TW202006038A - Reactive diluent, composition, sealing material, cured product, substrate, electronic component, epoxy compound, and method of producing compound - Google Patents

Abstract

A reactive diluent including a compound represented by general formula (1) shown below (in formula (1), n is 0 or 1).

Description

Reactive diluent, composition, sealing material, hardened material, substrate, electronic parts, epoxy compound, and method of manufacturing the compound

The present invention relates to a reactive diluent, a composition, a sealing material, a cured product, a substrate, an electronic component, an epoxy compound, an intermediate in the production of the aforementioned epoxy compound, a method for producing the aforementioned intermediate, and a method for producing the aforementioned epoxy compound . This application claims priority based on Japanese Patent Application No. 2018-134435 and Japanese Patent Application No. 2018-134436 filed in Japan on July 17, 2018, and the contents are cited here.

Epoxy resin compositions are widely used in interlayer insulating materials such as printed circuit boards of electrical and electronic equipment, sealing materials, matrix materials of various structural members, and adhesive materials due to their excellent electrical properties and adhesion. In particular, in current electronic devices, high-speed and large-capacity information can be sent and received. However, with the miniaturization of equipment, the miniaturization of wiring has progressed. In the conventional interlayer insulating materials, due to the large capacity of the wiring room, the delay of the transmission of electrical signals becomes large, which hinders the transmission and reception of high-speed and large-capacity information . The delay time is proportional to the capacity of the wiring room. Therefore, by reducing the interlayer insulating material to reduce the capacity of the wiring room, the transmission of electrical signals can be speeded up.

As the dielectric characteristics, two characteristics of dielectric tangent and specific permittivity are important. As a method of making the epoxy resin less dielectric, a method of increasing the amount of silica filler is known. However, when the amount of silica filler is increased, although the dielectric tangent can be reduced, there are problems such as an increase in the dielectric rate.

Epoxy resin compositions are widely used in various applications due to their excellent adhesion and electromechanical properties. The epoxy resin composition is usually added with various additives and the like, and is provided with preferable characteristics suitable for use. For example, when an epoxy resin composition is used as a semiconductor sealing material, with the recent miniaturization of electronic devices, it is necessary to fill the sealing material in a fine gap, so the resin composition is required to have a low viscosity. As a means to reduce the viscosity of a high-viscosity resin composition, a thinner is used. The diluent is divided into non-reactive and reactive. The reactive diluent reacts with the resin component of the resin composition and hardens together with the resin composition to become a part of the cured product, so it has the advantage that the diluent component does not bleed out easily. As a reactive diluent that lowers the viscosity of the resin composition and exerts its excellent dielectric properties, for example, Non-Patent Document 1 discloses that the isostearic acid raw material described is bonded to an epoxypropyl group via an ester bond Compound (trade name: FOLDI). [Prior Technical Literature] [Non-patent literature]

[Non-Patent Document 1] Nissan Chemical Industry Co., Ltd. Chemicals Division Planning and Development Department, "Low Dielectric Reactive Diluent FOLDI" [online], Japan October 5, 2008, [Heisei 30 June Search on the 13th], Internet <URL: https://www.nissanchem.co.jp/products/ chemicals/pdf/FOLDI.pdf＞

[Problems to be solved by the invention]

When the epoxy resin composition is made into a hardened product, the hardened system has a high elastic modulus and is rigid, thermal expansion or hardening shrinkage occurs, and stress is easily applied to peripheral members. As a result, if a dimensional deviation or crack occurs, it may cause a malfunction. Therefore, a material having flexibility when it becomes a hardened material is required.

The present invention was completed in order to eliminate the above-mentioned problems, and the object is to provide a novel reactive diluent which can achieve a low viscosity of the resin composition and a low dielectric in the hardened material of the resin composition Sex and flexibility. In addition, an object of the present invention is to provide a composition containing the reactive diluent. In addition, an object of the present invention is to provide a sealing material including the aforementioned composition. In addition, an object of the present invention is to provide a cured product which is a cured product of the aforementioned composition. In addition, an object of the present invention is to provide a substrate including the hardened product. In addition, an object of the present invention is to provide an electronic component including the aforementioned hardened product. In addition, an object of the present invention is to provide a novel epoxy compound that can reduce the viscosity of a resin composition, and can achieve low dielectric properties and impart flexibility in a cured product of the resin composition. In addition, an object of the present invention is to provide an intermediate which is an intermediate in the production of the aforementioned epoxy compound. In addition, the object of the present invention is to provide a method for manufacturing the aforementioned intermediate. In addition, an object of the present invention is to provide a method for producing the aforementioned epoxy compound. [Means to solve the problem]

(式(1)中，n為0或1)。 [2]一種組成物，其包含以下之成分A及成分B， 成分A：以下述通式(1)所示的化合物，

(式(1)中，n為0或1)； 成分B：在分子內具有2個以上的包含環氧環的基之化合物。 [3]如前述[2]記載之組成物，其進一步包含以下之成分C， 成分C：硬化劑。 [4]如前述[3]記載之組成物，其進一步包含以下之成分D， 成分D：硬化促進劑。 [5]一種密封材，其包含如前述[3]或[4]記載之組成物。 [6]一種硬化物，其係如前述[3]或[4]記載之組成物的硬化物。 [7]一種基板，其具備如前述[6]記載之硬化物。 [8]一種電子零件，其具備如前述[6]記載之硬化物。 [9]一種以下述通式(1)所示的化合物，

(式(1)中，n為0或1)。 [10]一種以下述通式(2)所示的化合物，

(式(2)中，n為0或1)。 [11]一種以下述通式(2)所示的化合物之製造方法，其包含羥基化以下述通式(3)所示的化合物，得到以下述通式(2)所示的化合物；

(式(3)中，n為0或1)；

(式(2)中，n為0或1)。 [12]一種以下述通式(1)所示的化合物之製造方法，其包含環氧化以下述通式(2)所示的化合物，得到以下述通式(1)所示的化合物；

(式(2)中，n為0或1)；

(式(1)中，n為0或1)。 [發明的效果][1] A reactive diluent comprising the following component A, component A: a compound represented by the following general formula (1);

(In formula (1), n is 0 or 1). [2] A composition comprising the following component A and component B, Component A: a compound represented by the following general formula (1),

(In formula (1), n is 0 or 1); Component B: A compound having two or more epoxy ring-containing groups in the molecule. [3] The composition as described in [2] above, further comprising the following component C, component C: hardener. [4] The composition as described in [3] above, further comprising the following component D, component D: hardening accelerator. [5] A sealing material comprising the composition described in [3] or [4] above. [6] A hardened product, which is a hardened product of the composition described in [3] or [4] above. [7] A substrate provided with the cured product described in [6] above. [8] An electronic component including the hardened product described in [6] above. [9] A compound represented by the following general formula (1),

(In formula (1), n is 0 or 1). [10] A compound represented by the following general formula (2),

(In formula (2), n is 0 or 1). [11] A method for producing a compound represented by the following general formula (2), which comprises hydroxylating a compound represented by the following general formula (3) to obtain a compound represented by the following general formula (2);

(In formula (3), n is 0 or 1);

(In formula (2), n is 0 or 1). [12] A method for producing a compound represented by the following general formula (1), which comprises epoxidizing a compound represented by the following general formula (2) to obtain a compound represented by the following general formula (1);

(In formula (2), n is 0 or 1);

(In formula (1), n is 0 or 1). [Effect of invention]

According to the present invention, a novel reactive diluent can be provided, which can achieve a low viscosity of a resin composition, and can achieve low dielectric properties and impart flexibility in a cured product of the resin composition. In addition, according to the present invention, there can be provided a composition comprising the reactive diluent. In addition, according to the present invention, it is possible to provide a sealing material including the aforementioned composition. In addition, according to the present invention, there can be provided a hardened product which is a hardened product of the aforementioned composition. Furthermore, according to the present invention, it is possible to provide a substrate provided with the above-mentioned cured product. In addition, according to the present invention, it is possible to provide an electronic component including the aforementioned hardened product. In addition, according to the present invention, a novel epoxy compound can be provided which can reduce the viscosity of the resin composition, and can achieve low dielectric properties and impart flexibility to the cured product of the resin composition. Furthermore, according to the present invention, an intermediate can be provided which is an intermediate in the production of the aforementioned epoxy compound. In addition, according to the present invention, a method for manufacturing the aforementioned intermediate can be provided. In addition, according to the present invention, a method for manufacturing the aforementioned epoxy compound can be provided.

[Forms for carrying out the invention]

Hereinafter, embodiments of the present invention will be described.

"Compound (1)" The compound of the embodiment of the present invention is a compound represented by the following general formula (1) (also simply referred to as "compound (1)").

(式(1)中，n為0或1)。

(In formula (1), n is 0 or 1).

With the compound (1), when it is blended into the resin composition, the viscosity of the resin composition can be reduced, and the hardening of the resin composition can achieve low dielectric properties and flexibility. Compound (1) has a saturated hydrocarbon structure in the molecule. Therefore, when it is blended into the resin composition, it is considered to contribute to the low dielectric properties of the cured product. The compound (1) has a branched chain saturated hydrocarbon structure in the molecule. Therefore, when it is blended into the resin composition, it is considered to contribute to the lowering of the viscosity of the resin composition. In addition, with this structure, when it is blended into the resin composition, it is considered to contribute to the flexibility of the cured product.

In this specification, the so-called "endowment of flexibility" refers to comparing a resin composition blended with the compound of the present invention with a resin composition not blended with the compound of the present invention. The resin composition is in a state of being easily deformed and not easily broken.

Moreover, the compound (1) may be colorless and transparent. Therefore, when the compound (1) is blended into the resin composition, the compound (1) is also prevented from becoming a cause of coloration of the resin composition.

"Compound (2)" The compound of the embodiment of the present invention is a compound represented by the following general formula (2) (also referred to as "compound (2)").

(式(2)中，n為0或1)。

(In formula (2), n is 0 or 1).

The compound (2) can be used as an intermediate in the production of the aforementioned compound (1).

"Method for producing compound (1), method for producing compound (2)" The compound (1) can be produced by the following method, for example. In addition, the compound (1) is not limited to those produced by the following method.

The compound (1) can be produced by hydroxylating a compound represented by the following general formula (3) (also simply referred to as "compound (3)") and then performing epoxidation. In addition, in this specification, the "epoxidation" is intended to guide the introduction of an epoxy ring or a group containing an epoxy ring unless otherwise specified.

(式(3)中，n為0或1)。

(In formula (3), n is 0 or 1).

The method for producing the compound (1) may include the following steps 1 to 2. Step 1: Hydroxylation of compound (3) to obtain compound (2). Step 2: Step of epoxidizing the compound (2) obtained in the previous step 1 to obtain the compound (1).

<Step 1> The production method of the compound (1) of the embodiment includes the step of hydroxylating the compound (3) to obtain the compound (2) (step 1). That is, a method for producing compound (2) is provided, which comprises hydroxylating compound (3) to obtain compound (2). The method for producing the compound (1) of the embodiment may further include the step of obtaining the compound (2) by borohydrating the compound (3) and then performing hydroxylation.

The aforementioned step 1 is a step in which the compound (3) is reacted with a borohydrating agent to be borohydrated, then reacted with a peroxide to be oxidized, and then hydroxylated to obtain the compound (2).

(式中，n為0或1)。

(In the formula, n is 0 or 1).

As the borohydrating agent, a substance that reacts with olefins to cause a borohydration reaction can be used, and can be selected from various substances capable of borohydration. Examples of the borohydrating agent include compounds having a BH bond in the molecule, and examples thereof include borane, borane derivatives, and complex compounds thereof. Examples of the borane derivatives include monoalkylborane, dialkylborane, compounds represented by the following general formula (3a), etc. From the viewpoint of yield and selectivity, 9-boron is preferred Bicyclo[3.3.1]nonane (9-BBN) or NH ₃ BH ₃ [R ¹ to R ⁶ in the compound represented by the following general formula (3a) are hydrogen atoms]. Examples of the complex include tetrahydrofuran (THF) complex and dimethyl sulfide complex. From the viewpoint of yield and selectivity, 9-BBN･THF complex or NH is preferred. ₃ BH ₃ ･THF complex.

(式中，R¹ ～R⁶ 各自獨立地為氫原子或烷基)。 R¹ ～R⁶ 的烷基可為碳數1～4之直鏈狀或支鏈狀的烷基。作為碳數1～4之直鏈狀或支鏈狀的烷基，可例示甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基等。 NH₃ BH₃ 係可使用市售者，也可在步驟1之前設置合成NH₃ BH₃ 之步驟。

(In the formula, R ¹ to R ⁶ are each independently a hydrogen atom or an alkyl group). The alkyl group of R ¹ to R ⁶ may be a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of linear or branched alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, and third butyl Base etc. The NH ₃ BH ₃ system may be commercially available, or a step of synthesizing NH ₃ BH ₃ may be provided before step 1.

Compound (3) can be obtained by polymerizing isobutylene. In addition, in the compound (3), there is an isomer of a compound represented by the following general formula (3') (also referred to as "compound (3')"), but as shown in the examples described later, the compound (3) is more reactive than compound (3') and undergoes hydroxylation. Therefore, the method for producing the compound (1) of the embodiment may include the step of hydroborating the raw material containing the compound (3) and the compound (3') and then hydroxylating to obtain the compound (2) (step 1). Even if the raw material contains the compound (3'), the compound (3') does not participate in the above reaction and can be removed after the reaction.

(式(3’)中，m為0或1)。

(In formula (3'), m is 0 or 1).

The amount of the borohydrating agent may be appropriately adjusted according to the type of the compound in the reaction system, but the BH bond is preferably in the range of 0.9 to 3 equivalents relative to 1 equivalent of the carbon-carbon unsaturated bond of the reaction, more The range of 1 to 3 equivalents is preferred, and the range of 1.1 to 1.5 equivalents is particularly preferred. Above the above lower limit, the yield change is good, and below the above upper limit, the purification change tends to be good.

The temperature (reaction temperature) of the borohydration reaction may be appropriately adjusted according to the type of compound in the reaction system, but as an example, it is preferably in the range of -80 to 120°C, more preferably -80 to 80°C The range is particularly preferably in the range of -30 to 50°C, and even more preferably in the range of -30 to 40°C. Alternatively, it is preferably in the range of -80 to 120°C, more preferably in the range of 0 to 100°C, and particularly preferably in the range of 50 to 90°C. Above the lower limit, the reaction rate is good and the reaction efficiency is good, and below the upper limit, there is a tendency to reduce the occurrence of decomposition of raw materials and products.

The reaction time (reaction time) of the borohydration reaction may be appropriately adjusted according to other conditions such as the reaction temperature, but as an example, it may be 0.5 to 100 hours.

As the peroxide, for example, hydrogen peroxide, perbenzoic acid, benzoyl peroxide, etc. may be exemplified, and hydrogen peroxide is preferred. Commercially available ones can be used for the hydrogen peroxide system. The amount of hydrogen peroxide used is not particularly limited, but it is preferably in the range of 1 to 5 equivalents, and more preferably in the range of 1 to 2 equivalents, relative to 1 equivalent of the carbon-carbon unsaturated bond to be reacted with the borohydride. range. Above the lower limit, the reaction can proceed efficiently, and below the upper limit, side reactions such as oxidation of the generated hydroxy compound tend to decrease and the yield tends to decrease.

The oxidation system in step 1 can be carried out under alkaline conditions. The so-called alkaline conditions include a condition in which peroxide and alkali are used in combination, and a solution in which peroxide and alkali are added is cited. Examples of the base include inorganic bases, and examples of the inorganic base include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, and magnesium carbonate. Calcium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, etc. Among these, from the viewpoints of reaction yield, reaction temperature, ease of operation, economy, etc., sodium hydroxide, potassium hydroxide, or lithium hydroxide is preferred.

The reaction temperature (reaction temperature) of the hydroxylation reaction may be appropriately adjusted according to the type of compound in the reaction system, but as an example, it is preferably in the range of -80 to 80°C, more preferably in the range of -30 to 50°C The range is particularly preferably in the range of -30 to 40°C. Above the above lower limit, the reaction rate is good and the reaction efficiency is good, and below the above upper limit, there is little risk of decomposition of raw materials and products.

The reaction time of the hydroxylation (reaction time) may be appropriately adjusted according to other conditions such as the reaction temperature, but as an example, it may be 0.5 to 100 hours.

The reaction in the aforementioned step 1 can be carried out in the presence of a solvent. One type of solvent system may be used alone, or two or more types may be used in combination. The solvent is not particularly limited, and examples thereof include n-hexane, pentane, cyclohexane, benzene, toluene, xylene, acetonitrile, acetone, ethyl acetate, diethyl ether, tetrahydrofuran, dimethyl sulfoxide, and dimethyl Thioether, trimethylamine, etc. are preferably diethyl ether, tetrahydrofuran, dimethyl sulfide, trimethylamine from the viewpoint of yield, and more preferably diethyl ether, tetrahydrofuran.

<Step 2> The method for producing the compound (1) according to the embodiment includes the step of epoxidizing the compound (2) obtained in the aforementioned step 1 to obtain the compound (1) (step 2). The method for producing the compound (1) of the embodiment may include the step of epoxidizing the compound (2) obtained in the aforementioned step 1, and introducing an epoxy ring or a group containing an epoxy ring to obtain the compound (1). The method for producing the compound (1) of the embodiment may also include the step of glycidizing the compound (2) obtained in the above step 1, and introducing the glycidyl group to obtain the compound (1).

The foregoing step 2 may be a step of reacting compound (2) with epihalohydrin to epoxidize (glycidylation) to obtain compound (1).

(式中，n為0或1)。

(In the formula, n is 0 or 1).

Examples of the epihalohydrin series include epichlorohydrin, bromopropylene oxide, and β-methylepichlorohydrin. The epihalohydrin may be a compound represented by the following general formula (4) (also simply referred to as "compound (4)"). These systems can be used individually or in combination of two or more types.

(式(4)中，X表示鹵素原子)。

(In formula (4), X represents a halogen atom).

Examples of the halogen atom include a fluorine atom (-F), a chlorine atom (-Cl), a bromine atom (-Br), and an iodine atom (-I).

Among them, the epichlorohydrin is preferably epichlorohydrin from the viewpoint of industrial availability and the like.

The amount of epihalohydrin used may be appropriately adjusted according to the type of the compound in the reaction system, but for example, it may be exemplified by adding a ring in the range of 2 to 10 equivalents relative to 1 equivalent of the hydroxyl group in the compound (2) Oxyhalogen propane.

The epoxidation reaction system can be carried out under alkaline conditions. Under the so-called alkaline conditions, it can be exemplified in the liquid to which an alkaline catalyst is added. Examples of alkaline catalysts include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, from the viewpoint of excellent epoxidation catalyst activity, alkali metal hydroxides are preferred, and examples thereof include sodium hydroxide and potassium hydroxide. In use, it may be in the form of an aqueous solution of about 10 to 55% by mass, using these alkaline catalysts, or in the form of a solid.

The amount of the basic catalyst used may be appropriately adjusted according to the type of the compound in the reaction system, etc. However, for example, it may be added together with 1 equivalent of the hydroxyl group in the compound (2) or slowly added 0.9 to Used with 2 equivalents of alkaline catalyst.

The temperature (reaction temperature) at which the compound (2) and the epoxyhalopropane are reacted may be appropriately adjusted according to the type of compound in the reaction system, but as an example, it may be 20 to 120°C.

The time for reacting the compound (2) with epihalohydrin (reaction time) may be appropriately adjusted according to other conditions such as the reaction temperature, but as an example, it may be 0.5 to 10 hours.

The reaction in the aforementioned step 2 can be carried out in the presence of a solvent. One type of solvent system may be used alone, or two or more types may be used in combination. The solvent is not particularly limited, and examples thereof include n-hexane, pentane, cyclohexane, benzene, toluene, xylene, acetonitrile, acetone, ethyl acetate, diethyl ether, tetrahydrofuran, dimethyl sulfoxide, and dimethyl Thioether, trimethylamine and the like are preferably diethyl ether, tetrahydrofuran, dimethyl sulfide or trimethylamine from the viewpoint of yield, and more preferably diethyl ether or tetrahydrofuran.

After the completion of the epoxidation reaction, after washing the reaction product with water, the unreacted epihalohydrin or the combined organic solvent can be distilled off under heating and reduced pressure. Furthermore, in order to further reduce the hydrolyzable halogen in the reaction product, the reaction product may be dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, etc., and sodium hydroxide, hydroxide An aqueous solution of an alkali metal hydroxide such as potassium is further reacted. At this time, for the purpose of improving the reaction rate, a phase transfer catalyst such as quaternary ammonium salt or crown ether may also be present. When the phase transfer catalyst is used, the amount used is preferably 0.1 to 3.0 parts by mass relative to 100 parts by mass of the reaction product. After the completion of the epoxidation reaction, the generated salt is removed by filtration, water washing, or the like, and the organic solvent is distilled off under heating and reduced pressure to purify the compound (1) from the resulting reaction product.

"Reactive Diluent, Composition" The compound (1) can be added to the resin component, and is suitably used as a reactive diluent for reducing the viscosity.

(式(1)中，n為0或1)。That is, the reactive diluent of the present invention is the following. The reactive diluent containing the following component A, component A: a compound represented by the following general formula (1).

(In formula (1), n is 0 or 1).

The reactive diluent of the present invention may be the following. Reactive diluent composed of the following component A, Component A: The compound represented by the above general formula (1).

The reactive diluent is preferably liquid at 25°C, and the viscosity at 25°C may be 0.01 to 1000 mPa･s, or 1 to 300 mPa･s, or 5 to 35 mPa･s, or 5.5 to 10 mPa･ s. Viscosity is measured under the measurement conditions described in the examples or under conditions that are interchangeable with the same results. The compound represented by the general formula (1) is preferably liquid at 25°C, and the viscosity at 25°C may be 0.01 to 1000 mPa･s, 1 to 300 mPa･s, or 5 to 35 mPa･s It can also be 5.5～10mPa･s. Viscosity is measured under the measurement conditions described in the examples or under conditions that are interchangeable with the same results. The upper limit value and the lower limit value of the numerical range of the viscosity illustrated above can be freely combined.

The resin component is not particularly limited, but is preferably an epoxy resin before curing such as monomers or prepolymers.

(式(1)中，n為0或1)。 成分B：在分子內具有2個以上的包含環氧環的基之化合物。That is, the composition of the present invention is the following. A composition comprising the following component A and component B Component A: a compound represented by the following general formula (1),

(In formula (1), n is 0 or 1). Component B: A compound having two or more epoxy ring-containing groups in the molecule.

The composition of the present invention containing component A and component B may further contain a hardener (component C) as needed. The composition of the present invention may further contain a hardening accelerator (component D), a filler (component E), etc. as needed. Hereinafter, each component will be described.

<Component A> Since component A is a compound represented by the aforementioned general formula (1) (the aforementioned compound (1)), it is the same as that described in the aforementioned "Compound (1)", and therefore its description is omitted here.

<Component B> Component B is a compound having two or more epoxy ring-containing groups (for example, epoxy group, epoxypropyl group) in the molecule. Examples of the compound having two or more epoxy ring-containing groups in the molecule include an epoxy compound or epoxy resin having at least two functions. The compound having two or more epoxy ring-containing groups in the molecule may be a 2- to 10-functional epoxy compound, a 2- to 6-functional epoxy compound, or a 2- to 4-functional epoxy compound. The compound having two or more epoxy ring-containing groups in the molecule may be a 2- to 10-functional epoxy resin, a 2- to 6-functional epoxy resin, or a 2- to 4-functional epoxy resin. Compounds having two or more epoxy ring-containing groups in the molecule can also be polymerized and used as epoxy resins, as epoxy compounds or epoxy compounds having two or more epoxy ring-containing groups in the molecule Resins include bisphenol epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol AD epoxy resin; alicyclic epoxy resin; phenol novolac epoxy resin Novolac epoxy resins such as resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, aralkyl novolac epoxy resin, etc.; diglycidyl ether of polyfunctional phenol ; These hydrides and so on. These epoxy resins can be used alone or in combination of two or more. As a bifunctional or more epoxy compound, a trifunctional or more epoxy compound or a tetrafunctional or more epoxy compound is preferable. The bifunctional or more epoxy compound system may be a 2 to 10 functional epoxy compound (a compound having 2 to 10 epoxy ring-containing groups in the molecule), may be a 2 to 6 functional epoxy compound, may be 2 to 4 functional epoxy compounds. As a bifunctional or more epoxy resin, a trifunctional or more epoxy resin or a tetrafunctional or more epoxy resin is preferable. The epoxy resin with 2 or more functions may be a 2 to 10 functional epoxy resin (a compound having 2 to 10 epoxy ring-containing groups in the molecule), or a 2 to 6 functional epoxy resin, which may be 2~4 functional epoxy resin.

For compounds having two or more epoxy ring-containing groups in the molecule, it is preferable to use a trifunctional epoxy compound or a tetrafunctional epoxy compound. Typical trifunctional epoxy compounds usable in the present invention include compounds having the following structural formula (product name: TEPIC (registered trademark)).

Typical tetrafunctional epoxy compounds usable in the present invention include compounds having the following structural formula (product name: jER (registered trademark) 1031S).

Typical other 4-functional epoxy compounds that can be used in the present invention include naphthalene-type epoxy compounds having the following structural formula ((product name: EPICLON EXA-4700)).

The blending ratio (A:B) of component A and component B, expressed on a weight basis, can be 1 to 80: 20 to 99, 5 to 70: 30 to 95, and 20 to 60: 40 to 80. The blending ratio of the total of component A and component B in the composition can be 1 to 99% by weight, can be 5 to 80% by weight, and can be 10 when the total weight of the entire composition is taken as 100% by weight ~60% by weight.

酚醛清漆樹脂。 作為胺系硬化劑，可舉出三伸乙四胺、四伸乙五胺、二乙基胺基丙胺等之脂肪族胺；間苯二胺、4,4’-二胺基二苯基甲烷等之芳香族胺等的胺化合物。 作為酸酐，可舉出鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐等之酸酐。 此等之硬化劑係可單獨使用，也可併用2種以上。 硬化劑之使用量，係相對於成分A及成分B的環氧當量1，較佳以硬化劑的反應基當量比成為0.3～1.5當量之量。若硬化劑之摻合量在前述範圍內，則硬化度的控制係容易，有生產性變良好之傾向。<Component C> As the curing agent (component C), various curing agents used as curing agents for epoxy compounds or epoxy resins can be exemplified. Examples of the hardener include phenol-based hardeners, amine-based hardeners, acid anhydrides, boron trifluoride monoethylamine, isocyanates, dicyandiamide, and the like, and urea resins. As the phenolic hardener, monomers, oligomers, and polymers with two or more phenolic hydroxyl groups in one molecule may be used. For example, phenol novolak resin, cresol novolak resin, and other novolak resins may be used. Type phenol resin; naphthalene type phenol resin, high ortho type novolak phenol resin, terpene modified phenol resin, terpene phenol modified phenol resin, aralkyl type phenol resin, dicyclopentadiene type phenol resin, water Phenolic resins such as salicylaldehyde type phenol resin and benzaldehyde type phenol resin. Among these, phenol novolak resin, cresol novolak resin, and a part of modified amino groups are preferred

Novolak resin. Examples of the amine hardener include aliphatic amines such as triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine; m-phenylenediamine, 4,4'-diaminodiphenylmethane Amine compounds such as aromatic amines. Examples of the acid anhydride include acid anhydrides such as phthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. These hardeners can be used alone or in combination of two or more. The amount of the hardener used is an epoxy equivalent of 1 to component A and component B, and it is preferably such that the reactive group equivalent ratio of the hardener becomes 0.3 to 1.5 equivalents. If the blending amount of the curing agent is within the aforementioned range, the control of the curing degree is easy, and the productivity tends to be good.

<Component D> Examples of the hardening accelerator (component D) include imidazole compounds, organic phosphorus compounds, tertiary amines, and quaternary ammonium salts. The imidazole compound may be a potential imidazole compound in which the secondary amine group of the imidazole is blocked by acrylonitrile, isocyanate, melamine, acrylate, etc. As the imidazole compound used herein, imidazole, 2-methylimidazole, 4-ethyl-2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2- Methylimidazole, 2-heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-ethyl-4-methylimidazoline, 2-undecylimidazoline, 2-benzene Yl-4-methylimidazoline, etc. In addition, a photoinitiator that generates free radicals, anions, or cations due to photolysis to start hardening can also be used. These hardening accelerators may be used alone or in combination of two or more. The blending amount of the hardening accelerator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of component A and component B. If it is more than the above upper limit value, a more favorable hardening promoting effect is obtained, and if it is less than the above lower limit value, the storage properties of the composition and the physical properties of the cured product are excellent, and the economy is also likely to be excellent.

<Component E> Examples of the filler (component E) include oxides such as silicon dioxide, aluminum oxide, zirconium oxide, mullite, and magnesium oxide; hydroxides such as aluminum hydroxide, magnesium hydroxide, and hydrotalcite; and nitriding Nitride ceramics such as aluminum, silicon nitride, boron nitride, etc.; natural minerals such as talc, montmorillonite, saponite; metal particles, carbon particles, etc. The average particle diameter of the inorganic filler is preferably 25 μm or less, more preferably 0.01 μm or more and 25 μm or less, particularly preferably 0.1 μm or more and 10 μm or less, and particularly preferably 0.3 μm or more and 7 μm or less. If the average particle diameter is equal to or greater than the above lower limit, the aggregation of the inorganic filler is easily suppressed, and the inorganic filler is easily dispersed in the resin. If the average particle diameter is equal to or less than the above upper limit, wire damage is easily suppressed during seal molding. The average particle size means the 50% volume cumulative diameter (D50) measured by a particle size distribution meter (laser diffraction scattering method). When the total weight of the entire composition is regarded as 100% by weight, the blending amount of the filler is preferably 5 to 90% by weight, more preferably 10 to 80% by weight.

<Other ingredients> The composition of the present invention may further contain other components that do not correspond to the aforementioned components A to E as necessary. As other components, other resins, solvents, additives, etc. may be mentioned. Examples of other resins include polyolefins, polyamides, and polyimides.

"Use of Composition" The composition of the present invention is suitable for the following applications. When the composition of the present invention is cured and used, the composition preferably contains the aforementioned components A to C, and more preferably contains the aforementioned components A to D.

(Sealing material) The composition of the present invention can be used as a sealing material for parts such as semiconductor parts. The sealing material of the present invention includes the composition of the present invention. As the sealing material, for example, between the semiconductor component and the substrate, the surrounding material of the semiconductor component is sealed with the sealing material, and the semiconductor component and the substrate are sealed with the sealing material (underfill). When using a sealing material as the underfill, for example, the following procedure can be used to fill the sealing material in the gap between the substrate and the semiconductor component. First, the substrate is coated with a sealing material while heating the substrate to 70 to 130°C. Then, the capillary phenomenon fills the gap between the substrate and the semiconductor component with the sealing material. At that time, in order to shorten the time required for the filling of the sealing material, the substrate may be tilted, or a pressure difference between the inside and outside of the gap may be generated. After the sealing material is filled in the gap, the gap can be sealed by heating and hardening the sealing material.

(Substrate material) The composition of the present invention can be used as a substrate material. For example, a substrate can be produced by impregnating the composition of the present invention with fibers such as glass fibers and carbon fibers, forming a prepreg in a sheet shape, and heating and hardening it. The prepreg can also be laminated more than 2 pieces.

"Hardener" The cured product of the present invention is a cured product of the composition of the present invention. The hardened product of the present invention can be obtained, for example, by heating the composition of the present invention at 80 to 200°C for 0.2 to 6 hours, and heating and hardening it.

When making the composition of the present invention a cured product, the composition preferably contains the aforementioned components A to C, and more preferably contains the aforementioned components A to D.

In addition, as one embodiment of the present invention, a substrate can be provided which includes a cured product of the composition of the present invention. The substrate is provided with a cured product of the composition of the present invention, as described later, may be selected from the group consisting of a cured product of a prepreg, a cured product of a resin sheet, a copper-clad laminate, a printed circuit board, and a multilayer printed circuit board At least one of the group.

As an embodiment of the present invention, there can be provided a prepreg including the composition and fiber of the present invention. In addition, as one embodiment of the present invention, a resin sheet can be provided which includes the composition of the present invention.

The aforementioned resin sheet is formed by molding the composition of the present invention into a sheet shape. In order to improve the moldability, the composition may be in a semi-cured state. The resin sheet is suitable as an interlayer insulating material. The substrate may be a hardened product provided with a prepreg having the composition and fiber of the present invention. The aforementioned prepreg may be laminated with more than two pieces. The substrate can be produced by, for example, heat-hardening and pressing the prepreg.

In addition, as one embodiment of the present invention, there can be provided a copper-clad laminate in which a substrate and a copper foil are laminated. The copper foil of the copper clad laminate can be processed to form a circuit. Therefore, as one embodiment of the present invention, a printed circuit board or a multilayer printed circuit board can be provided in which a circuit is formed on the substrate. The printed circuit board or the multilayer printed circuit board may further include the cured product of the resin sheet. The resin sheet system can be provided instead of the aforementioned substrate.

The copper-clad laminate can be manufactured by laminating the prepreg and copper foil, and forming by heating and pressing. The heating and pressurizing conditions can be appropriately adjusted in accordance with the thickness of the produced copper-clad laminate or the composition of the composition of the present invention. Printed circuit boards or multilayer printed circuit boards can be produced by common methods such as plating through-hole method or build-up method, and can be heated by laminating the above-mentioned prepreg or insulating resin sheet on the inner wiring board Compressed and formed. For example, after copper foil is laminated on one side or both sides of the prepreg of the present invention, a copper-clad laminate is produced by heating and pressurizing, a hole is formed in the copper-clad laminate, and through-hole plating is performed, including plating The coated copper foil is etched to form a circuit, and a printed circuit board or a multilayer printed circuit board can be manufactured.

The thickness of the prepreg, resin sheet, substrate, copper-clad laminate, printed circuit board, and multilayer printed circuit board is not particularly limited, but as an example, it may be 0.1 to 10 mm, and may be 0.3 to 5 mm.

The hardened product of the composition incorporating the reactive diluent of the present invention is imparted with moderate flexibility. The value of the bending elastic modulus of the hardened system of the present invention may be 3000 MPa or less, or 2500 MPa or less. The lower limit of the bending elastic modulus is not particularly limited, but the value of the bending elastic modulus may be 1500 MPa or more, or 2000 MPa or more. The flexural modulus of elasticity is measured under the measurement conditions described in the examples or under conditions that are interchangeable with the same results.

The hardened product of the composition blended with the reactive diluent of the present invention is imparted with excellent dielectric properties. The value of the specific permittivity of the hardened material of the present invention at 1 MHz or 1 GHz may be 2-10, 2-5, or 3-4. The specific dielectric is measured under the measurement conditions described in the examples or under conditions that are compatible with the same results. The value of the dielectric tangent of the hardened system of the present invention at 1 MHz or 1 GHz may be 0.005 to 0.07, 0.006 to 0.05, 0.007 to 0.035, or 0.008 or more and less than 0.01. The dielectric tangent is measured under the measurement conditions described in the examples or under conditions that are interchangeable with the same results. In addition, the hardened material having the above-mentioned dielectric properties may also be referred to as a substrate, a copper-clad laminate, a printed circuit board, and a multilayer printed circuit board. The value of the water absorption rate of the hardened material of the present invention may be 4% or less, 3% or less, or 1% or less. The lower limit of the water absorption rate is not particularly limited, but may be 0.5% or more. The water absorption rate below the upper limit value means that the cured product has excellent effect characteristics, and mean that it has excellent water resistance or water repellency. The water absorption rate is measured under the measurement conditions described in the examples or under conditions that are interchangeable with the same results.

In addition, as one embodiment of the present invention, there can be provided an electronic component including the hardened product of the present invention. In more detail, it is possible to provide an electronic component that seals a component such as a semiconductor component and a substrate with a hardened material of the sealing material of the present invention. For example, the electronic component may use a sealing material as an underfill to seal the component and the substrate with the sealing material, or may be sealed with the sealing material between the component and the substrate and around the component. Here, as components to be sealed, semiconductor elements, integrated circuits, large-scale integrated circuits, transistors, transistors, diodes, capacitors, etc. may be mentioned, and are not limited thereto. Electronic parts can include terminals, wires, lead frames, other structures, etc. in addition to the hardened products of substrates, parts, and sealing materials.

As described above, prepregs, resin sheets, substrates, copper-clad laminates, printed circuit boards, multilayer printed circuit boards, and electronic components can be manufactured from the composition of the present invention. These have low dielectric properties, flexibility, and excellent heat resistance, and can be suitably used in mobile communication equipment or its base station devices, servers, routers, and other electronic devices for networks that operate high-frequency signals above 1 GHz. And the use of parts for printed circuit boards for networks used in various electronic devices such as large computers.

The embodiments of the present invention have been described in detail above, but the configurations and their combinations in the embodiments are examples, and the combinations, additions, omissions, substitutions, and others of the configurations are within the scope of the scope of the present invention. Change to possible. In addition, the present invention is not limited by each embodiment, but is limited only by the scope of claims. [Example]

Next, examples are shown to explain the present invention in more detail, but the present invention is not limited to the following examples.

<Synthesis of Compounds>

[Synthesis Example 1] In a 1L reaction vessel, under an argon flow, a compound represented by the following formula (3-1) (also referred to as "compound (3-1)") and a compound represented by the following formula (3'-1) To 10 g (59.4 mmol) of a trimeric isobutylene raw material (manufactured by TCI) of the compound (also referred to as "compound (3'-1)"), 60 ml of dehydrated THF was added and stirred. Under ice cooling, 9-BBN (89.1 mmol) was dropped below 10°C, and after 30 minutes, the temperature was raised to 35°C. After stirring overnight, the disappearance of the raw material compound (3-1) was confirmed by gas chromatography (GC).

The reaction solution was ice-cooled again, and 79 ml (238 mmol) of 3M NaOHaq was dropped. Next, a 30% by mass H ₂ O ₂ solution (80 ml) was dropped. After 17 hours, the disappearance of the raw material compound (3-1) was confirmed by GC. After separating the organic layer and the water layer, K ₂ CO ₃ was added to the organic layer to separate the water remaining in the organic solvent. After separating the water layer, the same operation was repeated twice. The water layers were combined and extracted 3 times with ethyl acetate. Finally, the organic layer was collected and dried with MgSO ₄ . After filtering the desiccant, the solvent was distilled off under reduced pressure to obtain 18.22 g of a colorless transparent oily crude body. In addition, the unreacted internal olefin structure is removed during distillation under reduced pressure. Vacuum distillation (bath temperature: 100°C, top temperature: 45°C, reduced pressure: 1.3kPa) after crude and crude purification, a silica gel column (silica gel: 92.8g, eluent: heptane) /Ethyl acetate=7/1) purification, to obtain a white solid OH body. The yield is 2.74 g (14.7 mmol), the yield is 24.8%, and the GC purity is above 99.9%. Furthermore, using ¹ H-NMR, it was confirmed that a compound represented by the following formula (2-1) (also simply referred to as “compound (2-1)”) was synthesized.

The NMR data of the obtained compound (2-1) are shown below.

[Synthesis Example 2] Next, in a 30 mL reaction vessel, 1.0 g (5.37 mmol) of compound (2-1) synthesized in Synthesis Example 1 above, toluene, and 73 mg (Tetrabutyl ammonium Hydrogen Sulfate) 73 mg ( 0.215 mmol), 50% NaOHaq (5.4 mL), and after argon replacement, it was ice-cooled and stirred. 1.49 g (16.1 mmol) of epichlorohydrin was added dropwise thereto, stirred for 30 minutes, and warmed to room temperature. Two days later, the disappearance of the raw material compound (2-1-1) was confirmed by GC. After quenching with water, it was diluted with ethyl acetate. After separating the organic layer and the aqueous layer, the aqueous layer was extracted 3 times with ethyl acetate. The organic layers were collected, washed once with sat. NaClaq, and dried with Na ₂ SO ₄ . After filtering the drying agent, the solvent was distilled off under reduced pressure to obtain 1.94 g of a pale yellow oily crude body. The crude body was purified with a Kugelrohr distillation apparatus (heating temperature: 160 to 240° C., reduced pressure: 0.1 mmHg) to obtain a colorless, transparent, and liquid form of the present invention represented by the following formula (1-1) Compound (also referred to as "compound (1-1)"). Yield: 770 mg (3.18 mmol), yield: 59.2%, GC purity: 95.8%, viscosity: 5.8 mPa･s (25°C), epoxy equivalent: 242. Furthermore, using ¹ H-NMR, it was confirmed that compound (1-1) had been synthesized.

Use the following E-type viscometer to measure the 25-degree E-type viscosity. Machine used: TV20 viscometer manufactured by Toki Industry Co., Ltd. Measuring temperature: 25℃ Approximately 1.2 mL of compound (1-1) was placed in a cup attached to an E-type viscometer, and the cup was set at a temperature of 25°C. The measurement of the rotational viscosity of the above compound is started with an E-type viscometer, and the value of the rotational viscosity at the point where the indicated value of the rotational viscosity is stable is measured.

The NMR data of the obtained compound (1-1) are shown below.

[Synthesis Example 3] In addition to substituting the aforementioned trimeric isobutylene raw material, a compound represented by the following formula (3-2) (also referred to as "compound (3-2)") and a compound represented by the following formula (3'-2) (also used Except for the tetrameric isobutylene raw material (manufactured by TCI) (abbreviated as "compound (3'-2)"), a reaction was carried out in the same manner as in Synthesis Example 1 to synthesize a compound represented by the following formula (2-2) (also referred to as "compound" (2-2)").

The NMR data of the obtained compound (2-2) are shown below.

[Synthesis Example 4] Except for using the compound (2-2) obtained above instead of the compound (2-1), the reaction was carried out in the same manner as in Synthesis Example 2 to obtain a colorless, transparent and liquid invention of the present invention represented by the following formula (1 -2) The compound shown (also referred to as "compound (1-2)"). The total yield of compound (1-2) was 17.2%, GC purity was 98.2%, viscosity was 33 mPa･s (25°C), and epoxy equivalent was 298. Furthermore, using ¹ H-NMR, it was confirmed that compound (1-2) had been synthesized. The viscosity of the compound (1-2) was measured in the same manner as in Synthesis Example 2 above.

The NMR data of the obtained compound (1-2) are shown below.

[Synthesis Example 5] The above compound (2-1) was synthesized in the same manner as in Synthesis Example 1 except that NH ₃ BH _{3 was} used instead of the aforementioned 9-BBN. The details are described below.

作為事前準備，於冰冷下，將氨氣吹入THF中，而作成5%(v/v)NH₃ /THF溶液(200ml)及1M NH₃ /THF溶液(100ml)。 在大氣下，於500ml燒瓶中加入經冷卻的5%(v/v) NH₃ /THF溶液(200ml)。於其中在冰冷下添加氫化硼鈉、硫酸銨，在0℃攪拌2小時後，在室溫進行8小時攪拌。 於所得之白色懸浮液中，添加1M NH₃ /THF溶液(100ml)，攪拌30分鐘後，以矽藻土過濾，以THF進行溢洗。將所得之濾液濃縮，於室溫下減壓乾燥，得到4.73g白色固體的NH₃ BH₃ (產率：76.6%，無雜質波峰)。使用¹ B-NMR，確認已合成NH₃ BH₃ 。(NH ₃ BH ₃ synthesis) First, NH ₃ BH _{3 is} synthesized. The reagents used are as follows.

As a preparatory step, ammonia gas was blown into THF under ice cooling to prepare a 5% (v/v) NH ₃ /THF solution (200 ml) and a 1M NH ₃ /THF solution (100 ml). Under the atmosphere, a cooled 5% (v/v) NH ₃ /THF solution (200 ml) was added to a 500 ml flask. Sodium borohydride and ammonium sulfate were added thereto under ice cooling, and after stirring at 0°C for 2 hours, stirring was performed at room temperature for 8 hours. To the resulting white suspension, a 1M NH ₃ /THF solution (100 ml) was added, and after stirring for 30 minutes, it was filtered through celite and washed with THF. The obtained filtrate was concentrated and dried under reduced pressure at room temperature to obtain 4.73 g of NH ₃ BH _{3 as a} white solid (yield: 76.6%, no impurity peak). Using ¹ B-NMR, it was confirmed that NH ₃ BH ₃ had been synthesized.

In a 200 mL reaction vessel, under the atmosphere, 25 ml of dehydrated THF and 1.16 g (37.43 mmol) of NH ₃ BH _{3 were} added to the triisobutylene raw material (TCI company) containing compound (3-1) and compound (3′-1) 25.20g (149.7mmol) and stirred, heated at 78 ° C under reflux for 1 hour reaction, and then distilled 10ml of THF from the reaction solution, heated at 80 ° C under reflux for 2 hours, using gas chromatography (GC) Confirm the disappearance of the raw material compound (3-1).

To the reaction solution, 17 ml (49.9 mmol) of 3M NaOHaq was added, and the mixture was heated to reflux at 73°C for 3 hours. After cooling to 30°C, 17 ml (154.2 mmol) of a 30% by mass H ₂ O ₂ solution was dropped over 10 minutes. After the temperature was raised to 45°C, it was stirred at room temperature overnight. It was purified in the same manner as in Synthesis Example 1 above to obtain a white solid OH body. The yield is 6.7g, the yield is 24.0%, and the GC purity is over 99.0%. Furthermore, using ¹ H-NMR, it was confirmed that compound (2-1) had been synthesized.

<Modulation of composition 1> The following materials were blended at the blending ratio (parts by weight) shown in Table 1 to obtain the composition of the present invention.

(Reactive thinner) ･Compound (1-1) ･Compound (1-2) (Epoxy resin) ･Epoxy resin I: Phenol novolac type (liquid, epoxy equivalent 175g/eq, viscosity 4500Pa･s) ･Epoxy resin II: Bisphenol A liquid type (made by Nippon Steel & Sumitomo, model: YD-128, epoxy equivalent 190g/eq, viscosity 11,000mPa･s) (hardener) ･Hardener A: 2-ethyl-4-methylimidazole (amine equivalent 110g/eq) ･Hardener B: Phenol novolac resin (PR-HF-6 manufactured by Sumitomo Bucklet Co., Ltd.) ･Curing agent C: Methylhexahydrophthalic anhydride (Hardening accelerator) ･Hardening accelerator A: Triphenylphosphine (Hokuko TPP manufactured by Beixing Chemical Industry Co., Ltd.), hardening accelerator B: 2-ethyl-4-methylimidazole (Filler) ･Filler A: silica powder ･Filler B: Boron nitride powder

<Evaluation> (Viscosity) Use the following E-type viscometer to measure the 25-degree E-type viscosity. Machine used: TV20 Viscometer made by Toki Industry Co., Ltd. Measuring temperature: 25℃ Approximately 1.2 mL of each resin composition adjusted in the blending example was placed in a cup attached to an E-type viscometer, and the cup was set at a temperature of 25°C. The measurement of the rotational viscosity of the above compound is started with an E-type viscometer, and the value of the rotational viscosity at the point where the indicated value of the rotational viscosity is stable is measured.

(Tensile shear followed by strength) The tensile shear strength was measured under the following conditions. After degreasing the Cu plate (length 150mm×width 25mm×thickness 1.5mm) and Al plate (length 150mm×width 25mm×thickness 1.5mm) with acetone, each resin composition adjusted in the blending example was thinly coated with a brush For the cloth, the Cu plate and the Al plate were laminated at an overlap distance of 12.5 mm. Then, it was fixed with a jig and cured at 100°C for 1 hour and 180°C for 5 hours to produce a test piece. The test system starts the test at a tensile speed of 5 mm/min, and the load at the time of breaking the test piece is taken as the tensile shear adhesive strength.

Table 1 shows the evaluation results.

<Modulation of composition 2> The following materials were blended at the blending ratio (parts by weight) shown in Table 2 to obtain the composition of the present invention.

(Reactive thinner) ･Compound (1-1) (Epoxy compound 1) ･TEPIC-S (manufactured by Nissan Chemical Industry Co., Ltd., epoxy equivalent 100) (Epoxy compound 2) ･JER1031S (Mitsubishi Chemical Co., Ltd., epoxy equivalent 196) (hardener) ･MH-700 (MeHHPA, manufactured by New Japan Physical and Chemical Co., Ltd., anhydride equivalent 164) (Hardening accelerator) ･Curezol (2E4MZ, manufactured by Shikoku Chemical Industry Co., Ltd.)

<Evaluation> (Production of test piece) The materials of the reactive diluent, epoxy compound, and hardener were mixed in the specified blends shown in Table 2. Next, after blending as specified in Table 2, the hardening accelerator was added and mixed, and then flowed into the cavity for injection molding. The cavity for injection molding was placed in a hot-air circulation oven, heated at 100°C for 2 hours, and then hardened at 150°C for 5 hours to obtain a test piece.

(Bending test) The bending test was conducted under the following conditions. ･Test method: According to JIS K 7171 ･Measurement items: strength, elastic modulus ･Test piece shape: 65mm×25mm×3mm ･Measurement condition: test speed; 1.5mm/min ･Distance between pivot points: 48mm ･Number of measurements: n=3 ･Test environment: 23℃±1℃, 50%RH±5%RH ･Measurement device: Universal Material Testing Machine 5582 (manufactured by INSTRON)

(Specific permittivity, dielectric tangent) The specific permittivity and dielectric tangent were measured under the following conditions. ･Test method: According to IEC 60250 (automatic balance bridge method) ･Measurement items: specific permittivity, dielectric tangent ･Test piece shape: 60mm×60mm×3mm ･Measurement condition: frequency; 1MHz ･Measurement temperature: 23℃ ･Electrode size: main electrode diameter φ36mm, ring electrode inner diameter φ38mm ･Electrode material: conductive silver paint ･Number of measurements: n=2 (measure 1 piece twice) ･State adjustment: 23℃±2℃, 50%RH±5%RH, 48 hours ･Test environment: 23℃±2℃, 50%RH±5%RH ･Measurement device: Precision LCR meter E4980A (manufactured by AGILENT Technology Co., Ltd.)

(Water absorption) The water absorption rate was measured under the following conditions. ･Test piece shape: about 30mm×40mm×3mm ･Pretreatment: 50℃, 24 hours (hot air circulation oven) ･Test conditions: boiling water (100℃), 100 hours ･Number of measurements: n=2

Table 2 shows the evaluation results.

<Modulation of composition 3> The following materials were blended at the blending ratio (parts by weight) shown in Table 3 to obtain the composition of the present invention.

(Reactive thinner) ･Compound (1-1) ･Compound (1-2) (Epoxy compound) ･TEPIC-S (manufactured by Nissan Chemical Industry Co., Ltd., epoxy equivalent 100) (hardener) ･MH-700 (MeHHPA, manufactured by New Japan Physical and Chemical Co., Ltd., anhydride equivalent 164 (Hardening accelerator) ･Curezol (2E4MZ, manufactured by Shikoku Chemical Industry Co., Ltd.) (Filler) ･Silica dioxide powder (average particle size 25μm)

<Manufacture of prepreg and printed circuit board> Each resin composition prepared by the blending shown in Table 3 was impregnated with glass fiber, and then dried at 165°C for 3 to 10 minutes to produce a prepreg. After laminating the aforementioned two layers of prepreg (ply) with a copper foil having a thickness of 18 μm, it was pressed to obtain a laminated sheet having a thickness of 0.2 mm.

<Evaluation> (Copper foil adhesion (peel strength: P/S)) According to the evaluation specification of IPC-TM-650 2.4.8, the aforementioned laminated sheet was impregnated with copper etching solution to remove the copper foil, and the circuit pattern (copper foil) formed on the resulting printed circuit board was raised in the direction of 90° Pull to measure the peeling time point of the circuit pattern and evaluate (kgf/cm)

(PCT heat resistance evaluation (PCT)) For the above printed circuit board, a pressure cooker test device (ESPEC, EHS-411MD) was used, and after being left at 121°C and 0.2 MPa for 4 hours, the printed circuit board was dipped at Solder288°C at 10 second intervals Measure the time at which the peeling phenomenon occurs between the insulating layer and the copper foil, between the insulating layer and the metal core, or between the insulating layers, and evaluate. 2 hours or more is qualified.

(Specific permittivity and dielectric tangent) With respect to the above-mentioned printed circuit board, the specific permittivity measurement device (RF Impedence/Material Analyzer: manufactured by Agilent) was used to measure the specific permittivity and dielectric tangent at a frequency of 1 GHz.

Table 3 shows the evaluation results.

From the results shown above, it can be seen that the compound of the present invention can be suitably used as a reactive diluent mixed with an epoxy resin. The resin composition doped with the compound of the present invention is reduced in viscosity, and the cured composition of the resin composition exhibits excellent dielectric properties, and at the same time has good flexibility and has excellent properties that it is not easily broken even when applied from the outside .

Claims (12)

A reactive diluent comprising the following component A, component A: a compound represented by the following general formula (1);

(In formula (1), n is 0 or 1). A composition comprising the following component A and component B, Component A: a compound represented by the following general formula (1),

(In formula (1), n is 0 or 1); Component B: A compound having two or more epoxy ring-containing groups in the molecule. If the composition of claim 2, it further contains the following component C, Component C: hardener. If the composition of claim 3 further contains the following component D, Component D: Hardening accelerator. A sealing material comprising the composition according to claim 3 or 4. A hardened product which is the hardened product of the composition of claim 3 or 4. A substrate provided with the hardened product according to claim 6. An electronic part provided with the hardened product according to claim 6. A compound represented by the following general formula (1),

(In formula (1), n is 0 or 1). A compound represented by the following general formula (2),

(In formula (2), n is 0 or 1). A method for producing a compound represented by the following general formula (2), which comprises hydroxylating a compound represented by the following general formula (3) to obtain a compound represented by the following general formula (2);

(In formula (3), n is 0 or 1);

(In formula (2), n is 0 or 1). A method for producing a compound represented by the following general formula (1), which comprises epoxidizing a compound represented by the following general formula (2) to obtain a compound represented by the following general formula (1);

(In formula (2), n is 0 or 1);

(In formula (1), n is 0 or 1).