WO2016089182A2

WO2016089182A2 - Polybenzoxazine precursor and method for preparing same

Info

Publication number: WO2016089182A2
Application number: PCT/KR2015/013282
Authority: WO
Inventors: 조희진; 성도경; 박기현; 박상훈
Original assignee: 코오롱인더스트리 주식회사
Priority date: 2014-12-05
Filing date: 2015-12-07
Publication date: 2016-06-09
Also published as: WO2016089182A3; WO2016089182A9

Abstract

The present invention relates to a polybenzoxazine precursor and a method for preparing the same and, more specifically, to a polybenzoxazine precursor and a method for preparing the same, wherein the polybenzoxazine precursor can be prepared into a hardened material exhibiting excellent thermal characteristics, electric characteristics, and dimensional characteristics by comprising bezoxazine obtained by reaction of a phenol novolac resin, an aldehyde compound, and, as amine compounds, an allyl amine and diamine diphenyl methane, and thus the polybenzoxazine precursor can be, ultimately, favorably used for a copper clad laminate, a semiconductor sealing agent, a printed circuit board, adhesion, paint, molding, and the like.

Description

Polybenzoxazine Precursor and Manufacturing Method Thereof

The present invention relates to a polybenzoxazine precursor and a method for producing the same.

Conventionally, thermosetting resins such as phenol resins, melamine resins, epoxy resins, unsaturated polyester resins, and bismaleimide resins are based on the properties of thermosetting, and are excellent in water resistance, chemical resistance, heat resistance, mechanical strength, reliability, and the like. It is used in various fields.

However, phenol resins and melamine resins have disadvantages such as volatile by-products upon curing, epoxy resins and unsaturated polyester resins are poor in flame retardancy, and bismaleimide resins are very expensive.

In order to eliminate these drawbacks, polybenzoxazine has been studied in which the Benzoxazine ring is ring-opening-polymerized and thermally cured without the occurrence of problematic volatiles.

Thermosetting resins having a benzoxazine ring in the molecular structure are subject to encapsulation, impregnation, laminates, adhesives, paints, coatings, friction materials, FRP, and molding materials since the oxazine ring is opened by heating and polymerization proceeds without generation of byproducts. It is attracting attention as a thermosetting resin used for etc. The benzoxazine ring has a complex structure of a benzene ring and an oxazine ring.

These benzoxazines are well-balanced cured polymers with mechanical, electrical and chemical properties, including high glass transition temperature (Tg), low dielectric properties, high tension, low coefficient of thermal expansion, excellent elasticity, low hygroscopicity, and the like.

Techniques for further strengthening the characteristics of benzoxazines are continuously being developed. For example, Korean Unexamined Patent Publication No. 10-2012-0058566 relates to a "polybenzoxazine composition," wherein a curable composition comprising a benzoxazine compound and a pentafluoroantimonic acid catalyst is heated for a sufficient temperature and time to polymerize. By this, a method for producing a polybenzoxazine having good thermal stability is disclosed.

In addition, the Republic of Korea Patent Publication No. 10-0818254 relates to "polybenzoxazine-based compound, an electrolyte membrane including the same and a fuel cell employing the same", the acid trapping ability, mechanical and chemical stability, the ability to retain phosphoric acid at high temperature The improved novel polybenzoxazine compound, an electrolyte membrane using the same, and a method of manufacturing the same are disclosed.

Meanwhile, Copper Clad Laminate (CCL) refers to a laminated plate coated with a thin copper foil on an insulating material. Recently, copper clad laminates used in printed circuit boards (PCBs) are excellent due to high performance and high integration of smart devices. Heat resistance and low dielectric properties are required. Resin is used as the base material of copper foil laminated board and plays the role of an insulator in the printed circuit board. To be a good insulator, the permittivity must be low. Dielectric constant refers to the degree of polarization of molecules in an insulator against external electrical signals. The smaller the value, the better the insulation. In the operation of a printed circuit board, the smaller the dielectric constant of the insulator, the faster the signal processing speed and the lower the transmission loss.

As an alternative for satisfying the heat resistance and low dielectric properties of the copper-clad laminate, the use of polybenzoxazine, a phenol-based curing agent, has been highlighted. As described above, polybenzoxazine is a thermosetting polymer in which a benzoxazine-based monomer is polymerized by opening a ring in a molecule by heat, and is capable of self-curing without a by-product, and does not generate a volatile substance upon curing and does not have a volume change. Excellent dimensional stability. In addition, it is a high heat resistant polymer having a high glass transition temperature and having a decomposition property of pyrolysis temperature of less than 1% up to 350 ° C.

An object of the present invention is to provide a polybenzoxazine precursor capable of preparing a cured product having improved thermal properties, electrical properties, and dimensional stability as compared to a conventional polybenzoxazine precursor.

The present invention also provides a method for preparing such polybenzoxazine precursor.

The present invention also seeks to provide a cured product of such a polybenzoxazine precursor.

The present invention includes a benzoxazine compound represented by the following formula (1),

The following formula (1) provides a polybenzoxazine precursor comprising 5 to 50% of a benzoxazine compound having n1 = 0, n2 = 0 and m = 1.

[Formula 1]

In Formula 1, n1 and n2 are the same as or different from each other, an integer of 0 to 2, and m is an integer of 1 to 6.

The precursor according to the embodiment may have a weight average molecular weight of 1500 to 8000 g / mol, the glass transition temperature is 210 ℃ or more.

In one embodiment of the present invention provides a method for producing a polybenzoxazine precursor comprising the step of reacting an allylamine and diaminodiphenylmethane as an aldehyde compound and an amine compound to a phenol novolak resin. .

In a specific embodiment, the method comprises the steps of: (1) reacting a phenolic compound with an aldehyde compound in the presence of an acid catalyst to obtain a phenol novolak resin; And

(2) reacting the obtained phenol novolak resin with allylamine and diaminodiphenylmethane as an aldehyde compound and an amine compound.

In the method according to the embodiments, the phenol novolak resin is represented by the following formula (2), it may be one containing 65% or more components of n = 0 in the formula (2).

[Formula 2]

In Formula 2, n is an integer of 0 to 2.

In one embodiment, the step (1) uses an aldehyde compound in 0.05 to 0.3 mol with respect to 1 mol of the phenolic compound, the step (2) is based on 1 mol of the phenol novolak resin, 2 to 6 mol of the aldehyde compound , Allylamine 0.5 to 1.5 mol and diaminodiphenylmethane (diaminodiphenylmethane) can be used in 0.1 to 0.9 mol.

In one embodiment of the present invention provides a cured product of the polybenzoxazine precursor according to the above embodiments.

In one embodiment of the present invention provides a polybenzoxazine obtained by polymerization while ring-opening (oxazine) ring of the polybenzoxazine precursor including the benzoxazine compound represented by the formula (1).

Another embodiment of the present invention provides a method for preparing polybenzoxazine, comprising curing a polybenzoxazine precursor including a benzoxazine compound represented by Chemical Formula 1 at a temperature of 150 to 250 ° C.

The polybenzoxazine precursor according to the present invention can provide a cured product having improved electrical properties, thermal properties, and dimensional stability as compared to the existing polybenzoxazine precursor, and ultimately, copper foil laminate, semiconductor encapsulant, printed circuit board, adhesive It can be usefully used for paints, paints, molds and the like.

1 is a GPC graph (FIG. 1A) and ¹ H-NMR spectrum (FIG. 1B) of a polybenzoxazine precursor prepared in Example 1 of the present invention.

Figure 2 shows the GPC graph (eh 2a) and infrared spectroscopy (IR) spectrum of the polybenzoxazine precursor prepared in Example 2 of the present invention as compared to the phenol novolak resin as a raw material (Fig. 2b).

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless otherwise stated.

As used herein, the terms "about", "substantially", and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are intended to aid the understanding of the invention. Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers.

In one embodiment of the present invention comprises a benzoxazine compound represented by the following formula (1), and in the following formula 1 polybenzone containing 5 to 50% benzoxazine compounds of n1 = 0, n2 = 0 and m = 1 Provide a photo precursor.

[Formula 1]

In the above and the following description, the term "polybenzoxazine precursor" refers to a compound or a group of compounds in which an oxazine ring plays a precursor role of forming a thermosetting resin called a polybenzoxazine by ring-opening reaction. It includes a benzoxazine-based monomer of only, including an oligomer having the same repeating unit structure as the monomer in the main chain, or a combination of a group containing a part of a polymerized autocuring product when the oxazine ring of such monomer or oligomer is ring-opened. define.

The polybenzoxazine precursor according to an embodiment of the present invention includes the benzoxazine compounds having n1 = 0, n2 = 0, and m = 1 in Formula 1 as 5 to 50% of the precursors in terms of electrical properties, thermal properties, and It may be preferable in terms of improving dimensional stability.

% Is based on the peak area ratio of gel permeation chromatography (GPC) (Waters: Waters707), and strictly refers to the peak area ratio between the monomer and the polymer component when the polymer is included in the precursor. Same as below.

The polybenzoxazine precursor according to one embodiment of the present invention includes compounds satisfying n1, n2 and m values within the range defined in Chemical Formula 1 in addition to the compounds having n1 = 0, n2 = 0 and m = 1 in Chemical Formula 1 can do.

The polybenzoxazine precursor may have a weight average molecular weight of 1500 to 8000 g / mol to prevent the delay of curing or crystallization during curing, and the viscosity of the precursor It may be preferable in view of being raised or gelled to prevent deterioration in workability and deterioration in compatibility with other resins.

The weight average molecular weight may be defined in terms of polystyrene equivalents determined by gel permeation chromatography (GPC).

The polybenzoxazine precursor according to the present invention may provide a cured product having improved thermal properties, electrical properties, and dimensional stability as compared to the existing polybenzoxazine precursor.

Polybenzoxazine precursor of the present invention may be prepared by using a phenol novolak resin represented by the following formula (2) as a raw material.

[Formula 2]

In Formula 2, n is an integer of 0 to 2.

Specifically, in Formula 2, a phenol novolak resin containing 65% or more of a compound having n = 0 may be prepared as a raw material.

More specifically, (1) reacting a phenolic compound and an aldehyde compound in the presence of an acid catalyst to obtain a phenol novolak resin; And (2) reacting the obtained phenol novolak resin with a monoamine compound and a diamine compound as an aldehyde compound and an amine compound.

More specifically, by reacting the phenolic compound and the aldehyde compound in the presence of an acid catalyst to obtain a phenol novolak resin containing at least 65% (GPC Area%) of the n = 0 component of the compound represented by the formula (2) The phenol novolak resin may be condensed with an aldehyde compound, a monoamine compound, and a diamine compound in the presence of a solvent to prepare a polybenzoxazine precursor in which an aromatic content of benzoxazine is maximized.

As described above, the phenolic compound and the aldehyde compound may be reacted in the presence of an acid catalyst to obtain a phenol novolak resin containing 65% or more (GPC Area%) of a compound having n = 0 in Chemical Formula 2. When the amount of the compound of n = 0 in the case of less than 65%, the viscosity is due to the rapid reactivity in the subsequent benzoxazine production reaction and the large molecular weight of the raw material There may be a problem of elevated or gelling.

At this time, the water and the solvent generated in the reaction process can be removed by a known method such as distillation.

In the step (1), the aldehyde compound may be added at 0.05 to 0.3 mol, preferably 0.1 to 0.2 mol with respect to 1 mol of the phenolic compound. If the aldehyde compound is added to less than 0.05 mol with respect to 1 mole of the phenolic compound, the yield may be drastically reduced. If the aldehyde compound exceeds 0.3 mol, the phenol having n = 0 in the formula 2 is less than 65%. Novolak resin can be synthesized

The phenolic compound may be phenol or cresol.

In addition, the above and below aldehyde compounds are not particularly limited, but specific examples thereof include benzaldehyde, anisaldehyde, 4-methylbenzaldehyde, 2-methoxybenzaldehyde and 2-Methoxybenzaldehyde. 4-methoxybenzaldehyde, 3,4-methylenedioxybenzaldehyde, 3,4-dimethoxybenzaldehyde and 3-isopropoxy-benzaldehyde It may be one or more selected from the group consisting of (3-Isopropoxy-benzaldehyde).

The acid catalyst used in step (1) is para-toluene solfonic acid, methyl sulfonic acid, boron trifluorid, aluminum chloride and sulfo Nickel acid (Sulfuric acid) may be one or more selected from the group consisting of.

In the step (2), the amine compound is a combination of a monoamine and a diamine compound, wherein the monoamine is allylamine (diamine), diamine diaminediphenylmethane (diaminodiphenylmethane) may be advantageous in terms of reactivity and ease of production have. The monoamine compound may be used at 0.5 to 1.5 mol, preferably 0.7 to 1.4 mol, with respect to 1 mol of the phenol novolak resin, and the diamine compound may be used at 0.1 to 0.9 mol, preferably 0.2 mol with respect to 1 mol of the phenol novolak resin. To 0.6 mol, and the aldehyde compound may be added to 2 to 6 mol, preferably 3 to 5 mol, relative to 1 mol of the phenol novolak resin .

When the monoamine compound is added to less than 0.5 mol with respect to 1 mol of the phenol novolak resin, a ring close reaction does not occur and thus the benzoxazine reaction cannot be sufficiently formed (the benzoxazine ring cannot be sufficiently formed). If it exceeds 1.5 mol, the side reactions lower the thermal, electrical and dimensional stability.

In addition, when the diamine compound is added to less than 0.1 mol with respect to 1 mol of the phenol novolak resin, the molecular weight is too small to lower the heat resistance characteristics, and when it exceeds 0.9 mol, the molecular weight rises exponentially and the resin compatibility decreases. The problem of an increase in viscosity may occur.

In addition, when the aldehyde compound is added to less than 2 mol with respect to 1 mol of the phenol novolak resin, it does not induce a sufficient reaction with the amine compound does not form oxazine ring, the heat resistance is lowered, if it exceeds 6 mol Excess unreacted raw material may remain in the product.

The solvent used in the reaction is an aromatic hydrocarbon solvent such as toluene, xylene, trimethylbenzene; Halogen solvents such as chloroform, dichloroform and dichloromethane; Ether solvents such as THF, dioxane and the like can be used. In this case, the content of the solvent, it is preferable to use 25 to 100 parts by weight based on 100 parts by weight of the total phenol novolak resin, aldehyde compound, monoamine compound and diamine compound.

In the preparation of the polybenzoxazine precursor, when the content of the solvent is too small, the viscosity of the reactant becomes high, the stirring stress increases, and the workability decreases. When the content is excessively high, the cost of removing the solvent after the reaction increases. It can be economical. In addition, when the selection of the appropriate solvent and the mixing reaction is not made properly, the raw materials do not participate in the reaction, the yield may be lowered.

The polybenzoxazine precursor prepared as described above may include 5 to 50% of components having n1 = 0, n2 = 0, and m = 1 in the general formula (1).

In the above and the following description, the term "cured product" does not mean only a hardened product of the polybenzoxazine precursor alone, but also encompasses a cured product that is mixed with another resin-based composition in addition to the polybenzoxazine precursor resin. Can be.

In particular, the polybenzoxazine may be obtained through a method of curing a polybenzoxazine precursor including the benzoxazine compound represented by Chemical Formula 1 at a temperature of 150 to 250 ° C.

The temperature for curing the polybenzoxazine precursor is suitably in the range of 150 to 250 ° C, more preferably 190 to 220 ° C. If the temperature is less than 150 ° C., the curing time may be too long, and if the temperature exceeds 250 ° C., oxidation of impurities may be excessively induced, or too much energy may be consumed during the process. In 190-220 degreeC, it is more preferable from a viewpoint of process time, energy efficiency, etc. In the curing process of the benzoxazine, the oxazine ring of the benzoxazine compound represented by Chemical Formula 1 is polymerized while ring-opening.

The cured product obtained from the polybenzoxazine precursor according to the present invention exhibits excellent thermal properties, electrical properties and dimensional stability, and thus can be usefully used for copper clad laminates, semiconductor encapsulants, printed circuit boards, adhesives, paints, and mold applications.

Hereinafter, the content of the present invention will be described in detail through examples. However, these are intended to explain the present invention in more detail, and the scope of the present invention is not limited thereto.

<실시예 1><Example 1>

1-1: Preparation of Polybenzoxazine Precursor

202.97 g of benzaldehyde and 1200.0 g of phenol were added at 40 ° C, and reacted at 130 ° C for 5 hours under an acid catalyst, Para-toluene solfonic acid, to give 4,4- (phenylmethylene) diphenol. A compound having n = 0 in Chemical Formula 2) containing 77.14% (GPC Area%) and the remaining 22.86% obtained a phenol novolak resin consisting of a compound having n = 1 to 2 in Chemical Formula 2.

Next, 150 g (0.5286 mol) and 609.3 g of the synthesized phenol novolac resin and 609.3 g were added to a 3 L three-neck flask purged with nitrogen, and 30.83 g (0.540 mol) of allylamine and 52.40 g of diaminodiphenylmethane were added thereto. (0.2643 mol) was added followed by 158.75 g (2.114 mol) of aqueous formaldehyde solution (40%). When the addition was completed, the reaction solution was heated up to 100 ° C. at a rate 1.3 ° C./min and stirred for 5 hours. After heating to 120 ° C., the solvent was completely removed under a pressure of 10 torr for 60 minutes to obtain 281 g of a polybenzoxazine precursor having a weight average molecular weight of 2156 g / mol (n1 = 0, n2 = 0 and m = 1 in Formula 1). Phosphorus component, including 22.15%). In this case, the yield (relative to the theoretical yield according to the equivalence ratio of the reaction solution) is 99%. The percentage is the peak area ratio (ratio of monomer and polymer component) of gel permeation chromatography (GPC) (Waters: Waters707).

The molecular weight data of the polybenzoxazine precursor obtained using GPC was analyzed and the results are shown in FIG. 1A.

The obtained polybenzoxazine precursor was confirmed to have a structure by nuclear magnetic resonance analysis ( ¹ H-NMR) as shown in FIG. 1B, and -OH near 8.0-9.0 ppm derived from a raw material (Compound 2). The peak disappeared and it was confirmed that the peak due to oxazine was generated in a wide range of 5.2-5.4ppm, 4.3-4.6ppm, 4.5-4.8ppm and 3.7-4.0ppm.

In this case, the NMR apparatus used in the NMR analysis is a Bruance Avance 500 product.

1-2: hardened material manufacturing

The polybenzoxazine precursor obtained in Example 1-1 was introduced into an aluminum dish having a diameter of 30 mm, and hardened at 220 ° C. for 2 hours to prepare a cured product having a sheet thickness of 1.5 mm.

2-1: Preparation of Polybenzoxazine Precursor

197.33 g of benzaldehyde and 1250 g of phenol were added at 40 ° C., and reacted at 130 ° C. for 4 hours under an acid catalyst, Para-toluene solfonic acid, to give 4,4- (phenylmethylene) diphenol (the above formula). 2, n = 0 compound) and 75.27% (GPC Area%) and the remaining 24.73% obtained a phenol novolak resin consisting of a compound of n = 1 to 2 in the formula (2).

Next, 150 g (0.5286 mol) and 609.3 g of the synthesized phenol novolac resin and 609.3 g were added to a 3 L three-neck flask purged with nitrogen, and 30.83 g (0.540 mol) of allylamine and 52.40 g of diaminodiphenylmethane were added thereto. (0.2643 mol) was added followed by 158.75 g (2.114 mol) of aqueous formaldehyde solution (40%). When the addition was completed, the reaction solution was heated up to 100 ° C. at a rate 1.3 ° C./min and stirred for 5 hours. Thereafter, the temperature was raised to 120 ° C., and then the solvent was completely removed under a pressure of 10 torr for 60 minutes to obtain 279 g of a polybenzoxazine precursor having a weight average molecular weight of 2670 g / mol (n1 = 0, n2 = 0 and m = 1 in Formula 1). Phosphorus component, including 16.46%). In this case, the yield (relative to the theoretical yield according to the equivalence ratio of the reaction solution) is 99%. The percentage is the peak area ratio (ratio of monomer and polymer component) of gel permeation chromatography (GPC) (Waters: Waters707).

Molecular weight data of the polybenzoxazine precursor obtained using GPC was analyzed and the result is shown in FIG. 1B.

As a result of confirming the structure of the obtained polybenzoxazine precursor by using infrared spectroscopy, it was shown in FIG. 2B, and the hydrogen atom peak (CH out of plane bending) of the oxazine ring was confirmed. At this time, the infrared spectroscopy instrument is a spectrum 100 product of Perkin Elmer.

In the substrate of FIG. 2B, the raw material is a phenol novolak resin of Formula 2, in contrast to the polybenzoxazine precursor represented by Benzoxazine, -OH stretching peak due to -OH group disappears and a characteristic peak of Benzoxazine can be confirmed. (The out-of-plane bending vibration of CH) and 1234 cm-1 (COC asymmetric stretching modes)

2-2: hardened product manufacture

The polybenzoxazine precursor obtained in Example 2-1 was introduced into an aluminum dish having a diameter of 30 mm, and cured at 220 ° C. for 2 hours to prepare a cured product having a thickness of 1.5 mm.

<비교예 1>Comparative Example 1

1-1: Preparation of benzoxazine

484.2 g of toluene was added to a 3 L three-neck flask purged with nitrogen, and 652.71 g (2.0 mol) of aniline, 800 g (1 mol) of bisphenol A, and 1052.35 g (4.0 mol) of aqueous formaldehyde solution (40%) were added thereto. Added. When the addition was completed, the reaction solution was heated up to 100 ° C. at a rate 1.3 ° C./min and stirred for 5 hours. Then, after heating up to 120 ℃, the solvent was completely removed for 60 minutes under a pressure of 10torr to prepare a 1500g polybenzoxazine precursor having a weight average molecular weight of 698g / mol. The obtained polybenzoxazine precursor was 54.26% of the benzoxazine monomer, and the yield (relative to the theoretical yield according to the equivalence ratio of the reaction solution) was 92%. The percentage is the peak area ratio (ratio of monomer and polymer component) of gel permeation chromatography (GPC) (Waters: Waters707).

1-2: hardened material manufacturing

The polybenzoxazine precursor obtained in Comparative Example 1-1 was introduced into an aluminum dish having a diameter of 30 mm, and cured for 3 hours at 220 ° C. for 3 hours to prepare a cured product having a thickness of 1.5 mm.

<비교예 2>Comparative Example 2

2-1 : Preparation of benzoxazine

514.7 g of toluene was added to a 3 L three-neck flask purged with nitrogen, and aniline 744.18 g (2.0 mol), bisphenol F 800 g (1 mol), and aqueous formaldehyde solution (40%) 1199.82 g (4.0 mol) were added thereto. Added. When the addition was completed, the reaction solution was heated up to 100 ° C. at a rate 1.3 ° C./min and stirred for 5 hours. Thereafter, after heating up to 120 ° C., the solvent was completely removed under a pressure of 10 torr for 60 minutes to prepare 945 g of a polybenzoxazine precursor having a weight average molecular weight of 1240 g / mol. The obtained polybenzoxazine precursor was 22.58% of the benzoxazine monomer, and the yield (relative to the theoretical yield according to the equivalence ratio of the reaction solution) was 93%. The percentage is the peak area ratio (ratio of monomer and polymer component) of gel permeation chromatography (GPC) (Waters: Waters707).

2-2: hardened product manufacture

The polybenzoxazine precursor obtained in Comparative Example 2-1 was put in an aluminum dish having a diameter of 30 mm, and hardened at 220 ° C. for 2 hours to prepare a cured product having a sheet thickness of 1.5 mm.

The glass transition temperature, flame retardancy, dielectric constant and molecular weight of the cured product prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were measured by the following method, and the results are shown in Table 1 below.

<유리전이온도(Tg) 측정><Glass Transition Temperature (Tg) Measurement>

10 mg of the cured product prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were measured by DMA (Dynamic Mechanical Analysis; Dynamic Mechanical Analysis).

Specifically, using a TA Instruments DMA Q800 was measured at a temperature increase rate of 3 ℃ per minute from 30 ℃ to 350 ℃.

<Decomposition Temperature(Td 5) 측정><Decomposition Temperature (Td 5) measurement>

The cured products prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were measured using a TGA measuring device and measured using a TA Instruments TGA Q500 at a temperature increase rate of 10 ° C. per minute from 30 ° C. to 800 ° C. under a nitrogen atmosphere.

<유전율 측정>Dielectric constant measurement

Agilent's impedance analyzer (Agilent E4991A 1 MHz to 3 GHz) was used to measure the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product under the following conditions.

Measuring frequency: 1 GHz

Measuring temperature: 25-27 ℃

Measuring Humidity: 45-55%

Measurement sample: Thickness 1.5 mm (1.3 to 1.7 mm)

<분자량 측정><Molecular weight measurement>

Polystyrene reduced weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) (Waters: Waters707). The polymer to be measured was dissolved in tetrahydrofuran to a concentration of 4000 ppm, and 100 µl was injected into GPC. The mobile phase of GPC used tetrahydrofuran and was introduced at a flow rate of 1.0 mL / min, and the analysis was performed at 35 ° C. The column connected four Waters HR-05,1,2,4E in series. The detector was measured at 35 ° C using RI and PAD Detecter.

<열팽창계수 측정><Coefficient of Thermal Expansion>

TA Instruments TMA Q400 was used to measure a temperature increase rate of 10 ° C. per minute from 30 ° C. to 300 ° C. α1 is the coefficient of thermal expansion from room temperature to Tg and α2 is the coefficient of thermal expansion from Tg to 260 ° C.

Table 1

division	Mw (g / mol)	Tg (℃)	Td 5 (℃)	Coefficient of thermal expansion (α1 / α2)	Permittivity (Dk)	Dielectric loss factor (Df)
Example 1	2156	275.9	361.4	15.8 / 73.2	2.78	0.0047
Example 2	2670	276.2	364.5	17.2 /82.8	2.81	0.0049
Comparative Example 1	698	198.7	314.6	51.08 / 3979	3.00	0.0100
Comparative Example 2	1240	195.9	318.2	58.64 / 387.8	3.45	0.0150

As shown in Table 1, Examples 1 and 2, when compared with Comparative Examples 1 and 2, exhibit high thermal characteristics by showing high Tg and Td values, and in particular, permittivity (Dk) and dielectric loss tangent (Df). This low measurement resulted in an excellent electrical property, and the thermal expansion coefficient was remarkably low, indicating the excellent dimensional stability.

All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims

To include a benzoxazine compound represented by the formula (1),

A polybenzoxazine precursor comprising 5 to 50% of a benzoxazine compound having n1 = 0, n2 = 0, and m = 1 in Formula 1 below.

[Formula 1]

In Formula 1, n1 and n2 are the same as or different from each other, an integer of 0 to 2, and m is an integer of 1 to 6.
The polybenzoxazine precursor of claim 1, wherein the precursor has a weight average molecular weight of 1500 to 8000 g / mol and a glass transition temperature of 210 ° C. or more.
A method for producing a polybenzoxazine precursor comprising the step of reacting phenol novolak resin with allylamine and diaminodiphenylmethane as an aldehyde compound and an amine compound.
The method of claim 3, wherein

(1) reacting a phenolic compound with an aldehyde compound in the presence of an acid catalyst to obtain a phenol novolak resin; And

(2) a method for producing a polybenzoxazine precursor, comprising reacting an allylamine and diaminodiphenylmethane as an aldehyde compound and an amine compound to the obtained phenol novolak resin.
The method for producing a polybenzoxazine precursor according to claim 3 or 4, wherein the phenol novolak resin is represented by the following Chemical Formula 2, and contains n = 0 components of 65% or more in Chemical Formula 2.

[Formula 2]

In Formula 2, n is an integer of 0 to 2.
The phenol novolak resin according to claim 4, wherein the phenolic novolak resin is used in an amount of 0.05 to 0.3 mol with respect to 1 mol of the phenolic compound, and in step (2), 2 to 6 mol of an aldehyde compound, based on 1 mol of the phenol novolak resin, Allylamine 0.5 to 1.5 mol and diaminodiphenylmethane (diaminodiphenylmethane) using a method for producing a polybenzoxazine precursor, characterized in that using.
Hardened | cured material of the polybenzoxazine precursor of any one of Claims 1-2.
A polybenzoxazine obtained by polymerization while ring opening of an oxazine ring of a polybenzoxazine precursor including a benzoxazine compound represented by Formula 1 is ring-opened.

[Formula 1]

In Formula 1, n1 and n2 are the same as or different from each other, an integer of 0 to 2, and m is an integer of 1 to 6.
Next, the polybenzoxazine precursor comprising the benzoxazine compound represented by the formula (1) comprising the step of curing at a temperature of 150 to 250 ℃ polybenzoxazine.

[Formula 1]

In Formula 1, n1 and n2 are the same as or different from each other, an integer of 0 to 2, and m is an integer of 1 to 6.