JP2010195991A - Compound having benzoxazine ring, thermosetting resin composition containing the same, and manufacturing method of compound having benzoxazine ring - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin having a benzoxazine ring which has good solubility to solvent and is allowed to have a high molecular weight. <P>SOLUTION: The method of manufacturing a compound having a benzoxazine ring structure includes the step of reacting a bisphenol compound, amine compound and aldehyde compound in a mixed solvent of nonpolar solvent of aromatic system, and an alcohol. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a compound having a benzoxazine ring, a thermosetting resin composition containing the compound, and a method for producing a compound having a benzoxazine ring.

  Conventionally, a thermosetting resin having a benzoxazine ring in a molecular structure has been used as an electronic material such as a printed wiring board and a semiconductor sealing material, a brake shoe, an aircraft material, and the like.

As for the thermosetting resin having a benzoxazine ring, for example, techniques for producing phenols, diamines and aldehydes in a solvent are disclosed (see Patent Documents 1 and 2 and Non-Patent Document 1). ).
Specifically, in Example 3 of Patent Document 1, phenol, 4,4′-diamino-3,3 ′, 5,5′-tetramethyldiphenylmethane and paraformaldehyde were reacted in toluene to obtain benzoxazine. A method for producing a thermosetting resin having a ring is shown.
Non-Patent Document 1 discloses a benzoxazine resin having a diphenylbenzophenone skeleton and a diphenylmethane skeleton, and the obtained resin has an average molecular weight of 990 to 2700.
Non-Patent Document 1 and Patent Document 2 show that a benzoxazine resin having a diphenylbenzophenone skeleton and a diphenylmethane skeleton is obtained by reacting bisphenol, diamine, and formaldehyde in dioxane or chloroform.

  Patent Document 3 discloses a method for producing a phenolic resin having a benzoxazine ring by reacting phenols, formaldehyde, and monoamines in an alcohol solvent, and the obtained resin has a low molecular weight. It is shown that.

JP-A-2005-213301 JP 2003-64180 A JP 2000-273135 A

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

  However, it is expected that a molded article made of a material cured by utilizing the thermosetting property of a compound having a benzoxazine ring, for example, a film or the like, will require further higher characteristics with respect to dimensional stability in the future.

On the other hand, in the thermosetting resins disclosed in Non-Patent Document 1 and Patent Document 2, sufficient dimensional stability has not yet been obtained.
In addition, if chloroform is used as the reaction solvent, chlorine remains in the resin after the reaction, causing corrosion, so it is not possible to use the thermosetting resin finally obtained for electrical equipment parts such as printed boards. It is not preferable.
In order to prevent such corrosion, a process of washing the thermosetting resin is essential, which causes a problem that productivity is lowered.

  In the method disclosed in Patent Document 1, each raw material is added to the organic solvent all at once. However, the reaction solution gels due to a rapid progress of the reaction and the insolubilization of the reaction product is always great. Therefore, there is a problem that the process is complicated. Specifically, after adding the raw material to an aprotic solvent (excluding dioxane), two-stage temperature control is performed.

  Accordingly, in the present invention, a compound having a benzoxazine ring, which is excellent in dimensional stability, has a simple manufacturing process, is preferable from the viewpoint of environmental considerations, and can be used as a material for electronic equipment, and the like are included. It was decided to provide a thermosetting resin composition, a molded product using these, a cured product, and a method for producing a compound having a benzoxazine ring.

As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by the following means, and have completed the present invention.
That is, the present invention is as follows.

[1] A compound having a benzoxazine ring structure represented by the following formula (1).

In Formula (1), R ¹ and R ² are each independently hydrogen or an organic group having 1 to 20 carbon atoms, and n is an integer of 1 to 500. Also, R ¹ and R ² are not hydrogen at the same time. In formula (1), * indicates a binding site.

[2] The compound having a benzoxazine ring structure according to [1], wherein n is an integer of 7 to 500.

[3] R ¹ and R ² are each independently selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a sec-butyl group, and an isobutyl group. The compound which has a benzoxazine ring structure as described in said [1] or [2] containing at least any.

[4] A compound having a benzoxazine ring structure, which is represented by the following formula (2) and includes both the structure A and the structure B.

In the formula (2), R ³ and R ⁴ are each independently hydrogen or an organic group having 1 to 20 carbon atoms, n and m are each 1 to 250, and l is an integer of 1 to 500. . R ³ and R ⁴ are not hydrogen at the same time. In formula (2), * indicates a binding site.

[5] The compound having a benzoxazine ring structure according to [4], wherein n and m are each an integer of 2 to 250 and l is an integer of 4 to 500 in the formula (2).

[6] R ³ and R ⁴ are each independently selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a sec-butyl group, and an isobutyl group. The compound which has a benzoxazine ring structure as described in said [4] or [5] containing at least any.

[7] When the total value of the compound containing the benzoxazine ring structure including the structure A and the structure B is 100% by mass, the copolymer of the structure A and the structure B is 90% by mass or more, and the structure A: The compound having the benzoxazine ring structure according to any one of [4] to [6], wherein the mass ratio of the structure B is 41%: 59% to 91%: 9%.

[8] A thermosetting resin composition containing any one or more of the compounds having a benzoxazine ring structure according to any one of [1] to [7].

[9] Any one selected from the group consisting of the compound having the benzoxazine ring structure according to any one of [1] to [7] and the thermosetting resin composition according to [8]. Molded product obtained by molding.

[10] The compound having the benzoxazine ring structure according to any one of [1] to [7], the thermosetting resin composition according to [8], and the molded article according to [9] A cured product obtained by curing any one selected from the group consisting of:

[11] A bisphenol compound having a structure represented by the following formula (3), a diamine compound having a structure represented by the following formula (4), and an aldehyde compound are reacted in a mixed solvent of an aromatic nonpolar solvent and an alcohol. The manufacturing method of the compound which has a process and has a benzoxazine ring structure.

In the formula (4), R ⁵ and R ⁶ are each independently hydrogen or an organic group having 1 to 20 carbon atoms. Incidentally, R ⁵ and R ^6, except when simultaneously hydrogen.

[12] The diamine compound represented by the formula (4) is selected from the group consisting of 4,4′-diamino-3,3′-dimethyldiphenylmethane and 4,4′-diamino-3,3′-diethyldiphenylmethane. The compound having a benzoxazine ring structure according to [11] above.

[13] A bisphenol compound having a structure represented by the following formula (5), a diamine compound represented by the following formulas (6) and (7), and an aldehyde compound in a mixed solvent of an aromatic nonpolar solvent and an alcohol. In the case where the total of the diamine compound represented by the formula (6) and the diamine compound represented by the formula (7) is 100 mol%, the diamine compound represented by the formula (6): The manufacturing method of the compound which has the benzoxazine ring structure which made mol% of the diamine compound shown to (7) 40: 60-90: 10.

前記式（６）において、Ｒ⁷及びＲ⁸は、それぞれ独立して、水素又は炭素数１〜２０の有機基である。なお、Ｒ⁷及びＲ⁸は、同時に水素である場合を除く。

In the formula (6), R ⁷ and R ⁸ are each independently hydrogen or an organic group having 1 to 20 carbon atoms. Note that R ⁷ and R ⁸ are not hydrogen at the same time.

[14] The diamine compound represented by the formula (6) is selected from the group consisting of 4,4′-diamino-3,3′-dimethyldiphenylmethane or 4,4′-diamino-3,3′-diethyldiphenylmethane. The method for producing a compound having a benzoxazine ring structure according to [13], which is any selected.

[15] The process for producing a compound having a benzoxazine ring structure according to any one of the above [11] to [14], wherein the ratio of alcohol in the mixed solvent is 5% by volume to 50% by volume.

[16] The process for producing a compound having a benzoxazine ring structure according to any one of [11] to [15], wherein the aromatic nonpolar solvent is toluene, xylene or a mixture thereof.

[17] Any one of [11] to [16], wherein the alcohol is at least one selected from the group consisting of methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol and isobutanol. A method for producing a compound having a benzoxazine ring structure according to claim 1.

[18] The method for producing a compound having a benzoxazine ring structure according to any one of [11] to [17], wherein the mixed solvent is a mixed solvent of toluene and isobutanol.

  In the present invention, a compound having a benzoxazine ring having good solubility in a solvent, high molecular weight and excellent dimensional stability, a thermosetting resin composition containing the compound, and a method for producing them can be provided. .

The proton nuclear magnetic resonance spectrum (< ¹ > H-NMR spectrum) of the benzoxazine compound which has the benzophenone structure manufactured in Example 1 is shown. The proton nuclear magnetic resonance spectrum (< ¹ > H-NMR spectrum) of the benzoxazine compound which has the benzophenone structure manufactured in Example 2 is shown. The proton nuclear magnetic resonance spectrum (< ¹ > H-NMR spectrum) of the benzoxazine compound which has the benzophenone structure manufactured in Example 3 is shown. The proton nuclear magnetic resonance spectrum (< ¹ > H-NMR spectrum) of the benzoxazine compound which has the benzophenone structure manufactured in Example 4 is shown.

Hereinafter, modes for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail.
In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

[Compound having benzoxazine ring structure]
The compound having a benzoxazine ring structure in the first embodiment is a compound having a benzoxazine ring structure represented by the following formula (1).

In the formula (1), R ¹ and R ² are each independently hydrogen or an organic group having 1 to 20 carbon atoms, and n is an integer of 7 to 500. Also, R ¹ and R ² are not hydrogen at the same time.
In formula (1), * is a binding site.

  The organic group may contain oxygen, fluorine, or nitrogen.

R ¹ and R ² are not particularly limited as long as they are hydrocarbon groups having 1 to 20 carbon atoms. Examples thereof include linear structures such as methyl, ethyl, n-propyl, and n-butyl groups, isopropyl Group, a branched structure such as sec-butyl group and isobutyl group, and a cyclic structure such as cyclohexyl group.

  In the formula (1), n is an integer of 1 to 500, and further, heat resistance and flexibility of a final product such as a film obtained from a compound having a benzoxazine ring having a weight average molecular weight (Mw) of 3000 or more. N is more preferably an integer of 7 to 500, since various performances such as property and electrical insulation can be further improved.

  The compound having a benzoxazine ring structure in the second embodiment is a compound having a benzoxazine ring structure including both the structure A and the structure B represented by the following formula (2).

In the formula (2), R ³ and R ⁴ are each independently hydrogen or an organic group having 1 to 20 carbon atoms, n and m are each 1 to 250, and l is an integer of 1 to 500. . R ³ and R ⁴ are not hydrogen at the same time.
In formula (2), “*” represents a binding site.

The organic group may contain oxygen, fluorine, or nitrogen.
Except when R ³ and R ⁴ are simultaneously hydrogen.
In addition, the structure A and the structure B may be directly bonded or may be bonded via another structure.

R ³ and R ⁴ are not particularly limited as long as they are hydrocarbon groups having 1 to 20 carbon atoms. For example, linear structures such as methyl, ethyl, n-propyl, and n-butyl groups, isopropyl Group, a branched structure such as sec-butyl group and isobutyl group, and a cyclic structure such as cyclohexyl group.

  In the formula (2), n and m are each an integer of 1 to 250, and l is an integer of 1 to 500, and a film obtained from a compound having a benzoxazine ring having a weight average molecular weight (Mw) of 3000 or more. In addition, it is more preferable that n and m are each an integer of 2 to 250, and l is an integer of 4 to 500, since various performances such as heat resistance, flexibility, and electrical insulation of the final product can be further improved.

  In the formula (2), when the total value of the compound containing the benzoxazine ring structure including the structure A and the structure B is 100% by mass, the copolymer of the structure A and the structure B is 90% by mass or more, And it is preferable that the mass ratio of structure A: structure B is 41%: 59% -91%: 9%.

[Thermosetting resin composition]
The thermosetting resin composition in the present embodiment includes a compound having a benzoxazine ring structure represented by the formula (1) and a compound having a benzoxazine ring structure including the structure A and the structure B represented by the formula (2). It is a composition containing at least one of these and utilizing those thermosetting properties.
Moreover, what contains the said thermosetting resin as a main component, and contains another thermosetting resin as a subcomponent is mentioned.

Other thermosetting resins as by-products include, for example, epoxy resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, silicon resins, melamine resins, urea resins, allyl resins, phenol resins, Saturated polyester resin, bismaleimide resin, alkyd resin, furan resin, polyurethane resin, aniline resin and the like can be mentioned.
Among these, an epoxy resin, a phenol resin, and a thermosetting polyimide resin are more preferable from the viewpoint of further improving the heat resistance of a molded body formed from the composition.
These other thermosetting resins may be used alone or in combination of two or more.

In the thermosetting resin composition in the present embodiment, a compound having at least one benzoxazine ring in the molecule, preferably two benzoxazine rings in the molecule may be used as a subcomponent.
Such a compound is obtained by a condensation reaction between a compound having a phenolic hydroxyl group in the molecule and one of its ortho positions being H, a compound having a primary amino group in the molecule, and formaldehyde. can get.
At this time, when using a compound having a plurality of phenolic hydroxyl groups in the molecule, a compound having only one primary amino group in the molecule is used, and a compound having a plurality of primary amino groups in the molecule is used. In some cases, a compound having only one phenolic hydroxyl group in the molecule is used. Only 1 type may be used for the compound which has at least 1 benzoxazine ring in this molecule | numerator, and 2 or more types may be used together.

In addition, the thermosetting resin composition in the present embodiment includes a flame retardant, a nucleating agent, an antioxidant, a silane coupling agent, a heat stabilizer, a light stabilizer, an ultraviolet absorber, and a lubricant as necessary. In addition, various additives such as a flame retardant aid, an antistatic material, an antifogging agent, a filler, a softener, a plasticizer, and a colorant may be contained.
These may be used alone or in combination of two or more.
Moreover, when preparing the thermosetting resin composition which concerns on this embodiment, you may use a reactive or non-reactive solvent suitably.

[Molded body]
The molded body in the present embodiment is obtained by molding the above-described thermosetting resin or thermosetting resin composition.
The molded body is obtained by partially curing or curing the above-described thermosetting resin or a thermosetting resin composition containing the resin as necessary.
Since the thermosetting resin described above has moldability even before curing, it may be molded before curing and cured by applying heat later or simultaneously with molding. .
In addition, the dimensions and shape are not particularly limited, and examples thereof include a sheet shape (plate shape) and a block shape, and may further include another portion (for example, an adhesive layer).

[Hardened body]
The cured body in the present embodiment is obtained by curing the above-described thermosetting resin, thermosetting resin composition, and molded body.

Any conventionally known curing method can be applied to the method for producing the cured body, that is, the curing method. Generally, a cured body is obtained by heating the thermosetting resin, the thermosetting resin composition, and the molded body described above at about 120 to 260 ° C. for several hours.
If the heating temperature is too low or the heating time is insufficient, the curing may be insufficient and the mechanical strength may be insufficient in some cases. In addition, if the heating temperature is too high or the heating time is too long, side reactions such as decomposition may occur in some cases, and the mechanical strength may be disadvantageously reduced. Therefore, it is preferable to select appropriate conditions according to the characteristics of the thermosetting compound to be used.
When the curing temperature is assumed to be cured using pressurized heating steam, and when it is assumed to be heat-cured by other methods such as heating wire, from the viewpoint of energy saving, the curing is possible and the temperature is low. It is preferable that it is hardened | cured at 190 degrees C or less, and it is more preferable that it is hardened at 185 degrees C or less.
In view of the completion of curing, the lower limit of the curing time is 10 minutes or longer, preferably 15 minutes or longer, and more preferably 30 minutes.
In view of productivity, the upper limit of the curing time is 10 hours or less, preferably 5 hours or less, more preferably 3 hours or less.
When the curing treatment is carried out at the selected curing temperature and curing time, the crosslinking reaction and other curing reactions have sufficiently progressed, and these reactions have progressed 60% or more, more preferably 80% or more. It is preferable from the viewpoint of aging, aging, process suitability, and thermal shock resistance.

Moreover, you may add a hardening accelerator suitably in the case of a hardening process.
As the curing accelerator, any curing accelerator generally used in ring-opening polymerization of a benzoxazine compound can be used.
For example, polyfunctional phenols such as catechol and bisphenol A; sulfonic acids such as p-toluenesulfonic acid and p-phenolsulfonic acid; carboxylic acids such as benzoic acid, salicylic acid, oxalic acid and adipic acid; cobalt (II) acetylacetate Metal complexes such as calcium oxide, cobalt oxide, magnesium oxide and iron oxide; calcium hydroxide, imidazole and its derivatives, diaza Tertiary amines such as bicycloundecene and diazabicyclononene and their salts; triphenylphosphine, triphenylphosphine / benzoquinone derivative, triphenylphosphine / triphenylboron salt, tetraphenylphosphonium / tetraphenylvole Phosphorus compounds such as To, and derivatives thereof.
These may be used alone or in combination of two or more.

  The addition amount of the curing accelerator is not particularly limited. However, if the addition amount is excessive, the dielectric constant and dielectric loss tangent of the molded body are increased to deteriorate the dielectric properties and adversely affect the mechanical properties. May be affected. Therefore, generally, the curing accelerator is 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 10 parts by mass with respect to 100 parts by mass of the thermosetting resin (thermosetting resin composition, molded product). Used in the following ratio.

  Since the cured body in the present embodiment obtained as described above has a benzoxazine structure in the polymer structure, excellent dimensional stability can be realized.

  In addition, the cured body according to the present embodiment is excellent in reliability, flame retardancy, moldability, aesthetics, and the like based on the thermosetting property of the thermosetting resin or the thermosetting composition. In addition, since volatile by-products are not generated during the polymerization, such volatile by-products do not remain in the molded article, which is preferable in terms of hygiene management.

[Use]
The thermosetting resin, the thermosetting composition, the molded body, and the cured body in the present embodiment are a multilayer board, a laminated board, and a sealant that require particularly excellent dielectric properties as an electronic component / electronic device and its material. Suitable for applications such as adhesives.
Examples of the electronic device include a mobile phone, a display device, an in-vehicle device, a computer, and a communication device. In addition, it can be used for applications such as aircraft parts, automobile parts, building parts, etc., and is used as a heat-resistant binder for conductive materials, particularly metal fillers, to form circuits that can flow direct current or alternating current. It may be used.

〔Production method〕
Below, the manufacturing method in 1st Embodiment and the manufacturing method in 2nd Embodiment are demonstrated.
These production methods are commonly used in the first step of creating a mixed solvent of an aromatic nonpolar solvent and an alcohol, adding a bisphenol compound and an amine compound to the mixed solvent prepared in the first step, and mixing the solution. A second step of preparing Note that nitrogen gas may be purged as necessary. It is a production method including a third step of heating the mixed solution and further adding an aldehyde compound to obtain a target compound.
Between the second step and the third step, a reflux and distillation step may be added. Furthermore, it is preferable to add a step of refluxing, distilling, further refluxing, cooling, filtration, precipitation and drying after the third step.

First, the manufacturing method in 1st Embodiment is demonstrated.
By reacting a bisphenol compound having a structure represented by the following formula (3), a diamine compound having a structure represented by the following formula (4), and an aldehyde compound in a mixed solvent of an aromatic nonpolar solvent and an alcohol, A compound having a benzoxazine ring structure is produced.

In the formula (4), R ⁵ and R ⁶ are each independently hydrogen or an organic group having 1 to 20 carbon atoms. Incidentally, R ⁵ and R ^6, except when simultaneously hydrogen.

(Bisphenol compound)
The bisphenol component is not particularly limited, but preferably has a dihydroxybenzophenone skeleton. Examples of such bisphenol compounds include 4,4′-dihydroxybenzophenone.
Moreover, the hydrogen of the phenyl group of the bisphenol compound having the dihydroxybenzophenone skeleton may be substituted with another substituent. Examples of such a substituent include an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
In the range not departing from the gist of the invention, for example, 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′-biphenol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene 1,4-benzenediol (hydroquinone), 1,3-benzenediol (reso Shinoru), 1,2-benzenediol (catechol), or the like may be added.
These bisphenol compounds may be used alone or in combination of two or more.

(Amine compound)
The amine component is not particularly limited, but preferably has a diphenylmethane skeleton. In the amine compound having the diphenylmethane skeleton, the hydrogen of the phenyl group may be substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
Examples of such amine compounds include diamine compounds such as 4,4′-diamino-3,3′-dimethyldiphenylmethane and 4,4′-diamino-3,3′-diethyldiphenylmethane. The amine compound is preferably a diamine compound such as 4,4′-diamino-3,3′-dimethyldiphenylmethane or 4,4′-diamino-3,3′-diethyldiphenylmethane.
In the range not departing from the gist of the present invention, for example, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3 ′, 5,5′-tetramethyldiphenylmethane, 4,4′-diamino- 3,3 ′, 5,5′-tetraethyldiphenylmethane, 1,4-diaminobenzene 4,4′-diaminodiphenyl ether, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane (Wakayama Seika Kogyo) Product name BAPP), 4,4 '-[1,3-phenylenebis (1-methyl-ethylidene)] bisaniline (product name Bisaniline M, manufactured by Mitsui Chemicals, Inc.), 4,4'-[1,4 -Phenylenebis (1-methyl-ethylidene)] bisaniline (product name, bisaniline P, manufactured by Mitsui Chemicals, Inc.), 1,3-bis (4-aminophenoxy) benzene, and 1,4-bis (4-aminophenoxy) aromatic diamine compounds such as benzene; 3 (4), 8 (9), - bis (aminomethyl) tricyclo [5,2,1,0 ^2,6] decane ( Oxea product name TCD diamine), and alicyclic diamine compounds such as 2,5 (6) -bis (aminomethyl) bicyclo [2.2.1] heptane; 1,2-diaminoethane, 1,6- Linear aliphatic diamine compounds such as diaminohexane, 1,10-diaminodecane, 1,12-diaminododecane, 1,14-diaminotetradecane and 1,18-diaminooctadecane may be added.
These amine compounds may be used alone or in combination of two or more.

The use ratio of the bisphenol compound and the amine compound is preferably 0.9 mol to 1.2 mol with respect to 1.0 mol of 4,4′-dihydroxybenzophenone.
When the amount of the amine compound used exceeds 1.20 mol, the reaction solution tends to gel. When the amount of the amine compound used is less than 0.90 mol, unreacted 4,4′-dihydroxybenzophenone remains. It is because it is in a tendency.

(Aldehyde compound)
As the aldehyde compound, formaldehyde is preferable.
As formaldehyde, it is more preferable to use it in the form of paraformaldehyde which is a polymer thereof, formalin which is in the form of an aqueous solution, or the like.
The amount of the aldehyde compound used is preferably 4.0 mol to 6.5 mol with respect to 1.0 mol of the diamine compound.
If the amount of aldehyde compound used exceeds 6.5 mol, the remaining aldehyde compound tends to increase the load on the human body and the environment. If the amount of aldehyde compound used is less than 4.0 mol, benzoxazine There exists a tendency for the thermosetting resin which has a ring to become high molecular weight.

(A mixture of aromatic nonpolar solvent and alcohol)
The aromatic nonpolar solvent is not particularly limited, and examples thereof include benzene, toluene, xylene, pseudocumene, and mesitylene. In particular, toluene, xylene, and the like are preferable because they have a low environmental and human load and are highly versatile. More preferably, it is toluene. Aromatic nonpolar solvents may be used alone or in combination of two or more.
Although it does not specifically limit as alcohol, For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, 2-methoxyethanol, 2-ethoxyethanol etc. are mentioned. The alcohol is preferably isobutanol. Alcohols may be used alone or in combination of two or more.
The mixed solvent of the aromatic nonpolar solvent and the alcohol is not particularly limited, but is preferably a combination of at least one of the above-mentioned aromatic nonpolar solvents and alcohols. Furthermore, a combination of toluene and isobutanol is more preferable.

The ratio of the alcohol in the mixed solvent of the aromatic nonpolar solvent and the alcohol is preferably 5% by volume to 50% by volume, and more preferably 10% by volume to 30% by volume with respect to the entire mixed solvent.
When the proportion of the alcohol in the mixed solvent is less than 5% by volume, the reaction suppressing effect due to the alcohol is reduced, and the risk of gelation of the reaction solution and insolubilization of the thermosetting resin having a benzoxazine ring as a synthetic product is increased. There is a fear. When the proportion of alcohol exceeds 50% by volume, a long time is required for the synthesis reaction of the thermosetting resin having a benzoxazine ring, which may reduce the synthesis efficiency.

The amount of the mixed solvent obtained by adding the aromatic nonpolar solvent and the alcohol is such that the molar concentration of 4,4′-dihydroxybenzophenone is 0.1 to 1.2 mol / L on the basis of 4,4′-dihydroxybenzophenone. It is preferable that the amount is L.
When the molar concentration of 4,4′-dihydroxybenzophenone is less than 0.1 mol / L, the raw material concentration in the mixed solvent is low, the synthesis reaction of the thermosetting resin having a benzoxazine ring is delayed, and the synthesis efficiency is lowered. There is a risk.
On the other hand, when the molar concentration of 4,4′-dihydroxybenzophenone exceeds 1.2 mol / L, during the synthesis reaction of the thermosetting resin having a benzoxazine ring, the gelation of the reaction solution and the synthesized benzoxazine ring are reduced. There is a possibility that the risk of insolubilization of the thermosetting resin is increased.

(Other materials-phenolic compounds)
In the present embodiment, a monofunctional phenol compound may be added and reacted together with 4,4′-dihydroxybenzophenone.
When a monofunctional phenol compound is used in combination, a polymer in which the reactive end is sealed with a benzoxazine ring is generated. As a result, the molecular weight during the synthesis reaction can be controlled, and gelation of the solution can be prevented. . In addition, the sealing of the reactive ends can improve the storage stability of the obtained thermosetting resin having a benzoxazine ring, and can prevent insolubilization.
Examples of the monofunctional phenol compound include phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, p-octylphenol, p-cumylphenol, dodecylphenol, o-phenylphenol, and p-phenyl. Examples include phenol, 1-naphthol, 2-naphthol, m-methoxyphenol, p-methoxyphenol, m-ethoxyphenol, p-ethoxyphenol, 3,4-dimethylphenol, 3,5-dimethylphenol. In particular, phenol is preferable from the viewpoint of versatility and cost.
The amount of the monofunctional phenol compound used is preferably 0.50 mol or less with respect to 1.00 mol of 4,4′-dihydroxybenzophenone.
When the amount of the monofunctional phenol compound used exceeds 0.50 mol with respect to 1.00 mol of 4,4′-dihydroxybenzophenone, the molecular weight of the thermosetting resin having a benzoxazine ring structure is increased during the synthesis reaction. In addition, a large amount of monofunctional phenolic compound tends to remain.

In the method for producing a thermosetting resin in the present embodiment, although not particularly limited, a bisphenol compound and an amine compound are added to a mixed solvent of an aromatic nonpolar solvent and an alcohol, and the mixture is thoroughly stirred, and an aldehyde compound is added. A method of further adding and allowing the reaction to proceed is preferred.
In order to efficiently mix and dissolve the raw materials, heating may be performed, and addition and mixing may be appropriately performed with stirring of the mixed solvent using a stirrer, a stirrer, or the like.

Although it does not specifically limit as a heating method, For example, after using a temperature regulator, such as an oil bath, to raise at a stretch to predetermined temperature, the method of keeping constant at the temperature is mentioned.
The temperature at the time of heating is not particularly limited as long as it is a temperature at which the efficiency of the synthesis reaction of the thermosetting resin having a benzoxazine ring is improved. For example, it is preferable to adjust so that it may become 50 to 130 degreeC.
When the reaction solution temperature is lower than 50 ° C., the synthesis reaction of the thermosetting resin having a benzoxazine ring is delayed, and the synthesis efficiency may be reduced. If the reaction solution temperature exceeds 130 ° C., the risk of gelation of the reaction solution during the synthesis reaction of the thermosetting resin having a benzoxazine ring and the risk of insolubilization of the thermosetting resin having a benzoxazine ring as a synthesized product may increase. is there.
Note that the mixed solvent may be refluxed during the heat treatment of the mixed solution.

Although reaction time is not specifically limited, It is preferable that it is about 1 to 10 hours after a heat processing start. Furthermore, it is more preferable that it is 3 to 10 hours. If the reaction time is 1 hour or less, the reaction does not proceed sufficiently, and the target compound cannot be obtained. Further, heating for 10 hours or more is not preferable because productivity decreases.
After heating is continued for 1 to 10 hours after the start of heating, it may be allowed to cool by releasing from contact with a temperature regulator such as an oil bath, or may be cooled using a refrigerant or the like.

During the production process of the thermosetting resin, the generated water may be distilled off.
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 effect of improving the reaction efficiency can be obtained.
The water can be distilled off by, for example, azeotroping with the mixed solvent in the reaction solution. For example, the water produced | generated can be distilled off by using an equal pressure dropping funnel with a cock, a Dimroth cooler, a Dean-Stark apparatus, etc.

After performing the reaction as described above, the thermosetting resin having a benzoxazine ring is recovered from the reaction solution.
Although it does not specifically limit about the collection | recovery method, For example, it can collect | recover by the reprecipitation method by a poor solvent, the concentration solidification method (solvent vacuum distillation), the spray-drying method, etc.

Moreover, the manufacturing method of the compound which has the benzoxazine ring structure in 2nd Embodiment is the bisphenol compound which has a structure shown to following formula (5), the diamine compound shown to following formula (6) and formula (7), and an aldehyde And a step of reacting the compound in a mixed solvent of an aromatic nonpolar solvent and an alcohol.
Here, when the total of the diamine compound represented by the formula (6) and the diamine compound represented by the formula (7) is 100 mol%, the diamine compound represented by the formula (6): The mol% of the diamine compound shown is 40%: 60% to 90%: 10%.
Note that nitrogen gas may be purged into the system as necessary.

In the formula (6), R ⁷ and R ⁸ are each independently hydrogen or an organic group having 1 to 20 carbon atoms. Note that R ⁷ and R ⁸ are not hydrogen at the same time.

(Bisphenol compound having the structure shown in the above formula (5))
The bisphenol compound having the structure represented by the above formula (5) does not have any other substituent.

(Diamine compound of the above formula (6))
As the diamine compound of the formula (6), those similar to the diamine compound of the formula (4) described above can be used.

(Diamine compound represented by the above formula (7))
The diamine compound represented by the above formula (7) has no other substituent.

(Aldehyde compound)
As the aldehyde compound, formaldehyde is preferable.
As formaldehyde, it is more preferable to use it in the form of paraformaldehyde which is a polymer thereof, formalin which is in the form of an aqueous solution, or the like.
The amount of the aldehyde compound used is preferably 4.0 mol to 6.5 mol with respect to 1.0 mol of the diamine compound. Furthermore, 4.5 mol-6.0 mol are more preferable with respect to 1.0 mol of diamine compounds.
If the amount of aldehyde compound used exceeds 6.5 mol, the remaining aldehyde compound tends to increase the load on the human body and the environment. If the amount of aldehyde compound used is less than 4.0 mol, benzoxazine There exists a tendency for the thermosetting resin which has a ring to become high molecular weight.

(A mixture of aromatic nonpolar solvent and alcohol)
The aromatic nonpolar solvent is not particularly limited, and examples thereof include benzene, toluene, xylene, pseudocumene, and mesitylene. In particular, toluene, xylene, and the like are preferable because they have a low environmental and human load and are highly versatile. More preferably, it is toluene. Aromatic nonpolar solvents may be used alone or in combination of two or more.
Although it does not specifically limit as alcohol, For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, 2-methoxyethanol, 2-ethoxyethanol etc. are mentioned. The alcohol is preferably isobutanol. Alcohols may be used alone or in combination of two or more.
The mixed solvent of the aromatic nonpolar solvent and the alcohol is not particularly limited, but is preferably a combination of at least one of the above-mentioned aromatic nonpolar solvents and alcohols. Furthermore, a combination of toluene and isobutanol is more preferable.
The ratio of the alcohol in the mixed solvent of the aromatic nonpolar solvent and the alcohol is preferably 5% by volume to 50% by volume, and more preferably 10% by volume to 30% by volume with respect to the entire mixed solvent.
When the proportion of the alcohol in the mixed solvent is less than 5% by volume, the reaction suppressing effect due to the alcohol is reduced, and the risk of gelation of the reaction solution and insolubilization of the thermosetting resin having a benzoxazine ring as a synthetic product is increased. There is a fear. When the proportion of alcohol exceeds 50% by volume, a long time is required for the synthesis reaction of the thermosetting resin having a benzoxazine ring, which may reduce the synthesis efficiency.
The amount of the mixed solvent obtained by adding the aromatic nonpolar solvent and the alcohol is such that the molar concentration of 4,4′-dihydroxybenzophenone is 0.1 to 1.2 mol / L on the basis of 4,4′-dihydroxybenzophenone. It is preferable that the amount is L.
When the molar concentration of 4,4′-dihydroxybenzophenone is less than 0.1 mol / L, the raw material concentration in the mixed solvent is low, the synthesis reaction of the thermosetting resin having a benzoxazine ring is delayed, and the synthesis efficiency is lowered. There is a risk.
On the other hand, when the molar concentration of 4,4′-dihydroxybenzophenone exceeds 1.2 mol / L, during the synthesis reaction of the thermosetting resin having a benzoxazine ring, the gelation of the reaction solution and the synthesized benzoxazine ring are reduced. There is a possibility that the risk of insolubilization of the thermosetting resin is increased.

(Reaction process)
A method is preferred in which a bisphenol compound and an amine compound are added to a mixed solvent of an aromatic nonpolar solvent and an alcohol, the mixture is stirred well, and an aldehyde compound is further added to advance the reaction.
In order to efficiently mix and dissolve the raw materials, heating may be performed, and addition and mixing may be appropriately performed with stirring of the mixed solvent using a stirrer, a stirrer, or the like.
Although it does not specifically limit as a heating method, For example, after using a temperature regulator, such as an oil bath, to raise at a stretch to predetermined temperature, the method of keeping constant at the temperature is mentioned.
The temperature at the time of heating is not particularly limited as long as it is a temperature at which the efficiency of the synthesis reaction of the thermosetting resin having a benzoxazine ring is improved. For example, it is preferable to adjust so that it may become 50 to 130 degreeC.
When the reaction solution temperature is lower than 50 ° C., the synthesis reaction of the thermosetting resin having a benzoxazine ring is delayed, and the synthesis efficiency may be reduced. If the reaction solution temperature exceeds 130 ° C., the risk of gelation of the reaction solution during the synthesis reaction of the thermosetting resin having a benzoxazine ring and the risk of insolubilization of the thermosetting resin having a benzoxazine ring as a synthesized product may increase. is there.
Note that the mixed solvent may be refluxed during the heat treatment of the mixed solution.
The heat treatment time is not particularly limited, but is preferably about 1 to 10 hours after the start of the heat treatment.
After heating is continued for 1 to 10 hours after the start of heating, it may be allowed to cool by releasing from contact with a temperature regulator such as an oil bath, or may be cooled using a refrigerant or the like.
During the production process of the thermosetting resin, the generated water may be distilled off.
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 effect of improving the reaction efficiency can be obtained.
The water can be distilled off by, for example, azeotroping with the mixed solvent in the reaction solution. For example, the water produced | generated can be distilled off by using an equal pressure dropping funnel with a cock, a Dimroth cooler, a Dean-Stark apparatus, etc.
After performing the reaction as described above, the thermosetting resin having a benzoxazine ring is recovered from the reaction solution.
Although it does not specifically limit about the collection | recovery method, For example, it can collect | recover by the reprecipitation method by a poor solvent, the concentration solidification method (solvent vacuum distillation), the spray-drying method, etc.

Moreover, the ratio of the usage-amount of the diamine compound shown to Formula (6) and the diamine compound shown to the said (7) is the sum total of the diamine compound shown to the said Formula (6), and the diamine compound shown to the said Formula (7). Is 100 mol%, the diamine compound represented by the formula (6): The mol% of the diamine compound represented by the above (7) is 40:60 to 90:10.
When the mol% of the diamine compound represented by formula (6) is 40% or more, good solubility in a mixed solvent can be obtained.
Moreover, Tg value of the thermosetting resin which has the target benzoxazine ring is improved especially that mol% of the diamine compound shown in said (7) is 10% or more.

Hereinafter, specific examples will be described in detail with reference to comparative examples.
First, methods for measuring physical properties in Examples and Comparative Examples are shown below.

[Measurement of Mw (weight average molecular weight)]
During the synthesis reaction, a part of the reaction solution is taken out and subjected to gel permeation chromatography measurement to measure Mw of the thermosetting resin having a benzoxazine ring during the reaction.
As a measuring device, a high performance liquid chromatograph system manufactured by Shimadzu Corporation was used.
Under the THF fluid phase, gel permeation chromatography measurement was performed under the conditions of a column temperature of 40 ° C., a flow rate of 1 mL / min, and an RI detector.
The obtained weight average molecular weight was calculated as a polystyrene equivalent value.
The detection conditions are shown below.
(High-performance liquid chromatograph system)
System controller: SCL-10A VP
Liquid feeding unit: LC-10AD VP
Degasser: DGU-12A
Differential refractometer (RI) detector: RID-10A
Autoinjector: SIL-10AD VP
Column oven: CTO-10AS VP
Column: SHODEX KF804L (exclusion limit molecular weight 400000) × 2 (in series)
Column temperature: 40 ° C
Flow rate: 1 mL / min Eluent: THF (manufactured by Wako Pure Chemical Industries, Ltd., without stabilizer, for HPLC)
Sample: 1% by mass
As the molecular weight calculation method, a standard polystyrene conversion method was used.
Specifically, Mw (Mw (weight average molecular weight) / Mn (number average molecular weight)) is 354000 (1.02), 189000 (1.04), 98900 (1.01), 37200 (1.01), respectively. ), 17100 (1.02), 9830 (1.02), 5870 (1.05), 2500 (1.05), 1050 (1.13), 500 (1.14) 300 (1.20) A standard curve was created using standard polystyrene and calculated.

[The ¹ H-NMR measurement]
The following measurement apparatus and solvent were used.
Measuring device: JEOL, ECX400 (400MHz)
Solvent: deuterated chloroform (manufactured by Cambridge Isotop Laboratories, 0.05% by volume TMS (tetramethylsilane)
Sample concentration: 1.3% by mass

(Measurement of linear expansion coefficient)
Using “TMA / SS6100” manufactured by SII NanoTechnology Co., Ltd., 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 linear expansion coefficients from 25 ° C. to 150 ° C. (CTE )
The measurement sample was cut into a width of 4 mm and a length of 20 mm, and set so that the distance between chucks was 10 mm.
[Measurement of glass transition temperature]
Using “TMA / SS6100” manufactured by SII Nano Technology, the tensile mode was measured under a nitrogen atmosphere, with a load of 5 mN, a heating rate of 5 ° C./min, and a dimensional change from 25 ° C. to 300 ° C. It was read from the inflection point of dimensional change.
The measurement sample was cut into a width of 4 mm and a length of 20 mm, and set so that the distance between chucks was 10 mm.

[Example 1]
Toluene (212 mL) and isobutanol (38 mL) were added and mixed at room temperature in a 500 mL flask in which a reflux tube, a constant pressure dropping funnel with a cock, and a Dimroth condenser were set.
Thereafter, 21.9 g (0.10 mol, manufactured by Wako Pure Chemical Industries, Ltd.) of 4,4′-dihydroxybenzophenone (hereinafter referred to as DHBP), 4,4′-diamino-3,3′-dimethyldiphenylmethane (hereinafter referred to as “DHBP”) 25.2 g (0.10 mol, manufactured by Nippon Kayaku Co., Ltd., product name “KAYABOND C-100”) was added and mixed in the flask under room temperature conditions. From this point, nitrogen gas purge was started into the system (flow rate: 15 mL / L).
The reaction solution was heated to 64 ° C. and stirred for 30 minutes, and then 19.7 g (0.60 mol, manufactured by Mitsubishi Gas Chemical Co., Inc., purity 91.60%) of paraformaldehyde (hereinafter referred to as PFA) The mixture was added and mixed in the flask to obtain a reaction solution in which all raw materials were mixed.
The reaction solution was refluxed and the reaction was allowed to proceed for 2 hours.
Thereafter, the water produced during the reaction was azeotroped with toluene and isobutanol, and the reaction was further advanced 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 having a benzoxazine ring.
The weight average molecular weight (Mw) obtained by gel permeation chromatography measurement of the obtained thermosetting resin having a benzoxazine ring was about 14,000. The compound thus obtained is referred to as Compound A.

The ¹ H-NMR spectrum of Compound A is shown in FIG.
In FIG. 1, since many peaks appear in the vicinity of 7 ppm, a structure having a benzenezophenone skeleton can be estimated.
Oxazine ring of DHBP_MDT Methylene proton peak at the 2-position of the oxazine ring: 5.21 ppm
Methylene proton peak at the 4-position of the oxazine ring: 4.39 ppm
Proton peak of MDT-derived methylene group (= -CH2-): 3.75 ppm
Proton peak of MDT-derived methyl group: 2.29 ppm

[Example 2]
170 mL of toluene and 30 mL of isobutanol were added and mixed at room temperature in a 500 mL flask in which a reflux tube, an isobaric dropping funnel with a cock, and a Dimroth condenser were set.
Thereafter, DHBP 17.5 g (0.08 mol, manufactured by Wako Pure Chemical Industries, Ltd.), MDT 9.1 g (0.04 mol, manufactured by Nippon Kayaku Co., Ltd., product name “KAYABOND C-100”), 4,4′-diamino Diphenylmethane (hereinafter referred to as MDA) 8.1 g (0.04 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added and mixed in the flask at room temperature. From this point, nitrogen gas purge was started into the system (flow rate: 15 mL / L).
The reaction solution was heated to 62 ° C. and stirred for 30 minutes, and then 13.6 g of PFA (0.42 mol, manufactured by Mitsubishi Gas Chemical Co., Inc., purity 91.60%) was added and mixed in the flask, and all the raw materials were mixed. To obtain a mixed reaction solution.
The reaction solution was refluxed and the reaction was allowed to proceed for 3 hours.
Thereafter, the water produced during the reaction was further azeotroped with toluene and isobutanol, and the reaction was further advanced while distilling out of the system.
Refluxing was performed for 5 hours after the start of distillation.
The obtained reaction solution was cooled to room temperature 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 having a benzoxazine ring.
Mw obtained by gel permeation chromatography measurement of the obtained thermosetting resin having a benzoxazine ring was about 9000.
The compound thus obtained is referred to as Compound B.

The ¹ H-NMR spectrum of Compound B is shown in FIG.
In FIG. 2, since many peaks appear in the vicinity of 7 ppm, a structure having a benzenezophenone skeleton can be estimated.
Oxazine ring of DHBP_MDT Methylene proton peak at the 2-position of the oxazine ring: 5.20 ppm
Methylene proton peak at the 4-position of the oxazine ring: 4.38 ppm
Oxazine ring of DHBP_MDA Methylene proton peak at the 2-position of the oxazine ring: 5.36 ppm
Methylene proton peak at the 4-position of the oxazine ring: 4.60 ppm
MDT, MDA-derived methylene group (= —CH ₂ —) proton peak: 3.75 ppm
Proton peak of MDT-derived methyl group: 2.29 ppm

Example 3
170 mL of toluene and 30 mL of isobutanol were added and mixed at room temperature in a 500 mL flask in which a reflux tube, an isobaric dropping funnel with a cock, and a Dimroth condenser were set.
Thereafter, DHBP 17.5 g (0.08 mol, manufactured by Wako Pure Chemical Industries, Ltd.), MDT 8.2 g (0.036 mol, manufactured by Nippon Kayaku Co., Ltd., product name “KAYABOND C-100”), MDA 8.9 g (0.8. 044 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added and mixed together in the flask at room temperature. From this point, nitrogen gas purge was started into the system (flow rate: 15 mL / L).
After raising the temperature of the reaction solution to 63 ° C. and stirring for 30 minutes, 13.6 g of PFA (0.42 mol, manufactured by Mitsubishi Gas Chemical Co., Inc., purity 91.60%) was added and mixed all at once into the flask. A reaction solution in which all raw materials were mixed was obtained.
The reaction solution was refluxed and the reaction was allowed to proceed for 6 hours.
The obtained reaction solution was cooled to room temperature 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 compound having a benzoxazine ring.
Mw obtained by gel permeation chromatography measurement of the obtained compound having a benzoxazine ring was about 7000.

The ¹ H-NMR spectrum of the thermosetting resin is shown in FIG.
In FIG. 3, since many peaks appear in the vicinity of 7 ppm, a structure having a benzenezophenone skeleton can be estimated.
Methylene proton peak at the 2-position of the oxazine ring oxazine ring of DHBP_MDT: 5.20 ppm
Methylene proton peak at the 4-position of the oxazine ring: 4.38 ppm
Methylene proton peak at the 2-position of oxazine ring oxazine ring of DHBP_MDA: 5.37 ppm
Methylene proton peak at the 4-position of the oxazine ring: 4.60 ppm
MDT, MDA-derived methylene group (= —CH 2 —) proton peak: 3.75 ppm
Proton peak of MDT-derived methyl group: 2.29 ppm

Example 4
170 mL of toluene and 30 mL of isobutanol were added and mixed at room temperature in a 500 mL flask in which a reflux tube, an isobaric dropping funnel with a cock, and a Dimroth condenser were set.
Thereafter, DHBP 17.5 g (0.08 mol, manufactured by Wako Pure Chemical Industries, Ltd.), MDT 7.3 g (0.032 mol, manufactured by Nippon Kayaku Co., Ltd., product name “KAYABOND C-100”), MDA 9.7 g (0. 048 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added and mixed in the flask at room temperature. From this point, nitrogen gas purge was started into the system (flow rate: 15 mL / L).
The reaction solution was heated to 62 ° C. and stirred for 30 minutes, and then 13.6 g of PFA (0.42 mol, manufactured by Mitsubishi Gas Chemical Co., Inc., purity 91.60%) was added and mixed in the flask. A mixed reaction solution was obtained.
The reaction solution was refluxed for 6 hours to allow the reaction to proceed.
The obtained reaction solution was cooled to room temperature and then poured into 1 L of methanol to precipitate the product.
The precipitated solid precipitate was dried under reduced pressure to obtain a compound having a benzoxazine ring.
Mw obtained by gel permeation chromatography measurement of the compound having a benzoxazine ring was about 6000.

The ¹ H-NMR spectrum of the thermosetting resin is shown in FIG.
In FIG. 4, since many peaks appear in the vicinity of 7 ppm, a structure having a benzenezophenone skeleton can be estimated.
Methylene proton peak at the 2-position of the oxazine ring oxazine ring of DHBP_MDT: 5.20 ppm
Methylene proton peak at the 4-position of the oxazine ring: 4.38 ppm
Methylene proton peak at the 2-position of oxazine ring oxazine ring of DHBP_MDA: 5.38 ppm
Methylene proton peak at the 4-position of the oxazine ring: 4.60 ppm
MDT, MDA-derived methylene group (= —CH ₂ —) proton peak: 3.75 ppm
Proton peak of MDT-derived methyl group: 2.29 ppm

[Synthesis Example 1]
190 mL of toluene and 10 mL of isobutanol were added and mixed at room temperature in a 500 mL flask in which a reflux tube, an isobaric dropping funnel with a cock, and a Dimroth condenser were set.
Thereafter, 41.6 g of bisphenol A (hereinafter referred to as BisA) (0.120 mol, manufactured by GE Plastics, Inc.), 2,2′-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter, 51.3 g (0.125 mol, manufactured by Wakayama Seika Kogyo Co., Ltd., product name “BAPP”) and 0.9 g (0.0096 mol) of phenol 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 / L).
Thereafter, the temperature of the reaction solution was raised to 65 ° C., and after confirming dissolution of each raw material, 19.7 g of PFA (0.6 mol, manufactured by Mitsubishi Gas Chemical Co., Inc., purity 91.60%) was added and mixed in the flask. Thus, a reaction solution in which all raw materials were mixed was obtained.
The reaction solution thus obtained was refluxed and the reaction was allowed to proceed for 2 hours.
Thereafter, the water produced during the reaction was azeotroped with toluene and isobutanol to allow the reaction to proceed while distilling out of the system.
Refluxing was performed for 6 hours after the start of distillation, and the reaction was further advanced.
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 compound having a benzoxazine ring.
Mw obtained by gel permeation chromatography measurement of the obtained compound having a benzoxazine ring was about 16000.
The resulting compound is designated C.

[Comparative Example 1]
Toluene (212 mL) and isobutanol (38 mL) were added and mixed at room temperature in a 500 mL flask in which a reflux tube, an isobaric dropping funnel with a cock, and a Dimroth condenser were set.
Thereafter, 21.9 g of DHBP (0.1 mol, manufactured by Wako Pure Chemical Industries, Ltd.) and 20.2 g of MDA (0.1 mol, manufactured by Wako Pure Chemical Industries, Ltd.) 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 / L).
The reaction solution thus obtained was heated to 64 ° C. and stirred for 30 minutes.
Thereafter, 19.7 g of PFA (0.6 mol, manufactured by Mitsubishi Gas Chemical Co., Inc., purity 91.60%) was added and mixed in the flask to obtain a reaction solution in which all raw materials were mixed.
The reaction solution thus obtained was refluxed to start the reaction.
However, in this example, it was confirmed that the compound having the target benzoxazine ring was not produced even after 7 hours had elapsed, so the reaction was interrupted.

[Comparative Example 2]
170 mL of toluene and 30 mL of isobutanol were added and mixed at room temperature in a 500 mL flask in which a reflux tube, a constant pressure dropping funnel with a cock, and a Dimroth condenser were set.
Thereafter, DHBP 17.5 g (0.08 mol, manufactured by Wako Pure Chemical Industries, Ltd.), MDT 4.6 g (0.02 mol, manufactured by Nippon Kayaku Co., Ltd., product name “KAYABOND C-100”), MDA 12.1 g (0. 06 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added and mixed in the flask at room temperature. From this point, nitrogen gas purge was started into the system (flow rate: 15 mL / L).
The reaction solution obtained as described above was heated to 62 ° C. and stirred for 30 minutes.
Thereafter, 13.6 g of PFA (0.42 mol, manufactured by Mitsubishi Gas Chemical Co., Inc., purity 91.60%) was added and mixed in the flask to obtain a reaction solution in which all raw materials were mixed.
The reaction solution was heated to 80 ° C. to initiate the reaction.
However, in this example, since it was confirmed that the thermosetting resin having the target benzoxazine ring was not produced even after 8 hours, the reaction was interrupted.

[Comparative Example 3]
170 mL of toluene and 30 mL of isobutanol were added and mixed at room temperature in a 500 mL flask in which a reflux tube, a constant pressure dropping funnel with a cock, and a Dimroth condenser were set.
Thereafter, DHBP 17.5 g (0.08 mol, Wako Pure Chemical Industries, Ltd.), MDT 6.4 g (0.028 mol, Nippon Kayaku Co., Ltd., product name “KAYABOND C-100”), MDA 10.5 g (0. 052 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added and mixed in the flask under room temperature conditions. From this point, nitrogen gas purge was started into the system (flow rate: 15 mL / L).
The reaction solution obtained as described above was heated to 60 ° C. and stirred for 30 minutes.
Thereafter, 13.6 g of PFA (0.42 mol, manufactured by Mitsubishi Gas Chemical Co., Inc., purity 91.60%) was added and mixed in the flask to obtain a reaction solution in which all raw materials were mixed.
The reaction solution was refluxed to initiate the reaction.
However, in this example, it was confirmed that the compound having the target benzoxazine ring was not produced even after 5 hours had elapsed, so the reaction was interrupted.

[Comparative Example 4]
In a 500 mL flask in which a reflux tube, an isostatic dropping funnel with a cock and a Dimroth condenser were set, 250 mL of dioxane, 21.9 g of DHBP (0.1 mol, manufactured by Wako Pure Chemical Industries, Ltd.), 20.2 g of MDA (0. 1 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added and mixed at room temperature. From this point, nitrogen gas purge was started into the system (flow rate: 15 mL / L).
After confirming dissolution of DHBP and MDA, 19.7 g of PFA (0.6 mol, manufactured by Mitsubishi Gas Chemical Co., Inc., purity 91.60%) was added and mixed in the flask.
However, immediately after heating was started, the solution gelled, stirring became difficult, and the reaction was interrupted.

[Comparative Example 5]
In a 500 mL flask in which a reflux tube, an isostatic dropping funnel with a cock, and a Dimroth condenser were set, 250 mL of toluene, 21.9 g of DHBP (0.1 mol, manufactured by Wako Pure Chemical Industries, Ltd.), 25.2 g of MDT (0. 10 mol, manufactured by Nippon Kayaku Co., Ltd., product name “KAYABOND C-100”) was added and mixed at room temperature. From this point, nitrogen gas purge was started into the system (flow rate: 15 mL / L).
After heating up the obtained reaction solution to 64 degreeC and stirring for 30 minutes, PFA19.7g (0.6 mol, Mitsubishi Gas Chemical Co., Inc. purity 91.60%) was added and mixed in the said flask, A reaction solution in which all raw materials were mixed was obtained.
Attempts were made to advance the reaction while refluxing the reaction solution, but immediately after the start of heating, the solution gelled, stirring became difficult, and the reaction was interrupted.

Example 5
In a glass container, 5 g of the compound A prepared in Example 1 was dissolved in 6 g of dimethylformamide to obtain a purple viscous liquid.
This viscous liquid was applied onto a release-treated PET film using an applicator, and at 80 ° C. for 10 minutes, 100 ° C. for 10 minutes, 150 ° C. for 10 minutes, 180 ° C. for 30 minutes, and 200 ° C. It was held for 30 minutes and 220 ° C. for 1 hour, respectively, and was thermoset in a gear open.
A film-like cured product was obtained by the thermosetting. This cured product was yellow and transparent, had a thickness of 54 μm, and had a glass transition temperature (Tg) of 218 ° C. Hereinafter, this cured product is referred to as film A.

Example 6
In a glass container, 0.05 g of STN (layered silicate, manufactured by Coop Chemical Co., Ltd.) was uniformly dispersed in 5 g of dimethylformamide to obtain a solution.
5 g of the compound B produced in Example 2 was dissolved in the obtained solution to obtain a purple viscous liquid.
This solution viscosity liquid was applied onto a release-treated PET film using an applicator, and at 80 ° C. for 10 minutes, 100 ° C. for 10 minutes, 150 ° C. for 10 minutes, 180 ° C. for 30 minutes, 200 ° C. For 30 minutes and at 220 ° C. for 1 hour, respectively, and heat-cured in gear open.
A film-like cured product was obtained by the thermosetting. The cured product was yellow and transparent, had a thickness of 50 μm, and had a glass transition temperature (Tg) of 230 ° C. Hereinafter, this cured product is referred to as film B.

[Comparative Example 6]
(Film creation example 1)
In a glass container, 5 g of Compound C prepared in Synthesis Example 1 was dissolved in 5 g of dimethylformamide to obtain a yellow viscous liquid.
This solution viscosity liquid was applied onto a release-treated PET film using an applicator, and at 80 ° C. for 10 minutes, 100 ° C. for 10 minutes, 150 ° C. for 10 minutes, 180 ° C. for 30 minutes, 200 ° C. For 30 minutes, at 220 ° C. for 30 minutes, and at 240 ° C. for 1 hour, and thermoset in gear open.
A film-like cured product was obtained by the thermosetting. The cured product was yellow and transparent and had a thickness of 51 μm. Hereinafter, this cured product is referred to as film C.

  Table 1 below shows the raw materials, reaction solvents, reaction time, synthesis availability, and weight average molecular weight of the compounds in Examples 1 to 4, Synthesis Example 1, and Comparative Examples 1 to 5.

(Terms in Table 1)
DHBP: 4,4′-dihydroxybenzophenone BisA: bisphenol A
MDT: 4,4′-diamino-3,3′-dimethyldiphenylmethane MDA: 4,4′-diaminodiphenylmethane BAPP: 2,2′-bis [4- (4-aminophenoxy) phenyl] propane PFA: paraformaldehyde

  As shown in Table 1 below, in Examples 1 to 4 of the present invention, a bisphenol compound, an amine compound, and an aldehyde compound are simply reacted in a mixed solvent of an aromatic nonpolar solvent and an alcohol. In this process, a compound having a prepolymer type benzoxazine ring having a weight average molecular weight (Mw) of 5000 or more was obtained.

Next, the linear expansion coefficient was measured for Example 5 (Film A), Example 6 (Film B), and Comparative Example 6 (Film C). The measurement conditions are shown below.
(Measuring method)
Using “TMA / SS6100” manufactured by SII Nanotechnology, measured under a nitrogen atmosphere as a tensile mode, a load of 5 mN, and a heating rate of 5 ° C./min. The average linear expansion coefficient (CTE) was determined.
(Measurement condition)
Mode: Tensile atmosphere: Nitrogen Tensile load: 5 mN
Temperature rising rate: 5 ° C./min Table 2 below shows the final curing conditions and average values of the linear expansion coefficients of the films A to C.

  As shown in Table 2, in Examples 5 and 6 of the present invention, the linear expansion coefficient is reduced as compared with the film of Comparative Example 6 which is the prior art, and the dimensional stability is excellent. I found out.

  The compound having a benzoxazine ring structure of the present invention has a high molecular weight, and has an excellent low linear expansion coefficient and solubility in a solvent. Can be manufactured. For example, such a resin composition uses a compound having a benzoxazine ring structure containing either the formula (1) or the formula (2) of the present invention, and a film, an electronic component / device, and a material thereof, particularly Industrial applicability for prepregs, laminates, flexible printed boards, printed boards, multilayer boards, sealants, adhesives, etc. that require excellent dielectric constants, aircraft parts, automobile parts, building parts, etc. Have.

Claims (18)

The compound which has a benzoxazine ring structure shown by following formula (1).

In Formula (1), R ¹ and R ² are each independently hydrogen or an organic group having 1 to 20 carbon atoms, and n is an integer of 1 to 500. Also, R ¹ and R ² are not hydrogen at the same time. In formula (1), * indicates a binding site.   2. The compound having a benzoxazine ring structure according to claim 1, wherein n is an integer of 7 to 500. R ¹ and R ² are each independently selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a sec-butyl group, and an isobutyl group. A compound having a benzoxazine ring structure according to claim 1 or 2. The compound which has both the structure A and the structure B which are shown by following formula (2), and has a benzoxazine ring structure.

In the formula (2), R ³ and R ⁴ are each independently hydrogen or an organic group having 1 to 20 carbon atoms, n and m are each 1 to 250, and l is an integer of 1 to 500. . R ³ and R ⁴ are not hydrogen at the same time. In formula (2), * indicates a binding site.   In the formula (2), n and m are each an integer of 2 to 250 and l is an integer of 4 to 500. The compound having a benzoxazine ring structure according to claim 4. R ³ and R ⁴ are each independently selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a sec-butyl group, and an isobutyl group. The compound which has benzoxazine ring structure of Claim 4 or 5 containing. When the total value of the compounds containing a benzoxazine ring structure including the structure A and the structure B is 100% by mass,
The copolymer of Structure A and Structure B is 90% by mass or more, and the mass ratio of Structure A: Structure B is 41%: 59% to 91%: 9%. The compound which has a benzoxazine ring structure as described in any one of the above.   The thermosetting resin composition containing any one or more of the compounds which have a benzoxazine ring structure as described in any one of Claims 1 thru | or 7.   A molded product obtained by molding any one selected from the group consisting of the compound having a benzoxazine ring structure according to any one of claims 1 to 7 and the thermosetting resin composition according to claim 8. .   Any selected from the group consisting of a compound having a benzoxazine ring structure according to any one of claims 1 to 7, a thermosetting resin composition according to claim 8, and a molded article according to claim 9. A cured product obtained by curing this. A bisphenol compound having a structure represented by the following formula (3), a diamine compound having a structure represented by the following formula (4), and an aldehyde compound,
A method for producing a compound having a benzoxazine ring structure, which comprises a step of reacting in a mixed solvent of an aromatic nonpolar solvent and an alcohol.

(In the formula (4), R ⁵ and R ⁶ are each independently hydrogen or an organic group having 1 to 20 carbon atoms. Except for the case where R ⁵ and R ⁶ are simultaneously hydrogen. ) The diamine compound represented by the formula (4) is
The benzoxazine ring according to claim 11, which is any one selected from the group consisting of 4,4'-diamino-3,3'-dimethyldiphenylmethane and 4,4'-diamino-3,3'-diethyldiphenylmethane. A compound having a structure. A bisphenol compound having a structure represented by the following formula (5), a diamine compound represented by the following formulas (6) and (7), and an aldehyde compound are reacted in a mixed solvent of an aromatic nonpolar solvent and an alcohol. Having a process,
When the total of the diamine compound represented by the formula (6) and the diamine compound represented by the formula (7) is 100 mol%, the diamine compound represented by the formula (6): the mole of the diamine compound represented by the above (7) Provided is a method for producing a compound having a benzoxazine ring structure, in which% is 40:60 to 90:10.

In the formula (6), R ⁷ and R ⁸ are each independently hydrogen or an organic group having 1 to 20 carbon atoms. Note that R ⁷ and R ⁸ are not hydrogen at the same time.

The diamine compound represented by the formula (6) is
The benzoxazine ring structure according to claim 13, which is any one selected from 4,4'-diamino-3,3'-dimethyldiphenylmethane and 4,4'-diamino-3,3'-diethyldiphenylmethane. The manufacturing method of the compound which has.   The manufacturing method of the compound which has a benzoxazine ring structure as described in any one of Claims 11 thru | or 14 whose ratio of alcohol is 5 volume%-50 volume% in the said mixed solvent.   The method for producing a compound having a benzoxazine ring structure according to any one of claims 11 to 15, wherein the aromatic nonpolar solvent is toluene, xylene, or a mixture thereof.   The benzoxazine according to any one of claims 11 to 16, wherein the alcohol is at least one selected from the group consisting of methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol and isobutanol. A method for producing a compound having a ring structure.   The method for producing a compound having a benzoxazine ring structure according to any one of claims 11 to 17, wherein the mixed solvent is a mixed solvent of toluene and isobutanol.

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