CN118591575A - Epoxy compound, epoxy resin, epoxy resin composition, cured product, prepreg, fiber-reinforced composite material, and methods for producing the same, sealing material, semiconductor device, method for sealing semiconductor element, and method for using as sealing material - Google Patents

Abstract

The present invention provides a glycidylamine-type fluorine-containing epoxy compound. The present disclosure relates to a fluorine-containing epoxy compound represented by the general formula (1). In the general formula (1), n is an integer of 0 to 4, R ¹ is a monovalent substituent, and R ¹ is one selected from the group consisting of halogen atom, alkyl group, alkoxy group, haloalkoxy group and aryl group.

Description

Epoxy compound, epoxy resin, epoxy resin composition, cured product, prepreg, fiber-reinforced composite material and method for producing the same, sealing material, semiconductor device, method for sealing semiconductor element and method for using as sealing material

Technical Field

The present disclosure relates to epoxy compounds, epoxy resins, epoxy resin compositions, cured products, prepregs, fiber-reinforced composite materials, and methods for producing the same, sealing materials, semiconductor devices, methods for sealing semiconductor elements, and methods for using the same as sealing materials. If described in further detail, the disclosure relates to epoxy compounds having a novel fluorine-containing skeleton, epoxy resins containing the epoxy compounds, epoxy resin compositions containing the epoxy compounds, cured products formed by curing the epoxy resin compositions, prepregs containing the epoxy resin compositions, methods for sealing semiconductor elements using the epoxy resin compositions, methods for using the same as sealing materials, fiber-reinforced composite materials containing the cured products, sealing materials, and semiconductor devices.

Background Art

Fiber reinforced composite materials (hereinafter sometimes recorded as FRP) comprising reinforcing fibers and matrix resins are widely used as electrical and electronic equipment components, aircraft components, spacecraft components, automobile components, railway vehicle components, ship components, and sports equipment components because of their excellent mechanical properties such as strength and rigidity. FRP is usually made by various methods, but among these methods, the method of using reinforcing fibers impregnated with uncured matrix resin as prepregs is widely practiced. In this method, the laminated prepreg sheets are heated to form a composite material. As a matrix resin used for prepregs, epoxy resins with excellent properties of heat resistance, dimensional stability and chemical resistance are used in most cases. Among them, for the purpose of improving the mechanical properties of the resin, it has been proposed to use multifunctional epoxy resins. For example, a resin composition using diaminodiphenyl sulfone as a curing agent and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane as a matrix resin, that is, a composition of an epoxy compound of a glycidylamine type.

Prior art literature

Patent Literature

Patent Document 1: Korean Patent No. 10-2015-0037376

Patent Document 2: Japanese Patent Application Publication No. 2009-237018

Summary of the invention

1. Technical issues to be resolved

However, the resin compositions commonly used so far have insufficient reactivity and require a relatively long curing time. In short, this means that they are limited to specific molding processes and productivity.

Thus, glycidylamine-based epoxy resins need to be improved from the viewpoint of curing time, but as examples of glycidylamine-based fluorinated epoxy resins, only the examples in Patent Documents 1 and 2 are known. The properties obtained by glycidylamine-based fluorinated epoxy resins are particularly interesting in the fields of prepregs, fiber-reinforced composite materials, and sealing materials.

The present invention aims to provide a glycidylamine-type fluorinated epoxy compound. In addition, the present invention further aims to provide a fluorinated epoxy resin composition, a cured product, a prepreg, a fiber-reinforced composite material, a sealing material, and a semiconductor device using the fluorinated epoxy compound.

(II) Technical solution

The inventors of the present application have completed the disclosure provided below through research.

[1] A fluorine-containing epoxy compound represented by the general formula (1):

[Chemical formula 1]

In the general formula (1), n is independently an integer of 0 to 4, ^R1 is independently a monovalent substituent, and ^R1 is one selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, and an aryl group.

[2] The fluorinated epoxy compound according to [1], which is a fluorinated epoxy compound represented by the general formula (2),

[Chemical formula 2]

In the general formula (2), n is independently an integer of 0 to 4, ^R1 is independently a monovalent substituent, and ^R1 is one selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, and an aryl group.

[3] A fluorinated epoxy resin comprising a byproduct or an unreacted product produced when preparing the fluorinated epoxy compound described in [1] or [2],

The fluorinated epoxy resin contains the fluorinated epoxy compound described in [1] or [2] in a ratio of 50% or more, as measured by area ratio in high performance liquid chromatography.

[4] A fluorinated epoxy resin composition, characterized in that it comprises the fluorinated epoxy compound described in [1] or [2] or the fluorinated epoxy resin described in [3] and a curing agent.

[5] A cured product, characterized in that it is obtained by curing the fluorinated epoxy resin composition according to [4].

[6] A prepreg characterized in that it is formed by impregnating reinforcing fibers with the fluorine-containing epoxy resin composition according to [4].

[7] A fiber-reinforced composite material comprising the cured product described in [5] and reinforcing fibers.

[8] A method for producing a prepreg, comprising impregnating reinforcing fibers with the fluorinated epoxy resin composition described in [4].

[9] A method for producing a fiber-reinforced composite material, comprising curing the prepreg described in [6].

[10] A method for producing a fiber-reinforced composite material, characterized in that the fluorinated epoxy resin composition described in [4] is impregnated into reinforcing fibers and then cured.

[11] A sealing material comprising the cured product described in [5].

[12] A semiconductor device comprising at least a semiconductor element, wherein the semiconductor element is sealed with the cured product according to [5].

[13] A method for sealing a semiconductor element, comprising curing the fluorinated epoxy resin composition according to [4] to thereby seal the semiconductor element.

[14] A method for using the fluorinated epoxy resin composition according to [4] as a sealing material, wherein the fluorinated epoxy resin composition according to [4] is cured to thereby use the sealing material.

[15] 1,1,1-trifluoro-2,2-bis(4-diglycidylaminophenyl)ethane represented by the general formula (3).

[Chemical formula 3]

[16] 1,1,1-trifluoro-2,2-bis(3-methyl-4-diglycidylaminophenyl)ethane represented by the general formula (4).

[Chemical formula 4]

[17] A method for producing a fluorinated epoxy compound, which is a method for producing a fluorinated epoxy compound represented by the general formula (1), comprising the step of reacting an aromatic diamine compound represented by the general formula (1A) with an epihalohydrin,

[Chemical formula 5]

In the general formula (1), n is independently an integer of 0 to 4, ^R1 is independently a monovalent substituent, and ^R1 is one selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, and an aryl group,

[Chemical formula 6]

In the general formula (1A), n is independently an integer of 0 to 4, ^R1 is independently a monovalent substituent, and ^R1 is one selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, and an aryl group.

(III) Beneficial effects

According to the embodiments of the present disclosure, a novel fluorinated epoxy compound can be provided. In addition, according to the embodiments of the present disclosure, a fluorinated epoxy resin composition, a cured product, a prepreg, a fiber-reinforced composite material, a sealing material, and a semiconductor device using the fluorinated epoxy compound can be provided.

DETAILED DESCRIPTION

Hereinafter, embodiments of the present disclosure are described in detail.

In this specification, unless otherwise specified, the expression "X to Y" in the description of a numerical range means greater than or equal to X and less than or equal to Y. For example, "1 to 5 mass %" means "greater than or equal to 1 mass % and less than or equal to 5 mass %".

In the description of the group (atomic group) in this specification, the description without describing whether it is substituted or unsubstituted includes both the case where there is no substituent and the case where there is a substituent. For example, "alkyl" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group with a substituent (substituted alkyl group).

In addition, in this specification, the fluorinated epoxy compound refers to the compound itself represented by each chemical formula. In addition, the fluorinated epoxy resin refers to a mixture containing the epoxy compound. That is, the fluorinated epoxy resin contains various by-products or unreacted products when preparing the fluorinated epoxy compound. The fluorinated epoxy resin composition refers to a composition in an uncured to semi-cured state containing at least a fluorinated epoxy compound and its curing agent. A resin cured product (also recorded as a cured product) refers to a cured product obtained by a curing reaction of a fluorinated epoxy resin composition.

＜Fluorinated Epoxy Compounds＞

The epoxy compound disclosed in the present invention is a fluorinated epoxy compound represented by the general formula (1). The fluorinated epoxy compound is characterized in that it has a structure in which "a 1,1,1-trifluoro-2,2-ethanediyl group (representing a -C(CF ₃ )H- group) and a diglycidylamino group are present in at least one aromatic ring." The inventors of the present application speculate that the heat resistance and dimensional stability of the cured resin are increased due to the specific stereostructure of the cured resin resulting from the asymmetric structure of the 1,1,1-trifluoro-2,2-ethanediyl group. In addition, the inventors of the present application speculate that the cured resin can be cured in a shorter time due to the asymmetric structure of the 1,1,1-trifluoro-2,2-ethanediyl group. Thus, since the fluorinated epoxy compound represented by the general formula (1) is characterized by the asymmetric structure of 1,1,1-trifluoro-2,2-ethanediyl, a cured resin having excellent heat resistance and dimensional stability can be obtained regardless of the position of the substituent, the type and number of ^R1 , and the curing can be performed in a shorter time.

[Chemical formula 7]

In the general formula (1), n is independently an integer of 0 to 4, ^R1 is independently a monovalent substituent, and ^R1 is one selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, and an aryl group.

n is preferably 0-3, more preferably 0-2, and further preferably 0-1.

The halogen atom of R ¹ is not limited, but is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The alkyl group of R ¹ is not limited, but preferably a straight chain or branched chain alkyl group having 1 to 6 carbon atoms (preferably 1 to 3), among which n-butyl, sec-butyl, isobutyl, tert-butyl, n-propyl, isopropyl, ethyl and methyl are preferred, and ethyl and methyl are particularly preferred. The alkoxy group of R ¹ is not limited, but preferably a straight chain or branched chain alkoxy group having 1 to 6 carbon atoms, among which n-butoxy, sec-butoxy, isobutyloxy, tert-butoxy, n-propoxy, isopropoxy, ethoxy and methoxy are preferred, and ethoxy and methoxy are particularly preferred. The alkyl group or alkoxy group of R ¹ may also be substituted with, for example, a halogen atom, an alkoxy group and a halogenated alkoxy group in any number and in any combination on any carbon thereof. The alkyl group or alkoxy group of R ¹ preferably has no substituent. Furthermore, when the number of R ¹ in the general formula (1) is 2 or more, the 2 or more R ¹ may also be connected to form a saturated or unsaturated monocyclic or polycyclic cyclic group having 3 to 10 carbon atoms.

The haloalkoxy group of R ¹ is not limited, but difluoromethoxy, trifluoromethoxy, tetrafluoroethoxy and 2,2,2-trifluoroethoxy are preferred, and trifluoromethoxy and 2,2,2-trifluoroethoxy are particularly preferred.

The aryl group of R ¹ is not limited, but phenyl, tolyl, xylyl, 1-naphthyl and 2-naphthyl are preferred, and phenyl is particularly preferred.

R ¹ is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. When the number of R ¹ in the general formula (1) is 2 or more, all R ¹ are preferably the same group.

It is also preferred that the fluorinated epoxy compound represented by the general formula (1) is bilaterally symmetrical about the 1,1,1-trifluoro-2,2-ethanediyl group (representing a -C(CF ₃ )H- group) as an axis. Specifically, the aromatic ring located on the right side of the 1,1,1-trifluoro-2,2-ethanediyl group (representing a -C(CF ₃ )H- group) and the aromatic ring located on the left side of the general formula (1) preferably have the same type, number, and position of each substituent (bilaterally symmetrical).

Among the compounds represented by the above-mentioned general formula (1), the fluorinated epoxy compounds represented by the following general formula (2) are particularly preferred.

[Chemical formula 8]

In the general formula (2), n is independently an integer of 0 to 4, ^R1 is independently a monovalent substituent, and ^R1 is one selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, and an aryl group.

n and ^R1 in the general formula (2) are the same as n and ^R1 in the general formula (1), and their preferred embodiments are also the same. That is, since the position of the diglycidylamino group in the compound represented by the general formula (1) is specified as belonging to the compound represented by the general formula (2), the form of the compound represented by the general formula (2) other than the position of the diglycidylamino group is the same as the compound represented by the general formula (1), and its preferred embodiments are also the same.

From the perspective of rapid curing, the viscosity of the fluorinated epoxy compound disclosed herein at 150° C. is preferably less than 200 mPa·s, more preferably less than 150 mPa·s, and particularly preferably less than 100 mPa·s, and the lower limit is not particularly limited.

In this specification, the viscosity of the epoxy compound at 150° C. can be measured by the method described in the Examples.

As suitable examples of such fluorinated epoxy compounds, the following compounds can be cited, among which 1,1,1-trifluoro-2,2-bis(4-diglycidylaminophenyl)ethane represented by the general formula (3) and 1,1,1-trifluoro-2,2-bis(3-methyl-4-diglycidylaminophenyl)ethane represented by the general formula (4) are preferred.

[Chemical formula 9]

The fluorinated epoxy compound may be synthesized by any method, and can be obtained, for example, by reacting a fluorinated aromatic diamine compound represented by the following general formula (1A) with an epihalohydrin such as epichlorohydrin to obtain a tetrahalohydrin, and then subjecting the tetrahalohydrin to a cyclization reaction using a basic compound.

[Chemical formula 10]

In the general formula (1A), n is independently an integer of 0 to 4, ^R1 is independently a monovalent substituent, and ^R1 is one selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, and an aryl group.

n and ^R1 in the general formula (1A) are the same as n and ^R1 in the general formula (1), and their preferred embodiments are also the same.

Among the compounds represented by the above general formula (1A), the fluorinated aromatic diamine compounds represented by the following general formula (2A) are particularly preferred.

[Chemical formula 11]

In the general formula (2A), n is independently an integer of 0 to 4, ^R1 is independently a monovalent substituent, and ^R1 is one selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, and an aryl group.

n and ^R1 in the general formula (2A) are the same as n and ^R1 in the general formula (1), and their preferred embodiments are also the same.

The fluorinated aromatic diamine compound represented by the general formula (2A) can be prepared, for example, by referring to the method described in WO2020-162411. The following are compounds that are particularly preferably used as the fluorinated aromatic diamine compound represented by the general formula (2A) in terms of performance and cost.

[Chemical formula 12]

The amount of epihalohydrin (typically epichlorohydrin or epibromohydrin) used for the reaction is preferably 0.1 to 100 mol, more preferably 1.0 to 75 mol, and even more preferably 2.0 to 50 mol per 1 mol of the amino groups of the fluorinated aromatic diamine represented by the general formula (2A).

As the base used in the reaction, alkali metal hydroxides, alkali metal alkoxides, alkali metal carbonates, etc. can be generally listed. Specifically, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium butoxide, potassium butoxide, lithium butoxide, sodium carbonate, potassium carbonate, lithium carbonate, etc. can be listed. Among the above-mentioned bases, only one can be used, or more than two can be used simultaneously. As a preferred form in the reaction, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide as a base are usually added to the reaction system in the state of a solid or aqueous solution, so that the reaction system is made into "alkaline conditions". Relative to 1 mol of the amino group of the fluorinated aromatic diamine represented by the general formula (2A), the addition amount of the base is preferably 0.1~100 mol, more preferably 2.0~50 mol.

The reaction can be carried out under normal pressure (0.1 MPa; absolute pressure) or under reduced pressure. Generally, the reaction temperature is 20 to 150°C in the case of a reaction under normal pressure, and 30 to 80°C in the case of a reaction under reduced pressure.

During the reaction, dehydration is performed as required by the following method: maintaining a specified temperature, azeotroping the reaction solution, separating the organic phase/water phase of the condensate obtained by cooling the volatilized vapor, and returning the organic phase from which the water phase is excluded to the reaction system. For the addition of alkali metal hydroxide, in order to suppress the rapid reaction, it usually takes 0.1 to 10 hours to gradually add a small amount of alkali metal hydroxide to the reaction system intermittently or continuously. The total reaction time is usually 1 to 15 hours.

The reaction is preferably analyzed using an analytical device such as a nuclear magnetic resonance apparatus (NMR) or a liquid chromatograph (LC), and the time point when the reaction conversion rate reaches a predetermined value is determined as the end point of the reaction.

Preferably, after the reaction is completed, the insoluble byproduct salt is filtered off or removed by washing. Then, the unreacted epihalohydrin is preferably removed by vacuum distillation. Thus, the target fluorine-containing epoxy compound can be obtained.

In the reaction, catalysts such as tertiary ammonium salts such as tetrabutylammonium hydrogen sulfate, tetramethylammonium chloride, and tetraethylammonium bromide; tertiary amines such as benzyldimethylamine and 2,4,6-tris(dimethylaminomethyl)phenol; imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole; phosphonium salts such as ethyltriphenylphosphonium iodide; and phosphines such as triphenylphosphine can be used.

In the reaction, inactive organic solvents such as alcohols such as ethanol and isopropanol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and ethylene glycol dimethyl ether; glycol ethers such as methoxypropanol; and aprotic polar solvents such as dimethyl sulfoxide and dimethylformamide may be used. These organic solvents may be used alone or in combination of two or more.

Compared with known fluorinated epoxy compounds not within the scope of the present disclosure, the fluorinated epoxy compounds of the present disclosure have the characteristics of being able to be prepared in good yield and having fewer byproducts and unreacted products. The reason for this is presumably that the excessive rigidity of the fluorinated aromatic diamine compound represented by the general formula (2A) is suppressed by the inclusion of an asymmetric (—C(CF ₃ )H— group) and the moderate content of fluorine atoms.

＜Fluorinated epoxy resin＞

The fluorinated epoxy compound represented by the general formula (1) or (2) does not necessarily need to be separated after synthesis, and can also be used in the form of a fluorinated epoxy resin containing byproducts or unreacted products when preparing the fluorinated epoxy compound represented by the general formula (1) or (2). The fluorinated epoxy resin disclosed herein is a fluorinated epoxy resin containing the fluorinated epoxy compound represented by the general formula (1) at a ratio of 50% or more, based on the area ratio determined by high performance liquid chromatography (HPLC). Based on the area ratio determined by HPLC, the fluorinated epoxy resin disclosed herein preferably contains the fluorinated epoxy compound represented by the general formula (1) at a ratio of 60% or more, and more preferably contains 70% or more. By containing it at a ratio of 50% or more, heat resistance and mechanical strength can be improved. In addition, based on the area ratio determined by HPLC, the fluorinated epoxy resin disclosed herein preferably contains the fluorinated epoxy compound represented by the general formula (1) at a ratio of 99.99% or less.

In the present specification, the area ratio of the fluorinated epoxy compound represented by the general formula (1) in the HPLC measurement of the fluorinated epoxy resin is measured by the method described in the Examples.

From the perspective of rapid curing, the viscosity of the fluorinated epoxy resin disclosed herein at 150° C. is preferably less than 200 mPa·s, more preferably less than 150 mPa·s, and particularly preferably less than 100 mPa·s, and the lower limit is not particularly limited.

In this specification, the viscosity of the fluorine-containing epoxy resin at 150° C. is measured by the method described in the Examples.

<Fluorine-containing epoxy resin composition>

The fluorine-containing epoxy resin composition disclosed in the present invention is a composition in an uncured to semi-cured state that at least contains the fluorine-containing epoxy compound disclosed in the present invention and a curing agent. In addition, the fluorine-containing epoxy resin composition disclosed in the present invention may also contain a thermosetting resin, a thermoplastic resin, and other additives. In addition, the fluorine-containing epoxy resin composition disclosed in the present invention may contain a fluorine-containing epoxy compound and a curing agent at the same time when being cured. Depending on the molding method used, a composition containing a fluorine-containing epoxy compound and a curing agent can be prepared in advance, or a composition containing a fluorine-containing epoxy compound and a composition containing a curing agent can be prepared separately and mixed in, for example, a molding mold. In addition, the fluorine-containing epoxy compound contained in the fluorine-containing epoxy resin composition disclosed in the present invention can of course also be a fluorine-containing epoxy resin containing impurities. In addition, of course, the fluorine-containing epoxy compound disclosed in the present invention and the fluorine-containing epoxy resin disclosed in the present invention can be used alone, or two or more kinds can be used simultaneously.

The viscosity of the fluorinated epoxy resin composition disclosed herein can be appropriately adjusted according to the molding method, but when used as a prepreg, for example, the viscosity at 150°C is preferably less than 2000mPa·s, and more preferably 0.001~1000mPa·s. In the case of exceeding 2000mPa·s, the operability sometimes decreases. In addition, when a fluorinated epoxy resin composition having a viscosity exceeding 2000mPa·s at 150°C is used to make a prepreg, it becomes easy to produce an unimpregnated portion in the prepreg. As a result, it becomes easy to form voids, etc. in the obtained fiber-reinforced composite material.

In the present specification, the viscosity of the fluorine-containing epoxy resin composition at 150° C. is measured by the method described in the Examples.

The content ratio of the fluorinated epoxy compound (fluorinated epoxy resin of the present disclosure) represented by the general formula (1) in the fluorinated epoxy resin composition of the present disclosure is preferably 10~90 mass %, more preferably 15~80 mass %, and further preferably 20~70 mass %. In the case of less than 10 mass %, the operability of the resin composition may sometimes deteriorate, or the strength or heat resistance of the obtained cured product may sometimes decrease. In the case of more than 90 mass %, the molar balance with the curing agent may sometimes become inappropriate, and various characteristics such as the mechanical properties of the cured product may sometimes decrease.

The curing agent used in the fluorine-containing epoxy resin composition of the present disclosure is not particularly limited, and is a well-known curing agent for curing epoxy resin. As a curing agent, any substance that cures epoxy resin can be selected appropriately according to the purpose of use. For example, an amine curing agent is suitable for curing epoxy resin compositions. An amine curing agent is a compound that has at least one nitrogen atom in the molecule and can react with an epoxy group in an epoxy resin for curing. Suitable types of amine curing agents are, for example, diaminodiphenyl sulfone. Specific examples of suitable diaminodiphenyl sulfones are not limited, but 4,4'-diaminodiphenyl sulfone (4,4'-DDS) and 3,3'-diaminodiphenyl sulfone (3,3'-DDS) and combinations thereof can be cited. The curing agent can be used alone or in combination with two or more.

The amount of curing agent contained in the fluorinated epoxy resin composition is an amount suitable for curing all epoxy resins blended in the fluorinated epoxy resin composition, and can be appropriately adjusted according to the type of epoxy resin or curing agent used. For example, when an amine curing agent is used, it is preferably 25 to 65 parts by mass, and more preferably 35 to 55 parts by mass, relative to 100 parts by mass of all epoxy resins. When it is less than 25 parts by mass or greater than 65 parts by mass, the curing of the fluorinated epoxy resin composition may sometimes become insufficient, which easily reduces the physical properties of the cured resin.

The fluorinated epoxy resin composition disclosed in the present invention includes the fluorinated epoxy compound and its curing agent as essential components, but may also contain other components. The other components may be used alone or in combination of two or more.

The fluorinated epoxy resin composition disclosed herein requires the fluorinated epoxy compound represented by the general formula (1), but may also include other epoxy resins other than the fluorinated epoxy compound disclosed herein. As other epoxy resins, conventionally known epoxy resins can be used. Specifically, epoxy resins containing aromatic groups are preferred, preferably epoxy resins containing any one of a glycidylamine structure and a glycidyl ether structure. In addition, alicyclic epoxy resins may also be preferably used. When the fluorinated epoxy compound represented by the general formula (1) and other epoxy resins are used simultaneously, the proportion of the fluorinated epoxy compound represented by the general formula (1) in all epoxy resins contained in the fluorinated epoxy resin composition is preferably 20% by mass or more, more preferably 50% by mass or more, and further preferably 60 to 100% by mass.

Examples of the epoxy resin containing a glycidylamine structure include tetraglycidyldiaminodiphenylmethane, N,N,O-triglycidyl-p-aminophenol, N,N,O-triglycidyl-m-aminophenol, N,N,O-triglycidyl-3-methyl-4-aminophenol, and various isomers of triglycidylaminocresol.

On the other hand, as epoxy resins containing glycidyl ether structures, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins can be exemplified. In addition, these epoxy resins can also have non-reactive substituents in the aromatic ring structure or alicyclic structure as required. As non-reactive substituents, alkyl groups such as methyl, ethyl, isopropyl, aromatic groups such as phenyl, or halogen groups such as alkoxy, aralkyl, fluorine, chlorine or bromine can be exemplified.

The fluorine-containing epoxy resin composition of the present disclosure may also contain a thermoplastic resin. Examples of the thermoplastic resin include epoxy resin-soluble thermoplastic resins and epoxy resin-insoluble thermoplastic resins. Epoxy resin-soluble thermoplastic resins are thermoplastic resins that are partially or completely soluble in epoxy resins at or below the temperature at which the FRP is molded. On the other hand, epoxy resin-insoluble thermoplastic resins are thermoplastic resins that are substantially insoluble in epoxy resins at or below the temperature at which the FRP is molded.

As specific examples of epoxy resin soluble thermoplastic resins, polyethersulfone, polysulfone, polyetherimide, polycarbonate, etc. can be listed. These epoxy resin soluble thermoplastic resins can be used alone or in combination of two or more. Such epoxy resin soluble thermoplastic resins can improve the dissolution stability of epoxy resin during the curing process. In addition, toughness, chemical resistance, heat resistance and moisture-heat resistance can be imparted to the FRP obtained after curing.

As epoxy resin insoluble thermoplastic resin, polyamide, polyacetal, polyphenylene ether, polyphenylene sulfide, polyester, polyamide-imide, polyimide, polyether ketone, polyether ether ketone, polyethylene naphthalate, polyether nitrile, polybenzimidazole can be exemplified. Among them, polyamide, polyamide-imide, polyimide have high toughness and heat resistance, so they are particularly preferred. Polyamide or polyimide has excellent effect on improving the toughness of cured resin. These epoxy resin insoluble thermoplastic resins can be used alone, or two or more can be used simultaneously. In addition, their copolymers can also be used.

The content of the thermoplastic resin contained in the epoxy resin composition can be appropriately adjusted according to the viscosity. From the perspective of the processability of the prepreg, relative to 100 parts by mass of the epoxy resin contained in the epoxy resin composition, it is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, and further preferably 20 to 40 parts by mass. When less than 5 parts by mass, the impact resistance of the obtained FRP may sometimes become insufficient. If the content of these thermoplastic resins becomes high, the viscosity may become significantly higher sometimes, and the operability of the prepreg may be significantly deteriorated.

Conductive particles or flame retardants, inorganic fillers, and internal mold release agents may also be blended into the fluorine-containing epoxy resin composition of the present disclosure. As conductive particles, conductive polymer particles such as polyacetylene particles, polyaniline particles, polypyrrole particles, polythiophene particles, polyisothianaphthene particles, and polyethylenedioxythiophene particles can be exemplified; carbon particles; carbon fiber particles; metal particles; particles formed by coating a core material formed of an inorganic material or an organic material with a conductive substance. As a flame retardant, a phosphorus-based flame retardant can be exemplified. As a phosphorus-based flame retardant, there is no particular limitation as long as the molecule contains a phosphorus atom, and for example, organic phosphorus compounds such as phosphates, condensed phosphates, phosphazene compounds, and polyphosphates or red phosphorus can be listed. As an inorganic filler, for example, aluminum borate, calcium carbonate, silicon carbonate, silicon nitride, potassium titanate, basic magnesium sulfate, zinc oxide, graphite, calcium sulfate, magnesium borate, magnesium oxide, and silicate minerals can be listed. Silicate minerals are particularly preferably used. Examples of the internal mold release agent include metal soaps, plant waxes such as polyethylene wax and palm wax, fatty acid ester-based mold release agents, silicone oils, animal waxes, and fluorine-based nonionic surfactants.

The preparation method of the fluorinated epoxy resin composition is not particularly limited, and any method known in the past may be used. As a mixing temperature, a range of 40 to 150° C. may be exemplified. When the temperature exceeds 150° C., the curing reaction may be partially carried out, and the impregnation into the reinforcing fiber substrate layer may decrease, or the storage stability of the obtained fluorinated epoxy resin composition and the prepreg produced using the same may decrease. When the temperature is less than 40° C., the viscosity of the epoxy resin composition may be high, and it may be difficult to mix substantially. The range of 50 to 120° C. is preferred.

As a mixing mechanical device, a previously known device can be used. As specific examples, a roller mill, a planetary mixer, a kneader, an extruder, a Banbury mixer, a mixing container with a stirring blade, a horizontal mixing tank, etc. can be listed. The mixing of each component can be carried out in the atmosphere or in an inert gas atmosphere. In the case of mixing in the atmosphere, an atmosphere in which the temperature and humidity are managed is preferred. Although not particularly limited, it is preferably mixed under a low humidity atmosphere in which the temperature is managed to be a fixed temperature below 30°C or a relative humidity is below 50%RH.

＜Solidified material＞

The cured product of the present disclosure is a cured product obtained by curing the fluorinated epoxy resin composition of the present disclosure. The curing reaction can be appropriately determined according to the epoxy resin or curing agent contained in the epoxy resin composition, but is usually carried out by heating at 20 to 250° C. for 0.07 hours or more. The heating time is also preferably within 0.13 hours, but the usual heating time is 0.5 hours or more.

The cured product of the present disclosure is characterized in that it can be cured in a short time. The reason for this is not entirely clear, but it is presumed to be related to the asymmetric structure of 1,1,1-trifluoro-2,2-ethanediyl.

The cured product disclosed herein is characterized by high heat resistance. Here, the heat resistance can be judged by the glass transition temperature of each cured product. The glass transition temperature of the cured product disclosed herein is preferably 180°C or more, more preferably 200°C or more, further preferably 220°C or more, and particularly preferably 230°C or more. The upper limit of the glass transition temperature is not particularly limited, but is usually less than 300°C.

In this specification, the glass transition temperature of a cured product is measured by the method described in Examples.

The cured product disclosed in the present invention is characterized in that it has high dimensional stability. Here, dimensional stability can be judged by the linear expansion coefficient at each temperature. The linear expansion coefficient α1 of the cured product disclosed in the present invention at 25 to 180°C below the glass transition temperature is preferably 120 ppm/°C or less, and more preferably 80 ppm/°C or less. In addition, the linear expansion coefficient α2 at 180 to 300°C above the glass transition temperature is preferably 200 ppm/°C or less, more preferably 160 ppm/°C or less, and further preferably 130 ppm/°C or less. The lower limit of the linear expansion coefficient at each temperature is not particularly limited, but is generally 20 ppm/°C or more.

In this specification, the linear expansion coefficient of the cured product is measured by the method described in the Examples.

The cured product disclosed herein is characterized in that the water absorption is low. Here, the water absorption refers to the mass increase rate after storage for 72 hours under the conditions of 25°C and water. The water absorption is preferably less than 3.0% by mass, more preferably less than 1.0% by mass, and further preferably less than 0.5% by mass. The lower limit of the water absorption is not particularly limited, but is generally 0.01% by mass or more. When the water absorption is 3.0% by mass or more, the strength of the cured resin, especially when formed into a thin plate, sometimes becomes easy to decrease.

In this specification, the water absorption of the cured product is measured by the method described in the Examples.

＜Prepreg＞

The prepreg disclosed in the present invention is formed by impregnating the fluorine-containing epoxy resin composition disclosed in the present invention into a material formed in the reinforcing fiber. In short, the prepreg disclosed in the present invention is a prepreg in which the fluorine-containing epoxy resin composition is impregnated in part or in its entirety in the reinforcing fiber. Based on the total mass of the prepreg, the content ratio of the fluorine-containing epoxy resin composition in the prepreg as a whole is preferably 15 to 60% by mass. In the case where the content ratio of the fluorine-containing epoxy resin composition is less than 15% by mass, voids may sometimes be generated in the obtained fiber-reinforced composite material, thereby reducing mechanical properties. In the case where the content ratio of the fluorine-containing epoxy resin composition is greater than 60% by mass, the reinforcement effect brought by the reinforcing fibers of the obtained fiber-reinforced composite material may sometimes become insufficient, and mechanical properties may substantially become lower.

The reinforcing fiber can be any one of twisted yarn, untwisted yarn or untwisted yarn, but untwisted yarn and untwisted yarn have excellent formability in fiber-reinforced composite materials, so they are preferred. Further, regarding the form of the reinforcing fiber, fibers or woven fabrics with twisted fibers in one direction can be used. In woven fabrics, it can be freely selected from plain weave, satin weave, etc. according to the location or purpose used. Specifically, in terms of excellent mechanical strength or durability, carbon fiber, glass fiber, polyaramid fiber, boron fiber, alumina fiber, silicon carbide fiber, etc. can be listed, and more than two of them can also be used simultaneously. Among them, from the point of view that the strength of the molded product is particularly good, carbon fiber is preferred, and various carbon fibers such as polyacrylonitrile, asphalt, and rayon can be used for the carbon fiber.

The method for producing the prepreg disclosed in the present invention is not particularly limited as long as it is characterized by impregnating the fluorine-containing epoxy resin composition disclosed in the present invention into reinforcing fibers, and any conventionally known method may be used. Specifically, a hot melt method or a solvent method may be preferably used.

The hot melt method is a method in which a resin composition is applied onto release paper in a thin film to form a resin composition film, the resin composition film is laminated on reinforcing fibers, and the epoxy resin composition is impregnated into the reinforcing fibers by heating under pressure.

The solvent method is a method in which an epoxy resin composition is made into a varnish using an appropriate solvent, and the varnish is impregnated into reinforcing fibers.

＜Fiber-reinforced plastics (FRP)＞

The fiber-reinforced composite material of the present disclosure comprises the cured product of the present disclosure and reinforcing fibers. The fiber-reinforced composite material is produced by curing the reinforcing fibers and the fluorine-containing epoxy resin composition of the present disclosure in a composite state.

In the fiber-reinforced composite material disclosed herein, the total content of the cured product disclosed herein and the reinforcing fibers is preferably 60% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, particularly preferably 95% by mass or more, and may be 100% by mass.

The method for obtaining a fiber-reinforced composite material using the fluorinated epoxy resin composition of the present disclosure is not particularly limited, and examples thereof include: a method in which each component constituting the fluorinated epoxy resin composition is uniformly mixed to produce a varnish, and then a method in which unidirectional reinforcing fibers twisted in one direction are impregnated with the obtained varnish (in a state before curing by a pultrusion method or a filament winding method); or a method in which a woven fabric of reinforcing fibers is overlapped and mounted on a concave mold, and then sealed with a convex mold and then a resin is injected to perform pressure impregnation (in a state before curing by an RTM method), etc.

The fiber-reinforced composite material of the present disclosure may be in a form in which the fluorinated epoxy resin composition is locally present near the surface of the fiber, and it is not essential that the fluorinated epoxy resin composition is impregnated into the interior of the fiber bundle.

On the other hand, as a method for producing FRP using a prepreg in which reinforcing fibers and an epoxy resin composition are compounded in advance, known molding methods such as autoclave molding and press molding can be cited.

The method for producing the FRP of the present disclosure is not particularly limited as long as it is characterized by curing the prepreg of the present disclosure or impregnating the fluorinated epoxy resin composition of the present disclosure into reinforcing fibers and curing them, and any conventionally known method may be employed.

As a method for manufacturing the FRP disclosed in the present invention, an autoclave molding method can be preferably used. The autoclave molding method is a method in which a prepreg and a film bag are laid in sequence on the lower mold of the mold, the prepreg is sealed between the lower mold and the film bag, the space formed by the lower mold and the film bag is made into a vacuum, and a autoclave molding device is used to heat and pressurize. Regarding the conditions during molding, it is preferred to set the heating rate to 1~50℃/min, and heat and pressurize at 0.2~0.8MPa and 100~180℃ for 30~300 minutes.

In addition, as a method for manufacturing the FRP of the present invention, a press molding method can be preferably used. The manufacture of FRP based on the press molding method is carried out in the following manner: using a mold, the prepreg of the present invention or the preform formed by stacking the prepreg of the present invention is heated and pressurized. The mold is preferably preheated to the curing temperature. The temperature of the mold during press molding is preferably 150~200°C. If the molding temperature is above 150°C, the curing reaction can be fully initiated, and FRP can be obtained with high productivity. In addition, if the molding temperature is below 200°C, the resin viscosity will not become too low, and the excessive flow of the resin in the mold can be suppressed. As a result, since the outflow of the resin from the mold or the meandering of the fiber can be suppressed, a high-quality FRP can be obtained. The pressure during molding is 0.05~2MPa, preferably 0.2~2MPa. If the pressure is above 0.05MPa, a moderate flow of the resin can be obtained, and the appearance is poor or the generation of voids can be prevented. In addition, since the prepreg is fully in close contact with the mold, FRP with good appearance can be manufactured. If the pressure is below 2 MPa, the resin will not flow excessively, so the resulting FRP is less likely to have a poor appearance. In addition, the mold will not be overloaded, so the mold is less likely to deform. The molding time is preferably 1 to 8 hours.

＜Sealing materials＞

The sealing material of the present disclosure is formed by containing the cured product of the present disclosure. The sealing material of the present disclosure is made by curing the fluorine-containing epoxy resin composition of the present disclosure. The sealing material of the present disclosure can be used as a sealing material for semiconductors and light-emitting diodes (LEDs), wherein it can be preferably used as a sealing material for semiconductors. In addition, the cured product of the present disclosure can also be used as a sealing material for power semiconductors because it shows high heat resistance.

The content ratio of the cured product of the present disclosure in the sealing material of the present disclosure is preferably 60% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, particularly preferably 95% by mass or more, and may be 100% by mass.

<Semiconductor device, method of sealing semiconductor, method of using as sealing material>

The semiconductor device disclosed in the present invention is a semiconductor device having at least a semiconductor element, which is formed by sealing at least the semiconductor element using a cured product of the fluorinated epoxy resin composition disclosed in the present invention. Other structures in the semiconductor device disclosed in the present invention are not particularly limited, and in addition to the semiconductor element, it may also be provided with semiconductor device components known in the past. As an example of such a semiconductor device component, for example, a base substrate, lead-out wiring, wire wiring, a control element, an insulating substrate, a heat sink, a conductive component, a die bonding material, a bonding pad, etc. can be listed. In addition, in addition to the semiconductor element, a part or all of the semiconductor device component may also be sealed by the cured product of the fluorinated epoxy resin composition disclosed in the present invention.

There are standards for power semiconductor packaging classified by JEDEC (Semiconductor Standards Association) or JEITA (Electronic Information Technology Industries Association), such as TO-3, TO-92, TO-220, TO-247, TO-252, TO-262, TO-263, D2, etc. As an example of the packaging type of the semiconductor device disclosed in the present invention, these standards can be cited, but other well-known industrial standards can also be adopted.

As an example of the semiconductor device of the present disclosure, for example, the semiconductor device shown in FIG. 1 of Japanese Patent Publication No. 2017-197591 can be cited. In addition, the structure shown in FIG. 1 of Japanese Patent Publication No. 2017-197591 is only an example of the semiconductor device of the present disclosure, and the structure of the frame, the mounting structure of the semiconductor element, etc. can be appropriately deformed, and other semiconductor device components can be appropriately added.

The semiconductor device of the present disclosure can be produced, for example, by molding the fluorine-containing epoxy resin composition of the present disclosure by cast molding, compression molding or transfer molding to obtain a cured product, and sealing a semiconductor element with the cured product.

The embodiments of the present disclosure are described above, but they are only examples of the present disclosure, and various configurations other than the above can be adopted. In addition, the present disclosure is not limited to the above embodiments, and modifications and improvements within the scope that can achieve the purpose of the present disclosure are included in the present disclosure.

Example

The embodiments of the present disclosure will be described in detail based on examples and comparative examples. For the sake of caution, it is mentioned above that the present disclosure is not limited to the examples.

(Identification and physical property and performance evaluation of epoxy compounds and their cured products)

First, the identification method and the method of evaluating the physical properties and performance of the polymer compounds obtained in Examples and Comparative Examples are described.

Purity of epoxy compounds

High performance liquid chromatography (HPLC) measurement was performed under the following conditions, and the purity of the epoxy compound was measured from the peak area fraction.

Mobile phase: acetonitrile/10 mM ammonium formate

Chromatographic column: YMC-Pack (ODS-AM, AM12SOJ-1506WT)

· Column oven temperature: 40°C

Column flow rate: 1.0mL/min

Detector: UV light with a wavelength of 254nm

Sample preparation method: About 10 mg of epoxy resin was dissolved in 2 g of acetonitrile to prepare the sample.

Epoxy equivalent

The epoxy equivalent of the epoxy resin was measured by the method described in JIS K7236:2009.

Viscosity

The viscosity of the epoxy resin at 150° C. and a shear rate of 100/s was measured at a standard atmospheric pressure using a rotational viscometer (manufactured by Anton Paar, product name: PHYSICA MCR51, measuring cone CP50-1). The conditions of the device were set as follows.

Shear rate: Logarithmic rise and fall (starting 10 [1/s] - ending 1000 [1/s])

Measurement interval: logarithmic (start 90 seconds - end 3 seconds)

·Measuring points: 21

Glass transition temperature

The glass transition temperature (Tg) of each cured product was measured using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Corporation, model name DSC7000) at a temperature increase rate of 10°C/min.

Dimensional stability

The dimensional stability was evaluated by measuring the coefficient of linear expansion (CTE) of each cured product obtained in the examples and comparative examples. Specifically, a thermomechanical analyzer (manufactured by Rigaku Corporation, product name: TMA8310) was used to obtain the CTE at 25-180°C (α1) and 180-300°C (α2) from the TMA curve obtained under the following conditions. In addition, two tests were performed on one sample sheet, and the CTE was calculated from the TMA curve obtained by the second measurement.

Mode: Compression mode

Specimen size: 4mm×5mm×20mm prism

Load: -98N

Heating conditions: from 20°C to 300°C at a rate of 10°C/min

·Water absorption determination

The water absorption rate is calculated with reference to the method described in JIS K7209:2000. Measure the mass W1 of a sample piece of 4mm×10mm×80mm size, and dry it in a 60℃ constant temperature bath for 24 hours. After drying, return to room temperature in the dryer, and measure the mass W2. When the difference between W1 and W2 is more than 0.5mg, dry it again, and repeat until the difference becomes less than 0.5mg. When the mass change is less than 0.5mg, sink the sample piece in more than 1L of water, leave it in a 25℃ constant temperature bath for 72 hours, take out the sample, wipe off the water, and quickly measure the mass W3. Calculate the water absorption rate based on the mass change between W2 and W3.

Water absorption (%) = (W3-W2)/W2×100

Curing speed

The curability of the epoxy compound was measured by the curing rate. 3 g of the epoxy resin composition prepared from each epoxy compound and a curing agent (4,4-DDS) was weighed into a glass vial equipped with a Teflon (registered trademark) stirring rod and stirred at 180° C. The time until the stirring was stopped due to the increase in the viscosity of the epoxy resin composition was measured.

Use monomer

The monomers used and their abbreviations are shown below.

[Chemical formula 13]

Table 1 shows the physical properties of the epoxy compounds used as the above-mentioned monomers.

[Table 1]

(Synthesis Example 1; BIS-A-EF-G; 1,1,1-trifluoro-2,2-bis(4-diglycidylaminophenyl)ethane)

[Chemical formula 14]

Under a nitrogen atmosphere, 40 g (0.15 mol) of 1,1,1-trifluoro-2,2-bis (4-aminophenyl) ethane synthesized according to the method described in WO2020-162411 and 167 g (1.8 mol) of epichlorohydrin were added to a four-necked flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer, and stirred at 80 ° C for 18 hours. After the stirring was completed, the unreacted epichlorohydrin was distilled off, 120 g of methyl isobutyl ketone and 1.2 g (0.0045 mol) of tetrabutylammonium hydrogen sulfate were added, and 180 g (0.9 mol) of 20% sodium hydroxide aqueous solution was added dropwise at 60 ° C for 2 hours. After the addition was completed, it was stirred at 60 ° C for 3 hours, and a closed ring reaction was confirmed by a liquid chromatograph. The organic layer was separated by a separatory funnel, and the obtained organic layer was further washed twice with 120 g of water. The organic layer obtained by washing was concentrated using a rotary evaporator to obtain 58 g of the epoxy resin (yield 82%).

[Physical properties]

Epoxy purity: 86%, epoxy equivalent: 114g/equivalent, viscosity: 54mPa·S@150℃

¹ H-NMR (400MHz, CDCl ₃ ) δ (ppm): 1.67 (1H, s), 2.54 (4H, q, J=8.0Hz), 2.76~2.79 (4H, m), 3.11~3.18 (4H, m) ), 3.36~3.47(4H, m), 3.69~3.76(4H, m), 6.75(4H,d, J=8.8Hz), 7.21(4H, d, J=8.8)

¹⁹ F-NMR (400MHz) δ (ppm): -67.1 (3F, s)

(Synthesis Example 2; BIS-3AT-EF-G; 1,1,1-trifluoro-2,2-bis(3-methyl-4-diglycidylaminophenyl)ethane)

[Chemical formula 15]

Under a nitrogen atmosphere, 44 g (0.15 mol) of 1,1,1-trifluoro-2,2-bis (3-methyl-4-aminophenyl) ethane synthesized according to the method described in WO2020-162411 and 167 g (1.8 mol) of epichlorohydrin were added to a four-necked flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer, and stirred at 80 ° C for 18 hours. After the stirring was completed, the unreacted epichlorohydrin was distilled off, 120 g of methyl isobutyl ketone and 1.2 g (0.0045 mol) of tetrabutylammonium hydrogen sulfate were added, and 180 g (0.9 mol) of 20% sodium hydroxide aqueous solution was added dropwise at 60 ° C for 2 hours. After the addition was completed, it was stirred at 60 ° C for 3 hours, and a closed ring reaction was confirmed by a liquid chromatograph. The organic layer was separated by a separatory funnel, and the obtained organic layer was further washed twice with 120 g of water. The organic layer obtained by washing was concentrated using a rotary evaporator to obtain 63 g of the epoxy resin (yield 52%).

[Physical properties]

Epoxy purity: 63%, epoxy equivalent: 119g/equivalent, viscosity: 18mPa·S@150℃

¹ H-NMR (400MHz, CDCl ₃ ) δ (ppm): 1.60 (1H, s), 2.16 (6H, s), 2.31~2.35 (4H, m), 2.45~2.49 (4H, m), 2.68~2.71 (4H, m), 3.06~3.14(4H, m), 3.26~3.34(4H, m),7.14~7.19(4H, m), 7.25(2H, s)

¹⁹ F-NMR (400 MHz) δ (ppm): -66.6 (3F, s)

(Synthesis Example 3; TFMB-G; N,N,N',N'-tetraglycidyl-4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl)

[Chemical formula 16]

In a nitrogen atmosphere, 48 g (0.15 mol) of 2,2'-bis (trifluoromethyl) diaminobiphenyl and 167 g (1.8 mol) of epichlorohydrin were added to a four-necked flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer, and stirred at 80 ° C for 18 hours. After the stirring was completed, the unreacted epichlorohydrin was distilled off, 120 g of methyl isobutyl ketone and 1.2 g (0.0045 mol) of tetrabutylammonium hydrogen sulfate were added, and 180 g (0.9 mol) of 20% sodium hydroxide aqueous solution was added dropwise at 60 ° C for 2 hours. After the dropwise addition was completed, it was stirred at 60 ° C for 3 hours, and the ring closure reaction was confirmed by liquid chromatography. The organic layer was separated by a separatory funnel, and the obtained organic layer was further washed twice with 120 g of water. The organic layer obtained by washing was concentrated by a rotary evaporator to obtain 72 g of the epoxy resin (yield 21%).

[Physical properties]

Epoxy purity: 24%, epoxy equivalent: 116g/equivalent, viscosity: 42mPa·S@150℃

(Synthesis Example 4; BIS-A-AF-G; 2,2-bis(4-diglycidylaminophenyl)hexafluoropropane)

[Chemical formula 17]

In a nitrogen atmosphere, 50 g (0.15 mol) of 2,2-bis (4-diglycidylaminophenyl) hexafluoropropane and 167 g (1.8 mol) of epichlorohydrin were added to a four-necked flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer, and stirred at 80 ° C for 18 hours. After the stirring was completed, the unreacted epichlorohydrin was distilled off, 150 g of methyl isobutyl ketone and 1.2 g (0.0045 mol) of tetrabutylammonium hydrogen sulfate were added, and 180 g (0.9 mol) of 20% sodium hydroxide aqueous solution was added dropwise at 60 ° C for 2 hours. After the dropwise addition was completed, it was stirred at 60 ° C for 3 hours, and the ring closure reaction was confirmed by liquid chromatography. The organic layer was separated by a separatory funnel, and the obtained organic layer was further washed twice with 120 g of water. The organic layer obtained by washing was concentrated by a rotary evaporator to obtain 61 g of the epoxy resin (yield 26%).

[Physical properties]

Epoxy purity: 36%, epoxy equivalent: 144g/equivalent, viscosity: 32mPa·S@150℃

As can be seen from Synthesis Examples 1 to 4, compared with Synthesis Examples 3 to 4 for preparing fluorinated epoxy compounds not within the scope of the present disclosure, Synthesis Examples 1 to 2 for preparing the fluorinated epoxy compounds of the present disclosure have high yields and significantly less amounts of byproducts and unreacted products.

(Examples 1-2, Comparative Examples 1-3)

4,4-DDS was measured into a glass beaker and pre-melted in an oven at 160°C. The epoxy resin in the mass parts listed in Table 2 was added thereto and stirred until a uniform solution was obtained. After degassing in a vacuum for 20 minutes, the mixture was introduced into a preheated silicon mold and cured at 180°C for 2 hours under normal pressure. The shape of the obtained cured product was adjusted using a diamond wheel and provided for physical property measurement.

[Table 2]

When using the disclosed fluorinated epoxy compound to make a cured product, advantages such as being able to cure in a shorter time and being excellent in operation can be cited. In addition, compared with the comparative examples, the heat resistance and dimensional stability of these cured products are excellent. In recent years, especially as a fiber-reinforced composite material or a sealing material used in electrical and electronic equipment components such as multilayer circuit substrates, it is required to withstand the material of operation at a higher temperature, so an epoxy resin with high heat resistance is sought. In addition, in order to improve reliability, it is necessary to suppress the generation of cracks caused by stress relaxation during thermal curing, and as one of its techniques, there is a method for matching the linear expansion coefficient of the resin combination with the linear expansion coefficient of the substrate. Usually, the linear expansion coefficient of epoxy resin is larger than that of metal substrates, so it is desired to develop an epoxy resin with a lower linear expansion coefficient and more excellent dimensional stability, and the utilization value of the disclosed fluorinated epoxy compound and fluorinated epoxy resin can be said to be very high.

This application claims priority under the Paris Convention and the laws of the countries entered into based on Japanese Patent Application No. 2022-050334 filed on March 25, 2022. The contents of that application are hereby incorporated by reference in their entirety into this application.

Industrial Applicability

The cured product of the glycidylamine-type fluorinated epoxy compound of the present disclosure can be cured in a short time. In addition, the cured product of the glycidylamine-type fluorinated epoxy compound of one form of the present disclosure, such as Examples 1 and 2, has excellent heat resistance and dimensional stability. Therefore, the utilization value in fiber-reinforced composite materials and sealing materials is very high, and can be suitably used in the manufacture of, for example, electrical and electronic equipment components, aircraft components, spacecraft components, automobile components, railway vehicle components, ship components, and sports equipment components.

Claims (17)

1.A fluorine-containing epoxy compound represented by the general formula (1),

[ Chemical formula 1]

Wherein in the general formula (1), n is an integer of 0 to 4 independently, R ¹ is a monovalent substituent independently, and R ¹ is one selected from the group consisting of halogen atom, alkyl group, alkoxy group, haloalkoxy group and aryl group.

2. The fluorine-containing epoxy compound according to claim 1, which is a fluorine-containing epoxy compound represented by the general formula (2),

[ Chemical formula 2]

Wherein in the general formula (2), n is an integer of 0 to 4 independently, R ¹ is a monovalent substituent independently, and R ¹ is one selected from the group consisting of halogen atom, alkyl group, alkoxy group, haloalkoxy group and aryl group.

3. A fluorine-containing epoxy resin comprising by-products or unreacted materials in the production of the fluorine-containing epoxy compound according to claim 1 or claim 2,

The fluorine-containing epoxy compound according to claim 1 or claim 2, wherein the fluorine-containing epoxy resin is contained in an amount of 50% or more based on an area ratio in a high performance liquid chromatography measurement.

4. A fluorine-containing epoxy resin composition comprising the fluorine-containing epoxy compound according to claim 1 or claim 2 and a curing agent.

5. A cured product obtained by curing the fluorine-containing epoxy resin composition according to claim 4.

6. A prepreg formed from the fluorine-containing epoxy resin composition according to claim 4 impregnated into reinforcing fibers.

7. A fiber-reinforced composite material comprising the cured product according to claim 5 and reinforcing fibers.

8. A method for producing a prepreg, wherein the fluorine-containing epoxy resin composition according to claim 4 is impregnated into a reinforcing fiber.

9. A method for producing a fiber-reinforced composite material, wherein the prepreg according to claim 6 is cured.

10. A method for producing a fiber-reinforced composite material, characterized in that the fluorine-containing epoxy resin composition according to claim 4 is impregnated into reinforcing fibers and cured.

11. A sealing material comprising the cured product according to claim 5.

12. A semiconductor device including at least a semiconductor element,

The semiconductor device wherein the semiconductor element is sealed with the cured product according to claim 5.

13. A method of sealing a semiconductor element, wherein the fluorine-containing epoxy resin composition according to claim 4 is cured to thereby seal the semiconductor element.

14. A method of using the fluorine-containing epoxy resin composition according to claim 4 as a sealing material, wherein the fluorine-containing epoxy resin composition according to claim 4 is cured to thereby be used as a sealing material.

15. 1, 1-Trifluoro-2, 2-bis (4-diglycidyl aminophenyl) ethane represented by general formula (3),

[ Chemical formula 3]

。

16. 1, 1-Trifluoro-2, 2-bis (3-methyl-4-diglycidyl aminophenyl) ethane represented by general formula (4),

[ Chemical formula 4]

。

17. A process for producing a fluorine-containing epoxy compound represented by the general formula (1), which comprises a step of reacting an aromatic diamine compound represented by the general formula (1A) with an epihalohydrin,

[ Chemical formula 5]

Wherein in the general formula (1), n is an integer of 0 to 4, R ¹ is a monovalent substituent, R ¹ is one selected from the group consisting of halogen atom, alkyl group, alkoxy group, haloalkoxy group and aryl group,

[ Chemical formula 6]

Wherein in the general formula (1A), n is an integer of 0 to 4 independently, R ¹ is a monovalent substituent independently, and R ¹ is one selected from the group consisting of halogen atom, alkyl group, alkoxy group, haloalkoxy group and aryl group.