KR20180003007A - Benzoxazine compound and the usage thereof - Google Patents

Abstract

The present invention relates to a benzoxazine compound and a use thereof, and more particularly, to a benzoxazine compound which can be applied to a sealing material, a molding material, a mold material, an adhesive, an insulating coating material, and the like used for a copper-clad laminate or an electronic part of a printed circuit board with excellent dielectric properties, heat resistance, and flame retardancy by including a benzoxazine ring inside a molecular structure. The present invention also relates to a use of a cured product of the benzoxazine compound.

Description

≪ / RTI > Benzoxazine compounds and the use thereof,

The present invention relates to a benzoxazine-based compound having excellent heat resistance and electrical properties, and its use.

BACKGROUND ART Conventionally, thermosetting resins such as phenol resin, melamine resin, epoxy resin, unsaturated polyester resin and bismaleimide resin are based on the property of thermosetting property and are excellent in water resistance, chemical resistance, heat resistance, mechanical strength, Is widely used in the field.

However, phenol resins and melamine resins have the drawback that volatile by-products are generated during curing, the epoxy resin and unsaturated polyester resin are poor in flame retardancy, and the bismaleimide resin is very expensive.

In order to solve these drawbacks, there has been studied a polybenzoxazine which thermally cures without generation of volatile components.

The benz photo has a complex structure of a benzene ring and a oxazine ring. In a thermosetting resin having a benzoxazine ring in its molecular structure, the oxazine ring is converted by heating, and polymerization proceeds without generation of by-products. The polybenzoxazines containing the benz photo are attracting attention as thermosetting resins for use in sealing materials, impregnation, laminated plates, adhesives, paints, coating materials, friction materials, FRP and molding materials.

These polybenzoxazines are known as cured polymers with well-balanced mechanical, electrical and chemical properties including high glass transition temperature (Tg), low dielectric constant, high tensile strength, low coefficient of thermal expansion, excellent stretchability and low hygroscopicity On the other hand, it has the disadvantage of hardening at relatively high temperature or slow curing.

The use of various curing agents such as phenol (JP 2000-178332A), amine (JP 2000-86863A), and phosphine (JP 2003-82099A) has been reported to lower the curing temperature of polybenzoxazines, Alternative curing agents based on ligand complexes have also been reported. WO2008 / 0348142 A2 discloses several modified acetylacetonate metal complexes as catalyst / curing agents for low temperature curing of benzylphoto-containing compositions.

However, some of the curing agents mentioned above are highly reactive and may even result in partial polymerization of the polybenzoxazines at temperatures below 25 DEG C, and further that some of the curing agents mentioned above may be added to the thermal stability of the polybenzoxazines, Lt; RTI ID = 0.0 > thermally < / RTI > As a result, there is a problem that undesired weight loss is caused, in particular during the polymerization / curing reaction of the polybenzoxazines.

Accordingly, there is a demand for a novel polybenzoxazine compound which exhibits high heat stability and low dielectric properties at a low temperature without using a curing agent while maintaining excellent physical properties of polybenzoxazines.

JP 2000-178332 A (Jun. 27, 2000), a thermosetting resin composition JP2000-086863 A (Mar. 23, 2000), thermosetting resin composition JP 2003-082099 (Mar. 19, 2003), a thermosetting resin composition WO2008 / 0348142 (2012.12.27), Benzoxazine-containing compositions

Accordingly, the inventors of the present invention have made continuous research to produce a benzoxazine-based compound having a novel structure, and when it is cured after polymerization, it is confirmed that it has excellent dielectric, heat resistance and flame retardancy.

Accordingly, an object of the present invention is to provide a benzoxazine-based compound having a novel structure and a process for producing the same.

Still another object of the present invention is to provide a use of the cured polybenzoxazine cured product of the benzoxazine-based compound.

In order to achieve the above object, the present invention provides a benzoxazine-based compound represented by the following formula (1)

[Chemical Formula 1]

(Wherein R ₁ to R ₄ are as described in the specification)

The present invention also provides a process for producing a polyfunctional phenolic compound, comprising: (a) mixing a polyfunctional phenolic compound and a monoamine compound; And (b) adding an aldehyde compound to the mixture to react. The present invention also provides a process for producing a benzoxazine-based compound represented by the formula (1).

The polyfunctional phenol compound is prepared by reacting a phenolic compound with a glyoxal, and a phenol compound is further reacted with the compound obtained by the reaction.

The present invention also provides a thermosetting resin composition comprising the benzoxazine-based compound represented by the above formula (1).

The present invention also provides a cured product comprising the cured polybenzoxazepine compound represented by the formula (1).

When the benzoxazine-based compound of the present invention is cured, it is possible to produce a cured product having excellent dielectric constant, heat resistance and flame retardancy.

The polybenzoxazine cured product is excellent in heat resistance and electrical properties while satisfying physical properties required for a copper clad laminate used for a printed circuit board or a sealing material used for electronic parts, a molding material, a mold material, an adhesive, There is an advantage.

1 is a ¹ H-NMR spectrum of the benzoxazine-based compound prepared in Example 1. Fig.
2 is a ¹ H-NMR spectrum of the benzoxazine-based compound prepared in Example 2. Fig.

The present invention relates to a benzoxazine-based compound having a novel structure applicable to various fields, a process for producing the same, and a polybenzoxazine cured product wherein the benzoxazine-based compound is cured.

Benz photo-based compound

The benzoxazine-based compounds proposed in the present invention are represented by the following formula (1)

(In the formula 1,

이고, R₂는 OH 또는

이고, R₃는 OH 또는

이며, R₄는 OH 또는

이고, 이때 R₁ 내지 R₄ 모두가 OH가 아니며, R ₁ is OH or

, R < ₂ > is OH or

, R < ₃ > is OH or

, R < ₄ > is OH or

, Wherein all of R &_lt; ₁ > to R &_lt; ₄ > are not OH,

Wherein R ₅ , R ₇ , R ₉ and R ₁₁ are the same or different and each independently represents a C 1 to C 20 alkyl group, a C 3 to C 20 cycloalkyl group, an allyl group, a C 3 to C 20 alkenyl group, C6-C20 aryl group, C7-C20 ara alkyl group, wherein the functional group is substituted or unsubstituted with halogen,

Wherein R _6, R _8, R ₁₀ and R ₁₂ are different from or equal to each other, and each independently represents H, a halogen atom, a carboxyl group, an alkyl group of C1~C20, a cycloalkyl group of C3~C20, an alkenyl group of C2~C20, C2~ C20 alkoxy group, C6-C20 aryl group, C7-C20 arylalkyl group, or allyl group, wherein the aryl group includes a fused ring,

로 치환되고, 이때 m은 0 내지 16의 정수이다.)When at least one of R ₁ to R ₄ is a benzylphosphine ring, at least one of the phenyl rings in the benzylphosphine ring is

, Wherein m is an integer from 0 to 16. < RTI ID = 0.0 >

As used herein, the term " halogen element " means F, Cl, Br, or I.

The term "alkyl group" as used herein includes a linear or branched alkyl group and includes, for example, methyl, ethyl, propyl, 2-propyl, n-butyl, iso-butyl, tert- butyl, pentyl, And when it is further substituted with a halogen element, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, iodomethyl, bromomethyl and the like can be given. Wherein the alkenyl group is an alkyl group containing a double bond in the molecular structure and the alkynyl group is an alkyl group containing a triple bond.

The cycloalkyl groups referred to herein include monocyclic, bicyclic or tricyclic, and include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl , Decahydronaphthalenyl, adamantyl, norbonyl (i.e., bicyclo [2,2,1] hept-5-enyl) and the like.

The alkoxy group referred to in the present specification includes a hydroxyl group (OH) group in the molecular structure, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy, And when it is further substituted by halogen, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chloromethoxy, dichloromethoxy, trichloromethoxy, iodomethoxy, bromomethoxy and the like.

The "aryl group" and "arylene group" referred to in the present specification each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or a multicyclic aromatic group, and neighboring substituents include aromatic rings formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a fluorene group, a spirobifluorene group, or a spirobifluorene group.

Wherein the prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, the arylalkyl group is an alkyl group substituted with an aryl group, the arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the carbon number described in the present specification.

R ₆ , R ₈ , R ₁₀ and R ₁₂ may be substituted with one or more hydrogen atoms in the phenyl ring. When two or more of them are substituted, they may be substituted with the same functional group or may be substituted with different functional groups. For example, dimethyl group, methyl group / bromine, and the like.

In the present specification, all the compounds or substituents may be substituted or unsubstituted unless otherwise specified. The term "substituted" as used herein means that hydrogen is substituted with at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amino group, a thio group, a methylthio group, an alkoxy group, a nitryl group, an aldehyde group, Which is selected from the group consisting of a carbonyl group, an acetal group, a ketone group, an alkyl group, a perfluoroalkyl group, a cycloalkyl group, a heterocycloalkyl group, an allyl group, a benzyl group, an aryl group, a heteroaryl group, It means that one has been replaced.

Preferably, the benzoxazine-based compound represented by Formula 1 is a diphenol-based benzoxazine compound represented by Formula 2, a triphenol-based benzoxazine compound represented by Formula 3, a tetraphenol-based benzoxazine compound represented by Formula 4, and a tetraphenol- May be in the form of a benzoxazine oligomer, and most preferably a tetraphenol-based benzoxazine compound of formula (4).

(In the above Chemical Formulas 2 to 5, R ₅ to R ₁₂ are as defined in Chemical Formula 1, and n is an integer of 1 to 14)

Preferably, R ₅ , R ₇ , R ₉ and R ₁₁ in Formula 1 are H, a C ₁ to C ₁₂ alkyl group, a C 2 to C 12 alkenyl group, a C 1 to C 12 alkoxy group, a C 4 to C 10 cycloalkyl group, An aryl group or an allyl group and more preferably a methyl group, an ethyl group, a butyl group, a propenyl group, a cyclohexyl group, a phenyl group, a naphthyl group, an allyl group, a fluorene group or a fluorobenzyl group.

In Formula 1, R ₆ , R ₈ , R ₁₀ and R ₁₂ may be H, Br, Cl, a C1 to C12 alkyl group, a C1 to C12 alkoxy group, a C6 to C12 aryl group, More preferred examples thereof include H, a methyl group, an ethyl group, a propyl group, a t-butyl group, a hexyl group, an octyl group, an octadecyl group, a dodecyl group, a cumyl group, a phenyl group, a fused phenyl group, a methoxy group, Allyl group.

n is an index related to the tetraphenol-based benzoxazine oligomer, wherein n is 1, a tetraphenol-based benzotrophic dimer, 2 is a tetraphenol-based benzotrophic trimer, and n is 3, Phenol-based benzoxazole tetramers, and further higher order oligomers. Preferably, n is an integer of 1 to 15, more preferably an integer of 1 to 10, most preferably an integer of 1 to 4.

More preferably, the compounds of formula (1) presented in the present invention are represented by the following formulas (6) and (7):

(1) Compound of formula 6: 1,1,2,2-tetrakis (3-allyl-3,4-dihydro-2H-benzo [e] [1,3] 1,1,2,2-tetrakis (3-allyl-3,4-dihydro-2H-benzo [e] [1,3] oxazin- 6- yl)

(2) Compound of formula 7: 6- (1,2-bis (3-allyl-3,4-dihydro-2H- benzo [e] [1,3] oxazin- Dihydro-3-phenyl-2H-benzo [e] [1,3] oxazin-6-yl) 1,3] oxazine (6- (1,2-bis (3-allyl-3,4-dihydro-2H-benzo [e] [1,3] oxazin- 2H-benzo [e] [1,3] oxazin-6-yl) ethyl] -3,4-dihydro-3-phenyl-2H-

The benzoxazine-based compounds represented by formula (1) according to the present invention can be applied to various fields. For example, by applying alkylphenol and fatty acid amine compounds, it is possible to increase the free volume inside the structure of the benzoxazine, It is possible to obtain an effect of improving the heat resistance at the same time.

Method for preparing benzoxazine-based compounds

The benzoxazine-based compounds of formula (I)

(a) mixing a polyfunctional phenolic compound and a monoamine compound; And

(b) adding an aldehyde compound to the obtained mixture and reacting the mixture.

Each step will be described in detail below.

(Step a) Mixing step of polyfunctional phenolic compound and monoamine compound

First, in step a, a polyfunctional phenolic compound and a monoamine compound are prepared.

The polyfunctional phenol compound used as the reactant in the above reaction may be prepared by reacting a phenol compound with glyoxal as a starting material and then reacting the obtained reaction product with the phenol compound several times to obtain a triphenol compound , Tetraphenol-based compounds, and tetraphenol-based oligomers.

Examples of the phenolic compound include phenol, o-cresol, p-cresol, m-cresol, p-tert-butylphenol, p-octylphenol, p-cumylphenol, dodecylphenol, Phenol, 1-naphthol, 2-naphthol, m-methoxyphenol, p-methoxyphenol, m-ethoxyphenol, xylenol, 2-bromo-4-methylphenol, This is possible.

More specifically, the polyfunctional phenolic compound according to the present invention is prepared by reacting a phenolic compound with glyoxal to prepare a hydroxyalkylphenol, followed by a reaction with a continuous phenol or a condensation reaction.

Specifically, as shown in Reaction Scheme 1, 4- (1,2,2-trihydroxyethyl) phenol, which is a hydroxyalkylphenol, is reacted with phenol and glyoxal, ).

[Reaction Scheme 1]

Next, for the production of a polyfunctional phenolic compound, a diphenolic compound is prepared by further reacting with phenol as shown in the following reaction formula (2).

[Reaction Scheme 2]

In order to prepare a triphenol compound with a polyfunctional phenol compound, the diphenol compound obtained through the above reaction scheme 2 is further reacted with phenol as shown in the following Reaction Scheme 3.

[Reaction Scheme 3]

Further, in order to prepare a tetraphenol-based compound, the triphenol-based compound is reacted with phenol again as shown in Reaction Scheme 4 below.

 [Reaction Scheme 4]

In addition, the tetraphenolic oligomer is prepared by a condensation reaction of a tetraphenolic compound or a condensation reaction with a hydroxyalkylphenol, as shown in the following reaction formula (5).

[Reaction Scheme 5]

As shown in the above Reaction Schemes 2 to 5, the polyfunctional phenolic compound can be prepared by an additional reaction of phenol.

(Iii) a triphenol compound, (iv) a tetraphenol compound, and (v) a tetraphenolic oligomer, which are prepared through the above Reaction Schemes 2 to 5, . A monoamine compound and an aldehyde compound are reacted with the phenol groups of the above (ii) to (v) to form an oxazine ring, and benzoxazine compounds having various structures can be prepared according to the number of phenol groups.

The reaction of each of the above steps is carried out in the presence of an acid catalyst. The acid usable is not limited to the present invention, and any known acid catalyst can be used. Typically, the acid catalyst includes sulfuric acid, nitric acid, hydrochloric acid, acetic acid, para-toluene sulfonic acid, methylsulfonic acid, boron trifluoride, aluminum chloride chloride, and sulfuric acid, preferably sulfuric acid.

Also, the reaction of each step is carried out at 70 to 90 ° C for 1 to 5 hours, and a vacuum degassing process is performed to remove unreacted substances after the reaction.

The phenolic compound containing the above-mentioned (ii) diphenol compound, (iii) triphenol compound, (iv) tetraphenol compound and (v) tetraphenol oligomer is mixed with a monoamine compound.

The monoamine compound may be any compound capable of satisfying the definition of the formula (1). For example, it is selected from among ethanolamine, allylamine, methylamine, ethylamine, propylamine, butylamine, isopropylamine, hexylamine, octadecylamine, cyclohexylamine, 2-aminofluorene and aniline, It is preferable to select allylamine and aniline in terms of reactivity and ease of production.

The reaction is carried out by adding a monoamine compound to a phenol compound at a molar ratio of 2 to 8 mol of a monoamine compound to 1 mol of the polyfunctional phenol compound to effect a stable reaction, Can also be used.

(b) Step of reacting with aldehyde compound

An aldehyde compound is added to the mixture obtained in (a) and reacted to prepare a benzoxazine-based compound represented by the formula (1).

The aldehyde-based compound includes formaldehyde, acetaldehyde, propionaldehyde, butylaldehyde, paraformaldehyde, polyoxymethylene, and the like. It is preferable to use formaldehyde and paraformaldehyde in terms of reactivity and economy. Preferably, a 40% formaldehyde aqueous solution is slowly added over a period of 30 minutes to 120 minutes.

At this time, the aldehyde compound is added in a molar ratio of 6 to 18 mol, preferably 8 to 16 mol, to 1 mol of the polyfunctional phenol compound in the step (a). If the content of the aldehyde compound to be used is less than the above-mentioned molar ratio, sufficient reaction with the monoamine compound can not be induced, so that the jade photoling is not formed and the heat resistance is deteriorated. On the other hand, Thereby deteriorating thermal properties, electrical properties and dimensional stability.

Examples of the solvent used in the reaction include aromatic hydrocarbon solvents such as toluene, xylene and trimethylbenzene; Halogen-based solvents such as chloroform, dichloroform and dichloromethane; Ether solvents such as THF and dioxane, and the like can be used. In this case, the content of the solvent is preferably 25 to 100 parts by weight based on 100 parts by weight of the total content of the polyfunctional phenol compound, the monoamine compound and the aldehyde compound.

When the content of the solvent is too small, the viscosity of the reactant is increased to increase the stirring stress, resulting in poor workability. If the content of the solvent is excessively large, the cost of removing the solvent after the reaction is increased, . In addition, if the selection and mixing of the appropriate solvent is not properly performed, the yield may be lowered because the raw materials can not participate in the reaction.

The reaction in step (b) is carried out with stirring for 30 minutes to 120 minutes while maintaining the temperature between 40 and 80 ° C, preferably between 55 and 65 ° C. When the reaction is carried out under the above-mentioned conditions, there is an effect that the Ring Closed reaction (formation of the jade photographic image) can be efficiently conducted.

The benzoxazine-based compound prepared by applying the phenol-based compound and the monoamine-based compound can increase the free volume inside the structure of the benzoxazine, thereby improving the low-dielectric property and improving the heat resistance .

Polybenzoxazine cured products and uses thereof

The benzoxazine-based compounds of formula (I) according to the present invention are capable of producing polybenzoxazine-cured products through a curing reaction.

The curing is carried out by ring-opening the oxazine ring of formula (1) to form a cured product. Here, the term cured product does not mean only self-cured products of the polybenzoxazolides but may also include cured products obtained by mixing other resin compositions other than the polybenzoxazine precursor resin.

The curing process may be performed by thermal curing. For example, the range of 150 to 250 ° C is preferable, and the range of 190 to 220 ° C is more preferable. If the temperature is lower than 150 ° C., the curing time may be excessively long. If the temperature is higher than 250 ° C., oxidation of the impurities may be excessively induced or excess energy may be consumed during the process. Particularly, in the range of 190 to 220 캜, it is more preferable in view of process time, energy efficiency and the like.

The polybenzoxazine cured product prepared by the above-described method has a dielectric constant of 2.7 and a dielectric constant of less than 0.01 (Df (dissipation factor)) to maintain excellent heat resistance And can be effectively used for a sealing material, a molding material, a mold material, an adhesive, and an electric insulating paint material used for a copper-clad laminate or an electronic part used for a printed circuit board due to such characteristics.

At this time, the benzoxazine-based compound of Chemical Formula 1 is prepared in the form of a thermosetting resin composition containing the same, and the resin composition may further include various resins and additives suitable for each use.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments.

[Example]

Example 1 Synthesis of 1,1,2,2-tetrakis (3-allyl-3,4-dihydro-2H-benzo [e] [1,3] , 2,2-tetrakis (3-allyl-3,4-dihydro-2H-benzo [e] [1,3] oxazin-6-yl)

A benzoxazine-based compound represented by the following formula (6) was prepared.

[Chemical Formula 6]

A nitrogen-purged 3 L three-necked flask was charged with 840 g (8.1 mol, Sigma) of 1,1,2,2-tetrakis (p-hydroxyphenyl) ethane Manufactured by Aldrich Co., purity of 90% or more) was dissolved with 1160.4 g of toluene and 438.87 g (7.68 mol) of allylamine.

1154.25 g (15.3 mol) of 40% formaldehyde aqueous solution was then added while maintaining the temperature in the flask at 55 占 폚. The reaction solution was heated to 100 DEG C and azeotropic distillation was carried out. After dehydration was completed, vacuum deaeration was performed to completely remove the used reaction solvent.

The compound was washed with 0.1 N NaOH aqueous solution to remove the water phase portion, and the oil phase portion was taken. And crystallization of the oil phase gave the title compound.

The obtained benzoxazine had a molecular weight (Mw) of 722 g / mol as determined by GPC and its structure was confirmed using nuclear magnetic resonance analysis (NMR, Spectrum 100 of Perkin Elmer).

<Example 2> Preparation of 6- (1,2-bis (3-allyl-3,4-dihydro -2H- benzo [e] [1,3] oxazin-6-yl) -2- (3,4 Benzo [e] [1,3] oxazin-6-yl) ethyl) -3,4-dihydro-3-phenyl- 3-allyl-3,4-dihydro-2H-benzo [e] [1,3] oxazin-6-yl) -2- (3,4- Preparation of 3-phenyl-2H-benzo [e] [1,3] oxazin-6-yl) ethyl) -3,4-dihydro-3-phenyl-2H-

A benzoxazine-based compound represented by the following formula (7) was prepared.

(7)

A 3 L three-necked flask purged with nitrogen was charged with 1,1,2,2-tetrakis (p-hydroxyphenyl) ethane (product of Sigma-Aldrich) ) Was dissolved in 1124.4 g of toluene, 182.7 g (3.2 mol) of allylamine and 298.0 g (3.2 mol) of aniline. 966.98 g (12.88 mol) of a 40% formaldehyde aqueous solution was then added while maintaining the temperature in the flask at 55 占 폚.

The reaction solution was heated to 100 DEG C and azeotropic distillation was carried out. After dehydration was completed, vacuum deaeration was performed to completely remove the used reaction solvent.

The compound was washed with 0.1 N NaOH aqueous solution to remove the water phase portion, and the oil phase portion was taken. And crystallization of the oil phase gave the title compound.

The obtained benzoxazine had a molecular weight (Mw) of 794 g / mol as determined by GPC and its structure was confirmed using nuclear magnetic resonance analysis (NMR, Spectrum 100 of Perkin Elmer), and is shown in FIG.

&Lt; Comparative Example 1 >

484.2 g of toluene was added to a 3 L three-necked flask purged with nitrogen, to which 652.71 g (2.0 mol) of aniline and 800 g (1 mol) of bisphenol A were added. When the addition was completed, the semi-applied solution was heated to 100 ° C at a rate of 1.3 ° C / min and stirred for 5 hours. Thereafter, the temperature was raised to 120 ° C, and the solvent was completely removed under a pressure of 10 torr for 60 minutes to prepare 1500 g of a benzoquinone having a weight average molecular weight of 698 g / mol. The obtained benzoxazine contained 54.26% by weight of the benzoximonomer represented by the following general formula (8), and the yield was 92% (based on theoretical yield according to the equivalent ratio of the reaction solution).

&Lt; Comparative Example 2 > Preparation of benzoxazine-based compound

To a 3 L three-necked flask purged with nitrogen, 514.7 g of toluene was added, 744.18 g (2.0 mol) of aniline (2.0 mol) and 800 g (1 mol) of bisphenol F were added. When the addition was completed, the reaction solution was heated to 100 ° C at a temperature raising rate of 1.3 ° C / min and stirred for 5 hours. Thereafter, the temperature was raised to 120 ° C, and the solvent was completely removed under a pressure of 10 torr for 60 minutes to prepare 945 g of a benzoquinone having a weight average molecular weight of 1240 g / mol. The benzoxazine thus obtained had 22.58% by weight of the benzoximonomer represented by the following formula (9), and the yield was 93% (based on the theoretical yield according to the equivalent ratio of the reaction solution).

<Experimental Example 1>

The benzoxazine-based compounds obtained in the above Examples and Comparative Examples were impregnated with glass fibers, naturally dried at room temperature for 1 hour, and then dried in an oven at 155 ° C for 5 minutes to prepare a prepreg.

Of a copper foil (1 once) before and after the prepared prepreg ply and 8, was prepared by pressing at 195 ℃ 120 minutes under 40 kgf / cm ² pressure.

&Lt; Property evaluation method &

(1) Glass transition temperature (캜) measurement

The copper clad laminate thus prepared was cut into 5 cm x 1 cm pieces by DMA (Dynamic Mechanical Analysis) and measured at a heating rate of 3 ° C per minute from 30 ° C to 350 ° C using a TA Instruments DMA Q800 .

(2) Measurement of dielectric constant

The dielectric constant (Dk) and dielectric tangent (Df) of the copper clad laminate were measured under the following conditions using an Agilent impedance analyzer (Agilent E4991A 1 MHz to 3GHz).

Measuring frequency: 1GHz

Measuring temperature: 25-27 ℃

Measured humidity: 45 to 55%

Measurement sample: thickness 1.5 mm (1.3-1.7 mm)

(3) Measurement of weight average molecular weight (Mw)

The weight average molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC) (Waters: Waters 707). The polymer to be measured was dissolved in tetrahydrofuran so as to have a concentration of 4000 ppm and 100 μl was injected into GPC. The mobile phase of GPC was run at a flow rate of 1.0 mL / min using tetrahydrofuran and the assay was performed at 35 &lt; 0 &gt; C. The column was connected in series with four Waters HR-05, 1, 2, and 4E. Detector was measured at 35 ℃ using RI and PAD Detector.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Tg (占 폚) > 300 291 198.7 195.9 Dk 2.46 2.57 3.00 3.45 Df 0.004 0.004 0.01 0.015 Mw (g / mol) 722 794 698 1240

As can be seen from the above results, when the benzoxazine-based compound of the present invention is used, the Tg is at least 290 ° C or more, which is high enough to ensure heat resistance and low dielectric properties.

Claims (11)

A benzoxazine-based compound represented by the following formula (1):
[Chemical Formula 1]

(In the formula 1,
R ₁ is OH or

, R &lt; ₂ &gt; is OH or

, R &lt; ₃ &gt; is OH or

, R &lt; ₄ &gt; is OH or

, Wherein all of R &_lt; ₁ &gt; to R &_lt; ₄ &gt; are not OH,
Wherein R ₅ , R ₇ , R ₉ and R ₁₁ are the same or different and each independently represents a C 1 to C 20 alkyl group, a C 3 to C 20 cycloalkyl group, an allyl group, a C 3 to C 20 alkenyl group, a C 3 to C 20 alkynyl group , A C6-C20 aryl group, a C7-C20 ara alkyl group, wherein the functional group is substituted or unsubstituted with halogen,
Wherein R _6, R _8, R ₁₀ and R ₁₂ are different from or equal to each other, and each independently represents H, a halogen atom, a carboxyl group, an alkyl group of C1~C20, a cycloalkyl group of C3~C20, an alkenyl group of C2~C20, C2~ C20 alkoxy group, C6-C20 aryl group, C7-C20 arylalkyl group, or allyl group, wherein the aryl group includes a fused ring,
When at least one of R ₁ to R ₄ is a benzylphosphine ring, at least one of the phenyl rings in the benzylphosphine ring is

, Wherein m is an integer from 0 to 16. &lt; RTI ID = 0.0 &gt; The method according to claim 1,
The benzoxazine-based compound of Formula 1 is represented by the following Formula 2 to 5:
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

(In the above Chemical Formulas 2 to 5, R ₅ to R ₁₂ are as defined in Chemical Formula 1, and n is an integer of 1 to 14) 3. The method according to claim 1 or 2,
Wherein R ₅ , R ₇ , R ₉ and R ₁₁ are independently selected from the group consisting of H, a C ₁ to C ₁₂ alkyl group, a C 2 to C 12 alkenyl group, a C 1 to C 12 alkoxy group, a C 4 to C 10 cycloalkyl group, a C 6 to C 12 aryl group, Or an allyl group,
Wherein R ₆ , R ₈ , R ₁₀ and R ₁₂ are H, Br, Cl, a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkoxy group, a C 6 to C 12 aryl group,
and n is an integer of 1 to 10. The method according to claim 1,
Wherein the compound of Formula 1 is represented by the following Formula 6 or 7:
[Chemical Formula 6]

(7)

(a) mixing a polyfunctional phenolic compound and a monoamine compound; And
(b) adding an aldehyde-based compound to the resulting mixture and reacting the resulting mixture with the aldehyde-based compound to prepare a benzoxazine-based compound represented by the general formula (1). 6. The method of claim 5,
Wherein the polyfunctional phenol compound is prepared by reacting a phenolic compound with glyoxal to prepare a hydroxyalkylphenol and then reacting or condensing the phenolic compound with a continuous phenol compound to prepare a benzoxazine compound . The method according to claim 6,
Wherein the phenolic compound is at least one selected from the group consisting of phenol, o-cresol, p-cresol, m-cresol, p-tert-butylphenol, p-octylphenol, p-cumylphenol, dodecylphenol, , 1-naphthol, 2-naphthol, m-methoxyphenol, p-methoxyphenol, m-ethoxyphenol, xylenol, 2-bromo-4-methylphenol, 2-allylphenol and xylenol Wherein the benzoxazine compound is at least one selected from the group consisting of benzoxazine-based compounds and benzoxazine-based compounds. 6. The method of claim 5,
The monoamine compound is selected from the group consisting of ethanolamine, allylamine, methylamine, ethylamine, propylamine, butylamine, isoprenamine, hexylamine, octadecylamine, cyclohexylamine, 2-aminofluorene and aniline Wherein the at least one benzyl group is at least one kind selected from the group consisting of benzyl group and benzyl group. 6. The method of claim 5,
Wherein the aldehyde-based compound is at least one selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, and butylaldehyde. A thermosetting resin composition comprising the benzoxazine-based compound according to any one of claims 1 to 4. 7. A cured product according to any one of claims 1 to 4, characterized in that the benzoxazine-based compound comprises a cured polybenzoxazine.

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