounds. Flame retardants such as antimony, bromo compounds, aluminum hydroxide, dyes and pigments, release agents and flow regulators, plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, defoamers, leveling agents, coloring agents, Titanium dioxide, a solvent and the like can be added, and the application amount can be arbitrarily applied as long as the effects of the present invention are not impaired.

As the reaction accelerator, for example, 2-ethyl-
4-methylimidazole, 2-methylimidazole, 1
Imidazoles such as -benzyl-2-methylimidazole, tertiary amines such as dimethylcyclohexylamine, benzyldimethylamine and tris (diaminomethyl) phenol, 1,8-diazabicyclo (5,4
0) diazabicycloalkenes such as undecene-7 and salts thereof, organometallic compounds such as zinc octylate, tin octylate and aluminum acetylacetone complex, and organic phosphorus compounds such as triphenylphosphine and triphenyl phosphite; Boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride piperidine complex, boron compounds such as triphenyl borate, metal halides such as zinc chloride and stannic chloride, quaternary ammonium compounds, Examples thereof include alkali metal alcoholates such as sodium alcoholate of 4-dihydroxy-3-hydroxymethylpentane, anacardic acid and salts thereof, and phenols such as cardol, cardanol, phenol, nonylphenol, and cresol.

The reaction diluents include butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p
-Sec-butylphenyl glycidyl ether, glycidyl methacrylate, tertiary carboxylic acid glycidyl ester, diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether,
Butanediol diglycidyl ether, diglycidylaniline, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether and the like.

Examples of fillers and reinforcing agents include coal tar, bitumen, woven fabric, glass fiber, asbestos fiber, boron fiber, carbon fiber, aramid fiber, mineral silicate, mica, quartz powder, aluminum hydroxide, bentonite, kaolin Silicate aerogel, and metal powders such as aluminum powder and iron powder.

Examples of the release agent and the flow control agent include silicone, aerosil, colloidal hydrated aluminum silicate, wax, stearate, calcium carbonate, and the like.
Talc and the like.

Examples of the plasticizer include pine oil, low-viscosity liquid polymer, rubber, tar, polysulfide, urethane prepolymer, polyol, diethyl phthalate, dibutyl phthalate, and a polymer of epichlorohydrin, dioctyl phthalate, dioctyl adipate, Cresyl phosphate and the like can be mentioned.

In the case where a curable composition is produced by blending the alicyclic group-containing ester compound of the present invention with these other components, there is no particular limitation such as melt kneading, and a conventional blending method can be applied.

The curable composition comprising the alicyclic group-containing ester compound of the present invention, formulated as described above, is heated or cured by light energy such as ultraviolet light to obtain weather resistance and heat resistance. A cured product having good properties and water resistance can be obtained.

For example, in the case of curing by heating, the curing reaction can be carried out usually at room temperature to 300 ° C., preferably at 80 to 250 ° C. The curing time depends on the composition, but usually ranges from a few seconds to 200 hours.

The alicyclic group-containing ester compound of the present invention can stabilize the acid component and the like contained therein by blending it with a thermoplastic resin containing an organic phosphorus compound as a flame retardant. Examples of the thermoplastic resin include a polycarbonate resin, a polymer alloy comprising a polycarbonate resin and an ABS resin or a HIPS resin, a polyphenylene resin and a resin in which a styrene resin is blended, a styrene resin, a polyamide resin, and a polyolefin resin. Resins, polyester resins, polyacetal resins, polymethyl methacrylate resins, polyvinyl chloride resins, and the like. Among them, polycarbonate resin, polycarbonate resin and ABS resin or HI
It can be suitably used for polymer alloys composed of PS resins, polyphenylene resins, and resins in which styrene resins are blended.

When the alicyclic group-containing ester compound of the present invention is blended with the flame-retardant thermoplastic resin, the amount used is as follows:
Although it depends on the epoxy equivalent of the alicyclic ester compound, the type of the flame retardant used and the acid value thereof, it is usually 0.001 to 30 parts by weight based on 100 parts by weight of the flame retardant.
When the amount is less than 0.001, the effect of stabilizing the acid component is low, and when the amount exceeds 30 parts by weight, the flame retardant effect and the impact resistance of the resin tend to decrease.

The alicyclic group-containing ester compound having a novel structure of the present invention and a method for producing the same will now be described with reference to Examples.

[0182]

[Example] <Measurement method> Nuclear magnetic resonance spectra of nuclear magnetic resonance spectra reaction products, with tetramethylsilane as a reference substance, in using heavy chloroform as a solvent, JEOL JNM-α400 (400MHz) ¹
1 H-NMR spectrum and ¹³ C-NMR data were obtained.

2. Measurement of infrared absorption spectrum (IR) The reaction product was applied to a potassium bromide plate, and Nicolet was
FT-IR spectrometer, Instrument400D, manufactured by Instrument Corporation
Was measured.

[0184] 3. Measurement of Gas Chromatography Measurement of gas chromatography was performed with the following apparatus and conditions. Apparatus: GC-14B manufactured by Shimadzu Corporation Column: GL Science Inc. Capillary column TC-1 (0.25 mm ID, 30 m length) Carrier gas: He Detection: FID Column temperature condition: 20 ° C./min after holding at 60 ° C. for 2 minutes
The temperature is raised to 300 ° C with and kept at 300 ° C for 15 minutes. Sample dissolving solvent: chloroform

[0185] 4. Liquid Chromatography Measurements Develop a solution of the sample dissolved in methanol under the following conditions.
Analysis was performed by detection. Detector: SPD-6A manufactured by Shimadzu Corporation Detection wavelength: 254 nm Developing solution: methanol / water = 8/2 (volume ratio) Developing solution flow rate: 1 ml / min Column: Finepak SILC manufactured by JASCO Corporation
18S Column temperature: 40 ° C

5. Measurement of epoxy equivalent 0.5000 g of compound, 50 parts of n-propyl alcohol
and a solution prepared by dissolving benzyl alcohol (3 ml) and potassium iodide (0.2 g) in distilled water. The mixture was refluxed by heating, then a BTB solution was added as an indicator, and 0.1N hydrochloric acid was used. The epoxy equivalent was measured by an indicator titration method by determining the equivalent point by performing titration.

Example 1 <Synthesis of an alicyclic group-containing ester compound having an unsaturated alicyclic ester group by transesterification>
194 g (1 mol) of dimethyl isophthalate having an acid value of 0.00001 equivalent / 100 g or less was placed in a 1-liter four-necked flask equipped with a nitrogen gas inlet tube and a T-shaped tube with a condenser for distillation. 392 g (4 mol) of -hydroxycyclohexene and 2.4 g of lithium hydroxide (0.4 g).
(1 mol). Next, the tip of the nitrogen inlet tube was set so as to enter the reaction solution, and the solution was bubbled by flowing nitrogen gas.

While stirring, the flask was heated so that the temperature of the reaction solution became 95 ° C.
The reaction was performed at 5 ° C. for 2 hours and at 115 ° C. for 1 hour. During this time,
Through the distillation condenser, methanol containing 3-hydroxycyclohexene was distilled. Then, nitrogen bubbling was stopped, a pressure reducing line was set up from the tip of the distillation cooling tube via a trap, and the temperature was kept at 115 ° C., and the degree of vacuum was reduced to 10 torr over about 3 hours. Hold for 2 hours.

After the completion of the reaction, the temperature of the flask was cooled to room temperature, 500 ml of hexane was added, and the product was dissolved.
Transfer to a liter separatory funnel and add 250m of hexane
1 was added. Then, the operation of adding 500 ml of distilled water and washing the hexane layer was performed five times. The obtained hexane layer was dried over anhydrous magnesium sulfate, and hexane was removed by evaporation. As a result, 324 g of a pale yellow viscous liquid was obtained.

As a result of measurement by gas chromatography, no dimethyl isophthalate as a raw material was observed, and the conversion was 100%. Further, as a result of measurement by liquid chromatography, the area ratio of the main product peak to the entire area of the detected peak was 98%.

The results of elemental analysis of the obtained product are shown in Table 1. FIG. 1 shows the results of IR measurement. Further, each magnetic resonance spectrum was measured, and the following results were obtained. FIG. 2 shows the obtained spectrum.

[0192] ^<1 H-NMR spectrum> δ (ppm): 7.40~8.80 ( 4H, protons located on the carbon atom in the aromatic ring) δ (ppm): 5.75~6.15 ( 4H , A proton on a carbon that forms a carbon-carbon unsaturated double bond in the alicyclic group) δ (ppm): 5.45 to 5.60 (2H, on a carbon bonded to an ester oxygen atom in the alicyclic group) Δ (ppm): 1.20 to 2.25 (12H, on a carbon atom that does not form a carbon-carbon unsaturated double bond in the alicyclic group and is not bonded to an ester oxygen atom) Proton) δ (ppm): 7.25 to 7.30 (proton derived from solvent chloroform used during measurement)

From the above results, the viscous liquid obtained in the present example is an alicyclic group-containing ester compound having an unsaturated alicyclic ester group obtained by the following formula (13).

[0194]

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Example 2 <Synthesis of an alicyclic group-containing ester compound having an unsaturated alicyclic ester group by transesterification> The same operation as in Example 1 was performed except that 202 g (1 mol) of dimethyl suberate was used. 333 g of a pale yellow liquid was obtained. As a result of measurement by gas chromatography, dimethyl suberate was not observed as a raw material at all, the conversion was 100%, and the area ratio of the main product peak to the entire detected peak area was 98%.
%Met.

Table 1 shows the results of elemental analysis of the obtained product. FIG. 3 shows the results of IR measurement. Further, each magnetic resonance spectrum was measured, and the following results were obtained. FIG. 4 shows the obtained spectrum.

< ¹ H-NMR spectrum> δ (ppm): 5.65 to 6.02 (4H, proton on carbon which forms carbon-carbon unsaturated double bond in alicyclic group) δ (ppm) : 5.20 to 5.35 (2H, proton on carbon bonded to ester oxygen atom in alicyclic group) δ (ppm): 2.22 to 2.40 (4H, bonded to carbon in ester group) Δ (ppm): 1.24 to 2.20 (20H, does not form a carbon-carbon unsaturated double bond in the alicyclic group and binds to an ester oxygen atom) Protons on carbon atoms, not
And a proton on a carbon in a methylene group that is not bonded to a carbon in the ester group) δ (ppm): 7.25 to 7.30 (proton derived from the solvent chloroform used during measurement)

From the above results, the viscous liquid obtained in this example is an alicyclic group-containing ester compound having an unsaturated alicyclic ester group obtained by the following formula (14).

[0199]

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Example 3 <Synthesis of an alicyclic group-containing ester compound having an unsaturated alicyclic ester group by transesterification>
In a 1-liter four-necked flask equipped with a nitrogen gas inlet tube and a T-shaped tube with a condenser for distillation, 230 g (1 mol) of dimethyl sebacate, 392 g (4 mol) of 3-hydroxycyclohexene, and titanium tetraisoform 2.84 g (0.01 mol) of propoxide was charged. Next, the tip of the nitrogen inlet tube was set so as to enter the reaction solution, and the solution was bubbled by flowing nitrogen gas.

While stirring, the flask was heated so that the temperature of the reaction solution became 120 ° C., and the reaction was carried out at that temperature for 4 hours at 120 ° C., 2 hours at 140 ° C., and 2 hours at 150 ° C. During this time, methanol containing 3-hydroxycyclohexene was distilled off through a condenser for distillation. Then, bubbling of nitrogen was stopped, and a pressure reducing line was set up from the tip of the distillation cooling tube through a trap, and the temperature was reduced to 15 ° C.
While maintaining the temperature at 0 ° C., the degree of vacuum was reduced to 10 torr over about 2 hours, and the pressure was maintained at 10 torr for 2 hours.

After completion of the reaction, the temperature of the flask was cooled to room temperature, 500 ml of hexane was added, and the product was dissolved.
Transfer to a liter separatory funnel and add 250m of hexane
1 was added. Then, the operation of adding 500 ml of distilled water and washing the hexane layer was performed five times. The obtained hexane layer was dried over anhydrous magnesium sulfate and evaporated to remove hexane. As a result, 361 g of a pale yellow viscous liquid was obtained.

As a result of measurement by gas chromatography, no starting material dimethyl sebacate was observed, and the conversion was 1%.
00%. The ratio of the area of the main product peak to the area of the entire detected peak was 99%.

The results of elemental analysis of the obtained product are shown in Table 1. FIG. 5 shows the results of IR measurement. Further, each magnetic resonance spectrum was measured, and the following results were obtained. FIG. 6 shows the obtained spectrum.

[0205] ^<1 H-NMR spectrum> δ (ppm): 5.65~6.00 ( 4H, carbon in alicyclic groups - proton on the carbon to form carbon unsaturated double bond) [delta] (ppm) : 5.20 to 5.35 (2H, proton on carbon bonded to ester oxygen atom in alicyclic group) δ (ppm): 2.20 to 2.35 (4H, bonded to carbon in ester group Proton on carbon in methylene group) δ (ppm): 1.20 to 2.20 (24H, not forming carbon-carbon unsaturated double bond in alicyclic group and bonding to ester oxygen atom Protons on carbon atoms, not
And a proton on a carbon in a methylene group that is not bonded to a carbon in the ester group) δ (ppm): 7.25 to 7.30 (proton derived from the solvent chloroform used during measurement)

From the above results, the viscous liquid obtained in this example is an alicyclic group-containing ester compound having an unsaturated alicyclic ester group obtained by the following formula (15).

[0207]

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Example 4 <Synthesis of an alicyclic group-containing ester compound having an unsaturated alicyclic ester group using an acid halide> A four-liter one-liter unit equipped with a stirrer, thermometer, dropping funnel and reflux condenser 20.3 g of isophthalic acid dichloride (0.
1 mol), 400 ml of chloroform and 40.4 g of triethylamine, and the flask was placed in a water bath at a temperature of 10 ° C. and stirred vigorously. Then, 23.52 g of 3-hydroxycyclohexene (0.
24 mol) was added dropwise over about 30 minutes. After dropping, 10 ° C
For 1 hour, then write the water tank temperature for about 1 hour
And stirred at the same temperature for 3 hours.
For 6 hours.

Then, the temperature of the flask was returned to room temperature, and
The operation of transferring the solution to a liter separatory funnel and washing the chloroform solution with 300 ml of distilled water was repeated five times. After drying the chloroform layer over anhydrous magnesium sulfate,
Evaporation removed chloroform as a solvent and residual 3-hydroxycyclohexene and triethylamine. As a result, 3 pale yellow viscous liquids
2.5 g were obtained.

As a result of measurement by liquid chromatography, the area ratio of the main product peak to the entire area of the detected peak was 98%.

The results of IR measurement and nuclear magnetic resonance spectrum measurement of the obtained product were the same as those obtained in Example 1. The compound obtained in this example was obtained in Example 1. It was the same alicyclic group-containing ester compound as the compound.

Example 5 <Synthesis of an alicyclic group-containing ester compound having an epoxidized alicyclic ester group by epoxidation using hydrogen peroxide> Tungsten was placed in a 500 ml three-necked flask equipped with a stirrer and a thermometer. sodium acid (Na ₂ WO ₄ · 2H ₂
O) (1.649 g, 5 mmol) and 30% hydrogen peroxide solution (51.0 g) were added to prepare a yellow solution. Then 8
A 5% phosphoric acid aqueous solution was added to adjust the pH of the aqueous solution to 1.75.
Was adjusted.

On the other hand, 400 ml of toluene, CH ₃ N
[(CH ₂ ) 7 CH ₃ ] ₃ Cl (Aldrich, Al
iqat336) 1.617 g (4 mmol) and the alicyclic group-containing ester compound 32.6 obtained in Example 1.
g (0.1 mol) of a homogeneous solution was prepared. This was added dropwise to the above aqueous solution using a dropping funnel over about 30 minutes. After completion of the dropwise addition, the mixture was stirred in a high-temperature bath at 41 ° C.
The reaction was completed over time.

After the completion of the reaction, the toluene tank was separated using a separating funnel, and a 1N aqueous sodium thiosulfate solution of 100 m
1, 300 ml of distilled water, 100 ml of a 1N aqueous solution of sodium hydrogen carbonate, and 400 ml of distilled water in this order, and the toluene solution was washed.

The thus obtained toluene solution was dried over anhydrous magnesium sulfate, the anhydrous magnesium sulfate was removed by filtration, 200 ml of toluene was added to the solution for dilution, and 400 g of dry silica gel was further added.
After stirring for 1 hour, the silica gel was removed by filtration, and toluene was removed by evaporating the toluene solution obtained as a filtrate to obtain 35.7 g of a slightly yellow, transparent, highly viscous liquid compound. As a result of analysis by liquid chromatography, the purity of the main product was 98.2%. In addition, as a result of measuring the epoxy equivalent, it was 183 g / equivalent.

The results of elemental analysis of the obtained product are shown in Table 1. FIG. 7 shows the results of IR measurement. Further, each magnetic resonance spectrum was measured, and the following results were obtained. FIG. 8 shows the obtained spectrum.

< ¹ H-NMR spectrum> δ (ppm): 7.50 to 8.80 (4H, proton on a carbon atom in an aromatic ring) δ (ppm): 3.20 to 3.50 (4H , (Proton on carbon bonded to epoxy oxygen in alicyclic group) δ (ppm): 5.30 to 5.40 (2H, proton on carbon bonded to ester oxygen atom in alicyclic group) δ (ppm ): 1.20 to 2.20 (12H, a proton on a carbon atom that does not form a carbon-carbon unsaturated double bond in the alicyclic group and is not bonded to an ester oxygen atom) δ (ppm) : 7.25 to 7.30 (proton derived from chloroform used in measurement)

From the above results, the highly viscous liquid obtained in this example is an alicyclic group-containing ester compound having an epoxidized alicyclic ester group obtained by the following formula (16).

[0219]

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Example 6 <Synthesis of an alicyclic group-containing ester compound having an epoxidized alicyclic ester group by epoxidation using a percarboxylic acid> 33.4 g of the compound obtained in Example 2 (0.1 Mol) was dissolved in 600 ml of chloroform and the solution was cooled with water while drying 20.7 g of dry m-chloroperbenzoic acid.
(0.12 mol) and stirred at room temperature for 12 hours.

After the reaction was completed, 13.3 g of calcium hydroxide was added to the above reaction solution, and the mixture was stirred for 1 hour. Then, the solution was filtered, and chloroform was removed under reduced pressure.
36.5 g of a slightly pale yellow transparent viscous liquid were obtained.

When the epoxy equivalent of the compound was measured, it was 187 g / equivalent, and an epoxy compound was formed.

The results of elemental analysis of the obtained compound are shown in Table 1. FIG. 9 shows the result of the IR measurement. Further, a nuclear magnetic resonance spectrum was measured, and the following results were obtained. FIG. 10 shows the obtained spectrum.

[0224] ^<1 H-NMR spectrum> δ (ppm): 5.00~5.25 ( 2H, protons on carbon linked to the ester oxygen atom in the alicyclic group) δ (ppm): 3.00~ 3.40 (4H, proton on carbon attached to epoxy oxygen in alicyclic group) δ (ppm): 2.25 to 2.45 (4H, carbon on methylene group attached to carbon in ester group) Δ (ppm): 1.20 to 2.10 (20H, proton on carbon atom not bonded to epoxy oxygen in alicyclic group and not bonded to ester oxygen atom, and in ester group Δ (ppm): 7.25 to 7.30 (protons derived from the solvent chloroform used at the time of measurement)

From the above results, the viscous liquid obtained by the above reaction is an alicyclic group-containing ester compound having an epoxidized alicyclic ester group represented by the following formula (17).

[0226]

[Table 1]

[0227]

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Example 7 <Synthesis of an alicyclic group-containing ester compound having an epoxidized alicyclic ester group by epoxidation using a percarboxylic acid> Except that 36.2 g of the compound obtained in Example 3 was used. Performed the same operation as in Example 6 to obtain 39.2 g of a product.
I got

When the epoxy equivalent of the obtained compound was measured, it was 202 g / equivalent, and an epoxy compound was formed.

The results of elemental analysis of the obtained compound are shown in Table 1. FIG. 11 shows the results of IR measurement. Further, a nuclear magnetic resonance spectrum was measured, and the following results were obtained. FIG. 12 shows the obtained spectrum.

< ¹ H-NMR spectrum> δ (ppm): 5.00 to 5.20 (2H, proton on carbon bonded to ester oxygen atom in alicyclic group) δ (ppm): 3.00 to 3.35 (4H, proton on carbon bonded to epoxy oxygen in alicyclic group) δ (ppm): 2.25 to 2.45 (4H, carbon on methylene group bonded to carbon in ester group) Δ (ppm): 1.22 to 2.10 (24H, proton on carbon atom not bonded to epoxy oxygen in alicyclic group and not bonded to ester oxygen atom, and in ester group Δ (ppm): 7.25 to 7.30 (protons derived from the solvent chloroform used at the time of measurement)

From the above results, the compound obtained by the above reaction is an alicyclic group-containing ester compound having an epoxidized alicyclic ester group represented by the following formula (18).

[0233]

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Example 8 <Synthesis of alicyclic group-containing ester compound using alicyclic epinol compound> 100 ml of a 4-tube equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a T-shaped tube with a cooling tube for distillation was attached. In a one-necked flask, 19.4 g (0.1 mol) of dimethyl isophthalate having an acid value of 0.00001 equivalent / 100 g or less, and 45.6 g (0.4 mol) of 2,3-epoxycyclohexane-1-ol. 0.2 g of lithium hydroxide
(0.083 mol). Next, the tip of the nitrogen inlet tube was set so as to enter the reaction solution, and the solution was bubbled by flowing nitrogen gas.

While stirring, the flask was heated so that the temperature of the reaction solution became 90 ° C., and the mixture was heated at 90 ° C. for 2 hours.
The reaction was carried out at 0 ° C. for 1 hour and at 110 ° C. for 2 hours.

Then, nitrogen bubbling was stopped, a pressure reducing line was set up from the tip of the distillation cooling tube via a trap, and the degree of vacuum was reduced to 10 torr for about 1 hour while maintaining the temperature at 110 ° C. And kept at 10 torr for 30 hours.

After the completion of the reaction, the temperature of the flask was cooled to room temperature, and while dissolving the product using 300 ml of toluene, the solution was transferred to a 1-liter separating funnel.
0 ml was added. Then, an operation of adding 300 ml of distilled water and washing the toluene layer was performed five times. The obtained toluene layer was dried over anhydrous magnesium sulfate and evaporated to remove toluene, and as a result, 32.5 g of a pale yellow viscous liquid was obtained.

As a result of measurement by liquid chromatography, no dimethyl isophthalate as a raw material was observed, and the conversion was 100%. Further, the area ratio of the main product peak to the entire area of the detected peak was 97%.
In addition, as a result of measuring the epoxy equivalent, it was 182 g / equivalent.

In addition, the IR spectrum and nuclear magnetic resonance spectrum of the obtained liquid showed a spectrum similar to that of the epoxy compound obtained in Example 5.

Example 9 <Preparation and evaluation of cured product of alicyclic group-containing ester compound> 10.0 g of the compound obtained in Example 5, 8.4 g of hexahydrophthalic anhydride as a curing agent and 2-g as a curing accelerator
0.3 g of ethyl-4-methylimidazole is added, and 5
A curable composition was prepared by kneading at 0 ° C. The composition was heated in an oven under a nitrogen atmosphere in the order of 80 ° C. for 3 hours, 100 ° C. for 2 hours, 120 ° C. for 2 hours, 140 ° C. for 2 hours, 160 ° C. for 2 hours, and 180 ° C. for 2 hours.
After cooling over time, a hardened product having a strong surface smoothness and gloss was obtained.

The weather resistance of the cured product was evaluated using a weatherometer XENOTEST 1200 CPS (He
black panel 63 ° C, 60
Xenon arc irradiation was performed on the cured product obtained above under a rainfall condition of W / m ² . As a result, the surface of the cured product after 500 hours was visually observed. As a result, the gloss, the color tone, and the surface smoothness of the surface were maintained.

Comparative Example 1 Bisphenol A having an epoxy equivalent of 186 g / equivalent
A curable composition and a cured product were prepared in the same manner as in Example 9 except that 15.4 g of hexahydrophthalic anhydride and 0.1 g of 2-ethyl-4-methylimidazole were used for 18.6 g of glycidyl ether. Thus, a hard cured product having a strong surface smoothness and gloss was obtained.

As a result of the same 500-hour weather resistance test as in Example 10, when the cured product was visually observed, the color tone changed, and the surface gloss and the surface smoothness were lost.

Example 10 <Blending to Flame-Retardant Resin and Evaluation thereof> Resin (a) 80 parts by weight, resin (b) 10 parts by weight, resin (c) shown below
10 parts by weight, 12 parts by weight of the organic phosphorus compound (d), and
0.1 part by weight of the alicyclic group-containing ester compound obtained in Example 5 was melt-kneaded at 250 ° C. by using a twin-screw extruder (ZSK-25, manufactured by W & P) and pelletized to obtain flame retardancy. A resin composition was obtained. Then, the obtained resin composition is dried, and the cylinder temperature is set to 240 ° C., 260 ° C., and 280 ° C. from the resin introduction section to the discharge nozzle, and the mold temperature is set to 80 ° C. Molding was performed to obtain a １ ／ inch thick strip.

The obtained strips were subjected to an Izod impact test, a hot water resistance test and a high temperature / high humidity resistance test by the following test methods. Table 2 shows the obtained test results.

(A) Bisphenol A-based polycarbonate having a weight average molecular weight of 20,500 and a hydroxy group terminal amount of 29%, produced from bisphenol A and diphenyl carbonate by a melt transesterification method.

(B) Acrylonitrile / styrene copolymer composed of 25.0% by weight of acrylonitrile units and 75.0% by weight of styrene units and having a weight average molecular weight of 140,000

(C) Powdery ABS resin having a residual content of less than 90% of 10 mesh (RC name, manufactured by Mitsubishi Rayon Co., Ltd.)

(Izod Impact Test) ASTM D25
Measured with 1/8 inch thickness and notch according to 6. (Unit: kgf · cm / cm)

(Hot Water Resistance Test) A 1/8 inch thick strip test piece was allowed to stand in an autoclave at 120 ° C. under a 2 atm saturated steam environment for 96 hours to evaluate the yellowing degree. ：: little yellowing ×: noticeable yellowing

(High Temperature and High Humidity Resistance Test) A 1/8 inch thick strip was left in an atmosphere of 60 ° C. and 85 RH% for 300 hours to conduct an Izod impact test.

Comparative Example 2 A flame-retardant resin molded product was prepared in the same manner as in Example 10 except that the alicyclic group-containing ester compound was not used, and the same evaluation was performed. The results are shown in Table 2.

[0253]

[Table 2]

[0254]

The alicyclic group-containing ester compound obtained by the present invention can be suitably used as a crosslinking structure-forming agent which gives a cured product having weather resistance, heat resistance and water resistance. Further, it can be suitably used as a stabilizer for a flame-retardant resin composition containing an organic phosphorus compound or the like.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of the compound obtained in Example 1.

FIG. 2 is a ¹ H-nuclear magnetic resonance spectrum of the compound obtained in Example 1.

FIG. 3 is an infrared absorption spectrum of the compound obtained in Example 2.

4 is a ¹ H-nuclear magnetic resonance spectrum of the compound obtained in Example 2. FIG.

FIG. 5 is an infrared absorption spectrum of the compound obtained in Example 3.

FIG. 6 is a ¹ H-nuclear magnetic resonance spectrum of the compound obtained in Example 3.

FIG. 7 is an infrared absorption spectrum of the compound obtained in Example 5.

FIG. 8 is a ¹ H-nuclear magnetic resonance spectrum of the compound obtained in Example 5.

FIG. 9 is an infrared absorption spectrum of the compound obtained in Example 6.

FIG. 10 is a ¹ H-nuclear magnetic resonance spectrum of the compound obtained in Example 6.

FIG. 11 is an infrared absorption spectrum of the compound obtained in Example 7.

FIG. 12 is a ¹ H-nuclear magnetic resonance spectrum of the compound obtained in Example 7.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 301/12 C07D 301/12 303/16 303/16 C08G 59/20 C08G 59/20 C08K 5/1515 C08K 5/1515 5/49 5/49 C08L 101/00 C08L 101/00 // C07B 61/00 300 C07B 61/00 300 F term (reference) 4C048 AA03 AA04 BB01 BC15 CC01 UU03 UU05 XX01 XX02 XX04 4H006 AA01 AA02 AA03 AB46 AB51 AB80 AC48 BA02 BA10 BA11 BA12 BA28 BA29 BA30 BA32 BA34 BA44 BA45 BA51 BA92 BB11 BB12 BB20 BB22 BB24 BB61 BC10 BC11 BC34 BD20 BT14 BT34 KA03 KA04 4H039 CA66 CE10 CG20 4J002 AA011 BB011 CB011 CB011 CB011 FD206 4J036 AA05 AJ01 AJ02 AJ03 AJ09 AJ10 AJ15 DA01 DB05 DC40 DC41 DC43 DC44 DC46 GA06 GA11 GA12 GA16 GA17 GA19 GA29

Claims (30)

[Claims] 1. An alicyclic group-containing ester compound represented by the following general formula (1). Embedded image (In the formula, y represents an integer selected from 1 or 2.
b represents 0 or 1. A, D and E each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent having 12 or less carbon atoms, or an alkoxyl group. X and Y each independently represent an unsaturated alicyclic ester group represented by the following general formula (2) or an epoxidized alicyclic ester group represented by (3). B represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent having 12 or less carbon atoms, an alkoxyl group, an allyl ester group, or a glycidyl ester group. ) (In the formula, m represents an integer selected from 1 or 2.) (In the formula, n represents an integer selected from 1 or 2.) 2. In the general formula (1), X and Y are both an unsaturated alicyclic ester group represented by the general formula (2), and B is a hydrogen atom, a halogen atom, and a carbon atom having 12 carbon atoms.
The alicyclic group-containing ester compound according to claim 1, which is an alkyl group, an alkoxyl group, or an allyl ester group which may have the following substituents. 3. The fat according to claim 1, wherein in the general formula (1), X and Y are both an unsaturated alicyclic ester group represented by the general formula (2), and B is a hydrogen atom. Ring group-containing ester compounds. 4. In the general formula (1), X and Y are both epoxidized alicyclic ester groups represented by the general formula (3), and B is a hydrogen atom, a halogen atom, and a carbon number of 12 or less. The alicyclic group-containing ester compound according to claim 1, which is an alkyl group, an alkoxyl group, or a glycidyl ester group which may have a substituent. 5. The fat according to claim 1, wherein in the general formula (1), X and Y are both epoxidized alicyclic ester groups represented by the general formula (3), and B is a hydrogen atom. Ring group-containing ester compounds. 6. An alicyclic group-containing ester compound represented by the following general formula (4). Embedded image (In the formula, R represents an aliphatic hydrocarbon group having 5 to 50 carbon atoms or a naphthalene skeleton. Also, r, s, p, and q
Represents an integer of 0 or more, (r + s + p + q) is 2 or more, and (r + s) is an integer of 1 or more. X ₁ represents an unsaturated alicyclic ester group represented by the following general formula (5). Embedded image (In the formula, m is an integer selected from 1 and 2.) X ₂ represents an epoxidized alicyclic ester group represented by the following general formula (6). Embedded image (In the formula, n is an integer selected from 1 and 2.) 7. In the general formula (4), s = 0,
7. The alicyclic group-containing ester compound according to claim 6, wherein q = 0. 8. In the general formula (4), r = 0,
7. The alicyclic group-containing ester compound according to claim 6, wherein p = 0. 9. In the general formula (4), p = 0,
7. The alicyclic group-containing ester compound according to claim 6, wherein q = 0. 10. In the general formula (4), s = 0 and p =
The alicyclic group-containing ester compound according to claim 6, wherein 0 and q = 0. 11. In the general formula (4), r = 0 and p =
The alicyclic group-containing ester compound according to claim 6, wherein 0 and q = 0. 12. The transesterification reaction using an organic ester compound and an unsaturated alicyclic alcohol compound, or the unsaturated alicyclic alcohol compound and allyl alcohol. 7 or 1
0. The process for producing an alicyclic group-containing ester compound according to item 0. 13. The process for producing an alicyclic group-containing ester compound according to claim 3, wherein an ester exchange reaction is carried out between the organic ester compound and the unsaturated alicyclic alcohol compound. 14. The process for producing an alicyclic group-containing ester compound according to claim 1, wherein the alicyclic group-containing ester compound according to claim 2 is subjected to an epoxidation reaction using an oxidizing agent. 15. The process for producing an alicyclic group-containing ester compound according to claim 5, wherein the alicyclic group-containing ester compound according to claim 3 is subjected to an epoxidation reaction using an oxidizing agent. 16. The method for producing an alicyclic group-containing ester compound according to claim 6, wherein the alicyclic group-containing ester compound according to claim 7 is subjected to an epoxidation reaction using an oxidizing agent. 17. The method for producing an alicyclic group-containing ester compound according to claim 9 or 11, wherein the alicyclic group-containing ester compound according to claim 10 is subjected to an epoxidation reaction using an oxidizing agent. 18. A method for producing an alicyclic group-containing ester compound, comprising subjecting an alicyclic group-containing ester compound represented by the following general formula (7) to an epoxidation reaction using hydrogen peroxide. Embedded image (In the formula, R represents an aliphatic hydrocarbon group having 4 or more carbon atoms.
Further, m and n represent an integer selected from 1 and 2. ) 19. The method according to claim 14, wherein the oxidizing agent is hydrogen peroxide. 20. The method according to claim 14, wherein the oxidizing agent is a percarboxylic compound. 21. An organic ester compound and one or more alicyclic alcohol compounds selected from unsaturated alicyclic alcohols and alicyclic epinol compounds, or the alicyclic alcohol compound, allyl alcohol and 2,3- The method for producing an alicyclic group-containing ester compound according to claim 1 or 6, wherein a transesterification reaction is carried out using one or more compounds selected from epoxy-1-propanol. 22. An organic ester compound and an alicyclic epinol compound, or the alicyclic epinol compound and 2,3
12. The method for producing an alicyclic group-containing ester compound according to claim 4, wherein the transesterification is carried out using -epoxy-1-propanol. 23. A method for producing an alicyclic group-containing ester compound, comprising subjecting an alkyl ester compound represented by the following general formula (8) to transesterification with an alicyclic epinol. Embedded image (In the formula, R represents an aliphatic hydrocarbon group having 4 or more carbon atoms.
R ₁ and R ₂ represent an alkyl group having 1 to 12 carbon atoms. ) 24. The method for producing an alicyclic group-containing ester compound according to claim 5, wherein the organic ester compound and the alicyclic epinol compound are transesterified. 25. The method according to claim 2, wherein the organic carboxylic acid halide compound is reacted with an unsaturated alicyclic alcohol compound, or the unsaturated alicyclic alcohol compound and allyl alcohol. 11. The method for producing an alicyclic group-containing ester compound according to item 10. 26. The method for producing an alicyclic group-containing ester compound according to claim 3, wherein the organic carboxylic acid halide compound is reacted with an unsaturated alicyclic alcohol compound. 27. The method for producing an alicyclic ester compound according to claim 5, wherein the organic carboxylic acid halide is reacted with an alicyclic epinol compound. 28. A composition comprising a mixture of two or more alicyclic group-containing ester compounds according to claim 1 and 6, wherein the composition comprises an alicyclic group-containing ester compound having a melting point of 160 ° C. or lower. 29. A composition comprising at least one alicyclic group-containing ester compound according to claim 1 and another epoxy compound. 30. A flame-retardant resin composition comprising (a) the alicyclic ester compound according to claim 1 and / or 6, (b) an organic phosphorus compound, and (c) a thermoplastic resin.