TW202337948A - Epoxy compound, epoxy resin, epoxy resin composition, cured product, prepreg, fiber-reinforced composite material, producing methods therefor, sealing material, semiconductor device, method for sealing semiconductor element, and method for using same as sealing material - Google Patents

Abstract

Provided is a glycidyl amine-type fluorine-containing epoxy compound. The present disclosure relates to a fluorine-containing epoxy compound represented by general formula (1). In general formula (1), n each independently represents an integer of 0 to 4, and R1 each independently represents a monovalent substituent and is one selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, and an aryl group.

Description

Epoxy compounds, epoxy resins, epoxy resin compositions, cured products, prepregs, fiber-reinforced composite materials and their manufacturing methods, compounds, sealing materials, semiconductor devices, methods of sealing semiconductor elements, and use as sealing materials Methods

The present disclosure relates to epoxy compounds, epoxy resins, epoxy resin compositions, cured materials, prepregs, fiber-reinforced composite materials and their manufacturing methods, sealing materials, semiconductor devices, methods of sealing semiconductor elements, and sealing materials The method of using materials. To elaborate further, it relates to an epoxy compound having a novel fluorine-containing skeleton, an epoxy resin containing this epoxy compound, an epoxy resin composition containing this epoxy compound, and curing of this epoxy resin composition. The cured product, the prepreg containing the epoxy resin composition, the method of sealing a semiconductor element using the epoxy resin composition and the method of using it as a sealing material, the fiber reinforced composite material containing the cured product, sealing materials and semiconductor devices.

Fiber-reinforced composite materials (hereinafter sometimes referred to as FRP) containing reinforcing fibers and matrix resins are widely used as electrical/electronic equipment parts, aircraft parts, spacecraft parts, automobile parts, etc. because they have excellent mechanical properties such as strength and rigidity. Railway vehicle parts, ship parts, sports equipment parts. FRP is generally produced by various methods, but among these methods, it is widely practiced to use reinforcing fibers impregnated with uncured matrix resin as prepregs. In this method, stacked sheets of prepreg are heated to form a composite material. The matrix resin used for prepregs is in most cases an epoxy resin that has excellent heat resistance, dimensional stability, and chemical resistance. Among them, the use of polyfunctional epoxy resin has been proposed for the purpose of improving the mechanical properties of the resin. For example, diaminodiphenyl sulfide is used as the curing agent and a resin composition designated as N,N,N′,N′-tetraepoxypropyl-4,4′-diaminodiphenylmethane is used. The material is a composition containing a glycidamine-type epoxy compound as a matrix resin.

"Patent documents" "Patent Document 1" Korean Patent Publication No. 10-2015-0037376 "Patent Document 2" Japanese Patent Publication No. 2009-237018

However, the aforementioned resin compositions commonly used so far have insufficient reactivity and require a relatively long curing time. In short, it means that it is subject to specific forming processes and productivity limitations.

Although this is a glycidamine-type epoxy resin that needs to be improved from the viewpoint of curing time, only the examples in Patent Documents 1 and 2 are known as examples of glycidamine-type fluorine-containing epoxy resins. The properties obtained by glycidamine-type fluorine-containing epoxy resins are of particular interest in the fields of prepregs or fiber-reinforced composite materials and sealants.

The purpose of this disclosure is to provide glycidamine-type fluorine-containing epoxy compounds. Furthermore, a further object of the present disclosure is to provide a fluorine-containing epoxy resin composition, cured product, prepreg, fiber-reinforced composite material, sealing material and semiconductor device using the fluorine-containing epoxy compound.

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

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

"Chemical 1"

Wherein, in the general formula (1), n is independently an integer of 0 to 4, R ¹ each independently represents a monovalent substituent, and is selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, and an aromatic group. One of the groups based on it.

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

"Chemical 2"

Wherein, in the general formula (2), n is independently an integer of 0 to 4, R ¹ each independently represents a monovalent substituent, and is selected from the group consisting of halogen atom, alkyl group, alkoxy group, haloalkoxy group, aromatic group, etc. One of the groups based on it.

[3] A fluorine-containing epoxy resin containing by-products or unreacted products when producing the fluorine-containing epoxy compound described in [1] or [2], which Contains the fluorine-containing epoxy compound described in [1] or [2] at a ratio of 50% or more based on the area ratio measured by high-performance liquid chromatography.

[4] A fluorine-containing epoxy resin composition, characterized by containing: a fluorine-containing epoxy compound as described in [1] or [2] or a fluorine-containing epoxy resin as described in [3], and a curing agent .

[5] A cured product characterized in that it is obtained by curing the fluorine-containing epoxy resin composition described in [4].

[6] A prepreg characterized in that it is made of the fluorine-containing epoxy resin composition described in [4] impregnated into reinforcing fibers.

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

[8] A method for manufacturing a prepreg, characterized in that the fluorine-containing epoxy resin composition according to [4] is impregnated into reinforcing fibers.

[9] A method for manufacturing a fiber-reinforced composite material, characterized by solidifying the prepreg according to [6].

[10] A method for manufacturing fiber-reinforced composite materials, characterized by impregnating the fluorine-containing epoxy resin composition described in [4] into reinforcing fibers and solidifying them.

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

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

[13] A method of sealing a semiconductor element by curing the fluorine-containing epoxy resin composition described in [4] to seal the semiconductor element.

[14] A method of using the fluorine-containing epoxy resin composition as described in [4] by curing it as a sealing material.

[15] 1,1,1-trifluoro-2,2-bis(4-diepoxypropylaminophenyl)ethane represented by chemical formula (3).

"Chemical 3"

[16] 1,1,1-trifluoro-2,2-bis(3-methyl-4-diepoxypropylaminophenyl)ethane represented by chemical formula (4).

"Chemical 4"

[17] A method for manufacturing a fluorine-containing epoxy compound, which is a method for manufacturing a fluorine-containing epoxy compound represented by general formula (1), including A step of reacting an aromatic diamine compound represented by general formula (1A) and epihalohydrin.

"Chemical 5"

Wherein, in the general formula (1), n is independently an integer of 0 to 4, R ¹ each independently represents a monovalent substituent, and is selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, and an aromatic group. One of the groups based on it.

"Chemical 6"

Wherein, in the general formula (1A), n is independently an integer of 0 to 4, R ¹ each independently represents a monovalent substituent, and is selected from the group consisting of halogen atom, alkyl group, alkoxy group, haloalkoxy group, aromatic group, etc. One of the groups based on it.

Through the embodiments of the present disclosure, novel fluorine-containing epoxy compounds can be provided. Moreover, according to the embodiment of the present disclosure, it is possible to provide a fluorine-containing epoxy resin composition, a cured product, a prepreg, a fiber-reinforced composite material, a sealing material, and a semiconductor device using the fluorine-containing epoxy compound.

Implementation forms of the present disclosure are described in detail below.

In this specification, the expression "X to Y" in the description of the numerical range means X or more and Y or less unless otherwise noted. For example, "1 to 5% by mass" means "1 to 5% by mass".

In the expressions of groups (groups) in this specification, expressions that do not describe substitution or unsubstitution include both those that do not have a substituent and those that have a substituent. For example, "alkyl group" 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 fluorine-containing epoxy compound means the compound itself represented by each chemical formula. Furthermore, the fluorine-containing epoxy resin means a mixture containing the epoxy compound. That is, the fluorine-containing epoxy resin contains various by-products or unreacted products in the production of the fluorine-containing epoxy compound. The fluorine-containing epoxy resin composition means a composition in an uncured to semi-cured state that contains at least a fluorine-containing epoxy compound and its curing agent. The so-called resin cured product (also described as cured product) means a cured product obtained by a curing reaction of a fluorine-containing epoxy resin composition.

〈Fluorinated epoxy compound〉

The epoxy compound disclosed in the present disclosure is a fluorine-containing epoxy compound represented by general formula (1). This fluorine-containing epoxy compound is characterized by "the presence of 1,1,1-trifluoro-2,2-ethanediyl (representing -C(CF ₃ )H- group) and bicyclic ring in at least one aromatic ring. The structure of "oxypropylamine group". The inventors speculate that the heat resistance and dimensional stability of the cured resin may be affected by the specific three-dimensional structure of the cured resin resulting from the asymmetric structure of 1,1,1-trifluoro-2,2-ethanediyl. get taller. In addition, the present inventors speculate that the asymmetric structure of 1,1,1-trifluoro-2,2-ethanediyl enables curing in a shorter time. In this way, since the fluorine-containing epoxy compound represented by the general formula (1) is characterized by an asymmetric structure of 1,1,1-trifluoro-2,2-ethanediyl, regardless of the position of the substituent, With the type or quantity of R ¹ , a resin cured product having excellent heat resistance and dimensional stability can be obtained, and can be cured in a shorter time.

"Chemical 7"

Wherein, in the general formula (1), n is independently an integer of 0 to 4, R ¹ each independently represents a monovalent substituent, and is selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, and an aromatic group. One of the groups based on it.

As n, 0 to 3 are preferred, 0 to 2 is more preferred, and 0 to 1 is more preferred.

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 a straight-chain or branched alkyl group with 1 to 6 carbon atoms (preferably 1 to 3) is preferred. Among them, n-butyl, secondary butyl, isobutyl are preferred. Base, tertiary butyl, n-propyl, isopropyl, ethyl and methyl are preferred, especially ethyl and methyl. The alkoxy group of R ¹ is not limited, but a straight-chain or branched alkoxy group with 1 to 6 carbon atoms is preferred. Among them, n-butoxy group, secondary butoxy group, isobutoxy group, Tertiary butoxy, n-propoxy, isopropoxy, ethoxy and methoxy are preferred, with ethoxy and methoxy being particularly preferred. The alkyl or alkoxy group of R ¹ may also be substituted on any carbon thereof by, for example, halogen atoms, alkoxy groups and haloalkoxy groups in any number and in any combination. 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, 2 or more R ¹ may be connected to form a saturated or unsaturated monocyclic or polycyclic ring having 3 to 10 carbon atoms. of ring base.

The haloalkoxy group of R ¹ is not limited, but difluoromethoxy, trifluoromethoxy, tetrafluoroethoxy and 2,2,2-trifluoroethoxy are preferred, especially trifluoroethoxy. Methoxy and 2,2,2-trifluoroethoxy are 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. Furthermore, when the number of R ¹ in the general formula (1) is 2 or more, it is preferable that all R ¹ have the same base.

It is also preferred that the fluorine-containing epoxy compound represented by the general formula (1) has a 1,1,1-trifluoro-2,2-ethanediyl group (representing a -C(CF ₃ )H- group) as the axis Symmetrical. Specifically, it is preferable that the aromatic ring located on the right side of 1,1,1-trifluoro-2,2-ethanediyl (representing -C(CF ₃ )H- group) in the general formula (1) and In the aromatic ring on the left, the type and number of substituents and the position of each substituent are the same (left-right symmetry).

Among the compounds represented by the general formula (1), the following fluorine-containing epoxy compound represented by the general formula (2) is particularly preferred.

"Chemical 8"

Wherein, in the general formula (2), n is independently an integer of 0 to 4, R ¹ each independently represents a monovalent substituent, and is selected from the group consisting of halogen atom, alkyl group, alkoxy group, haloalkoxy group, aromatic group, etc. One of the groups based on it.

n and R ¹ in the general formula (2) are the same as n and R ¹ in the general formula (1), and their favorable aspects are also the same. That is, among the compounds represented by the general formula (1), the compound having the diglycidylamine group at a specified position corresponds to the compound represented by the general formula (2), so the compound represented by the general formula (2) The aspect of the compound other than the position having the diepoxypropylamine group is the same as that of the compound represented by the general formula (1), and the preferred aspects thereof are also the same.

From the perspective of rapid curability, the viscosity of the fluorine-containing epoxy compound disclosed in the present disclosure at 150°C is preferably less than 200 mPa·s, preferably less than 150 mPa·s, and preferably less than 100 mPa·s. s is particularly preferred, 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.

Suitable examples of such fluorine-containing epoxy compounds include the following compounds. Among them, the aforementioned 1,1,1-trifluoro-2,2-bis(4-diepoxypropylaminophenyl)ethane represented by the chemical formula (3), the aforementioned 1 represented by the chemical formula (4) , 1,1-trifluoro-2,2-bis(3-methyl-4-diepoxypropylaminophenyl)ethane is preferred.

"Chinese 9"

The aforementioned fluorine-containing epoxy compound can be synthesized by any method, but for example, it can be synthesized by using a fluorine-containing aromatic diamine compound represented by the following general formula (1A) and an epihalohydrin such as epichlorohydrin. After the tetrahalohydrin is obtained by the reaction, it is obtained by cyclization reaction of a basic compound.

"Chemical 10"

Wherein, in the general formula (1A), n is independently an integer of 0 to 4, R ¹ each independently represents a monovalent substituent, and is selected from the group consisting of halogen atom, alkyl group, alkoxy group, haloalkoxy group, aromatic group, etc. One of the groups based on it.

n and R 1 in the general formula (1A) are the same as n and ^{R 1 in} the general formula (1), and their good aspects are also included.

Among the compounds represented by the general formula (1A), the following fluorine-containing aromatic diamine compound represented by the general formula (2A) is particularly preferred.

"Chemical 11"

Wherein, in the general formula (2A), n is independently an integer of 0 to 4, R ¹ each independently represents a monovalent substituent, and is selected from the group consisting of halogen atom, alkyl group, alkoxy group, haloalkoxy group, aromatic group, etc. One of the groups based on it.

n and R ¹ in the general formula (2A) are the same as n and R ¹ in the general formula (1), and their favorable aspects are also the same.

The fluorine-containing aromatic diamine compound represented by the general formula (2A) can be produced by the method described in WO2020-162411, for example. The following discloses a compound preferably used in terms of performance or cost as the fluorine-containing aromatic diamine compound represented by the general formula (2A).

"Chemical 12"

The amount of epihalohydrin (typically epichlorohydrin or epibromohydrin) used in the reaction is 0.1 to 100 mol relative to 1 mol of the amine group of the fluorine-containing aromatic diamine represented by the general formula (2A). Preferably, 1.0~75 mol is preferred, and 2.0~50 mol is even more preferred.

Examples of the base used in the reaction usually include alkali metal hydroxides, alkali metal alkoxides, alkali metal carbonates, and the like. Specific examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium butoxide, and potassium butoxide. , lithium butoxide, sodium carbonate, potassium carbonate, lithium carbonate, etc. Among these bases, only one type may be used, or two or more types may be used in combination. As a preferred aspect of the reaction, the reaction system is usually made into a "base" by adding an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide as a base to the reaction system in a solid or aqueous solution state. condition". The added amount of the base is preferably 0.1 to 100 mol, and more preferably 2.0 to 50 mol, based on 1 mol of the amine group of the fluorine-containing aromatic diamine represented by the general formula (2A).

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

During the reaction, the following methods are used to dehydrate the water as needed: maintain the specified temperature while making the reaction liquid azeotropic, and separate the organic phase/aqueous phase of the condensate obtained by cooling the volatilized vapor, excluding the organic phase of the aqueous phase. Back to the reaction system. Regarding the addition of alkali metal hydroxide, in order to suppress the rapid reaction, it usually takes 0.1 to 10 hours to gradually add alkali metal hydroxide to the reaction system in small amounts intermittently or continuously. The total reaction time is usually 1 to 15 hours.

For the reaction, it is best to use analytical equipment such as a nuclear magnetic resonance device (NMR) or a liquid chromatograph (LC), and determine the end point of the reaction when it is confirmed that the reaction conversion rate reaches a specified value.

It is better to filter out the insoluble by-product salt after the reaction or remove it by washing with water. Thereafter, unreacted epihalohydrin is preferably distilled off under reduced pressure and removed. In this way, the target fluorine-containing epoxy compound can be obtained.

In the reaction, quaternary ammonium salts such as tetrabutylammonium hydrogen sulfate, tetramethylammonium chloride, and tetraethylammonium bromide can also be used; benzyldimethylamine, 2,4,6-glycine (dimethyl Tertiary amines such as methylaminomethyl)phenol; imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole; phosphonium salts such as ethyltriphenylphosphonium iodide; phosphines such as triphenylphosphine Catalysts like this.

Moreover, in the reaction, alcohols such as ethanol and isopropanol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxygen and ethylene glycol dimethyl ether; Alcohol ethers; inert organic solvents such as aprotic polar solvents such as dimethyl sulfoxide and dimethyl formamide. Only one type of these organic solvents may be used, or two or more types may be mixed and used.

Compared with well-known fluorine-containing epoxy compounds that are not within the scope of this disclosure, the fluorine-containing epoxy compound of the present disclosure has the advantage that it can be produced with good yield and has fewer by-products or unreacted substances. The reason for this is presumably due to the fact that the fluorine-containing aromatic diamine compound represented by the general formula (2A) contains an asymmetric (-C(CF ₃ )H- group), which suppresses excessive rigidification and makes it moderate. The content of fluorine atoms.

〈Fluorinated epoxy resin〉

The aforementioned fluorine-containing epoxy compound represented by the general formula (1) or (2) does not have to be separated separately after synthesis, and can also be included in the production of the aforementioned fluorine-containing epoxy compound represented by the general formula (1) or (2). Oxygen compounds are used in the form of by-products or unreacted fluorine-containing epoxy resins. The fluorine-containing epoxy resin of the present disclosure contains the aforementioned fluorine-containing epoxy compound represented by the general formula (1) at a ratio of more than 50% based on the area ratio measured by high performance liquid chromatography (HPLC). Fluorinated epoxy resin. The fluorine-containing epoxy resin of the present disclosure preferably contains the above-mentioned fluorine-containing epoxy compound represented by the general formula (1) at a ratio of more than 60% based on the area ratio in HPLC measurement, and preferably contains more than 70%. good. By containing it at a ratio of 50% or more, heat resistance and mechanical strength can be improved. Moreover, the fluorine-containing epoxy resin of the present disclosure preferably contains the aforementioned fluorine-containing epoxy compound represented by the general formula (1) at a ratio of 99.99% or less based on the area ratio in HPLC measurement.

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

From the perspective of rapid curability, the viscosity of the fluorine-containing epoxy resin disclosed in the present disclosure at 150°C is preferably less than 200 mPa·s, preferably less than 150 mPa·s, and preferably less than 100 mPa·s. s is particularly preferred, 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 of the present disclosure is an uncured to semi-cured state composition that at least includes the fluorine-containing epoxy compound of the disclosure and a curing agent. The fluorine-containing epoxy resin composition of the present disclosure may also include thermosetting resin, thermoplastic resin, and other additives in addition to these. Moreover, the fluorine-containing epoxy resin composition of the present disclosure only needs to contain a fluorine-containing epoxy compound and a curing agent at the same time during curing. Depending on the molding method used, the composition containing the fluorine-containing epoxy compound and the curing agent can be prepared in advance, or the composition containing the fluorine-containing epoxy compound and the composition containing the curing agent can be prepared separately and mixed in, for example, a mold. . In addition, of course, the fluorine-containing epoxy compound contained in the fluorine-containing epoxy resin composition of the present disclosure may also be a fluorine-containing epoxy resin containing impurities. Furthermore, of course, the fluorine-containing epoxy compound of the present disclosure and the fluorine-containing epoxy resin of the present disclosure can be used alone, or two or more types can be used in combination.

The viscosity of the fluorine-containing epoxy resin composition disclosed in the present disclosure can be appropriately adjusted according to the molding method. However, when it is used as a prepreg, for example, the viscosity at 150°C is preferably less than 2000 mPa·s. 0.001～1000 mPa·s is preferred. When the pressure exceeds 2000 mPa·s, operability may decrease. Furthermore, when a prepreg is produced using a fluorine-containing epoxy resin composition having a viscosity of more than 2000 mPa·s at 150° C., non-wetted portions are likely to occur in the prepreg. As a result, voids etc. become easily formed in the obtained fiber-reinforced composite material.

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

In the fluorine-containing epoxy resin composition of the present disclosure, the content ratio of the aforementioned fluorine-containing epoxy compound represented by the general formula (1) (the fluorine-containing epoxy resin of the present disclosure) is preferably 10 to 90 mass%. The content is preferably 15 to 80% by mass, and more preferably 20 to 70% by mass. When the content is less than 10% by mass, the handleability of the resin composition may deteriorate, or the strength or heat resistance of the obtained cured product may decrease. When the content is more than 90 mass %, the molar balance with the curing agent may become inappropriate, and various characteristics such as mechanical properties of the cured product may 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. The curing agent may be any one that can cure the epoxy resin, and can be appropriately selected depending on the purpose of use, etc. For example, amine-based curing agents are suitable for curing epoxy resin compositions. Amine-based curing agents are compounds that have at least one nitrogen atom in the molecule and can react with the epoxy group in the epoxy resin for curing. A suitable type of amine-based curing agent is, for example, diaminodiphenyl sulfide. Specific examples of suitable diaminodiphenyl sulfone are not limited, but may include: 4,4′-diaminodiphenyl sulfide (4,4′-DDS) and 3,3′- Diaminodiphenyl sulfone (3,3′-DDS) and combinations thereof. The curing agent can be used alone, or two or more types can be used in combination.

The amount of curing agent included in the fluorine-containing epoxy resin composition is an amount suitable for curing all the epoxy resin blended in the fluorine-containing epoxy resin composition, and may depend on the type of epoxy resin or curing agent used. to adjust appropriately. For example, when an amine-based curing agent is used, the amount is preferably 25 to 65 parts by mass, and more preferably 35 to 55 parts by mass based on 100 parts by mass of the total amount of epoxy resin. When it is less than 25 parts by mass or exceeds 65 parts by mass, the curing of the fluorine-containing epoxy resin composition may become insufficient, and the physical properties of the cured resin may be easily reduced.

The fluorine-containing epoxy resin composition of the present disclosure requires the aforementioned fluorine-containing epoxy compound and its curing agent, but may also include other components. Other components may be used individually or in combination of 2 or more types.

The fluorine-containing epoxy resin composition of the present disclosure requires the aforementioned fluorine-containing epoxy compound represented by the general formula (1), but may also include other epoxy resins other than the fluorine-containing epoxy compounds of the present disclosure. As other epoxy resins, conventionally known epoxy resins can be used. Specifically, an epoxy resin containing an aryl group is preferred, and an epoxy resin containing either a glycidylamine structure or a glycidyl ether structure is preferred. Furthermore, alicyclic epoxy resin can also be suitably used. When a fluorine-containing epoxy compound represented by the general formula (1) and other epoxy resins are used together, among all the epoxy resins contained in the fluorine-containing epoxy resin composition, the fluorine-containing epoxy compound represented by the general formula (1) contains The content ratio of the fluorine epoxy compound is preferably 20 mass% or more, more preferably 50 mass% or more, and more preferably 60 to 100 mass%.

Examples of epoxy resins containing a glycidylamine structure include: tetraepoxypropyldiaminodiphenylmethane, N,N,O-triepoxypropyl-p-aminophenol, N,N,O-tris Various isomers of glycidyl meta-aminophenol, N,N,O-triepoxypropyl-3-methyl-4-aminophenol, and triepoxypropylaminocresol, etc.

On the other hand, examples of epoxy resins containing a glycidyl ether structure include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, and phenol novolac-type epoxy. Resin, cresol novolak type epoxy resin. Moreover, these epoxy resins may also have non-reactive substituents on the aromatic ring structure or alicyclic structure as required. Examples of the non-reactive substituent include alkyl groups such as methyl, ethyl and isopropyl, aryl groups such as phenyl, or alkoxy groups, aralkyl groups, halogen groups such as fluorine, chlorine or bromine.

The fluorine-containing epoxy resin composition of the present disclosure may also include thermoplastic resin. Examples of the thermoplastic resin include epoxy resin-soluble thermoplastic resin and epoxy resin-insoluble thermoplastic resin. The so-called epoxy resin-soluble thermoplastic resin refers to a thermoplastic resin that is partially or completely dissolved in the epoxy resin at or below the temperature at which FRP is molded. On the other hand, an epoxy resin-insoluble thermoplastic resin refers to a thermoplastic resin that does not substantially dissolve in the epoxy resin at the temperature at which the FRP is molded or at a temperature lower than the temperature.

Specific examples of the epoxy resin-soluble thermoplastic resin include polyether sulfide, polysulfone, polyetherimide, polycarbonate, and the like. These may be used individually or 2 or more types may be used together. This kind of epoxy resin soluble thermoplastic resin can improve the dissolution stability during the curing process of the epoxy resin. In addition, toughness, chemical resistance, heat resistance, and moisture and heat resistance can be imparted to the FRP obtained after curing.

Examples of the epoxy resin-insoluble thermoplastic resin include: polyamide, polyacetal, polyphenylene ether, polyphenylene sulfide, polyester, polyamide imine, polyimide, polyether ketone, and polyether ether. Ketone, polyethylene naphthalate, polyether nitrile, polybenzimidazole. Among these, polyamide, polyamideimide, and polyimide are particularly preferred because of their high toughness and heat resistance. Polyamide or polyimide has an excellent effect on improving the toughness of cured resin. These may be used individually or 2 or more types may be used together. Moreover, these copolymers can also be used.

The content of the aforementioned thermoplastic resins contained in the epoxy resin composition can be appropriately adjusted according to the viscosity. From the viewpoint of processability of the prepreg, relative to 100 parts by mass of the epoxy resin contained in the epoxy resin composition, 5 to 60 parts by mass is preferred, 10 to 50 parts by mass is more preferred, and 20 parts by mass is preferred. ~40 parts by mass is more preferred. When the amount is less than 5 parts by mass, the impact resistance of the FRP obtained may become insufficient. If the content of such thermoplastic resin becomes high, the viscosity may become significantly higher and the operability of the prepreg may significantly deteriorate.

The fluorine-containing epoxy resin composition of the present disclosure may also be blended with conductive particles or flame retardants, inorganic fillers, and internal release agents. Examples of the conductive particles include conductive polymer particles such as polyacetylene particles, polyaniline particles, polypyrrole particles, polythiophene particles, polyisobenzothiophene particles, and polyethylenedioxythiophene particles; carbon particles; and carbon fibers. Particles; metal particles; particles that have a core material made of inorganic materials or organic materials covered with a conductive substance. As the flame retardant, a phosphorus-based flame retardant can be exemplified. The phosphorus-based flame retardant is not particularly limited as long as it contains a phosphorus atom in the molecule. Examples include organic phosphorus compounds such as phosphate esters, condensed phosphate esters, phosphazene compounds, and polyphosphates, or red phosphorus. Examples of inorganic fillers include aluminum borate, calcium carbonate, silicon carbonate, silicon nitride, potassium titanate, basic magnesium sulfate, zinc oxide, graphene, calcium sulfate, magnesium borate, magnesium oxide, and silicate. Minerals. In particular, silicate minerals are preferred. Examples of internal release agents include metallic soaps, vegetable waxes such as polyethylene wax and palm wax, fatty acid ester release agents, silicone oils, animal waxes, and fluorine-based nonionic surfactants.

The manufacturing method of the fluorine-containing epoxy resin composition is not particularly limited, and any conventionally known method may be used. As a mixing temperature, the range of 40-150 degreeC can be exemplified. When the temperature exceeds 150°C, the curing reaction may partially proceed and the wettability into the reinforced fiber base material layer may decrease, or the obtained fluorine-containing epoxy resin composition and the prepreg produced using it may be stored. Stability will decrease. When the temperature is less than 40° C., the viscosity of the epoxy resin composition may be high, making it substantially difficult to mix. The best range is 50~120℃.

As the mixing mechanism, conventionally known ones can be used. Specific examples include roller mills, planetary mixers, kneaders, extruders, Banbury kneaders, mixing containers with stirring blades, and horizontal mixing tanks. The components can be mixed in the atmosphere or under an inert gas environment. When mixing in the atmosphere, a gas environment with controlled temperature and humidity is preferred. Although not particularly limited, for example, it is preferable to mix in a low-humidity gas environment where the temperature is controlled to be a fixed temperature of 30° C. or lower or a relative humidity of 50% RH or lower.

〈Cured product〉

The cured product of the present disclosure is a cured product obtained by curing the fluorine-containing 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 performed 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 more than 0.5 hours.

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

The cured product of the present disclosure is characterized by high heat resistance. Here, heat resistance can be judged from the glass transition temperature of each cured product. The glass transition temperature of the cured product of the present disclosure is preferably above 180°C, more preferably above 200°C, more preferably above 220°C, and particularly preferably above 230°C. The upper limit of the glass transition temperature is not particularly limited, but it usually does not reach 300°C.

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

The cured product of the present disclosure is characterized by high dimensional stability. Here, the so-called dimensional stability can be judged from the linear expansion coefficient at each temperature. The linear expansion coefficient α1 of the cured product of the present disclosure at 25 to 180°C is preferably 120 ppm/°C or less, and 80 ppm/°C or less below the glass transition temperature. Furthermore, 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 more preferably 130 ppm/°C or less. The lower limit of the linear expansion coefficient at each temperature is not particularly limited, but is usually 20 ppm/℃ 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 of the present disclosure is characterized by low water absorption. Here, the water absorption rate refers to the mass increase rate after storage under conditions of 25° C. and water for 72 hours. The water absorption rate is preferably less than 3.0 mass%, more preferably less than 1.0 mass%, and even more preferably less than 0.5 mass%. The lower limit of the water absorption is not particularly limited, but is usually 0.01% by mass or more. When the water absorption rate is 3.0% by mass or more, the strength of the cured resin molded into a thin plate may be likely to decrease.

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

〈Prepreg〉

The prepreg system of the present disclosure is formed by impregnating the fluorine-containing epoxy resin composition of the present disclosure into reinforcing fibers. In short, the prepreg system of the present disclosure is a prepreg in which part or all of the reinforcing fibers are impregnated with the fluorine-containing epoxy resin composition. The content ratio of the fluorine-containing epoxy resin composition in the entire prepreg is preferably 15 to 60 mass % based on the total mass of the prepreg. When the content ratio of the fluorine-containing epoxy resin composition is less than 15% by mass, voids, etc. may be generated in the obtained fiber-reinforced composite material, resulting in reduced mechanical properties. When the content ratio of the fluorine-containing epoxy resin composition exceeds 60 mass %, the reinforcing effect due to the reinforcing fibers of the obtained fiber-reinforced composite material may become insufficient and the mechanical properties may be substantially low.

The reinforcing fibers may be twisted, untwisted or untwisted, but untwisted or untwisted yarns are preferred as they have excellent formability in fiber-reinforced composite materials. Furthermore, the reinforcing fiber can be formed by twisting the fibers in one direction or fabric. Among the fabrics, you can freely choose from plain weave, satin weave, etc. according to the location or purpose of use. Specifically, those having excellent mechanical strength or durability include carbon fibers, glass fibers, aramid fibers, boron fibers, alumina fibers, silicon carbide fibers, and the like, and two or more of these fibers may be used in combination. Among these, carbon fiber is preferred in terms of providing a molded product with particularly good strength, and as such carbon fiber, various types such as polyacrylonitrile-based, pitch-based, and rayon-based carbon fibers can be used.

The manufacturing method of the prepreg of the present disclosure is not particularly limited as long as it is characterized by impregnating the fluorine-containing epoxy resin composition of the present disclosure into the reinforcing fibers, and any method known in the past can be used. Specifically, a hot melt method or a solvent method may be suitably used.

The hot melt method is a method in which a resin composition is coated in a thin film on a release paper to form a resin composition film, and the resin composition film is stacked on reinforcing fibers and heated under pressure, thereby making the epoxy resin The composition is infiltrated into the reinforcing fibers.

The solvent method is as follows: use an appropriate solvent to make the epoxy resin composition into a varnish, and make the varnish soak into the reinforcing fibers.

〈Fiber reinforced composite material (FRP)〉

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

In the fiber-reinforced composite material of the present disclosure, the total content ratio of the cured product and reinforcing fibers of the present disclosure is preferably 60 mass% or more, more preferably 80 mass% or more, more preferably 90 mass% or more, and 95 mass% or more. It is especially preferable that it is % by mass or more, and it may be 100 % by mass.

The method of obtaining a fiber-reinforced composite material using the fluorine-containing epoxy resin composition of the present disclosure is not particularly limited, but may include, for example, " uniformly mixing each component constituting the fluorine-containing epoxy resin composition to produce a varnish, and then "The method of impregnating the reinforced fibers twisted in one direction into the obtained varnish (in the state before curing by pultrusion or winding forming)" or "overlapping and installing the reinforcing fiber fabrics" Methods such as "injecting resin into the female mold and then sealing it with a male mold to pressure-wet it" (the state before curing by the RTM method), etc.

The fiber-reinforced composite material of the present disclosure may also be in a form in which "the aforementioned fluorine-containing epoxy resin composition does not have to be infiltrated into the interior of the fiber bundle, but the fluorine-containing epoxy resin composition is localized near the surface of the fiber." .

On the other hand, as a method of manufacturing FRP using a prepreg in which reinforcing fibers and an epoxy resin composition are composited in advance, well-known molding methods such as autoclave molding and pressure molding can be cited.

The manufacturing method of 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 fluorine-containing epoxy resin composition of the present disclosure into the reinforcing fiber and solidifying it, and well-known methods in the past can also be used. any method.

As the manufacturing method of the FRP disclosed in the present disclosure, the autoclave forming method can be preferably used. The autoclave forming method is the following forming method: lay the prepreg and film bag in sequence under the mold, seal the prepreg between the lower mold and the film bag, and create a space formed by the lower mold and the film bag. Vacuum, while using an autoclave forming device to heat and pressurize. Good conditions during molding are to set the temperature rise rate to 1 to 50°C/min, and to heat and pressurize at 0.2 to 0.8 MPa and 100 to 180°C for 30 to 300 minutes.

Furthermore, as the manufacturing method of the FRP of the present disclosure, the press forming method can be suitably used. The production of FRP using the pressure forming method is performed by heating and pressurizing the prepreg of the present disclosure or the preform formed by stacking the prepregs of the present disclosure using a mold. It is better to pre-heat the mold to the curing temperature. The temperature of the mold during pressure forming is preferably 150 to 200°C. If the molding temperature is 150°C or higher, the curing reaction can be sufficiently initiated, and FRP can be obtained with high productivity. Furthermore, if the molding temperature is 200° C. or lower, the resin viscosity will not become too low, and excessive flow of the resin in the mold can be suppressed. As a result, since the flow of resin from the mold and the meandering of fibers can be suppressed, high-quality FRP can be obtained. The pressure during molding is 0.05 to 2 MPa, preferably 0.2 to 2 MPa. If the pressure is 0.05 MPa or above, moderate flow of the resin can be achieved and the appearance of defects or voids can be prevented. In addition, since the prepreg is fully adhered to the mold, FRP with good appearance can be produced. If the pressure is 2 MPa or less, the resin will not flow excessively, so the appearance of the FRP obtained is less likely to have defects. Furthermore, since excessive load is not exerted on the mold, deformation of the mold is unlikely to occur. The optimal forming time is 1 to 8 hours.

〈Sealing material〉

The sealing material of the present disclosure contains the cured product of the present disclosure. The sealing material of the present disclosure is produced 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), and can be suitably used as a sealing material for semiconductors. In addition, since the cured product of the present disclosure exhibits high heat resistance, it can also be used as a sealing material for power semiconductors.

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

〈Semiconductor device, method of sealing semiconductor, method of using as sealing material〉

The semiconductor device of the present disclosure is a semiconductor device including at least a semiconductor element, and is formed by sealing at least the semiconductor element with a cured product of the fluorine-containing epoxy resin composition of the present disclosure. Other structures in the semiconductor device of the present disclosure are not particularly limited, and conventionally well-known semiconductor device components may also be provided in addition to the semiconductor elements. Examples of such semiconductor device components include: base substrate, lead-out wiring, wire wiring, control element, insulating substrate, heat sink, conductive member, die bonding material, bonding Mat etc. Furthermore, in addition to the semiconductor elements, part or all of the semiconductor device components may also be sealed with the cured product of the fluorine-containing epoxy resin composition of the present disclosure.

The packaging of power semiconductors has specifications classified by JEDEC (Semiconductor Specifications Association) or JEITA (Electronics and Information Technology Industries Association), for example: TO-3, TO-92, TO-220, TO-247, TO-252 , TO-262, TO-263, D2 and other package specifications. These specifications can be cited as an example of the packaging type of the semiconductor device of the present disclosure, but other well-known industry specifications can also be used.

As an example of the semiconductor device of the present disclosure, 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. The structure of the frame, the mounting structure of the semiconductor element, etc. can be appropriately deformed, and other semiconductor devices can be added appropriately. part.

The semiconductor device of the present disclosure can be manufactured, for example, by sealing the semiconductor element with a cured product obtained by molding the fluorine-containing epoxy resin composition of the present disclosure by injection molding, compression molding or transfer molding. .

The implementation forms of the present disclosure have been described above, but these are 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-mentioned embodiments, and modifications, improvements, etc. within the scope that can achieve the purpose of the disclosure are included in the present disclosure.

"Example"

The implementation aspects of the present disclosure will be described in detail based on the embodiments and comparative examples. For the sake of caution, this disclosure is not limited only to the embodiments.

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

First, the identification method and the physical property/performance evaluation method of the polymer compound obtained in the Examples and Comparative Examples will be described.

． Epoxy compound purity

High-performance liquid chromatography (HPLC) measurement is performed under the following conditions, and the purity of the epoxy compound is measured based on the peak area fraction. ． Mobile phase: acetonitrile/10 mM ammonium formate ． Pipe string: YMC-Pack (ODS-AM, AM12SOJ05-2546WT) ． Column oven temperature: 40℃ ． Column flow: 1.0 mL/min ． Detector: UV light with wavelength 254 nm ． Sample preparation method: Dissolve about 10 mg of epoxy resin in 2 g of acetonitrile to prepare the sample.

． Epoxy equivalent

The epoxy equivalent weight of epoxy resin is measured according to the method described in JISK7236:2009.

． viscosity

Use a rotational viscometer (manufactured by ANTON PAAR, product name: PHYSICAMCR51, measuring cone CP50-1) under 1 atmosphere to measure the viscosity of the epoxy resin at 150°C and a shear rate of 100/S. The installation conditions are 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. The glass transition temperature was measured using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Corporation, model name: DSC7000) at a heating rate of 10°C/min.

． Dimensional stability

Dimensional stability was evaluated by measuring the coefficient of linear expansion (CTE) of each cured product obtained in Examples and Comparative Examples. Specifically, a thermomechanical analysis device (manufactured by Rigaku, product name: TMA8310) was used to determine the CTE to 25 to 180°C (α1) and 180 to 300°C (α2) from the TMA curve obtained under the following conditions. In addition, the test was carried out twice for one sample piece, and the TMA curve obtained by the second measurement was calculated. ． Mode: Compression mode ． Sample size: 4 mm×5 mm×20 mm corner prism shape ． Load: -98 N ． Heating conditions: from 20℃ to 300℃ at a speed of 10℃/min

． Water absorption measurement

The water absorption rate is calculated using the method described in JISK7209:2000 as a reference. Measure the mass W1 of the sample piece with dimensions of 4 mm × 10 mm × 80 mm, and dry it in a constant temperature bath at 60°C for 24 hours. After drying, return to room temperature in the desiccator and measure the mass W2. When the difference between W1 and W2 is 0.5 mg or more, drying is performed again and repeated until the difference becomes less than 0.5 mg. If the mass change is less than 0.5 mg, immerse the sample piece in more than 1 L of water, place it in a constant temperature bath at 25°C for 72 hours, take out the sample, wipe off the water, and quickly measure the mass W3. Calculate the water absorption rate from the mass changes of W2 and W3. Water absorption rate (%) = (W3-W2)/W2×100

． Cure speed

The curability of epoxy compounds is measured by cure rate. Weigh 3 g of the epoxy resin composition prepared from each epoxy compound and the curing agent (4,4′-DDS) into a glass vial equipped with a stirrer made of Teflon (registered trademark), and place it at 180 Stir at ℃. The time from the viscosity increase of the epoxy resin composition to the stopping of stirring was measured.

． Use a singleton

The following discloses the use of monomers and their abbreviations.

"Chemical 13"

Table 1 shows the physical properties of the epoxy compound using the above monomer.

"Table 1" Epoxy compound Synthesis example 1 Synthesis example 2 Synthesis example 3 Synthesis example 4 TGDDM Purity 86 63 twenty four 36 85 (area%) Epoxy equivalent 114 119 116 144 106 (g/equivalent) viscosity 54 18 42 32 10 (mPa·S@150℃)

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

"Chemical 14"

In a four-necked flask equipped with a thermometer, a dropping funnel, a cooling tube and a stirrer, add 1,1,1-trifluoro-2,2-bis(4-amino) synthesized according to the method described in WO2020-162411 under a nitrogen atmosphere. Phenyl)ethane 40 g (0.15 mol), epichlorohydrin 167 g (1.8 mol), stir at 80°C for 18 hours. After stirring, distill off unreacted epichlorohydrin, add 120 g of methyl isobutyl ketone and 1.2 g of tetrabutylammonium hydrogen sulfate (0.0045 mol), and drop 20% sodium hydroxide aqueous solution at 60°C for 2 hours. 180 g (0.9 mol). After completion of the dropping, the mixture was stirred at 60° C. for 3 hours, and the progress of the ring-closure reaction was confirmed with a liquid chromatograph. The organic layer was separated using a separatory funnel, and then the obtained organic layer was washed twice with 120 g of water. The organic layer obtained after washing was concentrated with a rotary evaporator to obtain 58 g of the epoxy resin (yield 82%).

[Physical data]

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

¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 1.67 (1H, s), 2.54 (4H, q, J = 8.0 Hz), 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＝8.8 Hz）, 7.21（4H,dJ＝8.8）

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

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

"Chemical 15"

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

[Physical data]

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

¹ H-NMR (400 MHz, 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′-tetraepoxypropyl-4,4′-diamino-2,2′-bis(trifluoromethyl)diphenyl)

"Chemical 16"

In a four-necked flask equipped with a thermometer, dropping funnel, cooling tube and stirrer, add 48 g (0.15 mol) of 2,2′-bis(trifluoromethyl)benzidine and 167 g (1.8 mol) of epichlorohydrin under a nitrogen atmosphere. ), stir at 80°C for 18 hours. After stirring, distill off unreacted epichlorohydrin, add 120 g of methyl isobutyl ketone and 1.2 g of tetrabutylammonium hydrogen sulfate (0.0045 mol), and drop 20% sodium hydroxide aqueous solution at 60°C for 2 hours. 180 g (0.9 mol). After completion of the dropping, the mixture was stirred at 60° C. for 3 hours, and the progress of the ring-closure reaction was confirmed with a liquid chromatograph. The organic layer was separated using a separatory funnel, and then the obtained organic layer was washed twice with 120 g of water. The organic layer obtained after washing was concentrated with a rotary evaporator to obtain 72 g of the epoxy resin (yield 21%).

[Physical data]

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

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

"Chemical 17"

In a four-necked flask equipped with a thermometer, dropping funnel, cooling tube and stirrer, add 50 g (0.15 mol) of 2,2-bis(4-aminophenyl)hexafluoropropane and 167 g of epichlorohydrin ( 1.8 mol), stir at 80°C for 18 hours. After stirring, distill off unreacted epichlorohydrin, add 150 g of methyl isobutyl ketone and 1.2 g of tetrabutylammonium hydrogen sulfate (0.0045 mol), and drop 20% sodium hydroxide aqueous solution at 60°C for 2 hours. 180 g (0.9 mol). After completion of the dropping, the mixture was stirred at 60° C. for 3 hours, and the progress of the ring-closure reaction was confirmed with a liquid chromatograph. The organic layer was separated using a separatory funnel, and then the obtained organic layer was washed twice with 120 g of water. The organic layer obtained after washing was concentrated with a rotary evaporator to obtain 61 g of the epoxy resin (yield 26%).

[Physical data]

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

It is obvious from Synthesis Examples 1 to 4 that Synthesis Examples 1 to 2 for producing fluorine-containing epoxy compounds of the present disclosure have higher yields than Synthesis Examples 3 to 4 for producing fluorine-containing epoxy compounds that are not within the scope of the present disclosure. , the amount of by-products or unreacted substances is significantly small, and it is now clear.

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

4,4′-DDS was measured in a glass beaker and melted in advance in an oven at 160°C. The mass parts of epoxy resin described in Table 2 were added here, and the mixture was stirred until it became a uniform solution. After defoaming in a vacuum for 20 minutes, the mixture was poured into a preheated silicon mold and cured at 180° C. for 2 hours under normal pressure. The obtained solidified product was shaped with a diamond wheel saw and used for physical property measurement.

"Table 2" Cured product evaluation Example 1 Example 2 Comparative example 1 Comparative example 2 Comparative example 3 resin composition Epoxy resin (mass parts) Synthesis example 1 100 0 0 0 0 Synthesis example 2 0 100 0 0 0 Synthesis example 3 0 0 100 0 0 Synthesis example 4 0 0 0 100 0 TGDDM 0 0 0 0 100 Curing agent (mass parts) 4,4′-DDS 54 53 55 43 59 Resin cured product properties Glass transition temperature (℃) 265 241 210 221 212 linear expansion coefficient α1(25～180℃) 62 66 74 68 80 (ppm/℃) α2(180～300℃) 99 114 164 144 162 Water absorption (%) 0.24 0.14 0.19 0.20 0.27 Cure speed (minutes) 5 6 10 10 9

When the disclosed fluorine-containing epoxy compound is used to form a cured product, the advantages include being able to be cured in a shorter time and having excellent operation. Furthermore, these cured products are excellent in heat resistance and dimensional stability compared with comparative examples. In recent years, fiber-reinforced composite materials or sealing materials used in electrical/electronic equipment components such as multilayer circuit boards have been required to withstand operation at higher temperatures. Therefore, epoxy resins with high heat resistance are required. In addition, in order to improve reliability, it is necessary to suppress the occurrence of cracks due to stress relaxation during thermal curing. One of the methods is to match the linear expansion coefficient of the resin composition to the linear expansion coefficient of the substrate. Generally speaking, the linear expansion coefficient of epoxy resin is larger than that of metal substrates, so the development of epoxy resins with lower linear expansion coefficient and excellent dimensional stability is desired. The fluorine-containing epoxy compounds and fluorine-containing epoxy resins of the present disclosure The utilization value can be said to be very high.

This application is based on Japanese Patent Application No. 2022-050334 filed on March 25, 2022, and claims priority based on the Paris Convention and even the regulations in the country of transfer. The contents of that application are incorporated by reference into this application in its entirety.

The cured product utilizing the glycidamine-type fluorine-containing epoxy compound disclosed in the present disclosure can be cured in a short time. Furthermore, the cured products of the glycidamine-type fluorine-containing epoxy compound according to one aspect of the present disclosure, such as those in Examples 1 and 2, have excellent heat resistance and dimensional stability. Therefore, the utilization value of fiber-reinforced composite materials and sealing materials is very high, and they can be suitably used in the manufacturing of electrical/electronic equipment parts, aircraft parts, spacecraft parts, automobile parts, railway vehicle parts, ship parts, and sports equipment parts. .

without

without.

without.

Claims (17)

A fluorine-containing epoxy compound represented by the general formula (1), "Chemical 1" (Wherein, in the general formula (1), n is each independently an integer of 0 to 4, R ¹ each independently represents a monovalent substituent, and is selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, 1 of the group consisting of aryl groups). The fluorine-containing epoxy compound described in claim 1 is a fluorine-containing epoxy compound represented by the general formula (2), "Chemical Formula 2" (Wherein, in the general formula (2), n is each independently an integer of 0 to 4, R ¹ each independently represents a monovalent substituent, and is selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, One of the group consisting of aryl groups). A fluorine-containing epoxy resin, which is a fluorine-containing epoxy resin containing by-products or unreacted products when manufacturing the fluorine-containing epoxy compound as described in claim 1 or claim 2, which is used in a high-efficiency liquid phase layer The fluorine-containing epoxy compound as described in Claim 1 or Claim 2 is contained in a proportion of more than 50% based on the area ratio measured by the analytical method. A fluorine-containing epoxy resin composition, characterized by comprising the fluorine-containing epoxy compound described in claim 1 or claim 2 and a curing agent. A cured product, characterized in that it is obtained by curing the fluorine-containing epoxy resin composition described in claim 4. A prepreg characterized in that it is made of the fluorine-containing epoxy resin composition as described in claim 4 that is infiltrated into reinforcing fibers. A fiber-reinforced composite material comprising the cured product as described in claim 5 and reinforcing fibers. A method for manufacturing a prepreg, characterized by impregnating the fluorine-containing epoxy resin composition as described in claim 4 into reinforcing fibers. A method for manufacturing fiber-reinforced composite materials, characterized by solidifying the prepreg as described in claim 6. A manufacturing method of fiber-reinforced composite materials, characterized by infiltrating the fluorine-containing epoxy resin composition as described in claim 4 into the reinforcing fibers and solidifying them. A sealing material containing the cured product according to claim 5. A semiconductor device including at least a semiconductor element, wherein the semiconductor element is sealed by the cured product according to claim 5. A method of sealing a semiconductor element, which is to cure the fluorine-containing epoxy resin composition as described in claim 4 to seal the semiconductor element. A method of using the fluorine-containing epoxy resin composition as a sealing material by curing the fluorine-containing epoxy resin composition as described in claim 4 and using it as a sealing material. A compound consisting of 1,1,1-trifluoro-2,2-bis(4-diepoxypropylaminophenyl)ethane represented by chemical formula (3), "Chemical 3" . A compound consisting of 1,1,1-trifluoro-2,2-bis(3-methyl-4-diepoxypropylaminophenyl)ethane represented by chemical formula (4), 『Chemical 4』 . A method for producing a fluorine-containing epoxy compound represented by the general formula (1), including making an aromatic diamine compound represented by the general formula (1A) and an epihalohydrin The process of reaction, "Chemistry 5" (Wherein, in the general formula (1), n is each independently an integer of 0 to 4, R ¹ each independently represents a monovalent substituent, and is selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, One of the group consisting of aryl groups) "Chemical 6" (Wherein, in the general formula (1A), n is independently an integer of 0 to 4, R ¹ each independently represents a monovalent substituent, and is selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, 1 of the group consisting of aryl groups).