Allyl-containing bisphenol resin

Abstract

To provide an allyl-containing bisphenol resin.SOLUTION: An allyl-containing bisphenol resin comprises a first structural unit derived from a bisphenol compound and a polyfunctional maleimide compound containing two or more allyl groups per molecule, and the first structural unit contains one or more allyl groups. When the allyl-containing bisphenol resin is characterized by Fourier transform infrared spectroscopy (FTIR), the spectrum has three peaks in a certain range of frequencies, and their peak areas satisfy a certain relationship.EFFECT: The cured product prepared from the allyl-containing bisphenol resin has excellent heat resistance and dimensional stability, and also has excellent high temperature stability, toughness, hydrophobicity, adhesion to copper foil, and / or dielectric properties, thereby making the resin particularly suitable for use as a dielectric material in printed circuit boards.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present application provides allyl-containing bisphenol resins having specific infrared spectral characteristics and / or specific structures. [Background technology]

[0002] As electronic product applications gradually progress toward lighter, thinner, shorter, smaller, and more multi-functional designs, the requirements for electronic material properties have also increased. In particular, printed circuit boards (PCBs), which serve as the main support substrate for electronic components, should have properties such as high-density wiring, thinness, high dimensional stability, and efficient heat dissipation.

[0003] However, heat can be generated during PCB processing, especially through the high temperatures generated during drilling caused by the high rotational speed of the drill bit. This results in a low glass transition temperature (T g Resin systems with low thermal expansion (CTE) and low thermal expansion coefficient (CTE) tend to soften during PCB processing. This softening can lead to separation of copper wires and deformation of PCB, significantly affecting subsequent processing stages.

[0004] In addition, with the development of 5G systems, the requirements for high data transmission density and low latency transmission are becoming more stringent, and the resin systems used in electronic materials need to be improved to prevent signal loss or delay during the transmission process caused by material defects.

[0005] To solve the above-mentioned technical problems, the prior art has proposed using bismaleimide compounds as part of a resin system to improve the heat resistance, dimensional stability, and electrical properties of the electronic materials produced. However, bismaleimide compounds have drawbacks such as poor solubility and short shelf life, limiting their applications. Furthermore, even though the prior art resin systems employ bismaleimide compounds, the improvements in heat resistance, processability, and dimensional stability remain insufficient. Summary of the Invention [Problem to be solved by the invention]

[0006] In view of the above technical problems, the present application aims to modify bismaleimide compounds to solve the application limitations due to poor solubility and short shelf life. Through modification, the present application can provide novel resins with extremely good physicochemical properties. Specifically, the present application provides an allyl-containing bisphenol resin that includes structural units derived from a bisphenol compound containing two or more allyl groups per molecule and a polyfunctional maleimide compound. The cured product prepared from the allyl-containing bisphenol resin has excellent heat resistance and dimensional stability, and may also have excellent high temperature stability, toughness, hydrophobicity, adhesion to copper foil, and / or dielectric properties, making the resin particularly suitable for use as a dielectric material in printed circuit boards. Furthermore, the allyl-containing bisphenol resin exhibits good stability and allows for long-term storage. Due to its excellent properties, the allyl-containing bisphenol resin can be used in a smaller amount to achieve higher efficacy. This allows for a reduction in the amount of maleimide compound(s) used, which provides advantages such as improved solubility and ease of handling. [Means for solving the problem]

[0007] Therefore, an object of the present application is to provide an allyl-containing bisphenol resin comprising a bisphenol compound containing two or more allyl groups per molecule and a first structural unit derived from a polyfunctional maleimide compound, wherein the first structural unit contains one or more allyl groups, and when the allyl-containing bisphenol resin is characterized by Fourier transform infrared spectroscopy (FTIR), the FTIR spectrum of the allyl-containing bisphenol resin has a peak at 1615 cm -1 ~1765cm -1 A characteristic peak A at frequencies in the range of 1615 cm -1 ~1765cm -1 and a characteristic peak B at frequencies in the range of 1155 cm -1 ~1265cm-1 and characteristic peak C at a frequency in the range of 1615 cm -1 ~1690cm -1 The characteristic peak B is at 1690 cm -1 ~1765cm -1 The characteristic peaks A, B, and C have corresponding peak areas A A , A B , A C These include (A A / A C )+(A C / A B )=1.20 to 1.60, preferably, (A A / A C )+(A C / A B )=1.25~1.52.

[0008] In some embodiments of the present application, A A / A C =0.25~0.60.

[0009] In some embodiments of the present application, A C / A B =0.70~1.40.

[0010] In some embodiments of the present application, the Fourier transform infrared spectroscopy analysis is carried out by coating the allyl-containing bisphenol resin on a KBr pellet by a film method, and measuring the concentration of the allyl-containing bisphenol resin by 1 cm using a Fourier transform infrared spectrophotometer. -1 By using the transmission method under a resolution of 400 cm and a number of scans of 16, -1 ~4000cm -1 This is done by measuring the absorption spectrum of the coated KBr pellet over a scan range of 100 nm to 150 nm.

[0011] In some embodiments of the present application, the bisphenol compound containing two or more allyl groups per molecule is selected from the group consisting of bisphenol A containing two or more allyl groups per molecule, bisphenol B containing two or more allyl groups per molecule, bisphenol F containing two or more allyl groups per molecule, bisphenol S containing two or more allyl groups per molecule, bisphenol Z containing two or more allyl groups per molecule, 4,4'-dihydroxydiphenyl ether compounds containing two or more allyl groups per molecule, and combinations thereof.

[0012] In some embodiments of the present application, the allyl-containing bisphenol resin further comprises a multifunctional maleimide compound.

[0013] Another object of the present application is to provide an allyl-containing bisphenol resin comprising the structure of formula (I): [ka] Formula (I) (However, at least one R1 [ka] and at least one R1 is [ka] with the proviso that each R1 is independently -H, -CH3, [ka] or [ka] and R2 is a group derived from a polyfunctional maleimide, and T is -CH2-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -SO2-, -O-, or [ka] and in some embodiments, -CH- or -C(CH)-.

[0014] In some embodiments of the present application, the allyl-containing bisphenol resin comprises a structure of formula (I-1) below: [ka] Formula (I-1) (However, at least one R1 [ka] and the other R1 is [ka] and R2 is a group derived from a polyfunctional maleimide, and T is -CH2-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -SO2-, -O-, or [ka] and in some embodiments, -CH- or -C(CH)-.

[0015] In some embodiments of the present application, R2 is [ka] or [ka] and R3 is [ka] [ka] [ka] [ka] and, [ka] (where n is an integer between 1 and 10) is selected from the group consisting of:

[0016] In some embodiments of the present application, when the allyl-containing bisphenol resin is characterized by gel permeation chromatography (GPC) and an absorbance detector, the allyl-containing bisphenol resin has an absorbance peak at 254 nm, and the absorbance peak has an area A 254 The area A is the total area of ​​all the absorption peaks. 254 The ratio of is 15% or less, and the test conditions for gel permeation chromatography (GPC) and absorbance detector are as follows: the allyl-containing bisphenol resin is diluted with tetrahydrofuran to a concentration of 200 ppm, and fed to a series of columns including one column C1, one column C2, and two columns C3 in this order at a flow rate of 1.0 mL / min to perform separation; samples are taken during the elution time between 20 and 35 minutes and analyzed for all absorbance peaks within the range of 190 nm to 800 nm by the absorbance detector; and the area A of the absorbance peak at 254 nm relative to the total area of ​​all absorbance peaks is calculated. 254 The ratio of the total amount of the chromatograms is calculated. Column C1 is 30 cm long, has an inner diameter of 7.8 mm, and is packed with polystyrene-divinylbenzene having an average particle size of 5 μm and an average pore size of 7.5 nm. Column C2 is 30 cm long, has an inner diameter of 7.8 mm, and is packed with polystyrene-divinylbenzene having an average particle size of 5 μm and an average pore size of 2 nm. Column C3 is 30 cm long, has an inner diameter of 7.8 mm, and is packed with polystyrene-divinylbenzene having an average particle size of 5 μm and an average pore size of 1.5 nm.

[0017] In order to make the above objectives, technical features, and advantages of the present application clearer, the present application is hereinafter described in detail with reference to several specific embodiments. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] Some specific embodiments of the present application are described in detail, however, the present application may be embodied in various embodiments and should not be limited to the embodiments described herein.

[0019] Unless otherwise specified, the singular terms used in the specification and claims are to be construed as including both the singular and the plural.

[0020] Unless otherwise specified, the terms "first," "second," and the like in the specification and claims are used only to distinguish between exemplified elements or components without any special meaning, and these terms are not used to denote any priority.

[0021] Unless otherwise specified, the term "allyl-containing bisphenol resin" used in the specification and claims refers to a resin that contains an allyl group in the molecule and has a bisphenol structure.

[0022] The main advantage of the present application over the prior art is that it improves the stability of allyl-containing bisphenol resins and improves the heat resistance and dimensional stability of cured products derived from allyl-containing bisphenol resins. In some embodiments, the allyl-containing bisphenol resins further have excellent high temperature stability, toughness, hydrophobicity, adhesion to copper foil, and / or dielectric properties. This is achieved by controlling the infrared spectrum characteristics of the allyl-containing bisphenol resins and / or by incorporating specific structures into the allyl-containing bisphenol resins. The allyl-containing bisphenol resins can be used in any technical field requiring the above-mentioned properties, including the preparation of coating materials, dielectric materials or modifiers for printed circuit boards, heat dissipation materials, aircraft wing materials, 3D printing materials, impregnating resin materials for glass or carbon fibers, heat-resistant materials for substrates, spray coating materials, or bulletproof vest coating materials. However, the scope of the present application is not limited to these examples. Details regarding the allyl-containing bisphenol resins are provided below.

[0023] (1. Allyl-containing bisphenol resins having specific infrared spectral characteristics) One object of the present application is to provide an allyl-containing bisphenol resin comprising a first structural unit derived from a bisphenol compound containing two or more allyl groups per molecule and a polyfunctional maleimide compound, wherein the first structural unit contains one or more allyl groups, and having specific infrared spectral characteristics.

[0024] In some embodiments of the present application, the allyl-containing bisphenol resin may further contain a polyfunctional maleimide in a compound state in addition to the structural units derived from the polyfunctional maleimide compound, provided that the allyl-containing bisphenol resin has specific infrared spectral characteristics.

[0025] (1.1. Polyfunctional Maleimide Compounds) In the present application, a polyfunctional maleimide compound refers to a compound having at least two maleimide groups per molecule. Without being bound by any theory, the presence of monomaleimide in the raw materials may result in reactants lacking groups capable of undergoing polymerization. This may result in molecular chains of insufficient length and with undesirable polymer properties. Therefore, the present application selects difunctional maleimides and / or polyfunctional maleimides of higher functionality. However, the present application does not exclude the possibility of using monofunctional maleimides.

[0026] The type of polyfunctional maleimide is not limited to a specific one. Examples of polyfunctional maleimides include, but are not limited to, polyfunctional maleimide compounds having the following formula: [ka] (However, R3 is [ka] [ka] [ka] [ka] and, [ka] (where n is an integer between 1 and 10) can be selected from the group consisting of The above-mentioned polyfunctional maleimides can be used alone or in any combination.

[0027] (1.2. Bisphenol compounds containing two or more allyl groups per molecule) In this application, a bisphenol compound containing two or more allyl groups per molecule refers to a compound having at least two allyls, preferably four allyls, on the benzene ring(s) of the bisphenol structure, preferably located ortho to the hydroxyl group.

[0028] A bisphenol compound containing two or more allyl groups per molecule can be obtained by subjecting bisphenol to an allylation reaction. A specific preparation method is described in detail in the Examples. Examples of bisphenols include, but are not limited to, bisphenol A, bisphenol B, bisphenol F, bisphenol S, bisphenol Z, and 4,4'-dihydroxydiphenyl ether. Thus, examples of bisphenol compounds containing two or more allyl groups per molecule include bisphenol A containing two or more allyl groups per molecule, bisphenol B containing two or more allyl groups per molecule, bisphenol F containing two or more allyl groups per molecule, bisphenol S containing two or more allyl groups per molecule, bisphenol Z containing two or more allyl groups per molecule, and 4,4'-dihydroxydiphenyl ether compounds containing two or more allyl groups per molecule. The above-mentioned bisphenol compounds can be used alone or in any combination.

[0029] (1.3. Infrared Spectroscopic Characteristics of Allyl-Containing Bisphenol Resins) When the allyl-containing bisphenol resin was characterized by Fourier transform infrared spectroscopy (FTIR), the FTIR spectrum of the allyl-containing bisphenol resin showed a peak at 1615 cm -1 ~1765cm -1 A characteristic peak A at frequencies in the range of 1615 cm -1 ~1765cm -1 and a characteristic peak B at frequencies in the range of 1155 cm -1 ~1265cm -1 and characteristic peak C at a frequency in the range of 1615 cm. The frequency of characteristic peak A is lower than the frequency of characteristic peak B. Preferably, characteristic peak A is at a frequency in the range of 1615 cm.-1 ~1690cm -1 The characteristic peak B is at 1690 cm -1 ~1765cm -1 The vibration frequency is in the range of

[0030] The characteristic peaks A, B, and C have peak areas A A , A B , A C These include (A A / A C )+(A C / A B )=1.20 to 1.60, preferably, (A A / A C )+(A C / A B )=1.25~1.52. For example, (A A / A C )+(A C / A B ) can be 1.20, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.30, 1.31, 1.32, 1.33, 1.34, 1.35, 1.36, 1.37, 1.38, 1.39, 1.40, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, or 1.60, or within a range between any two of the values ​​recited herein. A / A C )+(A C / A B If the value of (R) is outside the above range, the allyl-containing bisphenol resin does not have the ability to simultaneously provide excellent heat resistance, dimensional stability, storage properties, and stability.

[0031] (A A / A C )+(A C / A B ) is satisfied, the peak area A A and peak area A C A A / AC For example, A = 0.25 to 0.60. A / A C can be 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, or 0.60, or within a range between any two of the values ​​recited herein.

[0032] (A A / A C )+(A C / A B ) is satisfied, the peak area A C and peak area A B A C / A B = 0.70 to 1.40, preferably A C / A B = 0.75 to 1.40, more preferably A C / A B For example, A = 0.80 to 1.40. C / A Bare 0.70, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, 1.00, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08 , 1.09, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.19, 1.20, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.30, 1.31, 1.32, 1.33, 1.34, 1.35, 1.36, 1.37, 1.38, 1.39, or 1.40, or within a range between any two of the values ​​recited herein. C / A B If the values ​​fall within the above ranges, the resin will exhibit a longer gel time and will be suitable for applications requiring a long gel time.

[0033] The infrared spectrum characteristics of the allyl-containing bisphenol resin were measured by coating the allyl-containing bisphenol resin on a KBr pellet by the film method and measuring the infrared spectrum characteristics of the allyl-containing bisphenol resin by a 1 cm Fourier transform infrared spectrophotometer. -1 By using the transmission method under a resolution of 400 cm and a number of scans of 16, -1 ~4000cm -1 The absorption spectrum of the coated KBr pellet can be obtained by Fourier transform infrared spectroscopy, which measures the absorption spectrum of the coated KBr pellet over a scan range of 100 nm to 150 nm. The peak areas A, B, and C of the characteristic peaks are A , A B , and A C is determined by calculating the integrated area defined by a line connecting the start and end points of the absorbance peaks within a specific range. For example, the peak area A of characteristic peak A is A is 1615cm -1 ~1690cm -1 The peak area A of characteristic peak B is calculated by calculating the integral area defined by the line connecting the start and end points of the absorption peak ofB is 1690cm -1 ~1765cm -1 The peak area A of characteristic peak C is calculated by calculating the integral area bounded by a line connecting the start and end points of the absorption peak of C is 1155cm -1 ~1265cm -1 The characteristic peak is obtained by calculating the integrated area bounded by a line connecting the beginning and end of the absorbance peak of the characteristic peak. Specifically, software can be used to identify the points where the first derivative is zero as the beginning, apex, and end of the characteristic peak. The software then calculates the integrated area defined between the beginning, apex, and end of the characteristic peak, resulting in an area measurement for the characteristic peak.

[0034] The infrared spectrum characteristics of the allyl-containing bisphenol resin can be controlled by adjusting the raw materials (such as the type or equivalent amount of raw materials) used in the preparation of the allyl-containing bisphenol resin, or by adjusting the processing conditions (such as the reaction temperature or reaction time) of the allyl-containing bisphenol resin. Those skilled in the art can prepare the allyl-containing bisphenol resin having the above-mentioned infrared spectrum characteristics by referring to the present specification, particularly by relying on the specific examples in the examples.

[0035] (1.4. First structural unit) In some embodiments of the present application, the first structural unit of the allyl-containing bisphenol resin has the structure of formula (I): [ka] Formula (I) (However, at least one R1 [ka] and at least one R1 is [ka] with the proviso that each R1 is independently -H, -CH3, [ka] or [ka] and R2 is a group derived from a polyfunctional maleimide, and T is -CH2-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -SO2-, -O-, or [ka] and in some embodiments, -CH- or -C(CH)-.

[0036] More specifically, the first structural unit of the allyl-containing bisphenol resin may have a structure of the following formula (I-1): [ka] Formula (I-1) (However, at least one R1 [ka] and the other R1 is [ka] and R2 is a group derived from a polyfunctional maleimide, and T is -CH2-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -SO2-, -O-, or [ka] and in some embodiments, -CH- or -C(CH)-.

[0037] Preferably, in the structures of formula (I) and formula (I-1), R2 is preferably derived from a polyfunctional maleimide having the structure of the following formula: [ka] Therefore, R2 is preferably [ka] or [ka] and R3 is [ka] [ka] [ka] [ka] and, [ka] (where n is an integer between 1 and 10) is selected from the group consisting of:

[0038] In some embodiments of the present application, T in formula (I) and formula (I-1) is -SO2-, and the cured product of the allyl-containing bisphenol resin further has improved high temperature stability and toughness.

[0039] In some embodiments of the present application, T in formula (I) and formula (I-1) is -O-, and the cured product of the allyl-containing bisphenol resin further has improved hydrophobicity and adhesion to copper foil.

[0040] In some embodiments of the present application, T in formula (I) and formula (I-1) is [ka] and the cured products of the allyl-containing bisphenol resins further have improved dielectric properties.

[0041] 1.5. Preparation of Allyl-Containing Bisphenol Resins Allyl-containing bisphenol resins can be prepared via crosslinking reactions involving a multifunctional maleimide compound and a bisphenol compound containing two or more allyl groups per molecule, such as a bisphenol compound containing four allyl groups per molecule. The FTIR characteristics of the allyl-containing bisphenol resins can be controlled by the selection of the bisphenol compound containing two or more allyl groups per molecule, as well as by adjusting the reaction temperature and reaction time of the multifunctional maleimide compound and the bisphenol compound containing two or more allyl groups per molecule. For example, allyl-containing bisphenol resins can be prepared by using a bisphenol compound containing four allyl groups per molecule and reacting at a reaction temperature of 90°C to 130°C for 90 minutes to 500 minutes.

[0042] (2. Allyl-containing bisphenol resins having specific structures) Another object of the present application is to provide an allyl-containing bisphenol resin comprising the structure of formula (I): [ka] Formula (I) (However, at least one R1 [ka] and at least one R1 is [ka] with the proviso that each R1 is independently -H, -CH3, [ka] or [ka] and R2 is a group derived from a polyfunctional maleimide, and T is -CH2-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -SO2-, -O-, or [ka] and in some embodiments, -CH- or -C(CH)-.

[0043] In some embodiments of the present application, the allyl-containing bisphenol resin comprises a structure of formula (I-1) below: [ka] Formula (I-1) (However, at least one R1 [ka] and the other R1 is [ka] and R2 is a group derived from a polyfunctional maleimide, and T is -CH2-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -SO2-, -O-, or [ka] and in some embodiments, -CH- or -C(CH)-.

[0044] Preferably, in the structures of formula (I) and formula (I-1), R2 is preferably derived from a polyfunctional maleimide having the structure of the following formula: [ka] Therefore, R2 is preferably [ka] or [ka] and R3 is [ka] [ka] [ka] [ka] and, [ka] (where n is an integer between 1 and 10) is selected from the group consisting of:

[0045] The allyl-containing bisphenol resin can be prepared by subjecting a polyfunctional maleimide compound and a bisphenol compound containing two or more allyl groups per molecule, such as a bisphenol compound containing four allyl groups per molecule, to a crosslinking reaction. The bisphenol compound containing two or more allyl groups per molecule can be prepared by subjecting bisphenol to an allylation reaction. A specific preparation method is shown in the examples.

[0046] In some embodiments of the present application, when the allyl-containing bisphenol resin is characterized by gel permeation chromatography (GPC) and an absorbance detector, the allyl-containing bisphenol resin has an absorbance peak at 254 nm, and the absorbance peak has an area A 254 The area of ​​the 254 nm absorbance peak relative to the total area of ​​all absorbance peaks, A 254The test conditions for gel permeation chromatography (GPC) and absorbance detector were as follows: allyl-containing bisphenol resin was diluted with tetrahydrofuran to a concentration of 200 ppm, and fed to a series of gel permeation chromatography columns in series at a flow rate of 1.0 mL / min to carry out separation; samples were taken at elution times ranging from 20 to 35 minutes and analyzed for total absorbance peaks within the range of 190 nm to 800 nm by the absorbance detector; the area A relative to the total area of ​​all absorbance peaks was calculated. 254 In this application, the above-mentioned columns are a series of columns including one column C1, one column C2, and two columns C3 in this order, where column C1 is 30 cm long, has an inner diameter of 7.8 mm, and is filled with polystyrene-divinylbenzene having an average particle size of 5 μm and an average pore size of 7.5 nm, such as a product with the model number TSK gel G3000Hxl, column C2 is 30 cm long, has an inner diameter of 7.8 mm, and is filled with polystyrene-divinylbenzene having an average particle size of 5 μm and an average pore size of 2 nm, such as a product with the model number TSK gel G2000Hxl, and column C3 is 30 cm long, has an inner diameter of 7.8 mm, and is filled with polystyrene-divinylbenzene having an average particle size of 5 μm and an average pore size of 1.5 nm, such as a product with the model number TSK gel G1000Hxl. In this application, software can be used to identify the points where the first derivative is zero as the beginning, apex, and end of the absorption peak, which then calculates the integrated area defined between the beginning, apex, and end of the absorption peak, resulting in an area measurement of the absorption peak.

[0047] 3. Working Examples (3.1. Test Method) Hereinafter, the present application will be described more specifically using an embodiment, and a test device and method in the embodiment are as follows.

[0048] [Infrared spectroscopic analysis test] 1 mg of synthetic allyl-containing bisphenol resin is coated onto a 1 mm thick KBr pellet by the film method. The coated KBr pellet is placed in a pellet holder and inserted into a Fourier transform infrared spectrophotometer. The absorbance spectrum of the coated KBr pellet is 1 cm -1 By using the transmission method under a resolution of 400 cm and a number of scans of 16, -1 ~4000cm -1 The peak area A is measured over a scan range of A , A B , and A C is determined by calculating the integrated area subtended by a line connecting the beginning and ending points of absorbance peaks located within a given range using PerkinElmer® Spectrum version 10.5.3 software.

[0049] [Glass transition temperature (T g )test] The prepared resin is placed in a high temperature oven. The resin is kept at 180°C for 1 hour under vacuum conditions to remove the solvent. The resin then undergoes pre-crosslinking at 200°C for 2 hours and proceeds to full cure at 250°C for 6 hours. The cured product is cut into pieces with dimensions of 10mm x 10mm x 5mm. The cut product is then subjected to analysis using a thermal mechanical analyzer (TMA, model: Waters Q400). The test conditions are heating from 30°C to 330°C at a heating rate of 10°C / min, then cooling from 330°C to 30°C at a cooling rate of 10°C / min to complete the calibration, and then the glass transition temperature (T g ) while heating from 30°C to 330°C at a heating rate of 10°C / min.

[0050] [Thermogravimetric analysis test (TGA test)] The prepared resin is placed in a high temperature furnace. The resin is kept at 180°C for 1 hour under vacuum conditions to remove the solvent. Then, the resin undergoes pre-crosslinking at 200°C for 2 hours and proceeds to full cure at 250°C for 6 hours. 10 mg of the cured product is subjected to analysis using a thermogravimetric analyzer (TGA, model: Waters Q500) under the following temperature conditions: equilibration at 50°C for 5 minutes, followed by heating to 800°C at a rate of 10°C / min. The weight loss percentage of the thermoset product is 5 wt% (T d5 ) is recorded.

[0051] [Coefficient of thermal expansion (CTE) test] The prepared resin is placed in a high temperature furnace. The resin is kept at 180°C for 1 hour under vacuum conditions to remove the solvent. The resin then undergoes pre-crosslinking at 200°C for 2 hours and proceeds to full cure at 250°C for 6 hours. The cured product is cut into pieces with dimensions of 10mm x 10mm x 5mm. The cut products are then subjected to analysis using a thermal mechanical analyzer (TMA, model number: Waters Q400). The test conditions are: heating from 30°C to 330°C at a heating rate of 10°C / min, followed by cooling from 330°C to 30°C at a cooling rate of 10°C / min to complete the calibration, followed by heating from 30°C to 330°C at a heating rate of 10°C / min while recording the thermal coefficient of expansion (CTE) from 50°C to 260°C.

[0052] [GPC test] The prepared resin is diluted to 200 ppm with tetrahydrofuran and then placed in an autosampler (model: Waters 717 plus Autosampler). The sample is pumped by a pump (model: Waters 515 pump) at a flow rate of 1.0 mL / min into a series of gel permeation chromatography columns (models and numbers: TSK gel G3000HXL×1+G2000HXL×1+G1000HXL×2) for separation, and the samples eluted from 20 to 35 minutes are collected. An absorbance detector (model: Waters 2487 Dual λ Absorbance Detector) is used to analyze the total absorbance peaks within the range of 190 nm to 800 nm. The area A of the absorbance peak at 254 nm relative to the total area of ​​all absorbance peaks is then calculated. 254 To calculate the percentage, chromatographic analysis software SISC32-GPC available from Scientific Information Service Company is used.

[0053] [Precipitation test] The prepared resin is placed in a high temperature furnace. The resin is maintained at 180°C for 1 hour under vacuum conditions to remove the solvent. Then the resin undergoes pre-crosslinking at 200°C for 2 hours to obtain the pre-crosslinked product. The pre-crosslinked product is dissolved in a 1:1 mixed solvent of methyl ethyl ketone (MEK) and propylene glycol methyl ether (PGME) to form a solution with a solid content of 60% to 75% by weight. The resulting solution is left at 30°C for 3 days and observed for precipitation, which indicates the formation of phase heterogeneity.

[0054] (3.2. Synthesis of bisphenol compounds containing two or more allyl groups per molecule) [Synthesis Example 1] 228 g of bisphenol A (commercially available from Chang Chun Plastics Company, CAS number: 80-05-7) was dissolved in dimethyl sulfoxide (CAS number: 67-68-5). Then, 170 g of 50% NaOH (CAS number: 1310-73-2) was added and stirred at room temperature until a clear solution was obtained. The resulting clear solution was then heated to 70° C. and 170 g of allyl chloride (CAS number: 107-05-1) was added until the reaction was complete. The reaction product was heated to 200° C. under vacuum conditions and stirred at 200° C. for 2 hours to obtain an intermediate product.

[0055] The intermediate product was dissolved in dimethyl sulfoxide (CAS number: 67-68-5). Then, 170g of 50% NaOH (CAS number: 1310-73-2) was added and stirred at room temperature until a clear solution was obtained. The resulting clear solution was then heated to 70°C and 170g of allyl chloride (CAS number: 107-05-1) was added until the reaction was complete. The reaction product was heated to 200°C under vacuum and stirred at 200°C for 2 hours to obtain bisphenol A containing four allyl groups.

[0056] 3.3. Preparation of Allyl-Containing Bisphenol Resins [Example 1] 58.2 g of bisphenol A containing four allyls synthesized in Synthesis Example 1 and 53.7 g of BMI-1000 (a bismaleimide available from DKK Company) were added to a 200 mL reactor. The mixture was stirred at a rotation speed of 200 rpm at 130° C. for 2 hours to initiate the reaction, and an allyl-containing bisphenol resin E1 of Example 1 was obtained.

[0057] [Example 2] 58.2 g of bisphenol A containing four allyls synthesized in Synthesis Example 1 and 55.8 g of BES1-5950 (a multifunctional maleimide available from Regina Company) were added to a 200 mL reactor. The mixture was stirred at a rotation speed of 200 rpm at 130° C. for 2 hours to initiate the reaction, and an allyl-containing bisphenol resin E2 of Example 2 was obtained.

[0058] [Example 3] 58.2 g of bisphenol A containing four allyl groups synthesized in Synthesis Example 1 and 66.4 g of BMI-70 (a bismaleimide available from KI Chemical Company) were added to a 200 mL reactor. The mixture was stirred at a rotation speed of 200 rpm at 130° C. for 2 hours to initiate the reaction, and an allyl-containing bisphenol resin E3 of Example 3 was obtained.

[0059] [Example 4] 58.2 g of bisphenol A containing four allyls synthesized in Synthesis Example 1 and 42.3 g of TDAB (a bismaleimide commercially available from EVONIK Company) were added to a 200 mL reactor. The mixture was stirred at a rotation speed of 200 rpm at 130° C. for 2 hours to initiate the reaction, and an allyl-containing bisphenol resin E4 of Example 4 was obtained.

[0060] [Example 5] 58.2 g of bisphenol A containing four allyls synthesized in Synthesis Example 1 and 53.7 g of BMI-1000 (a bismaleimide available from DKK Company) were added to a 200 mL reactor. The mixture was stirred at a rotation speed of 100 rpm at 130° C. for 2 hours to initiate the reaction, and an allyl-containing bisphenol resin E5 of Example 5 was obtained.

[0061] [Example 6] 58.2 g of bisphenol A containing four allyls synthesized in Synthesis Example 1 and 55.8 g of BES1-5950 (a multifunctional maleimide available from Regina Company) were added to a 200 mL reactor. The mixture was stirred at a rotation speed of 100 rpm at 130° C. for 2 hours to initiate the reaction, and an allyl-containing bisphenol resin E6 of Example 6 was obtained.

[0062] [Comparative Example 1] As resin CE1 of Comparative Example 1, 100 g of 8292N75 (a maleimide resin available from Huntsman Company) is taken.

[0063] [Comparative Example 2] 46.2 g of bisphenol containing two allyl groups (CAS number: 1745-89-7) and 53.7 g of Homide-121 (a bismaleimide available from HOS Company) were added to a 200 mL reactor. The mixture was stirred at a rotation speed of 200 rpm at 130° C. for 2 hours to initiate the reaction, and an allyl-containing bisphenol resin CE2 of Comparative Example 2 was obtained.

[0064] [Comparative Example 3] 46.2 g of bisphenol containing two allyl groups (CAS number: 1745-89-7) and 53.7 g of BMI-1000 (a bismaleimide available from DKK Company) were added to a 200 mL reactor. The mixture was stirred at a rotation speed of 200 rpm at 130° C. for 2 hours to initiate the reaction, and an allyl-containing bisphenol resin CE3 of Comparative Example 3 was obtained.

[0065] [Comparative Example 4] 58.2 g of bisphenol A containing four allyls synthesized in Synthesis Example 1 and 53.7 g of BMI-1000 (a bismaleimide commercially available from DKK Company) were added to a 200 mL reactor. The mixture was stirred at a rotation speed of 200 rpm at 130° C. for 0.5 hours to initiate the reaction, and an allyl-containing bisphenol resin CE4 of Comparative Example 4 was obtained.

[0066] [Comparative Example 5] 58.2 g of bisphenol A containing four allyl groups synthesized in Synthesis Example 1 and 53.7 g of BMI-1000 (a bismaleimide commercially available from DKK Company) were added to a 200 mL reactor. The mixture was stirred at a rotation speed of 200 rpm at 130° C. for 1 hour to initiate the reaction, and an allyl-containing bisphenol resin CE5 of Comparative Example 5 was obtained.

[0067] [Comparative Example 6] 58.2 g of bisphenol A containing four allyls synthesized in Synthesis Example 1 and 55.8 g of BES1-5950 (a polyfunctional maleimide available from Regina Company) were added to a 200 mL reactor. The mixture was stirred at a rotation speed of 200 rpm at 130° C. for 0.5 hours to initiate the reaction, and an allyl-containing bisphenol resin CE6 of Comparative Example 6 was obtained.

[0068] [Comparative Example 7] 58.2 g of bisphenol A containing four allyls synthesized in Synthesis Example 1 and 55.8 g of BES1-5950 (a multifunctional maleimide available from Regina Company) were added to a 200 mL reactor. The mixture was stirred at a rotation speed of 200 rpm at 130° C. for 1 hour to initiate the reaction, and an allyl-containing bisphenol resin CE7 of Comparative Example 7 was obtained.

[0069] (3.4. Allyl-containing bisphenol resin characteristic test) The resin properties of Examples E1-E6 and Comparative Examples CE1-CE7, including infrared spectrum properties, glass transition temperature, thermogravimetric properties, thermal expansion coefficient, GPC performance, and precipitation properties, were tested according to the test methods described above, and the results are summarized in Tables 1-1 and 1-2 below.

[0070] [Table 1-1]

[0071] [Table 1-2]

[0072] As shown in Tables 1-1 and 1-2, the cured products of the allyl-containing bisphenol resins of Examples E1 to E6 of the present application have excellent heat resistance and dimensional stability, and no precipitation occurs from these allyl-containing bisphenol resins, which indicates good stability. In contrast, Comparative Examples CE1 to CE7, which are not allyl-containing bisphenol resins of the present application, cannot simultaneously achieve excellent heat resistance, dimensional stability, and stability.

[0073] The above examples illustrate the principle and effectiveness of the present application, and show the inventive features of the present application. Those skilled in the art may develop various modifications and variations based on the disclosure and suggestions of the present invention described without departing from the principle of the present invention. Therefore, the scope of protection of the present application is as defined in the appended claims.

[0074] [Note] [Appendix 1] An allyl-containing bisphenol resin comprising a bisphenol compound containing two or more allyl groups per molecule and a first structural unit derived from a polyfunctional maleimide compound, wherein the first structural unit contains one or more allyl groups, and when the allyl-containing bisphenol resin is characterized by Fourier transform infrared spectroscopy (FTIR), the FTIR spectrum of the allyl-containing bisphenol resin has a peak at 1615 cm -1 ~1765cm -1 A characteristic peak A at frequencies in the range of 1615 cm -1 ~1765cm -1 and a characteristic peak B at frequencies in the range of 1155 cm -1 ~1265cm -1 and characteristic peak C at a frequency in the range of A, B, C, the frequency of characteristic peak A being lower than the frequency of characteristic peak B, said characteristic peaks A, B, C each having a corresponding peak area A A , A B , A C These include (A A / A C )+(A C / A B ) = 1.20 to 1.60.

[0075] [Appendix 2] The characteristic peak A is at 1615 cm -1 ~1690cm -1 and the characteristic peak B is at 1690 cm -1 ~1765cm -1 2. The allyl-containing bisphenol resin of claim 1, having a vibration frequency in the range of

[0076] [Appendix 3] The peak area A A , the peak area A B and the peak area A C is (A A / A C )+(A C / A B )=1.25 to 1.52.

[0077] [Appendix 4] A A / A C = 0.25 to 0.60.

[0078] [Appendix 5] A C / A B = 0.70 to 1.40.

[0079] [Appendix 6] The Fourier transform infrared spectroscopy was carried out by coating the allyl-containing bisphenol resin on a KBr pellet by a film method, and measuring the concentration of the allyl-containing bisphenol resin by 1 cm using a Fourier transform infrared spectrophotometer. -1 By using the transmission method under a resolution of 400 cm and a number of scans of 16, -1 ~4000cm -1 The allyl-containing bisphenol resin of claim 1, wherein the absorption spectrum of the coated KBr pellet is measured over a scan range of 100 nm to 150 nm.

[0080] [Appendix 7] The allyl-containing bisphenol resin according to any one of Appendices 1 to 6, wherein the bisphenol compound containing two or more allyl groups per molecule is selected from the group consisting of bisphenol A containing two or more allyl groups per molecule, bisphenol B containing two or more allyl groups per molecule, bisphenol F containing two or more allyl groups per molecule, bisphenol S containing two or more allyl groups per molecule, bisphenol Z containing two or more allyl groups per molecule, 4,4'-dihydroxydiphenyl ether compounds containing two or more allyl groups per molecule, and combinations thereof.

[0081] [Appendix 8] 7. The allyl-containing bisphenol resin of any one of claims 1 to 6, further comprising a polyfunctional maleimide compound.

[0082] [Appendix 9] An allyl-containing bisphenol resin comprising the structure of formula (I): [ka] Formula (I) (However, at least one R1 [ka] and at least one R1 is [ka] with the proviso that each R1 is independently -H, -CH3, [ka] or [ka] and R2 is a group derived from a polyfunctional maleimide, and T is -CH2-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -SO2-, -O-, or [ka] It is.)

[0083] [Appendix 10] The allyl-containing bisphenol resin according to claim 9, comprising the structure of the following formula (I-1): [ka] Formula (I-1) (However, at least one R1 [ka] and the other R1 is [ka] and R2 is a group derived from a polyfunctional maleimide, and T is -CH2-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -SO2-, -O-, or [ka] It is.)

[0084] [Appendix 11] R2 is [ka] or [ka] and R3 is [ka] [ka] [ka] [ka] and, [ka] (where n is an integer between 1 and 10) 11. The allyl-containing bisphenol resin according to claim 9 or 10, selected from the group consisting of:

[0085] [Appendix 12] When the allyl-containing bisphenol resin is characterized by gel permeation chromatography (GPC) and an absorbance detector, the allyl-containing bisphenol resin has an absorbance peak at 254 nm, and the absorbance peak has an area A 254 The area A is the total area of ​​all the absorption peaks. 254 The ratio of is 15% or less, and the test conditions of the gel permeation chromatography (GPC) and the absorbance detector are as follows: the allyl-containing bisphenol resin is diluted with tetrahydrofuran to a concentration of 200 ppm, and fed to a series of columns including one column C1, one column C2, and two columns C3 in this order at a flow rate of 1.0 mL / min to carry out separation; samples are taken during an elution time between 20 and 35 minutes and analyzed by an absorbance detector for total absorbance peaks within a range of 190 nm to 800 nm; and the ratio of the area A of the absorbance peak at 254 nm to the total area of ​​all absorbance peaks is 1.0 mL / min. 254 the column C1 is 30 cm long, has an inner diameter of 7.8 mm, and is packed with polystyrene-divinylbenzene having an average particle diameter of 5 μm and an average pore diameter of 7.5 nm; the column C2 is 30 cm long, has an inner diameter of 7.8 mm, and is packed with polystyrene-divinylbenzene having an average particle diameter of 5 μm and an average pore diameter of 2 nm; and the column C3 is 30 cm long, has an inner diameter of 7.8 mm, and is packed with polystyrene-divinylbenzene having an average particle diameter of 5 μm and an average pore diameter of 1.5 nm.

Claims

1. An allyl-containing bisphenol resin comprising a bisphenol compound containing two or more allyl groups per molecule and a first structural unit derived from a polyfunctional maleimide compound, wherein the first structural unit contains one or more allyl groups, and when the allyl-containing bisphenol resin is characterized by Fourier transform infrared spectroscopy (FTIR), the FTIR spectrum of the allyl-containing bisphenol resin has a peak at 1615 cm －１ ~1765cm －１ A characteristic peak A at frequencies in the range of 1615 cm －１ ~1765cm －１ and a characteristic peak B at frequencies in the range of 1155 cm －１ ~1265cm －１ and a characteristic peak C at a frequency in the range of A, B, and C, the frequency of the characteristic peak A being lower than the frequency of the characteristic peak B, and the characteristic peaks A, B, and C each have a corresponding peak area A Ａ , A Ｂ , A Ｃ These have the following structure: Ａ / A Ｃ ) + (A Ｃ / A Ｂ ) = 1.20 to 1.

60.

2. The characteristic peak A is at 1615 cm －１ ~1690cm －１ and the characteristic peak B is at a frequency in the range of 1690 cm －１ ~1765cm －１ 2. The allyl-containing bisphenol resin of claim 1, wherein the vibration frequency is in the range of

3. The peak area A Ａ , the peak area A Ｂ and the peak area A Ｃ (A Ａ / A Ｃ ) + (A Ｃ / A Ｂ 2. The allyl-containing bisphenol resin according to claim 1, wherein the allyl group content is 1.25 to 1.

52.

4. A Ａ / A Ｃ The allyl-containing bisphenol resin according to claim 1, wherein the allyl group is 0.25 to 0.

60.

5. A Ｃ / A Ｂ The allyl-containing bisphenol resin according to claim 1, wherein the allyl group is 0.70 to 1.

40.

6. The Fourier transform infrared spectroscopy was carried out by coating the allyl-containing bisphenol resin on a KBr pellet by a film method, and measuring the concentration of the allyl-containing bisphenol resin by 1 cm using a Fourier transform infrared spectrophotometer. －１ By using a transmission type method under a resolution of 400 cm and a number of scans of 16, －１ ~4000cm －１ 2. The allyl-containing bisphenol resin of claim 1, wherein the absorption spectrum is measured over a scan range of 100 nm to 150 nm.

7. The allyl-containing bisphenol resin according to any one of claims 1 to 6, wherein the bisphenol compound containing two or more allyl groups per molecule is selected from the group consisting of bisphenol A containing two or more allyl groups per molecule, bisphenol B containing two or more allyl groups per molecule, bisphenol F containing two or more allyl groups per molecule, bisphenol S containing two or more allyl groups per molecule, bisphenol Z containing two or more allyl groups per molecule, 4,4'-dihydroxydiphenyl ether compounds containing two or more allyl groups per molecule, and combinations thereof.

8. The allyl-containing bisphenol resin according to any one of claims 1 to 6, further comprising a polyfunctional maleimide compound.

9. An allyl-containing bisphenol resin comprising the structure of formula (I): 【Chemistry 1】 Formula (I) (However, at least one R １ teeth, 【Chemistry 2】 and at least one R １ teeth, 【Chemistry 3】 Provided that, for each R １ are independently -H, -CH ３ , 【Chemistry 4】 or 【Chemistry 5】 and R ２ is a group derived from a polyfunctional maleimide, and T is -CH ２ -, -C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ ) -, -SO ２ -, -O-, or 【Chemistry 6】 It is.)

10. The allyl-containing bisphenol resin according to claim 9, comprising a structure represented by the following formula (I-1): 【Chemistry 7】 Formula (I-1) (However, at least one R １ teeth, 【Chemistry 8】 and other R １ teeth, 【Chemistry 9】 and R ２ is a group derived from a polyfunctional maleimide, and T is -CH ２ -, -C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ ) -, -SO ２ -, -O-, or 【Chemistry 10】 It is.)

11. R ２ teeth, 【Chemistry 11】 or 【Chemistry 12】 and R ３ teeth, 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 and, 【Chemistry 17】 (where n is an integer from 1 to 10) 11. The allyl-containing bisphenol resin according to claim 9 or 10, selected from the group consisting of:

12. When the allyl-containing bisphenol resin is characterized by gel permeation chromatography (GPC) and an absorbance detector, the allyl-containing bisphenol resin has an absorbance peak at 254 nm, and the absorbance peak has an area A ２５４ and the area A relative to the total area of ​​all absorbance peaks ２５４ The ratio of is 15% or less, and the test conditions of the gel permeation chromatography (GPC) and the absorbance detector are as follows: the allyl-containing bisphenol resin is diluted with tetrahydrofuran to a concentration of 200 ppm, and fed to a series of columns including one column C1, one column C2, and two columns C3 in this order at a flow rate of 1.0 mL / min to carry out separation; samples are taken during an elution time between 20 and 35 minutes and analyzed by an absorbance detector for total absorbance peaks within a range of 190 nm to 800 nm; and the ratio of the area A of the absorbance peak at 254 nm to the total area of ​​all absorbance peaks is 1.0 mL / min. ２５４ The ratio of the allyl-containing bisphenol resin according to claim 9 is calculated, wherein the column C1 is 30 cm long, has an inner diameter of 7.8 mm, and is packed with polystyrene-divinylbenzene having an average particle diameter of 5 μm and an average pore diameter of 7.5 nm, the column C2 is 30 cm long, has an inner diameter of 7.8 mm, and is packed with polystyrene-divinylbenzene having an average particle diameter of 5 μm and an average pore diameter of 2 nm, and the column C3 is 30 cm long, has an inner diameter of 7.8 mm, and is packed with polystyrene-divinylbenzene having an average particle diameter of 5 μm and an average pore diameter of 1.5 nm.