JP5175499B2 - Method for producing thermosetting resin composition - Google Patents

Description

  The present invention relates to a thermosetting resin composition having excellent heat resistance, good electrical characteristics, and greatly improved brittleness, and a method for producing the same. Moreover, this invention relates to the molded object obtained from a thermosetting resin composition, a hardening body, and an electronic device containing them.

  Conventionally, thermosetting resins such as phenol resin, melamine resin, epoxy resin, unsaturated polyester resin, bismaleimide resin are based on their thermosetting properties, water resistance, chemical resistance, heat resistance, mechanical strength, It has excellent reliability and is used in a wide range of industrial fields.

  However, the phenol resin and the melamine resin generate volatile by-products upon curing, the epoxy resin and the unsaturated polyester resin are inferior in flame retardancy, and the bismaleimide resin is very expensive.

  In order to eliminate these drawbacks, a dihydrobenzoxazine ring undergoes a ring-opening polymerization reaction and is thermally cured without generation of a volatile matter causing a problem (hereinafter abbreviated as a benzoxazine compound). Have been studied). In addition to the basic characteristics of the thermosetting resin as described above, the benzoxazine compound has excellent storability, a relatively low viscosity when melted, and various advantages such as a wide degree of freedom in molecular design. It is resin which has. Such a benzoxazine compound is disclosed in, for example, Patent Document 1.

  In addition, signal transmission speed and high frequency by improving dielectric characteristics (low dielectric constant and low dielectric loss) to cope with recent high density (miniaturization) of electronic equipment and parts and high speed transmission signal. There is a need for improved properties.

Moreover, dihydrobenzoxazine compounds represented by the following formulas (1) and (2) are known as raw material materials for thermosetting resins having such excellent dielectric properties (for example, non-patent documents). 1).

  A resin obtained by ring-opening polymerization of the benzoxazine ring of such a dihydrobenzoxazine compound does not accompany the generation of a volatile component at the time of thermosetting, and is excellent in flame retardancy and water resistance.

  However, although the above-mentioned conventional dihydrobenzoxazine compounds have excellent dielectric properties among thermosetting resins, as described above, higher dielectric properties are expected in accordance with recent higher performance of electronic devices and parts. It is rare. For example, for a resin material of a multi-layer substrate that constitutes an IC package such as a memory or a logic processor, the dielectric constant is 3.5 or less and the same conditions as characteristics at 100 MHz and 1 GHz at an ambient temperature of 23 ° C. The dielectric loss is required to be 0.015 or less in terms of the dielectric loss tangent as the index.

  Further, in view of the technical trend expected in the future, a lower dielectric loss tends to be required. In other words, dielectric loss usually tends to be proportional to the frequency and the dielectric loss tangent of the material, while the frequency used in electronic equipment and components tends to be higher, so there is a demand for materials with a low dielectric loss tangent. Is even higher.

  Further, for example, Patent Document 2 proposes a technique for dealing with microfabrication in response to requests for improvement in electrical characteristics, heat resistance, toughness, and flexibility. However, this technique is disadvantageous in terms of hygroscopicity and electrical characteristics because there are free OH groups.

  For example, Patent Document 3 discloses a thermosetting resin having a benzoxazine structure in the main chain and excellent in heat resistance and mechanical properties, in which a bifunctional phenol part is bonded with a siloxane group. Are disclosed.

  The above document discloses a long-chain aromatic diamine as one that imparts flexibility, but as a result of studies by the present inventors, it has been found that the combination described in the above document does not provide sufficient flexibility. did. Also, those containing a highly polar group such as a sulfone group are disadvantageous in terms of electrical characteristics.

Non Patent Literature 2 and Patent Literature 4 also disclose a benzoxazine compound having a specific structure having a benzoxazine structure in the main chain. However, Non-Patent Document 3 discloses only compounds and does not describe property evaluation. In addition, Patent Document 4 does not disclose guidelines or compounds for improving heat resistance and imparting flexibility. Furthermore, Non-Patent Document 3 discloses a decomposition mechanism of a cured product of a benzoxazine compound. The anilines and monofunctional cresols described in this document are volatile at low temperatures. Furthermore, Patent Document 5 discloses a method for producing a benzoxazine compound in which both diamine and monoamine are essential as amines. However, the use of monoamine is disadvantageous from the viewpoint of heat resistance.
JP 49-47378 A Japanese Patent Laid-Open No. 2005-239827 JP 2003-64180 A JP 2002-338648 A Japanese Patent No. 3550814 Konishi Chemical Co., Ltd. website [searched August 16, 2007], “Benzoxazine Monomers and Polymers: New Phenolic Resins by Ring-Opening Polymerization,” JPLiu and H. Ishida, “The Polymeric Materials Encyclopedia,” JCSalamone, Ed., CRC Press, Florida (1996) pp.484-494 HYLow and H. Ishida, Polymer, 40, 4365 (1999)

  An object of this invention is to provide the manufacturing method of the thermosetting resin composition which was excellent in heat resistance, was excellent in the electrical property, and was greatly improved in brittleness.

〔式中、Ｘは芳香環を含む炭素数６以上の有機基であり、ヘテロ原子として、Ｎ、Ｏ、Ｆを有していてもよい。ただし、Ｘの両側のベンゼン環はＸ中の異なる原子に結合する。〕

〔式中、Ｙは炭素数５以上の有機基であり、ヘテロ原子として、Ｎ、Ｏ、Ｆを有していてもよい。ただし、Ｙの両側のベンゼン環はＹ中の異なる原子に結合する。〕

〔式中、Ｘは芳香環を含む炭素数６以上の有機基であり、ヘテロ原子として、Ｎ、Ｏ、Ｆを有していてもよい。ただし、Ｘの両側のベンゼン環はＸ中の異なる原子に結合する。Ｙは炭素数５以上の有機基であり、ヘテロ原子として、Ｎ、Ｏ、Ｆを有していてもよい。ただし、Ｙの両側のベンゼン環はＹ中の異なる原子に結合する。ｍは１〜５０の整数を示す。〕
一般式（Ｉ）中のＸが、両側のベンゼン環のＯＨ基に対してパラ位に結合しており、かつＸの構造が下記のいずれかである熱硬化性樹脂組成物の製造方法を要旨とする。

また本発明は、上述の一般式（Ｉ）中のＸが、以下の構造式のいずれか１つである熱硬化性樹脂組成物の製造方法を要旨とする。

〔式中、ａは０〜１０の整数を示す。〕

〔式中、ｂは０〜１０の整数を示す。〕

〔式中、ｃは０〜１０の整数を示す。〕 In the present invention, the polyfunctional phenol compound represented by the general formula (I), the diamine compound represented by the general formula (II), and the aldehyde compound are reacted by heating to be represented by the general formula (IV). A method for producing a thermosetting resin composition comprising obtaining a thermosetting resin having a dihydrobenzoxazine structure and further adding a layered silicate ,

[In formula, X is a C6 or more organic group containing an aromatic ring, and may have N, O, and F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X. ]

[Wherein Y is an organic group having 5 or more carbon atoms and may have N, O, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. ]

[In formula, X is a C6 or more organic group containing an aromatic ring, and may have N, O, and F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X. Y is an organic group having 5 or more carbon atoms, and may have N, O, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. m shows the integer of 1-50. ]
A summary of a method for producing a thermosetting resin composition in which X in the general formula (I) is bonded to the OH groups of the benzene rings on both sides and the structure of X is any of the following: And

Moreover, this invention makes a summary the manufacturing method of the thermosetting resin composition whose X in the above-mentioned general formula (I) is any one of the following structural formulas.

[In formula, a shows the integer of 0-10. ]

[Wherein, b represents an integer of 0 to 10. ]

[In formula, c shows the integer of 0-10. ]

  According to the present invention, there are provided a thermosetting resin composition having excellent heat resistance, good electrical characteristics, and greatly improved brittleness, and a method for producing the same. Moreover, according to this invention, the molded object obtained from said thermosetting resin composition, the hardening body, and the electronic device containing them are provided.

  Hereinafter, the present invention will be described with reference to embodiments, but the present invention is not limited to the following embodiments.

  As a result of intensive studies, the present inventor has developed a method for producing a thermosetting resin using a specific aromatic diamine and a specific phenol compound without using an aliphatic amine or an aromatic monoamine from the viewpoint of improving heat resistance. The present inventors have obtained knowledge that the above-mentioned purpose can be achieved. The present invention is based on such knowledge. That is, the configuration of the present invention is as follows.

  Hereinafter, the “benzoxazine resin” refers to a resin having the above-mentioned dihydrobenzoxazine ring structure.

〔式中、Ｘは芳香環を含む炭素数６以上の有機基であり、ヘテロ原子として、Ｎ、Ｏ、Ｆを有していてもよい。ただし、Ｘの両側のベンゼン環はＸ中の異なる原子に結合する。〕

〔式中、Ｙは炭素数５以上の有機基であり、ヘテロ原子として、Ｎ、Ｏ、Ｆを有していてもよい。ただし、Ｙの両側のベンゼン環はＹ中の異なる原子に結合する。〕

〔式中、Ｘは芳香環を含む炭素数６以上の有機基であり、ヘテロ原子として、Ｎ、Ｏ、Ｆを有していてもよい。ただし、Ｘの両側のベンゼン環はＸ中の異なる原子に結合する。Ｙは炭素数５以上の有機基であり、ヘテロ原子として、Ｎ、Ｏ、Ｆを有していてもよい。ただし、Ｙの両側のベンゼン環はＹ中の異なる原子に結合する。ｍは１〜５０の整数を示す。〕 [Method for producing thermosetting resin]
The method for producing a thermosetting resin composition according to the embodiment comprises heating and reacting a polyfunctional phenol compound represented by the general formula (I), a diamine compound represented by the general formula (II), and an aldehyde compound, A thermosetting resin having a dihydrobenzoxazine structure represented by the general formula (IV) is obtained, and a layered silicate is further added. The resulting thermosetting resin has excellent heat resistance, good electrical properties, and greatly improved brittleness.

[In formula, X is a C6 or more organic group containing an aromatic ring, and may have N, O, and F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X. ]

[Wherein Y is an organic group having 5 or more carbon atoms and may have N, O, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. ]

[In formula, X is a C6 or more organic group containing an aromatic ring, and may have N, O, and F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X. Y is an organic group having 5 or more carbon atoms, and may have N, O, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. m shows the integer of 1-50. ]

(A) Polyfunctional phenol compound The polyfunctional phenol compound represented by the general formula (I) is not particularly limited as long as it is a bifunctional or higher polyfunctional phenol. These bifunctional or higher polyfunctional phenols are used alone or in combination of two or more.

  In the polyfunctional phenol compound, X in the general formula (I) is an organic group having 6 or more carbon atoms, preferably 8 or more carbon atoms, more preferably 12 to 21 carbon atoms, including an aromatic ring. X may have N, O, or F as a hetero atom.

X is bonded to the OH groups of the benzene rings on both sides, particularly in terms of reactivity during synthesis of the thermosetting resin, heat resistance of the cured body, mechanical properties, and electrical properties, and It is preferable that the structure is any one or any of the following.

〔式中、ａは０〜１０、好ましくは０〜５の整数を示す。〕
また、Ｘは、特に熱硬化性樹脂合成時の反応性、硬化体の耐熱性、力学特性、電気特性の点で、下記で示される構造であることも好ましい。

〔式中、ｂは０〜１０、好ましくは０〜５の整数を示す。〕
また、Ｘは、特に熱硬化性樹脂合成時の反応性、硬化体の耐熱性、力学特性、電気特性の点で、下記で示される構造であることも好ましい。

〔式中、ｃは０〜１０の整数を示す。〕
このような多官能フェノール化合物の具体例としては、１，３−ビス（４−ヒドロキシフェノキシ）ベンゼン、１，４−ビス（３−ヒドロキシフェノキシ）ベンゼン、２，６−ビス（（２−ヒドロキシフェニル）メチル）フェノール、４，４‘−［１，４−フェニレンビス（１−メチル−エチリデン）］ビスフェノール（三井化学製：ビスフェノールＰ）、４，４‘−［１，３−フェニレンビス（１−メチル−エチリデン）］ビスフェノール（三井化学製：ビスフェノールＭ）、ビフェニルノボラック型フェノール樹脂（明和化成製：ＭＥＨ７８５１）、キシリレンノボラック型フェノール樹脂（明和化成製：ＭＥＨ７８００）、ジシクロペンタジエン変性フェノール樹脂（新日本石油製：日石特殊フェノール樹脂ＤＰＰシリーズ）等が挙げられる。これら多官能フェノール化合物は、使用に際して一種又は二種以上で用いられる。 X is preferably a structure shown below in terms of reactivity at the time of synthesizing the thermosetting resin, heat resistance of the cured body, mechanical characteristics, and electrical characteristics.

[Wherein, a represents an integer of 0 to 10, preferably 0 to 5. ]
X is also preferably a structure shown below from the viewpoints of reactivity at the time of synthesizing the thermosetting resin, heat resistance of the cured body, mechanical characteristics, and electrical characteristics.

[Wherein b represents an integer of 0 to 10, preferably 0 to 5. ]
X is also preferably a structure shown below from the viewpoints of reactivity at the time of synthesizing the thermosetting resin, heat resistance of the cured body, mechanical characteristics, and electrical characteristics.

[In formula, c shows the integer of 0-10. ]
Specific examples of such polyfunctional phenolic compounds include 1,3-bis (4-hydroxyphenoxy) benzene, 1,4-bis (3-hydroxyphenoxy) benzene, 2,6-bis ((2-hydroxyphenyl ) Methyl) phenol, 4,4 ′-[1,4-phenylenebis (1-methyl-ethylidene)] bisphenol (Mitsui Chemicals Co., Ltd .: bisphenol P), 4,4 ′-[1,3-phenylenebis (1- Methyl-ethylidene)] bisphenol (Mitsui Chemicals: Bisphenol M), biphenyl novolac type phenol resin (Maywa Kasei: MEH7851), xylylene novolac type phenol resin (Maywa Kasei: MEH7800), dicyclopentadiene modified phenolic resin (new) Nippon Petroleum: Nisseki Special Phenolic Resin DPP Series) That. These polyfunctional phenol compounds are used alone or in combination of two or more.

(B) Diamine Compound The diamine compound represented by the general formula (II) is mainly used from the viewpoint of improving flexibility.

  The diamine compound is a long-chain aromatic diamine compound, and Y in the general formula (II) is an organic group having 5 or more carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 5 to 15 carbon atoms. In addition, when Y has N, O, or F as a hetero atom, the electrical characteristics can be improved. Further, the benzene rings on both sides of Y are not bonded to the same atom in Y.

Y is preferably a group represented by the following formula, particularly in terms of solubility during synthesis of the thermosetting resin, mechanical properties of the cured product, and electrical properties.

  Further, Y preferably contains one benzene ring from the viewpoint of heat resistance, mechanical properties and electrical properties of the cured product.

A specific example of Y containing one benzene ring is one or more groups selected from the group of the following formulas, and Y is in the meta or para position with respect to the NH ₂ groups of the benzene rings on both sides thereof. The thing etc. which couple | bond are mentioned. When Y has these groups, it is particularly preferable because the cured product is excellent in heat resistance, mechanical properties, and electrical properties.

  Y preferably contains at least two benzene rings, particularly in terms of heat resistance, mechanical properties, and electrical properties of the cured product.

Specific examples of those in which Y contains at least two benzene rings are one or more groups selected from the group of the following formulas, and in the meta or para position with respect to the NH ₂ groups of the benzene rings on both sides of Y. The thing etc. which couple | bond are mentioned. When Y has these groups, it is particularly preferable because the cured product is excellent in heat resistance, mechanical properties, and electrical properties.

  Specific examples of such a diamine compound include 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) neopentane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [ 4- (4-aminophenoxy) phenyl] propane, 4,4′-bis [(3-aminophenoxy) phenyl] biphenyl, 4,4′-bis [(4-aminophenoxy) phenyl] biphenyl, 2,2- Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [3- (3-aminophenoxy) phenyl] ether, bis [3- ( - aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, and the like. These diamine compounds are used singly or in combination.

(C) Aldehyde compound Although it does not specifically limit as an aldehyde compound, Formaldehyde is preferable, As this formaldehyde, it uses in forms, such as paraformaldehyde which is the polymer, and formalin which is the form of aqueous solution. Is possible. The reaction proceeds more slowly when paraformaldehyde is used. As other aldehyde compounds, acetaldehyde, propionaldehyde, butyraldehyde and the like can also be used.

(D) Layered silicate As the layered silicate (= clay), various types can be used without particular limitation. For example, natural or synthetic Na-type tetralithic fluorine mica, Li-type tetrasilicic fluorine mica, Na-type fluorine teniolite, or swellable mica-group clay minerals such as Li-type fluorine teniolite, vermiculite, smectite, saponite, stevensite, viterite , Smectite group clay minerals such as montmorillonite, nontronite, or bentonite, or substitutions, derivatives or mixtures thereof. In addition, in the substituted body, a part of Na ⁺ or Li ⁺ ion of the interlayer ion is substituted by K ⁺ ion, or a part of Si ⁺ ion of the tetrahedral sheet is substituted by Mg ²⁺ ion. Is included.

  As the layered silicate, an organically modified layered silicate obtained by organically modifying a layered silicate with a quaternary ammonium salt type cationic surfactant or the like may be used. Specifically, synthetic smectite (Lucentite STN manufactured by Co-op Chemical Co., Ltd.) that has been subjected to organic treatment with dimethyldioctadecyl ammonium salt can be used. The amount of layered silicate is preferably 0.1 to 5 parts by weight, more preferably 2 to 3 parts by weight, when the total weight of the thermosetting resin is 100 parts by weight.

  In addition to the above components, the components described below may be added as appropriate.

〔式中、Ｚは炭素数４以上の有機基であり、ヘテロ原子として、Ｎ、Ｏ、Ｆを有していてもよい。〕
単官能フェノール化合物は、側鎖分子量が大きいものであり、一般式（III）中のＺは炭素数４以上、好ましくは炭素数６以上、更に好ましくは８〜２０の有機基である。炭素数が大きくなると自由体積が大きくなり、誘電率が低くなる場合もある。なお、Ｚがヘテロ原子として、Ｎ、Ｏ、Ｆを有していてもよい。 (E) Monofunctional phenolic compound As another embodiment of the production method according to the embodiment, it is possible to preferably provide a method of further using the monofunctional phenolic compound represented by the general formula (III) together with the components described above. . When the monofunctional phenol compound of component (e) is used, processability such as solubility can be ensured.

[Wherein, Z is an organic group having 4 or more carbon atoms, and may have N, O, or F as a hetero atom. ]
The monofunctional phenol compound has a large side chain molecular weight, and Z in the general formula (III) is an organic group having 4 or more carbon atoms, preferably 6 or more carbon atoms, and more preferably 8 to 20 carbon atoms. As the number of carbon atoms increases, the free volume increases and the dielectric constant may decrease. Z may have N, O, and F as heteroatoms.

［ｎは０から１０の整数を示す。］
中でも、上記のＺは、ＯＨ基に対してパラ位に置換されており、かつ下記式で示される基であることが好ましい。

In the monofunctional phenol compound represented by the general formula (III), the substituent Z is preferably bonded to the OH group at the para position, and the substituent Z is a group represented by the following formula.

[N represents an integer of 0 to 10. ]
Among these, Z is preferably substituted at the para position with respect to the OH group and is a group represented by the following formula.

Furthermore, the above Z is substituted mainly in the para position with respect to the OH group in the benzene ring in the general formula (III) in terms of dielectric properties such as non-volatility at high temperature, dielectric constant and dielectric loss tangent. And a group represented by the following formula is preferred.

In addition, the substituent Z of the monofunctional phenol compound represented by the general formula (III) is a benzene ring in the general formula (III) in terms of dielectric properties such as non-volatility, dielectric constant and dielectric loss tangent at high temperatures. , An OH group, and the substituent Z is preferably a group represented by the following formula.

  Specific examples of such monofunctional phenol compounds include 4-t-butylphenol, 2-cyclohexylphenol, 4-cyclohexylphenol, 2-phenylphenol, 4-phenylphenol, 2-benzylphenol, 4-benzylphenol, 2 -Hydroxybenzophenone, 4-hydroxybenzophenone, 4-hydroxybenzoic acid phenyl ester, 4-phenoxyphenol, 3-benzyloxyphenol, 4-benzyloxyphenol, 4- (1,1,3,3-tetramethylbutyl) phenol , 4-α-cumylphenol, 4-adamantylphenol, 4-triphenylmethylphenol and the like. These monofunctional phenol compounds are used alone or in combination of two or more.

(F) Epoxy resin As the epoxy resin, various resins can be used without particular limitation. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated epoxy resin, biphenyl type epoxy resin, substitution Bisphenol A type epoxy resin, cresol novolac type epoxy resin, trisphenolmethane type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol / biphenylene type epoxy resin, glycidyl ether type epoxy resin such as phenoxy resin, 3, Cycloaliphatic epoxy resins such as 4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, adipic acid diglycidyl ester type Glycidyl ester type epoxy resin such as diglycidyl phthalate type, diglycidyl aniline type, aminophenol type, aliphatic amine type, hydantoin type glycidyl amine type epoxy resin, hydroxybenzoic acid type ester type, α-methylstilbene Examples thereof include liquid crystal epoxy resins such as molds, epoxy resins having functions such as photosensitivity and decomposability, triglycidyl isocyanurate, and thiirane-modified epoxy resins. Among these, it is preferable to use a phenol / biphenylene type epoxy resin (for example, NC3000 series manufactured by Nippon Kayaku Co., Ltd.) from the viewpoint of flexibility and heat resistance.

(G) Inorganic filler As the material of the inorganic filler, when the cured molded body of the thermosetting resin composition is roughened, the surface roughness of the cured molded body is small, and adhesion between the copper plating and the cured molded body As long as the strength is increased, various inorganic fillers can be used without particular limitation. For example, powder of silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, etc. Or a bead obtained by spheroidizing these, glass fiber, and the like. These may be used alone or in combination of two or more. Of these, silica is preferable. Specifically, the product name “Admuffin” manufactured by Admatechs can be used. The blending amount of the inorganic filler subjected to the silane coupling treatment (excluding the solvent weight) is preferably 10 to 40 parts by weight, and 20 parts by weight when the total weight of the thermosetting resin composition is 100 parts by weight. 30 parts by weight is more preferable.

  As the inorganic filler, surface-treated silica, for example, silane-coupled silica may be used. This is because by adding silica treated with silane coupling, a resin having excellent heat resistance, good electrical characteristics, and greatly improved brittleness can be obtained. Specifically, as the surface-treated silica, a MEK dispersion (solid content concentration 60% by weight) of colloidal silica having a substantially spherical shape that has been surface-treated with epoxysilane can be used. The compounding amount (excluding the solvent weight) of the silica subjected to the silane coupling treatment is preferably 10 to 40 parts by weight, preferably 20 parts by weight when the total weight of the thermosetting resin composition is 100 parts by weight. 30 parts by weight is more preferable.

  Silica subjected to silane coupling treatment is preferably a spherical fine particle having a sharp particle size distribution. Specifically, it is preferable that the average particle diameter is 0.25 to 0.38 μm, the number ratio of the particle diameter is 0.15 μm is 5% or less, and the number ratio of 0.75 μm or more is 5% or less. It is more preferable that the particle size is 0.25 μm to 0.30 μm, the number ratio of the particle size is 0.15 μm is 5% or less, and the number ratio of 0.75 μm or more is 5% or less.

  In the production method according to the embodiment, for example, the components (a), (b), and (c) can be reacted by optionally heating the component (e) in an appropriate solvent. The component (f) and the component (g) can be blended as desired.

  In the production method according to the embodiment, a monofunctional phenol compound or a polyfunctional phenol compound may be further added.

  Examples of monofunctional phenol compounds that can be additionally added here include monofunctional phenols as described above. Examples of polyfunctional phenol compounds include polyfunctional phenols such as those described above, 4,4′-biphenol, and 2,2. '-Biphenol, 4,4'-dihydroxydiphenyl ether, 2,2'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylmethane, 2,2'-dihydroxydiphenylmethane, 2,2-bis (4-hydroxyphenyl) propane, 4 , 4′-dihydroxybenzophenone, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 2,2- Bis (4-hydroxyphenyl) butane, 1,1-bis (4-H Loxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) -1- Examples include phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and the like.

  The solvent used in the production method according to the embodiment is not particularly limited, but those having better solubility of the raw material phenol compound or diamine compound and the polymer as the product are those having a higher degree of polymerization. Easy to obtain. Examples of such a solvent include aromatic solvents such as toluene and xylene, halogen solvents such as chloroform and dichloromethane, ether solvents such as THF and dioxane, and the like.

  Although the reaction temperature and reaction time are not particularly limited, the reaction may usually be performed at a temperature of about room temperature to 120 ° C. for about 10 minutes to 24 hours. In particular, it is preferable to react at 30 to 110 ° C. for 20 minutes to 9 hours, because the reaction proceeds to a polymer that can exhibit the function as the thermosetting resin according to the embodiment. It is desirable to lower the reaction temperature or shorten the reaction time from the point that a resin having a higher molecular weight or a three-dimensionally crosslinked polymer is formed in a reaction at a high temperature and for a long time, and the reaction time is reduced. In this reaction, it is desirable to increase the reaction time or the reaction temperature in that a sufficiently large molecular weight resin suitable for coating cannot be synthesized.

  Further, removing water generated during the reaction out of the system is also an effective technique for promoting the reaction. For example, a polymer can be precipitated by adding a large amount of poor solvent such as methanol to the solution after the reaction, and the desired polymer can be obtained by separating and drying the polymer.

  In addition, a monofunctional amine compound, a trifunctional amine compound, and another diamine compound can also be used in the range which does not impair the characteristic of the thermosetting resin which concerns on embodiment. When a monofunctional amine is used, the degree of polymerization can be adjusted, and when a trifunctional amine is used, a branched polymer is obtained. Moreover, physical properties can be adjusted by the combined use of other diamine compounds. These can be used at the same time as the diamine compound essential to the present invention, but can be added to the reaction system and reacted later in consideration of the order of the reaction.

〔式中、Ｘは芳香環を含む炭素数６以上の有機基であり、ヘテロ原子として、Ｎ、Ｏ、Ｆを有していてもよい。ただし、Ｘの両側のベンゼン環はＸ中の異なる原子に結合する。Ｙは炭素数５以上の有機基であり、ヘテロ原子として、Ｎ、Ｏ、Ｆを有していてもよい。ただし、Ｙの両側のベンゼン環はＹ中の異なる原子に結合する。ｎは１〜５０の整数を示す。〕
上記構造は、ＩＲ，ＮＭＲ、ＧＣ−ＭＳ他の手法にて同定できる。 [Thermosetting resin composition]
The thermosetting resin composition according to the embodiment includes a thermosetting resin having a structure represented by the general formula (IV) and a layered silicate. The thermosetting resin composition according to the embodiment can also be obtained by the above-described method for producing a thermosetting resin composition.

[In formula, X is a C6 or more organic group containing an aromatic ring, and may have N, O, and F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X. Y is an organic group having 5 or more carbon atoms, and may have N, O, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. n represents an integer of 1 to 50. ]
The above structure can be identified by other methods such as IR, NMR, GC-MS.

  When m is 2 or more, X does not need to be all the same in the synthesized thermosetting resin, and may be different. Similarly, when m is 2 or more, Y does not have to be the same in the synthesized thermosetting resin, and may be different.

In the general formula (IV), X preferably has any structure of the following group of X: and Y preferably has any structure of the following group of Y :.

  The thermosetting resin composition according to the embodiment has particularly excellent heat resistance, good electric characteristics, and greatly improved brittleness.

  The thermosetting composition according to the embodiment preferably includes the thermosetting resin as a main component. For example, the thermosetting resin includes the thermosetting resin as a main component, and another thermosetting as a subcomponent. It may also contain a functional resin.

  Other thermosetting resins as subcomponents include, for example, thermosetting modified polyphenylene ether resin, thermosetting polyimide resin, silicon resin, melamine resin, urea resin, allyl resin, phenol resin, unsaturated polyester resin, bis Examples include maleimide resins, alkyd resins, furan resins, polyurethane resins, aniline resins, and the like. 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 composition according to the embodiment, it is preferable to use a compound having at least one, preferably two dihydrobenzoxazine rings in the molecule described in the publicly known literature as a subcomponent. Only one type of compound having at least one dihydrobenzoxazine ring in the molecule may be used, or two or more types may be used in combination.

  In addition, the thermosetting composition according to the embodiment includes a flame retardant, a nucleating agent, an antioxidant (anti-aging agent), a heat stabilizer, a light stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, if necessary. Various additives such as an auxiliary agent, an antistatic agent, 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 composition which concerns on embodiment, a reactive or non-reactive solvent can also be used.

  The thermosetting resin or thermosetting resin composition according to the embodiment may be dissolved in an organic solvent and cast, and the solvent may be dried to form a film.

  About the thermosetting resin or thermosetting resin composition concerning this invention, the one where the solubility in organic solvents, such as toluene, is larger is preferable. This makes it possible to reduce the amount of solvent when casting into a solution to form a film. Further, if the solvent content is low, the energy for solvent evaporation is small, the drying time is short, and rapid drying is possible. This is because there is a secondary effect that there is no blistering caused.

[Molded body]
The molded body according to the embodiment is obtained by semi-curing or not curing the above-described thermosetting resin or a thermosetting composition including the thermosetting resin.

Here, “semi-curing” is to stop the curing of the thermosetting resin at an intermediate stage, and refers to a state in which the curing can further proceed. The semi-cured thermosetting resin may be referred to as a B stage. (The following description is also synonymous)
As the molded body according to the embodiment, since the thermosetting resin described above has moldability before curing, the dimensions and shape thereof are not particularly limited. For example, a sheet shape (plate shape), a block shape And other parts (for example, an adhesive layer) may be provided. Moreover, the sheet-like thing may be formed on the support film.

[Hardened body]
The cured body according to the embodiment is obtained by applying heat to a thermosetting resin having thermosetting properties, a pre-base composition having thermosetting properties, and a molded body having thermosetting properties. As the curing method, any conventionally known curing method can be used. Generally, it may be heated at about 120 to 300 ° C. for several hours, but if the heating temperature is lower or the heating time is insufficient, In some cases, curing may be insufficient and mechanical strength may be insufficient. 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 desirable to select appropriate conditions according to the characteristics of the thermosetting compound to be used.

  Further, when curing is performed, an appropriate curing accelerator may be added. As the curing accelerator, any curing accelerator generally used in ring-opening polymerization of a dihydrobenzoxazine compound can be used. For example, polyfunctional phenols such as catechol and bisphenol A, p- Sulfonic acids such as toluenesulfonic acid and p-phenolsulfonic acid, carboxylic acids such as benzoic acid, salicylic acid, oxalic acid and adipic acid, cobalt (II) acetylacetonate, aluminum (III) acetylacetonate, zirconium (IV) acetyl Metal complexes such as acetonate, metal oxides such as calcium oxide, cobalt oxide, magnesium oxide, iron oxide, calcium hydroxide, imidazole and its derivatives, tertiary amines such as diazabicycloundecene, diazabicyclononene, and These salts, triphenylphosphine, triphenylphosphine Examples thereof include phosphorus compounds such as tin / benzoquinone derivatives, triphenylphosphine / triphenylboron salts, tetraphenylphosphonium / tetraphenylborate 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 may be increased to deteriorate the dielectric properties or adversely affect the mechanical properties. Therefore, in general, it is desirable to use the curing accelerator at a ratio of preferably 5 parts by weight or less, more preferably 3 parts by weight or less with respect to 100 parts by weight of the thermosetting resin.

  As described above, the cured product according to the embodiment made of the thermosetting resin or the thermosetting composition thus obtained has a benzoxazine structure in the polymer structure, so that excellent dielectric properties can be realized.

  Further, the cured body according to the embodiment is excellent in reliability, flame retardancy, moldability, and the like based on the thermosetting property of the thermosetting resin or the thermosetting composition, and also has a glass transition temperature ( Since Tg) is high, it can be applied to stressed parts and moving parts, and since no volatile by-product is generated during polymerization, such a volatile by-product is formed into a molded body. It does not remain inside, and is preferable in terms of hygiene management.

  The cured body according to the embodiment can be suitably used for applications such as electronic parts / electronic devices and materials thereof, multilayer boards, copper-clad laminates, sealants, adhesives and the like that particularly require excellent dielectric properties. .

  Here, the electronic component includes a substrate or an IC element having a terminal for electrical connection such as a flexible substrate, an electric conductor layer on the surface of the cured body according to the embodiment, a resistor, a capacitor, a coil, Refers to the board on which is mounted.

  Although the typical Example in this invention is shown below, this invention is not limited at all by this.

[Synthesis Example of Thermosetting Resin Having Dihydrobenzoxazine Ring of Formula (IV) (hereinafter referred to as BO1)]
In chloroform, bisphenol M (Mitsui Chemicals, 99.5%) 27.86 g (0.08 mol), bisaniline M (Mitsui Chemicals, 99.98%) 27.57 g (0.08 mol), paraformaldehyde (Japanese) 1003) 10.73 g (0.34 mol) was added and reacted for 6 hours under reflux while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 31.21 g of a thermosetting resin mainly composed of a benzoxazine compound having the following structure. In the molecular weight measurement of the obtained resin by GPC, the weight average molecular weight was 16,600.

Example 1
Synthetic smectite (Corp Chemical Co., Lucentite STN) 0.30 g organically treated with dimethyldioctadecylammonium salt as a layered silicate was charged into 9.50 g of toluene and 0.50 g of methyl ethyl ketone, and manufactured by IUCHI. The mixture was stirred and shaken with a shaker to dissolve. To this solution, 9.70 g of BO1 was added and rotated / dissolved with an IKA Disper for 60 minutes to obtain a solution. The resulting solution was further stirred and degassed for 3 minutes using a stirring deaerator made by Shinkey. The defoamed solution was drawn at a rate of 5 cm per second using a tester Sangyo Co., Ltd. model No. PI-1210 with an applicator manufactured by Tester Sangyo Co., Ltd., which was adjusted to a slit of 100 μm to obtain a film containing a solvent. The film was heated to 60 ° C. for 10 minutes, 80 ° C. for 20 minutes, 100 ° C. for 30 minutes, 160 ° C. for 30 minutes, and 180 ° C. for 2 hours to obtain a cured film. The cured film was 58 μm thick.
The obtained film having a thickness of 58 μm was prepared to have a width of 4 mm, and the expansion to temperature was measured with TMA6100 manufactured by Seiko Instruments Inc. (SII) to evaluate CTE (= α). α was 56 ppm / ° C. at 23 ° C. to 100 ° C.
Further, the obtained film was finely cut and evaluated for 5% weight loss temperature (Td5) in an air atmosphere at a heating rate of 10 ° C./min using SII TG / DTA6200. It was.
In addition to the thermosetting resin used in the above examples, by adding a layered silicate to the thermosetting resin as shown below, a thermosetting resin composition, and a molded product obtained therefrom and A cured molded body can be prepared. Reference examples such as thermosetting resins are shown below.

(Reference Example 1)
In chloroform, α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene (Tokyo Chemical Industry, 98%) 21.21 g (0.06 mol), 2,2-bis [4- (4 -Aminophenoxy) phenyl] propane (Tokyo Kasei, 98%) 25.13 g (0.06 mol), paraformaldehyde (Wako Pure Chemicals, 94%) 8.05 g (0.25 mol) was charged, and water generated Was allowed to react under reflux for 6 hours. The reaction scheme is shown below. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 40.78 g of a thermosetting resin mainly composed of a benzoxazine compound having the following structure.

For the measurement of molecular weight, Shimadzu GPC (gel permeation chromatograph) is used as a degasser DGU-12A, pump LC-10AD, controller SCL-10A, detector (RI) RID-10A, column oven CTO-10AS. I went. As the column, two SHODEX KF-804L (exclusion limit of 400,000) were used in series, and the solvent was THF, the flow rate was 1 ml / min, and the column temperature was 40 ° C. Standard calibration (Tosoh) 354000, 189000, 98900, 37200, 17100, 9830, 5870, 2500, 1050, 500 polystyrenes were used to produce a calibration equation with a cubic equation. The molecular weight of the resin synthesized based on the calibration formula was measured. In the molecular weight measurement of the obtained resin, the weight average molecular weight was 19,500.

(Reference Example 2)
The polymer obtained in Reference Example 1 was held at 180 ° C. for 1 hour by a hot press method to obtain a 0.5 mmt sheet-like cured body. The obtained cured product was brown, transparent and uniform, and excellent in flexibility.
About the obtained molded object, the dielectric constant and dielectric loss tangent in 23 degreeC, 100 MHz, and 1 GHz were measured with the capacitance method using the dielectric constant measuring apparatus (The product name "RF impedance / material analyzer E4991A" by AGILENT). The results are shown in Table 1. The cured product of Reference Example 2 showed good characteristics in both dielectric constant and dielectric loss tangent.
Further, the obtained sheet was finely cut, and 5% weight reduction temperature (Td5) in an air atmosphere at a heating rate of 10 ° C./min by a TGA method using a product name “DTG-60” manufactured by Shimadzu Corporation. Evaluated. The cured product of Reference Example 2 had a good value of Td5 of 415 ° C.

(Reference Example 3)
Reference Example 1 except that 21.21 g (0.06 mol) of bisphenol M (Mitsui Chemicals) was used in place of α, α'-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene in Reference Example 1. In the same manner, a thermosetting resin was synthesized. The yield was 40.56g. In the molecular weight measurement of the obtained resin by GPC, the weight average molecular weight was 10,600.

(Reference Example 4)
In the same manner as in Reference Example 2, the resin of Reference Example 3 was evaluated. The results are summarized in Table 2. The thermosetting resin of Reference Example 3 showed good results in both electrical characteristics and heat resistance.

(Reference Example 5)
In chloroform, α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene (Tokyo Chemical Industry, 98%) 20.68 g (0.0585 mol), 4-α-cumylphenol (Tokyo Chemical Industry) Manufactured, 98%) 2.82 g (0.013 mol), α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene (Tokyo Kasei, 98%) 22.85 g (0.065 mol), 8.72 g (0.27 mol) of paraformaldehyde (94% manufactured by Wako Pure Chemical Industries, Ltd.) was added and reacted for 6 hours under reflux while removing generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 37.21 g of a thermosetting resin mainly composed of a benzoxazine compound having the following structure. In the molecular weight measurement by GPC of the obtained resin, the weight average molecular weight was 7,200.

(Reference Example 6)
In the same manner as in Reference Example 2, the resin of Reference Example 5 was evaluated. The results are summarized in Table 3. The thermosetting resin of Reference Example 3 showed good results in both electrical characteristics and heat resistance.

(Reference Example 7)
In chloroform, 30.00 g of biphenyl novolac type phenol resin (“MEH7851SS” manufactured by Meiwa Chemical, OH equivalent 204), α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene (manufactured by Tokyo Chemical Industry, 98 %) 21.08 g (0.061 mol) and paraformaldehyde (manufactured by Wako Pure Chemical, 94%) 8.13 g (0.25 mol) were added and reacted for 6 hours under reflux while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 45.52 g of a thermosetting resin having a benzoxazine structure.

(Reference Example 8)
In Reference Example 7, instead of α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene (Tokyo Chemical Industry, 98%), 2,2-bis [4- (4-aminophenoxy) A thermosetting resin having a benzoxazine structure was synthesized in the same manner as in Reference Example 7 except that it was changed to 24.90 g (0.061 mol) of phenyl] propane (manufactured by Wakayama Seika, 99.9%). The yield was 45.80g.

(Reference Examples 9 and 10)
In the same manner as in Reference Example 2, the resins of Reference Examples 7 and 8 were evaluated. The results are summarized in Table 4. The thermosetting resins of Reference Examples 9 and 10 showed good results in both electrical characteristics and heat resistance.

(Reference Example 11)
In chloroform, bisphenol M (Mitsui Chemicals, 99.5%) 27.86 g (0.08 mol), bisaniline M (Mitsui Chemicals, 99.98%) 27.57 g (0.08 mol), paraformaldehyde (Japanese) 1003) 10.73 g (0.34 mol) was added and reacted for 6 hours under reflux while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 31.21 g of a thermosetting resin mainly composed of a benzoxazine compound having the following structure. In the molecular weight measurement of the obtained resin by GPC, the weight average molecular weight was 16,600.

(Reference Example 12)
In the same manner as in Reference Example 2, the resin of Reference Example 11 was evaluated. The results are summarized in Table 5. The thermosetting resin of Reference Example 11 showed good results in both electrical characteristics and heat resistance.

(Reference Example 13)
DPP 6085 (manufactured by Nippon Oil, 99%) 30.0 g (0.086 mol) and bisaniline P (Mitsui Chemicals, 99%) 29.91 g (0.086 mol) were added to chloroform, followed by stirring. Wako Pure Chemical Industries, Ltd. (94%) 11.53 g (0.344 mol) was added, and the mixture was reacted under reflux for 6 hours while removing generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 36.27 g of a thermosetting resin mainly composed of a benzoxazine compound having the following structure.

(Reference Example 14)
In the same manner as in Reference Example 2, the resin of Reference Example 13 was evaluated. The results are summarized in Table 6. The thermosetting resin of Reference Example 13 exhibited good electrical characteristics.

(Reference Example 15)
In chloroform, α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene (Tokyo Kasei, 98%) 20.68 g (0.0585 mol), 4-t-octylphenol (Tokyo Kasei, 95%) 2.82 g (0.013 mol), α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene (Tokyo Kasei, 98%) 22.85 g (0.065 mol), paraformaldehyde (72% manufactured by Wako Pure Chemical Industries, Ltd.) 8.72 g (0.27 mol) was added, and the mixture was reacted for 6 hours under reflux while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 41.95 g of a thermosetting resin mainly composed of a benzoxazine compound having the following structure.

(Reference Example 16)
In the same manner as in Reference Example 2, the resin of Reference Example 15 was evaluated. The results are summarized in Table 7. The thermosetting resin of Reference Example 15 showed good results in both electrical characteristics and heat resistance.

(Reference Example 17)
In chloroform, α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene (Tokyo Kasei, 98%) 13.85 g (0.040 mol), Bisaniline M (Tokyo Kasei, 98%) 13.78 g (0.040 mol) and paraformaldehyde (manufactured by Wako Pure Chemicals, 94%) 5.04 g (0.168 mol) were added, and the mixture was reacted for 6 hours under reflux while removing generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 34.52 g of a thermosetting resin mainly composed of a benzoxazine compound having the following structure.

(Reference Example 18)
In the same manner as in Reference Example 2, the resin of Reference Example 17 was evaluated. The results are summarized in Table 8. The thermosetting resin of Reference Example 17 showed good results in both electrical characteristics and heat resistance.

(Reference Comparative Example 1)
bis-A / MDA (2 nuclei + 2 nuclei)
Bisphenol A (Tokyo Kasei, 98%) 18.45 g (0.08 mol), 4,4′-diaminodiphenylmethane (Wako Pure Chemicals, 98%) 16.19 g (0.08 mol), paraformaldehyde in chloroform (Wako Pure Chemical Industries, 94%) 10.73 g (0.336 mol) was added and reacted under reflux for 6 hours while removing generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 26.44 g of a thermosetting resin mainly composed of a benzoxazine compound having the following structure.

(Reference Comparative Example 2)
The resin of Reference Comparative Example 1 was evaluated in the same manner as Reference Example 2. The results are summarized in Table 9. The thermosetting resin of Reference Comparative Example 1 was inferior in both electric characteristics and heat resistance.

(Reference Comparative Example 3)
bis-A / BAPP (2 nuclei + 4 nuclei)
Bisphenol A (Tokyo Kasei, 98%) 18.27 g (0.08 mol), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (Tokyo Kasei, 98%) in chloroform. 89 g (0.08 mol) and paraformaldehyde (manufactured by Wako Pure Chemicals, 94%) 10.73 g (0.336 mol) were added, and the mixture was reacted under reflux for 6 hours while removing generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 39.62 g of a thermosetting resin mainly composed of a benzoxazine compound having the following structure.

(Reference Comparative Example 4)
In the same manner as in Reference Example 2, the resin of Reference Comparative Example 3 was evaluated. The results are summarized in Table 10. The thermosetting resin of Reference Comparative Example 3 was inferior in electrical characteristics and heat resistance, and the film was whitened when bent.

(Reference Example 19)
In chloroform, α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene (Tokyo Kasei, 98%) 22.98 g (0.065 mol), Bisaniline P (Tokyo Kasei, 98%) 22.85 g (0.065 mol) and 8.72 g (0.273 mol) of paraformaldehyde (94% manufactured by Wako Pure Chemical Industries, Ltd.) were added and reacted for 6 hours under reflux while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 34.52 g of a thermosetting resin mainly composed of a benzoxazine compound having the following structure. The obtained polymer was insoluble in general-purpose solvents such as toluene and DMF. Moreover, even if hot pressing was performed, the film could not be formed due to infusibility.

(Reference Example 20)
Using toluene as a solvent, the benzoxazine resin synthesized in each Reference Example was added so that the respective weight percentages were 20, 30, 40, 50, and 60, and the mixture was stirred at room temperature for 24 hours to confirm whether it was dissolved. It was.

  In the benzoxazine resin of Reference Example 13, the benzoxazine resin of Reference Examples 1, 3, 5, 7, 8, 11, 15, 17 and Reference Comparative Examples 1 and 3 were dissolved in any confirmation experiment of 20 to 50% by weight. It melt | dissolved in any confirmation experiment of 20 to 60 weight%. The benzoxazine resin of Reference Example 19 did not dissolve in any of 20 to 60% by weight.

  The use of a bent M-form having a substituent at the meta position, such as bisphenol M and bisaniline M, improves the solubility even at a high molecular weight.

(Reference Example 21)
Sample films were prepared so as to have a width of 10 mm and a thickness of 75 μ with respect to the composites of Reference Examples 1, 3, 5, 7, 8, 11, 13, 15, 17 and Reference Comparative Examples 1 and 3. In preparing the sample film, a 50% by weight solution was prepared with toluene having the same weight as that of each resin, and the solution was drawn by an applicator, and then the solvent was dried and removed in an oven to prepare a sample. A bending test was performed on the produced film. In the bending test, the sample film was folded in half and pressed from both sides with a force of 3 kgf, and then the film was spread and transparent only with a crease: ○, the film whitened: Δ, the film cracked: X was evaluated.

  The evaluation results for Reference Examples 1, 3, 5, 7, 8, 11, 13, 15, and 17 were all “◯”, the reference comparison example 1 was “x”, and the reference comparison example 3 was “Δ”.

Claims (12)

A dihydrobenzoxazine represented by the general formula (IV) is obtained by heating and reacting the polyfunctional phenol compound represented by the general formula (I), the diamine compound represented by the general formula (II), and the aldehyde compound. Obtaining a thermosetting resin having a structure, and further adding a layered silicate, a method for producing a thermosetting resin composition,

[In formula, X is a C6 or more organic group containing an aromatic ring, and may have N, O, and F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X. ]

[Wherein Y is an organic group having 5 or more carbon atoms and may have N, O, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. ]

[In formula, X is a C6 or more organic group containing an aromatic ring, and may have N, O, and F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X. Y is an organic group having 5 or more carbon atoms, and may have N, O, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. m shows the integer of 1-50. ]
A thermosetting resin composition characterized in that X in the general formula (I) is bonded to the para position with respect to the OH groups of the benzene rings on both sides, and the structure of X is any of the following: Manufacturing method.

The thermosetting resin composition according to claim 1 , wherein the layered silicate is an organically modified layered silicate obtained by organically modifying a layered silicate with a quaternary ammonium salt type cationic surfactant. Production method. 2. The method for producing a thermosetting resin composition according to claim 1 , wherein the layered silicate is a synthetic smectite subjected to an organic treatment with dimethyldioctadecylammonium salt. The thermosetting resin according to claim 1 , wherein the layered silicate is blended in an amount of 0.1 to 5 parts by weight when the total weight of the thermosetting resin is 100 parts by weight. A method for producing the composition. Heating and reacting the polyfunctional phenol compound represented by the general formula (I), the diamine compound represented by the general formula (II), the aldehyde compound, and the monofunctional phenol represented by the general formula (III). The method for producing a thermosetting resin composition according to claim 1 , wherein the thermosetting resin composition has a dihydrobenzoxazine ring structure.

[In formula, X is a C6 or more organic group containing an aromatic ring, and may have N, O, and F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X. ]

[Wherein Y is an organic group having 5 or more carbon atoms and may have N, O, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. ]

[Wherein, Z is an organic group having 4 or more carbon atoms, and may have N, O, or F as a hetero atom. ] The monofunctional phenol compound represented by the general formula (III) is characterized in that the substituent Z is bonded to the OH group in the para position, and the substituent Z is a group represented by the following formula: The manufacturing method of the thermosetting resin composition of Claim 5 .

[N represents an integer of 0 to 10. ] The monofunctional phenol compound represented by the general formula (III) is characterized in that the substituent Z is bonded to the OH group in the para position, and the substituent Z is a group represented by the following formula: The manufacturing method of the thermosetting resin composition of Claim 5 .

The method for producing a thermosetting resin composition according to claim 1 , wherein Y in the general formula (II) is a group represented by the following formula.

The method for producing a thermosetting resin composition according to claim 1 , wherein Y in the general formula (II) contains one benzene ring. Y in the general formula (II) is one or more groups selected from the group of the following formulas, and Y is bonded to the meta position or the para position with respect to the NH ₂ groups of the benzene rings on both sides thereof. The manufacturing method of the thermosetting resin composition of Claim 9 .

The method for producing a thermosetting resin composition according to claim 1 , wherein Y in the general formula (II) contains at least two benzene rings. Y in the general formula (II) is one or more groups selected from the group of the following formulas, and is bonded to the meta or para position with respect to the NH ₂ groups of the benzene ring on both sides of Y. The manufacturing method of the thermosetting resin composition of Claim 11 .