JP2007146070A - Thermosetting resin, method for producing the same, thermosetting composition containing the resin, molded article obtained from the same, and electronic equipment containing the molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin excellent in dielectric properties, in particular, having further improved permittivity and dielectric loss as compared with prior art, and to provide a composition containing the same and a molded article obtained from the same. <P>SOLUTION: The thermosetting resin comprises a polymer having a dihydrobenzoxazine ring structure represented by general formula (I) in a main chain. There are provided a method of producing the same, a thermosetting composition containing the resin, a molded article obtained from the same, and electronic equipment containing the molded article. In the formula (I), Ar denotes a quadrivalent aromatic group; R<SP>1</SP>denotes an organic group having a siloxane group, wherein the part linked to the N atom in the formula (I) is an aliphatic (including alicyclic) hydrocarbon group; and n denotes an integer of 2-500. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a thermosetting resin in which dielectric properties, particularly dielectric constant and dielectric loss, are further improved as compared with the prior art, a method for producing the same, a thermosetting composition containing the resin, and a molded article obtained therefrom. The present invention relates to an electronic device including the molded body.

  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). ) Has 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.

  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.

  As raw material materials for thermosetting resins having such excellent dielectric properties, dihydrobenzoxazine compounds represented by the following formulas (1) and (2) are known (for example, Non-Patent Documents 1 and 2). reference).

  A resin obtained by ring-opening polymerization of a 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 are excellent in dielectric properties among thermosetting resins as described above, higher dielectric properties are desired in accordance with recent higher performance of electronic devices and parts. ing. 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.

  Japanese Patent Application Laid-Open No. 2003-64180 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. Have been disclosed (Patent Document 1).

However, the thermosetting resin disclosed in the above document uses an aromatic diamine as a raw material diamine compound. When an aromatic diamine is used, it is difficult to obtain a product having good dielectric properties when the obtained thermosetting resin is cured. The reason for this is not clear, but one reason is that when aromatic amines form a benzoxazine ring, the proportion of side reactions that do not form a ring is higher than aliphatic amines, and the structure tends to be irregular. Alternatively, the phenolic hydroxyl group formed by opening the benzoxazine ring when cured may have a low hydrogen bonding property with the aromatic amine. These are all thought to be due to the large difference in basicity between aromatic amines and aliphatic amines.
Japanese Patent Laid-Open No. 2003-64180 Konishi Chemical Co., Ltd. website [Searched on November 24, 2005], Internet <URL: http://www.konishi-chem.co.jp/cgi-data/jp/pdf/pdf_2.pdf> Shikoku Kasei Kogyo Co., Ltd. [Search on November 24, 2005], Internet <URL: http://www.shikoku.co.jp/products/benzo.html>

One of the problems to be solved by the present invention is the above problem.
Accordingly, the present invention has been made in view of such circumstances, and a thermosetting resin in which dielectric characteristics, particularly dielectric constant and dielectric loss are further improved as compared with the conventional one, and a composition containing the same, and It aims at providing the molded object obtained from it.

  Another object of the present invention is to provide a thermosetting resin having excellent dielectric properties and processability, a composition containing the same, and a molded product obtained therefrom.

  As a result of intensive studies, the present inventor has found that a thermosetting resin composed of a polymer having a specific structure can achieve the above-described object. The present invention is based on such knowledge. That is, the configuration of the present invention is as follows.

〔式（Ｉ）において、
Arは、４価の芳香族基を示し、
Ｒ¹は、シロキサン基を有する有機基であって、式（Ｉ）中のＮ原子に結合する部位が脂肪族（脂環族を含む）炭化水素基である基を示し、
ｎは、２〜５００の整数を示す。〕 1. A thermosetting resin comprising a polymer represented by the following general formula (I) and having a dihydrobenzoxazine ring structure in the main chain.

[In Formula (I),
Ar represents a tetravalent aromatic group,
R ¹ represents an organic group having a siloxane group, and the group bonded to the N atom in formula (I) is an aliphatic (including alicyclic) hydrocarbon group;
n represents an integer of 2 to 500. ]

  2. 2. The thermosetting resin according to 1, wherein Ar in the formula (I) is represented by any one of the following structures (i), (ii), and (iii).

〔各式中、*印は式（Ｉ）における酸素原子への結合部位、もう一方はオキサジン環４位のメチレン基への結合部位を示す。
また、各芳香環の水素は、炭素数１〜１０の脂肪族炭化水素基あるいは脂環式炭化水素基、置換もしくは無置換フェニル基で置換されていてもよい。
式（ｉ）におけるＸは、直接結合手（原子もしくは原子団が存在しない）、またはヘテロ元素もしくは官能基を含んでいても良い脂肪族、脂環式もしくは芳香族の炭化水素基を示す。〕

[In each formula, * indicates a binding site to the oxygen atom in formula (I), and the other indicates a binding site to the methylene group at the 4-position of the oxazine ring.
Moreover, hydrogen of each aromatic ring may be substituted with an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or a substituted or unsubstituted phenyl group.
X in the formula (i) represents a direct bond (no atom or atomic group), or an aliphatic, alicyclic or aromatic hydrocarbon group which may contain a hetero element or a functional group. ]

3. The thermosetting resin according to 1 or 2, wherein R ¹ in the general formula (I) is represented by the following (iv).

〔式（iv）において、
Ｒ²、Ｒ³は各々独立して炭素数２〜１０の炭化水素基であり、脂環族、芳香族等の環状骨格を有していてもよく、同じでも異なっていてもよい。ただし、式（Ｉ）中のＮ原子には脂肪族炭化水素基（脂環族を含む）で結合する。
Ｒ⁴〜Ｒ⁹は各々独立して炭素数１〜６の炭化水素基であり、脂環族、芳香族等の環状骨格を有していてもよく、同じでも異なっていてもよい。
ｏは０〜８の整数を表す。〕

[In Formula (iv),
R ² and R ³ are each independently a hydrocarbon group having 2 to 10 carbon atoms, and may have an alicyclic or aromatic cyclic skeleton, and may be the same or different. However, the N atom in the formula (I) is bonded with an aliphatic hydrocarbon group (including an alicyclic group).
R ^{4 to} R ⁹ are each independently a hydrocarbon group having 1 to 6 carbon atoms and may have an alicyclic or aromatic cyclic skeleton, and may be the same or different.
o represents an integer of 0 to 8. ]

  4). 4. In 2 or 3, Ar in the general formula (I) is a group represented by the structure of (i), and X in the structure (i) is at least one selected from the following group A Thermosetting resin.

〔式中、*印は（ｉ）におけるベンゼン環への結合部位を示す。〕

[In the formula, * indicates the binding site to the benzene ring in (i). ]

5. 4. The heat according to 2 or 3, wherein Ar in the general formula (I) is a group represented by the structure (i), and X in the structure (i) is a group represented by the formula (iv). Curable resin.

〔式中、*印は式（Ｉ）におけるＮへの結合部位を示す。〕 6). The thermosetting resin according to any one of 3 to 5, wherein the group represented by the formula (iv) as R ¹ in the formula (I) is at least one selected from the following group B.

[In the formula, * indicates a binding site to N in formula (I). ]

7). Ar in the general formula (I) is a group represented by the structure (i), and the group represented by the formula (iv) as X in the structure (i) is at least one selected from the group B The thermosetting resin as described in 5 or 6 above.

  8). Thermosetting produced by heating a phenol compound, a diamine compound having a siloxane group and an aliphatic (including alicyclic) hydrocarbon group bonded to an N atom, and an aldehyde compound in a solvent. resin.

  9. 9. The thermosetting resin according to 8, wherein the solvent is an aromatic solvent, a halogen solvent, or an ether solvent.

  10. 10. The thermosetting resin according to 8 or 9 above, which is reacted at a temperature of 30 to 110 ° C. for 20 minutes to 9 hours.

  11. A thermosetting resin that heats a phenol compound, a diamine compound having a siloxane group and an aliphatic (including alicyclic) hydrocarbon group bonded to an N atom, and an aldehyde compound in a solvent. Manufacturing method.

  12 The thermosetting composition containing at least the thermosetting resin in any one of said 1-10.

  13. 13. The thermosetting composition according to the above 12, comprising a compound having at least one dihydrobenzoxazine structure in the molecule.

  14 The molded object obtained from the thermosetting resin in any one of said 1-10, or the thermosetting composition in said 12 or 13.

  15. A cured product obtained by curing the thermosetting resin according to any one of 1 to 10 or the thermosetting composition according to 12 or 13.

  16. 15. A cured molded body obtained by curing the molded body according to 14.

  17. 15. An electronic device including the molded body according to 14, the cured body according to 15, or the cured molded body according to 16.

According to the present invention, a thermosetting resin whose dielectric properties, particularly dielectric constant and dielectric loss are further improved as compared to the conventional one, a method for producing the same, a composition containing the resin, a molded product obtained therefrom, and the An electronic device including a molded body is provided.
Further, according to the present invention, a thermosetting resin having excellent dielectric properties and excellent processability, a method for producing the same, a composition containing the resin, a molded product obtained therefrom, and an electronic device including the molded product Is provided.

Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.
[Thermosetting resin]
The thermosetting resin of the present invention is composed of a polymer represented by the following general formula (I) having a dihydrobenzoxazine ring structure in the main chain.

〔式（Ｉ）において、
Arは、４価の芳香族基を示し、
Ｒ¹は、シロキサン基を有する有機基であって、式（Ｉ）中のＮ原子に結合する部位が脂肪族（脂環族を含む）炭化水素基である基を示し、
ｎは、２〜５００の整数を示す。〕

[In Formula (I),
Ar represents a tetravalent aromatic group,
R ¹ represents an organic group having a siloxane group, and the group bonded to the N atom in formula (I) is an aliphatic (including alicyclic) hydrocarbon group;
n represents an integer of 2 to 500. ]

Since the thermosetting resin of the present invention has such a configuration, R ¹ is more excellent in heat resistance than a normal aliphatic resin, and more excellent in dielectric properties than those in which R ¹ is aromatic and bonded to an N atom. Is. Since the thermosetting resin of the present invention is composed of the polymer as described above, it is excellent in processability to a film, a sheet or the like and has sufficient moldability before curing. The thermosetting resin of the present invention can be cured without harmful volatile substances by the ring-opening polymerization reaction of the dihydrobenzoxazine.

〔式中、*印は式（Ｉ）における酸素原子への結合部位、もう一方はオキサジン環４位のメチレン基への結合部位を示す。また、各芳香環の水素は、炭素数１〜１０の脂肪族炭化水素基あるいは脂環式炭化水素基、置換もしくは無置換フェニル基で置換されていてもよい。式（ｉ）におけるＸは、直接結合手（原子もしくは原子団が存在しない）、またはヘテロ元素もしくは官能基を含んでいても良い脂肪族、脂環式もしくは芳香族の炭化水素基を示す。〕 In the formula (I), Ar represents a tetravalent aromatic group, and in particular, from the viewpoint of availability and reactivity, any one of the following structures (i), (ii), and (iii) What is shown is preferred.

[Wherein, * represents a bonding site to the oxygen atom in the formula (I), and the other represents a bonding site to the methylene group at the 4-position of the oxazine ring. Moreover, hydrogen of each aromatic ring may be substituted with an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or a substituted or unsubstituted phenyl group. X in the formula (i) represents a direct bond (no atom or atomic group), or an aliphatic, alicyclic or aromatic hydrocarbon group which may contain a hetero element or a functional group. ]

  In particular, the structure represented by the formula (i) is more preferable because the structural design of the resin according to the required characteristics is easy.

In the case where Ar in the formula (I) is the structure (i), it is more preferable that X in the structure (i) is at least one selected from the following group A.
Such a structure is very preferable because it is easily available and the polymer has excellent mechanical and electrical characteristics.

〔式中、*印は前記構造（ｉ）における芳香環への結合部位を示す。〕

[Wherein, * represents a binding site to the aromatic ring in the structure (i). ]

Moreover, when the structure of Ar in the formula (I) is (i), it is also preferable that X is a structure represented by the formula (iv). X is more preferably a group represented by the following group B.

〔式（iv）において、
Ｒ²、Ｒ³は各々独立して炭素数２〜１０の炭化水素基、好ましくは炭素数２から６，さらに好ましくは３の炭化水素基であり、脂環族、芳香族等の環状骨格を有していてもよく、同じでも異なっていてもよい。ただし、式（Ｉ）中のＮ原子には脂肪族炭化水素基（脂環族を含む）で結合する。
Ｒ⁴〜Ｒ⁹は各々独立して炭素数１〜６の炭化水素基であり、脂環族、芳香族等の環状骨格を有していてもよく、同じでも異なっていてもよい。
ｏは０〜８の整数を表す。〕

[In Formula (iv),
R ² and R ³ are each independently a hydrocarbon group having 2 to 10 carbon atoms, preferably a hydrocarbon group having 2 to 6 carbon atoms, more preferably 3 and having an alicyclic or aromatic cyclic skeleton. They may be the same or different. However, the N atom in the formula (I) is bonded with an aliphatic hydrocarbon group (including an alicyclic group).
R ^{4 to} R ⁹ are each independently a hydrocarbon group having 1 to 6 carbon atoms and may have an alicyclic or aromatic cyclic skeleton, and may be the same or different.
o represents an integer of 0 to 8. ]

〔式中、*印は式（Ｉ）におけるＮへの結合部位を示す。〕

[In the formula, * indicates a binding site to N in formula (I). ]

In the formula (I), R ¹ is an organic group having a siloxane group in that the effect of the present invention can be exhibited, and the site bonded to the N atom in the formula (I) is aliphatic (alicyclic). Groups which are hydrocarbon radicals (including groups) are used. In particular, R ¹ is a structure represented by the formula (iv) (in the formula (I), from the viewpoint of availability, reaction rate, electrical properties of the resulting polymer and final cured product, and workability. Ar is preferably the same as X in the case of (i).

Here, examples of the organic group having a siloxane group represented by R ¹ include an organic group in which a hydrocarbon group is bonded to both ends of a siloxane group having a methyl group, a phenyl group, and the like. And the like (the same as X in the case where Ar in the above formula (I) is (i)) is preferred.

  N in the formula (I) is a value indicating the degree of polymerization of the polymer, and is a value calculated by dividing the weight average molecular weight of the polymer by the molecular weight of the repeating structural unit, and represents an integer of 2 to 500. In particular, from the viewpoint of fluidity during molding and solubility during preparation of the composition, it is preferably 2 to 300.

  The method for synthesizing the polymer of the general formula (I) constituting the thermosetting resin of the present invention is not particularly limited. For example, a phenol compound, a specific diamine compound and an aldehyde compound are mixed in an appropriate solvent. An example is a synthesis method in which the reaction is performed by heating.

  The solvent used in the synthesis method of the above example is not particularly limited, but a material having a high degree of polymerization can be obtained if the raw material phenol compound or amine compound and the product polymer are more soluble. It is easy to be done. 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.

  The reaction temperature and reaction time are also not particularly limited, but usually the reaction may be carried out at a temperature from room temperature to about 120 ° C. for several tens of minutes to several hours. In the present invention, 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 present invention.

  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.

  Moreover, it does not specifically limit as a phenolic compound used for the synthesis method of the said example, For example, the compound etc. which have two phenolic hydroxyl groups in a molecule | numerator are mentioned. The compound having two phenolic hydroxyl groups in the molecule preferably has an OH group bonded to the * mark in the preferred structure (i) to (iii) of Ar in the formula (I). A compound in which H is bonded to the bond.

Specific examples of such compounds include the structure of (i): 4,4′-biphenol, 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'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenyl sulfide, 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-hydroxyphenyl) -2-methylpropane, , 1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) Diphenylmethane, 4,4 ′-[1,4-phenylenebis (1-methyl-ethylidene)] bisphenol (Mitsui Chemicals bisphenol P, Tokyo Chemical Co., “α, α′-bis (4-hydroxyphenyl) -1,4 -Diisopropylbenzene "), 4,4 '-[1,3-phenylenebis (1-methyl-ethylidene)] bisphenol (Mitsui Chemicals bisphenol M), 9,9-bis (4-hydroxyphenyl) ) Fluorene, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,3-bis (4-H Roxyphenoxy) benzene, 1,4-bis (3-hydroxyphenoxy) benzene, 2,6-bis ((2-hydroxyphenyl) methyl) phenol, etc. A compound in which one OH group is bonded to one benzene ring,
Structure of (ii): 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2, A compound having one naphthalene ring in the molecule and two OH groups bonded to the naphthalene ring, such as 7-dihydroxynaphthalene,
The structure of (iii): 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol), 1,4-dihydroxybenzene (hydroquinone) and having one benzene ring in the molecule, And compounds having two OH groups bonded to the ring.

  Moreover, when it is going to obtain the polymer in which X in the structure of said (i) which is a preferable structure of the thermosetting resin which concerns on this invention tries to obtain the polymer which has a siloxane group, two phenolic hydroxyl groups in the molecule | numerator used as a raw material (A) 1,3-bis (3- (4-hydroxyphenyl) propyl) -1,1,3,3-tetramethyldisiloxane, (b) 1,3-bis (3- (2-hydroxyphenyl) propyl) -1,1,3,3-tetramethyldisiloxane, (c) 1,5-bis (3- (4-hydroxyphenyl) propyl) -1,1,3,3 5,5-hexamethyltrisiloxane, (d) 1,5-bis (3- (2-hydroxyphenyl) propyl) -1,1,3,3,5,5-hexamethyltrisiloxane, (e) 1 , 7-bis (3- (4-hydroxy Phenyl) propyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane, (f) 1,7-bis (3- (2-hydroxyphenyl) propyl) -1,1, Examples thereof include phenol compounds having a siloxane group such as 3,3,5,5,7,7-octamethyltetrasiloxane.

  As an example of the above, in the aromatic ring to which the OH group is bonded, those other than the OH group and the linking group X (in the case of the structure of (i)) are unsubstituted, but both are in the ortho position of the OH group. Any one of them may be substituted H, and the other part of the aromatic ring may be various substituents such as a linear or branched aliphatic hydrocarbon group or alicyclic hydrocarbon having 1 to 10 carbon atoms. The group may be substituted with a substituted or unsubstituted aromatic group. In addition, even when the linking part X contains an aromatic ring, the aromatic ring may have various substituents such as a linear or branched aliphatic hydrocarbon group or alicyclic hydrocarbon group having 1 to 10 carbon atoms. May be substituted.

As a simple example of a substituted aromatic ring,
Structure of (i): 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) methane,
The structure of (ii): 2-methylresorcinol, 2,5-dimethylresorcinol, etc. are mentioned, but it is not limited to this.

  In the synthesis of the polymer of the general formula (I), a monofunctional phenol compound or a trifunctional phenol compound can also be used as long as the characteristics of the thermosetting resin of the present invention to be obtained are not impaired. When a monofunctional phenol is used, the degree of polymerization can be adjusted, and when a trifunctional phenol is used, a branched polymer is obtained. These can be used at the same time as the bifunctional phenol compound, but can also be added to the reaction system and reacted later in consideration of the order of the reaction. In addition, any of the bifunctional phenol compounds in the present invention may be used alone, or two or more kinds may be used in combination.

  The diamine compound used in the synthesis method of the above example is a diamine compound having a siloxane group and a site bonded to the N atom is an aliphatic (including alicyclic) hydrocarbon group. Specific examples of such a diamine compound include, for example, 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, 1,5-bis (3-aminopropyl)- 1,1,3,3,5,5-hexamethyltrisiloxane, 1,7-bis (3-aminopropyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane, Etc. These may be used alone or in combination.

  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 of this invention. 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.

  Further, the aldehyde compound used in the synthesis method of the above example is not particularly limited, but formaldehyde is preferable, and as the formaldehyde, paraformaldehyde which is a polymer thereof, formalin which is in the form of an aqueous solution, or the like. It can be used in the form. The reaction proceeds more slowly when paraformaldehyde is used. As other aldehyde compounds, acetaldehyde, propionaldehyde, butyraldehyde and the like can also be used.

  The thermosetting resin of the present invention comprising the polymer obtained as described above has very excellent characteristics particularly in terms of dielectric properties, but in addition, water resistance, chemical resistance, mechanical strength, reliability, It is a resin that has various advantages such as volatile by-products during curing and no problems in terms of cost, excellent storage stability, and a wide degree of freedom in molecular design. Etc. can be easily processed.

[Thermosetting composition]
The thermosetting composition of the present invention contains at least the thermosetting resin described above. The thermosetting composition according to the present invention preferably contains the thermosetting resin as a main component, for example, the thermosetting resin as a main component, and another thermosetting as a subcomponent. That contain a functional resin.

  Examples of other thermosetting resins as accessory components include epoxy resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, silicon resins, melamine resins, urea resins, allyl resins, phenol resins, and unsaturated resins. Examples include polyester resins, bismaleimide 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 present invention, a compound having at least one dihydrobenzoxazine ring in the molecule, preferably two dihydrobenzoxazine rings in the molecule is preferably used as a subcomponent. In this case, it is effective to maximize the excellent characteristics of the benzoxazine resin. 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 and a compound having a primary amino group in the molecule and formaldehyde. Can do. 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 dihydrobenzoxazine ring in this molecule | numerator, and 2 or more types may be used together.

  In addition, the thermosetting composition according to the present invention 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, as 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. In preparing the thermosetting composition according to the present invention, a reactive or non-reactive solvent can also be used.

[Molded body]
The molded body according to the present invention is obtained by the thermosetting resin described above or a thermosetting composition containing the same. As the molded body of the present invention, since the thermosetting resin described above has moldability before curing, even after being molded before curing and then cured by applying heat (cured molded body), What hardened | cured simultaneously with shaping | molding (hardening body) may be sufficient. Moreover, the dimension and shape in particular are not restrict | limited, For example, a sheet form (plate shape), block shape, etc. are mentioned, Furthermore, other site | parts (for example, adhesion layer) may be provided.

  As the curing method, any conventionally known curing method can be used. Generally, it may be heated at about 120 to 260 ° 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 a 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 molded article of the present invention made of the thermosetting resin or the thermosetting composition thus obtained has a benzoxazine structure and a siloxane group in the polymer structure, thereby realizing extremely excellent dielectric properties. can do.

  Moreover, since the molded article of the present invention has a siloxane group in the polymer structure, it exhibits excellent heat resistance as compared with an aliphatic hydrocarbon group or the like.

  Further, the molded article of the present invention is excellent in reliability, flame retardancy, moldability, aesthetics, etc. based on the thermosetting property of the thermosetting resin or the thermosetting composition, and Since the glass transition temperature (Tg) is high, it can be applied to stressed parts and moving parts, and since no volatile by-products are generated during polymerization, such volatile by-products are generated. The product does not remain in the molded body, which is preferable in terms of hygiene management.

  The molded article of the present invention can be suitably used for applications such as electronic parts / electronic devices and materials thereof, multilayer boards, laminates, sealants, adhesives, etc. that require particularly excellent dielectric properties, It can also be used for applications such as aircraft members, automobile members, and building members.

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

  In chloroform, 23.06 g (0.1 mol) of bisphenol A (manufactured by Tokyo Chemical Industry, 99%), 25.10 g (0% of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (manufactured by Amax), 97%) 0.1 mol) and 13.42 g (0.42 mol) of paraformaldehyde (manufactured by Wako Pure Chemical Industries, Ltd.) were added and reacted for 6 hours under reflux. The reaction scheme is shown below. The solution after the reaction was poured into a large amount of methanol to precipitate a polymer. Thereafter, the polymer was separated by filtration and washed with methanol. Thereafter, a polymer having the following structure was obtained by drying under reduced pressure. In measurement of molecular weight by GPC, the weight average molecular weight was 37,600 in terms of standard polystyrene.

The polymer obtained in Example 1 was formed into a sheet shape by a hot press method, and held at 140 ° C., 160 ° C., and 180 ° C. for 1 hour each to obtain a 0.5 mmt sheet-like cured molded body.
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 molded body of Example 2 showed good dielectric properties with a dielectric constant of 3.0 or less and a dielectric loss tangent of 0.01 or less.
Moreover, the obtained sheet | seat was cut | judged finely and 5% weight reduction | decrease temperature (Td5) was evaluated with the temperature increase rate of 10 degree-C / min by the TGA method using the Shimadzu Corporation make and brand name "DTG-60". The cured molded body of Example 2 had a good value of Td5 of 324 ° C.

  In chloroform, α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene (manufactured by Tokyo Chemical Industry, 98%) 22.98 g (0.065 mol), 1,3-bis (3-aminopropyl) ) Tetramethyldisiloxane (manufactured by Amax, 97%) 16.65 g (0.065 mol) and 8.72 g (0.27 mol) of paraformaldehyde (manufactured by Wako Pure Chemical Industries, Ltd.) were added and reacted 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 a polymer. Thereafter, the polymer was separated by filtration and washed with methanol. Thereafter, a polymer having the following structure was obtained by drying under reduced pressure. In the measurement of molecular weight by GPC, the weight average molecular weight was 23,500 in terms of standard polystyrene.

  Using the polymer obtained in Example 3, it was molded and evaluated in the same manner as in Example 2. The results are summarized in Table 1.

The present invention relates to a thermosetting resin in which dielectric properties, particularly dielectric constant and dielectric loss, are further improved as compared with the prior art, a method for producing the same, a thermosetting composition containing the resin, and a molded article obtained therefrom. As an electronic device including the molded body, it has industrial applicability.

Claims (17)

A thermosetting resin comprising a polymer represented by the following general formula (I) and having a dihydrobenzoxazine ring structure in the main chain.

[In Formula (I),
Ar represents a tetravalent aromatic group,
R ¹ represents an organic group having a siloxane group, and the group bonded to the N atom in formula (I) is an aliphatic (including alicyclic) hydrocarbon group;
n represents an integer of 2 to 500. ] The thermosetting resin according to claim 1, wherein Ar in the formula (I) is represented by any one of the following structures (i), (ii), and (iii).

[In each formula, * indicates a binding site to the oxygen atom in formula (I), and the other indicates a binding site to the methylene group at the 4-position of the oxazine ring.
Moreover, hydrogen of each aromatic ring may be substituted with an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or a substituted or unsubstituted phenyl group.
X in the formula (i) represents a direct bond (no atom or atomic group), or an aliphatic, alicyclic or aromatic hydrocarbon group which may contain a hetero element or a functional group. ] The thermosetting resin according to claim 1 or 2, wherein R ¹ in the general formula (I) is represented by the following (iv).

[In Formula (iv),
R ² and R ³ are each independently a hydrocarbon group having 2 to 10 carbon atoms, and may have an alicyclic or aromatic cyclic skeleton, and may be the same or different. However, the N atom in the formula (I) is bonded with an aliphatic hydrocarbon group (including an alicyclic group).
R ^{4 to} R ⁹ are each independently a hydrocarbon group having 1 to 6 carbon atoms and may have an alicyclic or aromatic cyclic skeleton, and may be the same or different.
o represents an integer of 0 to 8. ] The Ar in the general formula (I) is a group represented by the structure (i), and X in the structure (i) is at least one selected from Group A below. Thermosetting resin.

[In the formula, * indicates the binding site to the benzene ring in (i). ] The Ar in the general formula (I) is a group represented by the structure (i), and X in the structure (i) is a group represented by the formula (iv). Thermosetting resin. The thermosetting resin according to any one of claims 3 to 5, wherein the group represented by the formula (iv) as R ¹ in the formula (I) is at least one selected from the following group B.

[In the formula, * indicates a binding site to N in formula (I). ] Ar in the general formula (I) is a group represented by the structure (i), and the group represented by the formula (iv) as X in the structure (i) is at least one selected from the group B The thermosetting resin according to claim 5 or 6.   Thermosetting produced by heating a phenol compound, a diamine compound having a siloxane group and an aliphatic (including alicyclic) hydrocarbon group bonded to an N atom, and an aldehyde compound in a solvent. resin.   The thermosetting resin according to claim 8, wherein the solvent is an aromatic solvent, a halogen solvent, or an ether solvent.   The thermosetting resin according to claim 8 or 9, which is reacted at a temperature of 30 to 110 ° C for 20 minutes to 9 hours.   A thermosetting resin that heats a phenol compound, a diamine compound having a siloxane group and an aliphatic (including alicyclic) hydrocarbon group bonded to an N atom, and an aldehyde compound in a solvent. Manufacturing method.   A thermosetting composition comprising at least the thermosetting resin according to claim 1.   The thermosetting composition according to claim 12, comprising a compound having at least one dihydrobenzoxazine structure in the molecule.   The molded object obtained from the thermosetting resin in any one of Claims 1-10, or the thermosetting composition of Claim 12 or 13.   A cured product obtained by curing the thermosetting resin according to claim 1 or the thermosetting composition according to claim 12 or 13.   A cured molded body obtained by curing the molded body according to claim 14. An electronic device comprising the molded body according to claim 14, the cured body according to claim 15, or the cured molded body according to claim 16.