KR20240159464A - Phenolic hydroxyl-containing resin, curable composition, cured product, prepreg, circuit board, build-up film, semiconductor sealing material, and semiconductor device - Google Patents

Abstract

[Task] To provide a phenolic hydroxyl group-containing resin capable of achieving both excellent dielectric properties (low permittivity and low dielectric tangent) and high-temperature elastic modulus at a high level.
[Solution]
A phenolic hydroxyl group-containing resin which is a reaction product of a fluorene compound (provided that it does not have a substituent at the 9th position), a phenolic hydroxyl group-containing compound, and a compound represented by the general formula (1).

Description

Phenolic hydroxyl group-containing resin, curable composition, cured product, prepreg, circuit board, build-up film, semiconductor sealing material, and semiconductor device {PHENOLIC HYDROXYL-CONTAINING RESIN, CURABLE COMPOSITION, CURED PRODUCT, PREPREG, CIRCUIT BOARD, BUILD-UP FILM, SEMICONDUCTOR SEALING MATERIAL, AND SEMICONDUCTOR DEVICE}

The present invention relates to a phenolic hydroxyl group-containing resin, a curable composition, a cured product, a prepreg, a circuit board, a build-up film, a semiconductor encapsulating material, and a semiconductor device.

Epoxy resin compositions containing epoxy resins and their curing agents are widely used for electronic components such as semiconductors and multilayer printed circuit boards because the cured products exhibit excellent heat resistance and insulation properties.

However, against the backdrop of the high-speed and high-frequency signals in various recent electronic devices, it is becoming difficult to provide a resin composition that can form a cured product that exhibits a sufficiently low dielectric tangent while maintaining a sufficiently low permittivity.

In this regard, biphenyl aralkyl resins are attracting attention as materials with excellent dielectric properties, and are being introduced as curing agents for epoxy resins or as raw materials for epoxy resins (e.g., patent documents 1 to 5).

Japanese Special Publication No. 2003-301031 Japanese Special Publication No. 2006-342176 Japanese Special Publication No. 2007-308570 Japanese Special Publication No. 2003-113225 Japanese Special Publication No. 2010-229422

However, since a phenol resin having a biphenyl aralkyl structure forms a novolac-type resin based on a phenol structure, a cured product using it has a high crosslinking density and usually has a high elastic modulus even in a high temperature range (e.g., 200 to 280°C), so there is room for improvement in terms of elastic modulus.

There is still a need for a resin that can achieve both excellent dielectric properties and low elastic modulus in the high temperature range.

The present inventors, as a result of repeated studies to solve the above-described problems, have found that a phenolic hydroxyl group-containing resin having a structure in which the hydrogen atom at the 9th position of a fluorene structural unit is modified with aralkyl can achieve both excellent dielectric properties (low dielectric constant and low dielectric tangent) and low elastic modulus in a high temperature range to a high degree, thereby completing the present invention.

The gist of the present invention is as follows.

[1] A phenolic hydroxyl group-containing resin which is a reaction product of a fluorene compound (provided that it does not have a substituent at the 9th position), a phenolic hydroxyl group-containing compound, and a compound represented by the general formula (1).

(Here,

Ar is an aromatic ring group that may have a substituent,

R ¹ is, each independently, a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms,

X is a talisman)

[2] A phenolic hydroxyl group-containing resin according to [1], wherein the fluorene compound is present in an amount of 0.01 to 0.99 mol per 1 mol of the compound represented by the general formula (1).

[3] A resin containing a phenolic hydroxyl group, represented by the general formula (5).

(Here,

Z is, independently, the general formula (2A):

Structural units or general formulas represented by (3A):

is a structural unit represented by ,

Z' is, independently, the general formula (2A'):

Structural units or general formulas represented by (3A'):

It is a structural unit represented by

Ar is an aromatic ring group which may independently have a substituent,

R ¹ is, each independently, a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms,

R ² is, each independently, an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom,

m is an integer from 0 to 4, independently.

R ³ is, independently, an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom, or two R ³ may be combined with the carbon atom to which they are bonded to form a ring,

n is an integer from 0 to 3, each independently.

p is the mean and the number greater than 0,

R ^2' is, each independently, an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom,

m' is, independently, an integer from 0 to 4,

R ^3' may each independently be an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom, or two R ^3' may be combined with the carbon atom to which they are bonded to form a ring,

n' is an integer from 0 to 4, each independently,

However, the resin includes a structural unit represented by the general formula (2A) and/or the general formula (2A'), and a structural unit represented by the general formula (3A) and/or the general formula (3A').

[4] A phenolic hydroxyl group-containing resin according to [3], comprising at least one compound represented by general formula (5-1) and a compound represented by general formula (5-2).

(Here,

Ar, Z, R ¹ , R ^3' and n' are synonymous with [3])

[5] A phenolic hydroxyl group-containing resin of any one of [1] to [4], having a hydroxyl equivalent of 100 to 2000 g/eq.

[6] A phenolic hydroxyl group-containing resin having an average molecular weight of 100 to 10,000, and any one of [1] to [5].

[7] A curable composition containing a phenolic hydroxyl group-containing resin of any one of [1] to [6] and a curing agent.

[8] [7] A cured product of a curable composition.

[9] A prepreg having a reinforcing substrate and a semi-cured material of the curable composition of [7] impregnated into the reinforcing substrate.

[10] [9] A circuit board which is a laminate of prepreg and copper foil.

[11] A build-up film containing a curable composition of [7].

[12] A semiconductor encapsulating material containing a curable composition of [7].

[13] A semiconductor device comprising a cured product of a semiconductor encapsulating material of [12].

According to the present invention, it is possible to provide a phenolic hydroxyl group-containing resin capable of achieving both excellent dielectric properties (low permittivity and low dielectric tangent) and low elastic modulus in a high-temperature range to a high degree, and further, it is possible to provide a curable composition containing the phenolic hydroxyl group-containing resin and a cured product thereof. Furthermore, by using the curable composition or the cured product thereof, it is possible to provide a prepreg, a circuit board, a build-up film, a semiconductor encapsulating material, and a semiconductor device which achieve both excellent dielectric properties and low elastic modulus in a high-temperature range to a high degree.

[Figure 1] This is the result of GPC measurement of the phenolic hydroxyl group-containing resin synthesized in Example 1.
[Figure 2] This is the result of FD-MS measurement of the phenolic hydroxyl group-containing resin synthesized in Example 1.
[Figure 3] This is the result of ¹³ C-NMR measurement of the phenolic hydroxyl group-containing resin synthesized in Example 1.
[Figure 4] This is the result of GPC measurement of the phenolic hydroxyl group-containing resin synthesized in Example 2.
[Figure 5] This is the result of FD-MS measurement of the phenolic hydroxyl group-containing resin synthesized in Example 2.
[Figure 6] This is the result of ¹³ C-NMR measurement of the phenolic hydroxyl group-containing resin synthesized in Example 2.
[Figure 7] This is the result of GPC measurement of the phenolic hydroxyl group-containing resin synthesized in Example 3.
[Figure 8] This is the result of FD-MS measurement of the phenolic hydroxyl group-containing resin synthesized in Example 3.
[Figure 9] This is the result of ¹³ C-NMR measurement of the phenolic hydroxyl group-containing resin synthesized in Example 3.
[Figure 10] This is the result of GPC measurement of the phenolic hydroxyl group-containing resin synthesized in Example 4.
[Figure 11] This is the result of FD-MS measurement of the phenolic hydroxyl group-containing resin synthesized in Example 4.
[Figure 12] This is the result of ¹³ C-NMR measurement of the phenolic hydroxyl group-containing resin synthesized in Example 4.

Hereinafter, a detailed description will be given of a form for carrying out the invention, but the present invention is not limited to the description below, and can be carried out by making various modifications within the scope of the gist thereof.

[Term]

The term "reaction raw material" in this specification refers to a compound that is used to obtain a target compound through a chemical reaction such as combination or decomposition, and that partially constitutes the chemical structure of the target compound, and substances that play a role in facilitating the chemical reaction, such as a solvent or a catalyst, are excluded. In this specification, in particular, the term "reaction raw material" refers to a precursor for obtaining the target phenolic hydroxyl group-containing resin through a chemical reaction.

The term "structural unit" in this specification refers to a (repeating) unit of a chemical structure formed during a reaction or polymerization, and when reduced, refers to a partial structure other than the structure of the chemical bond involved in the reaction or polymerization in a product compound formed by the reaction or polymerization, and is the so-called residue.

The aliphatic hydrocarbon group in this specification may be any of straight-chain, branched, and cyclic types, and may have an unsaturated bond in its structure. Examples of the aliphatic hydrocarbon group include those having 1 to 20 carbon atoms.

The monovalent aliphatic hydrocarbon group in this specification includes an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and a cycloalkynyl group.

The alkyl group in the present specification may be either linear or branched, and may have 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, an amyl group, a cyclopentyl group, a hexyl group, a heptyl group, an octyl group, a cumyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and the like.

The alkenyl group in the present specification may be either linear or branched, and may have 2 to 20 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, a butadienyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, and the like.

The alkynyl group in the present specification may be either linear or branched, and may have 2 to 20 carbon atoms, and examples thereof include an ethynyl group, a propargyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, an undecynyl group, a dodecynyl group, and the like.

The cycloalkyl group in this specification may be a monocyclic group or a polycyclic group, and may have 3 to 30 carbon atoms, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a methylcyclohexyl group, an ethylcyclohexyl group, and the like.

The cycloalkenyl group in this specification may be a monocyclic group or a polycyclic group, and may have 3 to 30 carbon atoms, and examples thereof include a cyclohexenyl group, a methylcyclohexenyl group, and an ethylcyclohexenyl group.

The cycloalkynyl group in this specification may be a monocyclic group or a polycyclic group, and may have 4 to 30 carbon atoms, and examples thereof include a cyclohexynyl group, a methylcyclohexynyl group, an ethylcyclohexynyl group, and the like.

The divalent aliphatic hydrocarbon group in this specification includes an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkenylene group, and a cycloalkynylene group.

The alkylene group in this specification may be either linear or branched, and may have 1 to 20 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, and the like.

The alkenylene group in this specification may be either linear or branched, and may have 2 to 20 carbon atoms, and examples thereof include a vinylene group, a propenylene group, a butenylene group, a butadienylene group, an octenylene group, a decenylene group, a dodecenylene group, and the like.

The alkynylene group in the present specification may be either linear or branched, and may have 2 to 20 carbon atoms, and examples thereof include an ethynylene group, a propynylene group, a butynylene group, a butadienylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octynylene group, a nonynylene group, a decynylene group, an undecynylene group, a dodecynylene group, and the like.

The alkoxy group in this specification has a structure of alkyl-O-, and the description of the above alkyl group applies to the alkyl portion in the structure. Examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an allyloxy group, etc.

The cycloalkylene group in this specification may be a monocyclic group or a polycyclic group, and may have 3 to 30 carbon atoms. For example, it is a divalent group corresponding to the group exemplified as a cycloalkyl group.

The cycloalkenylene group in this specification may be a monocyclic group or a polycyclic group, and may have 3 to 30 carbon atoms. For example, it is a divalent group corresponding to the group exemplified as the cycloalkenyl group.

The cycloalkynylene group in this specification may be a monocyclic group or a polycyclic group, and may have 4 to 30 carbon atoms. For example, it is a divalent group corresponding to the group exemplified as a cycloalkynylene group.

The aromatic ring in this specification is a hydrocarbon ring consisting of a monocyclic ring or a condensed ring having aromaticity, and the number of carbon atoms may include 6 to 20, and examples thereof include a benzene ring, a naphthalene ring, an indene ring, an anthracene ring, and adamantane. The aromatic ring group is a residue of an aromatic ring.

The aryl group in this specification is a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and the like.

The arylalkyl group in the present specification is an alkyl group substituted with one or more aryl groups, preferably one or two, especially one, and with respect to the aryl group and the alkyl group, the description of the aryl group and the alkyl group above applies. Examples thereof include a benzyl group or a phenethyl group.

Halogen atoms in this specification are fluorine, chlorine, bromine and iodine.

The number average molecular weight (Mn) and weight average molecular weight (Mw) in this specification are values measured using gel permeation chromatography (hereinafter abbreviated as “GPC”) under the measurement conditions described in the examples described below.

The hydroxyl equivalent in this specification is a value measured by a titrimetric method. Here, the titrimetric method refers to a neutralization titrimetric method compliant with JIS K0070.

[Reaction raw material of phenolic hydroxyl group-containing resin]

The phenolic hydroxyl group-containing resin of the present invention uses a fluorene compound (provided that it does not have a substituent at the 9-position) (hereinafter, also simply referred to as a “fluorene compound”), a phenolic hydroxyl group-containing compound, and a compound represented by the general formula (1) as reaction raw materials.

<Fluorene compound>

The fluorene compound is not particularly limited as long as it does not have a substituent at the 9-position of fluorene, and may be unsubstituted or substituted at a position other than the 9-position.

As fluorene compounds, compounds represented by the following general formula (2) can be mentioned.

(Here,

m is an integer from 0 to 4, independently,

R ² is, each independently, an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom.

As the aliphatic hydrocarbon group, an alkyl group having 1 to 4 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, etc.

As the aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an indenyl group, and an indanyl group are preferable.

As the arylalkyl group, a benzyl group, a phenethyl group, and a cumyl group are preferable.

As the alkoxy group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are preferable.

As halogen atoms, fluorine, chlorine, and bromine are preferred.

m is, each independently, preferably an integer from 0 to 2, more preferably 0 or 1, and in particular 0.

The two m's may be the same or different, but it is preferable that they be the same.

When both m are 1 or greater, R ² substituted by the two benzene rings constituting the fluorene skeleton may be the same or different.

When m of one or both sides is 2 or more, two or more R ² substituted with the same benzene ring constituting the fluorene skeleton may be the same or different.

As a compound of general formula (2), fluorene can be preferably mentioned.

The compounds of general formula (2) can be used in combination of one or more types at any ratio.

<Phenolic hydroxyl group-containing compound>

A phenolic hydroxyl group-containing compound is a compound that has one phenolic hydroxyl group in the molecule.

As compounds containing phenolic hydroxyl groups, compounds represented by the following general formula (3) can be mentioned.

(Here,

n is an integer from 0 to 4,

R ³ is, each independently, an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom, or two R ^3'' may be combined with the carbon atom to which they are bonded to form a ring.

As the aliphatic hydrocarbon group, an alkyl group having 1 to 4 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.

As the aryl group, a phenyl group, a tolyl group, a xylyl group, and a naphthyl group are preferable.

As the arylalkyl group, a benzyl group, a phenethyl group, and a cumyl group are preferable.

As the alkoxy group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are preferable.

As halogen atoms, fluorine, chlorine, and bromine are preferred.

As R ³ , among them, an alkyl group or an aryl group is preferable.

Alternatively, the two R ^3'' may be combined with the carbon atoms to which they are bonded to form a ring. Examples of the ring include a hydrocarbon ring having 6 to 20 ring atoms, such as a benzene ring, a naphthalene ring, an anthracene ring, an adamantane ring, an indane ring, an indene ring, etc. These rings may have a substituent, and examples of the substituent include an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom.

n'' is preferably 0, 1 or 2.

When n'' is 2, it is preferable that the two R ^3'' become one with the carbon atoms to which they are bonded, forming a benzene ring or a naphthalene ring.

As preferred examples of compounds of general formula (3), the following compounds can be mentioned.

The compounds of general formula (3) can be used in combination of one or more types at any ratio.

<Compound represented by general formula (1)>

The compound represented by general formula (1) is a compound that can modify the hydrogen atom at position 9 of the fluorene structural unit into aralkyl, and can also react with a phenolic hydroxyl group-containing compound, and functions as a binder.

(Here,

Ar is an aromatic ring group that may have a substituent,

R ¹ is, each independently, a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms,

X is a talisman)

Ar is an aromatic cyclic group which may have a substituent. The aromatic cyclic group is not particularly limited, and a phenylene group, a naphthylene group, and an anthracenylene group are preferable. In the case of a phenylene group, it is preferable that there is a bond at the 1 and 4 positions, in the case of a naphthylene group, it is preferable that there is a bond at the 2 and 6 positions, and in the case of an anthracenylene group, it is preferable that there is a bond at the 9 and 10 positions.

As a substituent, an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom can be mentioned.

As the aliphatic hydrocarbon group, an alkyl group having 1 to 4 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, a propylene group, and a butylene group.

As the aryl group, a phenyl group, a tolyl group, a xylyl group, and a naphthyl group are preferable.

As the arylalkyl group, a benzyl group, a phenethyl group, and a cumyl group are preferable.

As the alkoxy group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are preferable.

As halogen atoms, fluorine, chlorine, and bromine are preferred.

As for the substituent, among them, an alkyl group, an aryl group, etc. are preferable.

X is a leaving group, and may be a hydroxyl group, a halogen atom, or an alkoxy group.

As halogen atoms, chlorine, bromine and iodine are preferred.

As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group.

As for X, among them, chlorine, bromine, iodine, hydroxyl and methoxy groups are preferable.

The two Xs can be the same or different.

R ¹ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

The aliphatic hydrocarbon group having 1 to 4 carbon atoms is not particularly limited, and a methyl group, an ethyl group, a propyl group, a butyl group, etc. are preferable.

As R ¹ , among others, a hydrogen atom and methyl are preferable. Four R ¹ may be the same or different, but the same is preferable.

Preferable examples of compounds of general formula (1) include the following.

[Method for producing phenolic hydroxyl group-containing resin]

The phenolic hydroxyl group-containing resin of the present invention is a reaction product of the above-mentioned reaction raw materials, and can be specifically manufactured as follows.

The amounts of the reaction raw materials, fluorene compound, phenolic hydroxyl group-containing compound, and compound of general formula (1), are as follows.

For 1 mole of fluorene compound, the compound of general formula (1) may be present in an amount exceeding 1 mole from the viewpoint of introducing general formula (3), and there is no particular limitation as long as it is present in an amount exceeding 1 mole.

For example, the amount of the fluorene compound used may be 0.01 mol or more, preferably 0.05 mol or more, and may be 0.99 mol or less, preferably 0.9 mol or less, per 1 mol of the compound of general formula (1).

In the reaction, since substantially all of the fluorene compound and the compound of general formula (1) react, the molar ratio of the fluorene compound used in the reaction and the compound of general formula (1) is substantially the same as the molar ratio of the structural unit derived from the fluorene compound in the obtained phenolic hydroxyl group-containing resin and the structural unit derived from the compound of general formula (1).

The amount of the phenolic hydroxyl group-containing compound to be used is not particularly limited, but with respect to the compound of general formula (1), the amount of the hydroxyl group of the phenolic hydroxyl group-containing compound can be 0.1 mol or more, preferably 0.02 mol or more, and further, the amount can be 10 mol or less, preferably 9.5 mol or less.

For phenolic hydroxyl group-containing compounds, unreacted residual phenolic hydroxyl group-containing compounds are also generated, but the amount of reacted phenolic hydroxyl group-containing compounds can be calculated from the hydroxyl group equivalent of the phenolic hydroxyl group-containing resin.

A phenolic hydroxyl group-containing resin can be manufactured, for example, by the following processes 1 and 2.

<Process 1>

It is preferable to react the entire amount of the fluorene compound and the entire amount of the compound of general formula (1) in an organic solvent using an alkaline catalyst without adding a phenolic hydroxyl group-containing compound at 10 to 100°C, or to react the entire amount of the fluorene compound and the entire amount of the compound of general formula (1) with part or all of the amount of the phenolic hydroxyl group-containing compound in an organic solvent using an alkaline catalyst at 10 to 100°C.

The amount of the phenolic hydroxyl group-containing compound to be used is not particularly limited, but with respect to the general formula (1), the amount of the hydroxyl group of the phenolic hydroxyl group-containing compound can be 0.1 mol or more, preferably 0.2 mol or more, and further, the amount can be 10 mol or less, preferably 9.5 mol or less. By using such an amount, the production of by-products can be suppressed.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, and sorbetho; alcohol solvents such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, sec-butanol, and tert-butanol; cellosolve solvents such as methyl cellosolve and ethyl cellosolve; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane; and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, and dimethylacetamide. In terms of solubility, toluene, xylene, mesitylene, sorbetho, isopropyl alcohol, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, etc. are preferable. These organic solvents may be used alone or in combination of two or more in any ratio.

The amount of organic solvent used is not particularly limited, but is preferably 50 to 500 mass% based on the total amount of the compound of general formula (1) and the fluorene compound introduced.

Examples of the alkaline catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methoxy, sodium ethoxy, tert-sodium butoxy, potassium methoxy, potassium ethoxy, potassium tert-butoxy, triethylamine, pyridine, dimethylaminopyridine, etc. In terms of reactivity, sodium hydroxide or potassium hydroxide is preferable. The amount of the alkaline catalyst to be used can be 10 to 1000 mol% with respect to the general formula (1) introduced. These catalysts can be used as a 1 to 50 mass% aqueous solution.

A phase transfer catalyst may be used in the reaction. Examples of the phase transfer catalyst include ammonium types such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium, tetrabutylammonium iodide, tetrabutylammonium hydroxide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltriethylammonium iodide, and benzyltriethylammonium hydroxide; phosphonium types such as tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, and tetrabutylphosphonium hydroxide; and crown ether types such as 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, and tribenzo-18-crown-6-ether. In terms of reactivity, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, and benzyltriethylammonium iodide are preferable. The phase transfer catalyst may be used alone or in combination of two or more.

Additives may be used to promote the reaction. Examples of additives include halides such as lithium bromide, sodium bromide, potassium bromide, cesium bromide, lithium iodide, sodium iodide, potassium iodide, and cesium iodide. Among them, sodium iodide and potassium iodide are preferable. The additives may be used alone or in combination of two or more.

The reaction temperature can be 10 to 100°C, and from the viewpoint of reactivity, it is preferably 20 to 80°C. The reaction time can be 1 to 72 hours, and is preferably 2 to 70 hours.

After the reaction is completed, the reaction product is separated into upper and lower layers, and the lower layer, which is the aqueous layer, is removed to obtain the reactant. At that time, if necessary, water may be added to dissolve the insoluble salt and the lower layer may be removed. In addition, the aqueous layer may be alkaline, neutralized by neutralization, or acidic. Neutralizing agents used for neutralization include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, sodium phosphate monobasic, and ammonium chloride; and organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts may be used alone or in combination of two or more.

<Process 2>

In the case where the phenolic hydroxyl compound is not added in process 1 or is added in part to cause the reaction, the entire amount or the remainder of the phenolic hydroxyl compound is added to the reactant obtained in process 1, and the reaction is performed at 60 to 250°C in the presence of an acid catalyst. In the case where the entire amount of the phenolic hydroxyl compound is added in process 1, the reactant obtained in process 1 is reacted at 60 to 250°C in the presence of an acid catalyst.

The phenolic hydroxyl group-containing compound used in process 2 may be the same as or different from the phenolic hydroxyl group-containing compound used in process 1.

Examples of acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid; and Lewis acids such as boron trifluoride, aluminum chloride, and zinc chloride. In terms of solubility, p-toluenesulfonic acid, methanesulfonic acid, and the like are preferable. These acid catalysts may be used alone or in combination of two or more.

The amount of acid catalyst is not particularly limited, but is preferably 0.001 to 10 mass% of the total amount of reactant materials introduced.

The reaction temperature is set to 60 to 250°C, and from the viewpoint of reactivity, it is preferably 80 to 240°C. The reaction time can be 1 to 72 hours, and is preferably 2 to 70 hours.

After the reaction is completed, neutralization treatment and water washing treatment are performed, and unreacted reaction raw materials, organic solvents, etc. are distilled off under reduced pressure and heating conditions to obtain a phenolic hydroxyl group-containing resin.

The method for producing a phenolic hydroxyl group-containing resin of the present invention is not limited to the above. For example, instead of step 1, a fluorene compound and a compound of general formula (1) may be reacted in an organic solvent in the presence of a catalyst at 10 to 100°C, then a portion of the phenolic hydroxyl group-containing compound may be added, and the reaction may be performed at 10 to 100°C, after which the aqueous layer may be removed, a water washing treatment may be performed, and the resulting reaction product may be subjected to step 2. At that time, the reaction product of step 1 may have a reactive group at the terminal, and the reactive group may be an ether reacted with phenols, a halide, or a hydroxyl group, depending on the type of compound used.

[Phenolic hydroxyl group containing resin]

The phenolic hydroxyl group-containing resin of the present invention is a reaction product of a fluorene compound, a phenolic hydroxyl group-containing compound, and a compound of general formula (1).

The fluorene compound represented by general formula (2), the phenolic hydroxyl group-containing compound represented by general formula (3), and the compound of general formula (1) can each produce a structural unit represented by general formula (2A) or general formula (2A'), a structural unit represented by general formula (3A) or general formula (3A'), and a structural unit represented by general formula (1A).

(Here,

The definitions, examples and preferred examples of m and m' are the same as m in general formula (2),

The definitions, examples and preferred examples of R ² and R ^2' are the same as R ² of general formula (2).

* indicates the number of combinations, respectively)

(Here,

n is an integer from 0 to 3, preferably 0, 1 or 2,

n' is an integer from 0 to 4, preferably 0, 1 or 2,

The definitions, examples and preferred examples of R ³ and R ^3' are the same as R'' of general formula (3),

* indicates the number of combinations, respectively)

(Here,

The definitions, examples and preferred examples of Ar and R ¹ are the same as in general formula (1).

* indicates the number of combinations, respectively)

The phenolic hydroxyl group-containing resin of the present invention may include a structure in which the structural unit of general formula (1A) is bonded to the structural unit of general formula (2A) and/or (2A').

At least one molecular chain terminal of the phenolic hydroxyl group-containing resin of the present invention is preferably a structural unit of general formula (3A'), and both molecular chain terminals are more preferably a structural unit of general formula (3A').

The phenolic hydroxyl group-containing resin of the present invention is composed of structural units of general formula (2A) and/or (2A'), structural units of general formula (3A) and/or (3A'), and structural units of general formula (1A), provided that the number of bonds of the structural unit of general formula (2A) may be bonded to the number of bonds of the structural unit of general formula (1A). When the structural unit of general formula (2A') is present, the structural unit constitutes a molecular chain terminal.

It is preferable that at least one of the molecular chain terminals is a structural unit of general formula (3A), and more preferably, both molecular chain terminals are structural units of general formula (3A).

Preferable examples of compounds of general formula (1-1) include the following.

As the phenolic hydroxyl group-containing resin of the present invention, a phenolic hydroxyl group-containing resin represented by the following general formula (5) can be exemplified.

(Here,

Z is, independently, the general formula (2A):

Structural units or general formulas represented by (3A):

is a structural unit represented by ,

Z' is, independently, the general formula (2A'):

Structural units or general formulas represented by (3A'):

It is a structural unit represented by

Ar is an aromatic ring group which may independently have a substituent,

R ¹ is, each independently, a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms,

R ² is, each independently, an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom,

m is an integer from 0 to 4, independently.

R ³ is, independently, an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom, or two R ³ may be combined with the carbon atom to which they are bonded to form a ring,

n is an integer from 0 to 3, each independently.

R ^2' is, each independently, an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom,

m' is an integer from 0 to 4, independently.

R ^3' is, independently, an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom, or two R ^3' may be combined with the carbon atom to which they are bonded to form a ring,

n' is an integer from 0 to 4, each independently.

p is the mean and the number greater than 0,

However, the resin includes a structural unit represented by the general formula (2A) and/or the general formula (2A'), and a structural unit represented by the general formula (3A) and/or the general formula (3A').

In the above, examples and preferred examples of Ar, R ¹ , R ² , R ³ , m, n, R ^2' , R ^3' , m', n' and p are the same as above.

The phenolic hydroxyl group-containing resin of general formula (5) is a mixture of compounds in which p of the general formula (5) is an integer greater than or equal to 0 (provided that not all of the compounds are compounds of general formula (5) in which p is 0), and preferably includes a compound containing both a structural unit represented by general formula (2A) and/or general formula (2A') and a structural unit represented by general formula (3A) and/or general formula (3A') in the molecule.

Among the resins, the total of the structural units of the general formula (3A) and the general formula (3A') is preferably 0.1 to 10 mol, and more preferably 0.5 to 9.5 mol, for 1 mol of the total of the structural units of the general formula (3A) and the general formula (3A').

As a preferred example, a phenolic hydroxyl group-containing resin represented by the following general formula (5-0) can be mentioned.

(In the formula, Ar, R ¹ , R ^3' , n' and p are the same as in general formula (5))

Here, examples and preferred examples of Ar, R ¹ , R ^3' , n' and p are the same as above. In addition, examples and preferred examples of R ² , m, R ³ and n in Z are also the same as above.

A more preferable example of the phenolic hydroxyl group-containing resin of the present invention is a phenolic hydroxyl group-containing resin represented by the following general formula (5-0').

(Here, R ² , m, R ³ , n, R ^3' and n' are as above,

Ar' is,

And,

s is the mean and is a number greater than 0,

t is the mean and is a number greater than or equal to 0,

The order of the structural units grouped by s and the structural units grouped by t is not limited.)

The phenolic hydroxyl group-containing resin of general formula (5) and the phenolic hydroxyl group-containing resin of general formula (5-0) can be a mixture of compounds each having a structural unit grouped with p as an integer greater than or equal to 0, but it is assumed that not all of the compounds are compounds of general formula (5) in which p is 0. It is preferable that the phenolic hydroxyl group-containing resin of general formula (5) contains at least one of a compound represented by general formula (5-1) and a compound represented by general formula (5-2).

(Here,

Ar, Z, R ¹ , R ^3' and n' are as above,

Z of general formula (5-1) and at least one Z of general formula (5-2) are structural units represented by general formula (2A)

The phenolic hydroxyl resin of the present invention may contain a compound of general formula (6) as part of its composition. The compound of general formula (6) corresponds to a compound in which p is 0 in the general formula (5).

(Here,

Ar, R ¹ , R ^3' and n' are as above)

The number average molecular weight (Mn) of the phenolic hydroxyl group-containing resin can be in the range of 100 to 10,000, and is preferably in the range of 200 to 8,000. In addition, the (Mw) of the phenolic hydroxyl group-containing resin can be in the range of 100 to 50,000, and is preferably in the range of 300 to 4,000.

The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the phenolic hydroxyl group-containing resin can be in the range of 1 to 5, and is preferably 1 to 4.

The hydroxyl equivalent of the phenolic hydroxyl group-containing resin can be in the range of 100 to 2000, and is preferably in the range of 200 to 1800.

[Curing composition]

The curable composition of the present invention can contain the phenolic hydroxyl group-containing resin of the present invention and a curing agent. By using the phenolic hydroxyl group-containing resin of the present invention, a cured product obtained from the curable composition can exhibit excellent dielectric properties (low dielectric constant and low dielectric tangent) and low elastic modulus in a high temperature range.

The curing composition may contain other phenolic hydroxyl group-containing compounds other than the phenolic hydroxyl group-containing resin of the present invention. Examples of the other phenolic hydroxyl group-containing compounds include various bisphenol compounds, various novolak resins, aralkylene group-containing phenol resins, and the like. These may be used alone or in combination of two or more. The ratio of the phenolic hydroxyl group-containing resin of the present invention to the total of the phenolic hydroxyl group-containing resin of the present invention and the other phenolic hydroxyl group-containing compounds may be appropriately adjusted depending on the desired cured product performance, etc., but is preferably 50 mass% or more, and more preferably 80 mass% or more.

The curing agent is not particularly limited as long as it is a compound having a functional group capable of reacting with the phenolic hydroxyl group-containing resin of the present invention, and examples thereof include epoxy resins. The epoxy resins are not particularly limited, and a wide variety of ones can be used. Examples thereof include various bisphenol-type epoxy resins, various novolac-type epoxy resins, and aralkylene group-containing epoxy resins. Each of these may be used alone, or multiple types may be used in combination.

The mixing ratio of the phenolic hydroxyl group-containing resin and the curing agent is appropriately adjusted depending on the desired cured product performance, etc., but it is preferable that the reactive group in the curing agent is in the range of 0.5 to 1.5 mol per 1 mol of the phenolic hydroxyl group in the phenolic hydroxyl group-containing resin. When using other phenolic hydroxyl group-containing compounds described above, it is preferable that the reactive group in the curing agent is in the range of 0.5 to 1.5 mol per 1 mol of the total of the phenolic hydroxyl groups in the curable composition.

When using an epoxy resin as the above-mentioned curing agent, a curing accelerator may be used as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. Each of these may be used alone, or multiple types may be used in combination. Among these, phosphorus compounds such as triphenylphosphine, or imidazoles are preferable in terms of excellent curing properties, heat resistance, electrical properties, moisture resistance reliability, and the like. The amount of the curing accelerator to be added is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total mass of the curable composition (excluding the solvent), for example.

The above-mentioned curable composition may contain other resin components. Examples of other resins include activated ester resins, maleimide resins, cyanate resins, unsaturated polyester resins, and polybutadiene resins.

The curable composition may contain various compounding agents such as a curing accelerator, a silane coupling agent, a release agent, a pigment, an emulsifier, a non-halogenated flame retardant, an inorganic filler, a flame retardant (e.g., an inorganic phosphorus flame retardant, an organic phosphorus flame retardant, a halogenated flame retardant), a solvent, etc.

The curable composition can be obtained by uniformly mixing the phenolic hydroxyl group-containing resin of the present invention, the curing agent, and any optional components (e.g., a curing catalyst, a compounding agent, etc.).

[Curing]

The cured product of the present invention can be obtained by curing the curable composition of the present invention. The curing method is not particularly limited, and a known method can be adopted. The cured product can be in the form of a laminate, a molded product, an adhesive layer, a coating film, a film, or the like.

[Semiconductor encapsulation material]

The semiconductor encapsulating material of the present invention can contain the curable composition of the present invention. Since the curable composition of the present invention contains the phenolic hydroxyl group-containing resin of the present invention, the semiconductor encapsulating material containing the curable composition can exhibit excellent dielectric properties (low permittivity and low dielectric tangent) and low elastic modulus in a high temperature range.

For semiconductor encapsulating materials, a curable composition of the present invention containing an inorganic filler can be used. The inorganic filler is not particularly limited, and examples thereof include barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, and the like.

For 100 parts by mass of the curable composition, the inorganic filler can be used in an amount of 0.5 to 1200 parts by mass.

In the semiconductor encapsulating material, various compounding agents may be mixed, and examples of the compounding agent include those described with respect to the curable composition.

The semiconductor encapsulating material can be obtained by mixing the curable composition of the present invention and, if necessary, a compounding agent. Examples of the method include a method of sufficiently melting and mixing until uniform using an extruder, kneader, roll, etc.

[Semiconductor Device]

The semiconductor device of the present invention may include a cured product of the semiconductor encapsulating material of the present invention. The semiconductor encapsulating material used in the semiconductor device of the present invention contains a curable composition containing the phenolic hydroxyl group-containing resin of the present invention. Since the semiconductor device of the present invention includes a cured product of the semiconductor encapsulating material, it exhibits excellent dielectric properties (low permittivity and low dielectric tangent) and low elastic modulus in a high temperature range.

A semiconductor device can be obtained by heat-curing the semiconductor encapsulating material of the present invention, and examples thereof include a method of molding the semiconductor encapsulating material by using a molding machine, a transfer molding machine, an injection molding machine, or the like, and further heat-curing the semiconductor encapsulating material at a temperature range of room temperature (20°C) to 250°C.

[Prepreg]

The prepreg of the present invention can have a reinforcing substrate and a semi-cured curable composition of the present invention impregnated into the reinforcing substrate.

The method for obtaining a prepreg from a curable composition is not particularly limited, and an example thereof includes a method in which the curable composition, which is varnished by mixing an organic solvent described below, is impregnated into a reinforcing substrate (e.g., paper, glass cloth, glass nonwoven fabric, aramid paper, aramid fabric, glass mat, glass rubbing cloth, etc.), and then heated at a heating temperature (preferably 50 to 170°C) depending on the solvent used, thereby semi-curing (or not curing) the curable composition.

The mass ratio of the curable composition and the reinforcing substrate used is not particularly limited, but it is preferable to prepare it so that the resin content in the prepreg is 20 to 60 mass%.

The semi-cured product of the curable composition can be obtained by adjusting the heating temperature and heating time so that the curing reaction is stopped in the middle without being completed. The degree of curing of the semi-cured product can be, for example, 85% or less and 5% or more. Here, the cured product can have a degree of curing higher than that of the semi-cured product.

The degree of curing of a semi-cured product can be calculated from the following equation by measuring the curing exotherm when heating a curable composition and the curing exotherm of the semi-cured product using DSC.

Degree of cure (%) = [1 - (curing heat of semi-cured material / curing heat of curable composition)] × 100

Examples of organic solvents used in the manufacture of prepregs include methyl ethyl ketone, acetone, dimethyl formamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. The selection and usage amount of the organic solvent can be appropriately selected depending on the application, and for example, when manufacturing a circuit board from a prepreg, a polar solvent having a boiling point of 160°C or lower, such as methyl ethyl ketone, acetone, and dimethyl formamide, is preferable, and the usage amount is preferably an amount such that the nonvolatile content is 40 to 80 mass%.

[Circuit board]

The circuit board of the present invention is formed by a laminate of the prepreg of the present invention and the copper foil. The method for obtaining the circuit board is not particularly limited, and for example, a method may be exemplified in which the prepreg of the present invention is laminated as necessary, copper foil is overlapped, and then heat-pressed at 170 to 300° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.

[Build-up film]

The build-up film of the present invention can contain the curable composition of the present invention. The method for producing the build-up film is not particularly limited, and for example, a method of applying the curable composition of the present invention onto a support film and forming a curable composition layer to form an adhesive film for a multilayer printed wiring board can be exemplified.

Since the build-up film is required to soften under the temperature conditions of lamination in the vacuum lamination method (normally 70 to 140°C) and to exhibit fluidity (resin flow) that enables resin filling in via holes or through holes existing in the circuit board at the same time as the circuit board is laminated, it is preferable that the curable composition be blended with the above-mentioned respective components so as to exhibit such characteristics.

Here, the diameter of the through-hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually desirable to enable resin filling within this range. Also, when laminating both sides of the circuit board, it is desirable that about half of the through-hole is filled.

The method for manufacturing the above-mentioned adhesive film can be produced by, specifically, preparing the above-mentioned curable composition in a varnish form, applying the varnish form composition to the surface of a support film (Y), and further drying the organic solvent by heating or hot air spraying, etc., to form a composition layer (X) made of the curable composition.

The thickness of the composition layer (X) formed is preferably set to be equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 ㎛, the thickness of the resin composition layer is preferably set to be 10 to 100 ㎛.

In addition, the composition layer (X) may be protected with a protective film as described later. By protecting with a protective film, attachment of foreign substances or scratches to the surface of the resin composition layer can be prevented.

The above-mentioned support film (Y) and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate, polycarbonate, polyimide, and metal foils such as release paper, copper foil, and aluminum foil. In addition, the support film and protective film may be subjected to release treatment in addition to matte treatment and corona treatment.

The thickness of the support film is not particularly limited, but is usually 10 to 150 ㎛, and preferably 25 to 50 ㎛. In addition, the thickness of the protective film is preferably 1 to 40 ㎛.

The above-mentioned support film (Y) is peeled off after laminating it on the circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after heat curing the adhesive film, adhesion of foreign substances, etc. during the curing process can be prevented. When peeling is performed after curing, the support film is usually subjected to a release treatment in advance.

[use]

The cured product obtained by the curable composition containing the phenolic hydroxyl group-containing resin of the present invention can be suitably used for heat-resistant members or electronic members, since it exhibits excellent dielectric properties (low permittivity and low dielectric tangent) and low elastic modulus in a high temperature range. In particular, it can be suitably used for prepregs, circuit boards, semiconductor encapsulating materials, semiconductor devices, build-up films, build-up boards, adhesives or resist materials using conductive pastes, and the like. In addition, it can be suitably used for a matrix resin of a fiber-reinforced resin, and is particularly suitable as a high-heat-resistant prepreg. Furthermore, the phenolic hydroxyl group-containing resin included in the curable composition can be used as a paint, since it exhibits excellent solubility in various solvents. The heat-resistant materials and electronic materials obtained in this way can be suitably used in various applications, and examples thereof include, but are not limited to, industrial machinery parts, general machinery parts, automobile, railway, and vehicle parts, space and aviation-related parts, electronic and electrical parts, building materials, container and packaging materials, household goods, sports and leisure goods, and casing materials for wind power generation.

[Example]

The present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the description below, and can be implemented by making various modifications within the scope of the gist thereof. In the following, “part” and “%” are based on mass, unless otherwise specified.

The physical properties of the phenolic hydroxyl group-containing resin were evaluated as follows.

(1) GPC measurement

Using the following measuring device and measuring conditions, the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw/Mn) of the phenolic hydroxyl group-containing resin obtained in the examples and comparative examples were calculated.

"Measuring Device"

"HLC-8320 GPC" manufactured by Dosogabushiki Kaisha

"Measurement conditions"

Column: Toso Kabushiki Kaisha Guard Column "HXL-L" + Toso Kabushiki Kaisha "TSK-GEL G2000HXL" + Toso Kabushiki Kaisha "TSK-GEL G2000HXL" + Toso Kabushiki Kaisha "TSK-GEL G3000HXL" + Toso Kabushiki Kaisha "TSK-GEL G4000HXL"

Detector: RI (Differential Refractometer)

Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Dosogabushiki Kaisha

Measurement conditions: Column temperature 40℃

Developing solvent: tetrahydrofuran

Flow rate 1.0ml/min

Standard: In accordance with the measurement manual of the above "GPC Workstation EcoSEC-WorkStation", the following monodisperse polystyrene with a known molecular weight was used.

(Used polystyrene)

"A-500" manufactured by Dosogabushiki Kaisha

"A-1000" manufactured by Dosogabushiki Kaisha

"A-2500" manufactured by Dosogabushiki Kaisha

"A-5000" manufactured by Dosogabushiki Kaisha

Dosogabushiki Kaisha "F-1"

Dosogabushiki Kaisha "F-2"

Dosogabushiki Kaisha "F-4"

Dosogabushiki Kaisha "F-10"

"F-20" by Dosogabushiki Kaisha

"F-40" manufactured by Tosogabushiki Kaisha

"F-80" manufactured by Tosogabushiki Kaisha

"F-128" by Dosogabushiki Kaisha

Sample: A 1.0 mass% tetrahydrofuran solution (in terms of resin solids) of the phenolic hydroxyl group-containing resin obtained in the synthesis example was filtered through a microfilter (50 μl).

(2) FD-MS measurement

The FD-MS spectrum of the phenolic hydroxyl group-containing resin obtained in the example was measured using the following measuring device and measuring conditions.

Measuring device: JMS-T100GC AccuTOF

Measurement conditions

Measurement range: m/z=4.00~2000.00

Rate of change: 51.2mA/min

Final current value: 45mA

Cathode voltage: -10kV

Record interval: 0.07 seconds

(3) ¹³ C-NMR measurement

The ¹³ C-NMR spectrum of the phenolic hydroxyl group-containing resin obtained in the example was measured using the following measuring device and measuring conditions.

¹³ C-NMR: “JNM-ECZ400S” manufactured by JEOL RESONANCE

Resonance frequency: 100MHz

Number of accumulations: 4000

Solvent: Chloroform-d

Sample concentration: 12 mass%

Easing agent: Chromium (III) acetylacetonate

<Example 1: Synthesis of phenolic hydroxyl group-containing resin (A-1)>

In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 100.0 parts by mass of fluorene, 273.4 parts by mass of α,α'-dichloro-p-xylene (hereinafter abbreviated as PXDC), 147.0 parts by mass of phenol, 520.4 parts by mass of toluene, and 520.4 parts by mass of dimethyl sulfoxide (hereinafter abbreviated as DMSO) were charged, and the temperature was raised to 40°C and homogenized. Subsequently, 269.4 parts by mass of a 49 mass% sodium hydroxide aqueous solution was added dropwise while being careful not to generate heat so that the temperature became 60°C or lower. After the dropping, the temperature was raised to 60°C, and after reacting at the same temperature for 8 hours, 383.9 parts by mass of water was charged, the insoluble salt was dissolved, and the lower layer was removed by liquid separation. Subsequently, the organic layer was neutralized with 6.88 parts by mass of an 89 mass% phosphoric acid aqueous solution, and then washed three times with 383.9 parts by mass of water.

Next, 283.1 parts by mass of phenol and 10.4 parts by mass of p-toluenesulfonic acid monohydrate were charged, and the temperature was raised to 160°C while causing an azeotrope of water and the solvent, and reacted at the same temperature for 3 hours. After completion of the reaction, the reaction was cooled, and the organic layer was neutralized with 4.52 parts by mass of a 49 mass% sodium hydroxide aqueous solution, and 812.8 parts by mass of methyl isobutyl ketone was charged, and the temperature was cooled to 80°C, and washed three times with 575.8 parts by mass of water at the same temperature. The obtained organic layer was heated and distilled under reduced pressure to remove all volatile matter, thereby obtaining a phenolic hydroxyl group-containing resin (A-1).

The GPC chart of the obtained phenolic hydroxyl group-containing resin (A-1) is shown in Fig. 1, ^{the 13C} -NMR chart in Fig. 2, and the FD-MS chart in Fig. 3.

According to the GPC chart of Fig. 1, the Mn of the obtained phenolic hydroxyl group-containing resin (A) was 587, the Mw was 879, and the Mw/Mn was 1.497. According to the ^13C -NMR chart of Fig. 2, it was confirmed that the reaction occurred from the 9-position of fluorene, and according to the FD-MS chart of Fig. 3, from m/z 558.3, 754.4, and 826.4, it was confirmed that the obtained phenolic hydroxyl group-containing resin (A) was the phenolic hydroxyl group-containing resin of the present invention. In addition, the hydroxyl equivalent of the obtained phenolic hydroxyl group-containing resin (A-1) was 225 g/eq, and the softening point was 56°C.

<Example 2: Synthesis of phenolic hydroxyl group-containing resin (A-2)>

In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 100.0 parts by mass of fluorene, 210.6 parts by mass of PXDC, 130.1 parts by mass of orthocresol, 440.7 parts by mass of toluene, and 440.7 parts by mass of DMSO were charged, and the temperature was raised to 40°C and homogenized. Subsequently, 297.7 parts by mass of a 49 mass% sodium hydroxide aqueous solution was added dropwise while being careful not to generate heat so that the temperature became 60°C or lower. After the dropping, the temperature was raised to 60°C, and after reacting at the same temperature for 8 hours, 424.2 parts by mass of water was charged, the insoluble salt was dissolved, and the lower layer was removed by liquid separation. Subsequently, the organic layer was neutralized with 3.97 parts by mass of an 89 mass% phosphoric acid aqueous solution, and then washed three times with 424.2 parts by mass of water.

Next, 325.3 parts by mass of orthocresol and 8.81 parts by mass of p-toluenesulfonic acid monohydrate were charged, the temperature was raised to 160°C while causing an azeotrope of water and the solvent, and the reaction was performed at the same temperature for 3 hours. After completion of the reaction, the reaction was cooled, and the organic layer was neutralized with 3.83 parts by mass of a 49 mass% sodium hydroxide aqueous solution, and 661.1 parts by mass of toluene was charged, the temperature was cooled to 80°C, and the mixture was washed three times with 424.2 parts by mass of water at the same temperature. The obtained organic layer was heated and distilled under reduced pressure to remove all volatile matter, thereby obtaining a phenolic hydroxyl group-containing resin (A-2).

The GPC chart of the obtained phenolic hydroxyl group-containing resin (A-2) is shown in Fig. 4, the ^13C -NMR chart is shown in Fig. 5, and the FD-MS chart is shown in Fig. 6. According to the GPC chart of Fig. 4, the Mn of the obtained phenolic hydroxyl group-containing resin (A-2) was 564, the Mw was 742, and the Mw/Mn was 1.315. According to the ^13C -NMR chart of Fig. 5, it was confirmed that the reaction occurred from the 9-position of fluorene, and according to the FD-MS chart of Fig. 6, from M/z 586.4, 796.5, and 1064.7, it was confirmed that the obtained phenolic hydroxyl group-containing resin (A-2) was the phenolic hydroxyl group-containing resin of the present invention. In addition, the hydroxyl equivalent of the obtained phenolic hydroxyl group-containing resin (A-2) was 254 g/eq, and the softening point was 55°C.

<Example 3: Synthesis of phenolic hydroxyl group-containing resin (A-3)>

In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 75.0 parts by mass of fluorene, 158.0 parts by mass of PXDC, 110.3 parts by mass of 2,6-dimethylphenol, 343.2 parts by mass of toluene, and 343.2 parts by mass of DMSO were charged, and the temperature was raised to 40°C and homogenized. Subsequently, 223.3 parts by mass of a 49 mass% sodium hydroxide aqueous solution was added dropwise while being careful not to generate heat so that the temperature became 60°C or lower. After the dropping, the temperature was raised to 60°C, and after reacting at the same temperature for 8 hours, 318.2 parts by mass of water was charged, the insoluble salt was dissolved, and the lower layer was removed by liquid separation. Subsequently, the organic layer was neutralized with 2.98 parts by mass of an 89 mass% phosphoric acid aqueous solution, and then washed three times with 318.2 parts by mass of water.

Next, 165.4 parts by mass of 2,6-dimethylphenol and 6.86 parts by mass of p-toluenesulfonic acid monohydrate were charged, the temperature was raised to 160°C while causing an azeotrope of water and the solvent, and the reaction was performed at the same temperature for 3 hours. After completion of the reaction, the reaction was cooled, and the organic layer was neutralized with 2.98 parts by mass of a 49 mass% sodium hydroxide aqueous solution, 343.2 parts by mass of toluene was charged, and the temperature was cooled to 80°C, and washed three times with 318.2 parts by mass of water at the same temperature. The obtained organic layer was heated and distilled under reduced pressure to remove all volatile matter, thereby obtaining a phenolic hydroxyl group-containing resin (A-3).

The GPC chart of the obtained phenolic hydroxyl group-containing resin (A-3) is shown in Fig. 7, the ^13C -NMR chart is shown in Fig. 8, and the FD-MS chart is shown in Fig. 9. According to the GPC chart of Fig. 7, the Mn of the obtained phenolic hydroxyl group-containing resin (A-3) was 699, the Mw was 1079, and the Mw/Mn was 1.544. According to the ^13C -NMR chart of Fig. 8, it was confirmed that the reaction occurred from the 9-position of fluorene, and according to the FD-MS chart of Fig. 9, it was confirmed that the obtained phenolic hydroxyl group-containing resin (A-2) was the phenolic hydroxyl group-containing resin of the present invention from m/z 614.4 and 838.5. In addition, the hydroxyl equivalent of the obtained phenolic hydroxyl group-containing resin (A-3) was 271 g/eq, and the softening point was 83°C.

<Example 4: Synthesis of phenolic hydroxyl group-containing resin (A-4)>

In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 75.0 parts by mass of fluorene, 158.0 parts by mass of PXDC, 130.1 parts by mass of β-naphthol, 363.1 parts by mass of toluene, and 363.1 parts by mass of DMSO were charged, and the temperature was raised to 40°C and homogenized. Subsequently, 223.3 parts by mass of a 49 mass% sodium hydroxide aqueous solution was added dropwise while being careful not to generate heat so that the temperature became 60°C or lower. After the dropping, the temperature was raised to 60°C, and after reacting at the same temperature for 8 hours, 318.2 parts by mass of water was charged, the insoluble salt was dissolved, and the lower layer was removed by liquid separation. Subsequently, the organic layer was neutralized with 2.98 parts by mass of an 89 mass% phosphoric acid aqueous solution, and then washed three times with 318.2 parts by mass of water.

Next, 195.2 parts by mass of β-naphthol and 7.26 parts by mass of p-toluenesulfonic acid monohydrate were charged, the temperature was raised to 160°C while causing an azeotrope of water and the solvent, and the reaction was performed at the same temperature for 3 hours. After completion of the reaction, the reaction was cooled, and the organic layer was neutralized with 3.15 parts by mass of a 49 mass% sodium hydroxide aqueous solution, and 544.6 parts by mass of toluene was charged, cooled to 80°C, and washed three times with 435.7 parts by mass of isopropyl alcohol and 318.2 parts by mass of water. The obtained organic layer was heated and distilled under reduced pressure to remove all volatile matter, thereby obtaining a phenolic hydroxyl group-containing resin (A-4).

The GPC chart of the obtained phenolic hydroxyl group-containing resin (A-4) is shown in Fig. 10, the ^13C -NMR chart is shown in Fig. 11, and the FD-MS chart is shown in Fig. 12. According to the GPC chart of Fig. 9, the Mn of the obtained phenolic hydroxyl group-containing resin (A-4) was 366, the Mw was 746, and the Mw/Mn was 2.037. According to the ^13C -NMR chart of Fig. 5, it was confirmed that the reaction occurred from the 9-position of fluorene. According to the FD-MS chart of Fig. 6, it was confirmed that the obtained phenolic hydroxyl group-containing resin (A-2) was the phenolic hydroxyl group-containing resin of the present invention from m/z 658.4, 904.5, and 1172.7. In addition, the hydroxyl equivalent of the obtained phenolic hydroxyl group-containing resin (A-3) was 337 g/eq and the softening point was 81°C.

A cured product of a synthetic phenolic hydroxyl group-containing resin was prepared, and its physical properties were evaluated as follows. The results are shown in Table 1.

(1) Measurement of dielectric constant and dielectric tangent

In accordance with JIS-C-6481, the permittivity and dielectric loss tangent at 1 GHz and 10 GHz of the test specimens were measured using an impedance material analyzer "HP4291B" manufactured by Agilent Technologies, Inc., after they were stored indoors at 23°C and 50% humidity for 24 hours after drying.

(2) Method for measuring elastic modulus at high temperature

The storage elastic modulus at 260°C was measured as the thermal elastic modulus using a viscoelasticity measuring device (DMA: Rheometric solid viscoelasticity measuring device RSAII, rectangular tension method; frequency 1 Hz, heating rate 3°C/min).

<Examples 5 to 8 and Comparative Example 1>

(1) Preparation of test specimens

The cresol novolac epoxy resin (EPICLON N-655-EXP-S manufactured by DIC Corporation, epoxy equivalent: 204 g/eq) and the phenolic hydroxyl group-containing resin (A) of Example 1, the phenolic hydroxyl group-containing resin (B) of Example 2, or the biphenyl aralkyl phenol resin (MEHC-7851SS manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent: 212 g/eq) were heated and melted at 130 to 150°C in the mass ratios shown in Table 1, and after uniformity, a catalyst (triphenylphosphine, hereinafter abbreviated as TPP) was added to obtain a resin composition. The obtained resin composition was pressed with a 150°C press for 10 minutes, cured, molded, and then further heated at 175°C for 5 hours to obtain a test piece. The physical properties of the obtained test piece were measured. The results are shown in Table 1.

[Table 1]

From the results shown in Table 1 above, it can be seen that by using the phenolic hydroxyl group-containing resins of Examples 1 to 4, excellent dielectric properties (low dielectric constant and low dielectric tangent) are obtained, and further, low elastic modulus in the high temperature range is achieved. It can be seen that when the phenolic hydroxyl group-containing resin of Example 2 is used, the thermal elastic modulus is also excellent.

According to the present invention, it is possible to provide a phenolic hydroxyl group-containing resin capable of achieving both excellent dielectric properties (low permittivity and low dielectric tangent) and low elastic modulus in a high-temperature range to a high degree, and further, it is possible to provide a curable composition containing the phenolic hydroxyl group-containing resin and a cured product thereof. Furthermore, by using the curable composition or the cured product thereof, it is possible to provide a prepreg, a circuit board, a build-up film, a semiconductor encapsulating material, and a semiconductor device which achieve both excellent dielectric properties (low permittivity and low dielectric tangent) and low elastic modulus in a high-temperature range to a high degree.

Claims (13)

A phenolic hydroxyl group-containing resin which is a reaction product of a fluorene compound (provided that it does not have a substituent at the 9th position), a phenolic hydroxyl group-containing compound, and a compound represented by the general formula (1).

(Here,
Ar is an aromatic ring group that may have a substituent,
R ¹ is, each independently, a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms,
X is a talisman) In the first paragraph,
A phenolic hydroxyl group-containing resin, wherein the fluorene compound is present in an amount of 0.01 to 0.99 mol per 1 mol of the compound represented by the general formula (1). A resin containing a phenolic hydroxyl group, represented by the general formula (5).

(Here,
Z is, independently, the general formula (2A):

Structural units or general formulas represented by (3A):

is a structural unit represented by ,
Z' is, independently, the general formula (2A'):

Structural units or general formulas represented by (3A'):

It is a structural unit represented by
Ar is an aromatic ring group which may independently have a substituent,
R ¹ is, each independently, a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms,
R ² is, each independently, an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom,
m is an integer from 0 to 4, independently.
R ³ is, independently, an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom, or two R ³ may be combined with the carbon atom to which they are bonded to form a ring,
n is an integer from 0 to 3, each independently.
p is the mean and the number greater than 0,
R ^2' is, each independently, an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom,
m' is, independently, an integer from 0 to 4,
R ^3' may each independently be an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom, or two R ^3' may be combined with the carbon atom to which they are bonded to form a ring,
n' is an integer from 0 to 4, each independently,
However, the resin includes a structural unit represented by the general formula (2A) and/or the general formula (2A'), and a structural unit represented by the general formula (3A) and/or the general formula (3A'). In the third paragraph,
A phenolic hydroxyl group-containing resin comprising at least one compound represented by general formula (5-1) and a compound represented by general formula (5-2).

(Here,
Ar, Z, R ¹ , R ^3' and n' are synonymous with clause 3) In clause 1 or 3,
A phenolic hydroxyl group-containing resin having a hydroxyl equivalent of 100 to 2000 g/eq. In clause 1 or 3,
A resin containing phenolic hydroxyl groups with an average molecular weight of 100 to 10,000. A curable composition containing a phenolic hydroxyl group-containing resin as described in claim 1 or claim 3 and a curing agent. A cured product of the curable composition described in Article 7. A prepreg having a reinforcing substrate and a semi-cured material of the curable composition described in claim 7 impregnated into the reinforcing substrate. A circuit board which is a laminate of prepreg and copper foil as described in Article 9. A build-up film containing the curable composition described in claim 7. A semiconductor encapsulating material containing the curable composition described in claim 7. A semiconductor device comprising a cured product of the semiconductor encapsulating material described in Article 12.

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