WO2023080132A1

WO2023080132A1 - Aralkyl resin, diluent for epoxy resin, curable resin composition, photosensitive resin composition, cured product, electronic device, and aralkyl resin production method

Info

Publication number: WO2023080132A1
Application number: PCT/JP2022/040860
Authority: WO
Inventors: 謙亮廣瀧; 啓二朗関; 裕力名倉; 健史細井
Original assignee: セントラル硝子株式会社
Priority date: 2021-11-02
Filing date: 2022-11-01
Publication date: 2023-05-11
Also published as: JPWO2023080132A1; CN118043368A; TW202330683A; KR20240088837A

Abstract

Provided is an aralkyl resin having a structural unit represented by general formula (1) or (2). In general formulas (1) and (2), R1 represents a monovalent substituent, excluding monovalent substituents in which an atom directly bonding to an aromatic ring is an oxygen atom, and may be identical or different when there are a plurality of R1. In general formula (1) n is an integer of 0-2, when n is 0, p is an integer of ≤4, when n is 1, p is an integer of ≤6, and when n is 2, p is an integer of ≤8. In general formula (2), m and k are each an integer of 0-2, when m+k is 0, p+q is an integer of ≤8, when m+k is 1, p+q is an integer of ≤10, when m+k is 2, p+q is an integer of ≤12, when m+k is 3, p+q is an integer of ≤14, when m+k is 4, p+q is an integer of ≤16, and X is a single bond or a divalent substituent other than an oxygen atom.

Description

Aralkyl resin, diluent for epoxy resin, curable resin composition, photosensitive resin composition, cured product, electronic device, method for producing aralkyl resin

TECHNICAL FIELD The present disclosure relates to aralkyl resins, diluents for epoxy resins, curable resin compositions, photosensitive resin compositions, cured products, electronic devices, and methods for producing aralkyl resins.

Fluorine-containing aralkyl resins are sometimes used for the manufacture of electronic devices. Patent Document 1 describes a composition for forming a resist upper layer film for lithography containing a fluorine-containing resin. Patent Document 2 describes a resin substrate for a circuit board containing a polymer having a fluorine atom. Patent Document 3 describes a resist underlayer film material containing a fluorine-containing resin. Further, Patent Document 4 discloses a fluorine-containing resin that can be preferably used for manufacturing electronic devices.

Japanese Patent No. 6319582 Japanese Patent No. 6206445 Japanese Patent No. 6502885 WO2021/193878

The resin described in Patent Document 4 is a novolac resin, and in particular, a resin containing a structure in which a monocyclic or polycyclic aromatic ring is directly substituted with an oxygen atom is disclosed. This novolak resin has also been required to have further improved properties.
The present inventors conducted studies with one object being to provide a fluorine-containing aralkyl resin having excellent properties that can be used for the production of electronic devices.

The present inventors have completed the disclosure provided below as a result of their studies.

[1]
An aralkyl resin having a structural unit represented by general formula (1) or (2) below.

In general formula (1), R ¹ represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R ^1s , they may be the same or different. Well, n is an integer of 0 to 2, when n is 0, it is an integer of p ≤ 4, when n is 1, it is an integer of p ≤ 6, and when n is 2, it is an integer of p ≤ 8 .

In general formula (2), R ¹ represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R ^1s , they may be the same or different. Well, m and k are integers of 0 to 2, p + q ≤ 8 when m + k is 0, p + q ≤ 10 when m + k is 1, and p + q ≤ 12 when m + k is 2 When m+k is 3, it is an integer of p+q≤14, when m+k is 4, it is an integer of p+q≤16, and X is a single bond or a divalent substituent other than an oxygen atom.

[2]
The aralkyl resin according to [1], which has a structural unit represented by the general formula (1).

[3]
The aralkyl resin according to [1], which has a structural unit represented by the general formula (2).

[4]
The aralkyl resin according to any one of [1] to [3], which further comprises a structural unit represented by general formula (3) below.

In general formula (3), R ¹ represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R ^1s , they may be the same or different. Well, t is an integer of 0 to 2, r is an integer of 1 or more, and s is an integer of 0 or more, provided that r + s ≤ 4 when t is 0, r + s ≤ 6 when t is 1, When t is 2, r+s≦8, R ² represents a hydrogen atom or a monovalent substituent, and when multiple R ² are present, they may be the same or different.

[5]
An aralkyl resin according to any one of [1] to [4], which has a structural unit represented by general formula (4) or (5) below.

In general formula (4), R ¹ represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R ^1s , they may be the same or different. Well, n is an integer of 0 to 2, when n is 0, it is an integer of p ≤ 4, when n is 1, it is an integer of p ≤ 6, and when n is 2, it is an integer of p ≤ 8 . R ² represents a hydrogen atom or a monovalent substituent, and when multiple R ² are present, they may be the same or different, t is an integer of 0 to 2, r is 1 or more is an integer and s is an integer greater than or equal to 0, provided that r+s≦4 when t is 0, r+s≦6 when t is 1, and r+s≦8 when t is 2.

In general formula (5), R ¹ represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R ^1s , they may be the same or different. Well, m and k are integers of 0 to 2, p + q ≤ 8 when m + k is 0, p + q ≤ 10 when m + k is 1, and p + q ≤ 12 when m + k is 2 When m+k is 3, it is an integer of p+q≤14, when m+k is 4, it is an integer of p+q≤16, and X is a single bond or a divalent substituent other than an oxygen atom. R ² represents a hydrogen atom or a monovalent substituent, and when multiple R ² are present, they may be the same or different, t is an integer of 0 to 2, r is 1 or more is an integer and s is an integer greater than or equal to 0, provided that r+s≦4 when t is 0, r+s≦6 when t is 1, and r+s≦8 when t is 2.

[6]
The aralkyl resin according to [4] or [5], wherein R ² contains a glycidyl group.

[7]
The aralkyl resin according to [4] or [5], wherein R ² contains a polymerizable carbon-carbon double bond.

[8]
An aralkyl resin according to [4] or [5], wherein R ² has a partial structure represented by general formula (6) below.

In general formula (6), ^R3 represents a hydrogen atom or a monovalent organic group, and ^R4 represents a hydrogen atom, a methyl group, or a fluorine atom.

[9]
The aralkyl resin according to [8], wherein ^R3 represents a monovalent organic group having a terminal carboxyl group.

[10]
An aralkyl resin according to [1], [2] or [4], which has a structural unit represented by the following general formula (7).

[11]
An aralkyl resin according to [1], [2] or [4], which has a structural unit represented by the following general formula (8).

[12]
An aralkyl resin according to [1], [3] or [4], which has a structural unit represented by the following general formula (9).

[13]
An aralkyl resin according to [1], [2] or [4], which has a structural unit represented by general formula (10) below.

[14]
The aralkyl resin according to any one of [1] to [13], which has a weight average molecular weight of 300 to 200,000.

[15]
[1] An epoxy resin diluent containing the aralkyl resin according to any one of [1] to [14].

[16]
The epoxy resin diluent according to [15], which has a hydroxyl equivalent of 130 g/equivalent or more.

[17]
A curable resin composition containing a diluent for the aralkyl resin according to any one of [1] to [14] or the epoxy resin according to [15] or [16].

[18]
The curable resin composition according to [17], further comprising an epoxy resin.

[19]
A photosensitive resin composition comprising the aralkyl resin according to any one of [1] to [14] and a photosensitive agent.

[20]
The photosensitive resin composition according to [19], which is a photoresist composition, a solder resist composition or an imprint composition.

[21]
A cured product obtained by curing the curable resin composition according to [17] or [18].

[22]
An electronic device comprising the cured product of [21].

[23]
A method for producing an aralkyl resin, comprising reacting an aromatic compound with fluoral in the presence of an acid catalyst to produce an aralkyl resin having a structural unit represented by the following general formula (1) or (2).

[24]
A structure represented by the following general formula (4) or (5) by reacting an aromatic compound represented by the following general formula (11) or (12) with a phenolic compound in the presence of an acid catalyst A method for producing an aralkyl resin, comprising producing an aralkyl resin having units.

In general formula (11), R ¹ represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R ^1s , they may be the same or different. Well, n is an integer of 0 to 2, a is an integer of 2 or more, when n is 0, it is an integer of p + a ≤ 6, when n is 1, it is an integer of p + a ≤ 8, and n is 2 is an integer of p+a≤10 when Z represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and when multiple Zs are present, they may be the same or different.

In general formula (12), R ¹ represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when multiple R ¹ are present, they may be the same or different. Well, m and k are integers of 0 to 2, a and b are integers of 1 or more, p + q + a + b ≤ 10 when m + k is 0, and p + q + a + b ≤ 12 when m + k is 1. , p + q + a + b ≤ 14 when m + k is 2, p + q + a + b ≤ 16 when m + k is 3, p + q + a + b ≤ 18 when m + k is 4, and X is a single bond or excluding an oxygen atom It is a divalent substituent. Z represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and when multiple Zs are present, they may be the same or different.

[25]
The structure represented by the general formula (4) or (5) is obtained by reacting an aromatic compound represented by the following general formula (13) or (14) with a phenolic compound in the presence of an acid catalyst. The method for producing an aralkyl resin according to [24], wherein an aralkyl resin having units is produced.

In general formula (13), R ¹ represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R ^1s , they may be the same or different. Well, n is an integer of 0 to 2, a is an integer of 2 or more, when n is 0, it is an integer of p + a ≤ 6, when n is 1, it is an integer of p + a ≤ 8, and n is 2 is an integer of p+a≤10 when

In general formula (14), R ¹ represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R ^1s , they may be the same or different. Well, m and k are integers of 0 to 2, a and b are integers of 1 or more, p + q + a + b ≤ 10 when m + k is 0, and p + q + a + b ≤ 12 when m + k is 1. , p + q + a + b ≤ 14 when m + k is 2, p + q + a + b ≤ 16 when m + k is 3, p + q + a + b ≤ 18 when m + k is 4, and X is a single bond or excluding an oxygen atom It is a divalent substituent.

INDUSTRIAL APPLICABILITY According to the present disclosure, it is possible to provide a fluorine-containing aralkyl resin with excellent properties that can be used for the production of electronic devices.

Hereinafter, embodiments of the present disclosure will be described in detail.

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

In the description of a group (atomic group) in the present specification, a description without indicating whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent. For example, the term “alkyl group” includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

The notation "(meth)acryl" used herein represents a concept that includes both acryl and methacryl. The same applies to similar notations such as "(meth)acrylate".

The term "substituent" as used herein means an atom or group of atoms having a bond. For example, the term "monovalent substituent" refers to an atom or atomic group having one bond, and the term "divalent substituent" refers to an atom or atomic group having two bonds. show.
The term "organic group" as used herein means an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified. For example, the term "monovalent organic group" refers to an atomic group obtained by removing one hydrogen atom from any organic compound, and the term "divalent organic group" refers to two hydrogen atoms from any organic compound. Represents the atomic group excluding
In the chemical formulas herein, the notation "Me" represents a methyl group ( _CH3 ).
As used herein, the term "fluoral" means trifluoroacetaldehyde.
The term "electronic device" in this specification refers to semiconductor chips, semiconductor elements, printed wiring boards, electric circuits, display devices, information communication terminals, light emitting diodes, physical batteries, chemical batteries, etc., to which electronic engineering technology is applied. It is used in the sense of including elements, devices, final products, etc.

Having a fluorine atom within a structural unit also provides advantages in, for example, imprint applications. Low adhesion to metal molds is expected as a property required for general imprinting resins. In the present disclosure, having a fluorine atom in a structural unit can reduce adhesion to a mold.

The description of the aralkyl resin in the present disclosure will be continued below.

The aralkyl resin in the present disclosure is an aralkyl resin having a structural unit represented by general formula (1) or (2) below.

In addition, the aralkyl resin of the present disclosure has a structural unit represented by general formula (1) or (2) and a structural unit represented by general formulas (3), (4) and/or (5) below. You may have

In general formula (3), ^R2 represents a hydrogen atom or a monovalent substituent, and when there are multiple ^R2s , they may be the same or different, and ^R1 is directly bonded to the aromatic ring. represents a monovalent substituent excluding those where the atom is an oxygen atom, and when there are multiple R ^1s , they may be the same or different, t is an integer of 0 to 2, r is 1 and s is an integer greater than or equal to 0, provided that when t is 0, r+s≤4, when t is 1, r+s≤6, and when t is 2, r+s≤8.

(Description of general formula (1))
When R ¹ is a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, examples of the monovalent substituent include an alkyl group, a cycloalkyl group, an aryl group and an alkenyl group. , an alkynyl group, a cyano group, and the like. Arbitrary carbon atoms of these groups may be substituted with any number and combination of substituents such as halogen atoms and haloalkoxy groups. The number of carbon atoms in the monovalent substituent is, for example, 1-20, preferably 1-10.
Examples of atoms in R ¹ directly bonded to the aromatic ring include hydrogen, fluorine, carbon, nitrogen, sulfur, silicon and phosphorus atoms. These atoms may be substituted with any number and any combination of substituents such as hydrogen atoms, alkyl groups, cycloalkyl groups and aryl groups.
Furthermore, when the number of R ¹ in general formula (1) is 2 or more, two or more R ¹ are linked to form a saturated or unsaturated, monocyclic or polycyclic, C 3-6 A cyclic group may be formed.
R ¹ is preferably a hydrogen atom, a fluorine atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, among which n-butyl, s-butyl, isobutyl, t-butyl, n-propyl, i- A propyl group, an ethyl group and a methyl group are preferred, and an ethyl group and a methyl group are particularly preferred.

n may be an integer of 0 to 2, preferably n=0 or 1. For example, from the viewpoint of transparency of light (g-line, i-line, h-line, etc.) often used in electronic device manufacturing, n=0 is preferable. In the case of electronic devices in a broad sense, n=1 may be preferable in terms of heat resistance, for example, in the underlayer film.

n is an integer of 0 to 2; when n is 0, p≤4; when n is 1, p≤6; and when n is 2, p≤8.
p is preferably an integer of 0 to 2 from the viewpoint of ease of preparation of raw materials and cost.

Preferred embodiments of the structural unit of the aralkyl resin having the partial structure represented by general formula (1) include structural units represented by the following structural formulas.

(Description of general formula (2))
R ¹ is the same as R ¹ in general formula (1), and preferred forms thereof are also the same. When X is a divalent substituent group excluding an oxygen atom, it is preferably a divalent organic group. Examples of the divalent organic group include a methylene group, an ethylene group, an ethylidene group, a propylene group and a propylidene group. , isopropylidene group, butylene group, hexafluoroisopropylidene group, 2,2,2-trifluoroethylidene group, carbonyl group, phenylene group, naphthalene-1,4-diyl group and the like.
Further, when X is a divalent substituent excluding an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, or the like is substituted with, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or the like. It may be a divalent substituent substituted with any number of groups in any combination. X is preferably a single bond or a divalent substituent in which a methylene group, an ethylene group, a hexafluoroisopropylidene group, a 2,2,2-trifluoroethylidene group, a nitrogen atom or a sulfur atom is the bonding site of X. is. Examples of divalent substituents in which a nitrogen atom serves as a binding site for X include -N(Me)- and -N(C ₆ H ₅ )-.

m and k may be integers from 0 to 2. For example, m+k=0 is preferable from the viewpoint of transparency of light (g-line, i-line, h-line, etc.) often used in electronic device manufacturing. When considering electronic devices in a broad sense, for example, in the case of an underlayer film, an integer of m+k=1 to 2 may be preferable from the viewpoint of heat resistance.

m and k are integers of 0 to 2; when m+k is 0, p+q≤8; when m+k is 1, p+q≤10; when m+k is 2, p+q≤12; , m+k is an integer of p+q≦14 when m+k is 3, and an integer of p+q≦16 when m+k is 4.
p+q is preferably an integer of 0 to 4 from the viewpoint of ease of preparation of raw materials and cost.

Preferred embodiments of the structural unit of the aralkyl resin having the partial structure represented by general formula (2) include structural units represented by the following structural formulas.

In addition, the aralkyl resin in the present disclosure may contain structural units that fit general formula (1) or (2) and structural units that do not fit general formulas (1) and (2).

Further, an aralkyl resin having a structural unit represented by general formula (1) or (2) and a structural unit represented by general formula (3), (4) and/or (5) is also used in the manufacture of electronic devices. It can be preferably used for

(Description of general formula (3))
R ¹ is the same as R ¹ in general formula (1), and preferred forms thereof are also the same. When R ² is a monovalent substituent, examples of the monovalent substituent include an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, a cyano group, a glycidyl group, and a (meth)acryl group. etc. can be mentioned. Any number and any combination of substituents such as halogen atoms, alkoxy groups and haloalkoxy groups may be substituted on any carbon of these groups.
R ² is preferably a partial structure containing a hydrogen atom, an alkyl group, a glycidyl group, a polymerizable carbon-carbon double bond, or a partial structure represented by general formula (6) below.

In general formula (6), ^R3 represents a hydrogen atom or a monovalent organic group, and ^R4 represents a hydrogen atom, a methyl group, or a fluorine atom. Having this partial structure is preferable from a synthetic point of view.

Further, it is more preferable that ^R3 in the partial structure represented by the general formula (6) is a monovalent organic group having a terminal carboxyl group. The presence of a carboxyl group at the end provides the effect of increasing developability.

t may be an integer from 0 to 2, preferably t=0. For example, t=0 is preferable from the viewpoint of transparency of light (g-line, i-line, h-line, etc.) often used in the manufacture of electronic devices. When considering an electronic device in a broad sense, t=1 may be preferable from the viewpoint of heat resistance in, for example, an underlayer film.

t is an integer of 0 to 2, r is an integer of 1 or more, s is an integer of 0 or more, r + s ≤ 4 when t is 0, r + s ≤ 6 when t is 1, t is 2 When r+s≦8. r+s is preferably 1 to 2 from the viewpoint of ease of preparation of raw materials and cost.

(Description of general formula (4))
R ¹ is the same as R ¹ in general formula (1), and preferred forms thereof are also the same. R ² is the same as R ² in general formula (3), and the same preferred forms are also included. n is an integer of 0 to 2; when n is 0, p≤4; when n is 1, p≤6; and when n is 2, p≤8. t is an integer of 0 to 2, r is an integer of 1 or more, and s is an integer of 0 or more, provided that r + s ≤ 4 when t is 0, r + s ≤ 6 when t is 1, and t is When 2, r+s≦8.
The structural unit represented by the general formula (4) means a structural unit in which the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3) are combined, and the general formula In the structural unit represented by (4), the molar ratio of the structural unit represented by general formula (1) to the structural unit represented by general formula (3) is 1:1.

(Description of general formula (5))
R ¹ is the same as R ¹ in general formula (1), and preferred forms thereof are also the same. X is the same as X in general formula (2), and the same preferred forms are also included. R ² is the same as R ² in general formula (3), and the same preferred forms are also mentioned. m and k are integers of 0 to 2; when m+k is 0, p+q≤8; when m+k is 1, p+q≤10; when m+k is 2, p+q≤12; , m+k is an integer of p+q≦14 when m+k is 3, and an integer of p+q≦16 when m+k is 4. t is an integer of 0 to 2, r is an integer of 1 or more, and s is an integer of 0 or more, provided that r + s ≤ 4 when t is 0, r + s ≤ 6 when t is 1, and t is When 2, r+s≦8.
The structural unit represented by the general formula (5) means a structural unit in which the structural unit represented by the general formula (2) and the structural unit represented by the general formula (3) are combined, and the general formula In the structural unit represented by (5), the molar ratio of the structural unit represented by general formula (2) to the structural unit represented by general formula (3) is 1:1.

(Molecular weight, dispersity)
The weight average molecular weight of the aralkyl resin in the present disclosure is preferably 300-500,000, more preferably 300-300,000, and even more preferably 300-200,000. By adjusting the weight-average molecular weight, it is possible to adjust alkali solubility, solvent solubility, physical properties when formed into a film, and the like. That is, by adjusting the weight-average molecular weight, the applicability of the aralkyl resin of the present disclosure to the manufacture of electronic devices can be further enhanced.
The polydispersity (weight average molecular weight/number average molecular weight) of the aralkyl resin in the present disclosure is preferably 1-40, more preferably 1-20. By setting the polydispersity within an appropriate numerical range, for example, it becomes easier to obtain a uniform film, and the mechanical properties of the film are improved.
The weight average molecular weight and polydispersity can be determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.

The aralkyl resins of the present disclosure are preferably used as diluents for epoxy resins.
Also disclosed herein are diluents for epoxy resins, including the aralkyl resins of the present disclosure.
Hereinafter, diluents for epoxy resins, including the aralkyl resins of the present disclosure, are referred to as diluents of the present disclosure.
A curable resin composition comprising an aralkyl resin of the present disclosure or a diluent of the present disclosure and an epoxy resin is expected to have a dielectric constant and/or dissipation factor suitable for electronic device manufacturing.
As used herein, the term "diluent" refers to a substance that has few or no reactive substituents with the substance to be diluted (epoxy resin), and is used in the resin composition. It is a substance that reduces the concentration of the substance to be diluted in.
When the substance to be diluted is an epoxy resin, it is preferable that the diluent has few or no hydroxyl groups reactive with the epoxy resin. From that point of view, the aralkyl resin used for the diluent of the epoxy resin or the diluent of the present disclosure preferably has a hydroxyl equivalent weight of 130 g/equivalent or more. It is also preferred that the aralkyl resin used for the diluent of the epoxy resin or the diluent of the present disclosure does not contain hydroxyl groups.

The aralkyl resin of the present disclosure has a lower melt viscosity than the resin having no aralkyl structure of the present disclosure, and is excellent in handleability when used as a resin composition and fine workability during extrusion molding. In addition, the aralkyl resin of the present disclosure has a slower alkali dissolution rate than the resin having no aralkyl structure of the present disclosure, and the alkali dissolution rate can be appropriately controlled, so that the developability and film reduction are improved. be able to.
Also, the aralkyl resin of the present disclosure has sufficient heat resistance to be used in electronic device applications.

In addition, the aralkyl resin of the present disclosure can employ a production method using a fluoral-containing mixture as a raw material in order to provide the “—CHCF ₃ —” structure on the right side of general formulas (1) and (2). This method provides a higher yield than using formaldehyde as a raw material to produce an aralkyl resin having a “—CH ₂ —” structure. From this point of view as well, the aralkyl resin of the present disclosure having the structure “—CHCF ₃ —” is excellent.

<Method for producing aralkyl resin I-1 (synthesis method I-1)>
An aralkyl resin having a structural unit represented by general formula (1) or (2) can be produced (synthesized) by reacting an aromatic compound with fluorol in the presence of an acid catalyst. Raw materials, reaction conditions, and the like are described below.

(aromatic compound)
Examples of aromatic compounds include alkylbenzenes such as benzene, toluene, ethylbenzene, propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene and tert-butylbenzene; xylenes such as o-xylene, m-xylene and p-xylene; trimethylbenzenes such as 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene and 1,3,5-trimethylbenzene; halogenated benzenes such as fluorobenzene, chlorobenzene, bromobenzene and iodobenzene; , biphenyl, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1,2-dimethylnaphthalene, 1,3-dimethylnaphthalene, 1,4-dimethylnaphthalene, 1,6-dimethylnaphthalene, 2,3-dimethylnaphthalene, 2,4-dimethylnaphthalene, 2,5-dimethylnaphthalene, 2,6-dimethylnaphthalene, 1-methylanthracene, 2-methylanthracene, 1,2-dimethylanthracene, 1,2,3-trimethylanthracene, fluorene, etc. Polycyclic aromatics may also be mentioned.
In addition, diphenylmethane, triphenylmethane, 1,1-diphenylethane, 1,2-diphenylethane, 1,1-diphenylpropane, 1,2-diphenylpropane, 1,3-diphenylpropane, 2,2-diphenylpropane, Aromatic compounds having multiple aromatic rings in the molecule, such as hexafluoro-2,2-diphenylpropane and trifluoro-2,2-diphenylethane, can also be mentioned.
Furthermore, aniline, toluidine, xylidine, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, diphenylamine, N-methyl Aromatic amines such as diphenylamine, triphenylamine and carbazole; aromatic thiols such as thiophenol, toluenethiol and naphthalenethiol; aromatics such as thioanisole, diphenylsulfide, bis(p-tolyl)sulfide and dibenzothiophene. Sulfides may also be mentioned.

(fluoral)
For the preparation of fluororal, commercially available hydrates (products of Tokyo Chemical Industry Co., Ltd.) and hemiacetal of fluororal can be used as its equivalents. A hydrate of fluoral and a hemiacetal of fluoral can also be prepared by the method described in Japanese Patent Application Laid-Open No. 5-97757.

In addition, as described in JP-A-3-184933, it is possible to convert chloral to fluoral almost quantitatively by catalytic gas-phase fluorination reaction of inexpensive chloral (trichloroethanal). Anhydrous fluoral can also be prepared by utilizing this. Fluorals are obtained in this manner in the examples described later.

Fluorals are low-boiling compounds, generally highly self-reactive, and difficult to handle. However, according to the findings of the present inventors, fluoral can be handled very stably in a hydrogen fluoride solution. When fluoral is treated in hydrogen fluoride, 1,2,2,2-tetrafluoroethanol, which is an adduct of fluoral and hydrogen fluoride, is produced as shown in the scheme below.

Thus, 1,2,2,2-tetrafluoroethanol is in an equilibrium relationship between fluoral and hydrogen fluoride. It is presumed that when hydrogen fluoride is excessively present in the system, the equilibrium shifts toward the 1,2,2,2-tetrafluoroethanol side, and as a result, the decomposition of fluororal is suppressed. According to the findings of the present inventors, it has been confirmed that fluoral in hydrogen fluoride not only improves the stability of the compound but also raises the boiling point. It can be easily handled as an adduct of hydrogen.

When the prepared fluororal is treated as a mixture with hydrogen fluoride, the amount of hydrogen fluoride to be added is usually 0.1 to 100 mol, preferably 1 to 75 mol, more preferably 2 to 50 mol, per 1 mol of the prepared fluororal. is. The amount of hydrogen fluoride to be added is determined from the viewpoint of sufficient stabilization effect and cost.
The fluoral/hydrogen fluoride mixture may also contain excess hydrogen fluoride. However, since hydrogen fluoride itself has a function as an acidic substance, hydrogen fluoride may act as an acid catalyst or a dehydrating agent, or act as an additive that accelerates the reaction. From these points, it can be said that there is an advantage in treating fluoral as a mixture of hydrogen fluoride.

The synthesis can be carried out, for example, at -20 to 150°C for 1 to 30 hours.
The pressure during synthesis can be carried out under conditions of 0.1 to 10 MPa in terms of absolute pressure. The pressure is preferably 0.1-5 MPa, more preferably 0.1-1 MPa. When reacting at a high pressure, a high-pressure reaction vessel is required, which increases equipment costs. Therefore, it is preferable to carry out the reaction at as low a pressure as possible.

A solvent may be used in the synthesis. Examples of solvents include ketones such as acetone and methyl ethyl ketone, alcohols such as ethanol and butanol, esters such as ethyl acetate and butyl acetate, and ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, diisopropyl ether, and tert-butyl methyl ether. , ether alcohols such as ethoxyethyl alcohol, ether esters such as propylene glycol monomethyl ether acetate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylimidazolidinone, etc. Nitriles such as amides, acetonitrile, propionitrile, and benzonitrile, sulfoxides such as dimethylsulfoxide, cyclic sulfones such as sulfolane, nitro hydrocarbons such as nitromethane and nitroethane, and nitro aromatic hydrocarbons such as nitrobenzene types can be mentioned. Halogen-based solvents such as 1,2-dichloroethane, chloroform, methylene chloride, carbon tetrachloride, and trichloroethane are also preferably used, particularly when fluoral is used as in the present disclosure.

The molar ratio of aromatic compound:fluoral during synthesis is preferably 2:1 to 1:3, more preferably 2:1 to 1:2, still more preferably 2:1 to 1:1. be. When the molar ratio is within the above range, the fluorine atoms are efficiently introduced into the aralkyl resin, and the solvent solubility when used in photosensitive resist applications can be made more suitable, making it suitable for imprint applications. Adhesion to the mold when used can be made more suitable.

Catalysts that can be used in the synthesis include inorganic acids such as hydrochloric acid, sulfuric acid, perchloric acid and phosphoric acid, organic acids such as formic acid, acetic acid, oxalic acid, trichloroacetic acid and p-toluenesulfonic acid, zinc acetate, zinc chloride. and divalent metal salts such as magnesium acetate. These may be used alone or in combination of two or more. Incidentally, as mentioned above, it is believed that when a fluoral/hydrogen fluoride mixture is used, the hydrogen fluoride acts as an acid catalyst.

When an acid catalyst is used in the synthesis, the amount of the acid catalyst is preferably 0.01 to 100 mol, more preferably 0.1 to 30 mol, still more preferably 0, per 1 mol of fluoral. .5 to 25 mol. By setting the amount of the acid catalyst within the above range, fluorine atoms are efficiently introduced into the aralkyl resin, and the solvent solubility and the adhesion to the mold when used for imprinting are more suitable. be able to.

(Other supplements)
For the obtained aralkyl resin, unreacted substances and impurities are removed by combining a precipitation treatment by putting it in a poor solvent (typically water), a washing treatment with water or sodium bicarbonate water, and a liquid separation operation. preferably. For specific methods of these treatments, known methods in polymer synthesis can be appropriately referred to.

The aralkyl resin of this embodiment may be in powder form. Alternatively, the above powder may be dissolved in any solvent and used as an aralkyl resin solution.

The total reaction time is usually 1 to 30 hours. Regarding the reaction, analytical instruments such as nuclear magnetic resonance (NMR), gas chromatography (GC), liquid chromatography (LC), and gel permeation chromatography (GPC) are used, and the reaction conversion rate reaches a predetermined value. The reaction is preferably terminated when it is confirmed that it has been reached.

<Manufacturing method I-2 of aralkyl resin (synthesis method I-2)>
By reacting an aromatic compound, a phenolic compound, and a fluoral in the presence of an acid catalyst, in addition to the structural unit represented by general formula (1) or (2), general formula (3), ( An aralkyl resin having structural units represented by 4) and/or (5) and having phenolic hydroxyl groups and/or alkoxy groups in the molecular chain can be produced (synthesized). Raw materials, reaction conditions, and the like are described below.

(aromatic compound)
The aromatic compound is the same as the aromatic compound in <Aralkyl resin production method I-1 (synthesis method I-1)>.

(Phenolic compound)
Examples of the phenolic compounds include phenol, cresols such as o-cresol, m-cresol and p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3 xylenols such as ,4-xylenol and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol; o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, etc. isopropylphenols, o-butylphenol, m-butylphenol, p-butylphenol, p-isobutylphenol, butylphenols such as p-tert-butylphenol, p-tert-amylphenol, p-octylphenol, p-nonylphenol, p- Alkylphenols such as millphenol, halogenated phenols such as fluorophenol, chlorophenol, bromophenol, iodophenol, monohydric phenol substituted products such as p-phenylphenol, aminophenol, nitrophenol, dinitrophenol, trinitrophenol can be mentioned.
Also included are polycyclic phenols such as 1-naphthol, 2-naphthol and 2-hydroxyanthracene, and dihydroxybenzenes such as hydroquinone, resorcinol and catechol.
Furthermore, bisphenols such as bisphenol A, bisphenol F, bisphenol E, bisphenol S, bisphenol AF, bisphenol M, bisphenol P, bisphenol Z, 1,1,1-trifluoro-2,2-bis(4-hydroxyphenyl)ethane types can also be mentioned.
Furthermore, alkoxybenzenes such as methoxybenzene, ethoxybenzene and propoxybenzene, alkoxynaphthalenes such as 1-methoxynaphthalene and 2-methoxynaphthalene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene and 1,4-dimethoxybenzene dialkoxybenzenes such as 1,2-dimethoxynaphthalene, 1,3-dimethoxynaphthalene, 1,4-dimethoxynaphthalene, 2,3-dimethoxynaphthalene, 2,4-dimethoxynaphthalene and other dialkoxynaphthalenes, fluoroanisole , chloroanisole, bromoanisole, iodoanisole, and other halogenated anisoles, and phenolic compounds having both a phenolic hydroxyl group and an alkoxy group on the aromatic ring, such as methoxyphenol and methoxynaphthol.

(fluoral)
The fluoral is the same as the fluoral in <Aralkyl resin production method I-1 (synthesis method I-1)>.

A solvent may be used in the synthesis. The solvent is the same as the solvent in the above <Aralkyl resin production method I-1 (synthesis method I-1)>.

The molar ratio of aromatic compound to phenolic compound during synthesis is preferably from 99:1 to 1:99, more preferably from 95:5 to 5:95. When the molar ratio is within the above range, the phenolic hydroxyl group and/or alkoxy group are efficiently introduced into the aralkyl resin, and the alkali solubility and solvent solubility are more suitable when used for photosensitive resist applications. can be

The molar ratio of the sum of the aromatic compound and the phenolic compound to the fluoral during the synthesis is preferably from 2:1 to 1:3, more preferably from 2:1 to 1:2, still more preferably 2: 1 to 1:1. When the molar ratio is within the above range, fluorine atoms are efficiently introduced into the aralkyl resin, and alkali solubility and solvent solubility can be made more suitable when used for photosensitive resist applications. Adhesion to a mold when used for imprinting can be made more suitable.

The catalyst that can be used in the synthesis is the same as the catalyst in <Aralkyl resin production method I-1 (synthesis method I-1)>.

When an acid catalyst is used in the synthesis, the amount of the acid catalyst is the same as the amount of the catalyst in <Aralkyl resin production method I-1 (synthesis method I-1)>.

Moreover, the obtained aralkyl resin having a phenolic hydroxyl group can be used as an epoxy resin by, for example, reacting epichlorohydrin. Also, the obtained epoxy resin can be reacted with a carboxylic acid such as (meth)acrylic acid and used as an epoxy (meth)acrylate resin. Furthermore, the resulting epoxy (meth)acrylate resin can be reacted with an acid anhydride or the like to be used as an acid-modified epoxy (meth)acrylate resin. At this time, the acid anhydride to be reacted may be a compound having a polymerizable carbon-carbon unsaturated bond.

<Manufacturing method II of aralkyl resin (synthesis method II)>
As a method for producing an aralkyl resin in the present disclosure, an aromatic compound represented by the following general formula (11) or (12) and a phenolic compound are reacted in the presence of an acid catalyst to obtain the general formula (1) Or having a structural unit represented by (2) and a structural unit represented by general formulas (3), (4) and/or (5), and having a phenolic hydroxyl group and/or an alkoxy group in the molecular chain It is possible to manufacture (synthesize) an aralkyl resin having

In general formula (11), R ¹ is the same as R ¹ in general formula (1), and preferred forms thereof are also the same. n is an integer of 0 to 2, a is an integer of 2 or more, when n is 0, it is an integer of p + a ≤ 6, when n is 1, it is an integer of p + a ≤ 8, and when n is 2 It is an integer of p+a≦10. Z represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and when multiple Zs are present, they may be the same or different.

In general formula (12), R ¹ is the same as R ¹ in general formula (1), and preferred forms thereof are also the same. X is the same as X in general formula (2), and the same preferred forms are also included. m and k are integers of 0 to 2, a and b are integers of 1 or more, p + q + a + b ≤ 10 when m + k is 0, p + q + a + b ≤ 12 when m + k is 1, m + k is an integer of p+q+a+b≤14 when is 2, an integer of p+q+a+b≤16 when m+k is 3, and an integer of p+q+a+b≤18 when m+k is 4.

(Aromatic compound having a structure represented by general formula (11))
In the aromatic compound having the structure represented by general formula (11), Z is preferably a hydroxyl group from the viewpoints of ease of preparation of raw materials and cost. For example, it can be prepared by methods described in the literature, such as Journal of Polymer Science (Hoboken, NJ, United States) (2020), 58(16), 2197-2210.

An aromatic compound having a structure represented by general formula (11), wherein Z is a hydroxyl group, is represented by general formula (13) below.
An aralkyl resin having a structural unit represented by general formula (4) can be produced by reacting an aromatic compound represented by general formula (13) with a phenolic compound in the presence of an acid catalyst. preferable.

(Aromatic compound having a structure represented by general formula (12))
In the aromatic compound having the structure represented by general formula (12), Z is preferably a hydroxyl group from the viewpoint of ease of preparation of raw materials and cost. For example, it can be prepared by methods described in literature such as Chinese Journal of Chemistry (2020), 38(9), 952-958.

An aromatic compound having a structure represented by general formula (12), wherein Z is a hydroxyl group, is represented by general formula (14) below.
An aralkyl resin having a structural unit represented by general formula (5) can be produced by reacting an aromatic compound represented by general formula (14) with a phenolic compound in the presence of an acid catalyst. preferable.

The synthesis can be carried out, for example, at -20 to 150°C for 2 to 30 hours.
The pressure during synthesis can be carried out under conditions of 0.1 to 10 MPa in terms of absolute pressure. The pressure is preferably 0.1-5 MPa, more preferably 0.1-1 MPa. When reacting at a high pressure, a high-pressure reaction vessel is required, which increases equipment costs. Therefore, it is preferable to carry out the reaction at as low a pressure as possible.

A solvent may be used in the synthesis. Examples of solvents include ketones such as acetone and methyl ethyl ketone, alcohols such as ethanol and butanol, esters such as ethyl acetate and butyl acetate, and ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, diisopropyl ether, and tert-butyl methyl ether. , ether alcohols such as ethoxyethyl alcohol, ether esters such as propylene glycol monomethyl ether acetate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylimidazolidinone, etc. Nitriles such as amides, acetonitrile, propionitrile, and benzonitrile, sulfoxides such as dimethylsulfoxide, cyclic sulfones such as sulfolane, nitro hydrocarbons such as nitromethane and nitroethane, and nitro aromatic hydrocarbons such as nitrobenzene types can be mentioned. Halogen solvents such as 1,2-dichloroethane, chloroform, methylene chloride, carbon tetrachloride and trichloroethane are also preferably used.

The molar ratio of the aromatic compound represented by the general formula (11) or (12) to the phenol compound during synthesis is preferably 1:5 to 2:1, more preferably 1:3 to 1: 1. When the molar ratio is within the above range, fluorine atoms are efficiently introduced into the aralkyl resin, and alkali solubility and solvent solubility can be made more suitable when used for photosensitive resist applications. Adhesion to a mold when used for imprinting can be made more suitable.

Catalysts that can be used in the synthesis include inorganic acids such as hydrochloric acid, sulfuric acid, hydrogen fluoride, perchloric acid and phosphoric acid; Organic acids, divalent metal salts such as zinc acetate, zinc chloride and magnesium acetate, and the like. These may be used alone or in combination of two or more.

When an acid catalyst is used in the synthesis, the amount of the acid catalyst is preferably 0.01 to 100 mol per 1 mol of the aromatic compound represented by the general formula (11) or (12). It is preferably 0.01 to 30 mol. By setting the amount of the acid catalyst within the above range, fluorine atoms are efficiently introduced into the aralkyl resin, and alkali solubility and adhesion to the mold when used for imprinting are more suitable. be able to.

Moreover, the obtained aralkyl resin having a phenolic hydroxyl group can be used as an epoxy resin by, for example, reacting epichlorohydrin. Also, the obtained epoxy resin can be reacted with a carboxylic acid such as (meth)acrylic acid and used as an epoxy (meth)acrylate resin. Furthermore, the resulting epoxy (meth)acrylate resin can be reacted with an acid anhydride or the like to be used as an acid-modified epoxy (meth)acrylate resin. At this time, the acid anhydride to be reacted may be a compound having a polymerizable carbon-carbon bond.

<<resin composition>>
The aralkyl resin in the present disclosure can be used as a resin composition by mixing with each component different from the aralkyl resin in the present disclosure.

<Curable resin composition in the present disclosure>
A curable resin composition can be mentioned as an application destination of the aralkyl resin in the present disclosure and the diluent in the present disclosure.
For example, a curable resin composition can be produced by using an aralkyl resin in the present disclosure in combination with an epoxy resin. In this case, the aralkyl resin in the present disclosure may act as a curing agent or a diluent for the epoxy resin. When the aralkyl resin in the present disclosure has a substituent, such as a hydroxyl group, that exhibits reactivity with the epoxy resin, the aralkyl resin in the present disclosure acts as a curing agent for the epoxy resin. When the aralkyl resin of the present disclosure does not have substituents, such as hydroxyl groups, that are reactive with the epoxy resin, the aralkyl resin of the present disclosure acts as a diluent for the epoxy resin.
Aralkyl resins in the present disclosure contain fluorine atoms. Therefore, a cured product formed from a curable resin composition containing an aralkyl resin in the present disclosure is expected to have a dielectric constant and/or dielectric loss tangent suitable for electronic device manufacture.

(Epoxy resin)
The epoxy resin to be combined with the aralkyl resin in the present disclosure is not particularly limited, and known epoxy resins may be used. Known epoxy resins include bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, bisphenol AD type epoxy resin, hydrogenated bisphenol A type epoxy resin, and hydrogenated bisphenol. F type epoxy resin, diglycidyl ether of bisphenol A-alkylene oxide adduct, diglycidyl ether of bisphenol F alkylene oxide adduct, bisphenol S type epoxy resin, tetramethylbisphenol A type epoxy resin, tetramethylbisphenol F type epoxy resin , thiodiphenol-type epoxy resin, dihydroxydiphenyl ether-type epoxy resin, terpene diphenol-type epoxy resin, biphenol-type epoxy resin, tetramethylbiphenol-type epoxy resin, hydroquinone-type epoxy resin, methylhydroquinone-type epoxy resin, dibutylhydroquinone-type epoxy resin, Resorcinol-type epoxy resins, methylresorcinol-type epoxy resins, dihydroxynaphthalene-type epoxy resins, 1,1,1-trifluoro-2,2-bis(4-glycidyloxyphenyl)ethane and the like can be mentioned.

Examples of polyfunctional epoxy resins include phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy resin, bisphenol AF novolak epoxy resin, dicyclopentadiene phenol epoxy resin, and terpene phenol epoxy resin. , phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol novolak type epoxy resin, polyhydric phenol resin obtained by condensation reaction with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, fluoral, petroleum heavy Epoxy resins, triglycidyl isocyanurates, etc. produced from various aromatic compounds such as modified phenolic resins obtained by polycondensing oils or pitches, formaldehyde polymers and phenols in the presence of acid catalysts, and epihalohydrin. can be mentioned.

Furthermore, epoxy resins produced from various amine compounds such as diaminodiphenylmethane, aminophenol and xylenediamine and epihalohydrin, and epoxy resins produced from various carboxylic acids such as methylhexahydroxyphthalic acid and dimer acid and epihalohydrin Resins, diluents for epoxy resins such as glycidyl ethers of aliphatic alcohols, alicyclic epoxy resins represented by 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, and the like are also included.

The amount ratio of the aralkyl resin and the epoxy resin in the present disclosure may be appropriately designed based on the epoxy equivalent of the epoxy resin. Typically, the mass ratio of aralkyl resin to epoxy resin in the present disclosure is about 1:10 to 10:1.

(curing agent)
The curable resin composition in the present disclosure may contain curing agents other than the aralkyl resin in the present disclosure. When the curable resin composition in the present disclosure contains a curing agent, the type of curing agent is not particularly limited. Examples of curing agents include amine-based curing agents, acid anhydride-based curing agents, and phenol-based curing agents.

More specifically, the amine curing agent includes diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N-aminoethylpiperazine, isophoronediamine, bis(4-aminocyclohexyl)methane, bis(aminomethyl)cyclohexane, m-xyl Aliphatic and alicyclic amines such as diamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraspiro[5,5]undecane, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenyl aromatic amines such as sulfone, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo-(5,4,0)-undecene-7,1,5-diazabicyclo- Tertiary amines such as (4,3,0)-nonene-7 and salts thereof, and the like can be mentioned.

More specifically, the acid anhydride curing agent includes aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride. alicyclic acid anhydrides such as acids, methylhexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, and the like.

More specifically, phenolic curing agents include catechol, resorcinol, hydroquinone, bisphenol F, bisphenol A, bisphenol AF, bisphenol S, biphenol, 1,1,1-trifluoro-2,2-bis(4-hydroxyphenyl ) dihydric phenols such as ethane, phenol novolacs, cresol novolaks, bisphenol A novolaks, trishydroxyphenylmethanes, aralkylpolyphenols, and various aldehydes and phenols such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, and fluoral polyhydric phenol resin obtained by condensation reaction with bisphenol-based compounds, modified phenol resin obtained by polycondensation of heavy petroleum oil or pitches, formaldehyde polymer and phenols in the presence of an acid catalyst, etc. Various phenolic compounds and the like can be mentioned.

Other curing agents include imidazole compounds and their salts, amine _BF3 complex compounds, aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts and Bronsted acid salts such as phosphonium salts, dicyandiamide, adipic acid dihydrazide and phthalate. Also included are organic acid hydrazides such as acid dihydrazides, adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and polycarboxylic acids such as carboxyl group-containing polyesters.

When the curable resin composition in the present disclosure contains a curing agent, it may contain only one curing agent, or may contain curing agents with two or more different chemical structures.
When the curable resin composition in the present disclosure contains a curing agent, the amount thereof may be appropriately adjusted based on the epoxy equivalent of the epoxy resin and the like. Typically, when a curing agent is used, its amount is about 0.1 to 1,000 parts by weight with respect to 100 parts by weight of the epoxy resin.

(Curing accelerator)
From the viewpoint of accelerating the curing speed and/or making the curing more complete, the curable resin composition in the present disclosure may contain a curing accelerator. As curing accelerators, curing accelerators for general epoxy resins such as tertiary amines, imidazoles, organic phosphine compounds or their salts, metal soaps such as zinc octylate and tin octylate can be used. can.

When the curable resin composition in the present disclosure contains a curing accelerator, it may contain only one curing accelerator, or may contain two or more curing accelerators with different chemical structures.
When the curable resin composition in the present disclosure contains a curing accelerator, the amount may be adjusted as appropriate. Typically, when a curing accelerator is used, its amount is about 0.001 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin.

(Other ingredients)
The curable resin composition in the present disclosure can contain one or more optional components in addition to the above components. Optional components include antioxidants, fillers, colorants, resins other than aralkyl resins, curable monomers, oligomers, and organic solvents.

Examples of antioxidants include phenol-based, sulfur-based, and phosphorus-based antioxidants. When an antioxidant is used, its amount is usually 0.005 to 5 parts by weight, preferably 0.01 to 1 part by weight, per 100 parts by weight of the aralkyl resin.

Fillers (fillers) include metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as fine powder silica, fused silica and crystalline silica, glass beads, metal hydroxides such as aluminum hydroxide, gold, silver, Metals such as copper and aluminum, fluororesin powders such as polytetrafluoroethylene particles, carbon, rubbers, kaolin, mica, quartz powder, graphite, molybdenum disulfide, and boron nitride can be used.
When a filler is used, its amount is, for example, 1,500 parts by mass or less, preferably 0.1 to 1,500 parts by mass, based on 100 parts by mass of the aralkyl resin.

Examples of the coloring agent include inorganic pigments such as titanium dioxide, molybdenum red, Prussian blue, ultramarine blue, cadmium yellow, and cadmium red, organic pigments, carbon black, phosphors, and the like.
When a coloring agent is used, its amount is usually 0.01 to 30 parts by weight per 100 parts by weight of the aralkyl resin.

Examples of flame retardants include antimony trioxide, bromine compounds, phosphorus compounds, and the like. When a flame retardant is used, its amount is usually 0.01 to 30 parts by weight per 100 parts by weight of the aralkyl resin.

Examples of resins other than epoxy resins include (meth)acrylate resins, epoxy (meth)acrylate resins, styrene resins, polyimide resins, polyamide resins, polyamic acid resins, active ester resins, and the like. The amount thereof is usually 0.01 to 30 parts by mass with respect to 100 parts by mass of the solid content of the resin composition.

Examples of curable monomers and oligomers include benzoxazine compounds and maleimide compounds. The amount thereof is usually 0.01 to 30 parts by mass with respect to 100 parts by mass of the solid content of the resin composition.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate and amyl acetate; ethers such as ethylene glycol monomethyl ether; One or more of amides such as formamide and N,N-dimethylacetamide, alcohols such as methanol and ethanol, and hydrocarbons such as toluene and xylene can be used.
The curable resin composition of the present embodiment may contain a solvent, and may be solid or varnish-like.

A cured product of a curable resin composition containing the aralkyl resin of the present disclosure has sufficient heat resistance to be used for electronic devices.
Moreover, the curable resin composition containing the aralkyl resin of the present disclosure has a lower water absorption rate of the cured product than the curable resin composition containing the resin having no aralkyl structure of the present disclosure. The low water absorption of the cured product is effective when used in electronic devices from the viewpoint of dielectric properties and insulation reliability.

<Photosensitive resin composition>
A photosensitive resin composition can be preferably mentioned as an application destination of the aralkyl resin in the present disclosure. Specifically, a photosensitive resin composition can be prepared by mixing the aralkyl resin of the present disclosure with at least a photosensitive agent.
As already mentioned, aralkyl resins tend to have good transparency to certain light and/or alkali solubility. By using an aralkyl resin having such good properties, a photosensitive resin composition having good performance can be prepared. In particular, the photosensitive resin composition herein can be patterned by exposure using a photoresist composition, ie, a photomask, followed by development, and selectively protects the substrate surface from processing such as etching in the manufacture of electronic devices. It is useful as a composition capable of protecting against This is due to the specific light transmittance, alkali solubility, and etching resistance of the aromatic ring contained in the aralkyl resin.

In addition, the above-mentioned photosensitive resin composition can be patterned by a solder resist composition or an imprint composition, that is, by light, and can selectively protect the substrate surface from processing such as etching in the manufacture of electronic devices. It is also useful as a possible composition. This is due to the specific light transmittance described above and the etching resistance of the aromatic ring contained in the aralkyl resin.

The amount of the aralkyl resin in the present disclosure is, for example, 20 to 99% by weight, preferably 50 to 98% by weight, based on the total non-volatile components of the photosensitive resin composition.

When the aralkyl resin of the present disclosure is used in the photosensitive resin composition, a quinonediazide compound is typically used as the photosensitive agent. A quinonediazide compound is particularly preferably used when preparing a positive photosensitive resin composition. There are no particular restrictions on the quinonediazide compounds that can be used. Examples of the quinonediazide compound include those in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy compound via an ester bond, the sulfonic acid of quinonediazide to a polyamino compound in a sulfonamide bond, and the sulfonic acid of quinonediazide to a polyhydroxypolyamino compound in an ester bond and/or a sulfone bond. Examples thereof include those with an amide bond. It is preferable that 50 mol % or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.

As the structural unit of quinonediazide, both a 5-naphthoquinonediazidesulfonyl group and a 4-naphthoquinonediazidesulfonyl group are preferably used. A 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region and is suitable for i-line exposure. A 5-naphthoquinonediazide sulfonyl ester compound has absorption extending to the g-line region and is suitable for g-line exposure. It is preferable to select a 4-naphthoquinonediazide sulfonyl ester compound or a 5-naphthoquinone diazidesulfonyl ester compound depending on the wavelength of exposure. Further, a naphthoquinonediazide sulfonyl ester compound having a 4-naphthoquinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group in the same molecule may be contained, and a 4-naphthoquinonediazide sulfonyl ester compound and a 5-naphthoquinonediazide sulfonyl ester compound may be contained. It may contain both.

Moreover, you may use a photoinitiator as a photosensitive agent. A polymerization initiator is preferably used for preparing a negative photosensitive resin composition, particularly when the above-described aralkyl resin contains a polymerizable carbon-carbon double bond.

The photopolymerization initiator is not particularly limited as long as it can generate active species such as radicals and polymerize polymerizable carbon-carbon double bonds upon irradiation with high-energy light such as ultraviolet rays. Specific examples include photoradical polymerization initiators.

Radical photopolymerization initiators include intramolecular cleavage type that generates radicals by cleaving intramolecular bonds, and hydrogen abstraction type that generates radicals by using hydrogen donors such as tertiary amines and ethers together. . Either can be used in the first embodiment. For example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, which is intramolecularly cleaved, generates radicals by cleaving the carbon-carbon bond upon exposure to light. Hydrogen-abstraction types include benzophenone, methyl orthobenzoin benzoate, 4-benzoyl-4'-methyldiphenyl sulfide, and the like.

The radical photopolymerization generator is not particularly limited as long as it is a compound that generates radicals by absorbing light, and commercially available radical photopolymerization initiators can be used. A photoradical polymerization initiator can be purchased, for example, from BASF.

The amount of the photosensitive agent is typically 1 to 90% by weight, preferably 1 to 50% by weight, based on the total non-volatile components in the photosensitive resin composition. In particular, when the photosensitizer is a photopolymerization initiator, its proportion is preferably in the range of 0.1 to 7% by mass based on the total mass of non-volatile components in the photosensitive resin composition.

The photosensitive resin composition preferably contains a solvent. In other words, the photosensitive resin composition preferably has components such as the aralkyl resin and the photosensitizer of the present disclosure dissolved or dispersed in a solvent.
Examples of solvents include aprotic polar solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide and dimethylsulfoxide; Examples include ethers, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone and diacetone alcohol, esters such as ethyl acetate, propylene glycol monomethyl ether acetate and ethyl lactate, and aromatic hydrocarbons such as toluene and xylene. The solvent may be a single solvent or a mixed solvent.

The amount of the solvent to be used may be appropriately adjusted according to the thickness of the film to be formed using the photosensitive resin composition. Typically, the amount of solvent used is such that the concentration of non-volatile components in the photosensitive resin composition is 1 to 95% by mass.

The photosensitive resin composition may contain optional components for performance adjustment in addition to the aralkyl resin, photosensitizer and solvent in the present disclosure. Examples of optional components include surfactants, antioxidants, sensitizers, resins other than aralkyl resins, fillers, colorants, curable monomers, oligomers, and the like.

A good pattern can be formed by using the photosensitive resin composition, for example, in the following procedure.
(1) A film forming step of applying a photosensitive resin composition on a substrate to form a photosensitive film (2) An exposure step of exposing the photosensitive film (3) Developing the photosensitive film after exposure to form a pattern development process to form

Descriptions of the above steps will be added below.

- Film forming step The substrate to which the photosensitive resin composition is applied is not particularly limited. Substrates made of silicon wafers, metals, glasses, ceramics and plastics can be mentioned. Alternatively, the photosensitive resin composition may be applied onto a substrate that has been previously coated with another polymer. As the coating method, known coating methods such as spin coating, dip coating, spray coating, bar coating, applicator, ink jet, and roll coater can be applied without any particular limitation.

The base material coated with the photosensitive resin composition is heated, for example, at 80 to 120° C. for about 30 seconds to 30 minutes to dry the solvent. A photosensitive film can be obtained by carrying out like this.

• Exposure process The photosensitive film obtained in the film formation process is usually irradiated with light through a photomask for forming a desired pattern. A known method and apparatus can be used for the exposure. A light source having a light source wavelength in the range of 100 to 600 nm can be used. Specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, KrF excimer lasers (wavelength: 248 nm), UV-LED lamps, and the like. The exposure dose is usually about 1 to 10,000 mJ/cm ² , preferably about 10 to 5,000 mJ/cm ² .

After exposure, post-exposure heating may be performed before or after the development step, if necessary. The post-exposure heating temperature is 60 to 180° C., and the post-exposure heating time is usually 0.1 to 60 minutes, preferably 0.5 to 10 minutes.

Developing process A patterned film is produced by developing the exposed photosensitive film obtained in the exposure process. By using an alkaline aqueous solution as a developer, the exposed portion is dissolved to form a pattern.

The developer is not particularly limited as long as it can remove the photosensitive film in the exposed area. Specific examples include alkaline aqueous solutions in which inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, quaternary ammonium salts, mixtures thereof, and the like are dissolved. More specifically, alkaline aqueous solutions such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (abbreviation: TMAH) can be mentioned. Among them, it is preferable to use a TMAH aqueous solution, and it is particularly preferable to use a 0.1 to 5% by mass TMAH aqueous solution.

As a developing method, a known method such as an immersion method, a puddle method, or a spray method can be used. The development time is usually 0.1 to 120 minutes, preferably 0.5 to 60 minutes. After that, washing, rinsing, drying, etc. are performed as necessary. In this way a pattern can be formed on the substrate.

The photosensitive resin composition containing the aralkyl resin of the present disclosure can be used as a photosensitive resin composition used in the manufacture of electronic devices such as photoresists, and used to form patterns on silicon wafers. can do.

<Cured product, electronic device>
A cured product can be obtained by curing the curable resin composition. Curing can be done by light and/or heat.
More specifically, the curable resin composition is usually heated at 100-200° C. for 0.1-20 minutes. Thereby, a cured product can be obtained. In order to improve the curing performance, "post-curing" may be performed at 70 to 200° C. for 0.1 to 10 hours.
The cured product may be in the form of a molded product, a cast product, a laminate having a cured film formed on one or both sides of a base material, a film, a base resin for biomaterials, and the like.

A cured product obtained by curing the curable resin composition has good transparency. From the viewpoint of this transparency, it is preferable to manufacture an optical member using the curable resin composition (manufacture an optical member comprising a cured product of the curable resin composition).
For example, the curable resin composition can be used as a transparent material for sealing optical elements such as optical sensors and imaging elements. The curable resin composition can also be used for the production of microlenses and as an optical adhesive.

An electronic device may be manufactured using the curable resin composition. That is, you may manufacture an electronic device provided with the said hardened|cured material. It is considered that the above-mentioned cured product has good dielectric properties (it tends to have a low dielectric constant and a low dielectric loss tangent) as well as transparency due to the inclusion of fluorine atoms. Good dielectric properties are desirable properties for electronic device applications.

As an example, the curable resin composition can be used as a sealing material for electronic parts. That is, by encapsulating an electronic component with a melted product obtained by heating a curable resin composition, an electronic device in which the electronic component is encapsulated with the cured product can be produced.
As another example, a substrate (preferably a fiber substrate) such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, paper, etc., is coated with a curable resin composition and / or impregnated to laminate. curable materials can be produced. This curable material for lamination can be suitably used for manufacturing printed wiring boards such as multilayer electrical laminates, build-up laminates, and flexible laminates.
As still another example, an insulating film can be provided by applying a varnish-like curable resin composition to a circuit-formed substrate to form a resin film and curing the resin film.

The embodiments of the present disclosure have been described above, but these are examples of the present disclosure, and various configurations other than those described above can be adopted. In addition, the present disclosure is not limited to the above-described embodiments, and includes modifications, improvements, and the like within a range that can achieve the purpose of the present disclosure.

Embodiments of the present disclosure will be described in detail based on examples and comparative examples. As a reminder, this disclosure is not limited to the examples only.

In the following, the weight average molecular weight Mw and number average molecular weight Mn were measured using gel permeation chromatography (GPC, HLC-8320 manufactured by Tosoh Corporation). Tetrahydrofuran (THF) was used as the mobile phase, and TSKgel SuperHZ (3000×1+2000×2)/(6.0 mm ID×15 cm×3) columns were used.

The hydroxyl equivalent was calculated from the hydroxyl value measured based on JIS K 0070:1992.

The epoxy equivalent was measured based on JIS K 7236:2009.

The solid content acid value was calculated by measuring the acid value of the solution based on JIS K 0070:1992 and calculating the solid content acid value from the solid content concentration.

The solid content concentration is calculated by dividing the mass of the residue after depressurizing distillation of the solvent in the solution containing the solvent by the total mass of the solution containing the solvent, or dividing the mass of the reaction substrate excluding the solvent into the solution containing the solvent. Calculated by dividing by the total mass.

[Preparation example of catalyst for fluoral synthesis]
896 g of special grade reagent CrCl ₃ .6H ₂ O was dissolved in pure water to make 3.0 L of solution. 400 g of granular alumina was immersed in this solution and left for a whole day and night. After standing, the solution was filtered to take out alumina, and the alumina was kept at 100° C. in a hot air circulation dryer and dried for one day. Chromium-supported alumina was thus obtained.
The obtained chromium-supported alumina was filled in a cylindrical SUS316L reaction tube (diameter: 4.2 cm, length: 60 cm) equipped with an electric furnace. The chromium-supported alumina was heated to 300° C. while nitrogen gas was passed through the reaction tube at a flow rate of about 20 mL/min. When water stopped flowing out of the reaction tube, hydrogen fluoride was allowed to accompany the nitrogen gas, and its concentration was gradually increased. The reactor temperature was raised to 350° C. at the timing when a hot spot due to fluorination of the filled chromium-supported alumina reached the outlet end of the reaction tube, and this state was maintained for 5 hours. A catalyst for fluoral synthesis was thus obtained. This catalyst is hereinafter referred to as "catalyst A".

[Preparation example of fluoral]
125 mL of catalyst A was packed in a gas phase reactor (made of SUS316L, diameter 2.5 cm, length 40 cm) having a cylindrical reaction tube equipped with an electric furnace.
While air was flowing through the gas phase reactor at a flow rate of about 100 mL/min, the temperature of the reaction tube was raised to 280° C. and hydrogen fluoride was introduced at a rate of about 0.32 g/min over 1 hour.
Next, chloral (trichloroethanal) was started to be supplied to the reaction tube at a rate of about 0.38 g/min (contact time 15 seconds). One hour after the start of the reaction, the reaction was stabilized. After the reaction was stabilized, the gas flowing out of the reactor was collected over 18 hours in a SUS304 cylinder with a blowing tube cooled with a -15°C refrigerant.
The hydrogen fluoride content, the hydrogen chloride content, and the organic substance content were calculated by titration for 484.8 g of the collected liquid containing fluororal obtained here. As a result of the calculation, hydrogen fluoride was 40% by mass, hydrogen chloride was 11% by mass, and the organic matter content was 49% by mass. In addition, when part of the recovered organic matter was collected in a resin NMR tube and the degree of fluorination was confirmed by 19F-NMR, almost no low-order fluorinated substances were detected, and the fluorination progressed quantitatively. confirmed that there is
Next, 150 g (hydrogen fluoride: 40% by mass, hydrogen chloride: 11% by mass, organic matter: 49% by mass) of a portion of the collected fluororal-containing mixture was passed through a -15°C refrigerant through a condenser tube. was charged into a 500 ml SUS reactor equipped with a thermometer and a stirrer, and the reactor was heated to 25°C. Hydrogen chloride passing through the top tower of the condenser was removed by being absorbed by water while hydrogen fluoride was refluxed in the condenser under normal pressure. After refluxing for 5 hours, the reactor was sampled, and the obtained samples were titrated to calculate the hydrogen fluoride content, the hydrogen chloride content, and the organic matter content. As a result of calculation, hydrogen fluoride: 44% by mass, hydrogen chloride: 1% by mass, and organic matter: 55% by mass.
[Physical property data]
1,2,2,2-tetrafluoroethanol:
19F-NMR (400MHz, _CFCl3 ) δ (ppm): -85.82 (3F, s), -137.95 (1F, d, J = 54.9Hz)
Hydrogen fluoride:
19F-NMR (400MHz, _CFCl3 ) δ (ppm): -193.37 (1F, s)

(Synthesis Example 1: Synthesis of aralkyl resin having a structural unit represented by general formula (7) below)

In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, the fluoral-containing mixture (hydrogen fluoride: 44 mass% , hydrogen chloride: 1% by mass, organic matter: 55% by mass), 16.8 g (fluoral: 94 mmol, hydrogen fluoride: 0.369 mol), hydrogen fluoride 9.6 g (0.479 mol), meta-xylene 10.0 g (94 mmol) was charged. Then, the reaction was carried out at 100° C. and an absolute pressure of 0.8 MPa for 20 hours. After that, the reaction solution was poured into 50 g of ice water, and organic matter was extracted with 50 g of methyl isobutyl ketone. The organic layer collected by the liquid separation operation was washed twice with 50 g of water, and further neutralized with an aqueous potassium hydrogencarbonate solution. The amount of meta-xylene in the organic layer recovered by the liquid separation operation was quantified by gas chromatography, and the meta-xylene conversion rate was calculated to be 99% or more. Then, it was concentrated by an evaporator to obtain 16.2 g of the desired aralkyl resin.
[Physical property data]
Number average molecular weight (Mn) = 592, weight average molecular weight (Mw) = 845, polydispersity (Mw/Mn) = 1.4

(Synthesis Example 2: Synthesis of aralkyl resin having a structural unit represented by general formula (8) below)

In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, the fluoral-containing mixture (hydrogen fluoride: 44 mass% , hydrogen chloride: 1% by mass, organic matter: 55% by mass) 14.6 g (fluoral: 82 mmol, hydrogen fluoride: 0.321 mol), hydrogen fluoride 8.3 g (0.416 mol), benzene 1.3 g ( 16 mmol) and 10.0 g (0.106 mol) of phenol were added. Then, the reaction was carried out at 25° C. and an absolute pressure of 0.2 MPa for 20 hours. Thereafter, the same operation as in Synthesis Example 1 was performed, and the organic layer was recovered. The amount of benzene in the collected organic layer was quantified by gas chromatography, and the conversion of benzene was calculated to be 89%. Then, it was concentrated by an evaporator to obtain 16.2 g of the desired aralkyl resin. The hydroxyl equivalent weight was 191 g/equivalent.
[Physical property data]
Number average molecular weight (Mn) = 622, weight average molecular weight (Mw) = 723, polydispersity (Mw/Mn) = 1.2

(Synthesis Example 3: Synthesis of aralkyl resin having a structural unit represented by general formula (9) below)

In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, the fluoral-containing mixture (hydrogen fluoride: 44 mass% , hydrogen chloride: 1% by mass, organic matter: 55% by mass) 14.6 g (fluoral: 82 mmol, hydrogen fluoride: 0.321 mol), hydrogen fluoride 8.3 g (0.416 mol), biphenyl 2.5 g ( 16 mmol) and 10.0 g (0.106 mol) of phenol were added. Then, the reaction was carried out at 25° C. and an absolute pressure of 0.2 MPa for 20 hours. Thereafter, the same operation as in Synthesis Example 1 was performed, and the organic layer was recovered. The amount of biphenyl in the collected organic layer was quantified by gas chromatography, and the conversion rate of biphenyl was calculated to be 99% or more. Then, it was concentrated by an evaporator to obtain 17.3 g of the desired aralkyl resin. The hydroxyl equivalent weight was 227 g/equivalent.
[Physical property data]
Number average molecular weight (Mn) = 924, weight average molecular weight (Mw) = 1185, polydispersity (Mw/Mn) = 1.3

(Synthesis Example 4: Synthesis of Aralkyl Resin Having Structural Unit Represented by General Formula (10) Below)

In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, the fluoral-containing mixture (hydrogen fluoride: 44 mass% , hydrogen chloride: 1% by mass, organic matter: 55% by mass), 14.6 g (fluoral: 82 mmol, hydrogen fluoride: 0.321 mol), hydrogen fluoride 8.3 g (0.416 mol), meta-xylene 1.7 g (16 mmol) and 10.0 g (0.106 mol) of phenol were added. Then, the reaction was carried out at 60° C. and an absolute pressure of 0.4 MPa for 20 hours. Thereafter, the same operation as in Synthesis Example 1 was performed, and the organic layer was recovered. The amount of meta-xylene in the recovered organic layer was quantified by gas chromatography, and the meta-xylene conversion rate was calculated to be 99% or more. Then, it was concentrated by an evaporator to obtain 17.4 g of the desired aralkyl resin. The hydroxyl equivalent weight was 206 g/equivalent.
[Physical property data]
Number average molecular weight (Mn) = 598, weight average molecular weight (Mw) = 691, polydispersity (Mw/Mn) = 1.2

(Synthesis Example 5: Synthesis of aralkyl resin having a structural unit represented by general formula (15) below)

A 50 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer was charged with 7.8 g of the aralkyl resin obtained in Synthesis Example 3 (hydroxyl equivalent: 227 g/equivalent), 19.1 g of epichlorohydrin (205 mmol), and 1-butanol. .9 g was charged and heated to 50° C. in a water bath. After that, 6.8 g (34 mmol) of a 20% by mass sodium hydroxide aqueous solution was dropped into the flask over 30 minutes. Further, after that, the temperature inside the flask was maintained at 50° C., and the reaction was carried out for 2 hours. After completion of the reaction, excess alkali was neutralized with hydrochloric acid, and the organic layer was collected by liquid separation operation and concentrated by an evaporator to obtain a crude epoxy resin.
A 50 mL glass flask equipped with a stirrer and a thermometer was charged with the above crude epoxy resin, 19.0 g of methyl isobutyl ketone, 1.9 g of 1-butanol, and 4.3 g of a 20% by mass sodium hydroxide aqueous solution. ℃ and alkaline treatment for 2 hours. After that, the excess alkali was neutralized with hydrochloric acid, and the organic layer was recovered by a liquid separation operation, added with 50 g of methyl isobutyl ketone, and then washed with 50 g of water three times. Then, the organic layer was collected by liquid separation operation and concentrated by an evaporator to obtain 7.6 g of the desired aralkyl resin (epoxy resin). The epoxy equivalent weight was 271 g/equivalent.
[Physical property data]
Number average molecular weight (Mn) = 1035, weight average molecular weight (Mw) = 1519, polydispersity (Mw/Mn) = 1.5

(Synthesis Example 6: Synthesis of aralkyl resin having a structural unit represented by general formula (16) below)

A 50 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer was charged with 6.8 g of the aralkyl resin obtained in Synthesis Example 4 (hydroxyl equivalent: 206 g/equivalent), 18.3 g (198 mmol) of epichlorohydrin, and 1-butanol. 0.8 g was charged and heated to 50° C. in a water bath. After that, 6.6 g (33 mmol) of a 20% by mass sodium hydroxide aqueous solution was dropped into the flask over 30 minutes. Thereafter, the same operation as in Synthesis Example 5 was performed to obtain 6.7 g of the desired aralkyl resin (epoxy resin). The epoxy equivalent weight was 257 g/equivalent.
[Physical property data]
Number average molecular weight (Mn) = 623, weight average molecular weight (Mw) = 821, polydispersity (Mw/Mn) = 1.4

(Synthesis Example 7: Synthesis of Aralkyl Resin Solution Having Structural Unit Represented by General Formula (9))

In a 500 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, the fluoral-containing mixture (hydrogen fluoride: 44 mass% , hydrogen chloride: 1% by mass, organic matter: 55% by mass), 104.7 g (fluoral: 664 mmol, hydrogen fluoride: 2.99 mol), hydrogen fluoride 60.0 g (3.00 mol), biphenyl 18.1 g ( 118 mmol) and 62.5 g (664 mmol) of phenol were added. Then, the reaction was carried out at 25° C. and an absolute pressure of 0.2 MPa for 20 hours. After that, the same operation as in Synthesis Example 1 was performed, the organic layer was recovered, and the organic layer was concentrated by an evaporator to recover 219.6 g of the desired aralkyl resin solution. The solid content concentration was 55.1% by mass, and the hydroxyl group equivalent weight of the solid content was 210 g/equivalent. A part of the solution was used for the operation of Example 4 after removing the solvent by an evaporator.
[Physical property data]
Number average molecular weight (Mn) = 793, weight average molecular weight (Mw) = 1058, polydispersity (Mw/Mn) = 1.5

(Synthesis Example 8: Synthesis of Aralkyl Resin Solution Having Structural Unit Represented by General Formula (10) Below)

In a 500 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, the fluoral-containing mixture (hydrogen fluoride: 44 mass% , hydrogen chloride: 1% by mass, organic matter: 55% by mass), 104.7 g (fluoral: 664 mmol, hydrogen fluoride: 2.99 mol), hydrogen fluoride 60.0 g (3.00 mol), meta-xylene 12.5 g (118 mmol) and 62.5 g (664 mmol) of phenol were added. Then, the reaction was carried out at 25° C. and an absolute pressure of 0.2 MPa for 20 hours. After that, the same operation as in Synthesis Example 1 was performed, the organic layer was recovered, and the organic layer was concentrated by an evaporator to recover 234.8 g of the desired aralkyl resin solution. The solid content concentration was 48.1% by mass, and the hydroxyl group equivalent weight of the solid content was 198 g/equivalent. A part of the solution was used for the operation of Example 5 after removing the solvent by an evaporator.
[Physical property data]
Number average molecular weight (Mn) = 712, weight average molecular weight (Mw) = 884, polydispersity (Mw/Mn) = 1.2

(Synthesis Example 9: Synthesis of aralkyl resin solution having structural unit represented by general formula (17) below)

-Synthesis of aralkyl resin solution I (epoxy resin solution) In a 50 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer, 100 g of the aralkyl resin solution obtained in Synthesis Example 7 (hydroxyl equivalent: 210 g/equivalent) and 146 g of epichlorohydrin were added. (1.57 mol) and 14.6 g of 1-butanol were charged and heated to an internal temperature of 50° C. in a water bath. After that, 57.7 g (289 mmol) of a 20% by mass sodium hydroxide aqueous solution was dropped into the flask over 1 hour. After that, the same operation as in Synthesis Example 5 was performed, the organic layer was recovered, and concentrated by an evaporator to recover 133.0 g of aralkyl resin solution I (epoxy resin solution). The solid content concentration was 48.1% by mass, and the epoxy equivalent weight of the solid content was 298 g/equivalent.

・Synthesis of aralkyl resin solution II (acid-modified epoxy acrylate resin solution) In a 100 mL glass flask equipped with a stirrer, a reflux condenser and a thermometer, 30.0 g of the aralkyl resin solution I (epoxy resin solution) obtained above ( Epoxy equivalent (298 g/equivalent), 3.5 g (48 mmol) of acrylic acid, 29 mg of 4-methoxyphenol, and 72 mg of triphenylphosphine were charged, and the internal temperature was raised to 110° C. while introducing dry air and allowed to react for 15 hours. rice field. After that, 4.4 g (29 mmol) of 1,2,3,6-tetrahydrophthalic anhydride was added and reacted for 6 hours. After cooling, the desired aralkyl resin solution II (acid-modified epoxy acrylate resin solution) was obtained. The solid content concentration was 59.0% by mass, and the solid content acid value was 85 mgKOH/g.
[Physical property data]
Number average molecular weight (Mn) = 1180, weight average molecular weight (Mw) = 2904, polydispersity (Mw/Mn) = 2.5

(Synthesis Example 10: Synthesis of Aralkyl Resin Solution Having Structural Unit Represented by General Formula (18) Below)

-Synthesis of aralkyl resin solution III (epoxy resin solution) Into a 50 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer, 100 g of the aralkyl resin solution obtained in Synthesis Example 8 (hydroxyl equivalent: 198 g/equivalent) and 135 g of epichlorohydrin were added. (1.46 mol) and 13.5 g of 1-butanol were charged and heated to 50° C. in a water bath. After that, 53.6 g (268 mmol) of a 20% by mass sodium hydroxide aqueous solution was dropped into the flask over 1 hour. After that, the same operation as in Synthesis Example 5 was performed, the organic layer was recovered, and the organic layer was concentrated by an evaporator to recover 103.5 g of aralkyl resin solution III (epoxy resin solution). The solid content concentration was 51.8% by mass, and the epoxy equivalent weight of the solid content was 274 g/equivalent.

・Synthesis of aralkyl resin solution IV (acid-modified epoxy acrylate resin solution) In a 100 mL glass flask equipped with a stirrer, a reflux condenser and a thermometer, 30.0 g of the aralkyl resin solution III (epoxy resin solution) obtained above ( Epoxy equivalent: 274 g/equivalent), 4.1 g (48 mmol) of acrylic acid, 31 mg of 4-methoxyphenol, and 77 mg of triphenylphosphine were charged, and the temperature was raised to 110° C. while introducing dry air, and the mixture was reacted for 15 hours. After that, 5.2 g (34 mmol) of 1,2,3,6-tetrahydrophthalic anhydride was added and reacted for 6 hours. After cooling, the desired aralkyl resin solution IV (acid-modified epoxy acrylate resin solution) was obtained. The solid content concentration was 63.3% by mass, and the solid content acid value was 84 mgKOH/g.
[Physical property data]
Number average molecular weight (Mn) = 1142, weight average molecular weight (Mw) = 1995, polydispersity (Mw/Mn) = 2.3

(Synthesis Example 11: Synthesis of aralkyl resin having a structural unit represented by general formula (19) below)

In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, the fluoral-containing mixture (hydrogen fluoride: 44 mass% , hydrogen chloride: 1% by mass, organic matter: 55% by mass), 18 g (fluoral: 103 mmol, hydrogen fluoride: 0.40 mol), hydrogen fluoride 10 g (0.50 mol), biphenyl 1.6 g (10 mmol), 2 - 10 g (92 mmol) of cresol and 40 g of chloroform were added. Then, the reaction was carried out at 70° C. and an absolute pressure of 0.4 MPa for 18 hours. Thereafter, the same operation as in Synthesis Example 1 was performed, the organic layer was recovered, 30 g of ethylene glycol was added, and methyl isobutyl ketone and chloroform were distilled off using an evaporator. The obtained aralkyl resin solution was poured into 150 g of strongly stirred water, and the precipitated solid was collected by filtration. The recovered solid was washed twice with 100 g of water, and the solid recovered by filtration was dried with an evaporator to obtain 18 g of the target aralkyl resin.
[Physical property data]
Number average molecular weight (Mn) = 9597, weight average molecular weight (Mw) = 79248, polydispersity (Mw/Mn) = 8.3

(Synthesis Example 12: Synthesis of aralkyl resin having a structural unit represented by general formula (20) below)

In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, the fluoral-containing mixture (hydrogen fluoride: 44 mass% , hydrogen chloride: 1% by mass, organic matter: 55% by mass), 18 g (fluoral: 103 mmol, hydrogen fluoride: 0.40 mol), hydrogen fluoride 10 g (0.50 mol), meta-xylene 1.1 g (10 mmol), 10 g (92 mmol) of 2-cresol and 40 g of chloroform were added. Then, the reaction was carried out at 70° C. and an absolute pressure of 0.4 MPa for 18 hours. Thereafter, the same operation as in Synthesis Example 1 was performed, the organic layer was recovered, 30 g of ethylene glycol was added, and methyl isobutyl ketone and chloroform were distilled off using an evaporator. The obtained aralkyl resin solution was poured into 150 g of strongly stirred water, and the precipitated solid was collected by filtration. The recovered solid was washed twice with 100 g of water, and the solid recovered by filtration was dried with an evaporator to obtain 18 g of the target aralkyl resin.
[Physical property data]
Number average molecular weight (Mn) = 5760, weight average molecular weight (Mw) = 27033, polydispersity (Mw/Mn) = 4.7

(Synthesis Example 1 of Novolac Resin: Synthesis of Novolak Resin A Having a Structural Unit Represented by General Formula (21))

In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, the fluoral-containing mixture (hydrogen fluoride: 44 mass% , hydrogen chloride: 1% by mass, organic matter: 55% by mass), 19.3 g (fluoral: 108 mmol, hydrogen fluoride: 0.421 mol), hydrogen fluoride 11.0 g (0.55 mol), phenol 13.5 g ( 0.144 mol) was added. Then, the reaction was carried out at 20° C. and an absolute pressure of 0.2 MPa for 20 hours. Thereafter, the same operation as in Synthesis Example 1 was carried out to obtain 21.5 g of the desired novolac resin (novolak resin A). The hydroxyl equivalent weight was 175 g/equivalent.
[Physical property data]
Number average molecular weight (Mn) = 806, weight average molecular weight (Mw) = 1272, polydispersity (Mw/Mn) = 1.6

(Synthesis Example of Epoxy Resin: Synthesis of Epoxy Resin A Having a Structural Unit Represented by General Formula (22) Below)

In a 50 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer, 5.8 g of the novolak resin A obtained in Synthesis Example 1 of the novolac resin (hydroxyl equivalent: 175 g/equivalent), 18.3 g (198 mmol) of epichlorohydrin, 1.8 g of 1-butanol was charged and heated to 50° C. in a water bath. After that, 6.6 g (33 mmol) of a 20% by mass sodium hydroxide aqueous solution was dropped into the flask over 30 minutes. Thereafter, the same operation as in Synthesis Example 5 was performed to obtain 5.8 g of an epoxy resin (epoxy resin A). The epoxy equivalent weight was 233 g/equivalent.
[Physical property data]
Number average molecular weight (Mn) = 956, weight average molecular weight (Mw) = 2236, polydispersity (Mw/Mn) = 2.3

(Synthesis Example 2 of Novolak Resin: Synthesis of Novolak Resin B Having a Structural Unit Represented by General Formula (23) Below)

107 g (5.35 mol) hydrogen fluoride, 115 g (1.07 mmol) 2-cresol, 400 g chloroform were placed in a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor. 188 g of the fluoral-containing mixture (hydrogen fluoride: 44% by mass, hydrogen chloride: 1% by mass, organic substance: 55% by mass) obtained in [Fluoral preparation example] above (fluoral: 1.06 mol, hydrogen fluoride : 5.37 mol) was introduced over 1 hour at 30°C. Then, the temperature was raised to 70° C. and the reaction was carried out for 15 hours at an absolute pressure of 0.4 MPa. Thereafter, the same operation as in Synthesis Example 1 was performed to obtain 180 g of the desired novolac resin (novolac resin B).
[Physical property data]
Number average molecular weight (Mn) = 7056, weight average molecular weight (Mw) = 21287, polydispersity (Mw/Mn) = 3.0

(Synthesis Example of Comparative Aralkyl Resin: Synthesis of Comparative Aralkyl Resin Having Structural Unit Represented by General Formula (24) Below)

25.4 g (1.27 mol) hydrogen fluoride, 15.0 g (159 mmol) phenol, 3 paraformaldehyde in a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, thermometer protection tube, insert tube, and stirring motor. .9 g (141 mmol) was added. Then, the reaction was carried out at 20° C. and an absolute pressure of 0.2 MPa for 20 hours. Thereafter, the same operation as in Synthesis Example 1 was performed, and the organic layer was recovered. At this time, a large amount of insoluble components was observed. Further, the amount of meta-xylene in the recovered organic layer was quantified by gas chromatography, and the meta-xylene conversion rate was calculated to be 69%.

In contrast to the synthesis examples of comparative aralkyl resins using formaldehyde as a starting material, in Synthesis Example 4 using a fluoral-containing mixture as a starting material, no insoluble components were generated and meta-xylene conversion was 99% or more. From the above, it is better to produce an aralkyl resin having a “—CHCF ₃ —” structure using fluoral as a raw material than to produce an aralkyl resin having a “—CH ₂ —” structure using formaldehyde as a raw material. It is understood that it is easy.

<Preparation and Evaluation I of Curable Resin Composition (Containing Epoxy Resin)>
A curable resin composition having the composition shown in Table 1 was prepared, and the glass transition temperature and 5% heat weight loss temperature of each cured product were measured.

In the above table, epoxy resins and curing accelerators are as follows.
Epoxy resin: bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical, jer828, epoxy equivalent = 186 g/equivalent)
- Curing accelerator: triphenylphosphine (0.4% by mass relative to the epoxy resin)

4 g of the resulting curable resin composition was weighed into an aluminum cup container of 51 mm diameter and heated in an oven under normal pressure at 160° C. for 2 hours and further at 180° C. for 6 hours. After heating, it was naturally cooled to obtain a cured product.

The glass transition temperature was measured using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Co., Ltd., model name: DSC7000) at a heating rate of 10°C/min.

The 5% thermogravimetric loss temperature was measured using a differential thermal/thermogravimetric simultaneous measurement device (manufactured by Hitachi High-Tech Science Co., Ltd., model name STA7200) under conditions of a temperature increase rate of 10° C./min in a nitrogen atmosphere.

From Examples 1 to 3, it is understood that the cured product of the curable resin composition containing the aralkyl resin of the present embodiment has sufficient heat resistance for use in electronic devices.

<Resin melt viscosity evaluation>
Under 1 atmospheric pressure, the viscosity of the aralkyl resin heated to 150° C. was measured using a rotational viscometer (manufactured by ANTONPAAR, product name: PHYSICAMCR51, measuring cone CP50-1). The device settings were as follows. The viscosity at a shear rate of 1000 [1/s] in this measurement is shown in the table below.
・Shear rate: logarithmic ascending/descending (starting 10 [1/s] - finishing 1000 [1/s])
・Measurement interval: logarithmic (start 90 seconds - end 3 seconds)
・Measurement points: 21

Table 2 shows the above measurement/evaluation results.

From the comparison of the melt viscosities of Synthesis Examples 2 to 4 and Novolac Resin A, and Synthesis Examples 5 and 6 and Epoxy Resin A, the aralkyl resin of the present embodiment having an aralkyl structure is a resin having no aralkyl structure (Patent Document 4 (equivalent to the novolac resin described in 1.), and has a relatively low melt viscosity, and is excellent in handleability when used as a resin composition and fine workability during extrusion molding.

<Preparation and Evaluation II of Curable Resin Composition (Containing Epoxy Resin)>
A curable resin composition having the composition shown in Table 3 was prepared, and the water absorption of the cured product was measured.

2.4 g of the obtained curable resin composition was weighed into a silicon mold and heated in an oven under normal pressure at 160° C. for 2 hours and further at 180° C. for 6 hours. After heating, the mixture was naturally cooled to obtain a cured product having a diameter of 2.8 cm and a thickness of 3 mm. The resulting cured product was dried in an oven at 50° C. for 24 hours and then cooled to room temperature in a desiccator. Let the mass at this time be W1. After drying, the cured product was immersed in water at 23° C. for 24 hours, after which the water on the surface was wiped off and the mass was measured. Let the mass at this time be W2. The water absorption was calculated from the formula of water absorption (%)={(W2−W1)/W1}×100.

From the comparison between Examples 4 and 5 and Comparative Example 1, the cured product of the curable resin composition comprising the aralkyl resin of the present embodiment is the resin having no aralkyl structure of the present disclosure (the novolak described in Patent Document 4 It is understood that the water absorption rate is lower than that of a cured product of a curable resin composition composed of (corresponding to resin). The low water absorption of the cured product is effective when used in electronic devices from the viewpoint of dielectric properties and insulation reliability.

<Resin evaluation>
The glass transition temperature and 5% heat weight loss temperature of the resin shown in Table 4 were measured.

From the comparison of the glass transition temperature and the 5% heat weight loss temperature of the resins obtained in Synthesis Examples 11 and 12 and the novolac resin B, the aralkyl resin of the present embodiment is the resin having no aralkyl structure of the present disclosure (Patent Document 4), the heat resistance is equivalent.

<Preparation and Evaluation of Resin Composition>
A resin composition shown in Table 5 was prepared and the alkali dissolution rate was measured.

The alkali dissolution rate of the resin was evaluated by the following procedure.
(1) The resins obtained in Synthesis Examples 11 and 12 and the novolac resin B, either alone or in mixture, were dissolved in PGMEA (propylene glycol monomethyl ether acetate) and then filtered through a filter with a pore size of 0.2 μm. By doing so, a PGMEA solution of the resin was obtained.
(2) A resin composition was applied by spin coating to the surface of a silicon wafer that had been subjected to HMDS treatment, and the PGMEA was dried using a hot plate. Thus, a resin film was formed on the surface of the silicon wafer. The details of the spin coating conditions are as follows.
・Spin coating conditions: slope 50 s, 1,000 rpm, 60 s
・Drying conditions: 110°C, 60s
・ Dry film thickness: 10 μm
(3) The resin film formed in (2) above was immersed together with the silicon wafer in an alkaline aqueous solution (2.38% by mass tetramethylammonium hydroxide aqueous solution). Then, the alkali dissolution rate was calculated from the relationship between the immersion time and the film thickness.

From the results of Examples 6 to 9 and Comparative Example 2, the alkali dissolution rate of the aralkyl resin of the present disclosure is higher than that of the resin having no aralkyl structure of the present disclosure (corresponding to the novolac resin described in Patent Document 4). It is understood that by using the aralkyl resin of the present disclosure, it is possible to appropriately control the alkali dissolution rate and improve developability and film reduction.

<Preparation and Evaluation of Photosensitive Resin Composition (Photoresist Composition)>
A photosensitive resin composition (photoresist composition) was prepared and evaluated by the following procedures.
(1) 75 parts by mass of the aralkyl resin obtained in Synthesis Example 12 and 25 parts by mass of a quinone diazide photosensitizer (NT200, manufactured by Toyo Gosei Co., Ltd.) were dissolved in 500 parts by mass of PGMEA (propylene glycol monomethyl ether acetate), Then, it was filtered through a filter with a pore size of 0.2 μm. By carrying out like this, the photosensitive resin composition (photoresist composition) was prepared.
(2) A photosensitive resin composition (photoresist composition) was applied to the surface of the HMDS-treated silicon wafer by spin coating, and the PGMEA was dried using a hot plate. Thus, a photosensitive resin film (photoresist film) was formed on the surface of the silicon wafer.
・Spin coating conditions: slope 10 s, 1,000 rpm, 60 s
・Drying conditions: 110°C, 60s
・ Dry film thickness: 1 μm
(3) A photomask having a line/space pattern of various widths is placed on the photosensitive resin film (photoresist film) formed in (2) above, and a g h line lamp (g and h lines are 200 mJ/cm ² of h-line converted light was irradiated with a device that emits light at the same time.
(4) The light-irradiated photosensitive resin film (photoresist film) was developed together with the silicon wafer by immersing it in a developer (2.38% by mass tetramethylammonium hydroxide aqueous solution) for 30 seconds. After the immersion, the resin film on the silicon wafer taken out was dried by blowing nitrogen gas. Thus, a "pattern" was obtained on the silicon wafer.
The "pattern" was observed under a microscope. As a result of observation, it was confirmed that a pattern of line/space=5 μm/5 μm was resolved. From this result, it is understood that the aralkyl resin of the present disclosure is preferably applied to photosensitive resin compositions such as photoresists used in the manufacture of electronic devices.

This application is based on Japanese Patent Application No. 2021-179571 filed on November 2, 2021, and claims priority based on the Paris Convention or the laws and regulations of transition countries. The contents of that application are incorporated herein by reference in their entirety.

Claims

An aralkyl resin having a structural unit represented by general formula (1) or (2) below.

In general formula (1), R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different. Well, n is an integer of 0 to 2, when n is 0, it is an integer of p ≤ 4, when n is 1, it is an integer of p ≤ 6, and when n is 2, it is an integer of p ≤ 8 .

In general formula (2), R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different. Well, m and k are integers of 0 to 2, p + q ≤ 8 when m + k is 0, p + q ≤ 10 when m + k is 1, and p + q ≤ 12 when m + k is 2 When m+k is 3, it is an integer of p+q≤14, when m+k is 4, it is an integer of p+q≤16, and X is a single bond or a divalent substituent other than an oxygen atom.
2. The aralkyl resin according to claim 1, which has a structural unit represented by the general formula (1).
2. The aralkyl resin according to claim 1, which has a structural unit represented by the general formula (2).
2. The aralkyl resin according to claim 1, further comprising a structural unit represented by general formula (3) below.

In general formula (3), R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different. Well, t is an integer of 0 to 2, r is an integer of 1 or more, and s is an integer of 0 or more, provided that r + s ≤ 4 when t is 0, r + s ≤ 6 when t is 1, When t is 2, r+s≦8, R 2 represents a hydrogen atom or a monovalent substituent, and when multiple R 2 are present, they may be the same or different.
2. An aralkyl resin according to claim 1, which has a structural unit represented by general formula (4) or (5) below.

In general formula (4), R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different. Well, n is an integer of 0 to 2, when n is 0, it is an integer of p ≤ 4, when n is 1, it is an integer of p ≤ 6, and when n is 2, it is an integer of p ≤ 8 . R 2 represents a hydrogen atom or a monovalent substituent, and when multiple R 2 are present, they may be the same or different, t is an integer of 0 to 2, r is 1 or more is an integer and s is an integer greater than or equal to 0, provided that r+s≦4 when t is 0, r+s≦6 when t is 1, and r+s≦8 when t is 2.

In general formula (5), R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different. Well, m and k are integers of 0 to 2, p + q ≤ 8 when m + k is 0, p + q ≤ 10 when m + k is 1, and p + q ≤ 12 when m + k is 2 When m+k is 3, it is an integer of p+q≤14, when m+k is 4, it is an integer of p+q≤16, and X is a single bond or a divalent substituent other than an oxygen atom. R 2 represents a hydrogen atom or a monovalent substituent, and when multiple R 2 are present, they may be the same or different, t is an integer of 0 to 2, r is 1 or more is an integer and s is an integer greater than or equal to 0, provided that r+s≦4 when t is 0, r+s≦6 when t is 1, and r+s≦8 when t is 2.
6. An aralkyl resin according to claim 4 or 5, wherein R2 comprises a glycidyl group.
6. The aralkyl resin of claim 4 or 5, wherein R2 contains a polymerizable carbon-carbon double bond.
6. The aralkyl resin according to claim 4 or 5, wherein R2 has a partial structure represented by general formula (6) below.

In general formula (6), R3 represents a hydrogen atom or a monovalent organic group, and R4 represents a hydrogen atom, a methyl group, or a fluorine atom.
9. The aralkyl resin according to claim 8, wherein R3 represents a monovalent organic group having a terminal carboxyl group.
5. An aralkyl resin according to claim 1 or 4, which has a structural unit represented by general formula (7) below.
5. An aralkyl resin according to claim 1 or 4, which has a structural unit represented by general formula (8) below.
5. An aralkyl resin according to claim 1 or 4, which has a structural unit represented by general formula (9) below.
5. An aralkyl resin according to claim 1 or 4, which has a structural unit represented by general formula (10) below.
5. The aralkyl resin according to claim 1 or 4, which has a weight average molecular weight of 300 to 200,000.
An epoxy resin diluent comprising the aralkyl resin according to claim 1 or 4.
16. The epoxy resin diluent according to claim 15, having a hydroxyl equivalent weight of 130 g/equivalent or more.
A curable resin composition comprising a diluent for the aralkyl resin of claim 1 or the epoxy resin of claim 15.
The curable resin composition according to claim 17, further comprising an epoxy resin.
A photosensitive resin composition comprising the aralkyl resin according to claim 1 or 4 and a photosensitive agent.
20. The photosensitive resin composition according to claim 19, which is a photoresist composition, a solder resist composition or an imprint composition.
A cured product obtained by curing the curable resin composition according to claim 17 .
An electronic device comprising the cured product according to claim 21.
A method for producing an aralkyl resin, comprising reacting an aromatic compound with fluoral in the presence of an acid catalyst to produce an aralkyl resin having a structural unit represented by the following general formula (1) or (2).

In general formula (1), R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different. Well, n is an integer of 0 to 2, when n is 0, it is an integer of p ≤ 4, when n is 1, it is an integer of p ≤ 6, and when n is 2, it is an integer of p ≤ 8 .

In general formula (2), R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different. Well, m and k are integers of 0 to 2, p + q ≤ 8 when m + k is 0, p + q ≤ 10 when m + k is 1, and p + q ≤ 12 when m + k is 2 When m+k is 3, it is an integer of p+q≤14, when m+k is 4, it is an integer of p+q≤16, and X is a single bond or a divalent substituent other than an oxygen atom.
A structure represented by the following general formula (4) or (5) by reacting an aromatic compound represented by the following general formula (11) or (12) with a phenolic compound in the presence of an acid catalyst A method for producing an aralkyl resin, comprising producing an aralkyl resin having units.

In general formula (11), R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different. Well, n is an integer of 0 to 2, a is an integer of 2 or more, when n is 0, it is an integer of p + a ≤ 6, when n is 1, it is an integer of p + a ≤ 8, and n is 2 is an integer of p+a≤10 when Z represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and when multiple Zs are present, they may be the same or different.

In general formula (12), R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when multiple R 1 are present, they may be the same or different. Well, m and k are integers of 0 to 2, a and b are integers of 1 or more, p + q + a + b ≤ 10 when m + k is 0, and p + q + a + b ≤ 12 when m + k is 1. , p + q + a + b ≤ 14 when m + k is 2, p + q + a + b ≤ 16 when m + k is 3, p + q + a + b ≤ 18 when m + k is 4, and X is a single bond or excluding an oxygen atom It is a divalent substituent. Z represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and when multiple Zs are present, they may be the same or different.

In general formula (4), R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different. Well, n is an integer of 0 to 2, when n is 0, it is an integer of p ≤ 4, when n is 1, it is an integer of p ≤ 6, and when n is 2, it is an integer of p ≤ 8 . R 2 represents a hydrogen atom or a monovalent substituent, and when multiple R 2 are present, they may be the same or different, t is an integer of 0 to 2, r is 1 or more is an integer and s is an integer greater than or equal to 0, provided that r+s≦4 when t is 0, r+s≦6 when t is 1, and r+s≦8 when t is 2.

In general formula (5), R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different. Well, m and k are integers of 0 to 2, p + q ≤ 8 when m + k is 0, p + q ≤ 10 when m + k is 1, and p + q ≤ 12 when m + k is 2 When m+k is 3, it is an integer of p+q≤14, when m+k is 4, it is an integer of p+q≤16, and X is a single bond or a divalent substituent other than an oxygen atom. R 2 represents a hydrogen atom or a monovalent substituent, and when multiple R 2 are present, they may be the same or different, t is an integer of 0 to 2, r is 1 or more is an integer and s is an integer greater than or equal to 0, provided that r+s≦4 when t is 0, r+s≦6 when t is 1, and r+s≦8 when t is 2.
The structure represented by the general formula (4) or (5) is obtained by reacting an aromatic compound represented by the following general formula (13) or (14) with a phenolic compound in the presence of an acid catalyst. 25. The method for producing an aralkyl resin according to claim 24, wherein an aralkyl resin having units is produced.

In general formula (13), R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different. Well, n is an integer of 0 to 2, a is an integer of 2 or more, when n is 0, it is an integer of p + a ≤ 6, when n is 1, it is an integer of p + a ≤ 8, and n is 2 is an integer of p+a≤10 when

In general formula (14), R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different. Well, m and k are integers of 0 to 2, a and b are integers of 1 or more, p + q + a + b ≤ 10 when m + k is 0, and p + q + a + b ≤ 12 when m + k is 1. , p + q + a + b ≤ 14 when m + k is 2, p + q + a + b ≤ 16 when m + k is 3, p + q + a + b ≤ 18 when m + k is 4, and X is a single bond or excluding an oxygen atom It is a divalent substituent.