JP2007217650A - Production method of thermosetting resin, thermosetting resin, thermosetting composition comprising the same, molded article, cured article, cured molded article, and electronic apparatus comprising them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method of a thermosetting resin having excellent heat resistance, satisfactory electrical characteristics and largely improved brittleness and a thermosetting resin produced by the same. <P>SOLUTION: This production method of a thermosetting resin having a dihydrobenzoxazine ring structure comprises reacting (a) a monofunctional phenol compound represented by General Formula (I): , (b) a diamine compound represented by General Formula (II) and (c) an aldehyde compound by heating them (wherein, X is an organic group having four or more carbon atoms; Y is an organic group having five or more carbon atoms; X and Y respectively may have N, O, F as a hetero atom; and two benzene rings in the both sides of Y are not bonded to the same atom in Y). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a thermosetting resin having excellent heat resistance, good electrical properties, and greatly improved brittleness, a thermosetting resin obtained thereby, a composition containing the thermosetting resin, and molding thereof The present invention relates to a body, a cured body, a cured molded body, and an electronic device including 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, JP-A-49-47378 (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 and 2).

  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.

  In response to demands for improvement in electrical characteristics, heat resistance, toughness, and flexibility, Japanese Patent Application Laid-Open No. 2005-239827 proposes a technique for dealing with fine processing (Patent Publication 2). ). However, this technique is disadvantageous in terms of hygroscopicity and electrical characteristics because there are free OH groups.

  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 moiety is bonded with a siloxane group. Has been disclosed (Patent Document 3).

  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. Further, this document discloses a long-chain aromatic diamine as one that imparts flexibility. However, depending on the compound, the polymer tends to be insoluble. Moreover, what contains groups with high polarity, such as a sulfone group, becomes disadvantageous.

Non Patent Literature 3 and Patent Literature 4 also disclose benzoxazine compounds 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. Further, Patent Document 4 does not disclose guidelines or compounds for improving heat resistance and imparting flexibility. Furthermore, Non-Patent Document 4 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.
JP 49-47378 A Japanese Patent Laid-Open No. 2005-239827 JP 2003-64180 A JP 2002-338648 A 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> "Benzoxazine Monomers and Polymers: New Phenolic Resins by Ring-Opening Polumerization," 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)

  Accordingly, an object of the present invention is to provide a method for producing a thermosetting resin having excellent heat resistance, good electrical characteristics, and greatly improved brittleness, and a thermosetting resin obtained thereby.

  Another object of the present invention is to provide a composition containing the above-mentioned thermosetting resin, a molded product, a cured product, a cured molded product, and an electronic device containing them.

  As a result of intensive studies, the present inventor achieved the above object by a method for producing a thermosetting resin using a specific aromatic diamine without using an aliphatic amine or an aromatic monoamine, from the viewpoint of improving heat resistance. I got the knowledge that I can do it. The present invention is based on such knowledge. That is, the configuration of the present invention is as follows.

1. A dihydrobenzoic acid characterized by heating a monofunctional phenol compound represented by the following general formula (I), b) a diamine compound represented by the following general formula (II), and c) an aldehyde compound. A method for producing a thermosetting resin having a sazine ring structure.

〔式中、Ｘ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。〕

[Wherein X is an organic group having 4 or more carbon atoms, and may have N, O, or F as a hetero atom. ]

〔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中の同一原子には結合しない。〕

[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 not bonded to the same atom in Y. ]

2. 2. The method for producing a thermosetting resin according to 1, wherein X is an organic group having 6 or more carbon atoms, which may have N, O, and F as a hetero atom.

3. 2. The method for producing a thermosetting resin according to 1 above, wherein X is a hydrocarbon group having 8 or more carbon atoms.

4). 2. The method for producing a thermosetting resin according to 1 above, wherein X is mainly substituted at the para position of the OH group and is a group represented by the following formula.

5. 2. The method for producing a thermosetting resin according to 1 above, wherein X is mainly substituted at the para position of the OH group and is a group represented by the following formula.

6). The manufacturing method of the thermosetting resin in any one of said 1-5 whose Y is group shown by a following formula.

7). The method for producing a thermosetting resin according to any one of 1 to 5, wherein Y contains at least one benzene ring.

8). Y is one or more groups selected from the group of the following formula, and bonded to the meta position or the para position with respect to the NH ₂ groups of the benzene ring on both sides of Y. A method for producing a thermosetting resin.

9. The method for producing a thermosetting resin according to any one of 1 to 5, wherein Y contains at least two benzene rings.

10. Y is one or more groups selected from the group of the following formula, and bonded to the meta position or the para position with respect to the NH ₂ groups of the benzene ring on both sides of Y. A method for producing a thermosetting resin.

11. d) The method for producing a thermosetting resin according to any one of 1 to 10, further comprising using a polyfunctional phenol compound.

12 12. The method for producing a thermosetting resin according to 11 above, wherein the polyfunctional phenol compound of d) is one or more selected from the group of the following formulae.

13. 12. The method for producing a thermosetting resin according to 11 above, wherein the polyfunctional phenol compound of d) is one or more selected from the group of the following formulae.

14 12. The method for producing a thermosetting resin according to 11 above, wherein the polyfunctional phenol compound of d) is represented by the following formula.

〔式中、Ｚは下記群より選択される基であり、ｎは０〜１０の整数を示す。〕

[In formula, Z is group selected from the following group, n shows the integer of 0-10. ]

15. The thermosetting resin obtained by the manufacturing method of the thermosetting resin in any one of said 1-14.

16. 16. A thermosetting composition comprising at least the thermosetting resin according to 15.

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

18. 16. A molded article obtained by subjecting the thermosetting resin according to 15 or the thermosetting composition according to 16 or 17 to partial curing or not curing as necessary.

19. 18. A cured product obtained from the thermosetting resin according to 15 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 production method capable of obtaining a thermosetting resin having excellent heat resistance, good electrical characteristics, and greatly improved brittleness, a thermosetting resin obtained by the production method, and the resin A composition comprising the same, a molded body thereof, a cured body, a cured molded body, and an electronic apparatus including the same are provided.

Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.
[Method for producing thermosetting resin]
The method for producing a thermosetting resin according to the present invention comprises: a) a monofunctional phenol compound represented by the following general formula (I); b) a diamine compound represented by the following general formula (II); and c) an aldehyde compound. It is characterized by reacting by heating. And the thermosetting resin which has a dihydrobenzoxazine ring structure can be obtained with the manufacturing method of this invention. The resulting thermosetting resin has excellent heat resistance, good electrical properties, and greatly improved brittleness.

〔式中、Ｘ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。〕

[Wherein X is an organic group having 4 or more carbon atoms, and may have N, O, or F as a hetero atom. ]

〔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中の同一原子には結合しない。〕

[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 not bonded to the same atom in Y. ]

  In the present invention, the monofunctional phenol compound represented by the general formula (I) is used as the component a). Such a monofunctional phenol compound is essential in that processability such as solubility can be secured.

  The monofunctional phenol compound of component a) used in the present invention has a large side chain molecular weight, and X in the general formula (I) has 4 or more carbon atoms, preferably 6 or more carbon atoms, more preferably 8 carbon atoms. ˜20 organic groups. In addition, when X has N, O, or F as a hetero atom, the electrical characteristics can be improved.

  X is an organic group having 6 or more carbon atoms, which may have N, O, and F as heteroatoms, particularly in terms of dielectric properties such as non-volatility at high temperatures, dielectric constant, and dielectric loss tangent. Is preferred.

  X is preferably a hydrocarbon group having 8 or more carbon atoms, particularly in terms of dielectric properties such as non-volatility at high temperatures, dielectric constant, and dielectric loss tangent.

Further, X is substituted mainly at the para position of the OH group in the benzene ring in the general formula (I) 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.

X is mainly substituted at the para-position of the OH group in the benzene ring in the general formula (I) 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.

  Specific examples of the monofunctional phenolic compound of component a) include 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 can be mentioned. These phenol compounds are used alone or in combination of two or more.

  In the present invention, the diamine compound represented by the general formula (II) is used as the component b). Such a diamine compound is particularly essential in terms of improving flexibility.

  The diamine compound as component b) used in the present invention is a long-chain aromatic diamine compound, and Y in the general formula (II) has 5 or more carbon atoms, preferably 5 to 15 carbon atoms, more preferably 5 to 5 carbon atoms. 12 organic groups. 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 stability at high temperatures, dielectric properties such as dielectric constant and dielectric loss tangent, and toughness.

  Y preferably contains at least one benzene ring from the viewpoint of stability at high temperatures, dielectric properties such as dielectric constant and dielectric loss tangent, and toughness.

Specific examples of those in which Y contains at least one benzene ring are one or more groups selected from the group of the following formulas, and are 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 it is excellent in stability at high temperatures, dielectric properties such as dielectric constant and dielectric loss tangent, and toughness.

  Further, Y preferably contains at least two benzene rings in view of excellent stability at high temperatures, dielectric properties such as dielectric constant and dielectric loss tangent, and toughness.

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 it is excellent in stability at high temperatures, dielectric properties such as dielectric constant and dielectric loss tangent, and toughness.

  Specific examples of the diamine compound as the component b) 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- (4-aminophenoxy) phenyl] propane, bis [(4-aminophenoxy) phenyl] biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [3- (3-aminophenoxy) phenyl] ether, bis [3- ( 4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophen) Noxy) phenyl] ether, 4,4 ′-[1,4-phenylenebis (1-methyl-ethylidene)] bisphenol (Bisphenol P, Mitsui Chemicals, “α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene ”), 4,4 ′-[1,3-phenylenebis (1-methyl-ethylidene)] bisphenol (Mitsui Chemicals bisphenol M), and the like. These diamine compounds are used singly or in combination.

  The aldehyde compound of the component c) used in the present invention is not particularly limited, but formaldehyde is preferable, and the formaldehyde includes paraformaldehyde as a polymer thereof, formalin in the form of an aqueous solution, and the like. Can be used. The reaction proceeds more slowly when paraformaldehyde is used. As other aldehyde compounds, acetaldehyde, propionaldehyde, butyraldehyde and the like can also be used.

  In the production method of the present invention, it is preferable to further use a polyfunctional phenol compound as the component d) together with the components a) to c) described above. When the polyfunctional phenol compound as component d) is used, the stability at high temperatures and the mechanical strength can be further improved.

  The polyfunctional phenolic compound d) is selected from the group of the following formulas, particularly in terms of availability, reactivity, and mechanical, thermal and electrical properties of the cured product obtained by curing the obtained compound. One or more are preferred.

  The polyfunctional phenolic compound d) is selected from the group of the following formulas, particularly in terms of availability, reactivity, and mechanical, thermal and electrical properties of the cured product obtained by curing the obtained compound. It is preferable that it is one or more.

  In addition, the polyfunctional phenol compound of d) is represented by the following formula, particularly in terms of availability, reactivity, and mechanical, thermal and electrical properties of a cured product obtained by curing the obtained compound. Is also preferable.

〔式中、Ｚは下記群より選択される基であり、ｎは０〜１０、好ましくは０〜５ の整数を示す。〕

[In the formula, Z is a group selected from the following group, and n is 0 to 10, preferably 0 to 5. Indicates an integer. ]

  Specific examples of such polyfunctional phenolic compounds as component d) include 4,4′-dihydroxydiphenylmethane (bisphenol F), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2- Bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 9,9-bis (4-hydroxyphenyl) fluorene, 4,4 ′-[1,4 -Phenylenebis (1-methyl-ethylidene)] bisphenol (Bisphenol P manufactured by Mitsui Chemicals, sold under the compound name "α, α'-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene" by Tokyo Chemical Industry) 4,4 ′-[1,3-phenylenebis (1-methyl-ethylidene)] bisphenol ( Well Kagaku bisphenol M), xylylene novolac type phenolic resin, biphenyl novolak type phenolic resin, and the like. These polyfunctional phenol compounds are used alone or in combination of two or more. However, when using a phenolic resin such as a xylylene novolac type phenolic resin or a biphenyl novolac type phenolic resin, since there are often two or more reaction points on the phenolic resin side, the mixing ratio with the monofunctional phenolic compound, Alternatively, it is preferable to prevent the molecular weight from becoming too large and insolubilizing by considering the stoichiometric ratio of the phenol resin and the diamine compound.

  In the production method of the present invention, for example, the components a), b) and c) and, if necessary, the component d) can be reacted by heating in an appropriate solvent.

  Although the solvent used here is not particularly limited, a solvent having a high degree of polymerization is more easily obtained when the raw material phenol compound or diamine compound and the product polymer are more soluble. 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.

  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.

〔式中、ＸおよびＹは、式（I）および式（II）におけるＸおよびＹと同一である。〕

ただし、多官能フェノール化合物を併用した場合には上記の限りではない。 [Thermosetting resin]
The thermosetting resin of the present invention is obtained by the above-described method for producing a thermosetting resin. The thermosetting resin of the present invention is represented by the following general formula.

[Wherein, X and Y are the same as X and Y in formula (I) and formula (II). ]

However, this is not the case when a polyfunctional phenol compound is used in combination.

  The thermosetting resin of the present invention has particularly excellent heat resistance, good electrical properties, and greatly improved brittleness, but also has excellent water resistance, chemical resistance, mechanical strength, reliability, etc. It is a resin that has various advantages such as volatile by-products during curing and cost, has excellent storage stability, and has a wide degree of freedom in molecular design. It 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 partially curing the thermosetting resin described above or a thermosetting composition containing the same as necessary, or without curing. 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 in the polymer structure, so that excellent dielectric properties can be realized. .

  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 body of the present invention can be suitably used for applications such as electronic parts / electronic devices and materials thereof, multilayer boards, laminates, sealants, adhesives and the like that are particularly required to have excellent dielectric properties.
Here, specific examples of the electronic device include a mobile phone, a display device, an in-vehicle device, a computer, and a communication device.
In addition, it can be used for applications such as aircraft 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, 21-66 g (0.1 mol) of 4-α-cumylphenol (Tokyo Chemical Industry, 98%), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (manufactured by Tokyo Chemical Industry, 98%) 20.94 g (0.05 mol) and 6.71 g (0.21 mol) of paraformaldehyde (94% 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 the product. Thereafter, the product was separated by filtration and washed with methanol. Then, the thermosetting resin which has a benzoxazine compound of the following structure as a main component was obtained by drying under reduced pressure.

The thermosetting resin obtained in Example 1 was molded into a sheet shape by a hot press method and held at 180 ° C. for 1 hour to obtain a 0.5 mmt sheet-shaped 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 characteristics in both dielectric constant and dielectric loss tangent.
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 375 ° C.

  Example 1 is the same as Example 1 except that 25.26 g (0.12 mol) of 4- (1,1,3,3-tetramethylbutyl) phenol was used instead of 4-α-cumylphenol. A thermosetting resin was synthesized in the same manner.

  The obtained thermosetting resin was evaluated in the same manner as in Example 2. The results are shown in Table 2.

The present invention relates to a method for producing a thermosetting resin having excellent heat resistance, good electrical properties, and greatly improved brittleness, a thermosetting resin obtained thereby, a composition containing the thermosetting resin, and molding thereof The present invention has industrial applicability as a body, a cured body, a cured molded body, and an electronic device including them.

Claims (21)

A dihydrobenzoic acid characterized by heating a monofunctional phenol compound represented by the following general formula (I), b) a diamine compound represented by the following general formula (II), and c) an aldehyde compound. A method for producing a thermosetting resin having a sazine ring structure.

[Wherein X is an organic group having 4 or more carbon atoms, and may have N, O, or F as a hetero atom. ]

[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 not bonded to the same atom in Y. ]   The method for producing a thermosetting resin according to claim 1, wherein X is an organic group having 6 or more carbon atoms which may have N, O, and F as heteroatoms.   The method for producing a thermosetting resin according to claim 1, wherein X is a hydrocarbon group having 8 or more carbon atoms. The method for producing a thermosetting resin according to claim 1, wherein X is mainly substituted at the para-position of the OH group and is a group represented by the following formula.

The method for producing a thermosetting resin according to claim 1, wherein X is mainly substituted at the para-position of the OH group and is a group represented by the following formula.

The manufacturing method of the thermosetting resin in any one of Claims 1-5 whose Y is group shown by a following formula.

  The method for producing a thermosetting resin according to claim 1, wherein Y contains at least one benzene ring. 6. Y is one or more groups selected from the group of the following formula, and is bonded to a meta position or a para position with respect to NH ₂ groups of benzene rings on both sides of Y. Of manufacturing thermosetting resin.

  The method for producing a thermosetting resin according to any one of claims 1 to 5, wherein Y contains at least two benzene rings. 6. Y is one or more groups selected from the group of the following formula, and is bonded to a meta position or a para position with respect to NH ₂ groups of benzene rings on both sides of Y. Of manufacturing thermosetting resin.

  The method for producing a thermosetting resin according to claim 1, further comprising d) a polyfunctional phenol compound. The manufacturing method of the thermosetting resin of Claim 11 whose polyfunctional phenolic compound of d) is one or more selected from the group of a following formula.

The manufacturing method of the thermosetting resin of Claim 11 whose polyfunctional phenolic compound of d) is one or more selected from the group of a following formula.

The method for producing a thermosetting resin according to claim 11, wherein the polyfunctional phenol compound of d) is represented by the following formula.

[In formula, Z is group selected from the following group, n shows the integer of 0-10. ]

  The thermosetting resin obtained by the manufacturing method of the thermosetting resin in any one of Claims 1-14.   A thermosetting composition comprising at least the thermosetting resin according to claim 15.   The thermosetting composition according to claim 16, comprising a compound having at least one dihydrobenzoxazine structure in the molecule.   A molded product obtained by partially curing the thermosetting resin according to claim 15 or the thermosetting composition according to claim 16 or 17 as necessary, or without curing.   A cured product obtained from the thermosetting resin according to claim 15 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.