WO2024070902A1

WO2024070902A1 - Compound, method for producing said compound, curable material, curable composition, method for producing cured article, and cured article

Info

Publication number: WO2024070902A1
Application number: PCT/JP2023/034362
Authority: WO
Inventors: 由依長谷川; 将太小林; 健一玉祖
Original assignee: 株式会社Adeka
Priority date: 2022-09-27
Filing date: 2023-09-21
Publication date: 2024-04-04

Abstract

Provided is a compound represented by formula (1). (In the formula, R¹ represents a hydrogen atom or a methyl group; R² represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group which may have a substituent, or a halogen atom; R³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a glycidyl ether group, a methyl glycidyl ether group, an acryloyloxymethyl group or a methacryloyloxymethyl group; R⁴ represents a hydrogen atom or a methyl group; the substituent is a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and a halogen atom; and n represents a numerical value of 0 to 4.)

Description

Compound, method for producing said compound, curable material, curable composition, method for producing cured product, and cured product

The present invention relates to a compound, more specifically, to a compound having a reactive unsaturated bond and an epoxy group, and further to a curable composition containing at least one of the compounds and at least one selected from a curing agent and a polymerization initiator.

In recent years, as mobile devices such as smartphones have become thinner, the camera modules installed in such devices have become smaller. As camera modules become smaller, the areas where the components of the camera module are bonded together have also become finer, so the adhesive layer formed from the adhesive that bonds them together must have high adhesive strength.

In addition, adhesives used in the assembly of camera modules and the like are required to have low-temperature curing properties to avoid thermal damage to image sensors and the like caused by high-temperature processing, and at the same time, they are also required to have short-time curing properties from the viewpoint of improving production efficiency. From this viewpoint, ultraviolet-curing adhesives and thermosetting epoxy resin adhesives are often used as low-temperature, short-time curing adhesives. However, while ultraviolet-curing adhesives can cure quickly, they have the disadvantage that they cannot be used to bond areas that are not exposed to light. On the other hand, even though thermosetting epoxy resin adhesives are low-temperature, short-time curing adhesives, they are not necessarily satisfactory because they require the members (components) to be bonded to be fixed with a jig or device in order to maintain the bonding position during bonding, and the viscosity decreases due to the temperature rise caused by heating, causing problems such as dripping just before curing or flowing to areas other than the desired area.

In order to solve the above problems, a type of adhesive has been proposed that is temporarily fixed by curing (pre-curing) by light irradiation, and then further cured (main curing) by heat to bond. For example, Patent Document 1 proposes a photo- and heat-curable composition containing a curable component consisting of a compound having a glycidyl group and a (meth)acryloyl group, a polythiol compound, and an epoxy curing accelerator. Patent Document 2 proposes a curable composition containing a compound having a (meth)acryloyl group, a polythiol compound, a photoradical generator, and a latent curing agent, and also describes a compound having a (meth)acryloyl group and an epoxy group.
However, the epoxy (meth)acrylates described in Patent Documents 1 and 2 are merely compounds obtained by reacting an epoxy resin having two or more epoxy groups with (meth)acrylic acid to esterify a portion of the epoxy groups, and the structure of the compounds is limited.

In addition, Patent Document 3 proposes a compound having a (meth)acryloyl group and a glycidyl group, but this compound does not have sufficient curability to be used as a material in a light and heat curing system.

JP 2009-51954 A WO2018/181421A1 US20200048301A1

The object of the present invention is therefore to provide a compound that can be used in a curable composition that can be cured by light and heat, and to provide a curable composition that has excellent curing properties by light and heat.

That is, the present invention provides a compound represented by the following general formula (1):

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a halogen atom as a substituent, or a halogen atom, R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a glycidyl ether group, a methyl glycidyl ether group, an acryloyloxymethyl group, or a methacryloyloxymethyl group, R ⁴ represents a hydrogen atom or a methyl group, and n represents a number from 0 to 4.

The present invention also provides a compound represented by the following general formula (2):

In the formula, ^R1 represents a hydrogen atom or a methyl group, ^R2 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a halogen atom as a substituent, or a halogen atom, ^R5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a glycidyl ether group, or a methylglycidyl ether group, and n represents a number from 0 to 4.

The present invention also provides a method for producing a compound represented by formula (1), which comprises reacting a compound represented by the following formula (3) with epihalohydrin to produce a compound represented by formula (2), and then esterifying the compound with an acrylic acid ester and/or a methacrylic acid ester.

In the formula, ^R2 's each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a halogen atom as a substituent, or a halogen atom. ^R6 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a hydroxymethyl group. n represents a number from 0 to 4.

The present invention also relates to a compound represented by formula (1),
The present invention provides a curable material containing at least one of a compound represented by formula (2) and a compound represented by the following general formula (4):

In the formula, R ⁷ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms as a substituent, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a hydroxyl group or a halogen atom, a hydroxyl group, or a halogen atom, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, a glycidyl ether group, a methyl glycidyl ether group, a glycidyloxyalkyl group, a β-methyl glycidyloxyalkyl group, an acryloyloxyalkyl group, or a methacryloyloxyalkyl group. R ⁹ represents a hydrogen atom or a methyl group. m represents a number from 0 to 4.

The present invention also provides a curable composition containing (A) at least one compound represented by the general formula (1) and (B) at least one curing agent, a cured product of the composition, and a method for producing the cured product, which includes a curing step of curing the composition.

The compound provided by the present invention is suitable as a material to be cured by light and heat. The curable composition provided by the present invention has sufficient photocurability and excellent thermosetting properties, and therefore can be suitably used for dual curing in which temporary curing is performed by light and then main curing is performed by heat.
Furthermore, according to the production method of the present invention, a compound suitable for a material cured by light and heat can be produced in an industrially advantageous manner.

FIG. 1 shows the results of DMA measurement of the resin composition obtained in Example 3. FIG. 2 shows the results of DMA measurement of the resin composition obtained in Example 6.

A. Compounds The compounds of the present invention are described in detail below.

The compound of the present invention represented by the general formula (1) (hereinafter also referred to as "compound (1)" or "component (A)") has a glycidyl ether group and a reactive unsaturated bond, as described above, and therefore can provide a cured product by applying light and/or heat when used in combination with various curing agents and various polymerization initiators. The reactive unsaturated bond is sometimes called an "ethylenically unsaturated bond."

In the general formula (1), examples of the alkyl group having 1 to 20 carbon atoms represented by ^R2 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an amyl group, an isoamyl group, a tert-amyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a benzyl group, and a phenethyl group.

In the general formula (1), examples of the alkoxy group having 1 to 20 carbon atoms represented by ^R2 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an amyloxy group, a hexyloxy group, a pentyloxy group, an octyloxy group, a nonyloxy group, and a decyloxy group.

In the general formula (1), examples of the halogen atom represented by ^R2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the general formula (1), examples of unsubstituted aryl groups among the aryl groups represented by R ² that may have a substituent include a phenyl group, a naphthyl group, etc. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an amyl group, an isoamyl group, a tertiary amyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, or a decyl group; an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an amyloxy group, a hexyloxy group, a pentyloxy group, an octyloxy group, a nonyloxy group, or a decyloxy group; and a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

In the general formula (1), n is preferably an integer of 0 to 2, and in particular, n is 0 or 1, which is preferred because of excellent light- and heat-curing properties and easy availability of raw materials. Also, n is 0, or n is 1 or more, and R ² is an alkyl group or methoxy group having 1 to 4 carbon atoms, which is preferred because of excellent light- and heat-curing properties and easy availability of raw materials. Among these, in the general formula (1), n is 0 or 1, and R ² is an alkyl group or methoxy group having 1 to 4 carbon atoms, which is preferred, and in particular, n is 0.

In the general formula (1), examples of the alkyl group having 1 to 10 carbon atoms represented by ^R3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an amyl group, an isoamyl group, a tert-amyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, and a decyl group.
R ³ is preferably an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a glycidyl ether group, or a methyl glycidyl ether group. Of these, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 5 carbon atoms is particularly preferred, and a methyl group or an ethyl group is particularly preferred, with an ethyl group being the most preferred. When R ³ is the above group, the raw materials are easily available, and curing by light and heat at low cost becomes easier.

^R4 is preferably ^a hydrogen atom in terms of excellent photocurability, and is preferably a methyl group in terms of excellent stability and cured product physical properties.
R ¹ is preferably a hydrogen atom in terms of excellent thermosetting properties, and R ¹ is preferably a methyl group in terms of excellent stability and physical properties of the cured product.

Compound (1) is a compound represented by any one of the following general formulas (1a), (1b) and (1c), and may exist as a mixture of these.
For example, the compound represented by formula (1a) is preferred in that it has good photocurability, and the compound represented by formula (1b) or (1c), especially (1c), is preferred in that the photo- and thermosetting product has high heat resistance and is less likely to crystallize.

In addition, R ¹ , R ² , R ³ , R ⁴ and n in the compounds represented by the general formulae (1a), (1b) and (1c) are those represented by the formula (1).

Specific examples of compounds represented by the general formulas (1a), (1b), and (1c) are given below.

The compound (1) of the present invention and mixtures thereof preferably have a total chlorine content of 3000 ppm or less by mass. If the total chlorine content exceeds 3000 ppm, the concentration of chloride ions will be high, making the material prone to ion migration, and there is a risk of reduced reliability when used, for example, as an adhesive or sealant for electric and electronic components. In addition, the titanium atom content is preferably 7000 ppm or less by mass. If the titanium atom content exceeds 7000 ppm, there is a risk of reduced radical polymerizability. The total chlorine content is measured in accordance with ASTM D5808. The titanium atom content can be measured in accordance with JIS K0116:2014.

Examples and preferred examples of R ¹ , R ² and n in the compound represented by the general formula (2) (hereinafter also referred to as "compound (2)") include those exemplified as R ¹ , R ² and n in the general formula (1) and those preferred examples thereof. Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁵ include those exemplified as R ³ in the general formula (1). The group represented by R ⁵ is preferably an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a glycidyl ether group or a methyl glycidyl ether group. Among these, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 5 carbon atoms is more preferred, a methyl group or an ethyl group is even more preferred, and an ethyl group is particularly preferred. When R ⁵ is the above group, raw materials are easily available, and a compound suitable for a photo- and heat-curable composition is easily provided.
^R5 of compound (2) used as a raw material for compound (1) is preferably the same as ^R3 of the target compound (1). In addition, when compound (1) and compound (2) coexist in the curable material or curable composition described below, ^R3 of compound (1) and ^R5 of compound (2) may be the same or different.

The compound represented by the general formula (2) has both an alcoholic hydroxyl group and a glycidyl group, and therefore can be used in a variety of applications. In addition, the compound represented by the general formula (2) is useful in the present invention as a raw material for the compound represented by the general formula (1).

The compound represented by the general formula (2) is a compound represented by any one of the following general formulas (2a), (2b) or (2c), but may exist as a mixture. The compounds represented by the formulas (2a), (2b) or (2c) are raw materials for the compounds represented by the formulas (1a), (1b) or (1c), respectively. In the curable material and curable composition described below, when the compound (1) and the compound (2) coexist, it is preferable that the compound represented by the formula (1a), (1b) or (1c) and the raw material compound (2) (the compound represented by the formula (2a), (2b) or (2c), respectively) coexist, but this is not limited to this embodiment.

In the compounds represented by the general formulae (2a), (2b) and (2c), R ¹ , R ² , R ⁵ and n are the same as those in the formula (2).

Specific examples of the compounds represented by the general formulas (2a), (2b), and (2c) are given below.

The compound (2) of the present invention and mixtures thereof preferably have a total chlorine content of 3000 ppm or less by mass. If the total chlorine content exceeds 3000 ppm, the concentration of chloride ions will be high, making the material prone to ion migration, and there is a risk of reduced reliability when used, for example, as an adhesive or sealant for electric/electronic components. In addition, it is preferable that the titanium atom content is 7000 ppm or less by mass. If the titanium atom content exceeds 7000 ppm, there is a risk of reduced radical polymerizability.

The method for producing the compound (1) of the present invention is not particularly limited, but it can be produced by utilizing the difference in reactivity between the phenolic hydroxyl group and the alcoholic hydroxyl group in a compound containing at least two hydroxyl groups represented by the following general formula (3), glycidyl etherifying only the phenolic hydroxyl group to produce compound (2), and acrylic esterifying or methacrylic esterifying the alcoholic hydroxyl group of compound (2). Conventional techniques such as Patent Documents 1 and 2 esterify a part of the epoxy groups in an epoxy resin containing two or more epoxy groups with acrylic acid. This method is not satisfactory for application to a light and heat curing system taking into consideration the purification cost, because it is difficult to control the composition of the reaction product, a relatively large amount of unreacted epoxy resin tends to remain during production, and the viscosity tends to be high. In contrast, the present production method can utilize the above-mentioned difference in reactivity, making it easy to control the composition of the reaction product, and can provide a curable material suitable for a light and heat curing system at low cost while reducing purification costs.
More specifically, in the present invention, for example, compound (1) can be produced by the production method described below.
The method for producing compound (2) of the present invention utilizes the difference in reactivity between a phenolic hydroxyl group and an alcoholic hydroxyl group in a compound represented by the following general formula (3) (hereinafter also referred to as "compound (3)") to glycidyl etherify only the phenolic hydroxyl group:

(In the formula, ^R2 's each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group which may have a substituent, or a halogen atom. The substituent is a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. ^R6 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a hydroxymethyl group. n represents a number from 0 to 4.)

Examples and preferred examples of R ² and n in compound (3) include those exemplified and preferred for R ² and n in the general formula (1). Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁶ in compound (3) include those exemplified as R ³ in the general formula (1). The group represented by R ⁶ is preferably an alkyl group having 1 to 10 carbon atoms or a hydroxymethyl group. Among them, for the same reasons as those described for R ⁵ , an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 5 carbon atoms is more preferred, a methyl group or an ethyl group is even more preferred, and an ethyl group is particularly preferred. It is preferable that R ⁶ of compound (3) used as a raw material for compound (2) is the same as R ⁵ of the target compound (2).

As a method for converting the phenolic hydroxyl group in the compound represented by the general formula (3) into a glycidyl ether, an alkali is added to a mixture of the compound represented by the general formula (3) and epihalohydrin to cause a reaction. Examples of the method for adding the alkali include a method of adding an aqueous alkali solution dropwise and a method of adding a solid alkali, preferably in multiple batches.

Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, and β-methylepichlorohydrin.
Examples of the alkali include metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide.

The amount of epihalohydrin used when reacting the compound represented by the general formula (3) with epihalohydrin is preferably 3 to 50 times, more preferably 4 to 30 times, in terms of molar ratio, relative to the compound represented by the general formula (3).
The amount of the alkali used is preferably in the range of 0.8 to 1.5 moles, more preferably 0.9 to 1.2 moles, per mole of the compound represented by the general formula (3).

The reaction between the compound represented by the general formula (3) and epihalohydrin does not require the use of a phase transfer catalyst such as tetrabutylammonium bromide. In this specification, "no phase transfer catalyst is used in the reaction between the compound represented by the formula (3) and epihalohydrin" means that the mass of the phase transfer catalyst is less than 1/100 of the mass of the compound represented by the formula (3).

The reaction of the compound represented by the general formula (3) with epihalohydrin is carried out under heating and increased or reduced pressure as necessary.
The reaction temperature is not particularly limited, but is preferably from 40° C. to 120° C., more preferably from 60° C. to 100° C., from the viewpoints of shortening the production time and improving the reaction efficiency.

The method for producing the compound represented by the general formula (1) by converting the compound represented by the general formula (2) into an acrylic acid ester or a methacrylic acid ester includes a method of esterification using an acrylic acid derivative and/or a methacrylic acid derivative.
Specifically, examples of such a method include an esterification method using an acrylic ester such as methyl acrylate and/or a methacrylic ester such as methyl methacrylate in the presence of a catalyst such as dialkyltin oxide, tetraalkyl titanate, etc., and an esterification method using acryloyl chloride and/or methacryloyl chloride in the presence of a neutralizing agent such as triethylamine, etc.
From the viewpoints of shortening the production time and reaction efficiency, the reaction temperature in the case where the former acrylic ester and/or methacrylic ester is used for esterification in the presence of a catalyst is preferably, for example, 50 to 100° C., and more preferably 70 to 90° C. From the viewpoints of shortening the production time and reaction efficiency, the reaction temperature in the case where the latter acryloyl chloride and/or methacryloyl chloride is used for esterification in the presence of a neutralizing agent is preferably, for example, 0 to 30° C.
In particular, the use of an acrylic acid ester and/or a methacrylic acid ester is preferred from the viewpoints of safety and reaction efficiency, particularly in terms of suppressing side reactions.
The amount of the acrylic acid derivative and/or methacrylic acid derivative used is preferably 2 times or more, more preferably 3 times or more, in terms of molar ratio, relative to the compound represented by the general formula (2). The amount of the acrylic acid derivative and/or methacrylic acid derivative used is preferably 10 times or less, more preferably 7 times or less, in terms of molar ratio, relative to the compound represented by the general formula (2), in terms of production efficiency, etc.

B. Curable Material Next, the curable material of the present disclosure will be described.
One of the features of the curable material of the present disclosure is that it contains a compound represented by the above formula (1) (hereinafter also referred to as "compound (1)").

As a preferred embodiment of the present disclosure, the compound (1) and
Examples of the curable material include a curable material containing at least one of compound (2) and a compound represented by the general formula (4) (hereinafter, also referred to as "compound (4)"). In particular, it is preferable that compounds (2) and (4) are impurities when compound (1) is produced by the above-mentioned preferred production method, in that the above-mentioned effects can be obtained while reducing production costs.

Examples of the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, the aryl group having 5 to 10 carbon atoms which may have a substituent, and the halogen atom represented by ^R7 include the same groups as the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, the aryl group having 5 to 10 carbon atoms which may have a substituent, and the halogen atom represented by ^R2 in formula (1).
With regard to the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, and the halogen atom as the substituent of the aryl group having 5 to 10 carbon atoms which is represented by ^R7 and which may be substituted, examples thereof include the same groups as those exemplified above as the substituent of the aryl group having 5 to 10 carbon atoms which may be substituted and which is represented by ^R2 in formula (1).
Preferable examples of the group represented by ^R7 include the same groups as those preferred for ^R2 .
The preferred range of m is the same as that of n. The preferred range of ^R9 is the same as that of ^R1 .

Examples of the hydroxyalkyl group in ^R8 include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
Examples of the glycidyloxyalkyl group include a glycidyloxymethyl group and a glycidyloxyethyl group.
Examples of the acryloyloxyalkyl group include an acryloyloxymethyl group and an acryloyloxyethyl group.
Examples of the methacryloyloxyalkyl group include a methacryloyloxymethyl group and a methacryloyloxyethyl group.

^R8 is preferably an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a glycidyl ether group, or a methyl glycidyl ether group, of which an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 5 carbon atoms is more preferred, a methyl group or an ethyl group is particularly preferred, and an ethyl group is most preferred.

It is preferable that R ⁷ , m, R ⁸ and R ⁹ of compound (4) generated as an impurity are the same as R ² , n, R ³ and R ¹ of the target compound (1), respectively. When compound (1) and compound (4) coexist in the curable material or curable composition described later, R ⁷ , m, R ⁸ and R ⁹ of compound (4) and R ² , n, R ³ and R ¹ of compound (1), respectively, may be the same or different.

The compound represented by the general formula (4) is a compound represented by any one of the following general formulas (4a), (4b) and (4c), and may exist as a mixture thereof.
The compounds represented by formula (4a), (4b) or (4c) are impurities of the compounds represented by formula (1a), (1b) or (1c), respectively. In the curable material and curable composition described later, when compound (1) and compound (4) coexist, it is preferable that the compound represented by formula (1a), (1b) or (1c) and the corresponding compound (4) (the compound represented by formula (4a), (4b) or (4c), respectively) coexist, but this is not limited thereto.

In the compounds represented by the general formulae (4a), (4b) and (4c), R ¹ , R ² , R ⁵ and n are the same as those in the formula (4).

Specific examples of compounds represented by the general formulas (4a), (4b), and (4c) are given below.

The curable material of the present disclosure preferably contains compound (4) out of compounds (2) and (4) in terms of the heat resistance of the cured product obtained after curing.

In the present disclosure, in a curable material containing compound (1) and at least one of compound (2) and compound (4), the proportion of compound (1) in the total of compound (1), compound (2) and compound (4) is preferably 80 mass% or more, more preferably 90 mass% or more, and particularly preferably 95 mass% or more. This is because the lower limit provides an excellent effect of good photo- and thermosetting properties due to the compound of formula (1). The upper limit of the proportion of compound (1) is preferably 100 mass% in the total of compound (1), compound (2) and compound (4), but when compound (2) and/or compound (4) are contained, it is preferably 99.5 mass% or less, more preferably 98 mass% or less, from the viewpoint of reducing production costs, etc.

In addition, in the curable material, the proportion of compound (2) in the total of compound (1), compound (2) and compound (4) is preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 6% by mass or less. This is because the content of the compound of formula (1) is ensured, and the effect of good photo- and heat-curing properties is excellent. When compound (2) is contained, the amount is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, in the total of compound (1), compound (2) and compound (4), in view of production costs, heat resistance, etc.

Furthermore, in the curable material, the proportion of compound (4) in the total of compound (1), compound (2) and compound (4) is preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. By having the proportion of compound (4) be less than this value, the content of the compound of formula (1) is ensured, and the effect of good photo- and heat-curing properties is excellent. When compound (4) is contained, the amount is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more, in view of production costs, heat resistance, etc.

C. Curable Composition Next, the curable composition of the present invention will be described in detail.

The curable composition of the present invention contains (A) at least one compound represented by the general formula (1) (hereinafter also referred to as "component (A)") and (B) a curing agent (hereinafter also referred to as "component (B)"). As component (A), only compound (1) may be used, or, for example, the above-mentioned curable material may be used.

The curable composition of the present invention may contain a compound having at least one reactive unsaturated bond and at least one epoxy group other than the component (A). Examples of such compounds include glycidyl methacrylate, glycidyl ether of allylphenol, diglycidyl monoallyl ether, and epoxy acrylates. In addition, when ^R8 is an acryloyloxyalkyl group or a methallyloyloxyalkyl group, the compound (4) may also be used.

The curable composition of the present invention may also contain a compound having only an epoxy group or a compound having only a reactive unsaturated bond, among those having reactive unsaturated bonds and epoxy groups.

Examples of the compound having only an epoxy group include compound (2) and compound (4) (wherein R ⁸ is other than an acryloyloxyalkyl group or a methallyloyloxyalkyl group).
Further, examples of the epoxy resin include known epoxy resins. Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis(ortho-cresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis(ortho-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxycumylbenzene), and 1,1,3-tris(4-hydroxy- polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as 1,1,2,2-tetra(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfonylbisphenol, oxybisphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcin novolac, and terpene phenol; polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, tetramethylolpropane ... Polyglycidyl ethers of polyhydric alcohols such as rhythritol, sorbitol, bisphenol A-alkylene oxide adducts, and dicyclopentadiene dimethanol diglycidyl ether; glycidyl esters of aliphatic, aromatic, or alicyclic polybasic acids such as maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and endomethylenetetrahydrophthalic acid; glycidyl methacrylates; epoxidized products of cyclic olefin compounds such as vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexane carboxylate, and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymers; and heterocyclic compounds such as triglycidyl isocyanurate. These epoxy resins may be internally crosslinked with a prepolymer of a terminal isocyanate, or may be polymerized using a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate, etc.).

Commercially available epoxy resins include, for example, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-830, Denacol EX-832, and Denacol EX- 841, Denacol EX-861, Denacol EX-920, Denacol EX-931, Denacol EX-201, Denacol EX-711, Denacol EX-721, (manufactured by Nagase ChemteX Corporation); Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolight 400P (manufactured by Kyoeisha Chemical Co., Ltd.), Adeka Resin EP-4088S, EP-4088L, EP-4080E, Adeka Resin EP -4000, ADEKA RESIN EP-4005, ADEKA RESIN EP-4100, ADEKA RESIN EP-4901 (manufactured by ADEKA CORPORATION); OGSOL PG-100, OGSOL EG-200, OGSOL EG-210, OGSOL EG-250 (manufactured by Osaka Gas Chemicals Co., Ltd.); YD series, YDF series, YDPN series, TDCN series (Nippon Steel & Sumikin Chemical Co., Ltd.); CELLOXIDE 2021P, CELLOXIDE 2081 (Daicel Corporation) Examples include TECHMORE VG-3101L (manufactured by Printec); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon Kayaku); YX8800 (manufactured by Mitsubishi Chemical); HP4032, HP4032D, HP4700 (manufactured by DIC Corporation), etc.

Examples of compounds having only reactive unsaturated bonds include N-alkyl group-containing (meth)acrylamide derivatives such as N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, and N-hexyl(meth)acrylamide; N-alkoxy group-containing (meth)acrylamide derivatives such as N-methylol(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-methylol-N-propane(meth)acrylamide, N-methoxymethylacrylamide, and N-ethoxymethylacrylamide; and N-acryloylmorphoacrylamide derivatives such as N-methylol(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-methylol-N-propane(meth)acrylamide, N-methoxymethylacrylamide, and N-ethoxymethylacrylamide. (meth)acrylamide derivatives such as phosphorus, N-acryloylpiperidine, N-methacryloylpiperidine, and N-acryloylpyrrolidine; unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate, and ω-carboxypolycaprolactone mono(meth)acrylate. Mono(meth)acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as acrylates; unsaturated polybasic acids such as hydroxyethyl (meth)acrylate maleate, hydroxypropyl (meth)acrylate maleate, dicyclopentadiene maleate, or polyfunctional (meth)acrylates having one carboxy group and two or more (meth)acryloyl groups; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isopropyl (meth)acrylate, Octyl, isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofuryl (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, tricyclodecane dimethyl Esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols, such as roll di(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, and polyester (meth)acrylate oligomers; metal salts of unsaturated polybasic acids, such as zinc (meth)acrylate and magnesium (meth)acrylate; unsaturated aldehydes, such as acrolein; unsaturated nitriles, such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, and vinyl sulfonate. unsaturated aromatic compounds such as vinyl ether, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, and vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, and vinylpiperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; 1,3-butadiene, isoprene, chloro Aliphatic conjugated dienes such as propylene; macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compounds of hydroxyl group-containing vinyl monomers and polyisocyanate compounds, and vinyl epoxy compounds of hydroxyl group-containing vinyl monomers and polyepoxy compounds.

In terms of curability, etc., the amount of component (A) (compound (1)) in the curable composition of the present invention is preferably 30% by mass or more and 99% by mass or less, and more preferably 50% by mass or more and 97% by mass or less. The total amount of compounds having an epoxy group and/or a reactive unsaturated bond, including component (A) and compounds other than component (A), may also be 30% by mass or more and 99% by mass or less, or 50% by mass or more and 97% by mass or less, in the curable composition. When the curable composition contains other compounds having an epoxy group and/or a reactive unsaturated bond in addition to component (A), in terms of curability, etc., the amount of the other compounds is preferably 100 parts by mass or less, and more preferably 70 parts by mass or less, per 100 parts by mass of component (A).

Preferred examples of the curing agent (B) used in the curable resin composition of the present invention include amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, polythiol-based curing agents, and polymerization initiators.

The amine-based curing agent may, for example, be alkylenediamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, or hexamethylenediamine; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, or tetraethylenepentamine; 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,3-diaminomethylcyclohexane, 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, or 4,4' alicyclic polyamines such as 1,3-diaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylpropane, bis(4-aminocyclohexyl)sulfone, 4,4'-diaminodicyclohexyl ether, 2,2'-dimethyl-4,4'-diaminodicyclohexylmethane, isophoronediamine, and norbornenediamine; m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diethyltoluenediamine, 1-methyl-3, Aromatic polyamines such as 5-diethyl-2,4-diaminebenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 3,5,3',5'-tetramethyl-4,4'-diaminodiphenylmethane; guanamines such as benzoguanamine and acetoguanamine; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2- Imidazoles such as phenylimidazole, 2-phenyl-4-methylimidazole, and 2-aminopropylimidazole; dihydrazides such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, and phthalic acid dihydrazide; N,N-dimethylaminoethylamine, N,N-diethylaminoethylamine, N,N-diisopropylaminoethylamine, N,N-diallylaminoethylamine, N,N-phenyl ... benzylmethylaminoethylamine, N,N-dibenzylaminoethylamine, N,N-cyclohexylmethylaminoethylamine, N,N-dicyclohexylaminoethylamine, N-(2-aminoethyl)pyrrolidine, N-(2-aminoethyl)piperidine, N-(2-aminoethyl)morpholine, N-(2-aminoethyl)piperazine, N-(2-aminoethyl)-N'-methylpiperazine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-diisopropylaminopropylamine, N,N-diallylaminopropylamine Propylamine, N,N-benzylmethylaminopropylamine, N,N-dibenzylaminopropylamine, N,N-cyclohexylmethylaminopropylamine, N,N-dicyclohexylaminopropylamine, N-(3-aminopropyl)pyrrolidine, N-(3-aminopropyl)piperidine, N-(3-aminopropyl)morpholine, N-(3-aminopropyl)piperazine, N-(3-aminopropyl)-N'-methylpiperidine, 4-(N,N-dimethylamino)benzylamine, 4-(N,N-diethylamino)benzylamine, 4-( N,N-diisopropylamino)benzylamine, N,N,-dimethylisophoronediamine, N,N-dimethylbisaminocyclohexane, N,N,N'-trimethylethylenediamine, N'-ethyl-N,N-dimethylethylenediamine, N'-ethyl-N,N-dimethylpropanediamine, N'-ethyl-N,N-dibenzylaminopropylamine; N,N-(bisaminopropyl)-N-methylamine, N,N-bisaminopropylethylamine, N,N-bisaminopropylpropylamine, N,N-bisaminopropylbutylamine, N,N- Examples include bisaminopropylpentylamine, N,N-bisaminopropylhexylamine, N,N-bisaminopropyl-2-ethylhexylamine, N,N-bisaminopropylcyclohexylamine, N,N-bisaminopropylbenzylamine, N,N-bisaminopropylallylamine, bis[3-(N,N-dimethylaminopropyl)]amine, bis[3-(N,N-diethylaminopropyl)]amine, bis[3-(N,N-diisopropylaminopropyl)]amine, and bis[3-(N,N-dibutylaminopropyl)]amine.

The amine-based curing agent may be an amine-based latent curing agent obtained by various modifications. Examples of modified amines include dehydration condensation products of the amine compound and a carboxylic acid, adducts of the amine compound and an epoxy compound (a compound exemplified as the epoxy resin), adducts of the amine compound and an isocyanate compound (an isocyanate compound exemplified below), Michael adducts of amine compounds, Mannich reaction products of amine compounds, condensates of amine compounds and urea, and condensates of amine compounds and ketones. In addition, for example, dibasic acid dihydrazides such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, and phthalic acid dihydrazide; guanamines such as benzoguanamine and acetoguanamine; dicyandiamide; and melamine can also be used as amine-based latent curing agents.

Examples of the isocyanate compound include aromatic diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthylene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, and tetramethylxylylene diisocyanate; isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, Examples of the diisocyanates include alicyclic diisocyanates such as trans-1,4-cyclohexyl diisocyanate and norbornene diisocyanate; aliphatic diisocyanates such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4 and/or (2,4,4)-trimethylhexamethylene diisocyanate and lysine diisocyanate; isocyanurate trimer, biuret trimer, trimethylolpropane adduct of the above-listed diisocyanates; triphenylmethane triisocyanate, 1-methylbenzene-2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, and the like.
Furthermore, these isocyanate compounds may be used in a form modified by carbodiimide, isocyanurate, biuret, or the like, or may be used in a form of blocked isocyanate blocked with various blocking agents.

Examples of the phenol-based hardener include polyhydric phenol compounds such as phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zylok resin), naphthol aralkyl resin, trisphenylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl modified phenol resin (a polyhydric phenol compound in which the phenol nucleus is linked by a bismethylene group), biphenyl modified naphthol resin (a polyhydric naphthol compound in which the phenol nucleus is linked by a bismethylene group), aminotriazine modified phenol resin (a compound having a phenol skeleton, a triazine ring, and a primary amino group in the molecular structure), and alkoxy group-containing aromatic ring modified novolac resin (a polyhydric phenol compound in which the phenol nucleus and the alkoxy group-containing aromatic ring are linked by formaldehyde).

Examples of acid anhydride curing agents include himic anhydride, phthalic anhydride, maleic anhydride, methyl himic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, benzophenonetetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and hydrogenated methylnadic anhydride.

Examples of the polythiol-based curing agent include pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(thioglycolate), dipentaerythritol hexakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptobutyrate), 1,3,4,6-tetrakis(2-mercaptoethyl)-1,3,4,6-tetraazaochydropentalene-2,5-dione, 1,3,5 ... 1,3,4,6-Tri(3-mercaptopropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-, 4,7- or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2 -mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetramercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)-2,3-dithiane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, bis(mercaptomethylthio)-3,4-dithiahexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)ethanethiol, tris(2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12 -Tetrathiatridecane, 3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-di Mercapto-2,5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis[3,5-bis(mercaptomethylthio) )-7-mercapto-2,6-dithiaheptylthio]-1,3-dithiane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-6-mercaptomethylthio-1,3-dithiane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-bis(mercaptomethylthio)propane, 1-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio) 1,5-bis[4-(6-mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 1,5-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2-(1,3-dithietanyl)]methyl-2,4-dithiapentane, 3-[2-(1,3-dithietanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-[2-(1,3-dithietanyl)]methyl-2,4-dithiapentane, 3-[2-(1,3-dithietanyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 3,7-bis[2-(1,3-dithietanyl)]methyl-1,9-dimercapto-2,4,6,8 -Tetrathianonane, 4,6-bis{3-[2-(1,3-dithietanyl)]methyl-5-mercapto-2,4-dithiapentylthio}-1,3-dithiane, 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-dithiane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl]- 5-mercaptomethylthio-1,3-dithiolane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-1,3-dithiolane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3-dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-tri thiooctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithietane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrakis(mercaptomethylthio) 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithietane, 4,5-bis{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-1,3-dithiolane, 4-{1-[2-(1,3-dithietanyl)]-3-mercapto mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane, 2-{bis[4-(5-mercaptomethylthio-1,3-dithiolanyl)thio]methyl}-1,3-dithietane, 4-[4-(5-mercaptomethylthio-1,3-dithiolanyl)thio]-5-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-1,3-dithiolane, and the like.
In particular, the use of a polythiol compound having a valence of 4 or more is preferred because it gives a curable composition having excellent curability.

The amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and polythiol-based curing agents are known as curing agents for epoxy resins, and examples of commercially available products thereof include ADEKA HARDENER EH-3636S (manufactured by ADEKA Corporation; dicyandiamide-type latent curing agent), ADEKA HARDENER EH-4351S (manufactured by ADEKA Corporation; dicyandiamide-type latent curing agent), ADEKA HARDENER EH-5011S (manufactured by ADEKA Corporation; imidazole-type latent curing agent), ADEKA HARDENER EH-5046S (manufactured by ADEKA Corporation; imidazole-type latent curing agent), ADEKA HARDENER EH-4357S (manufactured by ADEKA Corporation; polyamine-type latent curing agent), Examples include ADEKA HARDNER EH-5057P (manufactured by ADEKA Corporation; polyamine-type latent hardener), ADEKA HARDNER EH-5057PK (manufactured by ADEKA Corporation; polyamine-type latent hardener), AMICURE PN-23 (manufactured by Ajinomoto Fine-Techno Co., Ltd.; amine adduct-type latent hardener), AMICURE PN-40 (manufactured by Ajinomoto Fine-Techno Co., Ltd.; amine adduct-type latent hardener), AMICURE VDH (manufactured by Ajinomoto Fine-Techno Co., Ltd.; hydrazide-type latent hardener), FUJICURE FXR-1020 (manufactured by T&K Toka Corporation; latent hardener), TS-G manufactured by Shikoku Kasei Corporation, DPMP and PEMP manufactured by SC Organic Chemical Co., Ltd., and PETG manufactured by Yodo Chemical Co., Ltd.

The amount of the epoxy resin curing agent (a curing agent selected from the amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and polythiol-based curing agents) used is not particularly limited, but is preferably 100 parts by mass or less, and more preferably 2 to 50 parts by mass, per 100 parts by mass of component (A). When component (A) and other compounds having epoxy groups and/or reactive unsaturated bonds are contained, the amount is preferably 100 parts by mass or less, and more preferably 2 to 50 parts by mass, per 100 parts by mass of the total of the other compounds and component (A).

The curable composition of the present invention can also use a curing catalyst in combination with the epoxy resin curing agent. Examples of the curing catalyst include phosphine compounds such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; amines such as benzyldimethylamine and 2,4,6-tris(dimethylaminomethyl)phenol; quaternary ammonium salts such as trimethylammonium chloride; ureas such as 3-(p-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, isophorone diisocyanate-dimethylurea, and tolylene diisocyanate-dimethylurea; and complexes of boron trifluoride with tertiary amines, ether compounds, and the like. These curing catalysts may be used alone or in combination of two or more.

The amount of the curing catalyst used in the curable composition of the present invention is preferably 0.01 to 20 parts by mass per 100 parts by mass of component (A). When component (A) and other compounds having an epoxy group and/or a reactive unsaturated bond are contained, the amount is preferably 0.01 to 20 parts by mass per 100 parts by mass of the total of the other compounds and component (A).

The polymerization initiator may be a thermal radical polymerization initiator, a photoradical polymerization initiator, or a cationic polymerization initiator.

The thermal radical polymerization initiator is not particularly limited as long as it generates radicals when heated, and any conventionally known compound can be used. For example, preferred examples include azo compounds, peroxides, and persulfates.

Examples of the azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methyl isobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(1-acetoxy-1-phenylethane), etc.

Examples of the peroxide include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butyl peroxypivalate, and di(4-t-butylcyclohexyl) peroxydicarbonate.

Examples of the persulfate include ammonium persulfate, sodium persulfate, potassium persulfate, and other persulfates.

The photoradical polymerization initiator is not particularly limited as long as it generates radicals upon irradiation with light, and any conventionally known compound can be used. Preferred examples include acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and oxime ester-based compounds.

The acetophenone compounds include, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroacetophenone, Examples include cyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one.

Examples of the benzyl compounds include benzyl.

Examples of the benzophenone-based compounds include benzophenone, o-benzoylmethylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide.

Examples of the thioxanthone compounds include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

The oxime ester compound refers to a compound having an oxime ester group, and since it has good sensitivity among the photoradical polymerization initiators, it can be preferably used in the curable composition of the present invention.

Among the above oxime ester compounds, compounds having a carbazole skeleton, a diphenyl sulfide skeleton, or a fluorene skeleton have particularly high sensitivity and can therefore be preferably used in the curable composition of the present invention.

Other radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and titanocene compounds such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(pyr-1-yl)]titanium.

Commercially available radical polymerization initiators include ADEKA OPTOMER N-1414, N-1717, N-1919, ADEKA ARCLES NCI-831, NCI-930 (all manufactured by ADEKA); IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE 784 (all manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (all manufactured by Tronly); and the like.

The cationic polymerization initiator may be any compound capable of releasing a substance that initiates cationic polymerization by irradiation with energy rays or heating, but is preferably a double salt, which is an onium salt that releases a Lewis acid by irradiation with energy rays, or a derivative thereof. Representative examples of such compounds include those represented by the following general formula:
[A] ^r+ [B] ^r-
Examples of the salt include salts of cations and anions represented by the following formula:

Here, the cation [A] ^r+ is preferably an onium, and its structure is, for example, represented by the following general formula:
[( ^R12 ) _aQ ] ^r+
It can be expressed as:

Furthermore, R ¹² is an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms. a is an integer from 1 to 5. a R ¹² are each independent and may be the same or different. At least one is preferably an organic group having an aromatic ring as described above. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N=N. In addition, when the valence of Q in the cation [A] ^r+ is q, it is necessary that the relationship r=a-q holds (however, N=N is treated as having a valence of 0).

The anion [B] ^r- is preferably a halide complex, the structure of which is, for example, represented by the following general formula:
It can be represented by [LY _b ] ^r- .

Furthermore, here, L is a metal or semimetal (Metalloid) that is the central atom of the halide complex, and is B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. Y is a halogen atom. b is an integer of 3 to 7. In addition, when the valence of L in the anion [B] ^r- is p, it is necessary that the relationship r=b-p is established.

Specific examples of the anion [LY _b ] ^r- in the above general formula include tetrakis(pentafluorophenyl)borate, tetra(3,5-difluoro-4-methoxyphenyl)borate, tetrafluoroborate (BF ₄ ) ^- , hexafluorophosphate (PF ₆ ) ^- , hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarsenate (AsF ₆ ) ^- , hexachloroantimonate (SbCl ₆ ) ^- , and the like.

The anion [B] ^r- is represented by the following general formula:
[LY _b-1 (OH)] ^r
It is also preferable to use a structure represented by the following formula: L, Y and b are the same as above.
Other usable anions include perchlorate ion ( _ClO4 ) ^- , trifluoromethylsulfite ion ( _CF3SO3 ) ^- , fluorosulfonate ion ( _FSO3 ) ^- , toluenesulfonate anion, _{trinitrobenzenesulfonate} anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctane sulfonate, tetraarylborate, and tetrakis(pentafluorophenyl)borate.

In the present invention, among these onium salts, it is particularly effective to use the aromatic onium salts (a) to (c) below. Of these, one type may be used alone, or two or more types may be used in combination.

(a) Aryl diazonium salts such as phenyl diazonium hexafluorophosphate, 4-methoxyphenyl diazonium hexafluoroantimonate, and 4-methylphenyl diazonium hexafluorophosphate.

(b) Diphenyliodonium hexafluoroantimonate, di(4-methylphenyl)iodonium hexafluorophosphate, di(4-tert-butylphenyl)iodonium hexafluorophosphate, triaryliodonium tetrakis(pentafluorophenyl)borate, and other diaryliodonium salts

(c) Sulfonium cations represented by the following Group I or Group II and sulfonium salts such as hexafluoroantimony ion, hexafluorophosphate ion, and tetrakis(pentafluorophenyl)borate ion.

The amount of the polymerization initiator used in the hardener composition of the present invention is preferably 0.001 to 20 parts by mass per 100 parts by mass of component (A). When component (A) and other compounds having epoxy groups and/or reactive unsaturated bonds are contained, the amount of the polymerization initiator used can be 0.001 to 20 parts by mass per 100 parts by mass of the total of the other compounds and component (A). By keeping the amount to 20 parts by mass or less, the effect on various physical properties such as the water absorption rate and strength of the cured product can be suppressed.

When the curable composition of the present invention is photocured using a polymerization initiator, a sensitizer and a sensitizer assistant can be used. Examples of the sensitizer and the sensitizer assistant include anthracene-based compounds and naphthalene-based compounds.

Examples of the anthracene-based compounds include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentyloxyanthracene, 9,10-dihexyloxyanthracene, 9,10-bis(2-methoxyethoxy)anthracene, 9,10-bis(2-ethoxyethoxy)anthracene, 9,10-bis(2-butoxyethoxy)anthracene, 9,10-bis(3-butoxypropoxy)anthracene, 2-methyl- or 2-ethyl-9,10-dimethoxyanthracene, 2-methyl- or 2-ethyl-9,10-diethoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipropoxyanthracene, 2-methyl- or 2-ethyl-9,10-diisopropoxyanthracene, 2-methyl- or 2-ethyl-9,10-dibutoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipentyloxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene, etc.

Examples of the naphthalene compounds include 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyloxy-1-naphthol, 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, 1,4-dibutoxynaphthalene, etc.

The curable composition of the present invention may contain, as necessary, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-8-aminooctyltrimethoxysilane. aminosilane compounds such as 3-mercaptopropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxy ... Silane coupling agents such as epoxy silane compounds such as propyltriethoxysilane; reactive or non-reactive diluents (plasticizers) such as monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and coal tar; fillers or pigments such as glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, finely powdered silica, titanium dioxide, carbon black, graphite, iron oxide, and bituminous substances; lubricants such as candelilla wax, carnauba wax, Japan wax, Japanese ibote wax, beeswax, lanolin, spermaceti, montan wax, petroleum wax, fatty acid wax, fatty acid esters, fatty acid ethers, aromatic esters, and aromatic ethers; thickeners; thixotropic agents; antioxidants; light stabilizers; ultraviolet absorbers; flame retardants; defoamers; rust inhibitors; colloidal silica, colloidal alumina, and other known additives may be contained, and adhesive resins such as xylene resins and petroleum resins may also be used in combination.

The curable composition of the present invention can be cured by light and/or heat by changing the type of curing agent, which is the component (B), or by using a combination of multiple curing agents.
Among them, the curable composition of the present invention can be suitably adopted in a method of using a photopolymerization initiator and an amine-based curing agent as the component (B) in combination, provisionally curing by light irradiation, and then thermally curing. In that case, if a large amount of a compound having only an epoxy group and/or a compound having only a reactive unsaturated bond is contained, the curing may be insufficient or the physical properties of the cured product may be deteriorated. For this reason, the total amount of the compound having only an epoxy group and/or the compound having only a reactive unsaturated bond is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, relative to 100 parts by mass of the compound (A) component of the present invention. In addition, the photopolymerization initiator is preferably a photoradical polymerization initiator.

D. Cured product and method for producing the cured product The method for producing the cured product of the present disclosure includes a curing step of curing the curable composition. The curing method in the curing step is at least one of heating and light irradiation, and preferably both.
In photocuring, the light to be irradiated may include light having a wavelength of 300 nm to 450 nm. Examples of light sources used in photocuring include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, metal halogen lamps, electron beam irradiation devices, X-ray irradiation devices, and lasers (argon lasers, dye lasers, nitrogen lasers, LEDs, helium cadmium lasers, etc.).

The heating temperature for thermal curing may be any temperature that can stably cure the cured product, and is set appropriately depending on the type of curing agent, etc., but is preferably from 10°C to 250°C, and more preferably from 60°C to 200°C.

The cured product of the curable composition of the present invention is preferably a cured product obtained by photocuring followed by thermal curing, as this has excellent properties such as heat resistance. The applicant believes that this description describes a state. Even if this description were to specify an object by a manufacturing method, there are circumstances in which it would be impossible or impractical to specify a structure or properties other than those described in this specification for a cured product obtained by curing a curable compound under specified conditions, as this would require a significant amount of experimental time.

The curable composition of the present invention can be used in a wide range of applications, such as paints, adhesives, pressure sensitive adhesives, coating agents, fiber bundling agents, building materials, and electronic components. In particular, because it has excellent light and heat curing properties, it can be used in applications where dual curing is possible. Due to these properties, the curable composition of the present invention can be suitably used in applications such as liquid sealants, liquid adhesives, liquid crystal sealants, and adhesives for camera modules.

E. Other [1]
A compound represented by the following general formula (1):

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a halogen atom as a substituent, or a halogen atom, R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a glycidyl ether group, a methyl glycidyl ether group, an acryloyloxymethyl group, or a methacryloyloxymethyl group, R ⁴ represents a hydrogen atom or a methyl group, and n represents a number from 0 to 4.
[2]
A compound represented by the following general formula (2):

In the formula, ^R1 represents a hydrogen atom or a methyl group, ^R2 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a halogen atom as a substituent, or a halogen atom, ^R5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a glycidyl ether group, or a methylglycidyl ether group, and n represents a number from 0 to 4.
[3]
A method for producing a compound represented by the general formula (1), comprising reacting a compound represented by the following general formula (3) with epihalohydrin to produce a compound represented by the general formula (2), and then esterifying the compound with an acrylic acid derivative and/or a methacrylic acid derivative:

In the formula, ^R2 's each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a halogen atom as a substituent, or a halogen atom. ^R6 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a hydroxymethyl group. n represents a number from 0 to 4.
[4]
A compound represented by the general formula (1),
A curable material comprising at least one of a compound represented by the above general formula (2) and a compound represented by the following general formula (4):
In the formula, R ⁷ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms as a substituent, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a hydroxyl group or a halogen atom, a hydroxyl group, or a halogen atom, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, a glycidyl ether group, a methyl glycidyl ether group, a glycidyloxyalkyl group, a β-methyl glycidyloxyalkyl group, an acryloyloxyalkyl group, or a methacryloyloxyalkyl group. R ⁹ represents a hydrogen atom or a methyl group. m represents a number from 0 to 4.
[5]
The curable material according to [4], which contains a compound represented by the general formula (4).
[6]
A curable composition comprising (A) at least one compound according to the above item [1] and (B) at least one curing agent.
[7]
The curable composition according to [6], further comprising at least one of a compound represented by the general formula (2) and a compound represented by the general formula (4).
[8]
A method for producing a cured product, comprising a curing step of curing the curable composition according to [6] or [7].
[9]
The method for producing a cured product according to [8], wherein the curing method in the curing step is at least one of heating and light irradiation.
[10]
A cured product of the curable composition according to [6] or [7].

Next, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

[Example 1] Production of DOP-EP (compound represented by the following formula) 238g (1.0 mol) of DOP (compound represented by the following formula) and 463g (5.0 mol, 5.0 equivalents) of epichlorohydrin were charged into a flask equipped with a reflux device, a stirrer and a dropping device. 79g (0.95 mol) of 48% by mass aqueous sodium hydroxide solution was dropped at 65-70°C and 21.0 kPa over 2 hours and 30 minutes. After the reaction was completed, the excess epichlorohydrin was distilled off under reduced pressure. Thereafter, 450g (150% by mass) of toluene was added thereto, and the mixture was washed with water three times, after which the toluene was removed to obtain a crude product.
Crude yield: 277.35 g, crude yield: 93.7%, epoxy equivalent: 314 g/eq. (theoretical epoxy equivalent: 294 g/eq.), saponifiable chlorine: 4600 ppm
266 g of the crude product was dissolved in 450 g (150% by mass) of toluene, and 4.7 g (50 mmol) of a 48% by mass aqueous sodium hydroxide solution was added dropwise to the solution and reacted for 2 hours at 60° C. The reaction product was washed three times with water, and then the toluene was removed to obtain the target product.
Yield: 277.35 g, yield: 93.7%, epoxy equivalent: 298 g/eq. (theoretical epoxy equivalent: 294 g/eq.), total chlorine: 1500 ppm by mass
The results of H ¹ -NMR measurement of the obtained compound (DOP-EP) are shown below. NMR was measured using an ECX-400 manufactured by JEOL Ltd. Deuterated dimethyl sulfoxide (deuterated DMSO) was used as the measurement solvent.

( ^1H -NMR Measurement Results of the Compound Obtained in Example 1)

[Example 2] Production of DOP-EP-AC (compound represented by the following formula) In a flask equipped with a reflux device and a stirrer, 236 g (0.80 mol) of the compound DOP-EP obtained above and 310 g (3.6 mol, 4.5 equivalents) of methyl acrylate were charged. Furthermore, 6.8 g (2.5 mol%) of tetrabutoxytitanium and 353 g (150 mass%) of toluene were charged, and the mixture was stirred at 81°C to 87°C for 11 hours to remove methanol and carry out an esterification reaction. Water was added to the reaction product and the mixture was stirred at 60°C for 1 hour, followed by reflux dehydration at 60°C and 20 Pa, and the toluene was removed after filtration to obtain the target product (DOP-EP-AC below).
Yield: 238.5 g, yield: 93.7%, epoxy equivalent: 369 g/eq. (theoretical epoxy equivalent: 348 g/eq.), total chlorine: 770 ppm by mass, Ti atom content: 1.3 ppm by mass
The results of H ¹ -NMR measurement of the obtained compound DOP-EP-AC are shown below. NMR was measured using an ECX-NMR spectrometer manufactured by JEOL Ltd., ECX-400 manufactured by JEOL Ltd. Deuterated dimethyl sulfoxide (deuterated DMSO) was used as the measurement solvent.

( ^1H -NMR Measurement Results of the Compound Obtained in Example 2)

Example 3
100 parts by mass of DOP-EP-AC obtained in Example 2, 3 parts by mass of Irgacure 184 (manufactured by BASF; 1-hydroxycyclohexan-1-yl phenyl ketone), and 3 parts by mass of 2-ethyl-4-methylimidazole were kneaded with a planetary stirrer to prepare a curable composition. The curable composition prepared above was applied to a glass plate with a thickness of 300 μm with a bar coater to obtain a coating film. The obtained curable composition was photocured under the following conditions, or photocured and heat cured in this order, and the dynamic viscoelasticity test of the cured product was performed under the following conditions. The results are shown in FIG. 1. It was confirmed that after light irradiation, curing had progressed sufficiently before heat curing, and a releasable coating film was formed.
Photocuring: UV light was applied for 2.0 seconds at 0.5 W using a HOYA LED-UV irradiator LS series.
Heat curing: heated in a heat circulation oven at 150° C. for 2 hours.
Dynamic viscoelasticity test: The glass transition temperature (Tg) was measured using an RSA manufactured by TA Instruments Co., Ltd. A rectangular test piece having a width of 4 mm, a length of 60 mm, and a thickness of 300 μm was prepared.

[Example 4] Production of DOP2-EP (compound represented by the following formula) 160g (0.67 mol) of DOP2 (compound represented by the following formula) and 496g (5.4 mol, 8.0 equivalents) of epichlorohydrin were charged into a flask equipped with a reflux device, a stirrer and a dropping device. 53.3g (0.64 mol) of 48% by mass aqueous sodium hydroxide solution was dropped thereto at 65-70°C and 18.0 kPa over 2 hours and 30 minutes. After the reaction was completed, the excess epichlorohydrin was distilled off under reduced pressure. Thereafter, 298g (150% by mass) of toluene was added thereto, and the mixture was washed with water three times, after which the toluene was removed to obtain a crude product.
Crude yield: 181.2 g, crude yield: 91.7%, epoxy equivalent: 316 g/eq. (theoretical epoxy equivalent: 294 g/eq.), saponifiable chlorine: 3,400 ppm
166 g of the crude product was dissolved in 332 g (200% by mass) of toluene, and 2.0 g (24 mmol) of a 48% by mass aqueous sodium hydroxide solution was added dropwise to the solution and reacted for 2 hours at 60° C. The reaction product was washed three times with water, and then the toluene was removed to obtain the target product.
Yield: 159.9 g, yield: 96.3%, epoxy equivalent: 324 g/eq. (theoretical epoxy equivalent: 294 g/eq.), total chlorine: 736 ppm
The results of H ¹ -NMR measurement of the obtained compound (DOP2-EP) are shown below. NMR was measured using an ECX-400 manufactured by JEOL Ltd. Deuterated dimethyl sulfoxide (deuterated DMSO) was used as the measurement solvent.

( ^1H -NMR Measurement Results of the Compound Obtained in Example 4)

[Example 5] Production of DOP2-EP-AC (compound represented by the following formula) In a flask equipped with a reflux device and a stirrer, 130 g (0.44 mol) of the compound DOP2-EP obtained above and 148 g (1.7 mol, 3.9 equivalents) of methyl acrylate were charged. Furthermore, 3.8 g (2.5 mol%) of tetrabutoxytitanium and 195 g (150 mass%) of toluene were charged, and a methanol removal reaction was carried out while stirring at 81°C to 87°C for 21 hours. Water was added to the obtained reaction product, and the mixture was stirred at 60°C for 1 hour, followed by reflux dehydration at 60°C and 20 Pa, and the toluene was removed after filtration to obtain the target product (DOP2-EP-AC below).
Yield: 133.3 g, yield: 86.6%, epoxy equivalent: 395 g/eq. (theoretical epoxy equivalent: 348 g/eq.), total chlorine: 604 ppm by mass, Ti atom content: 22.0 ppm by mass
The results of H ¹ -NMR measurement of the obtained compound DOP2-EP-AC are shown below. NMR was measured using ECX-400 manufactured by JEOL Ltd. Deuterated dimethyl sulfoxide (DMSO) was used as the measurement solvent.

( ^1H -NMR Measurement Results of the Compound Obtained in Example 5)

Example 6
100 parts by mass of DOP2-EP-AC obtained in Example 5, 3 parts by mass of Irgacure 184 (manufactured by BASF; 1-hydroxycyclohexan-1-yl phenyl ketone), and 3 parts by mass of 2-ethyl-4-methylimidazole were kneaded with a planetary stirrer to prepare a curable composition. The curable composition prepared above was applied to a glass plate with a thickness of 300 μm using a bar coater to obtain a coating film. The obtained curable composition was photocured and heat cured in this order under the following conditions, and the dynamic viscoelasticity test of the cured product was performed under the following conditions. The results are shown in FIG. 2 (results of UV curing were not measured). It was confirmed that after light irradiation, curing had progressed sufficiently before heat curing, and a releasable coating film was formed.
Photocuring: UV light was applied for 2.0 seconds at 0.5 W using a HOYA LED-UV irradiator LS series.
Heat curing: heated in a heat circulation oven at 150° C. for 2 hours.
DMA (dynamic viscoelasticity measurement): The glass transition point (Tg) was measured using an RSA manufactured by TA Instruments Co., Ltd. A rectangular test piece having a width of 5 mm, a length of 60 mm, and a thickness of 300 μm was prepared.

As mentioned above, it was confirmed from Figure 1 that the compound obtained in Example 2 had sufficient photocurability and also excellent thermosetting properties. As mentioned above, the compound obtained in Example 5 also had sufficient photocurability. As shown in Figure 2, the photo- and thermosetting product using the compound obtained in Example 5 showed a certain degree of curability with no significant decrease in storage modulus E' up to the thermosetting temperature of over 150°C. It can also be seen that the photo- and thermosetting product using the compound of Example 5 has a glass transition point of 183°C and is therefore highly heat resistant. Thus, the compound provided by the present invention can provide a curable composition with excellent photo- and thermal curability.

[Example 7] Production of DOP2-EP/DOP2-EP-AC mixture In a flask equipped with a reflux device and a stirrer, 130 g (0.44 mol) of the compound DOP2-EP obtained above and 148 g (1.7 mol, 3.9 equivalents) of methyl acrylate were charged. Furthermore, 3.8 g (2.5 mol%) of tetrabutoxytitanium and 195 g (150 mass%) of toluene were charged, and a methanol removal reaction was carried out while stirring at 81°C to 87°C for 12 hours. Water was added to the obtained reaction product, and the mixture was stirred at 60°C for 1 hour, and then reflux dehydration was carried out at 60°C and 20 Pa, and the toluene was removed after filtration to obtain a curable material 1. When analyzed by gas chromatography, it was confirmed that the curable material 1 was a mixture of DOP2-EP and DOP2-EP-AC, and the mass ratio (DOP2-EP:DOP2-EP-AC) was 5:95.

[Example 8] Production of a mixture of DOP2-EP/DOP2-EP2 (compounds represented by the following formula) 160g (0.67 mol) of DOP2 and 496g (5.4 mol, 8.0 equivalents) of epichlorohydrin were charged into a flask equipped with a reflux device, a stirrer, and a dropping device. 53.3g (0.70 mol) of 48% by mass aqueous sodium hydroxide solution was dropped at 65-70°C and 18.0 kPa over 2 hours and 30 minutes. After the reaction was completed, the excess epichlorohydrin was distilled off under reduced pressure. Then, 298g (150% by mass) of toluene was added thereto, and the mixture was washed with water three times, after which the toluene was removed, and a curable material 2 was obtained. When analyzed by gas chromatography, it was confirmed that the curable material 2 was a mixture of DOP2-EP and DOP2-EP2, and the mass ratio (DOP2-EP:DOP2-EP2) was 97:3.

[Example 9] Production of DOP2-EP / DOP2-EP2 / DOP2-EP-AC mixture In a flask equipped with a reflux device and a stirrer, 130g (0.44 mol) of the curable material 2 obtained above and 148g (1.7 mol, 3.9 equivalents) of methyl acrylate were charged. Furthermore, 3.8g (2.5 mol%) of tetrabutoxytitanium and 195g (150 mass%) of toluene were charged, and a methanol removal reaction was carried out while stirring at 81 ° C to 87 ° C for 12 hours. Water was added to the obtained reaction product, and the mixture was stirred at 60 ° C for 1 hour, and then reflux dehydration was carried out at 60 ° C and 20 Pa, and the toluene was removed after filtration to obtain a curable material 3. Analysis by gas chromatography confirmed that the curable material 3 was a mixture of DOP2-EP, DOP2-EP-AC, and DOP2-EP-AC, with a mass ratio (DOP2-EP:DOP2-EP2:DOP2-EP-AC) of 5:3:92.

A curable composition was prepared by kneading 100 parts by mass of the curable material 1 obtained in Example 7 or the curable material 3 obtained in Example 9, 3 parts by mass of Irgacure 184 (manufactured by BASF; 1-hydroxycyclohexan-1-yl phenyl ketone) and 3 parts by mass of 2-ethyl-4-methylimidazole with a planetary stirrer. The curable composition prepared above was applied to a glass plate with a thickness of 300 μm with a bar coater to obtain a coating film. The obtained curable composition was subjected to photocuring and heat curing in this order under the following conditions, and the presence or absence of curing (A, B) was confirmed according to the following evaluation criteria.
Photocuring: UV light was applied for 2.0 seconds at 0.5 W using a HOYA LED-UV irradiator LS series.
(Evaluation Criteria for Photocurability)
A: After photocuring and before thermal curing, it was confirmed that curing had progressed sufficiently and a releasable coating film had been formed.
B: After photocuring and before thermal curing, it was confirmed that curing was insufficient and a releasable coating film was not formed.
Heat curing: heated in a heat circulation oven at 150° C. for 2 hours.
(Evaluation Criteria for Thermosetting)
A: After heat curing, it was confirmed that the curing had progressed sufficiently and a releasable coating film had been formed.
B: After heat curing, it was confirmed that the curing was insufficient and that a releasable coating film was not formed due to insufficient curing.

As described above, it was confirmed that the curable composition containing a mixture of the compound of formula (1) and the compound of formula (2) and/or the compound of formula (4) also has sufficient photocurability and thermosetting properties.

The compound of the present invention can be cured by light and heat, and the curable composition obtained by containing it has excellent curing properties by light and heat, so it can be used for applications such as liquid sealants, liquid adhesives, adhesives for camera modules, and liquid crystal sealants.

Claims

A compound represented by the following general formula (1):
In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a halogen atom as a substituent, or a halogen atom, R 3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a glycidyl ether group, a methyl glycidyl ether group, an acryloyloxymethyl group, or a methacryloyloxymethyl group, R 4 represents a hydrogen atom or a methyl group, and n represents a number from 0 to 4.
A compound represented by the following general formula (2):

In the formula, R1 represents a hydrogen atom or a methyl group, R2 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a halogen atom as a substituent, or a halogen atom, R5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a glycidyl ether group, or a methylglycidyl ether group, and n represents a number from 0 to 4.
A method for producing a compound represented by the following general formula (1), comprising reacting a compound represented by the following general formula (3) with epihalohydrin to produce a compound represented by the following general formula (2), and esterifying the compound with an acrylic acid derivative and/or a methacrylic acid derivative.

In the formula, R2 's each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a halogen atom as a substituent, or a halogen atom. R6 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a hydroxymethyl group. n represents a number from 0 to 4.

In the formula, R1 represents a hydrogen atom or a methyl group, R2 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a halogen atom as a substituent, or a halogen atom, R5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a glycidyl ether group, or a methylglycidyl ether group, and n represents a number from 0 to 4.
In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a halogen atom as a substituent, or a halogen atom, R 3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a glycidyl ether group, a methyl glycidyl ether group, an acryloyloxymethyl group, or a methacryloyloxymethyl group, R 4 represents a hydrogen atom or a methyl group, and n represents a number from 0 to 4.
A compound represented by the following general formula (1),
A curable material comprising at least one of a compound represented by the following general formula (2) and a compound represented by the following general formula (4):
In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a halogen atom as a substituent, or a halogen atom, R 3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a glycidyl ether group, a methyl glycidyl ether group, an acryloyloxymethyl group, or a methacryloyloxymethyl group, R 4 represents a hydrogen atom or a methyl group, and n represents a number from 0 to 4.

In the formula, R1 represents a hydrogen atom or a methyl group, R2 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a halogen atom as a substituent, or a halogen atom, R5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a glycidyl ether group, or a methylglycidyl ether group, and n represents a number from 0 to 4.
In the formula, R 7 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms as a substituent, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a hydroxyl group or a halogen atom, a hydroxyl group, or a halogen atom, R 8 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, a glycidyl ether group, a methyl glycidyl ether group, a glycidyloxyalkyl group, a β-methyl glycidyloxyalkyl group, an acryloyloxyalkyl group, or a methacryloyloxyalkyl group. R 9 represents a hydrogen atom or a methyl group. m represents a number from 0 to 4.
The curable material according to claim 4, which contains a compound represented by the general formula (4).
A curable composition containing at least one compound according to claim 1 and at least one curing agent selected from (A) and (B).
The curable composition according to claim 6, further comprising at least one of a compound represented by the following general formula (2) and a compound represented by the following general formula (4):

In the formula, R1 represents a hydrogen atom or a methyl group, R2 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a halogen atom as a substituent, or a halogen atom, R5 represents an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a glycidyl ether group, or a methyl glycidyl ether group, and n represents a number from 0 to 4.
In the formula, R 7 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms as a substituent, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms which may have a hydroxyl group or a halogen atom, a hydroxyl group, or a halogen atom, R 8 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, a glycidyl ether group, a methyl glycidyl ether group, a glycidyloxyalkyl group, a β-methyl glycidyloxyalkyl group, an acryloyloxyalkyl group, or a methacryloyloxyalkyl group. R 9 represents a hydrogen atom or a methyl group. m represents a number from 0 to 4.
A method for producing a cured product comprising a curing step of curing the curable composition according to claim 6 or 7.
The method for producing a cured product according to claim 8, wherein the curing method in the curing step is at least one of heating and light irradiation.
A cured product of the curable composition according to claim 6 or claim 7.