JP6389751B2 - Hydroxy resin, production method thereof, epoxy resin composition and cured product thereof - Google Patents

Description

  The present invention relates to a hydroxy resin excellent in dielectric characteristics and excellent in heat resistance and curability and a cured product thereof.

  In recent years, the signal band of information communication devices such as mobile phones and the CPU clock time of computers have reached the GHz band, and higher frequencies have been advanced.

  The dielectric loss of an electrical signal is proportional to the product of the square root of the dielectric constant of the insulator forming the circuit, the dielectric loss tangent and the frequency of the signal used. Therefore, the higher the frequency of the signal used, the greater the dielectric loss.

  Dielectric loss attenuates an electrical signal and impairs the reliability of the signal. Therefore, in order to suppress this, it is necessary to select a material having a small dielectric constant and dielectric loss tangent for the insulator.

  Therefore, polymer materials such as fluororesin, curable polyolefin, cyanate ester resin, curable polyphenylene oxide, allyl-modified polyphenylene ether, polyether imide modified with divinylbenzene or divinylnaphthalene have been proposed. Although these resins have a low number of polar groups and are low dielectric constant / low dielectric loss tangent materials, they have a problem that their adhesion to metals and adhesion to other resins are extremely poor due to the small number of polar groups. Moreover, the epoxy resin which is excellent in adhesive force has a problem that a dielectric constant and a dielectric loss tangent are increased because a secondary hydroxyl group derived from a glycidyl ether group is generated after curing.

  As a method of reducing the number of secondary hydroxyl groups derived from the glycidyl ether of the epoxy resin in order to reduce the dielectric loss tangent, there is a method of reducing the number of active hydrogen groups in the cured product. Patent Document 1 discloses an epoxy resin having an oxymethylene group, and a hydroxy resin having an oxymethylene group as an intermediate is disclosed, but when this is used as a curing agent, the molar volume is low, This is not preferable because the dielectric constant becomes high. Patent Document 2 discloses a technique of introducing aromatics into a polyfunctional phenol by a substitution reaction to increase the molar volume. However, even when the maximum substitution is performed, the reduction of active hydrogen groups is insufficient, Insufficient dielectric loss tangent. Further, when the aromatic group is introduced at a certain ratio or more, the glass transition temperature is remarkably lowered. Patent Document 3 discloses a hydroxy resin as an intermediate of an epoxy resin having an oxymethylene group containing an aromatic modification. However, when the amount of the aromatic modification is large, there is a problem that the glass transition temperature is remarkably lowered. It was.

JP 62-41222 A Japanese Patent No. 5324712 JP 2014-111712 A

  The present invention is excellent in low dielectric constant because the molar volume is increased by introduction of aromatic modification and oxymethylene groups, and has low active tangent properties and low dielectric loss tangent, and defines the amount of aromatic modification. It aims at providing the hydroxyl resin excellent also in heat resistance and sclerosis | hardenability, its manufacturing method, an epoxy resin composition, and hardened | cured material.

（式中、ｍは平均の繰り返し数であり０．１＜ｍ＜１０を示し、Ａ_１及びＡ_２は独立に炭素数６〜５０の２価の芳香族基を示し、Ｒ_１は下記式（２）又は（３）で表される置換基を示し、ｐは０．２〜３．５の数を示す。）

（式中、Ｒ_２及びＲ_３は独立に炭素数１〜１０の炭化水素基又はハロゲン原子を示し、ｎ及びｑは独立に０〜３の整数を示す。） That is, the present invention is a hydroxy resin represented by the following general formula (1).

(In the formula, m is the average number of repetitions and represents 0.1 <m <10, A ₁ and A ₂ independently represent a divalent aromatic group having 6 to 50 carbon atoms, and R ₁ represents the following formula: (2) The substituent represented by (3) is shown, p shows the number of 0.2-3.5.)

(Wherein, _{R 2} and _{R 3} independently represents a hydrocarbon group or a halogen atom having 1 to 10 carbon atoms, n and q is independently an integer of 0-3.)

（式中、Ｒ_４は単結合、炭素数１〜４のアルキル基もしくは炭素数６〜２０の芳香族基で置換してもよいメチレン基、炭素数１〜４のアルキル基で置換してもよいシクロヘキシレン基、フルオレニル基、−Ｏ−、−ＣＯ−、−Ｓ−、又は−ＳＯ_２−のいずれかを示し、Ｒ_５は独立に炭素数１〜１０の炭化水素基又はハロゲン原子のいずれかを示し、ｋは０〜３の整数を示す。）
上記ヒドロキシ樹脂は、２５℃におけるモル体積が４００〜１４００ｃｍ^３／ｍｏｌの範囲であることが好ましく、また水酸基当量が２４０〜８００ｇ／ｅｑ．の範囲であることが好ましい。 It is preferable that A ₁ and A ₂ are independently any of groups represented by the following formulas (4a), (4b), or (4c).

(In the formula, R ₄ may be substituted with a single bond, an alkyl group having 1 to 4 carbon atoms or an methylene group which may be substituted with an aromatic group having 6 to 20 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. good cyclohexylene group, a fluorenyl group, -O -, - CO -, - S-, or -SO ₂ - either indicates either, _{R 5} is independently a C1-10 hydrocarbon group or a halogen atom And k represents an integer of 0 to 3.)
The hydroxy resin preferably has a molar volume in the range of 400 to 1400 cm ³ / mol at 25 ° C. and a hydroxyl group equivalent of 240 to 800 g / eq. It is preferable that it is the range of these.

（式中、Ａ_１は炭素数６〜５０の２価の芳香族基を示す。）

（式中、Ｒ_２及びＲ_３は独立に炭素数１〜１０の炭化水素基又はハロゲン原子を示し、ｎ及びｑは独立に０〜３の整数を示す。）

（式中、Ａ_２は炭素数６〜５０の２価の芳香族基を示し、Ｘはハロゲン原子を示す。） Moreover, this invention is styrene represented by following General formula (6) with respect to 1 mol of divalent aromatic hydroxy compounds (a) represented by following General formula (5), and following General formula (7). Fragrance modified with aromatic olefins by reacting 0.2 to 3.5 moles of one or more aromatic olefins (b) selected from the indenes represented in the presence of an acid catalyst After obtaining the aromatic modified hydroxy compound (c), the aromatic modified hydroxy compound (c) and the bifunctional halogenated methyl group-containing compound (d) represented by the following general formula (8) are converted into a basic substance. It is made to react in presence of this, It is a manufacturing method of the said hydroxy resin characterized by the above-mentioned.

(In the formula, A ₁ represents a divalent aromatic group having 6 to 50 carbon atoms.)

(Wherein, _{R 2} and _{R 3} independently represents a hydrocarbon group or a halogen atom having 1 to 10 carbon atoms, n and q is independently an integer of 0-3.)

(In the formula, A ₂ represents a divalent aromatic group having 6 to 50 carbon atoms, and X represents a halogen atom.)

  A polar aprotic solvent having a boiling point of 185 ° C. or lower is used as the solvent for the divalent aromatic hydroxy compound (a) and the aromatic olefins (b), and 0 for the aromatic olefins (b). It is preferable to make it react at the temperature of 40-140 degreeC in presence of an acid catalyst of 0.01-1.0 mass%. In addition, the divalent aromatic hydroxy compound (a) is a hydroxyphenol, dihydroxynaphthalene, dihydroxybiphenyl, dihydroxydiphenyl ether, dihydroxydiphenyl sulfide, dihydroxy which may be substituted by a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom. Preference is given to compounds selected from the group consisting of phenylmethane, dihydroxyphenylcyclohexane and dihydroxyphenyltrimethylcyclohexane or mixtures thereof.

  Furthermore, this invention is an epoxy resin composition which has the said hydroxy resin and an epoxy resin as an essential component. Moreover, this invention is an epoxy resin hardened | cured material formed by hardening | curing the said epoxy resin composition.

  The hydroxy resin of the present invention is excellent as a phenol curing agent blended in an epoxy resin composition, improves the curability, dielectric constant, dielectric loss tangent, low elastic modulus, etc. of the epoxy resin composition or a cured product obtained therefrom, and is a semiconductor. It can be suitably used for applications such as substrate materials, interlayer insulating materials, sealing of electrical / electronic components, and printed wiring board materials.

1 is a GPC chart of a hydroxy resin obtained in Example 1. 2 is an IR chart of the hydroxy resin obtained in Example 1. FIG.

The hydroxy resin of the present invention is represented by the general formula (1).
In the general formula (1), m is an average number of repetitions and represents a number of 0.1 <m <10, preferably a number of 0.1-5. A ₁ and A ₂ independently represent a divalent aromatic group having 6 to 50 carbon atoms, preferably a divalent aromatic group having 6 to 21 carbon atoms, more preferably 2 having 6 to 12 carbon atoms. Valent aromatic group. R ₁ represents a substituent represented by the above formula (2) or (3), p represents a number of 0.2 to 3.5, preferably a number of 0.4 to 3, more preferably It is a number between 0.5 and 2.5. In formula (2) or (3), R ₂ and R ₃ independently represent a hydrocarbon group or halogen atom having 1 to 10 carbon atoms, preferably an alkyl group or phenyl group having 1 to 6 carbon atoms, and more Preferably it is a C1-C3 alkyl group. n and q independently represent an integer of 0 to 3, preferably 0 or 1.

Examples of A ₁ and A ₂ include groups represented by the formula (4a), (4b), or (4c). In the formula, R ₄ may be substituted with a single bond, an alkyl group having 1 to 4 carbon atoms or an methylene group which may be substituted with an aromatic group having 6 to 20 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. A cyclohexylene group, a fluorenyl group, —O—, —CO—, —S—, or —SO ₂ — is shown, and R ₅ is independently either a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom. And k represents an integer of 0 to 3, preferably 0, 1 or 2.

Hydroxy resin of the present invention is preferably from molar volume at 25 ° C. is 400~1400cm ³ / mol, more preferably in the range of 420~1350cm ³ / mol, more preferably in the range of 450~1000cm ³ / mol.

  The hydroxy resin of the present invention has a hydroxyl group equivalent of 240 to 800 g / eq. The range is preferably 300 to 600 g / eq. Is more preferable, 330-550 g / eq. The range of is more preferable.

  The hydroxy resin of the present invention can be advantageously produced by the method for producing a hydroxy resin of the present invention. However, the hydroxy resin of the present invention is not limited to the resin obtained by this production method.

  Hereinafter, the hydroxy resin of the present invention will be described while explaining the method for producing the hydroxy resin of the present invention. In the chemical formula, common symbols are understood to have the same meaning unless otherwise specified.

  The hydroxy resin of the present invention includes a divalent aromatic hydroxy compound (a) represented by general formula (5), styrenes represented by general formula (6), and indenes represented by general formula (7). After obtaining an aromatic modified hydroxy compound (c) modified with an aromatic olefin obtained by reacting one or more aromatic olefins (b) selected from the above in the presence of an acid catalyst The aromatic modified hydroxy compound (c) can be obtained by reacting the bifunctional halogenated methyl group-containing compound (d) represented by the general formula (8) in the presence of a basic substance.

Examples of the divalent aromatic hydroxy compound (a) include hydroxyphenol, dihydroxynaphthalene, dihydroxybiphenyl, and bisphenols, and these may have a substituent. Preferably, it is a divalent aromatic compound selected from the group consisting of hydroxyphenol, dihydroxynaphthalene, dihydroxybiphenyl, dihydroxydiphenyl ether, dihydroxydiphenyl sulfide, dihydroxyphenylmethane, dihydroxyphenylcyclohexane and dihydroxyphenyltrimethylcyclohexane, and these are carbon atoms. You may have a 1-10 hydrocarbon group or a halogen atom as a substituent.
Specifically, hydroquinone, resorcin, catechol, 4-phenylresorcinol, phenylhydroquinone, tert-butylhydroquinone, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6 -Dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 3-methyl-naphthalene-1,6-diol, 4,4'-biphenol, 3,3'-dimethyl-4,4'-biphenyldiol, 2,3'- Dimethyl-1,1′-biphenyl-4,4′-diol, 3,3′-diethyl-4,4′-biphenyldiol, 2,3′-diethyl-1,1′-biphenyl-4,4′- Diol, 3,3′-diphenyl-4,4′-biphenyldiol, 2,2′-dipropyl-1,1′-biphenyl-4 4'-diol, bisphenol A, bisphenol F, 4,4'-dihydroxydiphenyl ether, 4,4'-thiobisphenol, bisphenol S, bisphenol Z, bisphenol AP, 4,4'-phenylmethylene bisphenol, 4,4'- Diphenylmethylene bisphenol, bisphenol AF, bisphenol B, bisphenol E, bisphenol P, 4,4 ′-[1,3-phenylenebis (dimethylmethylene)] diphenol, 1,1-bis (4-hydroxyphenyl) -3, 3,5-trimethylcyclohexane, 4,4′-dihydroxybenzophenone, bisphenol fluorene, bisphenol C, dimethyl bisphenol A, dimethyl bisphenol F, dimethyl bisphenol S, biscresol fluorene, , 2- bis (4-hydroxy-3-isopropylphenyl) propane, 4,4'-isopropylidene-bis (2-phenylphenol) and the like but not limited thereto. Examples of the divalent aromatic hydroxy compound (a) other than the above include 3,7-dibenzofurandol, 1,1′-binaphthalene-4,4′-diol and the like. Moreover, when it has a halogen atom as a substituent, it is good to set it as the range which does not impair the objective (low dielectric constant etc.) of this invention.
From the viewpoint of being hardly accompanied by cleavage under an acid catalyst and having excellent heat resistance, the divalent aromatic hydroxy compound (a) includes 4,4′-dihydroxydiphenyl ether, 4,4′-thiobisphenol, bisphenol S, Bisphenol fluorene and 4,4′-biphenol are preferred, and among these, 4,4′-dihydroxydiphenyl ether and 4,4′-thio, which are highly reactive with the above indenes and styrenes and can reduce the amount of acid catalyst. Bisphenol is more preferred. These divalent aromatic hydroxy compounds (a) may be used alone or in combination of two or more.

The aromatic olefins (b) include one or more selected from styrenes represented by the general formula (6) and indenes represented by the general formula (7).
The aromatic olefins (b) may contain a small amount of other reaction components other than styrenes and indenes. When the other reactive component includes an unsaturated bond-containing component such as α-methylstyrene, coumarone, benzothiophene, indole, vinylnaphthalene, and indane, the resulting aromatic modified hydroxy compound (c) includes a group derived therefrom. Are substituted on the aromatic ring. Therefore, the hydroxy resin of the present invention can include a hydroxy resin having such a substituent.

In the general formula (6), R ₂ represents a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, preferably a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 0 to 3, preferably Is 0 or 1. Specific examples include styrene and C1-C3 alkyl-substituted styrene.

In the general formula (7), R ₃ represents a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, preferably a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 0 to 3, preferably Is 0 or 1. Specific examples include indene and alkyl-substituted indene having 1 to 3 carbon atoms.

  As a method of reacting the aromatic olefin (b) with the divalent aromatic hydroxy compound (a), the reaction is performed at a high temperature of 120 to 170 ° C. in the presence of an acid catalyst such as hydrochloric acid. It is common. However, when the reaction is carried out at a high temperature in the presence of an acid catalyst, when the divalent aromatic hydroxy compound has a methylene bond, an ether bond, a sulfide bond, or the like in the linking group portion, there is a problem that these phenols are cleaved and a unit price phenol is by-produced. there were. In order to suppress such side reactions, the reaction temperature is lowered to a range of 40 to 140 ° C., and the catalyst is set to a range of 0.01 to 1.0% by mass of the total amount of the aromatic olefins (b) to be used. By reducing the amount, the by-product of unit price phenol can be reduced. When a hydroxy resin with reduced by-products is used as a curing agent for an epoxy resin, physical properties excellent in curability and heat resistance are exhibited.

  Therefore, the reaction temperature is preferably in the range of 40 to 140 ° C. If it is higher than this, the by-product phenol produced as a by-product increases, and when the target hydroxy resin is blended with the epoxy resin, curability and heat resistance are lowered. On the other hand, if it is lower than this, the reactivity is lowered, the reaction time becomes longer, and a lot of unreacted monomers remain. A more preferred reaction temperature is in the range of 80 ° C to 135 ° C, and even more preferably in the range of 100 ° C to 135 ° C.

  This reaction is carried out in the presence of an acid catalyst. The acid catalyst can be appropriately selected from well-known inorganic acids, organic acids, Lewis acids and the like. For example, mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, formic acid, oxalic acid, trifluoroacetic acid, p -Lewis acids, such as organic acids, such as toluenesulfonic acid and methanesulfonic acid, and zinc chloride, aluminum chloride, iron chloride, boron trifluoride, and a solid acid.

  The amount of the acid catalyst when the aromatic olefin (b) is reacted with the divalent aromatic hydroxy compound (a) is preferably in the range of 0.01 to 1.0% by mass. If it is more than this, the by-product of the unit price phenol component will increase, and if it is less than this, the reactivity will be lowered, the reaction time will be long, and a lot of unreacted monomers will remain. More preferably, it is the range of 0.03-0.5 mass%.

The aromatic olefin (b) is used in an amount of 0.2 mol to 3.5 mol with respect to 1 mol of the divalent aromatic hydroxy compound (a). When the amount is less than 0.2 mol, the dielectric constant does not decrease. When the amount is more than 3.5 mol, the glass transition temperature decreases, the gel time increases, and the productivity is remarkably deteriorated. Therefore, 0.4 mol or more and 3.0 mol or less are preferable, and 0.5 mol or more and 2.5 mol or less are more preferable. In addition, the amount of modification when the styrenes and the indenes are used in combination is the total molar amount of the styrenes and the indenes.
Here, almost all of the aromatic olefins (b) used in the reaction undergo an addition reaction with the aromatic ring of the divalent aromatic hydroxy compound (a). Therefore, in the obtained aromatic modified hydroxy compound (c) This is consistent with the amount of modification (also referred to as the modification rate). Therefore, when the aromatic olefin (b) is used in an amount of 0.2 mol to 3.5 mol with respect to 1 mol of the divalent aromatic hydroxy compound (a), the amount of modification is also 0.2 mol to 3.5 mol. Become.

  If the amount of modification exceeds 3.5 mol, the glass transition temperature of the cured epoxy resin may not be 100 ° C or higher. The operating temperature of the microprocessor unit used in personal computers and servers is less than 100 ° C. However, if the glass transition temperature of the surrounding material is lower than the operating temperature, the connection is based on the difference in thermal expansion coefficient before and after the glass transition temperature. Since the defect such as cracking or peeling occurs in the part, the connection reliability is remarkably lowered. For this reason, the glass transition temperature of the cured resin must be 100 ° C. or higher.

In the above reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl ether, diethyl ether, diethylene glycol dimethyl ether , Ethers such as diisopropyl ether, tetrahydrofuran and dioxane, and aromatic compounds such as benzene, toluene, chlorobenzene and dichlorobenzene can be used as the solvent.
In particular, when the reaction with the halogenated methyl group-containing compound (d) is subsequently carried out after the above reaction, the solvent used for the subsequent reaction with the halogenated methyl group-containing compound (d) is omitted in order to eliminate the solvent replacement work. And a polar aprotic solvent such as ethers such as ethylene glycol dimethyl ether is preferred.

As a specific method for carrying out this reaction, (1) all raw materials are charged in a lump and allowed to react at a predetermined temperature for 1 to 20 hours, or (2) a divalent aromatic hydroxy compound (a) and a catalyst. The two methods are generally used, in which the aromatic olefins (b) are allowed to react while dropping, while maintaining a predetermined temperature. In the case of the method (2), the dropping time is usually 1 to 10 hours, but preferably 5 hours or less. Moreover, in order to make the dripped aromatic olefin (b) react completely, it is preferable to make it react for 1 to 10 hours after completion | finish of dripping.
When a solvent is used after the reaction, the aromatic modified hydroxy compound (c) can be obtained by removing the catalyst component, if necessary, and then distilling off the solvent. When no solvent is used, the aromatic-modified hydroxy compound (c) can be obtained by discharging directly when heated. Further, depending on the purpose, it can be made into a solution diluted with a solvent.
Here, the aromatic modified hydroxy compound (c) is a compound having a structure in which the substituent represented by the formula (2) or (3) is bonded to the aromatic ring of the divalent aromatic hydroxy compound (a). is there. The amount of substituents corresponds to the amount of modification.

  Next, the aromatic modified hydroxy compound (c) thus obtained and the bifunctional halogenated methyl group-containing compound (d) represented by the general formula (8) are reacted in the presence of a basic substance. The resulting hydroxy resin represented by the general formula (1) is obtained.

In the general formula (8), A ₂ represents a divalent aromatic group having 6 to 50 carbon atoms, preferably a divalent aromatic group having 6 to 18 carbon atoms, X represents a halogen atom, preferably Is chlorine or bromine. Specific examples of the halogenated methyl group-containing compound (d) include α, α′-dichloro-p-xylene, α, α′-dibromo-p-xylene, α, α′-dichloro-m-xylene, α , Α′-dibromo-m-xylene, α, α′-dichloro-o-xylene, 4,4′-bis (chloromethyl) biphenyl, 4,4′-bis (bromomethyl) biphenyl, bischloromethylnaphthalene, bis Examples thereof include bromomethylnaphthalene and bisbromomethylfluorene, which can be used alone or as a mixture of two or more.

  The ratio of the halogenated methyl group-containing compound (d) to the aromatic modified hydroxy compound (c) is 0.05 mol of the halogenated methyl group-containing compound (d) with respect to 1.0 mol of the aromatic modified hydroxy compound (c). It is good to make -1.0 mol react, Preferably it is 0.1-0.8 mol, More preferably, it is 0.2-0.5 mol. When the halogenated methyl group-containing compound (d) is larger than 1.0 mol, some or all of the terminal groups become halogen atoms and are not suitable as an epoxy resin curing agent. If it is less than 0.05 mol, the dielectric loss tangent may not be lowered when cured with an epoxy resin.

  The reaction temperature of the halogenated methyl group-containing compound (d) and the aromatic modified hydroxy compound (c) is 20 ° C. or higher to the reflux temperature, preferably 50 ° C. or higher to the reflux temperature, and the reaction time is usually 1 to 10 hours.

  As the basic substance, sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonia, sodium methylate, triethylamine and the like are preferable. Sodium hydroxide and potassium hydroxide, which are alkali metal salts that can be used stably even at the reaction temperature, are more preferred. This usage-amount is 1.6-2.4 mol with respect to 1 mol of aromatic modified hydroxy compounds (c). When the amount is less than 1.6 mol, the reaction site is limited, so that it tends to be a high molecular weight product. On the other hand, when the amount is more than 2.4 mol, an unreacted basic substance that does not contribute to the reaction increases, so that an acid required for neutralization increases, which is not preferable from the viewpoint of environmental burden. Since the basic substance neutralizes and reacts with the hydrogen halide (HX) generated by the reaction between the halogenated methyl group-containing compound (d) and the aromatic modified hydroxy compound (c), the halogenated methyl group-containing compound (D) 2 equivalents of the basic substance are required per 1 mol. However, since the aromatic modified hydroxy compound (c) is phenolated with a basic substance and then neutralized with dehydrohalogenation, in order to smoothly carry out such phenolation and dehalogenation, aromatic The amount of the basic substance is preferably adjusted according to the molar ratio between the modified hydroxy compound (c) and the halogenated methyl group-containing compound (d). As described above, the aromatic modified hydroxy compound (c) 1 It is good to adjust and use suitably in the range of 1.6-2.4 mol with respect to mol.

The hydroxy resin of the present invention is represented by the general formula (1). Here, m is the number of repetitions, and the average value (number average) is 0.1 <m <10. Preferably, the average value needs to be 0.1 <m <5. When m is 0.1 or less, the amount of hydroxyl groups is not sufficiently reduced, and there is no effect on low dielectric properties, and when m is 10 or more, there is a possibility that the viscosity becomes high. m can be adjusted by controlling the reaction molar ratio of the halogenated methyl group-containing compound (d) and the aromatic modified hydroxy compound (c).
Moreover, said p respond | corresponds to the modification amount of the said aromatic olefin (b) with respect to the said bivalent aromatic hydroxy compound (a), and is the range of 0.2-3.5. If it is less than 0.2, the dielectric constant is not lowered, and if it is more than 3.5, the glass transition temperature is lowered, the gel time is prolonged, and the productivity is remarkably deteriorated. The p (modification amount) is preferably 0.4 to 3.0, more preferably 0.5 to 2.5.

  The solvent used for the reaction of the aromatic modified hydroxy compound (c) and the halogenated methyl group-containing compound (d) in the presence of a basic substance is 110 parts by mass with respect to 100 parts by mass of the aromatic modified hydroxy compound (c). The amount is preferably 1900 parts by mass or less. When the amount of the solvent is less than 110 parts by mass, as the hydroxyl resin of the present invention is produced, the viscosity increases, which may make stirring difficult. On the other hand, when the amount is more than 1900 parts by mass, the reactivity is remarkably lowered and the yield may be lowered. The amount of the solvent is preferably 130 parts by mass or more and 550 parts by mass or less, more preferably 150 parts by mass or more and 400 parts by mass or less, and further preferably 170 parts by mass or more and 300 parts by mass or less.

  This reaction is preferably carried out in the presence of a solvent. The solvent is preferably a polar aprotic solvent or a mixed solvent of a polar aprotic solvent and a polar protic solvent. In the case of a mixed solvent, the polar aprotic solvent is 20% by mass or more. If the polar aprotic solvent is less than 20% by mass in all the solvents, the reactivity of the hydroxyl group of the aromatic modified hydroxy compound (c) and the methyl halide group of the halogenated methyl group-containing compound (d) as a whole However, local reaction proceeds, the ratio of the high molecular weight polymer of the hydroxy resin of the present invention tends to increase, and there is a risk of causing side reactions such as electrophilic substitution reaction. When the proportion of the high molecular weight substance is large, the viscosity increases, and when an epoxy resin cured product is to be produced, there is a possibility that a uniform cured product such as voids may not be obtained, which is not preferable. In addition, when a side reaction occurs, the halogenated terminal tends to remain unreacted, which may cause migration or the like that causes disconnection when a metal wiring is formed on the cured product. Therefore, the proportion of the polar aprotic solvent is preferably 50% by mass or more and more preferably 80% by mass or more in the total solvent. On the other hand, the polar protic solvent can uniformly dissolve or disperse the basic substance, and can efficiently convert the aromatic modified hydroxy compound (c) into an alkali metal salt. It is good to use together. The ratio of the polar protic solvent in all the solvents is preferably 0.5 to 10% by mass, and more preferably 1 to 5% by mass.

Examples of the polar aprotic solvent include ketones such as acetone, esters such as methyl acetate, dimethyl carbonate and propylene carbonate, nitriles such as acetonitrile, ethers such as diethylene glycol dimethyl ether, cyclic ethers such as tetrahydrofuran, N- Amides such as methylformamide and N, N-dimethylformamide are exemplified. Further, when a polar aprotic solvent having a boiling point of 185 ° C. or higher is used, it must be distilled off at a high temperature or dropped into an excess poor solvent for extraction, which is not preferable from the viewpoint of environmental burden. Therefore, the boiling point of the solvent is preferably less than 185 ° C, and more preferably 170 ° C or less. As the polar aprotic solvent, cyclic ethers such as tetrahydrofuran and ethers such as diethylene glycol dimethyl ether are preferable.
Examples of polar protic solvents that may be used in combination include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, and isobutanol, acetic acid, water, and the like.

  Along with these polar solvents, a nonpolar solvent may be used in combination as long as it is less than 10% by mass in the total solvent. Nonpolar solvents that may be used in combination include aromatic hydrocarbons such as toluene, xylene, and mesitylene, and linear hydrocarbons such as hexane. These may be used as a mixture.

  These solvents are preferably added to the intermediate product or reaction mixture as necessary in the course of the reaction.

  The hydroxy resin synthesized by the production method of the present invention can be stored in the form of a solution without distilling off the solvent.

In the production method of the present invention, if necessary, the aromatic modified hydroxy compound (c) as an intermediate is produced in advance, and after neutralization, the product is taken out of the system as a product. You may obtain the hydroxy resin of this invention in another manufacturing process using a modified | denatured hydroxy compound (c). However, after obtaining the intermediate aromatic-modified hydroxy compound (c), the reaction with the halogenated methyl group-containing compound (d) is preferably performed continuously. It is preferable because the steps after neutralization for obtaining the above can be omitted.
In the production method of the present invention, the reaction step in the previous stage, that is, the divalent aromatic hydroxy compound (a) and the aromatic olefin (b) are reacted to form an aromatic modified hydroxy compound (c) as an intermediate. Is obtained in the presence of an acid catalyst, while a subsequent reaction step, that is, a step of reacting the aromatic modified hydroxy compound (c) with the halogenated methyl group-containing compound (d) to obtain a hydroxy resin. In the presence of a basic substance. Therefore, when taking out the intermediate (c) as a product, it is necessary to add a basic substance as a neutralizing agent in order to neutralize the remaining acid catalyst. Since the latter reaction step is performed in the presence of a basic substance, in most cases, it is not necessary to add a neutral substance for neutralization separately. In the subsequent reaction step, an acidic substance is added as a neutralizing agent to neutralize the remaining basic substance.

The hydroxy resin obtained by the production method of the present invention has a molar volume at 25 ° C. of 400 to 1400 cm ³ / mol, preferably 420 to 1350 cm ³ / mol, more preferably 450 to 1000 cm ³ / mol, and Hydroxyl equivalent weight is 240-800 g / eq. , Preferably 300 to 600 g / eq. 330-550 g / eq. It is in the range. Therefore, it becomes a cured product having a low dielectric constant and dielectric loss tangent, excellent dielectric properties, and excellent heat resistance and curability.

The molar volume (cm ³ / mol) can be obtained by dividing the molar mass (g / mol) by the density (g / cm ³ ). Moreover, since the hydroxy resin obtained by the production method of the present invention is necessarily bifunctional and has two hydroxyl groups in one mole, the hydroxyl equivalent (g / eq.) Of the hydroxy resin is doubled (eq./mol). ), The molar mass (g / mol) is obtained. Therefore, the molar volume (cm ³ / mol) can be calculated by the following formula.
Molar volume [cm ³ / mol] = hydroxyl equivalent [g / eq. ] × 2 [eq. / Mol] ÷ density [g / cm ³ ]

ここで、ＤＨＤＥは２つのベンゼン環を有し、２つのベンゼン環に置換する置換基の数の和（Ｐ_１＋Ｐ_１）は、式（１）のＰに対応する。なお、２つのＰ_１は同一であっても異なってもよい。また、ｍ_１は式（１）のｍに対応する。 The typical example of the manufacturing method of this invention is represented by Reaction formula (9) and (10) below. In this reaction raw material, the divalent aromatic hydroxy compound (a) is 4,4′-dihydroxydiphenyl ether (DHDE), the aromatic olefin (b) is styrene, and the halogenated methyl group-containing compound (d) is 4, This is an example of 4′-bis (chloromethyl) biphenyl. The intermediate aromatic modified hydroxy compound (c) is a product of the reaction formula (9).

Here, DHDE has two benzene rings, and the sum (P ₁ + P ₁ ) of the number of substituents substituted on the two benzene rings corresponds to P in the formula (1). Two P ₁ may be the same or different. Also, _{m 1} corresponds to m of formula (1).

  Next, the epoxy resin composition of the present invention will be described. Specific examples of the epoxy resin used in the epoxy resin composition include bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene, 4,4′-biphenol, 3,3 ′, 5,5′-tetramethyl-4, Epoxidized products of divalent phenols such as 4′-dihydroxybiphenyl, resorcin, naphthalenediols, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol Epoxides of trivalent or higher phenols such as novolak and o-cresol novolak, epoxidized products of cocondensation resins obtained from dicyclopentadiene and phenols, and cocondensation resins obtained from cresols, formaldehyde and alkoxy group-substituted naphthalenes Epoxidized material, Fe It is synthesized from epoxidized phenol aralkyl resins obtained from alcohols and paraxylylene dichloride, epoxidized biphenyl aralkyl type phenol resins obtained from phenols and bischloromethylbiphenyl, naphthols and paraxylylene dichloride, etc. And epoxidized naphthol aralkyl resins. These epoxy resins may be used alone or in combination of two or more.

  The epoxy resin composition of the present invention uses the hydroxy resin represented by the above general formula (1) as an essential hydroxy resin as a curing agent component, but is within a range that does not impair the object of the present invention, for example, with respect to the total amount of the curing agent. The other curing agent can be used in combination in an amount of less than 50% by mass.

  Examples of the curing agent that may be used in combination with the epoxy resin composition of the present invention include various phenol resins, active esters, cyanate esters, acid anhydrides, amines, hydrazides and other commonly used epoxy resins. Curing agents can be used, and these curing agents may be used alone or in combination of two or more. For lowering the dielectric loss tangent, a curing agent that lowers the functional group concentration after curing is preferred, and high hydroxyl equivalent phenol resins and active esters are preferred.

  Specific examples of the type of curing agent include phenolic resins such as tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o- Cresol novolak, naphthol novolak, dicyclopentadiene type phenol resin, trivalent or higher phenolic compounds represented by phenol aralkyl resin, etc., phenols, naphthols, or bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, biphenol, Dihydric phenol compounds such as hydroquinone, resorcin, catechol, naphthalene diol, and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol, p-ki Obtained from polyhydric phenol compounds synthesized by reaction with crosslinkers such as rylene glycol dimethyl ether, divinylbenzene, diisopropenylbenzene, dimethoxymethylbiphenyl, divinylbiphenyl, diisopropenylbiphenyl, phenols and bischloromethylbiphenyl, etc. And biphenylaralkyl type phenol resins, naphthol aralkyl resins synthesized from naphthols and paraxylylene dichloride, and the like.

  When active esters are used as curing agents, the active esters generally include ester groups having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compound esters. A compound having two or more in one molecule is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like.

  When cyanate esters are used as curing agents, the cyanate esters include novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type curing agents, dicyclopentadiene type cyanate ester type curing agents, and bisphenol type (bisphenol A). Type, bisphenol F type, bisphenol S type, etc.) cyanate ester curing agents. More specifically, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′- Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) Bifunctional cyanate resins such as methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, phenol novolac, cresol Novolac and Dish Polyfunctional cyanate resin derived from Ropentajien structure-containing phenol resin, these cyanate resins prepolymers and the like obtained by partly triazine of.

  Specific examples of acid anhydrides include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, methyl nadic acid and the like. Specific examples of amines include diethylenetriamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and dicyandiamide. Specific examples of hydrazides include adipic acid hydrazide, sepatin hydrazide, and isophthalic acid hydrazide. It is done.

In the epoxy resin composition of the present invention, the blending amount of the epoxy resin and the curing agent is preferably in the range of 0.4 to 1.2 mol of the active hydrogen group of the curing agent with respect to 1 mol of the epoxy group of the epoxy resin, 0.5-1.1 mol is more preferable, and 0.7-1.0 mol is more preferable. For example, when phenol resins, active esters, or amines are used as the curing agent, the active hydrogen groups are mixed in an equimolar amount with respect to the epoxy groups. When acid anhydrides are used as the curing agent, 0.5 to 1.2 mol, preferably 0.6 to 1.0 mol, of acid anhydride group is added to 1 mol of epoxy group. When cyanate esters are used as the curing agent, it is preferably used in an amount of less than 50% by mass with respect to the total amount of the curing agent. Cyanate esters are cured with an epoxy resin to form an oxazolidone ring, and the cyanate esters are cured to form a triazine ring. For this reason, the curing reaction proceeds even if used excessively with respect to the epoxy resin, but if the ratio of the cyanate ester is large, the adhesion with the conductor layer may be lowered. Further, when the reaction proceeds by contact like imidazole compounds or cationic polymerization initiators, they may be blended at a predetermined mass ratio with respect to the epoxy resin.
The active hydrogen group in the present invention is a functional group having an active hydrogen reactive with an epoxy group, and specifically includes an acid anhydride group, a carboxyl group, an amino group, a phenolic hydroxyl group, and active esters. And arylcarbonyloxy group. In addition, regarding an active hydrogen group, 1 mol of carboxyl groups and phenolic hydroxyl groups are calculated as 1 mol, and an amino group (—NH ₂ ) is calculated as 2 mol.

  A curing accelerator can be used in the epoxy resin composition of the present invention as necessary. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, and 1,8-diaza. -Tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine and triphenylphosphine triphenylborane, and metal compounds such as tin octylate. A hardening accelerator may be used independently or may be used together 2 or more types. 0.02-5.0 mass parts is used as needed for a hardening accelerator with respect to 100 mass parts of epoxy resins in the epoxy resin composition of this invention. By using a curing accelerator, the curing temperature can be lowered and the curing time can be shortened.

  An organic solvent as a viscosity modifier can also be used in the epoxy resin composition of the present invention. Specifically, amides such as N, N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, aromatics such as benzene and toluene And hydrocarbons. These viscosity modifiers may be used alone or in combination of two or more.

  The epoxy resin composition of the present invention may be blended with a curable resin or a thermoplastic resin other than the epoxy resin as long as the characteristics are not impaired. Specifically, phenol resin, acrylic resin, petroleum resin, indene resin, indene coumarone resin, phenoxy resin, cyanate resin, epoxy acrylate resin, vinyl compound, polyurethane, polyester, polyamide, polyimide, polyamideimide, polyether Examples thereof include, but are not limited to, imide, bismaleimide triazine resin, polyethersulfone, polysulfone, polyetheretherketone, polyphenylene sulfide, and polyvinyl formal.

  A filler can be used for the epoxy resin composition of this invention as needed. Specific examples include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium hydroxide, glass powder, silica balloon, etc., but organic or inorganic moisture resistant pigments, scaly You may mix | blend pigments, such as a pigment. The reason for using a general inorganic filler is an improvement in impact resistance. Moreover, fibrous fillers, such as glass fiber, a pulp fiber, a synthetic fiber, a ceramic fiber, organic fillers, such as fine particle rubber and a thermoplastic elastomer, etc. can be mix | blended.

  Moreover, you may mix | blend additives, such as a flame retardant, a thixotropic agent, and a fluidity improver, with the epoxy resin composition of this invention as needed. Examples of the thixotropic agent include silicon, castor oil, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite. Further, if necessary, the resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a colorant such as carbon black, a flame retardant such as antimony trioxide, a low stress agent such as silicon oil, A lubricant such as calcium stearate can be blended.

  Moreover, if the epoxy resin composition of the present invention is cured by heating, an epoxy resin cured product can be obtained, and this cured product is excellent in terms of low dielectric properties, heat resistance, low hygroscopicity, and the like. This hardened | cured material can be obtained by shape | molding an epoxy resin composition by methods, such as casting, compression formation, and transfer formation. The temperature at this time is usually in the range of 120 to 250 ° C.

  Since the epoxy resin composition of the present invention gives a cured product excellent in low dielectric properties and high heat resistance, it is preferably used in electrical materials such as laminates and insulating sheets. Moreover, since it has the outstanding adhesiveness, use with a prepreg, an adhesive agent, or an adhesive sheet is more preferable.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to this. In Examples, unless otherwise specified, “part” represents part by mass, and “%” represents mass%. In the present invention, the following test method was used.

(1) Molar volume: The molar volume was determined by the following formula.
Molar volume [cm ³ / mol] = hydroxyl equivalent [g / eq.] × 2 [eq./mol]÷density [g / cm ³ ]
The hydroxyl group equivalent was determined by the measurement method described later. Further, the density was measured at 25 ° C. using an electronic hydrometer MD-300S (manufactured by Alpha Mirage Co., Ltd.) based on JIS K-7112, an underwater substitution method.

(2) Hydroxyl equivalent: Tetrahydrofuran containing 4% methanol was added to the sample and completely dissolved, 10% tetrabutylammonium hydroxide was added, and the absorbance between 400 nm and 250 nm was measured using an ultraviolet-visible spectrophotometer. The phenolic hydroxyl group was measured as the number of grams of the sample per equivalent of hydroxyl group.

(3) Measurement of softening point It measured based on JISK7234 specification and the ring and ball method. Specifically, an automatic softening point apparatus (manufactured by Meitec Co., Ltd., ASP-MG4) was used.

(4) Glass transition temperature: Measured according to JIS K-7121, differential scanning calorimetry. Using an EXTERDSC6200 manufactured by SII, the temperature was measured at a rate of temperature increase from 20 ° C. to 10 ° C./min, and was determined from the extrapolated glass transition start temperature (Tig) of the DSC chart obtained in the second cycle.

(5) Dielectric constant and dielectric loss tangent: 1 GHz at 25 ° C. by cavity resonance method (vector network analyzer (VNA) E8363B (manufactured by Agilent Technologies), cavity resonator perturbation method dielectric constant measurement device (manufactured by Kanto Electronics Application Development)) The value of was measured.

Example 1
200 parts of dihydroxydiphenyl ether (DHDE, hydroxyl group equivalent 101 g / eq.) As a divalent aromatic hydroxy compound component in a 4-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introducing device, polar aprotic solvent Was charged with 50 parts of diethylene glycol dimethyl ether (hereinafter referred to as diglyme) and 0.15 part of p-toluenesulfonic acid (0.05% with respect to styrene) as an acid catalyst, and the temperature was raised to 135 ° C. Next, with stirring, 308.9 parts of styrene (3.0 moles relative to 1 mole of DHDE) as an aromatic olefin was added dropwise over 3 hours to react, and after completion of the dropwise addition, the reaction was further carried out at 135 ° C. for 2 hours. At that time, a part (0.1 part) of the intermediate product was extracted and placed in another container, 0.3 parts of methyl isobutyl ketone (MIBK) was added, neutralized, washed with water, dehydrated, filtered, and then decompressed. The completion of the reaction was confirmed by GPC using a sample obtained by distilling off the solvent. Next, 940 parts of MIBK and 0.23 part of 20% potassium hydroxide aqueous solution were added to the reaction product to neutralize it, and then washed twice with water. After dehydration, the temperature was raised to 120 ° C., MIBK was recovered, and 168 parts of diglyme was added as a diluent solvent (diluent for the intermediate product) to a solid content of 70%. 712 parts of resin varnish (A1) was obtained.

200 parts of the resulting intermediate product resin varnish (A1), 32 parts of potassium hydroxide as basic substance, 191 parts of diglyme, 3.2 parts of water as polar proton solvent, stirrer, thermometer, cooling The solution was put into a four-necked flask equipped with a tube and a nitrogen gas introducing device, and stirred at room temperature to obtain an alkali metal salt. Next, 27.4 parts of 4,4′-bis (chloromethyl) biphenyl (hereinafter referred to as BCMB) was added as a halogenated methyl group-containing compound, and the temperature was stirred and heated to 80 ° C. to initiate the reaction. One hour after the start of the reaction, a part (0.1 part) of the reaction product was extracted and placed in another container, 0.3 parts of toluene was added, neutralized, washed with water, dehydrated, filtered, and then distilled off under reduced pressure. The completion of the reaction was confirmed by GPC using a sample obtained by distilling off the solvent. A GPC chart is shown in FIG. To the remaining reaction product, 372 parts of toluene was added as a diluent solvent (a diluent for the reaction product), 76 parts of 20% aqueous phosphoric acid was added as a neutralizing agent to neutralize it, and then washed twice with water. After dehydration and filtration, the solvent was distilled off under reduced pressure to obtain 147 parts of a brown solid resin 1 (m in the general formula (1) was 0.4, p was 3.0). The obtained resin 1 has a molar volume of 850 cm ³ / mol and a hydroxyl group equivalent of 488 g / eq. The softening point was 84 ° C. Moreover, the measurement result of IR spectrum of the obtained resin 1 is shown in FIG.

Example 2
Example 1 except that the resin varnish (A1) obtained in Example 1 was used as it was, and changed to 170 parts of diglyme, 13.7 parts of BCMB, 349 parts of toluene, and 101 parts of 20% aqueous phosphoric acid solution. The same apparatus and procedure were used to obtain 138 parts of a brown solid resin 2 (m = 0.2, p = 3.0). The obtained resin 2 has a molar volume of 620 cm ³ / mol and a hydroxyl group equivalent of 344 g / eq. The softening point was 61 ° C.

Example 3
Same as Example 1 except that the resin varnish (A1) obtained in Example 1 was used as it was, and changed to 212 parts of diglyme, 41 parts of BCMB, 395 parts of toluene, and 50 parts of 20% aqueous phosphoric acid solution. And 155 parts of a brown solid resin 3 (m = 0.6, p = 3.0) was obtained. The obtained resin 3 has a molar volume of 1310 cm ³ / mol and a hydroxyl group equivalent of 776 g / eq. The softening point was 98 ° C.

Example 4
The resin varnish (A1) obtained in Example 1 was used as it was, 179 parts of diglyme, 19.1 parts of α, α'-dichloro-p-xylene (DCX) instead of BCMB, 353 parts of toluene, 20 parts The synthesis was performed in the same apparatus and procedure as in Example 1 except that the amount of the aqueous phosphoric acid solution was changed to 76 parts to obtain 139 parts of a brown solid resin 4 (m = 0.4, p = 3.0). The obtained resin 4 has a molar volume of 790 cm ³ / mol and a hydroxyl group equivalent of 462 g / eq. The softening point was 76 ° C.

Example 5
As aromatic olefins, instead of styrene, 344.6 parts of indene (3.0 moles per mole of DHDE), 0.17 parts of p-toluenesulfonic acid (0.05% of indene), and 183 parts of diglyme Except having changed, it synthesize | combined by the apparatus and procedure similar to Example 1, and obtained 762 parts of resin varnish (A2) of an intermediate product.

200 parts of resin varnish (A2) instead of resin varnish (A1), 188 parts of diglyme, 29.9 parts of potassium hydroxide, 3 parts of water, 25.6 parts of BCMB, 369 parts of toluene, 20% The synthesis was performed in the same apparatus and procedure as in Example 1 except that the phosphoric acid aqueous solution was changed to 71 parts, and 145 parts of a brown solid resin 5 (m = 0.4, p = 3.0) was obtained. The obtained resin 5 has a molar volume of 900 cm ³ / mol and a hydroxyl group equivalent of 518 g / eq. The softening point was 88 ° C.

Example 6
As aromatic olefins, 154.5 parts of styrene (1.5 moles per mole of DHDE), 172.3 parts of indene (1.5 moles per mole of DHDE), and 0.16 parts of p-toluenesulfonic acid ( The synthesis was performed in the same apparatus and procedure as in Example 1 except that diglyme was changed to 176 parts, and 737 parts of an intermediate product resin varnish (A3) was obtained. .

200 parts of resin varnish (A3) instead of resin varnish (A1), 190 parts of diglyme, 30.9 parts of potassium hydroxide, 3.1 parts of water, 26.4 parts of BCMB, 370 parts of toluene, The synthesis was performed in the same apparatus and procedure as in Example 1 except that the 20% phosphoric acid aqueous solution was changed to 73 parts to obtain 146 parts of brown solid resin 6 (m = 0.4, p = 3.0). . The obtained resin 6 has a molar volume of 870 cm ³ / mol and a hydroxyl group equivalent of 503 g / eq. The softening point was 86 ° C.

Example 7
30.9 parts styrene as aromatic olefins (0.3 moles per mole of DHDE), 0.02 parts p-toluenesulfonic acid (0.05% based on styrene) as acid catalyst, 49 parts diglyme Except having changed, it synthesize | combined with the apparatus and procedure similar to Example 1, and obtained 320 parts of resin varnish (A4) of an intermediate product.

200 parts of resin varnish (A4) instead of resin varnish (A1), 240 parts of diglyme, 70.5 parts of potassium hydroxide, 7.1 parts of water, 60.3 parts of BCMB, 427 parts of toluene, The synthesis was performed in the same apparatus and procedure as in Example 1 except that the 20% phosphoric acid aqueous solution was changed to 167 parts, and 168.2 parts of brown solid resin 7 (m = 0.4, p = 0.3) was obtained. Obtained. The obtained resin 7 has a molar volume of 430 cm ³ / mol and a hydroxyl group equivalent of 254 g / eq. The softening point was 75 ° C.

Example 8
200 parts of dihydroxydiphenyl sulfide (DHDS, hydroxyl group equivalent 109 g / eq.) As a divalent aromatic hydroxy compound component, 286.2 parts of styrene as an aromatic olefin (3.0 moles per mole of DHDS), p-toluene Synthesis was performed in the same apparatus and procedure as in Example 1 except that 0.14 part of sulfonic acid (0.05% with respect to styrene) and diglyme were changed to 158 parts, and 681 parts of resin varnish (A5) as an intermediate product Got.

200 parts of resin varnish (A5) instead of resin varnish (A1), 190 parts of diglyme, 31 parts of potassium hydroxide, 3.1 parts of water, 26.5 parts of BCMB, 371 parts of toluene, 20% The synthesis was performed in the same apparatus and procedure as in Example 1 except that the phosphoric acid aqueous solution was changed to 73 parts, and 146 parts of brown solid resin 8 (m = 0.4, p = 3.0) was obtained. The obtained resin 8 has a molar volume of 870 cm ³ / mol and a hydroxyl group equivalent of 501 g / eq. The softening point was 76 ° C.

Example 9
In a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introducing device, 79 parts of DHDE, 20 parts of diglyme as a divalent aromatic hydroxy compound component, and 0.03 of p-toluenesulfonic acid as an acid catalyst Part (0.05% with respect to styrene) was charged and the temperature was raised to 135 ° C. Next, with stirring, 61 parts of styrene (1.5 mol with respect to 1 mol of DHDE) as an aromatic olefin was added dropwise over 3 hours to react, and after completion of the addition, reaction was further performed at 135 ° C. for 2 hours. After confirming the completion of the reaction by the same operation as in Example 1, 249 parts of diglyme (total of 40 parts of diluted intermediate product solvent and 209 parts of reaction solvent), 46 parts of potassium hydroxide as basic substance, polar proton 4.6 parts of water was added as a solvent and stirred at room temperature to obtain an alkali metal salt. Next, 39.3 parts of BCMB was added as a halogenated methyl group-containing compound, and the temperature was stirred and heated to 80 ° C. to initiate the reaction. After confirming the completion of the reaction by the same operation as in Example 1, 392 parts of toluene was added as a dilution solvent for the reaction product, neutralized by adding 109 parts of a 20% aqueous phosphoric acid solution, and then washed twice with water. . After dehydration and filtration, the solvent was distilled off under reduced pressure to obtain 155 parts of brown solid resin 9 (m = 0.4, p = 1.5). The obtained resin 9 had a molar volume of 620 cm ³ / mol, a hydroxyl group equivalent of 358 g / eq., And a softening point of 80 ° C.

Example 10
200 parts of bisphenol F (BPF, hydroxyl group equivalent 100 g / eq.) As a divalent aromatic hydroxy compound component, 156 parts of styrene as aromatic olefins (1.5 mol with respect to 1 mol of BPF), p-toluenesulfonic acid 0 .08 parts (0.05% with respect to styrene), except that diglyme was changed to 103 parts, synthesis was performed in the same apparatus and procedure as in Example 1 to obtain 499 parts of an intermediate product resin varnish (A6). .

200 parts of resin varnish (A6) instead of resin varnish (A1), 209 parts of diglyme, 45.8 parts of potassium hydroxide, 4.6 parts of water, 39.1 parts of BCMB, 391 parts of toluene, The synthesis was performed in the same apparatus and procedure as in Example 1 except that the 20% phosphoric acid aqueous solution was changed to 108 parts, and 154 parts of a brown solid resin 10 (m = 0.4, p = 1.5) was obtained. . The obtained resin 10 has a molar volume of 640 cm ³ / mol and a hydroxyl group equivalent of 359 g / eq. The softening point was 78 ° C.

Comparative Example 1
10.3 parts of styrene as aromatic olefins (0.1 mole per mole of DHDE), 0.01 parts of p-toluenesulfonic acid (0.05% of styrene) as acid catalyst, 40 parts of diglyme Except having changed, it synthesize | combined with the apparatus and procedure similar to Example 1, and obtained 294 parts of resin varnish (A7) of the intermediate product.

200 parts of resin varnish (A7) instead of resin varnish (A1), 249 parts of diglyme, 77.5 parts of potassium hydroxide, 7.7 parts of water, 66.2 parts of BCMB, 436 parts of toluene, The synthesis was performed in the same apparatus and procedure as in Example 1 except that the 20% phosphoric acid aqueous solution was changed to 183 parts, and 172 parts of a brown solid comparative resin 1 (m = 0.4, p = 0.1) was obtained. It was. The molar volume of the obtained comparative resin 1 is 390 cm ³ / mol, and the hydroxyl group equivalent is 236 g / eq. The softening point was 72 ° C.

Comparative Example 2
45.8 parts DHDE, 94.2 parts styrene (4.0 moles per mole of DHDE), 11 parts initial diglyme, 0.05 parts p-toluenesulfonic acid (0.05% based on styrene), 233 parts of additional diglyme (total of 49 parts of diluting solvent for intermediate product and 184 parts of reaction solvent), 26.6 parts of potassium hydroxide, 2.7 parts of water, 22.8 parts of BCMB, instead of toluene Synthesis was performed using the same apparatus and procedure as in Example 9 except that 364 parts of MBIK and 63 parts of 20% phosphoric acid aqueous solution were changed, and comparative resin 2 (m = 0.4, p = 4.0) of brown solid. 144 parts) were obtained. The molar volume of the obtained comparative resin 2 is 1080 cm ³ / mol, and the hydroxyl group equivalent is 574 g / eq. The softening point was 88 ° C.

  The composition and physical properties of the hydroxy resins of Examples 1 to 10 are shown in Table 1. Table 2 shows the composition and physical properties of the hydroxy resins of Comparative Examples 1 and 2. In addition,-in a table | surface represents non-use.

Example 11
6.7 parts of the resin 9 obtained in Example 9 as a hydroxy resin and 3. YDPN-638 (phenol novolac type epoxy resin, epoxy equivalent = 176 g / eq., Manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) as an epoxy resin After mixing 3 parts until uniform at a temperature of 170 ° C., 0.10 parts of 2E4MZ (2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei Co., Ltd.) is added as a curing accelerator, stirred, dissolved, and epoxy A resin composition was obtained. The composition was degassed under reduced pressure, poured into a mold, and cured in an oven at 190 ° C. for 2 hours to obtain a cured product test piece.

Example 12
Except for using 6.78 parts of the resin 9 as a hydroxy resin and 3.22 parts of ESN-375 (a naphthalene aralkyl epoxy resin, epoxy equivalent = 170 g / eq., Manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) as an epoxy resin. A cured product test piece was obtained using the same apparatus and procedure as in Example 11.

Example 13
6.77 parts of the resin 9 as a hydroxy resin, 1.65 parts of the YDPN-638 as an epoxy resin and ZX-1059 (mixed epoxy resin of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent = 170 g) / Eq., Manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), a cured product specimen was obtained using the same apparatus and procedure as in Example 11.

Example 14
3.42 parts of the above resin 9 as a hydroxy resin and 1.94 parts of BRG-557 (phenol novolac type curing agent, hydroxyl group equivalent = 105 g / eq., Showa Denko KK) and ZX-1059 as an epoxy resin A cured product test piece was obtained by the same apparatus and procedure as in Example 11 except that 4.63 parts were used.

Comparative Example 3
A cured product test piece was obtained by the same apparatus and procedure as in Example 11 except that 3.74 parts of BRG-557 as a hydroxy resin and 6.26 parts of YDPN-638 as an epoxy resin were used.

Comparative Example 4
A cured product test piece was prepared in the same apparatus and procedure as in Example 11 except that 5.73 parts of Comparative Resin 1 obtained in Comparative Example 1 as a hydroxy resin and 4.27 parts of YDPN-638 as an epoxy resin were used. Obtained.

Comparative Example 5
A cured product test piece was prepared in the same apparatus and procedure as in Example 11 except that 7.65 parts of Comparative Resin 2 obtained in Comparative Example 2 was used as the hydroxy resin and 2.35 parts of YDPN-638 was used as the epoxy resin. Obtained.

  Table 3 shows the measurement results of glass transition temperature (Tg), relative dielectric constant, and dielectric loss tangent of the obtained cured product. In addition,-in a table | surface shows non-use.

  As is apparent from Tables 1 to 3, the cured product using the hydroxy resin of the present invention has a high glass transition temperature and excellent dielectric properties, so that it can be suitably used for electronic materials. On the other hand, Comparative Example 3 was an example in which the hydroxy resin of the present invention was not used, and although it had a high glass transition temperature, it was a cured product having a high dielectric constant and dielectric loss tangent and poor dielectric properties. Further, Comparative Example 4 was a cured product having a high dielectric constant and dielectric loss tangent and inferior dielectric properties, although the glass transition temperature was the same as that of the Example because of the low amount of styrene modification. Comparative Example 5 was a cured product having a low glass transition temperature and problematic in practical use because of its high styrene modification amount.

Claims (9)

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

(In the formula, m is the average number of repetitions and represents 0.1 <m <10, A ₁ and A ₂ independently represent a divalent aromatic group having 6 to 50 carbon atoms, and R ₁ represents the following formula: (2) The substituent represented by (3) is shown, p shows the number of 0.2-3.5.)

(Wherein, _{R 2} and _{R 3} independently represents a hydrocarbon group or a halogen atom having 1 to 10 carbon atoms, n and q is independently an integer of 0-3.) The hydroxy resin according to claim _1, wherein A ₁ and A ₂ are each independently a group represented by the following formula (4a), (4b), or (4c).

(In the formula, R ₄ may be substituted with a single bond, an alkyl group having 1 to 4 carbon atoms or an methylene group which may be substituted with an aromatic group having 6 to 20 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. good cyclohexylene group, a fluorenyl group, -O -, - CO -, - S-, or -SO ₂ - either indicates either, _{R 5} is independently a C1-10 hydrocarbon group or a halogen atom And k represents an integer of 0 to 3.) The hydroxy resin according to claim 1 or 2, wherein the molar volume at 25 ° C is 400 to 1400 cm ³ / mol.   Hydroxyl equivalent weight is 240-800 g / eq. The hydroxy resin according to claim 1 or 2, which is in a range of From 1 mole of the divalent aromatic hydroxy compound (a) represented by the following general formula (5), from styrene represented by the following general formula (6) and indene represented by the following general formula (7) An aromatic modified hydroxy compound (c) modified with an aromatic olefin by reacting 0.2 to 3.5 mol of one or more selected aromatic olefins (b) in the presence of an acid catalyst. ), The aromatic modified hydroxy compound (c) is reacted with the bifunctional halogenated methyl group-containing compound (d) represented by the following general formula (8) in the presence of a basic substance. The method for producing a hydroxy resin according to claim 1.

(In the formula, A ₁ represents a divalent aromatic group having 6 to 50 carbon atoms.)

(Wherein, _{R 2} and _{R 3} independently represents a hydrocarbon group or a halogen atom having 1 to 10 carbon atoms, n and q is independently an integer of 0-3.)

(In the formula, A ₂ represents a divalent aromatic group having 6 to 50 carbon atoms, and X represents a halogen atom.)   A polar aprotic solvent having a boiling point of 185 ° C. or lower is used as the solvent for the divalent aromatic hydroxy compound (a) and the aromatic olefins (b), and the aromatic olefins (b) have a concentration of 0. 6. The method for producing a hydroxy resin according to claim 5, wherein the reaction is carried out at a temperature of 40 to 140 [deg.] C. in the presence of an acid catalyst of 01 to 1.0 mass%.   The divalent aromatic hydroxy compound (a) is a hydroxyphenol, dihydroxynaphthalene, dihydroxybiphenyl, dihydroxydiphenyl ether, dihydroxydiphenyl sulfide, dihydroxyphenylmethane, each of which a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom may be substituted. The method for producing a hydroxy resin according to claim 5, wherein the hydroxy resin is one or more compounds selected from the group consisting of dihydroxyphenylcyclohexane and dihydroxyphenyltrimethylcyclohexane.   An epoxy resin composition comprising the hydroxy resin according to any one of claims 1 to 4 and an epoxy resin as essential components.   An epoxy resin cured product obtained by curing the epoxy resin composition according to claim 8.

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