JP2023118158A - Dihydroxy resin, epoxy resin, method for producing the same, and epoxy resin composition, and cured product - Google Patents

Abstract

To provide an epoxy resin and a dihydroxy compound which enable production of a cured product having good flame retardancy, and excellent heat resistance and humidity resistance, and are useful for applications of lamination, molding, casting and bonding.SOLUTION: An epoxy resin is obtained by reaction of a dihydroxy resin represented by the following general formula (1) with epichlorohydrin. In the general formula (1), A, B and D represent specific aromatic groups.SELECTED DRAWING: None

Description

The present invention relates to an epoxy resin that provides a cured product having excellent heat resistance, flame retardancy, moisture resistance, etc., an epoxy resin composition using the epoxy resin composition, and a cured product thereof. It is suitably used in fields such as insulating materials in the electrical and electronic fields such as semiconductor encapsulation, and carbon fiber composite materials.

In recent years, especially with the progress in the field of advanced materials, there is a demand for the development of higher performance base resins. There is a demand for the development of resins with excellent properties. In addition, the improvement of handleability such as solvent solubility when preparing the epoxy resin composition is also an important issue.

However, none of the known epoxy resins that sufficiently satisfy these requirements has yet been known. For example, Patent Document 1 proposes an epoxy resin having an ether ether ketone structure, which is classified as a super engineering plastic. In order to improve these characteristics, Patent Document 2 proposes an epoxy resin composition using a bisphenol compound having an imide structure as a curing agent, but the compatibility and heat resistance of the resin are not sufficient. Ta. Patent document 3 discloses an epoxy resin having an imide structure with improved solvent solubility, but it is not fully satisfactory from the viewpoint of heat resistance.

JP 2012-46615 A JP-A-4-328121 JP 2014-132074 A

An object of the present invention is to obtain a cured product having excellent heat resistance and moisture resistance, and is useful for lamination, molding, casting, adhesion, etc. It is an object of the present invention to provide an epoxy resin composition and a cured product thereof.

（ここで、Ａは独立してベンゼン、ナフタレン、または下記一般式（２）、

（但し、Ｘは単結合、－ＣＨ２－、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ２－、－Ｃ（ＣＦ３）２－、－Ｏ－φ－Ｏ－を示す。ここでφはフェニレン基を示す。）
で表されるビスフェニレン骨格を有する４価の芳香族基を示し、Ｂは独立してナフタレン、または下記一般式（３）、

（但し、Ｙは単結合、－ＣＨ２－、－Ｏ－、－Ｃ（ＣＨ３）２－を示し、Ｒ１、Ｒ２は、それぞれ独立して水素原子、炭素数１～９の炭化水素基を示し、ｍは０～２の数を示す。）
で表される２価の芳香族基を示し、Ｄは独立にナフタレン、または下記一般式（４）、

（但し、Ｚは単結合、－ＣＨ２－、－Ｏ－、－Ｃ（ＣＨ３）２－、－Ｃ（ＣＦ３）２－、シクロヘキシル基、メチルシクロヘキシル基、フルオレニル基を示し、Ｒ３、Ｒ４は、それぞれ独立して水素原子、炭素数１～９の炭化水素基を示す。）
で表される２価の芳香族基を示し、ｎは０．１～２５の数を表す。） That is, the present invention is a dihydroxy resin represented by the following general formula (1).

(Here, A is independently benzene, naphthalene, or the following general formula (2),

(where X represents a single bond, -CH2-, -O-, -CO-, -S-, -SO2-, -C(CF3)2-, -O-φ-O-, where φ is indicates a phenylene group.)
A tetravalent aromatic group having a bisphenylene skeleton represented by B is independently naphthalene, or the following general formula (3),

(where Y represents a single bond, -CH2-, -O-, -C(CH3)2-, R1 and R2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms, m indicates a number from 0 to 2.)
represents a divalent aromatic group represented by D is independently naphthalene, or the following general formula (4),

(where Z represents a single bond, -CH2-, -O-, -C(CH3)2-, -C(CF3)2-, a cyclohexyl group, a methylcyclohexyl group, a fluorenyl group, and R3 and R4 are each independently represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms.)
represents a divalent aromatic group represented by n represents a number from 0.1 to 25. )

（ここで、Ａ、Ｂ、Ｄおよびｎは、式（１）と同義である。）
で表されるエポキシ樹脂であり、上記一般式（１）で表されるジヒドロキシ樹脂とエピクロルヒドリンを反応させることを特徴とする式（５）で表されるエポキシ樹脂の製造方法である。 Further, the present invention provides the following general formula (5),

(Here, A, B, D and n are synonymous with formula (1).)
A method for producing an epoxy resin represented by the formula (5), characterized by reacting a dihydroxy resin represented by the general formula (1) with epichlorohydrin.

Further, in the present invention, the dihydroxy resin of the general formula (1) or the epoxy resin of the general formula (5) is blended as a curing agent in the curing agent component or as an essential component of the epoxy resin in the epoxy resin component. It is an epoxy resin composition and a cured product obtained by curing these epoxy resin compositions.

The cured product obtained by curing the epoxy resin composition containing the dihydroxy resin or epoxy resin having an imide structure of the present invention as an essential component has excellent heat resistance, moisture resistance, etc. It can be suitably used for applications such as molds and adhesion.

1 shows a GPC chart of dihydroxy resin A obtained in Example 1. FIG. 1 shows an IR spectrum of dihydroxy resin A obtained in Example 1. FIG. 1 shows a GPC chart of dihydroxy resin A obtained in Example 5. FIG. 1 shows a GPC chart of epoxy resin A obtained in Example 6. FIG. 4 shows an IR spectrum of epoxy resin A obtained in Example 6. FIG.

ここで、Ａは独立してベンゼン、ナフタレン、または下記一般式（２）、

で表されるビスフェニレン骨格を有する４価の芳香族基を示し、Ｘは単結合、－ＣＨ２－、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ２－、－Ｃ（ＣＦ３）２－、－Ｏ－φ－Ｏ－を示す。ここでφはフェニレン基を示す。 The present invention will be described in detail below.
The dihydroxy resin of the present invention is represented by general formula (1).

Here, A is independently benzene, naphthalene, or the following general formula (2),

represents a tetravalent aromatic group having a bisphenylene skeleton represented by X is a single bond, -CH2-, -O-, -CO-, -S-, -SO2-, -C(CF3)2- , -O-φ-O-. Here, φ represents a phenylene group.

From the viewpoint of heat resistance, it is preferable that A in formula (1) is benzene, or X in formula (2) is a single bond, -CO-, and from the viewpoint of compatibility with the curing agent, solvent solubility, etc. , wherein X in formula (2) is -C(CF3)2-, -O-, -SO2-, -O-φ-O-.

で表される２価の芳香族基を示す。ここで、Ｙは単結合、－ＣＨ２－、－Ｏ－、－Ｃ（ＣＨ３）２－を示し、Ｒ１、Ｒ２は、それぞれ独立して水素原子、炭素数１～９の炭化水素基を示し、ｍは０～２の数を示す。 In formula (1), B is naphthalene, or the following general formula (3),

represents a divalent aromatic group represented by Here, Y represents a single bond, -CH2-, -O-, -C(CH3)2-, R1 and R2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms, m represents a number from 0 to 2;

From the viewpoint of heat resistance, B is preferably naphthalene, or Y in formula (3) is preferably a single bond, and from the viewpoint of compatibility with epoxy resins, solvent solubility, etc., B is naphthalene or formula (3) Y in is preferably -CH2-, -O- or -C(CH3)2-. In particular, from the viewpoint of compatibility with epoxy resins, solvent solubility, etc., B is naphthalene, or at least one of R1 or R2 adjacent to the carbon atom substituted by the imide group in formula (3) has 1 to 1 carbon atoms. 9 is preferably a hydrocarbon group. Desirable naphthalene skeletons include 1,4-substituted, 1,5-substituted, 1,6-substituted, 2,6-substituted and 2,7-substituted compounds. And from the viewpoint of heat resistance, it is a 1,5-substituted product. Desirable R1 or R2 in formula (3) is a methyl group, an ethyl group, or a phenyl group. With these structures, the steric hindrance reduces the planarity of the imide ring and the aromatic ring of B, inhibits the orientation between molecules, and improves compatibility with epoxy resins, solvent solubility, and the like. m is a number from 0 to 2, preferably 0 or 1;

で表される２価の芳香族基を示す。ここで、Ｚは単結合、－ＣＨ２－、－Ｏ－、－Ｃ（ＣＨ３）２－、－Ｃ（ＣＦ３）２－、シクロヘキシル基、メチルシクロヘキシル基、フルオレニル基を示し、Ｒ３、Ｒ４は、それぞれ独立して水素原子、炭素数１～９の炭化水素基を示し、ｐは０～２の数を示す。 In formula (1), D is independently naphthalene, or the following general formula (4),

represents a divalent aromatic group represented by Here, Z represents a single bond, -CH2-, -O-, -C(CH3)2-, -C(CF3)2-, a cyclohexyl group, a methylcyclohexyl group, a fluorenyl group, and R3 and R4 are each Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms, and p represents a number of 0 to 2.

From the viewpoint of heat resistance, D is naphthalene, or Z in formula (4) is preferably a single bond, -CO-, or a fluorenyl group. From the viewpoint of compatibility with epoxy resins, solvent solubility, etc., -CH2 -, -O-, -C(CH3)2-, -C(CF3)2-, cyclohexyl group, methylcyclohexyl group and fluorenyl group are preferred. In particular, from the viewpoint of heat resistance and solvent solubility, it is preferable that D is a naphthalene skeleton, or Z in formula (4) is a fluorenyl group, and further R3 adjacent to the carbon atom substituted with an imide group in formula (4) Alternatively, at least one of R4 is particularly preferably a hydrocarbon group having 1 to 9 carbon atoms. A preferable naphthalene skeleton is a 1,5-substituted compound, and preferable R3 or R4 in formula (4) is a methyl group, an ethyl group, or a phenyl group. These structures reduce the planarity of the imide ring and the aromatic ring of D due to the steric hindrance, inhibiting the orientation of the molecules and improving the compatibility with the curing agent and solvent solubility. p is a number from 0 to 2, preferably 1 or 2;

In general formula (1), n is the number of repetitions and represents a number from 0.1 to 25. In the case of a mixture of a plurality of compounds with different repeating numbers, the average value of n (Σn/Σnumber of molecules) is in the range of 0.1 to 25. The preferred value of n or its average value depends on the application. For example, for applications of semiconductor encapsulating materials that require a high filler filling rate, low viscosity is desirable, and the value of n or its average value is 0.1 to 15, preferably 0.5 to 10 , more preferably 1.0 to 7.0, and particularly preferably 1.1 to 5.0. When applied to applications such as circuit materials and fiber-reinforced composite materials, the value of n or its average value is 3 to 25, preferably 5 to 25, more preferably 5 to 25, from the viewpoint of imparting film properties and toughness. 8 to 25.

The dihydroxy compound of the present invention preferably has a weight average molecular weight of 500-15,000. The range of 500 to 2,500 is desirable for applications requiring low viscosity, and the range of 2,000 to 15,000 is desirable for applications requiring film properties and toughness. . Moreover, the hydroxyl equivalent of the dihydroxy compound of the present invention is preferably 300 to 3,000 g/eq. , more preferably 350 to 2,000 g/eq. More preferably 400 to 1,500 g/eq. , more preferably 500 to 1,300 g/eq. is in the range of Also, the softening point is preferably in the range of 120 to 350°C, more preferably 150 to 300°C.

ここで、Ａ、Ｂ、Ｄおよびｎは、式（１）と同義である。 Moreover, the epoxy resin of this invention is represented by General formula (5).

Here, A, B, D and n are synonymous with formula (1).

The preferred weight average molecular weight of the epoxy resin of the present invention is in the range of 600-18,000, more preferably in the range of 600-3,000. Also, the epoxy equivalent is preferably in the range of 400 to 9,000, more preferably in the range of 400 to 5,000, even more preferably in the range of 400 to 3,000, particularly preferably in the range of 500 to 1,000. If it is larger than this, the viscosity and softening point will increase, making it difficult to adjust the epoxy resin composition, and the moldability will deteriorate. The preferred softening point of the epoxy resin of the present invention is in the range of 100-350°C, more preferably 100-280°C. Also, hydrolyzable chlorine is preferably 1000 ppm or less, more preferably 500 ppm or less.

Although the epoxy resin of the present invention is not particularly limited, it can be produced by reacting a dihydroxy resin represented by general formula (1) with epichlorohydrin. This reaction can be carried out in the same manner as a normal epoxidation reaction.

For example, after dissolving the dihydroxy resin represented by the general formula (1) in excess epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, the temperature is 50 to 150°C, preferably 60°C. A method of reacting at a temperature of up to 120° C. for 1 to 10 hours may be mentioned. In this case, the alkali metal hydroxide is used in an amount of 0.8 to 2 mol, preferably 0.9 to 1.2 mol, per 1 mol of hydroxyl group in the dihydroxy resin. Epichlorohydrin is used in an excess amount relative to the hydroxyl groups in the dihydroxy resin, usually in the range of 1.5 to 15 mol, preferably 2 to 8 mol, per 1 mol of hydroxyl groups in the dihydroxy resin. Moreover, a quaternary ammonium salt or the like can be added during the reaction. Quaternary ammonium salts include, for example, tetramethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride and the like, and the amount added is preferably in the range of 0.1 to 2.0 wt% with respect to the dihydroxy compound. . If the amount is less than this, the effect of adding the quaternary ammonium salt will be small, and if it is more than this, the generation of hardly hydrolyzable chlorine will increase, making it difficult to achieve high purity. Furthermore, a polar solvent such as dimethylsulfoxide, diglyme, N-methylpyrrolidone, etc. may be used, and the amount added is preferably in the range of 10 to 200 wt% with respect to the dihydroxy resin. If it is less than this, the effect of addition is small, and if it is more than this, the volumetric efficiency is lowered, which is economically unfavorable. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and the solvent is distilled off to obtain the desired epoxy. resin can be obtained.

The epoxy resin composition of the present invention comprises an epoxy resin and a curing agent, and contains a dihydroxy resin represented by the general formula (1) or an epoxy resin represented by the general formula (5) as an essential component. .

In the epoxy resin composition obtained by blending the dihydroxy resin represented by the general formula (1) as an essential component of the curing agent component, the epoxy resin may be any ordinary epoxy resin having two or more epoxy groups in the molecule. Available. Examples include dihydric phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcinol, or tris-(4-hydroxyphenyl)methane. , 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol novolak, o-cresol novolak, and other trihydric or higher phenols, or halogenated bisphenols, such as tetrabromobisphenol A There are a glycidyl etherate, an epoxy resin represented by the above general formula (5), and the like. These epoxy resins can be used singly or in combination of two or more.
When the dihydroxy resin of the present invention represented by the general formula (1) is used as an essential component of the curing component of the epoxy resin composition of the present invention, other curing agents exemplified below can also be mixed and used. In this case, the amount of the hydroxy resin represented by the general formula (1) is preferably in the range of 5 to 100 wt%, more preferably in the range of 30 to 100 wt%, still more preferably in the range of 50 to 100 wt% in the curing agent component. , more preferably 70 to 100 wt %.

When the epoxy resin represented by the general formula (5) is used as an essential component, any curing agent generally known as a curing agent for epoxy resins can be used. Examples include dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines, and the like. Specific examples of polyhydric phenols include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcinol, naphthalenediol, and the like. Dihydric phenols, or tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, etc. Representative trihydric or higher phenols, further phenols, naphthols or bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, naphthalene diols and other divalent phenols such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, and polyhydric phenolic compounds synthesized with condensing agents such as p-xylylene glycol. Phthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhimic anhydride, nadic anhydride, trimellitic anhydride and the like. As amines, aromatic amines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine and p-xylylenediamine, Aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine and triethylenetetramine, or dihydroxy compounds represented by general formula (4) are available. One or a mixture of two or more of these curing agents can be used in the resin composition of the present invention.
When the epoxy resin of the present invention represented by general formula (5) is used as an essential component of the epoxy resin composition of the present invention, other epoxy resins can be mixed and used. The other epoxy resins are the same as the exemplified compounds of the epoxy resins when the dihydroxy resin represented by the general formula (1) is an essential component of the curing component, and one or two of the exemplified epoxy resins. More than one species can be mixed and used. In this case, the amount of the epoxy resin represented by general formula (5) is preferably in the range of 5 to 100 wt%, more preferably in the range of 10 to 70%, still more preferably in the range of 20 to 50%, in the epoxy resin component. is in the range of

The mixing ratio of the epoxy resin and the curing agent is preferably in the range of 0.8 to 1.5 in terms of the equivalent ratio of the epoxy groups to the functional groups in the curing agent. Outside this range, unreacted epoxy groups or functional groups in the curing agent may remain even after curing.
The weight ratio of the epoxy resin represented by formula (5) to the curing agent is preferably in the range of 0.2 to 1.0.

In the epoxy resin composition of the present invention, oligomers or polymer compounds such as polyesters, polyamides, polyimides, polyethers, polyurethanes, petroleum resins, indene cumarone resins, and phenoxy resins may be appropriately blended, or inorganic fillers may be added. Additives such as agents, pigments, flame retardants, thixotropic agents, coupling agents, fluidity improvers and the like may be added. Examples of inorganic fillers include spherical or crushed fused silica, silica powder such as crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like. Examples thereof include organic or inorganic extender pigments and scaly pigments. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, organic bentonite-based, and the like.

Conventionally known curing accelerators can be used in the epoxy resin composition of the present invention. Examples include amines, imidazoles, organic phosphines, Lewis acids and the like. The amount to be added is usually in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin. Further, if necessary, the epoxy resin composition of the present invention may contain release agents such as carnauba wax and OP wax, coupling agents such as γ-glycidoxypropyltrimethoxysilane, colorants such as carbon black, Flame retardants such as antimony trioxide, stress reducing agents such as silicone oil, and lubricants such as calcium stearate can be used.

The cured product of the present invention can be obtained by molding the epoxy resin composition by methods such as casting, compression molding and transfer molding. The temperature during molding is usually in the range of 120-280°C.

ここでＧＰＣ測定は、装置：ＨＬＣ－８３２０（東ソー（株）製）及びカラム：ＴＳＫｇｅｌ ＳｕｐｅｒＨＺ２５００×２本及びＴＳＫｇｅｌ ＳｕｐｅｒＨＺ２０００×２本（何れも東ソー（株）製）を用い、溶媒：テトラヒドロフラン（ＴＨＦ）、流速：０．３５ｍｌ／分、温度：４０℃、検出器：ＲＩの条件で行った。また、水酸基当量は、塩化アセチル溶液中で、水酸化カリウムによる電位差滴定を行うことにより測定した。得られた樹脂のシクロペンタノンへの溶解度は２０以上であった。赤外吸収スペクトルは日本分光製、ＦＴ／ＩＲ－６１００型赤外吸収分析計を用いてＫＢｒ錠剤法により測定した。 The present invention will be specifically described below based on examples and comparative examples.
Example 1 (Production of dihydroxy resin A)
A separable flask was charged with 31.7 g (0.10 mol) of 4,4'-oxydiphthalic dianhydride, 10.2 g (0.05 mol) of 4,4'-diaminodiphenyl ether, and 16.5 g (0.05 mol) of 5-amino-1-naphthol. 8 g (0.10 mol) was dissolved in 200 mL of N-methylpyrrolidone (NMP) and reacted at 80° C. for 2 hours. 120 mL of toluene was added to the reaction solution and the temperature was raised to remove water produced by azeotropy. After that, the temperature was raised to 160° C. and the reaction was carried out for 3 hours. During this time, the generated water was removed from the system. After cooling to room temperature, 1 L of distilled water was added, and the precipitate was collected by filtration, washed with water and dried to obtain 52 g of powdery product (dihydroxy resin A). The hydroxyl equivalent is 820 g/eq. , the softening point was 180°C. GPC measurement revealed a weight average molecular weight of 1,670 and a number average molecular weight of 1,070. A chart is shown in FIG. 1, and an infrared absorption spectrum is shown in FIG. The structure of the obtained resin was represented by the following formula (6), and the average value of n was 1.5 from GPC measurement.

Here, GPC measurement is performed using an apparatus: HLC-8320 (manufactured by Tosoh Corporation) and columns: TSKgel SuperHZ2500 × 2 and TSKgel SuperHZ2000 × 2 (both manufactured by Tosoh Corporation), solvent: tetrahydrofuran (THF) , flow rate: 0.35 ml/min, temperature: 40°C, detector: RI. Moreover, the hydroxyl group equivalent was measured by performing potentiometric titration with potassium hydroxide in an acetyl chloride solution. The solubility of the obtained resin in cyclopentanone was 20 or more. The infrared absorption spectrum was measured by the KBr tablet method using an FT/IR-6100 type infrared absorption spectrometer manufactured by JASCO Corporation.

得られた樹脂のＮＭＰへの溶解度は２０以上であった。 Example 2 (Production of dihydroxy resin B)
3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride 53.7 g (0.150 mol), 1,5-diaminonaphthalene 12.2 g (0.075 mol), 4-amino-m- Using 18.9 g (0.150 mol) of cresol, the same reaction as in Example 1 was carried out to obtain 79 g of a powdery product (dihydroxy resin B). The hydroxyl equivalent is 642 g/eq. , the softening point was 273°C. GPC measurement revealed a weight average molecular weight of 1,500 and a number average molecular weight of 1,090. The structure of the obtained resin was represented by the following formula (7), and the average value of n was 1.3 from GPC measurement.

The solubility of the obtained resin in NMP was 20 or more.

得られた樹脂のシクロペンタノンへの溶解度は２０以上であった。 Example 3 (Production of dihydroxy resin C)
4,4′-hexafluoroisopropylidene diphthalic dianhydride 31.7 g (0.070 mol), 4,4′-diaminodiphenyl ether 7.2 g (0.035 mol), 4-amino-m-cresol 8 Using .8 g (0.070 mol), the same reaction as in Example 1 was carried out to obtain 36 g of a powdery product (dihydroxy resin C). The hydroxyl equivalent is 657 g/eq. , the softening point was 155°C. GPC measurement revealed a weight average molecular weight of 1,900 and a number average molecular weight of 1,270. The structure of the obtained resin was the following formula (8), and the average value of n was 1.3 from GPC measurement.

The solubility of the obtained resin in cyclopentanone was 20 or more.

得られた樹脂のシクロペンタノンへの溶解度は２０以上であった。 Example 4 (Production of dihydroxy resin D)
4,4′-oxydiphthalic dianhydride 38.0 g (0.120 mol), 9,9-bis(4-amino-3-methylphenyl)fluorene 23.1 g (0.060 mol), 4-amino- Using 15.1 g (0.120 mol) of m-cresol, the same reaction as in Example 1 was carried out to obtain 70 g of a powdery product (dihydroxy resin D). The hydroxyl equivalent is 712 g/eq. , the softening point was 280°C. GPC measurement revealed a weight average molecular weight of 2,020 and a number average molecular weight of 1,240. The structure of the obtained resin was represented by the following formula (9), and the average value of n was 1.7 from GPC measurement.

The solubility of the obtained resin in cyclopentanone was 20 or more.

得られた樹脂のＮＭＰへの溶解度は１０であった。 Example 5 (Production of dihydroxy resin E)
44.3 g (0.140 mol) of 4,4'-oxydiphthalic dianhydride, 21.5 g (0.105 mol) of 4,4'-diaminodiphenyl ether, 8.8 g (0.105 mol) of 4-amino-m-cresol. 070 mol), the same reaction as in Example 1 was carried out to obtain 68 g of a powdery product (dihydroxy resin E). The hydroxyl equivalent is 1,228 g/eq. , the softening point was 300° C. or higher. GPC measurement revealed a weight average molecular weight of 4,290 and a number average molecular weight of 2,350. A GPC chart is shown in FIG. The structure of the obtained resin was the following formula (10), and the average value of n was 4.5 from GPC measurement.

The solubility of the resulting resin in NMP was 10.

Example 6 (synthesis of epoxy resin A)
24 g of the dihydroxy resin A obtained in Example 1 was dissolved in 90 g of epichlorohydrin and 90 g of NMP, and 4.8 g of a 48.6% sodium hydroxide aqueous solution was added dropwise at 65° C. under reduced pressure (about 130 mmHg) over 4 hours. During this time, the generated water was removed from the system by azeotroping with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the reaction, epichlorohydrin was distilled off under reduced pressure, and the reaction solution was added dropwise to a large amount of distilled water. After the product was filtered and washed with water, it was dried to obtain 21 g of a yellowish brown epoxy resin (epoxy resin A). GPC measurement revealed a weight average molecular weight of 1,340 and a number average molecular weight of 950. The epoxy equivalent is 980 g/eq. , the softening point was 145°C. The solubility of the obtained resin in cyclopentanone was 20 or more. A GPC chart is shown in FIG. 4, and an infrared absorption spectrum is shown in FIG.
Here, the epoxy equivalent was measured by performing potentiometric titration with perchloric acid in an acetic acid solution of tetraethylammonium bromide. Hydrolyzable chlorine was obtained by dissolving 0.5 g of a resin sample in 30 ml of 1,4-dioxane, boiling under reflux for 30 minutes in 5 ml of a 1N-KOH/methanol solution, and performing potentiometric titration with a silver nitrate solution. Ta.

Example 7 (Synthesis of epoxy resin B)
Using 30 g of the dihydroxy compound B obtained in Example 2, 130 g of epichlorohydrin, 130 g of NMP, and 7.7 g of a 48.6% sodium hydroxide aqueous solution, the reaction was carried out in the same manner as in Example 6 to obtain 32 g of a brownish white epoxy resin (epoxy Resin B). GPC measurement revealed a weight average molecular weight of 1,200 and a number average molecular weight of 940. The epoxy equivalent is 710 g/eq. , the softening point was 266°C. The solubility of the obtained resin in cyclopentanone was 20 or more.

Examples 8-12 and Comparative Examples 1-4
Resins synthesized in Examples 3 to 5 (dihydroxy resins C to E), epoxy resins synthesized in Examples 6 and 7 (epoxy resins A and B), diphenyl ether type epoxy resins (epoxy resin C: manufactured by Nippon Steel Chemical & Material , YSLV-80DE, epoxy equivalent 163 g / eq.), biphenyl type epoxy resin (epoxy resin D: YX-4000H manufactured by Mitsubishi Chemical, epoxy equivalent 193), 4,4'-dihydroxydiphenyl ether (curing agent A: hydroxyl equivalent 101 g / eq.), using phenol novolac (curing agent B; manufactured by Aica Kogyo Co., Ltd., BRG-557, hydroxyl equivalent 104, softening point 83 ° C.), as a curing accelerator
1644818577457_1
(TPP) was used to prepare a resin composition according to the formulation shown in Table 1.
After molding (180° C., 5 minutes) using this, post-curing (180° C., 4 hours) was performed to obtain test pieces, which were subjected to various physical property tests. The test method is as follows. Table 1 shows the results.

[evaluation]
(1) Glass transition temperature (Tg), coefficient of linear expansion Measured at a heating rate of 10°C/min using a TMA7100 type thermomechanical measurement device manufactured by Hitachi High-Tech Science.
(2) Pyrolysis start temperature, residual carbon rate Measured under nitrogen flow with a TG/DTA7300 type thermogravimetry device manufactured by Hitachi High-Tech Science under conditions of a temperature increase rate of 10 ° C./min, and a 10 wt% weight loss temperature is pyrolyzed. The starting temperature was used, and the residual carbon ratio was defined as the weight residual ratio at 700°C.
(3) Water Absorption A disk having a diameter of 50 mm and a thickness of 3 mm was formed, and after post-curing, it was subjected to moisture absorption for 100 hours under the conditions of 85° C. and 85% relative humidity, and the weight change rate was obtained.

Claims (6)

A dihydroxy resin represented by the following general formula (1).

(Here, A is independently benzene, naphthalene, or the following general formula (2),

(where X represents a single bond, -CH2-, -O-, -CO-, -S-, -SO2-, -C(CF3)2-, -O-φ-O-, where φ is indicates a phenylene group.)
A tetravalent aromatic group having a bisphenylene skeleton represented by B is independently naphthalene, or the following general formula (3),

(where Y represents a single bond, -CH2-, -O-, -C(CH3)2-, R1 and R2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms, m indicates a number from 0 to 2.)
represents a divalent aromatic group represented by D is independently naphthalene, or the following general formula (4),

(where Z represents a single bond, -CH2-, -O-, -C(CH3)2-, -C(CF3)2-, a cyclohexyl group, a methylcyclohexyl group, a fluorenyl group, and R3 and R4 are each independently represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms, and p represents a number of 0 to 2.)
represents a divalent aromatic group represented by n represents a number from 0.1 to 25. ) An epoxy resin represented by the following general formula (5).

(Here, A, B, D and n are synonymous with formula (1).) 3. The method for producing an epoxy resin according to claim 2, wherein the dihydroxy resin according to claim 1 and epichlorohydrin are reacted. An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the dihydroxy resin according to claim 1 is blended. An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin composition according to claim 2 is blended. A cured product obtained by curing the epoxy resin composition according to claim 4 or 5.

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