Patent Description:
<CIT> discloses a polyhydric hydroxy resin represented by the following general formula (<NUM>) wherein a monohydric hydroxy compound represented by the following general formula (<NUM>) accounts for <NUM>% or less by area when detected by gel permeation chromatography (GPC, RI detector); Here, RI, is a hydrogen atom or a hydrocarbon group of <NUM> to <NUM> carbon atoms; R2 is a substituent represented by the following formula (a); n is a number of <NUM> to <NUM>; p is a number of <NUM> to <NUM>; and R3 is a hydrogen atom or a hydrocarbon group of <NUM> to <NUM> carbon atoms; OH HC-CH3 (<NUM>) Here, p is a number of <NUM> to <NUM> and each of Ri and R3 is a hydrogen atom or a hydrocarbon group of <NUM> to <NUM> carbon atoms.

<CIT> discloses dielectric epoxy resin composition having a low permittivity and a low dielectric loss tangent and being useful for, e.g. a copper- clad laminate for electronic circuit boards by mixing a specified epoxy resin with a curing agent comprising a specified phenolic resin or a specific amine. The composition is prepared by mixing an epoxy resin (A) containing a styrene-modified phenolic novolac epoxy resin of formula I with a curing agent (B). At least part of the curing agent (B) should be a curing agent comprising a styrene-modified novolac phenolic resin or an aromatic amine. The composition allegedly has a low permittivity and a low dielectric loss tangent and is suited for an electrical insulation material, a sealing agent, a molding material, an adhesive, a casting material or the like used in copper-clad laminates used as electronic circuit boards or electronic components.

<CIT> discloses an epoxy resin which obtains a cured material excellent in flame retardancy, moisture resistance, low elasticity, or the like, which is used for sealing electronic components and is suitable for a circuit board material or the like, and to provide a polyvalent hydroxy resin and an epoxy resin composition.

The styrene-modified polyvalent hydroxy resin is obtained by reacting <NUM> mole polyvalent hydroxy compound such as a phenol novolac resin with <NUM>-<NUM> moles styrenes in the presence of an acid catalyst and has <NUM>-<NUM>/eq. hydroxyl equivalent. The epoxy resin is obtained by reacting the polyvalent hydroxy compound with epichlorohydrin and has <NUM>-<NUM>/eq. epoxy equivalent. The epoxy resin composition contains the polyvalent hydroxy resin or the epoxy resin as an essential component.

Epoxy resins are widely used in the semiconductor industry as circuit board material; they are liquid at room temperature, have good workability, and can easily be mixed with hardeners and additives. However, conventional epoxy resins are insufficient in thermal resistance and water absorption, necessitating further modifications to provide the required low water absorption (high moisture resistance), high thermal resistance, high flame retardance, and excellent dielectric properties of circuit boards.

It is known that styrene can be used to modify an epoxy resin to improve the moisture resistance of the epoxy resin. However, the by-products (e.g., styrene oligomers) generated during the modification would adversely affect the thermal resistance and flame retardance of the epoxy resin. Thus, there is a need for an epoxy resin with low water absorption, high thermal resistance, high flame retardance, and excellent dielectric properties.

Given the above, the present invention provides a polyhydric phenol resin, which comprises a specific amount of styrene oligomers and is capable of providing a glycidyl ether that can impart low water absorption, high thermal resistance, high flame retardance, and excellent dielectric properties to the electronic material prepared therefrom.

Thus, an objective of the present invention is to provide a polyhydric phenol resin, which comprises a polyhydric phenol resin component and a first component, wherein when the polyhydric phenol resin is characterized by high-performance liquid chromatography (HPLC), the first component is eluted at a retention time ranging from <NUM> minutes to <NUM> minutes, and based on the total area of the chromatographic peaks of the polyhydric phenol resin, the area percentage of the chromatographic peak of the first component at the corresponding retention time in the spectrum ranges from <NUM>% to <NUM>%.

The embodiments of the invention are defined in the independent claims. Preferred embodiments are reflected in the dependent claims.

In some embodiments of the present invention, when the polyhydric phenol resin is characterized by carbon-<NUM> nuclear magnetic resonance (<NUM>C-NMR), the <NUM>C-NMR spectrum of the polyhydric phenol resin has an integral value A of signals from <NUM> ppm to <NUM> ppm and an integral value B of signals from <NUM> ppm to <NUM> ppm, and the ratio of A to B (A/B) ranges from <NUM> to <NUM>, wherein the solvent used in the <NUM>C-NMR is dimethyl sulfoxide, and the reference substance used in the <NUM>C-NMR is tetramethylsilane.

In some embodiments of the present invention, the polyhydric phenol resin is styrenated polyhydric phenol resin.

According to the present invention, when the polyhydric phenol resin is characterized by gas chromatography-mass spectrometry (GC-MS), the first component is eluted at a retention time ranging from <NUM> minutes to <NUM> minutes, and a fragmentation pattern of the first component comprises one or more signals at a mass-to-charge ratio (m/z) selected from the group consisting of <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and <NUM>.

In some embodiments of the present invention, wherein the polyhydric phenol resin has a hydroxyl equivalent weight ranging from <NUM>/eq to <NUM>/eq.

In some embodiments of the present invention, the softening point temperature of the polyhydric phenol resin ranges from <NUM> to <NUM>, wherein the softening point temperature is measured in accordance with JIS K <NUM> ring and ball method.

Another objective of the present invention is to provide glycidyl ether of polyhydric phenol resin, which comprises a component of glycidyl ether of polyhydric phenol resin and a first component, wherein when the glycidyl ether of polyhydric phenol resin is characterized by high-performance liquid chromatography (HPLC), the first component is eluted at a retention time ranging from <NUM> minutes to <NUM> minutes, and based on the total area of the chromatographic peaks of the glycidyl ether of polyhydric phenol resin, the area percentage of the chromatographic peak of the first component at the corresponding retention time in the spectrum ranges from <NUM>% to <NUM>%.

In some embodiments of the present invention, when the glycidyl ether of polyhydric phenol resin is characterized by carbon-<NUM> nuclear magnetic resonance (<NUM>C-NMR), the <NUM>C-NMR spectrum of the glycidyl ether of polyhydric phenol resin has an integral value A of signals from <NUM> ppm to <NUM> ppm and an integral value B of signals from <NUM> ppm to <NUM> ppm, the ratio of A to B (A/B) ranges from <NUM> to <NUM>, wherein the solvent used in the <NUM>C-NMR is dimethyl sulfoxide, and the reference substance used in the <NUM>C-NMR is tetramethylsilane.

In some embodiments of the present invention, the glycidyl ether of polyhydric phenol resin is glycidyl ether of styrenated polyhydric phenol resin.

According to the present invention, when the glycidyl ether of polyhydric phenol resin is characterized by GC-MS, the first component is eluted at a retention time ranging from <NUM> minutes to <NUM> minutes, and a fragmentation pattern of the first component comprises one or more signals at a mass-to-charge ratio (m/z) selected from the group consisting of <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and <NUM>.

In some embodiments of the present invention, the glycidyl ether of polyhydric phenol resin has an epoxy equivalent weight (EEW) ranging from <NUM>/eq to <NUM>/eq.

In some embodiments of the present invention, the glycidyl ether of polyhydric phenol resin comprises <NUM> ppm or less of hydrolyzable chlorine (HyCl).

In some embodiments of the present invention, the glycidyl ether of polyhydric phenol resin has a hydroxyl value (HV) ranging from <NUM> eq/<NUM> to <NUM> eq/<NUM>.

In some embodiments of the present invention, the glycidyl ether of polyhydric phenol resin comprises <NUM> meq/g to <NUM> meq/g of α-glycol.

Yet another objective of the present invention is to provide a curable composition, which comprises (a1) the aforementioned glycidyl ether of polyhydric phenol resin, and (b1) a hardener.

Furthermore, yet another objective of the present invention is to provide a copper-clad laminate, which comprises: (a2) a dielectric layer, which comprises a dielectric material obtained by curing the aforementioned curable composition; and (b2) a copper foil, which is disposed on the surface of the dielectric layer.

To render the above objectives, technical features and advantages of the present invention more apparent, the present invention will be described in detail regarding some embodiments hereinafter.

Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention may be embodied in various embodiments and should not be limited to the embodiments described in the specification.

Unless it is additionally explained, the expressions "a," "the," or the like recited in the specification and the claims should include both the singular and the plural forms.

Unless it is additionally explained, the expressions "first", "second" or the like recited in the specification and the claims are merely used to distinguish the illustrated elements or constituents without special meanings, and those expressions do not intend to represent any priority.

Unless it is additionally explained, the "softening point temperature" is measured in accordance with JIS K <NUM> ring and ball method.

Unless it is additionally explained, the "hydrolyzable chlorine (HyCl) amount" is measured in accordance with ASTM-D1652.

Unless it is additionally explained, the "α-glycol amount" is measured in accordance with JIS-K-<NUM>.

Unless it is additionally explained, in the specification and the claims, the term "normal pressure" refers to a pressure of <NUM> (one) atmosphere (<NUM> torrs), and the term "normal temperature" refers to a temperature of <NUM>.

In the specification and the claims, a specific component being eluted at a specific range of retention time means that the chromatographic peaks appearing within the specific range of retention time indicate the region representing the specific component. The integral area of the chromatographic peaks of the specific component is calculated from the integral area of the chromatographic peaks within the retention time range. In addition, in the NMR detection, the integral value represents the integral value of the total areas of the signals within the given ppm range.

In the specification and the claims, in the HPLC spectrum and NMR spectrum, the determination of the area of a chromatographic peak is as follows. A B-V-B (baseline-valley-baseline) approach is applied, wherein all the chromatographic peaks or signal values use the same baseline, and a straight line is extended vertically to the baseline from each of the valleys of a specific chromatographic peak or a specific signal value down to the baseline to determine the area to be integrated for the specific chromatographic peak or the specific signal value. The baseline means a signal of a mobile phase or a background signal detected when no test sample passes through the detector.

The polyhydric phenol resin and the glycidyl ether of polyhydric phenol resin of the present invention each have excellent thermal resistance, flame retardance, moisture resistance, and electrical properties. The polyhydric phenol resin and the glycidyl ether of polyhydric phenol resin as well as their uses will be described in detail as follows.

The polyhydric phenol resin of the present invention comprises a polyhydric phenol resin component and a first component and has features characterized by HPLC spectrum. In some embodiments of the present invention, the polyhydric phenol resin component is a styrenated polyhydric phenol resin component. The styrenated polyhydric phenol resin component can have a structure represented by the following chemical formula (I).

In chemical formula (I), R<NUM> is
<CHM>
n is an integer of <NUM> to <NUM>; and m is <NUM> to <NUM>, such as <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>, or within a range between any two of the values described herein. Here, m refers to the average number of styryl bonded to one phenol ring. For example, when n is <NUM>, and the phenol ring at the left end has two styryl groups bonded thereto while other phenol rings each has one styryl bonded thereto, m is <NUM>.

When the polyhydric phenol resin is characterized by HPLC, the first component is eluted at a retention time ranging from <NUM> minutes to <NUM> minutes; that is, the wave crest (peak value) of the chromatographic peak of the first component can fall at <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, or <NUM> minutes, or within a range between any two of the values described herein. In addition, based on the total area of the chromatographic peaks of the polyhydric phenol resin, the area percentage of the chromatographic peak of the first component at the corresponding retention time in the spectrum ranges from <NUM>% to <NUM>%. For example, the area percentage of the chromatographic peak of the first component at the corresponding retention time in the spectrum can be <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, or <NUM>%, or within a range between any two of the values described herein. By means of controlling the amount of the first component in the polyhydric phenol resin within the aforementioned range, the thermal resistance and flame retardance of the polyhydric phenol resin can be improved, and the epoxy resin (also referred to "glycidyl ether of polyhydric phenol resin" herein) formed from the polyhydric phenol resin is particularly useful for circuit board material or high-frequency adhesives.

The aforementioned HPLC analysis is performed as follows. First, the polyhydric phenol resin is loaded into an octadecylsilane (ODS) column which is <NUM> in length and <NUM> in inner diameter and has fillers with a particle size of <NUM>. Then, the HPLC analysis is performed under the following conditions: a detector applying <NUM> wavelength ultraviolet light; a column temperature of <NUM>; a detector temperature of <NUM>; a mobile phase flow rate of <NUM>/min; a sample which is formulated with acetonitrile (ACN) as a solvent and has a sample concentration of <NUM> wt% in ACN; an injection amount of <NUM>µL; and a composition of mobile phase as follows: from <NUM> minutes to the <NUM>th minute of the washing time, the mobile phase is a mixture of <NUM> vol% of water and <NUM> vol% of acetonitrile; from the <NUM>th minute to the <NUM>th minute of the washing time, the mobile phase changes from a mixture of <NUM> vol% of water and <NUM> vol% of acetonitrile to <NUM> vol% of acetonitrile in a linear gradient manner with respect to time, and from the <NUM>th minute to the <NUM>th minute of the washing time, the mobile phase is <NUM> vol% of acetonitrile. Detailed descriptions regarding the linear gradient manner will be described in the following measuring method section of the Examples.

In some embodiments of the present invention, the first component is a compound represented by the following chemical formula (II). The compound represented by the chemical formula (II) is a dimer of styrene.

In some embodiments of the present invention, when the polyhydric phenol resin is characterized by carbon-<NUM> nuclear magnetic resonance (<NUM>C-NMR), the <NUM>C-NMR spectrum of the polyhydric phenol resin has an integral value A of signals from <NUM> ppm to <NUM> ppm and an integral value B of signals from <NUM> ppm to <NUM> ppm, and the ratio of A to B (A/B) ranges from <NUM> to <NUM>. For example, the ratio of A to B can be <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>, or within a range between any two of the values described herein.

In the present invention, <NUM>C-NMR is obtained by performing measurement using dimethyl sulfoxide as the solvent, and tetramethylsilane as the reference substance. In some embodiments of the present invention, <NUM>C-NMR is performed by using a nuclear magnetic resonance spectrometer under the following conditions: a test temperature of <NUM>, a resonance frequency of <NUM>, a pulse width of <NUM>, a waiting time of <NUM> (one) second, a scan number of <NUM> times, and a signal of tetramethylsilane being set as <NUM> ppm.

When the polyhydric phenol resin is characterized by gas chromatography-mass spectrometry (GC-MS), the first component is eluted at a retention time ranging from <NUM> minutes to <NUM> minutes, that is, the wave crest (peak value) of the chromatographic peak of the first component can fall at <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, or <NUM> minutes, or falls within a range between any two of the values described herein. The fragmentation pattern of the first component comprises one or more signals at a mass-to-charge ratio (m/z) selected from the group consisting of <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and <NUM>.

The aforementioned GC-MS analysis is performed as follows, wherein before performing the GC-MS analysis, it is preferred that the sample of the polyhydric phenol resin to be analyzed is subjected to pretreatment in the following manners. First, the sample of the polyhydric phenol resin is heated in an oven at <NUM> for <NUM> (one) hour to make the sample uniform. Then, the sample is mixed with acetone (i.e., a solvent) to prepare a solution with a weight percentage concentration of <NUM>% to complete pretreatment of the sample to be analyzed.

First, the pretreated sample of polyhydric phenol resin is loaded into a gas chromatograph, the gas chromatograph is equipped with a Phenomenex Zebron ZB-<NUM> capillary column (stationary phase composition: <NUM>% phenyl, <NUM>% dimethylpolysiloxane) which is <NUM> meters in length and <NUM> in inner diameter and has a film thickness of <NUM>. Under an inlet temperature of <NUM> and a carrier gas of helium with a flow rate of <NUM>/min, the oven of the gas chromatograph is subjected to the following stepped heating operation: the temperature is maintained at <NUM> for <NUM> minutes, then raised from <NUM> to <NUM> with a heating rate of <NUM>/min and maintained at <NUM> for <NUM> minutes. Afterwards, the gas chromatograph is connected with a mass spectrograph, and the GC-MS analysis is operated under the following conditions: electron energy of <NUM> eV, an ion source temperature of <NUM>, use of a quadrupole mass filter, an interface temperature of <NUM>, a mass scan range of <NUM> daltons to <NUM> daltons, a solvent delay time of <NUM> minutes, and a scan rate of <NUM> u/sec.

In some embodiments of the present invention, the polyhydric phenol resin further has a hydroxyl equivalent weight ranging from <NUM>/eq to <NUM>/eq. For example, the hydroxyl equivalent weight of the polyhydric phenol resin can be <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, or <NUM>/eq, or within a range between any two of the values described herein.

In some embodiments of the present invention, the polyhydric phenol resin further has a softening point temperature ranging from <NUM> to <NUM>. For example, the softening point temperature of the polyhydric phenol resin can be <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>, or within a range between any two of the values described herein. The aforementioned softening point temperature is measured in accordance with the ring and ball method of JIS K <NUM>.

The polyhydric phenol resin of the present invention can be prepared by reacting phenols with formaldehyde. For example, a styrenated polyhydric phenol resin can be prepared by reacting phenols with styrene to form styrenated phenols and then reacting styrenated phenols with formaldehyde. Alternatively, a styrenated polyhydric phenol resin can be prepared by reacting phenols with formaldehyde to form polyhydric phenol resin and then reacting styrene with the polyhydric phenol resin via addition reaction.

Examples of the aforementioned phenols include but are not limited to phenol, m-cresol, p-cresol, o-cresol, ethylphenol, isopropylphenol, t-butylphenol, allylphenol and phenylphenol. In some embodiments of the present invention, the polyhydric phenol is prepared by using phenol and styrene.

The aforementioned reaction of styrenated phenols and formaldehyde can be performed in the presence of acid catalysts. The acid catalysts include organic acids and inorganic acids. Examples of inorganic acids include but are not limited to hydrochloric acid, sulfuric acid, and phosphoric acid. Examples of organic acids include but are not limited to methanoic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, and dimethylsulfuric acid. In some embodiments of the present invention, the polyhydric phenol is prepared by using oxalic acid, p-toluenesulfonic acid, or methanesulfonic acid. In addition, the aforementioned reaction of phenols with formaldehyde and the addition reaction of styrene and polyhydric phenol resin can also be performed in the presence of an acid catalyst, and examples of the acid catalysts includes the aforementioned organic acids and inorganic acids suitable for the reaction of styrenated phenols and formaldehyde.

The styrene used in the present invention can further comprise one or more substituents. Examples of substituents include methyl, ethyl, propyl, dimethyl, and diethyl. The oligomer formed from the styrene can also comprise the aforementioned substituents.

The reaction of styrenated phenols and formaldehyde can be performed under the following conditions. Formaldehyde is dripped into a mixture of styrenated phenols and an acid catalyst at <NUM> to <NUM> in <NUM> (one) hour to <NUM> hours, and then the temperature is raised to <NUM> to <NUM> to remove water by distillation under normal pressure for <NUM> (one) hour to <NUM> hours. Afterwards, a neutralizing agent is added, and the temperature is raised to <NUM> to <NUM> to perform reduced pressure distillation under an absolute pressure of <NUM> mmHg to <NUM> mmHg for <NUM> hours to <NUM> hours to obtain styrenated polyhydric phenol resin. Examples of neutralizing agents include but are not limited to sodium hydroxide, sodium hydrogen carbonate, potassium hydroxide, sodium acetate, and sodium carbonate.

The reaction of phenols and formaldehyde can be performed under the following conditions. Formaldehyde is dripped into a mixture of phenols and an acid catalyst at <NUM> to <NUM> in <NUM> (one) hour to <NUM> hours, and then the temperature is raised to <NUM> to <NUM> to remove water by distillation under normal pressure for <NUM> (one) hour to <NUM> hours. Afterwards, the temperature is raised to <NUM> and <NUM> to perform reduced pressure distillation under an absolute pressure of <NUM> mmHg to <NUM> mmHg for <NUM> hours to <NUM> hours to obtain polyhydric phenol resin.

The addition reaction of styrene and polyhydric phenol resin can be performed under the following conditions. Styrene is dripped into a mixture of polyhydric phenol resin and an acid catalyst at <NUM> to <NUM> for <NUM> (one) hour to <NUM> hours, and the reaction is performed for <NUM> hours to <NUM> hours. Then, the temperature is raised to <NUM> and <NUM> to perform reduced pressure distillation under an absolute pressure of <NUM> mmHg to <NUM> mmHg for <NUM> hours to <NUM> hours to obtain styrenated polyhydric phenol resin.

The present invention also provides a glycidyl ether of polyhydric phenol resin, which can be obtained by performing glycidyl etherification of the polyhydric phenol resin of the present invention. The glycidyl ether of polyhydric phenol resin of the present invention has features characterized by HPLC spectrum, and the glycidyl ether of polyhydric phenol resin of the present invention comprises a component of glycidyl ether of polyhydric phenol resin and a first component. In some embodiments of the present invention, the component of glycidyl ether of polyhydric phenol resin is a component of glycidyl ether of styrenated polyhydric phenol resin. In some embodiments of the present invention, the component of glycidyl ether of styrenated polyhydric phenol resin has a structure represented by the following chemical formula (III). <CHM>
<CHM>.

In chemical formula (III), R<NUM> is
<CHM>
n is an integer of <NUM> to <NUM>; and m is <NUM> to <NUM>, such as <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>, or within a range between any two of the values described herein. Here, m refers to the average number of styryl bonded to one phenol ring. For example, when n is <NUM>, and the phenol ring at the left end has two styryl groups bonded thereto while other phenol rings each has one styryl bonded thereto, m is <NUM>.

When the glycidyl ether of polyhydric phenol resin is characterized by HPLC, the first component is eluted at a retention time ranging from <NUM> minutes to <NUM> minutes, that is, the wave crest (peak value) of the chromatographic peak of the first component can fall at <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, or <NUM> minutes, or falls within a range between any two of the values described herein. In addition, based on the total area of the chromatographic peaks of the glycidyl ether of polyhydric phenol resin, the area percentage of the chromatographic peak of the first component at the corresponding retention time in the spectrum ranges from <NUM>% to <NUM>%. For example, the area percentage of the chromatographic peak of the first component at the corresponding retention time in the spectrum can be <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, or <NUM>%, or within a range between any two of the values described herein. By means of controlling the amount of the first component of the glycidyl ether of polyhydric phenol resin within the aforementioned range, the thermal resistance and flame retardance of the glycidyl ether of polyhydric phenol resin can be improved, and the glycidyl ether of polyhydric phenol resin is particularly useful for circuit board material or high-frequency adhesives.

The aforementioned HPLC is performed as below. First, the glycidyl ether of polyhydric phenol resin is loaded into an ODS column of <NUM> in length, <NUM> in inner diameter and has fillers with a filler particle size of <NUM>. Then, HPLC analysis is performed under the following conditions: a detector applying <NUM> wavelength ultraviolet light; a column temperature of <NUM>; a detector temperature of <NUM>; a mobile phase flow rate of <NUM>/min; a sample which is formulated with acetonitrile (CAN) as a solvent and has a sample concentration of <NUM> wt% in ACN; an injection amount of <NUM>µL; and a composition of mobile phase as follows: from <NUM> minutes to the <NUM>th minute of the washing time, the mobile phase is a mixture of <NUM> vol% of water and <NUM> vol% of acetonitrile; from the <NUM>th minute to the <NUM>th minute of the washing time, the mobile phase changes from a mixture of <NUM> vol% of water and <NUM> vol% of acetonitrile to <NUM> vol% of acetonitrile in a linear gradient manner with respect to time; and from the <NUM>th minute to the <NUM>th minute of the washing time, the mobile phase is <NUM> vol% of acetonitrile.

In some embodiments of the present invention, the first component is a compound represented by the following chemical formula (II). <CHM>
<CHM>.

In some embodiments of the present invention, when the glycidyl ether of polyhydric phenol resin is characterized by <NUM>C-NMR, the <NUM>C-NMR spectrum of the glycidyl ether of polyhydric phenol resin has an integral value A of signals from <NUM> ppm to <NUM> ppm and an integral value B of signals from <NUM> ppm to <NUM> ppm, and the ratio of A to B (A/B) ranges from <NUM> to <NUM>, such as <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>, or within a range between any two of the values described herein.

When the glycidyl ether of polyhydric phenol resin is characterized by GC-MS, the first component is eluted at a retention time ranging from <NUM> minutes to <NUM> minutes, that is, the wave crest (peak value) of the chromatographic peak of the first component can fall at <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, <NUM> minutes, or <NUM> minutes, or falls within a range between any two of the values described herein. The fragmentation pattern of the first component comprises one or more signals at a mass-to-charge ratio (m/z) selected from the group consisting of <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and <NUM>.

The aforementioned GC-MS analysis is performed as follows, wherein before performing the GC-MS analysis, it is preferred that the sample of the glycidyl ether of polyhydric phenol resin to be analyzed is subjected to pretreatment in the following manners. First, the sample of the glycidyl ether of polyhydric phenol resin is heated in an oven at <NUM> for <NUM> (one) hour to make the sample uniform. Then, the sample is mixed with acetone (i.e., a solvent) to prepare a solution with a weight percentage concentration of <NUM>% to complete pretreatment of the sample to be tested.

The pretreated sample of glycidyl ether of polyhydric phenol resin is loaded into a gas chromatograph, the gas chromatograph is equipped with a Phenomenex Zebron ZB-<NUM> capillary column (stationary phase composition: <NUM>% phenyl, <NUM>% dimethylpolysiloxane) which is <NUM> meters in length and <NUM> in inner diameter and has a film thickness of <NUM>. Under a carrier gas of helium with a flow rate of <NUM>/min and an inlet temperature of <NUM>, the oven of the gas chromatograph is subjected to the following stepped heating operation: the temperature is maintained at <NUM> for <NUM> minutes, then raised from <NUM> to <NUM> with a heating rate of <NUM>/min and maintained at <NUM> for <NUM> minutes. Then, the gas chromatograph is connected with a mass spectrograph, and the GC-MS analysis is operated under the following conditions: electron energy of <NUM> eV, an ion source temperature of <NUM>, use of a quadrupole mass filter, an interface temperature of <NUM>, a mass scan range of <NUM> daltons to <NUM> daltons, a solvent delay time of <NUM> minutes, and a scan rate of <NUM> u/sec.

In some embodiments of the present invention, the glycidyl ether of polyhydric phenol resin further has an EEW ranging from <NUM>/eq to <NUM>/eq, such as an EEW of <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, <NUM>/eq, or <NUM>/eq, or an EEW within a range between any two of the values described herein.

In some embodiments of the present invention, the glycidyl ether of polyhydric phenol resin comprises <NUM> ppm or less of HyCl. For example, the content of HyCl can be <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, or <NUM> ppm, or within a range between any two of the values described herein.

In some embodiments of the present invention, the glycidyl ether of polyhydric phenol resin further has a HV ranging from <NUM> eq/<NUM> to <NUM> eq/<NUM>, such as a HV of <NUM> eq/<NUM>, <NUM> eq/<NUM>, <NUM> eq/<NUM>, <NUM> eq/<NUM>, <NUM> eq/<NUM>, <NUM> eq/<NUM>, <NUM> eq/<NUM>, <NUM> eq/<NUM>, <NUM> eq/<NUM>, <NUM> eq/<NUM>, <NUM> eq/<NUM>, <NUM> eq/<NUM>, or <NUM> eq/<NUM>, or a HV within a range between any two of the values described herein.

In some embodiments of the present invention, the glycidyl ether of polyhydric phenol resin further comprises <NUM> meq/g to <NUM> meq/g of α-glycol. For example, the content of α-glycol can be <NUM> meq/g, <NUM> meq/g, <NUM> meq/g, <NUM> meq/g, <NUM> meq/g, <NUM> meq/g, <NUM> meq/g, <NUM> meq/g, <NUM> meq/g, <NUM> meq/g, <NUM> meq/g, <NUM> meq/g, or <NUM> meq/g, or within a range between any two of the values described herein.

The glycidyl ether of polyhydric phenol resin of the present invention can be prepared by reacting polyhydric phenol resin with epihalohydrin. For example, glycidyl ether of styrenated polyhydric phenol resin can be prepared by reacting a styrenated polyhydric phenol resin with an epihalohydrin or can be prepared by reacting a styrenated polyhydric phenol resin with allyl halide to form allyl ether of styrenated polyhydric phenol resin and then reacting allyl ether of styrenated polyhydric phenol resin with peroxides. Examples of epihalohydrin include but are not limited to epichlorohydrin. Examples of allyl halide include but are not limited to allyl chloride.

The reaction of styrenated polyhydric phenol resin and epichlorohydrin can be performed in the presence of alkali metal hydroxides. Examples of the alkali metal hydroxides include but are not limited to sodium hydroxide, potassium hydroxide and lithium hydroxide.

Specifically, the reaction of styrenated polyhydric phenol resin and epichlorohydrin can be performed under the following conditions. Styrenated polyhydric phenol resin, epichlorohydrin and a solvent are mixed under normal pressure to obtain a mixture. The mixture is heated to <NUM> to <NUM> under an absolute pressure of <NUM> mmHg to <NUM> mmHg, and then an alkali metal hydroxide is dripped thereinto while the mixture is maintained at <NUM> to <NUM> for <NUM> hours to <NUM> hours to react. The unreacted epichlorohydrin and the solvent are recovered via vacuum and the product is washed by the solvent. Afterwards, the solvent is removed by vacuum to obtain glycidyl ether of styrenated polyhydric phenol resin.

Alternatively, the reaction of styrenated polyhydric phenol resin and epichlorohydrin can be performed under the following conditions. Styrenated polyhydric phenol resin, epichlorohydrin and a coupling agent are mixed under normal pressure at <NUM> to <NUM> to form a mixture with uniform composition. Then, the mixture is heated to <NUM> to <NUM> within <NUM> hours to <NUM> hours and maintained at said temperature for <NUM> hours to <NUM> hours. Afterwards, an alkali metal hydroxide is dripped into the mixture at <NUM> to <NUM> within <NUM> hours to <NUM> hours. The mixture is subjected to azeotropic distillation and condensation at an absolute pressure of <NUM> mmHg to <NUM> mmHg and maintained for <NUM> hours to <NUM> hours to perform dehydrohalogenation, and during the azeotropic distillation and condensation, the organic phase is recovered back to the reactor. Next, after the unreacted epichlorohydrin is removed under reduced pressure, dehydrohalogenation is performed again and an alkali metal hydroxide is added at <NUM> to <NUM> under normal pressure. The obtained crude product is washed with a solvent and the solvent is then filtered and removed under reduced pressure to obtain a glycidyl ether of styrenated polyhydric phenol resin.

The glycidyl ether of polyhydric phenol resin of the present invention can be cured to form a dielectric material or a high-frequency adhesive. Thus, the present invention also provides a curable composition, which comprises (a1) the aforementioned glycidyl ether of polyhydric phenol resin, and (b1) a hardener.

Examples of the aforementioned hardener include but are not limited to guanidine-based hardeners, anhydride-based hardeners, polyvalent phenol-based hardeners, aromatic amine-based hardeners, and aliphatic amine-based hardeners. Examples of guanidine-based hardeners include but are not limited to dicyandiamide. Examples of anhydride-based hardeners include but are not limited to phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylbicycloheptenedicarboxlic anhydride, dodecylsuccinic anhydride, and trimellitic anhydride. Examples of polyvalent phenol-based hardeners include but are not limited to bisphenol A, bisphenol F, bisphenol S, <NUM>,<NUM>'-diphenol, <NUM>,<NUM>'-diphenol, hydroquinone, resorcinol, naphthalenediol, tri-(<NUM>-hydroxyphenyl)methane, and <NUM>,<NUM>,<NUM>,<NUM>,-tetra(<NUM>-hydroxyphenyl)ethane. Examples of aromatic amine-based hardeners include but are not limited to <NUM>,<NUM>'-diaminodiphenyl methane, <NUM>,<NUM>'-diaminodiphenyl propane, m-phenylene diamine, and p-xylenediamine. Examples of aliphatic amine-based hardeners include but are not limited to ethylenediamine, hexamethylenediamine, diethylenetriamine, and diethylenetetraamine. In the appended examples, dicyandiamide is used as the hardener.

The curable composition of the present invention can be used to prepare a circuit board material. Thus, the present invention also provides a copper-clad laminate. The copper-clad laminate comprises (a2) a dielectric layer, which comprises a dielectric material obtained by curing the aforementioned curable composition; and (b2) a copper foil, which is disposed on the surface of the dielectric layer. The copper-clad laminate of the present invention can pass the <NUM> floating solder test, and has good peeling strength, flame retardance and thermal resistance (e.g., low glass transition temperature (Tg), especially low water absorption and low coefficient of thermal expansion (CTE)).

In addition, the glycidyl ether of polyhydric phenol resin of the present invention can also be used as a material of high-frequency adhesive. For example, a high-frequency adhesive film can be obtained by mixing the glycidyl ether of polyhydric phenol resin, polytetrafluoroethylene, polyimide, a hardener, and a hardening promoter to form a mixture, and then coating the mixture onto a release film and baking the coated mixture. Examples of the hardener include but are not limited to imidazoles, amines, phenols, and organic metal salts, but the present invention is not limited thereto. The high-frequency adhesive of the present invention can pass the <NUM> floating solder test and has good peeling strength as well as dielectric properties.

The present application is further illustrated by the embodiments hereinafter, wherein the testing instruments and methods are as follows:.

The polyhydric phenol resin or glycidyl ether of polyhydric phenol resin is injected into a high-performance liquid chromatograph (model no. : Waters <NUM>), and the high-performance liquid chromatograph is equipped with an ODS column which is <NUM> in length, <NUM> in inner diameter and has a filler with a particle size of <NUM>. HPLC analysis is performed under the following conditions: a detector applying <NUM> wavelength ultraviolet light; a column temperature of <NUM>; a detector temperature of <NUM>; a mobile phase flow rate of <NUM>/min; a sample which is formulated with acetonitrile (ACN) as a solvent and has a sample concentration of <NUM> wt% in ACN; an injection amount of <NUM>µL; and a composition of mobile phase as follows: from <NUM> minutes to the <NUM>th minute of the washing time, the mobile phase is a mixture of <NUM> vol% of water and <NUM> vol% of acetonitrile; from the <NUM>th minute to the <NUM>th minute of the washing time, the mobile phase changes from a mixture of <NUM> vol% of water and <NUM> vol% of acetonitrile to <NUM> vol% of acetonitrile in a linear gradient manner with respect to time, and from the <NUM>th minute to the <NUM>th minute of the washing time, the mobile phase is <NUM> vol% of acetonitrile. The meaning of changing mobile phase in a linear gradient manner are as follows: a mixture of <NUM> vol% of water and <NUM> vol% of acetonitrile is used at the beginning of the <NUM>th minute; a mixture of <NUM> vol% of water and <NUM> vol% of acetonitrile is used at the beginning of the <NUM>th minute; a mixture of <NUM> vol% of water and <NUM> vol% of acetonitrile is used at the beginning of the <NUM>th minute; a mixture of <NUM> vol% of water and <NUM> vol% of acetonitrile is used at the beginning of the <NUM>th minute; and <NUM> vol% of acetonitrile is used at the beginning of the <NUM>th minute.

<NUM> of the polyhydric phenol resin or glycidyl ether of polyhydric phenol resin is added into <NUM> of dimethyl sulfoxide to prepare a test sample. Tetramethylsilane is added to the test sample as a reference substance for chemical shift referencing, and the test sample is measured by using a nuclear magnetic resonance spectrometer (model no. : DRX-<NUM>, available from Bruker) to obtain the <NUM>C-NMR spectrum of the test sample. The measuring conditions are as follows: a test temperature of <NUM>, a resonance frequency of <NUM>, a pulse width of <NUM> microseconds, a waiting time of <NUM> (one) second, a scan number of <NUM>, and a signal of tetramethylsilane being set as <NUM> ppm.

A sample of the polyhydric phenol resin or glycidyl ether of polyhydric phenol resin is heated in an oven at <NUM> for <NUM> (one) hour to make the sample uniform. Then, the sample is mixed with acetone (i.e., a solvent) to prepare a solution with a weight percentage concentration of <NUM>% to complete pretreatment of the sample to be tested.

The pretreated sample is loaded into a gas chromatograph, the gas chromatograph is equipped with a Phenomenex Zebron ZB-<NUM> capillary column (stationary phase composition: <NUM>% phenyl, <NUM>% dimethylpolysiloxane) which is <NUM> meters in length and <NUM> in inner diameter and has a film thickness of <NUM>. Under a carrier gas of helium with a flow rate of <NUM>/min and an inlet temperature of <NUM>, the oven of the gas chromatograph is subjected to the following stepped heating operation: the temperature is maintained at <NUM> for <NUM> minutes, then raised from <NUM> to <NUM> with a heating rate of <NUM>/min and maintained at <NUM> for <NUM> minutes. Then, the gas chromatograph is connected with a mass spectrograph, and the GC-MS analysis is operated under the following conditions: electron energy of <NUM> eV, an ion source temperature of <NUM>, use of a quadrupole mass filter, an interface temperature of <NUM>, a mass scan range of <NUM> daltons to <NUM> daltons, a solvent delay time of <NUM> minutes, and a scan rate of <NUM> u/sec.

First, the hydroxyl value (unit: mg KOH/g) of polyhydric phenol resin is determined in accordance with the acetylation method recited in HG/T <NUM>. Next, the hydroxyl value is converted to a hydroxyl equivalent weight (unit: g/eq) by the following formula.

The softening point temperature is measured in accordance with the ring and ball method as recited in JIS-K-<NUM>.

The epoxy equivalent weight of the glycidyl ether of polyhydric phenol resin is measured in accordance with ASTM-D1652.

The hydrolysable chlorine content of the glycidyl ether of polyhydric phenol resin is measured in accordance with ASTM-D1726.

The α-glycol content of the glycidyl ether of polyhydric phenol resin is measured in accordance with JIS-K-<NUM>.

The Gardner color scale of the glycidyl ether of polyhydric phenol resin is measured in accordance with ASTM-D6166, wherein the concentration of the polyphenolic condensate in cresol is <NUM> wt%, and the concentration of polyfunctional epoxy resin in methanol is <NUM> wt%.

The hydroxyl value (HV) of the glycidyl ether of polyhydric phenol resin is measured in accordance with ASTM-E222 Method C, wherein the hydroxyl value is converted in accordance with the following formula: <MAT> wherein:.

The <NUM> floating solder test is performed in accordance with JIS-C-<NUM>, wherein the copper-clad laminate or a high-frequency adhesive is dipped into a <NUM> soldering furnace, and the time required for delamination of the copper-clad laminate or a high-frequency adhesive is recorded. The standards are as follows: if delamination of the copper-clad laminate occurs within <NUM> seconds, it means that the copper-clad laminate fails in the <NUM> floating solder test, and the result is recorded as "failed"; if no delamination of the copper-clad laminate occurs within <NUM> seconds, it means that the copper-clad laminate passes the <NUM> floating solder test, and the result is recorded as "passed"; if delamination of the high-frequency adhesive occurs within <NUM> seconds, it means that the high-frequency adhesive fails in the <NUM> floating solder test, and the result is recorded as "failed"; if no delamination of the high-frequency adhesive occurs within <NUM> seconds, it means that the high-frequency adhesive passes the <NUM> floating solder test is passed, and the result is recorded as "passed".

The peeling strength of the copper-clad laminate or high-frequency adhesive is measured in accordance with IPC-TM-<NUM>-<NUM>. The peeling strength refers to the bonding strength between the copper foil and the laminated dielectric layer or the bonding strength between the copper foil and the laminated high-frequency adhesive film. In this test, the peeling strength is expressed as the force required to vertically peel a copper foil of <NUM> (one) ounce from the surface of the laminated layer or laminated adhesive film. The unit of the peeling strength is kilogram-force/centimeter (kgf/cm).

The flame retardance test is carried out according to UL94V (Vertical Burn), wherein the copper-clad laminate is vertically held and burned using a Bunsen burner, and the required period (unit: second) for the copper-clad laminate to stop burning is recorded.

First, the weight of the copper-clad laminate is measured. Then, the copper-clad laminate is placed in <NUM> water for <NUM> days, and the weight of the copper-clad laminate after being dipped in water for <NUM> days is measured to calculate the ratio of the increased weight (wt%).

The Td (i.e., <NUM>% weight loss temperature) of the copper-clad laminate is measured in accordance with IPC-TM-<NUM>-<NUM>. The instrument used to measure Td is a thermogravimetric analyzer (model no. : Q500, available from TA Instruments), wherein the scanning rate is <NUM>/min.

The Tg of the copper-clad laminate is measured in accordance with IPC-TM-<NUM>-<NUM>. The instrument used to measure Tg is a dynamic mechanical analyzer (model no. : Q800, available from TA Instruments), wherein the scanning rate is <NUM>/min.

The CTE-α1 and CTE-α2 of the copper-clad laminate are measured in accordance with IPC-TM-<NUM>-<NUM>. The instrument used to measure CTE-α1 and CTE-α2 is a thermomechanical analyzer (model no. : TMA <NUM>, available from Perkin Elmer), wherein CTE-α1 is a CTE at a temperature lower than Tg, and CTE-α2 is a CTE at a temperature higher than Tg.

The dielectric constant (Dk) and dissipation factor (Df) of the high-frequency adhesive film are measured in accordance with IPC-TM-<NUM>. <NUM> under an operating frequency of <NUM>.

First, the purification of styrenated phenol was performed. A <NUM> (one) liter four-necked glass reaction kettle was equipped with a condensing tube, a collection bottle, and a vacuum device. <NUM> of styrenated monophenol (available from Sanko Chemical, purity: <NUM>%, OH equivalent: <NUM>/eq) was put into the glass kettle to perform a reduced pressure distillation purification, wherein the absolute pressure was reduced to <NUM> mmHg, the substances with a boiling point ranging from <NUM> to <NUM> were collected, and the collected substances were weighed <NUM>. The purified styrenated monophenol has a purity of <NUM>% and an OH equivalent of <NUM>/eq as analyzed by GC.

Next, a styrenated polyhydric phenol resin was synthesized by reacting the styrenated monophenol and formaldehyde. <NUM> of the purified styrenated monophenol (purity: <NUM>%, OH equivalent: <NUM>/eq, <NUM> mol) and <NUM> of p-toluenesulfonic acid monohydrate (<NUM> mol) were put into a <NUM> (one) liter four-necked glass reaction kettle, and temperature was set to <NUM>. After <NUM> of <NUM> wt% formaldehyde aqueous solution (<NUM> mol) was continuously dripped into the four-necked glass reaction kettle within <NUM> hours, the temperature was raised to <NUM> and distillation was performed under normal pressure for <NUM> hours to remove water. <NUM> of <NUM> wt% NaOH aqueous solution was added to neutralize, and reduced pressure distillation was performed under an absolute pressure of <NUM> mmHg and the temperature was raised to <NUM> and maintained for <NUM> (one) hour to obtain <NUM> of the styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM> (OH equivalent: <NUM>/eq).

First, the synthesis of polyhydric phenol resin was performed. <NUM> of phenol (<NUM> mol) and <NUM> of oxalic acid dehydrate (<NUM> mol) were put into a <NUM> liter four-necked glass reaction kettle, and the temperature was set to <NUM>. After <NUM> of <NUM> wt% formaldehyde aqueous solution (<NUM> mol) was continuously dripped into the four-necked glass reaction kettle within <NUM> hours, the temperature was raised to <NUM> and distillation was performed under normal pressure for <NUM> hours to remove water. Then, reduced pressure distillation was performed under an absolute pressure of <NUM> mmHg and the temperature was raised to <NUM> and maintained for <NUM> (one) hour to obtain <NUM> of the polyhydric phenol resin (OH equivalent: <NUM>/eq).

Then, the polyhydric phenol resin was modified with styrene. <NUM> of the aforementioned polyhydric phenol resin (OH equivalent: <NUM>/eq, <NUM> mol) and <NUM> of methanesulfonic acid (<NUM> ppm) were put into a <NUM> (one) liter four-necked glass reaction kettle, and the temperature was set to <NUM>. After <NUM> of styrene (<NUM> mol) was continuously dripped into the four-necked glass reaction kettle within <NUM> hours and then reacted for <NUM> (one) hour, <NUM> of <NUM> wt% NaHCO<NUM> aqueous solution was added to neutralize. Next, reduced pressure distillation was performed under an absolute pressure of <NUM> mmHg and the temperature was raised to <NUM> and maintained for <NUM> (one) hour to obtain <NUM> of the styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM> (OH equivalent: <NUM>/eq).

The preparation procedures of Synthesis Example <NUM>-<NUM> were repeated to prepare the styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM>, except that in the modification of polyhydric phenol resin with styrene, the amount of methanesulfonic acid was <NUM> (<NUM> ppm), <NUM> of toluene was additionally added as a solvent, the temperature was set to <NUM>, the amount of continuously dripped styrene was <NUM> (<NUM> mol), and <NUM> of <NUM> wt% NaOH aqueous solution was used to neutralize. The obtained styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM> has a weight of <NUM> and an OH equivalent of <NUM>/eq.

The preparation procedures of Synthesis Example <NUM>-<NUM> were repeated to prepare the styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM>, except that in the modification of polyhydric phenol resin with styrene, the amount of methanesulfonic acid was <NUM> (<NUM> ppm), the amount of continuously dripped styrene was <NUM> (<NUM> mol), and <NUM> of <NUM> wt% NaHCO<NUM> aqueous solution was used to neutralize. The obtained styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM> has a weight of <NUM> and an OH equivalent of <NUM>/eq.

The preparation procedures of Synthesis Example <NUM>-<NUM> were repeated to prepare the styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM>, except that in the modification of polyhydric phenol resin with styrene, the amount of methanesulfonic acid was <NUM> (<NUM> ppm), the temperature was set to <NUM>, the amount of continuously dripped styrene was <NUM> (<NUM> mol), and <NUM> of <NUM> wt% NaOH aqueous solution was used to neutralize. The obtained styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM> has a weight of <NUM> and an OH equivalent of <NUM>/eq.

The preparation procedures of Synthesis Example <NUM>-<NUM> were repeated to prepare the styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM>, except that in the modification of polyhydric phenol resin with styrene, methanesulfonic acid was replaced with <NUM> (<NUM> ppm) of p-toluenesulfonic acid monohydrate, <NUM> of water was additionally added as a solvent, the temperature was set to <NUM>, the amount of continuously dripped styrene was <NUM> (<NUM> mol), and <NUM> of <NUM> wt% NaOH aqueous solution was used to neutralize. The obtained styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM> has a weight of <NUM> and an OH equivalent of <NUM>/eq.

The preparation procedures of Synthesis Example <NUM>-<NUM> were repeated to prepare the styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM>, except that in the modification of polyhydric phenol resin with styrene, methanesulfonic acid was replaced with <NUM> (<NUM> ppm) of p-toluenesulfonic acid monohydrate, <NUM> of isopropyl ethanoate was additionally added as a solvent, the temperature was set to <NUM>, the amount of continuously dripped styrene was <NUM> (<NUM> mol), and <NUM> of <NUM> wt% NaOH aqueous solution was used to neutralize. The obtained styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM> has a weight of <NUM> and an OH equivalent of <NUM>/eq.

<NUM> of styrenated monophenol (purity: <NUM>%, OH equivalent: <NUM>/eq), <NUM> of <NUM> wt% polyoxymethylene and <NUM> of water were put into a <NUM> (one) liter four-necked glass reaction kettle, and the temperature was set to <NUM>. After <NUM> of <NUM> wt% p-toluenesulfonic acid aqueous solution was continuously dripped into the four-necked glass reaction kettle within <NUM> minutes, the reaction was carried out at <NUM> to <NUM> for <NUM> hours. Afterwards, <NUM> of <NUM> wt% NaOH aqueous solution was added to neutralize, <NUM> of <NUM> wt% of oxalic acid aqueous solution was added and the temperature was raised to <NUM> to remove water. Next, the temperature was raised to <NUM> under <NUM> mmHg to obtain <NUM> of the styrenated polyhydric phenol resin of Comparative Synthesis Example <NUM>-<NUM> (OH equivalent: <NUM>/eq).

<NUM> of polyhydric phenol (model: PF-<NUM>, OH equivalent: <NUM>/eq, <NUM> mol, available from Chang Chun Plastics), <NUM> of toluene and <NUM> (<NUM> ppm) of p-toluenesulfonic acid monohydrate were put into a <NUM> (one) liter four-necked glass reaction kettle, and the temperature was set to <NUM>. After <NUM> of styrene (<NUM> mol) was continuously dripped into the four-necked glass reaction kettle within <NUM> hours and the reaction was performed for <NUM> hours, <NUM> of <NUM> wt% Na<NUM>CO<NUM> aqueous solution was added to neutralize. Next, the mixture in the reaction kettle was dissolved in <NUM> of methyl isobutyl ketone and then washed with water at <NUM> for <NUM> times. Afterwards, reduced pressure distillation was performed under an absolute pressure of <NUM> mmHg to remove solvent to obtain <NUM> of the styrenated polyhydric phenol resin of Comparative Synthesis Example <NUM>-<NUM> (OH equivalent: <NUM>/eq).

The preparation procedures of Comparative Synthesis Example <NUM>-<NUM> were repeated to prepare the styrenated polyhydric phenol resin of Comparative Synthesis Example <NUM>-<NUM>, except that the amount of p-toluenesulfonic acid monohydrate was <NUM> (<NUM> ppm), the amount of styrene was <NUM> (<NUM> mol), and the amount of Na<NUM>CO<NUM> aqueous solution was <NUM>. The obtained styrenated polyhydric phenol resin of Comparative Synthesis Example <NUM>-<NUM> has a weight of <NUM> and an OH equivalent of <NUM>/eq.

The preparation procedures of Comparative Synthesis Example <NUM>-<NUM> were repeated to prepare the styrenated polyhydric phenol resin of Comparative Synthesis Example <NUM>-<NUM>, except that p-toluenesulfonic acid monohydrate was replaced with <NUM> (<NUM> ppm) of methanesulfonic acid, the amount of styrene was <NUM> (<NUM> mol), and the amount of Na<NUM>CO<NUM> aqueous solution was <NUM>. The obtained styrenated polyhydric phenol resin of Comparative Synthesis Example <NUM>-<NUM> has a weight of <NUM> and an OH equivalent of <NUM>/eq.

The preparation procedures of Comparative Synthesis Example <NUM>-<NUM> were repeated to prepare the styrenated polyhydric phenol resin of Comparative Synthesis Example <NUM>-<NUM>, except that polyhydric phenol PF-<NUM> was replaced with <NUM> of polyhydric phenol of Synthesis Example <NUM>-<NUM> (OH equivalent: <NUM>/eq, <NUM> mol), p-toluenesulfonic acid monohydrate was replaced with <NUM> (<NUM> ppm) of methanesulfonic acid, the amount of styrene was <NUM> (<NUM> mol), and the amount of Na<NUM>CO<NUM> aqueous solution was <NUM>. The obtained styrenated polyhydric phenol resin of Comparative Synthesis Example <NUM>-<NUM> has a weight of <NUM> and an OH equivalent of <NUM>/eq.

The properties of the styrenated polyhydric phenol resin of Synthesis Examples <NUM>-<NUM> to <NUM>-<NUM> and Comparative Synthesis Examples <NUM>-<NUM> to <NUM>-<NUM>, including hydroxyl equivalent, softening point, the area percentage of the chromatographic peak of the first component at the corresponding retention time in the HPLC spectrum, and the A/B value in the <NUM>C-NMR spectrum, were measured according to the aforementioned measuring methods. The results are listed in Table <NUM>.

First, a <NUM> liter four-necked glass reaction kettle was equipped with a condensing oil-water separating tube, a vacuum device, a feeding tube and an electric stirring bar, and the reaction kettle is wrapped with a constant temperature electric heating pack. Then, <NUM> (<NUM> mol) of the styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM>, <NUM> (<NUM> mol) of epichlorohydrin (available from TRIPLEX CHEMICAL CORP. ) and <NUM> of isopropyl acetate were put into the reaction kettle and mixed under normal pressure to obtain a homogeneous solution. Afterwards, the temperature was raised to <NUM> under an absolute pressure of <NUM> mmHg, <NUM> of <NUM> wt% NaOH aqueous solution was dripped into the homogeneous solution, and temperature was maintained at <NUM> for <NUM> hours. After the reaction was completed, reduced pressure distillation was performed under an absolute pressure of <NUM> mmHg and the temperature was raised to <NUM> to recover unreacted epichlorohydrin and isopropyl acetate. Then, toluene and pure water were added to perform washing, and the indissoluble hydrolysate in the delamination between oil and water was visually checked and recorded. After washing three times, reduced pressure distillation was performed under an absolute pressure of <NUM> mmHg and <NUM> to remove the solvent of the organic phase to obtain <NUM> of the glycidyl ether of styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM>.

The preparation procedures of Synthesis Example <NUM>-<NUM> were repeated to prepare the glycidyl ether of styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM>, except that <NUM> (<NUM> mol) of the styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM>, <NUM> (<NUM> mol) of epichlorohydrin, and <NUM> of <NUM> wt% NaOH aqueous solution were used. The obtained glycidyl ether of styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM> has a weight of <NUM>.

The preparation procedures of Synthesis Example <NUM>-<NUM> were repeated to prepare the glycidyl ether of styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM>, except that <NUM> (<NUM> mol) of the styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM>, <NUM> (<NUM> mol) of epichlorohydrin, and <NUM> of <NUM> wt% NaOH aqueous solution were used while isopropyl acetate was not used. The obtained glycidyl ether of styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM> has a weight of <NUM>.

First, a <NUM> liter four-necked reactor was prepared and equipped with the following devices: a device for controlling and displaying temperature and pressure, and a device for condensing a co-distillation mixture of water and epichlorohydrin and separating the co-distillation mixture into an organic phase and a water phase. <NUM> (<NUM> mol) of the styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM>, <NUM> (<NUM> mol) of epichlorohydrin and <NUM> (<NUM>,<NUM> ppm with respect to the polyhydric phenol resin) of benzyl triethyl ammonium chloride as a coupling agent were added into the reactor to obtain a mixture, and the mixture was stirred under normal pressure and <NUM> to form a homogeneous solution. Next, the temperature was raised from <NUM> to <NUM> within <NUM> hours and maintained at <NUM> for <NUM> hours. Afterwards, a dehydrohalogenation step was performed, wherein <NUM> of <NUM> wt% NaOH aqueous solution was added into the mixture at a constant rate under <NUM> within <NUM> hours; in the meantime, water contained in the reaction system was subjected to azeotropic distillation and condensation at an absolute pressure of <NUM> torr. The condensed azeotrope was separated into an organic phase and a water phase, and the organic phase (mainly epichlorohydrin) was recovered back to the reactor while the water phase was discarded. After the addition of NaOH aqueous solution was completed, the reaction system was maintained for <NUM> (one) hour to accomplish the dehydrohalogenation step. The unreacted epichlorohydrin was removed by reduced pressure distillation under an absolute pressure of <NUM> mmHg and <NUM>. The dehydrohalogenation step was repeated, except that <NUM> of <NUM> wt% NaOH aqueous solution was added into the mixture under <NUM> and normal pressure within <NUM> hours. Next, sodium chloride contained in the obtained crude product was dissolved in toluene and ionized water and washed by water. The organic solvent was removed from the obtained mixture by reduced pressure distillation under an absolute pressure of <NUM> mmHg and <NUM> to obtain <NUM> of glycidyl ether of styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM>.

The preparation procedures of Synthesis Example <NUM>-<NUM> were repeated to prepare the glycidyl ether of styrenated polyhydric phenol resin of Comparative Synthesis Example <NUM>-<NUM>, except that <NUM> (<NUM> mol) of the styrenated polyhydric phenol resin of Comparative Synthesis Example <NUM>-<NUM>, <NUM> (<NUM> mol) of epichlorohydrin, and <NUM> of <NUM> wt% NaOH aqueous solution were used. The obtained glycidyl ether of styrenated polyhydric phenol resin of Comparative Synthesis Example <NUM>-<NUM> has a weight of <NUM>.

The properties of the glycidyl ether of styrenated polyhydric phenol resin of Synthesis Examples <NUM>-<NUM> to <NUM>-<NUM> and Comparative Synthesis Examples <NUM>-<NUM> to <NUM>-<NUM>, including epoxy equivalent weight (EEW), hydrolyzable chlorine (HyCl) content, hydroxyl value (HV), α-glycol content, Gardner Color Scale, the area percentage of the chromatographic peak of the first component at the corresponding retention time in the HPLC spectrum, and A/B value in the <NUM>C-NMR spectrum, were measured according to the aforementioned measuring methods. The results are listed in Table <NUM>.

First, <NUM> of the glycidyl ether of styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM>, <NUM> of dicyandiamide diluent (dicyandiamide dissolved in methanol, concentration: <NUM> wt%, available from Juyi Chemical), <NUM> of <NUM>-methylimidazole diluent (<NUM>-methylimidazole dissolved in methanol, concentration: <NUM> wt%, available from Juyi Chemical) and <NUM> of acetone were mixed using a stirrer to form a resin composition. Glass fiber cloths (model no. : GF-<NUM>, thickness: <NUM>) were immersed in the aforementioned resin composition and dried under <NUM> to form a prepreg. Afterwards, <NUM> pieces of the prepregs were superimposed, and two sheets of copper foils (<NUM>) were superimposed respectively on the two external surfaces of the superimposed prepregs. Then, a high-temperature hot-pressing curing operation was performed on the superimposed prepregs under <NUM> and <NUM>/cm<NUM> to obtain the copper-clad laminate of Example <NUM>.

The preparation procedures of Example <NUM> were repeated to prepare the copper-clad laminate of Example <NUM>, except that the resin composition was formed by using <NUM> of the glycidyl ether of styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM>, <NUM> of dicyandiamide diluent (dicyandiamide dissolved in methanol, concentration: <NUM> wt%), <NUM> of <NUM>-methylimidazole diluent (<NUM>-methylimidazole dissolved in methanol, concentration: <NUM> wt%) and <NUM> of acetone.

The preparation procedures of Example <NUM> were repeated to prepare the copper-clad laminate of Comparative Example <NUM>, except that the resin composition was formed by using <NUM> of the glycidyl ether of styrenated polyhydric phenol resin of Comparative Synthesis Example <NUM>-<NUM>, <NUM> of dicyandiamide diluent (dicyandiamide dissolved in methanol, concentration: <NUM> wt%), <NUM> of <NUM>-methylimidazole diluent (<NUM>-methylimidazole dissolved in methanol, concentration: <NUM> wt%) and <NUM> of acetone.

The properties of the copper-clad laminate of Examples <NUM> to <NUM> and Comparative Examples <NUM> to <NUM>, including <NUM> floating solder test, peeling strength, flame retardance, water absorption, Td, Tg, CTE-α1 and CTE-α2, were measured according to the aforementioned testing methods. The results are listed in Table <NUM>.

As shown in Table <NUM>, the copper-clad laminates prepared from the glycidyl ethers of polyhydric phenol resin of the present invention can pass the <NUM> floating solder test, and have good physicochemical properties (e.g., high peeling strength, high flame retardance, high Td, high Tg, and the like), especially low water absorption and low CTE. By contrast, as shown in Comparative Examples <NUM> to <NUM>, when the area percentage of the chromatographic peak of the first component at the corresponding retention time in the HPLC spectrum falls outside the designated range, the prepared copper-clad laminates prepared cannot pass the <NUM> floating solder test or do not have good physicochemical properties, especially in terms of water absorption and CTE. Thus, the copper-clad laminates of Comparative Examples <NUM> to <NUM> cannot provide the desired efficacy of the present invention.

First, <NUM> of toluene as a solvent and <NUM> of polytetrafluoroethylene (model no. : POLYFLON PTFE L-<NUM>, available from DAIKIN CHEMICAL) were mixed and stirred for <NUM> minutes using a stirrer to obtain a uniform slurry. Next, <NUM> of polyimide (model no. : PIAD200, available from ARAKAWA CHEMICAL) and <NUM> of the glycidyl ether of styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM> were added into the slurry and stirred for <NUM> minutes using a stirrer to obtain a uniform resin slurry. The resin slurry was homogenized by using a high-speed homogenizer at <NUM> rpm for <NUM> minutes to make the appearance uniform without granules. <NUM> of dicyandiamide diluent (dicyandiamide dissolved in dimethylacetamide, concentration: <NUM> wt%) as a hardener and <NUM> of <NUM>-methylimidazole diluent (<NUM>-methylimidazole dissolved in dimethylacetamide, concentration: <NUM> wt%) as a hardening promoter were added into the homogenized resin slurry and stirred for <NUM> minutes to obtain a coating composition. After the coating composition was coated onto a release polyethylene terephthalate (PET) film by using an automatic coating machine with a gap of <NUM>, the coated film was baked in an oven at <NUM> for <NUM> minutes and then cooled to obtain a semi-cured (B-stage) high-frequency adhesive film of Example <NUM>.

The preparation procedures of Example <NUM> were repeated to prepare the high-frequency adhesive of Example <NUM>, except that <NUM> of the glycidyl ether of styrenated polyhydric phenol resin of Synthesis Example <NUM>-<NUM>, <NUM> of the hardener and <NUM> of the hardening promoter were used.

The preparation procedures of Example <NUM> were repeated to prepare the high-frequency adhesive of Comparative Example <NUM>, except that <NUM> of the glycidyl ether of styrenated polyhydric phenol resin of Comparative Synthesis Example <NUM>-<NUM>, <NUM> of the hardener and <NUM> of the hardening promoter were used.

The properties of the high-frequency adhesive of Examples <NUM> to <NUM> and Comparative Examples <NUM> to <NUM>, including <NUM> floating solder test, peeling strength, Dk and Df, were measured according to the aforementioned testing methods. The results are listed in Table <NUM>.

As shown in Table <NUM>, the high-frequency adhesives prepared from the glycidyl ethers of polyhydric phenol resin of the present invention can pass the <NUM> floating solder test and have excellent peeling strength and dielectric properties (Dk, Df). By contrast, as shown in Comparative Examples <NUM> to <NUM>, when the area percentage of the chromatographic peak of the first component at the corresponding retention time in the HPLC spectrum falls outside the designated range, the high-frequency adhesives prepared thereby cannot pass the <NUM> floating solder test, or the high-frequency adhesives prepared thereby do not have good physicochemical properties. Thus, the high-frequency adhesives of Comparative Examples <NUM> to <NUM> cannot provide the desired efficacy of the present invention.

Claim 1:
A polyhydric phenol resin, which comprises a polyhydric phenol resin component and a first component, wherein when the polyhydric phenol resin is characterized by high-performance liquid chromatography (HPLC), the first component is eluted at a retention time ranging from <NUM> minutes to <NUM> minutes, and based on the total area of the chromatographic peaks of the polyhydric phenol resin, the area percentage of the chromatographic peak of the first component at the corresponding retention time in the spectrum ranges from <NUM>% to <NUM>%,
wherein the HPLC analysis is performed under the following conditions: a detector applying <NUM> wavelength ultraviolet light; an octadecylsilane (ODS) column which is <NUM> in length and <NUM> in inner diameter and has fillers with a particle size of <NUM>; a column temperature of <NUM>; a detector temperature of <NUM>; a mobile phase flow rate of <NUM>/min; a sample which is formulated with acetonitrile (ACN) as a solvent and has a sample concentration of <NUM> wt% in ACN; an injection amount of <NUM>µL; and a composition of mobile phase as follows: from <NUM> minutes to the <NUM>th minute of the washing time, the mobile phase is a mixture of <NUM> vol% of water and <NUM> vol% of acetonitrile; from the <NUM>th minute to the <NUM>th minute of the washing time, the mobile phase changes from a mixture of <NUM> vol% of water and <NUM> vol% of acetonitrile to <NUM> vol% of acetonitrile in a linear gradient manner with respect to time, and from the <NUM>th minute to the <NUM>th minute of the washing time, the mobile phase is <NUM> vol% of acetonitrile,
wherein when the polyhydric phenol resin is characterized by gas chromatography-mass spectrometry (GC-MS), the first component is eluted at a retention time ranging from <NUM> minutes to <NUM> minutes, and a fragmentation pattern of the first component comprises one or more signals at a mass-to-charge ratio (m/z) selected from the group consisting of <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and <NUM>.