JP2012072319A - Method for producing thermosetting resin having benzoxazine ring, and thermosetting resin having benzoxazine ring - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing thermosetting resin having a benzoxazine ring made to have a desired high molecular weight without gelating in a reaction.SOLUTION: There is provided a method for producing thermosetting resin having a benzoxazine ring including a step of reacting a bifunctional phenol compound, diamine compound and aldehyde compound in a mixed solvent of a solvent having one or more ether groups and alcoholic hydroxy groups in the molecule and an amide-based solvent.

Description

  The present invention relates to a method for producing a thermosetting resin having a benzoxazine ring, a thermosetting resin having a benzoxazine ring, a molded body thereof, and a cured body thereof.

  Thermosetting resins having a benzoxazine ring in the molecular structure are not found in other thermosetting resins such as dimensional stability, electrical insulation, and low water absorption in addition to heat resistance and flame retardancy. Because of its excellent characteristics, it has attracted attention as a binder such as electronic materials such as laminates and semiconductor encapsulants, friction materials and grindstones.

  A thermosetting resin having a benzoxazine ring is a thermosetting resin having a structure in which an oxazine ring is adjacent to a benzene ring, and is produced by reacting a phenol compound, an amine compound, and an aldehyde compound.

The thermosetting resin having a benzoxazine ring exemplified in Scheme 1 is a thermosetting resin having a benzoxazine ring manufactured using phenol as a phenol compound, aniline as an amine compound, and formaldehyde as an aldehyde compound. In Scheme 1, a thermosetting resin having a benzoxazine ring (left) undergoes ring-opening polymerization when heated to become polybenzoxazine (right).
Scheme 1:

  In recent years, various studies have been made on methods for efficiently synthesizing thermosetting resins having a benzoxazine ring having excellent characteristics. For example, Patent Document 1 discloses a production method in which a phenol resin is obtained by reacting phenols, paraformaldehyde, and monoamines in an alcohol solvent. In Patent Document 2 and Patent Document 3, phenols, paraformaldehyde, and amines are all reacted together in an aprotic solvent (excluding dioxane) such as toluene, methyl ethyl ketone, and ethyl acetate to produce a benzoxazine ring. A method for producing a thermosetting resin having the following is disclosed. Patent Document 4 and Non-Patent Document 1 disclose a method for producing a curable resin having a benzoxazine ring by reacting a bifunctional phenol compound, an aldehyde compound, and a diamine compound in dioxane or chloroform. . Non-Patent Document 2 discloses a method for producing a curable resin having a benzoxazine ring by reacting monofunctional phenol, paraformaldehyde, and monoamine in toluene and 2-methoxyethanol (methyl cellosolve). It is disclosed.

JP 2000-273135 A JP 2002-338648 A JP-A-2005-213301 JP 2003-064180 A

Polymer Preprints, Japan Vol. 57, no. 1, p1480 (2008) Polymer Preprints, Japan Vol. 59, no. 1, p461 (2010)

  However, in the methods disclosed in Patent Documents 1 to 4 and Non-Patent Documents 1 and 2 and the like, gelation may occur in the reaction, and thus thermosetting having a desired high molecular weight benzoxazine ring. There is a problem that it is difficult to synthesize a resin.

  This invention is made | formed in view of the said situation, and provides the manufacturing method which can obtain the thermosetting resin which has a desired high molecular weight benzoxazine ring, without gelatinizing in reaction. Is the main purpose.

  As a result of earnest research, the inventor conducted the above reaction by conducting a reaction in a mixed solvent containing at least an ether group and an alcoholic hydroxyl group in the molecule and an amide solvent. The present invention has been completed.

That is, the present invention is as follows.
[1]
A benzoxazine ring having a step of reacting a bifunctional phenol compound, a diamine compound, and an aldehyde compound in a solvent containing one or more ether groups and alcoholic hydroxyl groups in the molecule and a mixed solvent containing an amide solvent. The manufacturing method of the thermosetting resin which has this.
[2]
A step of mixing a bifunctional phenol compound, a diamine compound, a solvent having one or more ether groups and alcoholic hydroxyl groups in the molecule, and a mixed solvent containing an amide solvent to obtain a mixed solution;
A step of further adding an aldehyde compound to the mixed solution and reacting them;
A method for producing a thermosetting resin having a benzoxazine ring.
[3]
The solvent having at least one ether group and one alcoholic hydroxyl group in the molecule is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol mono Selected from the group consisting of ethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, polyethylene glycol monomethyl ether, and 3-methoxy-3-methyl-1-butanol Or at least one selected from the group consisting of Method for producing a thermosetting resin having a benzoxazine ring according to 2.
[4]
The solvent having at least one ether group and one alcoholic hydroxyl group in the molecule is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and triethylene glycol monomethyl ether. The method for producing a thermosetting resin having a benzoxazine ring according to any one of [1] to [3], which is at least one selected.
[5]
The amide solvent is at least one selected from the group consisting of N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone. [1] A method for producing a thermosetting resin having a benzoxazine ring according to any one of [4].
[6]
The amide solvent is at least one selected from the group consisting of N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone, [1] to [5 ] The manufacturing method of the thermosetting resin which has a benzoxazine ring as described in any one of.
[7]
Ratio of solvent having at least one ether group and alcoholic hydroxyl group in the molecule relative to the amide solvent (solvent having at least one ether group and alcoholic hydroxyl group in the molecule / amide solvent) : Volume ratio) is 20 / 80-90 / 10, The manufacturing method of the thermosetting resin which has a benzoxazine ring as described in any one of [1]-[6].
[8]
Solvent Ratio of the solvent having at least one ether group and alcoholic hydroxyl group in the molecule relative to the amide solvent (solvent having at least one ether group and alcoholic hydroxyl group in the molecule / the amide solvent) : Volume ratio) is 30 / 70-80 / 20, The manufacturing method of the thermosetting resin which has a benzoxazine ring as described in any one of [1]-[7].
[9]
Ratio of solvent having at least one ether group and alcoholic hydroxyl group in the molecule relative to the amide solvent (solvent having at least one ether group and alcoholic hydroxyl group in the molecule / the amide solvent: The method for producing a thermosetting resin having a benzoxazine ring according to any one of [1] to [8], wherein the volume ratio) is 40/60 to 70/30.
[10]
The method for producing a thermosetting resin having a benzoxazine ring according to any one of [1] to [9], wherein the mixed solvent further contains an aromatic nonpolar solvent.
[11]
The method for producing a thermosetting resin having a benzoxazine ring according to [10], wherein the aromatic nonpolar solvent is at least one selected from the group consisting of benzene, toluene, xylene, pseudocumene, and mesitylene.
[12]
In the said mixed solvent, the ratio of the said aromatic nonpolar solvent is 0-50 volume%, The manufacturing method of the thermosetting resin which has a benzoxazine ring as described in [10] or [11].
[13]
In the mixed solvent, the total proportion of the solvent having at least one ether group and alcoholic hydroxyl group in the molecule and the amide solvent is 50 to 100% by volume, according to [1] to [12] The manufacturing method of the thermosetting resin which has a benzoxazine ring as described in any one.
[14]
The bifunctional phenol is 4,4′-dihydroxybenzophenone (DHBP), 4,4′-biphenol, bis (4-hydroxyphenyl) sulfone (bisphenol S), 1,4-benzenediol (hydroquinone), 1,5 -At least one selected from the group consisting of dihydroxynaphthalene and 2,6-dihydroxynaphthalene,
The diamine compound is at least one selected from the group consisting of p-phenylenediamine (PDA), 4,4′-diaminodiphenylmethane (MDA), and 4,4′-diaminobiphenyl,
The method for producing a thermosetting resin having a benzoxazine ring according to any one of [1] to [13], wherein the aldehyde compound is at least formaldehyde.
[15]
A benzo compound obtained by reacting a bifunctional phenol compound, a diamine compound, and an aldehyde compound in a solvent containing at least one ether group and an alcoholic hydroxyl group in the molecule and a mixed solvent containing at least an amide solvent. A thermosetting resin having an oxazine ring.
[16]
React bifunctional phenolic compounds, diamine compounds, and aldehyde compounds in a mixed solvent containing at least one ether group and one alcoholic hydroxyl group in the molecule, an amide solvent, and an aromatic nonpolar solvent. The thermosetting resin which has a benzoxazine ring obtained by making it.
[17]
[15] A molded article comprising the thermosetting resin according to [16].
[18]
[15] A cured product comprising the thermosetting resin according to [16].
[19]
An electronic device comprising the molded product according to [17] or the cured product according to [18].

  According to the production method of the present invention, a thermosetting resin having a high molecular weight and having a benzoxazine ring can be obtained without gelation in the reaction.

2 is a proton nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum) of a thermosetting resin having a benzoxazine ring produced in Example 1. FIG. 2 is a proton nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum) of a thermosetting resin having a benzoxazine ring produced in Example 2. FIG. 3 is a proton nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum) of a thermosetting resin having a benzoxazine ring produced in Example 3. FIG. 4 is a proton nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum) of a thermosetting resin having a benzoxazine ring produced in Example 4. FIG. 6 is a proton nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum) of a thermosetting resin having a benzoxazine ring produced in Example 5. FIG.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention.

  The method for producing a thermosetting resin having a benzoxazine ring according to the present embodiment includes a bifunctional phenol compound, a diamine compound, and an aldehyde compound, each having one or more ether groups and alcoholic hydroxyl groups in the molecule, and A step of reacting in a mixed solvent containing an amide solvent.

It does not specifically limit as a bifunctional phenol compound, For example, the compound etc. which have two phenolic hydroxyl groups represented by following formula (I) are mentioned.
Formula (I):

HO-R ¹ -OH

R ¹ represents an aromatic organic group that may contain a hetero element.

  It does not specifically limit as a bifunctional phenol compound, For example, the compound etc. which are represented by following formula (1), (2), and (3) are mentioned.

In the formula (1), X is a direct bond (no atoms and atomic groups are present), a linear, branched, or cyclic aliphatic group that may contain a hetero element or a functional group, or an aromatic group Represents an organic group. Y each independently represents a direct bond or an aliphatic or aromatic organic group having a linear, branched, or cyclic structure which may contain a hetero element or a functional group. Each of the aliphatic organic group and the aromatic organic group may have a substituent.
The substituent is not particularly limited, and examples thereof include an aliphatic hydrocarbon group having a linear, branched, or cyclic structure having 1 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group.
Y in Formula (1) is not particularly limited as long as it is independently an organic group selected from a direct bond or the above organic group, and may be the same or different.
n and m each independently represent an integer of 0 to 10.

In the formula (1), X may be bonded at any of the ortho, meta, and para positions with respect to the left and right Y bonding positions, and the X bonding positions are the same in the left and right benzene rings. The positions may be different from each other, such as the ortho position and the para position.
Y only needs to be bonded at the ortho position, the meta position, or the para position with respect to the bonding position of the left and right phenolic hydroxyl groups, and the bonding position of Y is the same position in the left and right benzene rings. It may be different as in the ortho position and the para position.

When the bifunctional phenol compound is a compound represented by the formula (1) and X in the formula (1) is any one of the organic groups, X is at least one selected from the group consisting of the following group A: It is preferable that
Group A:

In group A, * represents a binding site to the aromatic ring in the formula (1).

The bifunctional phenol compound is more preferably a compound represented by the formula (1), wherein X is at least one selected from the group consisting of the following group A ′.
Group A ':

In the group A ′, * represents a binding site to the aromatic ring in the formula (1).

When the bifunctional phenol compound is a compound represented by the formula (1) and Y is the organic group, Y is preferably at least one selected from the group consisting of the following group B.
Group B:

In group B, * represents a binding site to the aromatic ring in the formula (1).

The bifunctional phenol compound is more preferably a compound represented by the formula (1), wherein Y is at least one selected from the group consisting of the following group B ′.
Group B ':

In group B ′, * represents a binding site to the aromatic ring in the formula (1).

  In Formula (1), n and m are each independently preferably an integer of 0 to 10, and more preferably an integer of 0 to 5.

  In the formula (1), when n and m are 0, it means a compound represented by the following formula (4).

In formula (4), X represents a direct bond, an aliphatic or aromatic organic group having a linear, branched, or cyclic structure which may contain a hetero element or a functional group. Each of the aliphatic organic group and the aromatic organic group may have a substituent.

  In the formula (4), X may be bonded at any of the ortho, meta, and para positions with respect to the bond positions of the left and right phenolic hydroxyl groups. , May be the same position, and may be different as in the ortho position and the para position.

  The bifunctional phenol compound is not particularly limited, and examples thereof include 4,4′-dihydroxydiphenyl-2,2-propane (bisphenol A), 4,4 ′-[1,3-phenylenebis (1-methyl-ethylidene). )] Bisphenol (bisphenol M), 4,4 ′-[1,4-phenylenebis (1-methyl-ethylidene)] bisphenol (bisphenol P), 4,4′-methylenediphenol (bisphenol F), bis (4 -Hydroxyphenyl) sulfone (bisphenol S), 4,4'-dihydroxybenzophenone (DHBP), 4,4'-biphenol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2, , 6-Dihydroxynaphthalene, 2,7-dihydroxynaphthalene , 1,4-benzenediol (hydroquinone), 1,3-benzenediol (resorcinol), 1,2-benzenediol (catechol), and the like. Among these, 4,4′-dihydroxybenzophenone (DHBP), 4,4′-biphenol, and bis (4-hydroxyphenyl) sulfone are used from the viewpoint of further improving the heat resistance of a molded body such as a film and a cured body described later. At least one selected from the group consisting of (bisphenol S), 1,4-benzenediol (hydroquinone), 1,5-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene is preferable. A bifunctional phenol compound may be used individually by 1 type, and may use 2 or more types together.

It does not specifically limit as a diamine compound, For example, the compound etc. which have two amino groups represented by following formula (II) are mentioned.
Formula (II):

H ₂ N—R ² —NH ₂

R ² represents an aliphatic or aromatic organic group having a linear, branched, or cyclic structure that may contain a hetero element.

  Examples of the diamine compound include an alicyclic diamine compound, a linear aliphatic diamine compound, and an aromatic diamine compound.

  It does not specifically limit as an alicyclic diamine compound, For example, the compound etc. which are represented by following formula (5) or (6) are mentioned.

  The compounds represented by the formulas (5) and (6) may be cis isomers, trans isomers, or any mixture of cis isomers and trans isomers.

Although it does not specifically limit as a linear aliphatic diamine compound, For example, the compound etc. which are selected from the group which consists of the following group C are mentioned.
Group C:

  It does not specifically limit as an aromatic diamine compound, For example, the compound etc. which are represented by following formula (7), (8), and (9) are mentioned.

In the formula (7), X ′ represents an aliphatic or aromatic organic group having a direct bond, a linear, branched or cyclic structure which may contain a hetero element or a functional group. Y ′ each independently represents a direct bond, or an aliphatic or aromatic organic group having a linear, branched, or cyclic structure which may contain a hetero element or a functional group. Each of the aliphatic organic group and the aromatic organic group may have a substituent.
The substituent is not particularly limited, and examples thereof include an aliphatic hydrocarbon group having a linear, branched, or cyclic structure having 1 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group.
In Formula (7), Y ′ may be any functional group selected from a direct bond or the above organic group independently, and the kind thereof is not particularly limited.
n ′ and m ′ each independently represent an integer of 0 to 10.

In Formula (7), X ′ may be bonded at any of the ortho, meta, and para positions with respect to the left and right Y ′ bonding positions. May be the same position, or may be different as in the ortho position and the para position.
Y ′ may be bonded at the ortho position, the meta position, or the para position with respect to the bonding position of the left and right amino groups, and the bonding position of Y ′ is the same position in the left and right benzene rings. It may be different and may be different, such as the ortho position and the para position.

When the diamine compound is a compound represented by the formula (7) and X ′ is the organic group, X ′ may be at least one organic group selected from the group consisting of the following group D.
Group D:

In group D, * represents a binding site to the aromatic ring in the formula (7).

When the diamine compound is a compound represented by the formula (7) and Y ′ is the above organic group, Y ′ may be at least one organic group selected from the group consisting of the following group E.
Group E:

In group E, * represents the binding site to the aromatic ring in the formula (7).

  In Formula (7), n ′ and m ′ are each independently preferably an integer of 0 to 10, and more preferably an integer of 0 to 5.

  In the formula (7), when n ′ and m ′ are 0, it means a compound represented by the following formula (10).

In formula (10), X ′ represents a direct bond, an aliphatic or aromatic organic group having a linear, branched, or cyclic structure which may contain a hetero element or a functional group. Each of the aliphatic organic group and the aromatic organic group may have a substituent.

  In the formula (10), X ′ may be bonded at any of the ortho, meta, and para positions with respect to the bonding positions of the left and right amino groups. May be the same position, or may be different as in the ortho position and the para position.

It does not specifically limit as a diamine compound, For example, 4,4'-bis (4-aminophenoxy) biphenyl, 3 (4), 8 (9), -bis (aminomethyl) tricyclo [5.2.1. Alicyclic diamine compounds such as 0 ^2,6 ] decane, 2,5 (6) -bis (aminomethyl) bicyclo [2.2.1] heptane; 1,2-diaminoethane, 1,6-diaminohexane, Linear aliphatic diamine compounds such as 1,10-diaminodecane, 1,12-diaminododecane, 1,14-diaminotetradecane, 1,18-diaminooctadecane; p-phenylenediamine (PDA), 4,4′-diamino Diphenylmethane (MDA), 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, 4,4′-diamino 3,3 ′, 5,5′-tetramethyldiphenylmethane, 4,4′-diamino-3,3 ′, 5,5′-tetraethyldiphenylmethane, 4,4′-diaminodiphenyl ether, 2,2′-bis [4 -(4-aminophenoxy) phenyl] propane, 4,4 '-[1,3-phenylenebis (1-methyl-ethylidene)] bisaniline (bisaniline M), 4,4'-[1,4-phenylenebis ( 1-methyl-ethylidene)] bisaniline (bisaniline P), 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-diaminobiphenyl, 4,4 And aromatic diamine compounds such as' -bis (4-aminophenoxy) biphenyl. Among these, from the viewpoint of improving the heat resistance of a cured body such as a film, from the group consisting of p-phenylenediamine (PDA), 4,4′-diaminodiphenylmethane (MDA), and 4,4′-diaminobiphenyl. At least one selected is preferred. A diamine compound may be used individually by 1 type, and may use 2 or more types together.

  The amount of the diamine compound used is preferably 0.1 to 2 mol, more preferably 0.3 to 1.8 mol, and more preferably 0.5 to 1.5 mol with respect to 1 mol of all bifunctional phenol compounds. More preferably it is. For example, when the compound represented by the formula (4) is used as the bifunctional phenol compound, it means that the amount of the diamine compound used is within the above range with respect to 1 mol of the compound represented by the formula (4). By making the usage-amount of the diamine compound with respect to 1 mol of bifunctional phenolic compounds 2 mol or less, gelatinization of a reaction solution can be suppressed effectively. By making the amount of the diamine compound used relative to 1 mol of the bifunctional phenol compound 0.1 mol or more, the bifunctional phenol compound is sufficiently reacted without remaining to further increase the molecular weight of the thermosetting resin having a benzoxazine ring. Can be made.

  The aldehyde compound is not particularly limited, and examples thereof include acetaldehyde, benzaldehyde, formaldehyde and the like. Among these, at least formaldehyde is preferable from the viewpoint of increasing the molecular weight. As formaldehyde, it can be used in the form of paraformaldehyde which is a polymer thereof, formalin which is in the form of an aqueous solution, or the like. Moreover, it can also be used as a hemiacetal obtained by reacting formaldehyde or paraformaldehyde with an alcohol. Although it does not specifically limit as alcohol in that case, Methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol etc. are mentioned. Among these, methanol is preferable from the viewpoint of ease of distillation. Alcohol may be used individually by 1 type and may use 2 or more types together.

  The amount of the aldehyde compound used is preferably 4 to 8 mol, more preferably 4 to 7 mol, and still more preferably 4 to 6 mol with respect to 1 mol of the diamine compound. By making the usage-amount of an aldehyde compound 8 mol or less, the influence on a human body and an environment can be reduced. By making the usage-amount of an aldehyde compound 4 mol or more, the thermosetting resin which has a benzoxazine ring can be made high molecular weight further.

  In the method for producing a thermosetting resin having a benzoxazine ring, a monofunctional phenol compound may be added and reacted together with a bifunctional phenol compound. When a monofunctional phenol compound is used in combination, a polymer having a reactive end sealed with a benzoxazine ring is generated. As a result, the molecular weight during the synthesis reaction can be controlled, and the gelation of the solution can be prevented. Moreover, the sealing of the reactive terminal can also improve the storage stability of the obtained thermosetting resin having a benzoxazine ring and prevent insolubilization.

  It does not specifically limit as a monofunctional phenol compound, For example, phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, p-octylphenol, p-cumylphenol, dodecylphenol, o-phenyl Phenol, p-phenylphenol, 1-naphthol, 2-naphthol, m-methoxyphenol, p-methoxyphenol, m-ethoxyphenol, p-ethoxyphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, etc. Can be mentioned. Among these, phenol, o-cresol, m-cresol, p-cresol, 1-naphthol, and 2-naphthol are preferable from the viewpoint of the end-capping effect. A monofunctional phenol compound may be used individually by 1 type, and may use 2 or more types together.

  Although the usage-amount of a monofunctional phenol compound is not specifically limited, 0.5 mol or less is preferable with respect to 1 mol of bifunctional phenol compounds. When the amount of the monofunctional phenol compound used is 0.5 mol or less with respect to 1 mol of the bifunctional phenol compound, the thermosetting resin having a benzoxazine ring structure can be increased in molecular weight during the synthesis reaction. By sufficiently reacting the monofunctional phenol compound, the remaining amount can be reduced.

  In the method for producing a thermosetting resin having a benzoxazine ring, the reaction between the bifunctional phenol compound, the diamine compound, and the aldehyde compound includes a solvent having at least one ether group and an alcoholic hydroxyl group in the molecule, And a mixed solvent containing an amide solvent. As a result, gelation during the reaction can be suppressed, and a sufficiently high thermosetting resin having a benzoxazine ring can be obtained. Further, the thermosetting resin having a benzoxazine ring obtained by using such a mixed solvent has a reduced thermal linear expansion coefficient as compared with the conventional one, and has excellent dimensional stability.

  The solvent having at least one ether group and one alcoholic hydroxyl group in the molecule is not particularly limited. For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, polyethylene glycol monomethyl ether, and 3-methoxy-3-methyl-1 A small amount selected from the group consisting of butanol It is preferably Kutomo one. Among these, from the viewpoint of the solubility of the resulting resin, at least one selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and triethylene glycol monomethyl ether More preferably. A solvent having one or more ether groups and one or more alcoholic hydroxyl groups in the molecule may be used alone or in combination of two or more.

  The amide solvent is not particularly limited, but is selected from the group consisting of, for example, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone. It is preferable that it is at least one kind. Among these, at least one selected from the group consisting of N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone from the viewpoint of the solubility of the resulting resin. It is more preferable. An amide solvent may be used individually by 1 type, and may use 2 or more types together.

  Ratio of solvent having at least one ether group and alcoholic hydroxyl group in the molecule relative to the amide solvent (solvent having at least one ether group and alcoholic hydroxyl group in the molecule / amide solvent: volume ratio) Is not particularly limited, but is preferably 20/80 to 90/10, more preferably 30/70 to 80/20, and still more preferably 40/60 to 70/30.

  The total ratio of the solvent having one or more ether groups and alcoholic hydroxyl groups in the molecule and the amide solvent in the mixed solvent is not particularly limited, but is preferably 50 to 100% by volume, and 60 to 100 More preferably, it is volume%. That is, another solvent can be further used in combination. The type of the other solvent to be used in combination can be appropriately selected in consideration of the reaction conditions and the like, but preferably further contains an aromatic nonpolar solvent. Thereby, productivity can be further improved.

  Although it does not specifically limit as an aromatic nonpolar solvent, As a preferable thing, the solvent etc. which are at least 1 sort (s) chosen from the group which consists of benzene, toluene, xylene, pseudocumene, and mesitylene, etc. are mentioned, for example. Among these, toluene and xylene are more preferable from the viewpoint of versatility and low cost. An aromatic nonpolar solvent may be used individually by 1 type, and may use 2 or more types together.

  Although it does not specifically limit as content of an aromatic nonpolar solvent, It is preferable that it is 0-50 volume% in a mixed solvent, and it is more preferable that it is 0-40 volume%. By setting the content of the aromatic nonpolar solvent in the above range, gelation during the reaction can be effectively suppressed, and the solubility of the resulting resin can be further improved.

  In a mixed solvent containing a solvent having at least one ether group and an alcoholic hydroxyl group in the molecule, an amide solvent, and an aromatic nonpolar solvent, the combination of the solvents is not particularly limited, but the boiling point, etc. From the viewpoint of ethylene glycol monomethyl ether and N, N-dimethylformamide (DMF) and toluene, ethylene glycol monomethyl ether and DMF and xylene, ethylene glycol monoethyl ether and DMF and toluene, ethylene glycol monoethyl ether and DMF and xylene, The mixed solvent is preferable.

  The ratio of the aromatic nonpolar solvent in the mixed solvent of the solvent having at least one ether group and alcoholic hydroxyl group in the molecule, the amide solvent, and the aromatic nonpolar solvent is not particularly limited. From the viewpoint of not reducing the solubility of the product, the ratio of the aromatic nonpolar solvent to the entire mixed solvent is preferably 50% by volume or less, and more preferably 40% by volume or less. By setting the ratio of the aromatic nonpolar solvent in the above range, the product can be effectively dissolved, and the synthesis efficiency can be further increased.

  Although the quantity of the mixed solvent used for reaction of a bifunctional phenol compound, a diamine compound, and an aldehyde compound is not specifically limited, It is the quantity from which the molar concentration of a bifunctional phenol compound will be 0.1-5.0 mol / L. Is more preferable, the amount is preferably 0.2 to 4.0 mol / L, and still more preferably 0.3 to 3.0 mol / L. When the molar concentration of the bifunctional phenol compound is 0.1 mol / L or more, the synthesis reaction rate of the thermosetting resin having a benzoxazine ring can be further accelerated, and the synthesis efficiency can be increased. When the molar concentration of the bifunctional phenol compound is 5.0 mol / L or less, during the synthesis reaction of the thermosetting resin having a benzoxazine ring, the gelation of the reaction solution can be more effectively suppressed, Insolubilization of the thermosetting resin having a benzoxazine ring can be prevented.

  The order of adding and mixing the raw materials such as the bifunctional phenol compound, the diamine compound, and the aldehyde compound is not particularly limited. For example, the bifunctional phenol compound, the diamine compound, and the aldehyde compound may be sequentially added to and mixed with the mixed solvent. In addition, each raw material may be added and mixed at once, but includes a bifunctional phenol compound, a diamine compound, a solvent having at least one ether group and an alcoholic hydroxyl group in the molecule, and an amide solvent. It is preferable to mix with the mixed solvent first.

  As a method for producing a thermosetting resin having a benzoxazine ring, a bifunctional phenol compound, a diamine compound, a solvent each having one or more ether groups and alcoholic hydroxyl groups in the molecule, and a mixture containing an amide solvent It is preferable that the production method includes a step of mixing a solvent to obtain a mixed solution, and a step of further adding an aldehyde compound to the mixed solution and causing the mixture to react. Thereby, gelatinization of the reaction solution can be more effectively suppressed.

  In order to efficiently mix and dissolve the raw materials, it is preferable to warm the solvent, and appropriately add a bifunctional phenol compound and the like while stirring the solvent using a stirrer, a stirrer, etc. Also good. During the reaction, an inert gas such as nitrogen gas may be purged as necessary. Although it does not specifically limit as a method of a heating process, For example, after using a temperature controller, such as an oil bath, to raise at a stretch to predetermined temperature, the method of keeping constant at the temperature etc. is mentioned.

  The temperature at the time of the heating treatment is not particularly limited as long as the synthesis reaction of the thermosetting resin having a benzoxazine ring is made efficient, but the reaction solution temperature is in the range of 10 to 150 ° C. Is preferable, it is more preferable that it is 30-150 degreeC, and it is still more preferable that it is the range of 50-150 degreeC. By setting the reaction solution temperature to 10 ° C. or higher, the synthesis reaction of the thermosetting resin having a benzoxazine ring can be effectively promoted, and the reaction efficiency can be further increased. By setting the reaction solution temperature to 150 ° C. or lower, gelation of the reaction solution can be effectively suppressed, and insolubilization of the resulting thermosetting resin having a benzoxazine ring can be effectively prevented. While the reaction solution is heated, the solvent may be refluxed.

  From the viewpoint of improving reaction efficiency, before adding an aldehyde compound, a mixture containing a bifunctional phenol compound, a diamine compound, a solvent having at least one ether group and an alcoholic hydroxyl group in the molecule, and an amide solvent It is preferable to heat the mixed solution of the solvent in advance.

  In the manufacturing method of the thermosetting resin which has a benzoxazine ring, you may further have the process of distilling off the water to produce | generate. By distilling off the water produced by the reaction, the synthesis reaction time of the thermosetting resin having a benzoxazine ring can be shortened, and the efficiency of the reaction can be improved. The method and timing for distilling off the produced water are not particularly limited, and can be performed, for example, by azeotroping with the solvent in the reaction solution. More specifically, the generated water can be distilled off by using an isobaric dropping funnel with a cock, a Dimroth cooler, a Dean-Stark device, or the like. Moreover, you may remove the water to produce | generate out of the system by reducing the pressure inside the reaction vessel during the reaction step.

  Although the processing time of a heating process is not specifically limited, For example, it is preferable that it is about 1 to 15 hours after a heating start, and about 2 to 10 hours are more preferable. After heating, the reaction solution may be allowed to cool by being released from contact with a temperature controller such as an oil bath, or may be cooled using a refrigerant or the like.

  In the manufacturing method of the thermosetting resin which has a benzoxazine ring, you may further have the process of wash | cleaning the mixed solution which complete | finished reaction with basic aqueous solution after synthetic reaction. By further performing the washing step, the unreacted bifunctional phenol compound or monofunctional phenol compound can be effectively removed from the reaction solution. After washing with a basic aqueous solution in the washing step, ions derived from the basic aqueous solution such as sodium ions can be removed by washing several times with distilled water or the like.

  The basic aqueous solution used for the washing is not particularly limited as long as it is an aqueous solution in which a basic compound is dissolved in water. Examples of the basic compound include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like. Among these, sodium hydroxide is preferable from the viewpoint of versatility.

  The method for recovering the thermosetting tree having the synthesized benzoxazine ring from the reaction solution is not particularly limited, and a known method can be adopted. Examples thereof include a reprecipitation method using a poor solvent, a concentration and solidification method (solvent distillation under reduced pressure), and a spray drying method. If necessary, the reaction solution may be filtered after the reaction.

  The thermosetting resin having a benzoxazine ring obtained by the production method of the present invention has a sufficiently high molecular weight. Therefore, physical properties such as heat resistance and flexibility such as glass transition temperature and thermal decomposition temperature of a final product such as a film obtained by the subsequent ring-opening reaction can be improved. Further, according to the production method of the present invention, since gelation of the reaction solution can be suppressed, even a thermosetting resin having a rigid skeleton such as a benzophenone skeleton or a biphenyl skeleton (for example, see formula (4)). Can be manufactured.

  The weight average molecular weight (Mw) in terms of polystyrene obtained by gel permeation chromatography (GPC) measurement of the thermosetting resin having a benzoxazine ring according to the present invention is preferably 2000 to 300,000, more preferably. It is 2000-100000, More preferably, it is 3000-50000, More preferably, it is 4000-30000.

  Here, “high molecular weight” means that a thermosetting resin having a benzoxazine ring in a repeating unit, that is, a prepolymer type benzoxazine ring before thermosetting, has a weight average molecular weight of 2000 to 2000. It means that it is controlled to about 300,000. When the weight average molecular weight is 2000 or more, the heat resistance and flexibility of the final product obtained by the subsequent ring-opening reaction can be increased. Further, the thermosetting resin having a synthesized benzoxazine ring can be used. It is preferable because the recovery workability can be increased.

  The weight average molecular weight of the thermosetting resin having a benzoxazine ring can be measured by extracting a part of the reaction solution and performing gel permeation chromatography measurement during the synthesis reaction.

  A thermosetting resin having a benzoxazine ring can have a structure in which halogen is not included in the structure, and can also be produced using a solvent that does not contain halogen as a so-called impurity. It is also possible to obtain a thermosetting resin substantially free of halogen.

  For thermosetting resins having a benzoxazine ring, curing accelerators, flame retardants, inorganic fillers, mold release agents, adhesion-imparting agents, surfactants, colorants, coupling agents, leveling agents are included as necessary. Other thermosetting resins and the like can be added to obtain a thermosetting resin composition. In addition, the thermosetting resin composition which has a benzoxazine ring may contain the various solvent mentioned above. The thermosetting resin composition having a benzoxazine ring is suitably used as an electronic material such as a laminate or a semiconductor encapsulant, a binder such as a friction material or a grindstone, etc. by causing a ring-opening reaction of the benzoxazine ring or the like. be able to.

  In this embodiment, it can be set as the molded object containing the thermosetting resin which has the benzoxazine ring mentioned above. Moreover, it can be set as the hardening body containing the thermosetting resin which has a benzoxazine ring. Such a molded body or cured body is obtained by molding or curing a thermosetting resin or thermosetting resin composition having a benzoxazine ring by a conventionally known method. Such a molded body or cured body can be used as an electronic component / electronic device and its material. In particular, it is suitable for uses such as multilayer substrates, laminates, sealants, adhesives and the like that require a low coefficient of thermal expansion (low CTE). Examples of the electronic device include a mobile phone, a display device, an in-vehicle device, a computer, and a communication device. As an electronic component, it can be used for aircraft parts, automobile parts, building parts, etc., and forms a circuit that can flow direct current or alternating current by using it as a heat-resistant binder for conductive materials, especially metal fillers. You may use for the use to do. As an electronic device, it can use as materials, such as a mobile phone, a display apparatus, vehicle equipment, a computer, a communication apparatus, for example.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, this invention is not limited to a following example. In addition, the evaluation method and measurement method used for a present Example are as follows.

[Measurement of weight average molecular weight (Mw)]
High-performance liquid chromatograph system, manufacturer: SHIMADZU
System controller: SCL-10A VP
Liquid feeding unit: LC-10AD VP
VP degasser: DGU-12A
Differential refractometer (RI) detector: RID-10A
Autoinjector: SIL-10AD VP
Column oven: CTO-10AC VP
Column: Tosoh TSKgel α-4000 (exclusion limit molecular weight 1000000) × 2 (in series)
Column temperature: 50 ° C
Flow rate: 0.8 mL / min Eluent: DMF (manufactured by Wako Pure Chemical Industries, no stabilizer, for HPLC), LiBr 10 mmol / L sample: 0.1 wt%
Detector: RI
Under the measurement conditions described above, calibration curves were prepared using standard polystyrenes (manufactured by Tosoh Corporation) having Mw of 707000, 354000, 189000, 98900, 37200, 17100, 9830, 5870, 2500, 1050, and 500, respectively. And the weight average molecular weight (Mw) of the sample was measured based on the polypolystyrene conversion value obtained by the gel permeation chromatography measurement.

[Measurement of ¹ H-NMR]
¹ H-NMR was measured at a sample concentration of 2% by weight using the following measuring apparatus and solvent.
Measuring device: JEOL, ECX400 (400MHz)
Solvent: Heavy DMSO (Sigma Aldrich, 0.05 vol% TMS (tetramethylsilane) contained

[Measurement of thermal expansion coefficient]
Using “TMA / SS6100” manufactured by SII Nano Technology, measured in a tensile mode under a nitrogen atmosphere with a load of 5 mN and a heating rate of 5 ° C./min, the average value of the coefficient of thermal expansion from 25 ° C. to 150 ° C. (ppm / ° C.).
The obtained film was cut into a width of 4 mm and a length of 20 mm to obtain a measurement sample, which was set so that the distance between chucks was 10 mm, and measured.

Example 1
In a 300 mL flask at room temperature, 90.0 mL of ethylene glycol monomethyl ether (hereinafter also referred to as MC) (product name “Hisolv MC” manufactured by Toho Chemical Industry Co., Ltd.), N, N-dimethylformamide (hereinafter also referred to as DMF). 70.0 mL (manufactured by Gordo), xylene 40.0 mL (manufactured by Wako Pure Chemical Industries, Ltd.), 4,4′-dihydroxybenzophenone (hereinafter also referred to as DHBP) 77.66 g (0.36 mol, Wako Pure) Yakuhin Kogyo Co., Ltd.), p-phenylenediamine (hereinafter also referred to as PDA) 37.56 g (0.35 mol, manufactured by Daishin Kasei Kogyo Co., Ltd., product name “Paramine”) was charged, and nitrogen gas purge was started. (Flow rate 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 94.36 g of methyl hemi-formal solution (hereinafter also referred to as “formit M”) (formaldehyde content 46.4%, methanol content 45.0%) , Manufactured by Guangei Chemical Industry Co., Ltd., product name “KOEI HOLMIT M”) was added dropwise. After completion of dropping, the inside of the flask was depressurized to 0.05 MPa and reacted at a reaction solution temperature of 75 ° C for 4 hours. The reaction solution thus obtained was cooled to room temperature to obtain a solution in which the thermosetting resin A having a benzoxazine ring as a product was dissolved.
The resulting thermosetting resin A having a benzoxazine ring had a weight average molecular weight (Mw) of about 12,000.
The ¹ H-NMR spectrum of the obtained thermosetting resin A is shown in FIG.
Oxazine ring of DHBP_PDA Methylene proton peak at the 2-position of the oxazine ring: 5.46 ppm
Methylene proton peak at the 4-position of the oxazine ring: 4.65 ppm

(Example 2)
At room temperature, in a 300 mL flask, 82.5 mL of MC (product name: Hisolv MC, manufactured by Toho Chemical Industry Co., Ltd.), 87.5 mL of DMF (manufactured by Gordo Company), 77.66 g of DHBP (0.36 mol, Wako Pure Chemical Industries, Ltd.) Product), PDA 40.40 g (0.37 mol, manufactured by Daishin Kasei Kogyo Co., Ltd., product name “Paramine”) was added, and nitrogen gas purge into the system was started (flow rate 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 101.48 g of Formit M (formaldehyde content: 46.4%, methanol content: 45.0%, manufactured by Koei Chemical Industry Co., Ltd., product name “KOEI” Formit M ") was added dropwise. After completion of dropping, the inside of the flask was depressurized to 0.05 MPa and reacted at a reaction solution temperature of 75 ° C. for 1 hour. Thereafter, the inside of the flask was once returned to normal pressure, and 4.08 g of 2-naphthol (0.028 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the reaction solution. The inside of the flask was again evacuated to 0.05 MPa and reacted at a reaction solution temperature of 75 ° C. for 3 hours. The reaction solution thus obtained was cooled to room temperature to obtain a solution in which the thermosetting resin B having a product benzoxazine ring was dissolved.
The resulting thermosetting resin B having a benzoxazine ring had a weight average molecular weight (Mw) of about 15,000.
The ¹ H-NMR spectrum of the obtained thermosetting resin B is shown in FIG.
Oxazine ring of DHBP_PDA Methylene proton peak at the 2-position of the oxazine ring: 5.46 ppm
Methylene proton peak at the 4-position of the oxazine ring: 4.65 ppm
Oxazine ring of 2-naphthol_PDA Methylene proton peak at the 2-position of naphthoxazine ring: 5.41 ppm
Methylene proton peak at the 4-position of the naphthoxazine ring: 4.88 ppm

(Example 3)
In a 300 mL flask at room temperature, MC 90.0 mL (manufactured by Toho Chemical Co., Ltd., product name Hisolv MC), DMF 80.0 mL (manufactured by Gordo), xylene 50.0 mL (manufactured by Wako Pure Chemical Industries, Ltd.), DHBP 77.66 g (0.36 mol, manufactured by Wako Pure Chemical Industries, Ltd.) and PDA 40.40 g (0.37 mol, manufactured by Daishin Kasei Kogyo Co., Ltd., product name “Paramine”) were added, and nitrogen gas purge was started into the system. (Flow rate 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 105.47 g of Formit M (formaldehyde content: 46.4%, methanol content: 45.0%, manufactured by Koei Chemical Industry Co., Ltd., product name “KOEI” Formit M ") was added dropwise. After completion of dropping, the inside of the flask was depressurized to 0.05 MPa and reacted at a reaction solution temperature of 75 ° C. for 1 hour. Thereafter, the inside of the flask was once returned to normal pressure, and 4.08 g of 2-naphthol (0.028 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the reaction solution. The inside of the flask was again evacuated to 0.05 MPa and reacted at a reaction solution temperature of 75 ° C. for 3 hours. The reaction solution thus obtained was cooled to room temperature to obtain a solution in which the thermosetting resin C having a product benzoxazine ring was dissolved.
The obtained thermosetting resin C having a benzoxazine ring had a weight average molecular weight (Mw) of about 13,000.
The ¹ H-NMR spectrum of the obtained thermosetting resin C is shown in FIG.
Oxazine ring of DHBP_PDA Methylene proton peak at the 2-position of the oxazine ring: 5.46 ppm
Methylene proton peak at the 4-position of the oxazine ring: 4.65 ppm
Oxazine ring of 2-naphthol_PDA Methylene proton peak at the 2-position of naphthoxazine ring: 5.42 ppm
Methylene proton peak at the 4-position of the naphthoxazine ring: 4.88 ppm

Example 4
At room temperature, in a 300 mL flask, MC 75.0 mL (manufactured by Toho Chemical Co., Ltd., product name Hisolv MC), DMF 85.0 mL (manufactured by Gordo), xylene 40.0 mL (manufactured by Wako Pure Chemical Industries, Ltd.), DHBP 77.66 g (0.36 mol, manufactured by Wako Pure Chemical Industries, Ltd.) and PDA 40.40 g (0.37 mol, manufactured by Daishin Kasei Kogyo Co., Ltd., product name “Paramine”) were added, and nitrogen gas purge was started into the system. (Flow rate 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 101.48 g of formit M (formaldehyde content 46.4%, methanol content 45.0%, manufactured by Guangei Chemical Industry Co., Ltd., product name “KOEI” Formit M ") was added dropwise. After completion of dropping, the inside of the flask was depressurized to 0.05 MPa and reacted at a reaction solution temperature of 75 ° C. for 1 hour. Thereafter, the inside of the flask was once returned to normal pressure, and 4.08 g of 2-naphthol (0.028 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the reaction solution. The inside of the flask was again evacuated to 0.05 MPa and reacted at a reaction solution temperature of 75 ° C. for 3 hours. The reaction solution thus obtained was cooled to room temperature to obtain a solution in which the thermosetting resin D having a benzoxazine ring as a product was dissolved.
The obtained thermosetting resin D having a benzoxazine ring had a weight average molecular weight (Mw) of about 13,000.
The ¹ H-NMR spectrum of the obtained thermosetting resin D is shown in FIG.
Oxazine ring of DHBP_PDA Methylene proton peak at the 2-position of the oxazine ring: 5.46 ppm
Methylene proton peak at the 4-position of the oxazine ring: 4.64 ppm
Oxazine ring of 2-naphthol_PDA Methylene proton peak at the 2-position of naphthoxazine ring: 5.42 ppm
Methylene proton peak at the 4-position of the naphthoxazine ring: 4.88 ppm

(Example 5)
In a 300 mL flask at room temperature, MC 90.0 mL (manufactured by Toho Chemical Co., Ltd., product name Hisolv MC), DMF 70.0 mL (manufactured by Gordo), xylene 40.0 mL (manufactured by Wako Pure Chemical Industries, Ltd.), DHBP 77.66 g (0.36 mol, manufactured by Wako Pure Chemical Industries, Ltd.) and PDA 40.40 g (0.37 mol, manufactured by Daishin Kasei Kogyo Co., Ltd., product name “Paramine”) were added, and nitrogen gas purge was started into the system. (Flow rate 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 101.48 g of Formit M (formaldehyde content: 46.4%, methanol content: 45.0%, manufactured by Koei Chemical Industry Co., Ltd., product name “KOEI” Formit M ") was added dropwise. After completion of dropping, the inside of the flask was depressurized to 0.05 MPa and reacted at a reaction solution temperature of 75 ° C. for 1 hour. Thereafter, the inside of the flask was once returned to normal pressure, and 4.08 g of 2-naphthol (0.028 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the reaction solution. The inside of the flask was again evacuated to 0.05 MPa and reacted at a reaction solution temperature of 75 ° C. for 3 hours. The reaction solution thus obtained was cooled to room temperature to obtain a solution in which the thermosetting resin E having a benzoxazine ring as a product was dissolved.
The obtained thermosetting resin E having a benzoxazine ring had a weight average molecular weight (Mw) of about 11,000.
A ¹ H-NMR spectrum of the obtained thermosetting resin E is shown in FIG.
Oxazine ring of DHBP_PDA Methylene proton peak at the 2-position of the oxazine ring: 5.46 ppm
Methylene proton peak at the 4-position of the oxazine ring: 4.65 ppm
Oxazine ring of 2-naphthol_PDA Methylene proton peak at the 2-position of naphthoxazine ring: 5.42 ppm
Methylene proton peak at the 4-position of the naphthoxazine ring: 4.88 ppm

(Comparative Example 1)
In a 300 mL flask at room temperature, dioxane 200 mL (manufactured by Wako Pure Chemical Industries), DHBP 77.66 g (0.36 mol, manufactured by Wako Pure Chemical Industries), PDA 37.56 g (0.35 mol, Daishin Kasei Kogyo) The product name “Paramin”) was introduced, and nitrogen gas purge into the system was started (flow rate 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 94.36 g of Formit M (formaldehyde content 46.4%, methanol content 45.0%, manufactured by Guangei Chemical Industry Co., Ltd., product name “KOEI” Formit M ") was added dropwise. After completion of the dropwise addition, the reaction was interrupted because the reaction solution gelled.

(Comparative Example 2)
In a 300 mL flask at room temperature, chloroform 200 mL (manufactured by Wako Pure Chemical Industries), DHBP 77.66 g (0.36 mol, manufactured by Wako Pure Chemical Industries), PDA 37.56 g (0.35 mol, Daishin Kasei Kogyo) The product name “Paramin”) was introduced, and nitrogen gas purge into the system was started (flow rate 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 94.36 g of Formit M (formaldehyde content 46.4%, methanol content 45.0%, manufactured by Guangei Chemical Industry Co., Ltd., product name “KOEI” Formit M ") was added dropwise. After completion of the dropwise addition, the reaction was interrupted because the reaction solution gelled.

(Comparative Example 3)
At room temperature, in a 300 mL flask, methyl ethyl ketone 200 mL (manufactured by Wako Pure Chemical Industries), DHBP 77.66 g (0.36 mol, manufactured by Wako Pure Chemical Industries), PDA 37.56 g (0.35 mol, Daishin Kasei Kogyo) The product name “Paramin”) was introduced, and nitrogen gas purge into the system was started (flow rate 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 94.36 g of Formit M (formaldehyde content 46.4%, methanol content 45.0%, manufactured by Guangei Chemical Industry Co., Ltd., product name “KOEI” Formit M ") was added dropwise. After completion of the dropwise addition, the reaction was interrupted because the reaction solution gelled.

(Comparative Example 4)
At room temperature, in a 300 mL flask, 200 mL of ethyl acetate (manufactured by Wako Pure Chemical Industries), 77.66 g of DHBP (0.36 mol, manufactured by Wako Pure Chemical Industries), 37.56 g of PDA (0.35 mol, Daishin Kasei Co., Ltd.) Kogyo Co., Ltd., product name “Paramin”) was added, and nitrogen gas purge was started into the system (flow rate: 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 94.36 g of Formit M (formaldehyde content 46.4%, methanol content 45.0%, manufactured by Guangei Chemical Industry Co., Ltd., product name “KOEI” Formit M ") was added dropwise. After completion of the dropwise addition, the reaction was interrupted because the reaction solution gelled.

(Comparative Example 5)
At room temperature, in a 300 mL flask, cyclopentanone 200 mL (manufactured by Wako Pure Chemical Industries), DHBP 77.66 g (0.36 mol, manufactured by Wako Pure Chemical Industries), PDA 37.56 g (0.35 mol, Daishin) Kasei Kogyo Co., Ltd., product name “Paramin”) was added, and nitrogen gas purge into the system was started (flow rate: 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 94.36 g of Formit M (formaldehyde content 46.4%, methanol content 45.0%, manufactured by Guangei Chemical Industry Co., Ltd., product name “KOEI” Formit M ") was added dropwise. After completion of the dropwise addition, the reaction was interrupted because the reaction solution gelled.

(Comparative Example 6)
In a 300 mL flask at room temperature, MC 200 mL (manufactured by Toho Chemical Co., Ltd., product name Hisolv MC), DHBP 77.66 g (0.36 mol, manufactured by Wako Pure Chemical Industries, Ltd.), PDA 37.56 g (0.35 mol, Daishin Kasei Kogyo Co., Ltd., product name “Paramin”) was introduced, and nitrogen gas purge into the system was started (flow rate: 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 94.36 g of Formit M (formaldehyde content 46.4%, methanol content 45.0%, manufactured by Guangei Chemical Industry Co., Ltd., product name “KOEI” Formit M ") was added dropwise. After completion of the dropping, the pressure in the flask was reduced to 0.05 MPa, and when the reaction was performed at a reaction solution temperature of 75 ° C. for 1 hour, the reaction solution was gelled, so the reaction was interrupted.

(Comparative Example 7)
At room temperature, in a 300 mL flask, DMF 200 mL (manufactured by Gordo), DHBP 77.66 g (0.36 mol, manufactured by Wako Pure Chemical Industries), PDA 37.56 g (0.35 mol, manufactured by Daishin Kasei Kogyo Co., Ltd.) The product name “Paramin”) was added, and nitrogen gas purge into the system was started (flow rate: 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 94.36 g of Formit M (formaldehyde content 46.4%, methanol content 45.0%, manufactured by Guangei Chemical Industry Co., Ltd., product name “KOEI” Formit M ") was added dropwise. After completion of the dropping, the pressure in the flask was reduced to 0.05 MPa, and when the reaction was performed at a reaction solution temperature of 75 ° C. for 1 hour, the reaction solution was gelled, so the reaction was interrupted.

(Comparative Example 8)
At room temperature, in a 300 mL flask, N, N′-dimethylacetamide (hereinafter also referred to as DMAc) 200 mL (manufactured by Wako Pure Chemical Industries, Ltd.), DHBP 77.66 g (0.36 mol, Wako Pure Chemical Industries, Ltd.) Product), PDA 37.56 g (0.35 mol, manufactured by Daishin Kasei Kogyo Co., Ltd., product name “Paramine”), and nitrogen gas purge was started in the system (flow rate 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 94.36 g of Formit M (formaldehyde content 46.4%, methanol content 45.0%, manufactured by Guangei Chemical Industry Co., Ltd., product name “KOEI” Formit M ") was added dropwise. After completion of the dropping, the pressure in the flask was reduced to 0.05 MPa, and when the reaction was performed at a reaction solution temperature of 75 ° C. for 1 hour, the reaction solution was gelled, so the reaction was interrupted.

(Comparative Example 9)
At room temperature, in a 300 mL flask, xylene 200 mL (manufactured by Wako Pure Chemical Industries, Ltd.), DHBP 77.66 g (0.36 mol, manufactured by Wako Pure Chemical Industries, Ltd.), PDA 37.56 g (0.35 mol, Daishin) Kasei Kogyo Co., Ltd., product name “Paramin”) was added, and nitrogen gas purge into the system was started (flow rate: 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 94.36 g of Formit M (formaldehyde content 46.4%, methanol content 45.0%, manufactured by Guangei Chemical Industry Co., Ltd., product name “KOEI” Formit M ") was added dropwise. After completion of the dropwise addition, the reaction was interrupted because the reaction solution gelled.

(Comparative Example 10)
At room temperature, in a 300 mL flask, 200 mL of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), 77.66 g of DHBP (0.36 mol, manufactured by Wako Pure Chemical Industries, Ltd.), 37.56 g of PDA (0.35 mol, Daishin) Kasei Kogyo Co., Ltd., product name “Paramin”) was added, and nitrogen gas purge into the system was started (flow rate: 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 94.36 g of Formit M (formaldehyde content 46.4%, methanol content 45.0%, manufactured by Guangei Chemical Industry Co., Ltd., product name “KOEI” Formit M ") was added dropwise. After completion of the dropwise addition, the reaction was interrupted because the reaction solution gelled.

(Comparative Example 11)
In a 300 mL flask at room temperature, MC 100 mL (product name: Hisolv MC, manufactured by Toho Chemical Co., Ltd.), xylene 100 mL (manufactured by Wako Pure Chemical Industries, Ltd.), DHBP 77.66 g (0.36 mol, Wako Pure Chemical Industries, Ltd.) Co., Ltd.) and PDA 37.56 g (0.35 mol, manufactured by Daishin Kasei Kogyo Co., Ltd., product name “Paramin”) were introduced, and nitrogen gas purge into the system was started (flow rate 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 94.36 g of Formit M (formaldehyde content 46.4%, methanol content 45.0%, manufactured by Guangei Chemical Industry Co., Ltd., product name “KOEI” Formit M ") was added dropwise. After completion of the dropwise addition, the reaction was interrupted because the reaction solution gelled.

(Comparative Example 12)
In a 300 mL flask at room temperature, DMF 100 mL (manufactured by Gordo), xylene 100 mL (manufactured by Wako Pure Chemical Industries, Ltd.), DHBP 77.66 g (0.36 mol, manufactured by Wako Pure Chemical Industries, Ltd.), PDA 37. 56 g (0.35 mol, manufactured by Daishin Kasei Kogyo Co., Ltd., product name “Paramin”) was charged, and nitrogen gas purge was started into the system (flow rate: 150 mL / min).
After the flask was immersed in an oil bath and the temperature of the reaction solution reached 45 ° C., 94.36 g of Formit M (formaldehyde content 46.4%, methanol content 45.0%, manufactured by Guangei Chemical Industry Co., Ltd., product name “KOEI” Formit M ") was added dropwise. After completion of the dropwise addition, the reaction was interrupted because the reaction solution gelled.

(Example 6)
10 g of a solution in which the thermosetting resin E prepared in Example 5 is dissolved is applied onto a polyimide (hereinafter referred to as PI) film using an applicator, and is applied at 80 ° C. for 10 minutes and at 100 ° C. for 10 minutes. Minutes, 150 ° C for 10 minutes, 180 ° C for 30 minutes, 200 ° C for 30 minutes, 220 ° C for 30 minutes, 240 ° C for 30 minutes, 260 ° C for 1 hour, heat cured in an oven, and film A cured product (film E) was obtained. This cured product was red and transparent and had a thickness of 45 μm.

(Production Example 1)
At room temperature, 190 mL of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) and 10 mL of isobutanol (manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a 500 mL flask in which a constant pressure dropping funnel with a cock and a Dimroth condenser are set. Were added and mixed at room temperature.
Thereafter, 41.6 g of bisphenol A (0.120 mol, manufactured by GE Plastics), 51.3 g of 2,2′-bis [4- (4-aminophenoxy) phenyl] propane (0.125 mol, Wakayama Seika Kogyo) Product name “BAPP”) and phenol 0.9 g (0.0096 mol) were added and mixed in the flask at room temperature. From this point, nitrogen gas purge was started into the system (flow rate: 15 mL / min).
After immersing the flask in an oil bath and visually confirming that the powdery substance disappeared after the temperature of the reaction solution reached 65 ° C., 19.7 g of PFA (0.6 mol, manufactured by Mitsubishi Gas Chemical Company, purity 91.60). %) Was added to the flask and refluxed for 2 hours.
Thereafter, the water produced during the reaction was reacted with toluene and isobutanol while distilling out of the system. After the start of the distillation, reflux was performed for 6 hours.
The reaction solution thus obtained was cooled to room temperature and filtered, and then poured into 1 L of methanol to precipitate the product. The precipitated solid thus precipitated was dried under reduced pressure to obtain a thermosetting resin F having a benzoxazine ring.
The obtained thermosetting resin F had a weight average molecular weight (Mw) of about 16,000.

  In a glass container, 5 g of thermosetting resin F was dissolved in 5 g of dimethylformamide to obtain a yellow viscous liquid. This viscous liquid is applied on a PI film using an applicator, and is 10 minutes at 80 ° C., 10 minutes at 100 ° C., 10 minutes at 150 ° C., 30 minutes at 180 ° C., 30 minutes at 200 ° C., 220 The film was held at 30 ° C. for 30 minutes and at 240 ° C. for 1 hour, and cured in an oven to obtain a film-like cured product (film F). The cured product was yellow and transparent and had a thickness of 51 μm. In addition, since the film F thermally decomposes when heated to 260 ° C., the film F was thermally cured at an upper limit of 240 ° C.

  Table 1 shows the physical properties of the film of Example 6 and the film of Production Example 1.

  As described above, it was confirmed that in the production methods of each Example, a thermosetting resin having a sufficiently high molecular weight benzoxazine ring can be obtained without gelation in the reaction. On the other hand, in the manufacturing method of each comparative example, it was confirmed that a desired thermosetting resin could not be obtained due to gelation during the reaction. Furthermore, as shown in Table 1, the film of Example 6 has a reduced thermal linear expansion coefficient and is excellent in dimensional stability as compared with a film obtained from a conventional thermosetting resin. Was confirmed.

  Thermosetting resins having a benzoxazine ring obtained by the production method of the present invention are industrially used in a wide range of fields including electronic materials such as laminates and semiconductor encapsulants, and binders such as friction materials and grindstones. With the availability of

Claims (19)

  A benzoxazine ring having a step of reacting a bifunctional phenol compound, a diamine compound, and an aldehyde compound in a solvent containing one or more ether groups and alcoholic hydroxyl groups in the molecule and a mixed solvent containing an amide solvent. The manufacturing method of the thermosetting resin which has this. A step of mixing a bifunctional phenol compound, a diamine compound, a solvent having one or more ether groups and alcoholic hydroxyl groups in the molecule, and a mixed solvent containing an amide solvent to obtain a mixed solution;
A step of further adding an aldehyde compound to the mixed solution and reacting them;
A method for producing a thermosetting resin having a benzoxazine ring.   The solvent having at least one ether group and at least one alcoholic hydroxyl group in the molecule is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol mono Selected from the group consisting of ethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, polyethylene glycol monomethyl ether, and 3-methoxy-3-methyl-1-butanol Or at least one selected from the group consisting of Method for producing a thermosetting resin having a benzoxazine ring according to 2.   The solvent having at least one ether group and one alcoholic hydroxyl group in the molecule is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and triethylene glycol monomethyl ether. The method for producing a thermosetting resin having a benzoxazine ring according to any one of claims 1 to 3, which is at least one selected.   The amide solvent is at least one selected from the group consisting of N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone. The manufacturing method of the thermosetting resin which has a benzoxazine ring as described in any one of Claims 1-4.   The amide solvent is at least one selected from the group consisting of N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone. The manufacturing method of the thermosetting resin which has a benzoxazine ring as described in any one.   Ratio of solvent having at least one ether group and alcoholic hydroxyl group in the molecule relative to the amide solvent (solvent having at least one ether group and alcoholic hydroxyl group in the molecule / amide solvent) : Volume ratio) is 20 / 80-90 / 10, The manufacturing method of the thermosetting resin which has a benzoxazine ring as described in any one of Claims 1-6.   Solvent Ratio of the solvent having at least one ether group and alcoholic hydroxyl group in the molecule relative to the amide solvent (solvent having at least one ether group and alcoholic hydroxyl group in the molecule / the amide solvent) : Volume ratio) is 30 / 70-80 / 20, The manufacturing method of the thermosetting resin which has a benzoxazine ring as described in any one of Claims 1-7.   Ratio of solvent having at least one ether group and alcoholic hydroxyl group in the molecule relative to the amide solvent (solvent having at least one ether group and alcoholic hydroxyl group in the molecule / the amide solvent: The manufacturing method of the thermosetting resin which has a benzoxazine ring as described in any one of Claims 1-8 whose volume ratio is 40 / 60-70 / 30.   The method for producing a thermosetting resin having a benzoxazine ring according to any one of claims 1 to 9, wherein the mixed solvent further contains an aromatic nonpolar solvent.   The method for producing a thermosetting resin having a benzoxazine ring according to claim 10, wherein the aromatic nonpolar solvent is at least one selected from the group consisting of benzene, toluene, xylene, pseudocumene, and mesitylene.   The manufacturing method of the thermosetting resin which has the benzoxazine ring of Claim 10 or 11 whose ratio of the said aromatic nonpolar solvent is 0-50 volume% in the said mixed solvent.   13. The mixed solvent according to claim 1, wherein a total ratio of the solvent having one or more ether groups and alcoholic hydroxyl groups in the molecule and the amide solvent is 50 to 100% by volume. A method for producing a thermosetting resin having a benzoxazine ring according to one item. The bifunctional phenol is 4,4′-dihydroxybenzophenone (DHBP), 4,4′-biphenol, bis (4-hydroxyphenyl) sulfone (bisphenol S), 1,4-benzenediol (hydroquinone), 1,5 -At least one selected from the group consisting of dihydroxynaphthalene and 2,6-dihydroxynaphthalene,
The diamine compound is at least one selected from the group consisting of p-phenylenediamine (PDA), 4,4′-diaminodiphenylmethane (MDA), and 4,4′-diaminobiphenyl,
The method for producing a thermosetting resin having a benzoxazine ring according to any one of claims 1 to 13, wherein the aldehyde compound is at least formaldehyde.   A benzo compound obtained by reacting a bifunctional phenol compound, a diamine compound, and an aldehyde compound in a solvent containing at least one ether group and an alcoholic hydroxyl group in the molecule and a mixed solvent containing at least an amide solvent. A thermosetting resin having an oxazine ring.   React bifunctional phenolic compounds, diamine compounds, and aldehyde compounds in a mixed solvent containing at least one ether group and one alcoholic hydroxyl group in the molecule, an amide solvent, and an aromatic nonpolar solvent. The thermosetting resin which has a benzoxazine ring obtained by making it.   The molded object containing the thermosetting resin of Claim 15 or 16.   A cured product comprising the thermosetting resin according to claim 15.   The electronic device containing the molded object of Claim 17, or the hardening body of Claim 18.