JP6487233B2 - Polyfunctional epoxy compound and method for producing the same - Google Patents

Description

  The present invention relates to a novel polyfunctional epoxy compound that can be used in various applications such as composite materials, coating agents, adhesives, sealants, transparent materials, optical materials, and electronic materials, and a method for producing the same. Moreover, this invention relates to the resin composition using the said polyfunctional epoxy compound, and its hardened | cured material.

  At present, epoxy compounds (epoxy resins) are used in various applications in industry. Among these, alicyclic epoxy compounds (alicyclic epoxy resins) are known as epoxy compounds excellent in heat resistance and light resistance. As such alicyclic epoxy compounds, for example, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adducts of polyhydric alcohols are industrially produced and used (for example, patent documents). 1 and 2 etc.).

Japanese Patent Laid-Open No. 60-161973 JP-A-60-166675

  The above 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of polyhydric alcohol is an epoxy compound having a good balance of various properties such as heat resistance, light resistance and water resistance. As the use expands more and more, development of an epoxy compound capable of forming a cured product having even more excellent heat resistance (for example, a cured product that is less susceptible to yellowing by heating) is required.

  Therefore, the objective of this invention is providing the novel epoxy compound which can form the hardened | cured material excellent in heat resistance, and its manufacturing method.

  As a result of intensive studies to solve the above problems, the present inventors have found that a novel polyfunctional epoxy compound having a specific structure can form a cured product having excellent heat resistance, and have completed the present invention.

［式（１）中、Ｒ¹〜Ｒ¹⁰は、同一又は異なって、水素原子、酸素原子を含んでいてもよい炭素数１〜１０の炭化水素基、ハロゲン原子、式（ａ１）で表される基、式（ａ２）で表される基、又は式（ａ３）で表される基を示す。但し、式（１）におけるＲ¹〜Ｒ¹⁰の少なくとも１つは、式（ａ１）で表される基である。

［式（ａ３）中、Ｒ¹¹は、水素原子、カルボキシ基、アシル基、又は炭化水素基を示す。］］
で表される構成単位を含む多官能エポキシ化合物を提供する。 That is, the present invention has two or more epoxy groups in the molecule, and has the following formula (1)

In Expression ^(1), R 1 ~R ¹⁰ are the same or different, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom, a halogen atom, represented by the formula (a1) A group represented by formula (a2), or a group represented by formula (a3). However, at least one of R ^{1 to} R ^{10 in} the formula (1) is a group represented by the formula (a1).

[In formula (a3), R ¹¹ represents a hydrogen atom, a carboxy group, an acyl group, or a hydrocarbon group. ]]
The polyfunctional epoxy compound containing the structural unit represented by this is provided.

［式（１）中、Ｒ¹〜Ｒ¹⁰は、同一又は異なって、水素原子、酸素原子を含んでいてもよい炭素数１〜１０の炭化水素基、ハロゲン原子、式（ａ１）で表される基、式（ａ２）で表される基、又は式（ａ３）で表される基を示す。但し、式（１）におけるＲ¹〜Ｒ¹⁰の少なくとも１つは、式（ａ１）で表される基である。

［式（ａ３）中、Ｒ¹¹は、水素原子、カルボキシ基、アシル基、又は炭化水素基を示す。］］
で表される構成単位を含む多官能エポキシ化合物の製造方法であって、
分子内に２つ以上の脂肪族炭素−炭素二重結合を有し、下記式（２）

［式（２）中、Ｒ¹〜Ｒ¹⁰は、同一又は異なって、水素原子、酸素原子を含んでいてもよい炭素数１〜１０の炭化水素基、ハロゲン原子、又は式（ａ２）で表される基を示す。但し、式（２）におけるＲ¹〜Ｒ¹⁰の少なくとも１つは、式（ａ２）で表される基である。］
で表される構成単位を含む不飽和化合物を酸化剤により酸化させることによって前記多官能エポキシ化合物を生成させる工程を含む多官能エポキシ化合物の製造方法を提供する。 Moreover, this invention has two or more epoxy groups in a molecule | numerator, following formula (1)

In Expression ^(1), R 1 ~R ¹⁰ are the same or different, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom, a halogen atom, represented by the formula (a1) A group represented by formula (a2), or a group represented by formula (a3). However, at least one of R ^{1 to} R ^{10 in} the formula (1) is a group represented by the formula (a1).

[In formula (a3), R ¹¹ represents a hydrogen atom, a carboxy group, an acyl group, or a hydrocarbon group. ]]
A method for producing a polyfunctional epoxy compound containing a structural unit represented by:
It has two or more aliphatic carbon-carbon double bonds in the molecule, and has the following formula (2)

[In Formula (2), R < ¹ > -R < ¹⁰ > is the same or different, and is represented by the C1-C10 hydrocarbon group which may contain a hydrogen atom and an oxygen atom, a halogen atom, or Formula (a2). Represents a group. However, at least one of R ^{1 to} R ^{10 in} the formula (2) is a group represented by the formula (a2). ]
The manufacturing method of the polyfunctional epoxy compound including the process of producing | generating the said polyfunctional epoxy compound by oxidizing the unsaturated compound containing the structural unit represented by an oxidizing agent is provided.

  Furthermore, the manufacturing method of the said polyfunctional epoxy compound whose oxidizing agent is a peracid is provided.

  Moreover, this invention provides the resin composition containing the said polyfunctional epoxy compound.

  Moreover, this invention provides the hardened | cured material obtained by hardening the said resin composition.

  Since the polyfunctional epoxy compound of this invention has the said structure, the cured | curing material excellent in heat resistance can be formed by hardening the said polyfunctional epoxy compound or the resin composition containing this.

<Polyfunctional epoxy compound>
The polyfunctional epoxy compound (polyfunctional epoxy resin) of the present invention is a polyfunctional epoxy compound containing a structural unit represented by the following formula (1) as an essential structural unit. The polyfunctional epoxy compound of the present invention is a polyfunctional epoxy compound having two or more epoxy groups (oxiranyl groups) in the molecule.

In formula (1), R ^{1 to} R ¹⁰ are the same or different and are represented by a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom, a halogen atom, and the following formula (a1). A group represented by the following formula (a2) or a group represented by the following formula (a3).

However, at least one of R ^{1 to} R ^{10 in} the formula (1) is a group (epoxy group) represented by the formula (a1). That is, the polyfunctional epoxy compound of the present invention includes a structural unit (expressed by the formula (1)) containing at least a cyclohexane ring, an epoxy group bonded (substituted) to the cyclohexane ring, and a carbonate bond bonded to the cyclohexane ring. A structural unit). By including the structural unit represented by the formula (1), the polyfunctional epoxy compound of the present invention can exhibit excellent heat resistance and impact resistance to the cured product. The number of groups represented by among Formula (a1) of R ¹ to R ¹⁰ in the formula (1) is not particularly limited, 1 to 3 by weight, more preferably 1 or 2.

  In particular, the polyfunctional epoxy compound of the present invention preferably contains two or more structural units represented by the formula (1) as repeating structural units in the molecule. In this case, since the polyfunctional epoxy compound of the present invention is also a polycarbonate, the cured product can exhibit more excellent heat resistance and impact resistance.

The C1-C10 hydrocarbon group (monovalent hydrocarbon group) which may contain the above-described oxygen atom as R ^{1 to} R ¹⁰ has any structure of linear, branched or cyclic Moreover, any of a saturated hydrocarbon group and an unsaturated hydrocarbon group may be sufficient. Specifically, examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkyl group [for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group. An alkyl group having 1 to 10 carbon atoms, etc.], an alkenyl group [for example, allyl group, methallyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl Group, alkenyl group having 3 to 10 carbon atoms such as 2-pentenyl group, 3-pentenyl group, 4-pentenyl group and 5-hexenyl group], alkynyl group [for example, 2 to 2 carbon atoms such as ethynyl group and propynyl group] 10 alkynyl group, etc.], cycloalkyl group [e.g., cycloalkyl group having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, etc. ], A cycloalkenyl group [for example, a cycloalkenyl group having 3 to 10 carbon atoms such as a cyclohexenyl group], a bridged cyclic hydrocarbon group [for example, a carbon number of 5 to 10 such as bicycloheptanyl group, bicycloheptenyl group, etc. A bridged cyclic hydrocarbon group, etc.], an aryl group [for example, an aryl group having 6 to 10 carbon atoms such as a phenyl group], an aliphatic hydrocarbon group and an alicyclic hydrocarbon group. A group [for example, a cycloalkyl-alkyl group such as a cyclohexylmethyl group; an alkyl-substituted cycloalkyl group such as a methylcyclohexyl group], a group formed by linking an aliphatic hydrocarbon group and an aromatic hydrocarbon group [ For example, alkyl-substituted aryl groups such as tolyl groups; alkenyl-substituted aryl groups such as styryl groups; aryl-alkenyl groups such as cinnamyl groups; benzyl groups and phenethyl groups It includes aralkyl groups, etc.] or the like. As the hydrocarbon group containing an oxygen atom (hydrocarbon group containing an oxygen atom having 1 to 10 carbon atoms), for example, one or more hydrogen atoms in the above-described hydrocarbon group having 1 to 10 carbon atoms are oxygen. Examples include a group substituted with an atom-containing group (for example, a hydroxy group, a carboxy group, etc.), a group in which one or more carbon atoms in the above-described hydrocarbon group having 1 to 10 carbon atoms are substituted with an oxygen atom, and the like. . In addition, the groups represented by the formulas (a1) to (a3) are not included in “the hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom” as R ^{1 to} R ¹⁰ .

As a halogen atom as R < ¹ > -R < ¹⁰ >, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.

In formula (a3), R ¹¹ represents a hydrogen atom, a carboxy group, an acyl group, or a hydrocarbon group. Examples of the hydrocarbon group, for example, illustrated like hydrocarbon group having 1 to 10 carbon atoms as R ¹ to R ¹⁰ can be mentioned. As an acyl group, C1-C10 acyl groups, such as an acetyl group, a propionyl group, a benzoyl group, etc. are mentioned, for example. In addition, when the polyfunctional epoxy compound of the present invention has two or more groups represented by the formula (a3), it may have only one group represented by the formula (a3). It may have a group represented by the formula (a3) of a species or more.

  The polyfunctional epoxy compound of the present invention only needs to contain the structural unit represented by the formula (1) (particularly the repeating structural unit), and contains other structural units (for example, the repeating structural unit). May be. As other structural units, for example, structural units formed by the reaction of an epoxy compound other than the compound represented by the following formula (3) with carbon dioxide, the carbonate bond in the formula (1) is replaced with an ether bond. Examples of the structural unit. The arrangement of each structural unit in the case where the polyfunctional epoxy compound of the present invention has two or more structural units is not particularly limited, and may be a random copolymer mode or a block copolymer mode. There may be. In addition, although the terminal structure of the polyfunctional epoxy compound of this invention is not specifically limited, For example, the structure (for example, chlorine atom) derived from a catalyst, a hydroxyl group, a hydrogen atom, a hydrocarbon group etc. are mentioned.

  The proportion of the structural unit represented by the formula (1) in the polyfunctional epoxy compound (100% by weight) of the present invention is not particularly limited, but is 60% by weight or more from the viewpoint of heat resistance and impact resistance of the cured product. It is preferably 80% by weight or more, more preferably 90% by weight or more (for example, 90 to 98% by weight).

  The polyfunctional epoxy compound of the present invention may have any structure such as a straight chain or a branched chain. When the proportion of the structural unit represented by the formula (1) in the polyfunctional epoxy compound of the present invention is large (for example, 80% by weight or more), the polyfunctional epoxy compound of the present invention usually has a linear structure. Have

  The polyfunctional epoxy compound of the present invention may be a single compound or an aggregate of two or more compounds (for example, an aggregate of two or more polyfunctional epoxy compounds of the present invention having different molecular weights). It may be.

  Although the epoxy equivalent of the polyfunctional epoxy compound of this invention is not specifically limited, 80-2000 are preferable, More preferably, it is 140-500. By setting the epoxy equivalent to 80 or more, the toughness of the cured product tends to be further improved. On the other hand, when the epoxy equivalent is 2000 or less, the mechanical strength and heat resistance of the cured product tend to be further improved. The epoxy equivalent is measured according to JIS K7236.

  Although the oxirane oxygen concentration of the polyfunctional epoxy compound of this invention is not specifically limited, 1-20% is preferable, More preferably, it is 3-12%. By setting the oxirane oxygen concentration to 1% or more, the mechanical strength and heat resistance of the cured product tend to be further improved. On the other hand, by setting the oxirane oxygen concentration to 20% or less, the toughness of the cured product tends to be further improved. The oxirane oxygen concentration is measured according to ASTM-D1652 method (hydrobromic acid method).

  Although the softening point of the polyfunctional epoxy compound of this invention is not specifically limited, 150 degreeC or less is preferable, More preferably, it is 140 degreeC or less, More preferably, it is 130 degreeC or less. When the softening point is 150 ° C. or lower, the handleability tends to be further improved. The softening point is measured according to JIS K7234.

  Although the weight average molecular weight (Mw) of the polyfunctional epoxy compound of this invention is not specifically limited, 350-100000 are preferable, More preferably, it is 900-10000. When the weight average molecular weight is 350 or more, the mechanical strength and heat resistance of the cured product tend to be further improved. On the other hand, when the weight average molecular weight is 100,000 or less, the compatibility with other components becomes higher, and the transparency and mechanical strength of the cured product tend to be further improved. In addition, a weight average molecular weight is computed from the molecular weight of standard polystyrene conversion measured by a gel permeation chromatography (GPC) method.

  The polydispersity (Mw / Mn) of the polyfunctional epoxy compound of the present invention is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.1 to 3.0, and still more preferably 1.1. ~ 2.0. By setting the polydispersity in the above range, the heat resistance of the cured product tends to be further improved. In addition, polydispersity is calculated | required from Mw calculated from the molecular weight of standard polystyrene conversion measured by GPC method, and a number average molecular weight (Mn).

<Production method of polyfunctional epoxy compound>
The polyfunctional epoxy compound of the present invention has, for example, two or more aliphatic carbon-carbon double bonds (for example, vinyl group) in the molecule, and a structural unit represented by the following formula (2) is essential. It can be produced by oxidizing an unsaturated compound contained as a structural unit with an oxidizing agent. That is, the polyfunctional epoxy compound of the present invention requires, for example, a step of generating the polyfunctional epoxy compound of the present invention by oxidizing the unsaturated compound with an oxidizing agent (sometimes referred to as an “epoxidation step”). (This method may be referred to as “the method for producing a polyfunctional epoxy compound of the present invention”).

[Epoxidation process]
The structural unit represented by the formula (2) corresponds to the precursor structure of the structural unit represented by the formula (1). That is, R ^{1 to} R ¹⁰ in the formula (2) are the same or different and are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom, a halogen atom, or the formula (a2). The group represented is shown. However, at least one of R ^{1 to} R ^{10 in} the formula (2) is a group represented by the formula (a2). In the epoxidation step, part or all of the group represented by the formula (a2) in the formula (2) is converted to the group represented by the formula (a1) (in some cases, in the formula (a1) A part of the represented group is further converted into a group represented by the formula (a3), whereby the polyfunctional epoxy compound of the present invention is produced. In addition, although the number of group represented by Formula (a2) among R < ¹ > -R < ¹⁰ > in Formula (2) is not specifically limited, 1-3 are preferable, More preferably, it is 1 or 2.

  As an unsaturated compound containing the structural unit represented by Formula (2), what is obtained using a known or conventional production method can be used. Specifically, for example, those produced according to the method described in the paragraph of the polymerization step described later can be used. In the epoxidation step, the unsaturated compound containing the structural unit represented by formula (2) can be used alone or in combination of two or more. As an unsaturated compound containing the structural unit represented by Formula (2), the structural unit represented by Formula (1) in the polyfunctional epoxy compound of this invention is a structural unit represented by Formula (2), for example. Except that there are the same compounds and the like.

  As an oxidizing agent used in the epoxidation step, at least a part of the group represented by the formula (a2) in the structural unit represented by the formula (2) can be converted into a group represented by the formula (a1). Any known oxidizing agent can be used as long as it is a known one. More specifically, as the oxidizing agent, hydrogen peroxide, peracids such as performic acid, peracetic acid, perbenzoic acid, and trifluoroperacetic acid (for example, organic peracids) can be used. Among them, peracid (particularly peracetic acid) is preferable because it is industrially available at low cost and has high stability. The oxidizing agent can be used as it is or in the form of a solution, a dispersion, or the like. In addition, in an epoxidation process, an oxidizing agent can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  In the reaction (oxidation reaction) between the unsaturated compound containing the structural unit represented by the formula (2) and the oxidizing agent, a known or commonly used catalyst may be used. Examples of the catalyst include alkalis such as sodium carbonate and acids such as sulfuric acid.

  The oxidation reaction can be carried out by determining the presence or absence of the use of a solvent or appropriately adjusting the conditions such as the reaction temperature according to the equipment used and the physical properties of the raw materials.

  The temperature (reaction temperature) at which the oxidation reaction proceeds can be appropriately determined depending on the reactivity of the oxidizing agent to be used, and is not particularly limited. For example, when peracetic acid is used as the oxidizing agent, 0 to It is preferable to set it as 70 degreeC. By setting the reaction temperature to 0 ° C. or higher, the oxidation reaction tends to proceed at an excellent reaction rate. On the other hand, by making reaction temperature 70 degrees C or less, there exists a tendency for decomposition | disassembly of a peracetic acid to be suppressed and productivity of a polyfunctional epoxy compound to improve more.

  In the oxidation reaction, a solvent can be used for the purpose of, for example, reducing the viscosity of the raw material or stabilizing it by diluting the oxidizing agent. When peracetic acid is used as the oxidizing agent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ethers such as diethyl ether; esters such as ethyl acetate; ketones such as acetone, methyl isobutyl ketone, and methyl ethyl ketone Etc. can be used.

  The amount of the oxidizing agent used in the oxidation reaction can be appropriately adjusted depending on the purpose such as how much the group represented by the formula (a2) is to remain in the polyfunctional epoxy compound of the present invention, and is particularly limited. Not. For example, when the purpose is to obtain a polyfunctional epoxy compound of the present invention having a small residual amount of the group represented by the formula (a2), the oxidant is represented by the formula (a2) having the unsaturated compound. It is preferable to use equimolar amount or more with respect to the group. However, it is usually disadvantageous to use the oxidizing agent in an amount exceeding 2 moles relative to the group represented by the formula (a2) from the economical viewpoint and the problem of the side reaction described below. For example, when peracetic acid is used as the oxidizing agent, the amount used is preferably 1 to 1.5 times the amount of the group represented by the formula (a2).

  Through the epoxidation step, part or all of the group represented by the formula (a2) in the structural unit represented by the formula (2) is epoxidized and converted into the structural unit represented by the formula (a1). As a result, the polyfunctional epoxy compound of the present invention is produced. In addition, the group represented by the formula (a3) in the polyfunctional epoxy compound of the present invention is, for example, a group represented by the formula (a2) in the structural unit represented by the formula (2) and an organic peracid (oxidation). The organic acid (for example, acetic acid) produced by the reaction of the agent), water, alcohol, etc. present in the system reacts with the group represented by the formula (a1) (side reaction). In addition, the ratio (ratio) of groups represented by the formulas (a1) to (a3) in the polyfunctional epoxy compound of the present invention is, for example, the type of oxidizing agent, the amount of oxidizing agent used (the oxidizing agent and the formula (a2)). The molar ratio of the group represented by formula (1) and the reaction conditions can be adjusted as appropriate.

  The manufacturing method of the polyfunctional epoxy compound of this invention may include processes other than the above-mentioned epoxidation process. Examples of steps other than the epoxidation step include a step of purifying and isolating the produced polyfunctional epoxy compound of the present invention, a step of generating an unsaturated compound containing the structural unit represented by the formula (2), and the like. Is mentioned. The method for purifying and isolating the polyfunctional epoxy compound of the present invention is not particularly limited. For example, separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc. Known or conventional methods such as combined separation means can be used.

As a process of producing an unsaturated compound containing the structural unit represented by the formula (2) in the method for producing a polyfunctional epoxy compound of the present invention, for example, a compound (epoxy compound) represented by the following formula (3) and Examples include a step of reacting (copolymerizing) carbon dioxide (sometimes referred to as a “polymerization step”).

[Polymerization process]
In formula (3), R ^{1 to} R ¹⁰ are the same as those in formula (2). That is, R ^{1 to} R ¹⁰ in the formula (3) are the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom, a halogen atom, or the formula (a2). The group represented is shown. However, at least one of R ^{1 to} R ¹⁰ in the formula (3) is a group represented by the formula (a2). In addition, although the number of group represented by Formula (a2) among R < ¹ > -R < ¹⁰ > in Formula (3) is not specifically limited, 1-3 are preferable, More preferably, it is 1 or 2. The compound represented by the formula (3) can be produced by a known or conventional production method, or a commercially available product can be obtained. In addition, the compound represented by Formula (3) in a superposition | polymerization process can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The reaction of the compound represented by the formula (3) with carbon dioxide is, for example, disclosed in JP2010-1443A, WO2012 / 102101, WO2012 / 114939, Macromolecules 2011, 44, 9882- The method disclosed in 9886, etc. (a method in which the reaction between an epoxy compound and carbon dioxide proceeds in the presence of a specific cobalt catalyst); the method disclosed in JP 2012-180445 A, etc. (metal such as a zinc catalyst) For example, a method in which a reaction between an epoxy compound and carbon dioxide proceeds in the presence of a catalyst).

  In the polymerization step, only the compound represented by formula (3) and carbon dioxide may be reacted, or the compound represented by formula (3) and other epoxy compounds (other epoxy compounds) One or more types may be reacted with carbon dioxide. As other epoxy compounds, known or conventional epoxy compounds can be used. The proportion of the compound represented by formula (3) in the polymerization step is not particularly limited, but it is 60 with respect to the total amount (100% by weight) of the epoxy compound to be used from the viewpoint of heat resistance and impact resistance of the cured product. % By weight or more (for example, 60 to 100% by weight) is preferable, more preferably 80% by weight or more, and further preferably 90% by weight or more. In addition, the usage-amount of the compound represented by Formula (3) in a superposition | polymerization process may be substantially whole quantity (for example, 98-100 weight%) of the epoxy compound to be used.

  The unsaturated compound containing the structural unit represented by the formula (2) obtained by the polymerization process is used in the subsequent epoxidation process after purification by a conventional method (for example, filtration, drying, etc.) after the completion of the above reaction. It can also be used in the subsequent epoxidation step without being isolated after completion of the above reaction (in the form contained in the reaction solution).

  In addition to the above-described epoxidation step and polymerization step, the method for producing a polyfunctional epoxy compound of the present invention includes, for example, a step of forming a structural unit in which the carbonate bond in formula (1) is replaced with an ether bond, and the like. May be included. As the said process, the polymerization reaction of the compound represented by Formula (3) from the active hydrogen group (hydrogen atom etc. of a hydroxy group) in the unsaturated compound containing the structural unit represented by Formula (2) as a starting point, for example (For example, a process described in JP-A-4-10471).

  The polyfunctional epoxy compound of the present invention can be used for various applications in which an epoxy compound (epoxy resin) is used, and the application is not particularly limited. For example, adhesives; paints; inks; Various electrical and electronic materials such as plates and semiconductor element sealing materials; resists, transparent substrates, transparent sheets, transparent films, optical elements, optical lenses, optical members, stereolithography, electronic paper, touch panels, solar cell substrates, optical waveguides And various optical materials such as a light guide plate, a holographic memory, and a sealing material for optical semiconductor elements; and various structural materials such as a sealant and a structural material. In various applications, the polyfunctional epoxy compound of the present invention can be used alone or in other forms such as a resin composition.

<Resin composition and cured product thereof>
The resin composition of the present invention is a composition (curable epoxy resin composition) containing the polyfunctional epoxy compound of the present invention as an essential component, and by curing this, a cured product ("cured product of the present invention") May be obtained). When curing, one or more of known or conventional means (heating, active energy ray irradiation, etc.) can be used. The cured product of the present invention exhibits excellent heat resistance by including a structure derived from the polyfunctional epoxy compound of the present invention. In addition, the resin composition of this invention may have only 1 type of the polyfunctional epoxy compound of this invention, and may have 2 or more types.

  The content (blending amount) of the polyfunctional epoxy compound of the present invention in the resin composition of the present invention is not particularly limited, but is preferably 1 to 99% by weight with respect to the total amount (100% by weight) of the resin composition, More preferably, it is 5 to 95% by weight. By controlling the content of the polyfunctional epoxy compound of the present invention within the above range, the heat resistance and impact resistance of the cured product tend to be further improved.

  The resin composition of the present invention may contain one or more epoxy compounds (epoxy resins) other than the polyfunctional epoxy compound of the present invention. Examples of such epoxy compounds include aromatic epoxy compounds (for example, bisphenol A type epoxy compounds), alicyclic epoxy compounds, aliphatic epoxy compounds, and the like. From the viewpoint of heat resistance and light resistance of the cured product, an alicyclic epoxy compound is preferable. Examples of the alicyclic epoxy compound include trade names “Celoxide 2021P”, “Celoxide 2081”, “Celoxide 3000”, “Celoxide 2000”, “Epolide GT400”, “Selvinus B0084”, “Selvinus B0177” (and above). , Manufactured by Daicel Corporation). Although content of epoxy compounds other than the polyfunctional epoxy compound of this invention in the resin composition of this invention is not specifically limited, 1-99 weight% is preferable with respect to the whole quantity (100 weight%) of an epoxy compound, More Preferably it is 5-95 weight%.

  The resin composition of the present invention may contain components other than the epoxy compound. Examples of the component include components for curing a resin composition such as a curing agent (for example, acid anhydride and polyamine), a curing accelerator, a curing catalyst; an antifoaming agent, a leveling agent, a coupling agent, and an interface. Activators, inorganic fillers such as silica and alumina, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments, mold release agents, phosphors, low molecular compounds having hydroxy groups (such as ethylene glycol) ) And other conventional additives. The content of these components is not particularly limited and can be appropriately selected.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Production Example 1
[Production of poly (vinylcyclohexene carbonate)]
4- vinyl by the method described in the literature (Macromolecules 2011, 44, 9882-9886, “Fully Degradable and Well-Defined Brush Copolymers from Combination of Living CO ₂ / Epoxide Copolymerization, ThiolEne Click Reaction and ROP of ε-caprolactone”) A reaction (copolymerization reaction) between cyclohexene -1,2-epoxide and carbon dioxide was carried out to produce poly (vinylcyclohexene carbonate). When the poly (vinylcyclohexene carbonate) obtained above was analyzed by GPC, the weight average molecular weight Mw was 6600, and the polydispersity Mw / Mn was 1.17. The molecular weight was measured as a value in terms of standard polystyrene.
The poly (vinylcyclohexene carbonate) obtained above is a compound (polymer) containing a repeating structural unit represented by the formula (2).

Production Example 2
[Production of epoxidized poly (vinylcyclohexene carbonate)]
100.0 g of poly (vinylcyclohexene carbonate) obtained in Production Example 1 and 100.0 g of ethyl acetate were put into a reactor to prepare a solution, and then stirred at 30 ° C., 30 wt% ethyl acetate in peracetic acid 180.9g was dripped over 2 hours, and also it stirred for 5 hours.
Subsequently, 400.0 g of distilled water and 20.0 g of ethyl acetate were added to the solution after the reaction and stirred for 30 minutes. Then, let stand, separate the organic layer and aqueous layer, extract and remove the aqueous layer, and measure this work (work to add distilled water and ethyl acetate, stir, separate and extract the aqueous layer). Performed 4 times. Next, the organic layer was desolvated using an evaporator at 120 ° C. and 10 Torr (about 1330 Pa) to obtain 98.6 g of epoxidized poly (vinylcyclohexene carbonate). When the GPC of the epoxidized poly (vinylcyclohexene carbonate) obtained above was analyzed, the weight average molecular weight Mw was 7160 and the polydispersity Mw / Mn was 1.16. The molecular weight was measured as a value in terms of standard polystyrene. The epoxy equivalent was 212.
The epoxidized poly (vinylcyclohexene carbonate) obtained above is a compound (polymer) containing a repeating structural unit represented by the formula (1).

Example 1
[Production of resin composition and cured product thereof]
The epoxidized poly (vinylcyclohexene carbonate) obtained in Production Example 2 with a blending ratio (unit: parts by weight) shown in Table 1, trade name “Celoxide 2021P” (epoxy compound, manufactured by Daicel Corporation), trade name “ Rikacid MH-700F "(curing agent, manufactured by Shin Nippon Rika Co., Ltd.), trade name" U-CAT 12XD "(curing accelerator, manufactured by San Apro Co., Ltd.), and ethylene glycol (EG) (diluent, Wako Jun) Yaku Kogyo Co., Ltd.) is uniformly mixed using a self-revolving stirrer (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.), defoamed, and resin composition (Curable epoxy resin composition) was produced.
Furthermore, the resin composition obtained above was cast into a molding die (a casting mold having a thickness of 3 mm), placed in a resin curing oven, and the curing conditions shown in Table 1 [100 ° C. for 2 hours, Cured by heating at 150 ° C. for 2 hours to produce a cured product.

Comparative Example 1
Except having changed the composition of the resin composition as shown in Table 1, it carried out similarly to Example 1, and manufactured the resin composition (curable epoxy resin composition) and its hardened | cured material.
In addition, “EHPE3150” in Table 1 is a product name “EHPE3150” (produced by Daicel Corporation) (1,2-epoxy-4- (2-oxiranyl) of 2,2-bis (hydroxymethyl) -1-butanol. ) Cyclohexane adduct).

(Evaluation of heat resistance)
First, the transmittance of light having a wavelength of 400 nm of each cured product obtained in Example 1 and Comparative Example 1 was measured. Thereafter, the cured product was heated in an oven at 150 ° C. for 24 hours, taken out, and the transmittance of light having a wavelength of 400 nm was measured again. If the difference in the transmittance of the cured product before and after heating [= transmittance before heating (%) − transmittance after heating (%)] is less than 12.0% point, ○ (good heat resistance) If it was 12.0% point or more, it was evaluated as x (having poor heat resistance).
In addition, it shows that the grade which a hardened | cured material yellows by heating is so large that the difference of the transmittance | permeability of the hardened | cured material before and behind heating is large (it is inferior to heat resistance).

  As shown in Table 1, the cured product of the resin composition containing the polyfunctional epoxy compound of the present invention was confirmed to have excellent heat resistance because yellowing due to heating was suppressed (Example 1). .

Claims (5)

It has two or more epoxy groups in the molecule and has the following formula (1)

[In Formula (1), R < ¹ > and R < ² > are the same or different, and show a C1-C10 hydrocarbon group which may contain the hydrogen atom and the oxygen atom, or a halogen atom. R ^{3 to} R ¹⁰ are the same or different and are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom, a halogen atom, a group represented by the formula (a1), a formula (a2) Or a group represented by the formula (a3). However, at least one of R ^{3 to} R ^{10 in} the formula (1) is a group represented by the formula (a1).

[In formula (a3), R ¹¹ represents a hydrogen atom, a carboxy group, an acyl group, or a hydrocarbon group. ]]
The polyfunctional epoxy compound containing the structural unit represented by these. It has two or more epoxy groups in the molecule and has the following formula (1)

[In Formula (1), R < ¹ > and R < ² > are the same or different, and show a C1-C10 hydrocarbon group which may contain the hydrogen atom and the oxygen atom, or a halogen atom. R ^{3 to} R ¹⁰ are the same or different and are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom, a halogen atom, a group represented by the formula (a1), a formula (a2) Or a group represented by the formula (a3). However, at least one of R ^{3 to} R ^{10 in} the formula (1) is a group represented by the formula (a1).

[In formula (a3), R ¹¹ represents a hydrogen atom, a carboxy group, an acyl group, or a hydrocarbon group. ]]
A method for producing a polyfunctional epoxy compound containing a structural unit represented by:
It has two or more aliphatic carbon-carbon double bonds in the molecule, and has the following formula (2)

[In Formula (2), R < ¹ > and R < ² > are the same or different, and show a C1-C10 hydrocarbon group which may contain the hydrogen atom and the oxygen atom, or a halogen atom. R ^{3 to} R ¹⁰ are the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom, a halogen atom, or a group represented by the formula (a2). However, at least one of R ^{3 to} R ^{10 in} the formula (2) is a group represented by the formula (a2). ]
The manufacturing method of the polyfunctional epoxy compound including the process of producing | generating the said polyfunctional epoxy compound by oxidizing the unsaturated compound containing the structural unit represented by an oxidizing agent.   The method for producing a polyfunctional epoxy compound according to claim 2, wherein the oxidizing agent is a peracid.   A resin composition comprising the polyfunctional epoxy compound according to claim 1. The cured product of the resin composition of claim 4.