JP2007154018A - Thermosetting resin, its manufacturing method, thermosetting composition containing the resin, molded product obtained therefrom and electronic equipment containing the molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin which excels in dielectric properties and further improves particularly the dielectric constant and the dielectric loss compared to the conventional thermosetting resin, a composition containing the same, and a molded product obtained therefrom. <P>SOLUTION: The thermosetting resin is composed of a polymer having a dihydrobenzoxazine ring structure represented by formula (I) (wherein Ar<SP>1</SP>is a tetravalent aromatic group; R<SP>1</SP>is a branched chain aliphatic hydrocarbon group; and n is an integer of 2-500) in the main chain. Its manufacturing method is disclosed and the thermosetting composition comprises the resin. The molded product is obtained from the thermosetting composition and electronic equipment comprises the molded product. <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.

  Non-Patent Document 3 discloses that a soluble high molecular weight polybenzoxazine precursor can be prepared by the reaction of bisphenol, diamine, and formaldehyde. And as a diamine used here, aliphatic diamine is mentioned as an example. However, in the above-mentioned document, although it is described as an aliphatic diamine, no more specific examples are given. Moreover, no description is made regarding electrical characteristics.

The present inventors have often found that general linear aliphatic diamines such as hexamethylene diamine and octamethylene diamine are insolubilized in a solvent when the target polymer is isolated after synthesis, and the subsequent molding process is performed. It is confirmed that it is inferior in suitability. However, the cured body has excellent dielectric properties.
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> APME-6, International Symposium on Advanced Polymers via Macromolecular Engineering L-42, August, 2005

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 excellent processability such as solvent solubility, a composition containing the same, and a molded product obtained therefrom. To do.

  As a result of intensive studies, the present inventors have found that a polymer having a dihydrobenzoxazine ring structure in the main chain obtained by using a branched chain aliphatic diamine has good handleability after isolation, In addition, the inventors have found that the dielectric properties are good and the above object can be achieved.

  The present invention is based on such knowledge. That is, the configuration of the present invention is as follows.

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

〔式（Ｉ）において、
Ar¹は、４価の芳香族基を示し、
Ｒ¹は、分岐を有する鎖状脂肪族炭化水素基であり、
ｎは、２〜５００の整数を示す。〕

[In Formula (I),
Ar ¹ represents a tetravalent aromatic group,
R ¹ is a branched chain aliphatic hydrocarbon group,
n represents an integer of 2 to 500. ]

2. 2. The thermosetting resin according to 1 above, wherein R ¹ is a chain aliphatic hydrocarbon group having a C 3-20 branch of the main chain.

〔式中、*印は前記式（Ｉ）におけるＮへの結合部位を示す。〕 3. 2. The thermosetting resin according to 1 above, wherein R ¹ is a group represented by the following (i) or (ii).

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

〔式中、*印は前記式（Ｉ）におけるＮへの結合部位を示す。〕 4). 2. The thermosetting resin according to 1 above, wherein R ¹ is a group represented by the following (iii).

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

〔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（iv）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。〕 5. The thermosetting resin according to any one of 1 to 4, wherein Ar ¹ in the formula (I) is represented by any one of the following structures (iv), (v), and (vi):

[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 (iv) 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. ]

6). 6. The thermosetting resin according to 5, wherein Ar ¹ in the formula (I) is represented by the structure of (iv).

〔式中、*印は前記構造（iv）における芳香環への結合部位を示す。〕 7). 6. The thermosetting resin according to 5 above, wherein Ar ¹ in the formula (I) is the structure (iv), and X in the structure (iv) is at least one selected from the following group A.

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

〔式中、*印は前記構造（iv）における芳香環への結合部位を示す。〕 8). 6. The thermosetting resin according to 5 above, wherein Ar ¹ in the formula (I) is the structure (iv), and X in the structure (iv) is at least one selected from the following group B.

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

〔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。〕 9. 2. The thermosetting resin according to 1, wherein Ar ¹ in the formula (I) is at least one selected from the following group C.

[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. ]

10. 10. The thermosetting resin according to 9, wherein R ¹ is a group represented by the above (i) or (ii).

11. 10. The thermosetting resin according to 9 above, wherein R ¹ is a group represented by (iii).

  12 A thermosetting resin obtained by heating a phenol compound, a diamine compound having a branched chain aliphatic hydrocarbon group, and an aldehyde compound in a solvent.

  13. 13. The thermosetting resin according to 12, wherein the solvent is an aromatic solvent, a halogen solvent, or an ether solvent.

  14 The thermosetting resin according to 12 or 13, which is reacted at a temperature of 30 to 110 ° C. for 20 minutes to 9 hours.

  15. A method for producing a thermosetting resin, comprising: heating a phenol compound, a diamine compound having a branched chain aliphatic hydrocarbon group, and an aldehyde compound in a solvent.

  16. The thermosetting composition containing at least the thermosetting resin in any one of said 1-14.

  17. 17. The thermosetting composition according to 16, which comprises a compound having at least one dihydrobenzoxazine structure in the molecule.

  18. The molded object obtained from the thermosetting resin in any one of said 1-14, or the thermosetting composition in said 16 or 17.

  19. A cured product obtained by curing the thermosetting resin according to any one of 1 to 14 or the thermosetting composition according to 16 or 17.

  20. A cured molded product obtained by curing the molded product according to 18.

  21. 21. An electronic device comprising the molded article according to 18., the cured article according to 19, or the cured molded article according to 20.

  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、Ar¹は、４価の芳香族基を示し、Ｒ¹は、分岐を有する鎖状脂肪族炭化水素基であり、ｎは、２〜５００の整数を示す。〕

[In Formula (I), Ar ¹ represents a tetravalent aromatic group, R ¹ represents a branched chain aliphatic hydrocarbon group, and 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 processability such as solvent solubility than a normal linear aliphatic one, and more excellent in dielectric properties than an aromatic one. 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（iv）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 ¹ represents a tetravalent aromatic group, and in particular from the viewpoint of availability and reactivity, any one of the following structures (iv), (v), and (vi) 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 (iv) 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 (iv) is more preferable because the structural design of the resin according to the required characteristics is easy.

In the case where Ar ¹ in the formula (I) is the structure (iv), it is more preferable that X in the structure (iv) 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（iv）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 (iv). ]

  Among the groups A, those having a structure shown in the following group B are particularly preferable because they are excellent in electric characteristics and heat resistance.

〔式中、*印は前記構造（iv）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 (iv). ]

In the formula (I), a branched chain aliphatic hydrocarbon group having a branch is used as R ¹ in that the effect of the present invention can be exhibited.
Here, as the chained aliphatic hydrocarbon group having a branch represented by R ¹ , the main chain is selected from the viewpoints of availability, reaction rate, electrical properties of the resulting polymer and final cured product, and workability. A chain aliphatic hydrocarbon group having a branch having 3 to 20 carbon atoms, particularly 5 or 6 carbon atoms in the main chain is preferable, and the branched group is preferably a hydrocarbon group having 1 to 6 carbon atoms. A chain aliphatic hydrocarbon group having a branched group such as a methyl group, an ethyl group or a phenyl group, among them, a 2,4,4-trimethylhexamethylene group or a 2,2,4-trimethylhexamethylene group, 2 -A methylpentamethylene group, 2,2-dimethylpropylene group, etc. are preferable.

〔式中、*印は前記式（Ｉ）におけるＮへの結合部位を示す。〕 In particular, R ¹ is preferably a group represented by the following (i) or (ii) from the viewpoint of easy availability, reactivity of raw materials, and electrical characteristics of a cured product.

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

〔式中、*印は前記式（Ｉ）におけるＮへの結合部位を示す。〕 Further, R ¹ is preferably a group represented by the following (iii) from the viewpoints of availability, reactivity of raw materials, and electrical characteristics of the cured product.

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

〔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。］ In the formula (I), Ar ¹ representing a tetravalent aromatic group has at least one structure selected from the following group C particularly from the viewpoint of availability, electrical properties of the cured product, and heat resistance. Also preferred are those shown.

[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.
Further, the 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. ]

In the case where Ar ¹ is at least one selected from the above group C, the same reason is given as in the case where Ar ¹ is represented by any one of the structures (iv), (v), (vi). Therefore, R ¹ representing a branched chain aliphatic hydrocarbon group is preferably the group represented by (i) or (ii) or the group represented by (iii).

  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, it is preferably 2 to 100.

  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 (iv) to (vi) of Ar ¹ in the formula (I). It is a compound in which H is bonded to one bond.

Specific examples of such compounds include the structure of (iv): 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-hydride) 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 (v): 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,
(Vi) structure: 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.

  As an example of the above, in the aromatic ring to which the OH group is bonded, an unsubstituted ring is exemplified except for the OH group and the linking group X (in the case of the structure of (iv)). 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 (iv): 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) methane,
The structure of (v): 2-methylresorcinol, 2,5-dimethylresorcinol and the like can be mentioned, but of course not limited thereto.

  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.

  Moreover, the diamine compound used for the synthesis method of the above example is a diamine compound having a branched chain aliphatic hydrocarbon group. Examples of the diamine compound include compounds having a branched chain aliphatic hydrocarbon group and two primary amino groups. Specific examples of such a compound include, for example, trimethylhexamethylenediamine (usually a mixture of 2,4,4-trimethyl and 2,2,4-trimethyl, “VESTAMIN TMD” manufactured by Degussa), Examples include 2-methyl-1,5-pentamethylenediamine and 2,2-dimethyl-1,3-diaminopropane. 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 is preferably used as an auxiliary component. 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 comprising the thermosetting resin or the thermosetting composition thus obtained is a chain aliphatic having a branch represented by the group R ¹ in the polymer structure. Since it is composed of a hydrocarbon group, extremely excellent dielectric properties can be realized mainly by lowering the density by increasing the molecular gap. In addition, since a branched chain aliphatic hydrocarbon is used, the crystallinity of the polymer is lowered, the fluidity is increased, and as a result, good coating properties are given.

  Further, since the molded product of the present invention uses a benzoxazine compound having a polymer structure in a state before curing, the cured product is a cured product obtained from a generally used bifunctional or other low molecular weight benzoxazine compound. Better heat resistance.

  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 / 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 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, bisphenol A (Tokyo Kasei, 99%) 23.06 g (0.10 mol), trimethylhexamethylenediamine (Tokyo Kasei, 98%, 2,2,4-trimethyl and 2,4,4- (Trimethyl compound mixture) 16.15 g (0.10 mol) and paraformaldehyde (Wako Pure Chemicals, 94%) 13.42 g (0.42 mol) were added and reacted under reflux for 6 hours. The reaction scheme is shown below (the diamine compound shows 2,4,4-form as a representative, but 2,2,4-form also exists). 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. The shape was a white powder. In the measurement of molecular weight by GPC, the weight average molecular weight was 5,400 in terms of standard polystyrene. The solubility of the polymer in THF and chloroform was good.

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 10% weight reduction temperature (Td10) 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 Td10 of 314 ° C.
[Comparative Example 1]

  In Example 1, a polymer was prepared in the same manner as in Example 1 except that 15.19 g (0.1 mol) of 1,8-diaminooctane (95% manufactured by Tokyo Chemical Industry) was used instead of trimethylhexamethylenediamine. Synthesized. After the reaction, the solution was uniform. The solution after the reaction was poured into a large amount of methanol to precipitate a polymer, and the polymer was separated by filtration and washed with methanol. Thereafter, the polymer was isolated by drying under reduced pressure. The obtained polymer was insoluble in THF. Also, the solubility in chloroform was poor, and the composition of 3 wt% did not completely dissolve even if it took one night, and the solution gelled if left standing after that.

  In chloroform, α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene (Tokyo Kasei, 98%) 22.98 g (0.065 mol), 2-methylpentamethylenediamine (Tokyo Kasei) 98%) 7.71 g (0.065 mol) and paraformaldehyde (Wako Pure Chemical Industries, 94%) 8.72 g (0.27 mol) 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. The shape was a white powder. In the measurement of molecular weight by GPC, the weight average molecular weight was 8,200 in terms of standard polystyrene. The solubility of the polymer in THF and chloroform was good.

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 (21)

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 ¹ represents a tetravalent aromatic group,
R ¹ is a branched chain aliphatic hydrocarbon group,
n represents an integer of 2 to 500. ] The thermosetting resin according to claim 1, wherein R ¹ is a chain aliphatic hydrocarbon group having a main chain branched chain having 3 to 20 carbon atoms. The thermosetting resin according to claim 1, wherein R ¹ is a group represented by the following (i) or (ii).

[In the formula, * indicates a binding site to N in the formula (I). ] The thermosetting resin according to claim 1, wherein R ¹ is a group represented by the following (iii).

[In the formula, * indicates a binding site to N in the formula (I). ] The thermosetting resin according to any one of claims 1 to 4, wherein Ar ¹ in the formula (I) is represented by any one of the following structures (iv), (v), and (vi).

[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 (iv) 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 5, wherein Ar ¹ in the formula (I) is represented by the structure of (iv). The thermosetting resin according to claim 5, wherein Ar ¹ in the formula (I) is the structure (iv), and X in the structure (iv) is at least one selected from the following group A. .

[Wherein, * represents a binding site to the aromatic ring in the structure (iv). ] The thermosetting resin according to claim 5, wherein Ar ¹ in the formula (I) is the structure (iv), and X in the structure (iv) is at least one selected from the following group B. .

[Wherein, * represents a binding site to the aromatic ring in the structure (iv). ] The thermosetting resin according to claim 1, wherein Ar ¹ in the formula (I) is at least one selected from the following group C.

[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. ] The thermosetting resin according to claim 9, wherein R ¹ is a group represented by (i) or (ii). The thermosetting resin according to claim 9, wherein R ¹ is a group represented by (iii).   A thermosetting resin obtained by heating a phenol compound, a diamine compound having a branched chain aliphatic hydrocarbon group, and an aldehyde compound in a solvent.   The thermosetting resin according to claim 12, wherein the solvent is an aromatic solvent, a halogen solvent, or an ether solvent.   The thermosetting resin according to claim 12 or 13, which is reacted at a temperature of 30 to 110 ° C for 20 minutes to 9 hours.   A method for producing a thermosetting resin, comprising: heating a phenol compound, a diamine compound having a branched chain aliphatic hydrocarbon group, and an aldehyde compound in a solvent.   A thermosetting composition comprising at least the thermosetting resin according to claim 1.   The thermosetting composition according to claim 16, 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 1-14, or the thermosetting composition of Claim 16 or 17.   A cured product obtained by curing the thermosetting resin according to any one of claims 1 to 14 or the thermosetting composition according to claim 16 or 17.   A cured molded body obtained by curing the molded body according to claim 18. An electronic device comprising the molded body according to claim 18, the cured body according to claim 19, or the cured molded body according to claim 20.