KR20220141151A - Poly phenylene ether resin mixture - Google Patents

Abstract

One aspect of the present invention relates to a polyphenylene ether (meth)acrylate resin mixture which includes a polyphenylene ether-based resin that has a structure of chemical formula 1, and is acrylated in an ester-based solvent, a ketone-based solvent, or a first solvent that is a mixture thereof, wherein a total content of benzene, toluene, and xylene is less than 500 ppm. In the chemical formula, R is each independently methyl(CH_3) or hydrogen (H), Y is sulfur (S) or oxygen (O), X is a direct connection, -CH_2-, -(C)(CH_3)_2 -, -CO-, -S-, -SO_2-, -C(CF_3)_2-, -(C)(CH_2CH_3)_2- or -(CH)(CH_2CH_3)-, l is an integer from 1 to 100, m is 0 or 1, and when m = 0, n = 0, and when m = 1, n is an integer from 1 to 100. According to the present invention, excellent electrical properties are secured.

Description

Poly phenylene ether resin mixture

The present invention relates to a polyphenylene ether-based resin mixture, and more particularly, to a resin containing a polyphenylene ether structure, a mixture containing the same, and a method for preparing the same.

In accordance with the recent trend of high integration, high miniaturization, flexibility, and high functionality of electronic devices, copper clad laminates have excellent transmission characteristics due to low dielectric loss in the GHz region, and have a low coefficient of thermal expansion to ensure the design, processability and reliability of parts. (CCL, copper clad laminate) or semiconductor encapsulant (EMC, Epoxy Molding Compound) material is required. Examples of organic materials having a low dielectric constant include epoxy resin, Teflon resin, polyphenylene ether (PPE), and the like. Among them, Teflon material is known as a material exhibiting the best dielectric properties.

However, in the case of Teflon, it is required for next-generation integrated circuit substrates, printed circuit boards, packaging, organic thin film transistors, flexible display substrates, etc. There is a disadvantage in that the adhesive properties are remarkably deteriorated, and in the case of cyanate resin, high energy is required when curing at a temperature of 230 ° C. In addition, polyphenylene ether (PPE) is a polymer that does not have a hydrolyzable bond or a polar group. Compared with other resins, polyphenylene ether (PPE) has a significantly superior low dielectric constant and low dielectric loss ratio. It provides a blend with additional overall properties such as, but suffers from a lack of compatibility between the resins in blending PPE with other resins, often resulting in delamination and/or poor physical properties such as, for example, low ductility. indicates characteristics.

For this reason, an increasing number of cases are using epoxy resins that are easy to use as materials for CCL or EMC materials with high adhesive properties, low dielectric constant, and low dielectric loss factors. Therefore, it is difficult to realize an insulating layer having sufficiently excellent dielectric properties when an insulating layer is manufactured using an epoxy resin. One useful way to improve the compatibility between resins known in the PPE art is to create reaction products between the polymers that act as compatibilizers for the resins. The reaction product is often thought to be a copolymer of resin. One challenge in preparing the reaction product is the need for reactive sites in the resin to form the reaction product. Some polymers, such as polyamides, inherently have both amine and carboxylic acid end groups that can readily react with other resins containing a wide range of possible reactive moieties. Polymers such as PPE contain predominantly phenolic end groups and are generally not sufficiently reactive to produce the above reaction products in a commercially feasible process, so methods and processes for introducing functionality into PPE have been extensively studied and studied. have.

The present invention has been devised to solve the above problems, and (meth)acrylate having very excellent electrical properties while obtaining desired heat resistance, curing reactivity, adhesiveness and coefficient of thermal expansion required for CCL or EMC is introduced. An object of the present invention is to provide a method for preparing a radical-curable polyphenylene ether-based resin.

Republic of Korea Patent No. 10-0595771

In one aspect of the present invention, the BTX (benzene, toluene, xylene)-based compound, which is an environmental regulation material, is not used or the BTX-based organic solvent is not used to contain a trace amount, and the moisture absorption rate is low and has excellent electrical properties. An object of the present invention is to provide a polyphenylene ether-based resin mixture and a method for preparing the same.

In addition, the purpose of providing a polyphenylene ether-based resin composition having excellent low dielectric properties, excellent peel strength, and excellent heat resistance such as glass transition temperature and mass reduction temperature due to low moisture absorption after prepreg production and curing. do.

Furthermore, the present invention provides a resin mixture that can be used in a low-k material that can be used in 5G wireless communication (5G) technology having low dielectric and heat resistance properties that can be used even in the high-frequency range of hundreds of MHz or more or several GHz bands. aim to

One aspect of the present invention is

It is synthesized in a first solvent that is an ester-based solvent, a ketone-based solvent, or a mixture thereof, and includes a polyphenylene ether-based resin having the structure of the following Chemical Formula 1,

It is a polyphenylene ether (meth)acrylate resin mixture having a total content of benzene, toluene and xylene of less than 500 ppm.

(Formula 1)

Here, each R is independently methyl (CH ₃ ) or hydrogen (H),

Y is sulfur (S) or oxygen (O), X is a direct connection, -CH ₂ -, -(C)(CH ₃ ) ₂ -, -CO-, -S-, -SO ₂ -, -C( CF ₃ ) ₂ -, -(C)(CH ₂ CH ₃ ) ₂ - or -(CH)(CH ₂ CH ₃ )-,

l is an integer from 1 to 100, m is 0 or 1, when m=0, n=0, and when m=1, n is an integer from 1 to 100.

Here, the (meth) acrylate terminal of the polyphenylene ether (meth) acrylate resin is preferably derived from (meth) acrylic acid anhydride of the following formula (3).

(Formula 3)

In Formula 3, each R is independently methyl (CH ₃ ) or hydrogen (H).

In addition, it is preferable to include less than 0.7 wt% of (meth)acrylic acid, which is a by-product of the acrylate reaction of (meth)acrylic acid anhydride,

The content of (meth)acrylic acid is preferably calculated from the acid value of the polyphenylene ether (meth)acrylate resin having the structure of Formula 1,

The first solvent is preferably an aprotic solvent having a dielectric constant of 5 to 25 at 20 °C.

Here, the polyphenylene ether (meth)acrylate resin may have a structure represented by the following Chemical Formula 10.

(Formula 10)

Here, x and y are integers from 1 to 100.

In addition, the polyphenylene ether compound of Formula 2 and the (meth)acrylic anhydride of Formula 3 are acrylated in a first solvent, which is a non-aromatic organic solvent, having (meth)acrylate ends. polyphenylene ether (meth)acrylate resin,

It is preferable that the total content of benzene, toluene and xylene is less than 500 pmm.

(Formula 1)

(Formula 2)

(Formula 3)

(In Formulas 1 to 3, R is each independently methyl (CH ₃ ) or hydrogen (H),

Y is sulfur (S) or oxygen (O),

X is a direct connection, -CH ₂ -, -(C)(CH ₃ ) ₂ -, -CO-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, -(C)(CH ₂ CH ₃ ) ₂ - or -(CH)(CH ₂ CH ₃ )-,

l is an integer from 1 to 100, m is 0 or 1, when m=0, n=0, and when m=1, n is an integer from 1 to 100.)

In addition, it is preferable that the content of (meth)acrylic acid produced after the reaction of the (meth)acrylic acid anhydride is less than 0.7 wt%,

Preferably, the first solvent is an aprotic solvent having a dielectric constant of 5 to 25 at 20 °C,

The polyphenylene ether (meth)acrylate resin is preferably washed with a second solvent, which is a mixed solvent containing water and alcohol, to be solidified.

In the method for preparing a polyphenylene ether-based resin mixture according to an aspect of the present invention, the acrylate reaction of the resin is performed using an aprotic solvent having a dielectric constant of about 5 to 25 at a temperature of 20° C. as a first solvent to obtain benzene, Compared to organic solvents such as toluene or xylene, the reaction efficiency is high, and the amount of alcohol used during work-up and separation after the reaction is small and the time is shortened.

In addition, unreacted monomers and (meth)acrylic acid can be well removed and the amount of catalyst used can be reduced.

In addition, there is an advantage of high efficiency of washing and drying by using a second solvent in which water and alcohol are mixed during washing and drying of the product.

In addition, the polyphenylene ether (meth)acrylate resin mixture prepared by the manufacturing method may contain a BTX-based material in a low content of less than 500 ppm in the resin mixture in which (meth)acrylate is introduced at the end.

When the resin composition is prepared by using the polyphenylene ether-based resin mixture of the present invention, the content of BTX included in the entire resin composition may be lowered, so that it can be safely manufactured and used within strict environmental regulation conditions.

The above resin composition may have low dielectric properties due to low moisture absorption after curing, and has excellent heat resistance.

In addition, by utilizing the low dielectric properties of the resin composition, it has properties suitable for use in high-frequency circuits and packages of several hundred MHz to several GHz, such as 5G communication.

Prior to describing the present invention in detail below, it is to be understood that the terminology used herein is for the purpose of describing specific embodiments and is not intended to limit the scope of the present invention, which is limited only by the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art, unless otherwise stated.

Throughout this specification and claims, unless stated otherwise, the term comprise, comprises, comprising is meant to include the stated object, step or group of objects, and steps, and any other object. It is not used in the sense of excluding a step or a group of objects or groups of steps.

On the other hand, various embodiments of the present invention may be combined with any other embodiments unless clearly indicated to the contrary. Any feature indicated as particularly preferred or advantageous may be combined with any other feature and features indicated as preferred or advantageous.

The polyphenylene ether (meth)acrylate resin of the present invention is a polyphenylene ether (meth)acryl having a structure of Formula 1 below in which a (meth)acrylate functional group is bonded to a polymer chain structure made of a polyphenylene ether-based compound. It is a resin containing a rate compound, and a resin containing a polyphenylene ether (meth)acrylate compound may be obtained as a solid crystalline resin.

As shown in Chemical Formula 1 below, the polyphenylene ether (meth)acrylate resin has at least one (meth)acrylate functional group with respect to the terminal of the polyphenylene ether polymer chain structure, preferably on both sides of the polymer chain structure. It is preferable to have each (meth)acrylate functional group at the end.

(Formula 1)

In Formula 1,

R is each independently methyl (CH ₃ ) or hydrogen (H),

Y is sulfur (S) or oxygen (O),

X is a direct connection, -CH ₂ -, -(C)(CH ₃ ) ₂ -, -CO-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, -(C)(CH ₂ CH ₃ ) ₂ -or-(CH)(CH ₂ CH ₃ )-,

l is an integer from 1 to 100, m is 0 or 1, when m=0, n=0, and when m=1, n is an integer from 1 to 100.

In this case, Y is preferably oxygen (O), and X is preferably a structure including sp 3 hybridized carbon. For example, X is -CH ₂ -, -(C)(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(C)(CH ₂ CH ₃ ) ₂ - or-(CH)(CH ₂ CH ₃ )-, preferably a structure in which sp 3 hybridized carbon or sulfur is connected between aromatic rings, preferably -CH ₂ -, -(C)(CH ₃ ) ₂ - or -(CH) A hydrocarbon having 3 or less carbon atoms, such as (CH ₂ CH ₃ )-, is preferably selected.

If the sp2 hybridized carbon is located at the position connecting the aromatic rings in the structure of X, the low dielectric properties may deteriorate due to the easy movement of electrons due to the resonance structure, and it is difficult to rotate or deform the polymer chain around X. There may be a problem in that the formation of cross-links is less likely to occur.

When a sulfur atom is included in the structure of X, the polarity is partially increased, but the heat resistance properties of the resin may be improved.

The resin mixture including the polyphenylene ether (meth)acrylate resin may contain a small amount of compounds or impurities in addition to the product resin.

In this case, the organic compound is an organic solvent used for the synthesis of polyphenylene ether (meth)acrylate resin, and the first solvent may be partially included in the resin mixture, and crystallization, washing or isolation of the product after the resin synthesis reaction ), the second solvent or alcohol-based compound used in the case may be partially included in the resin mixture.

The first solvent of the present invention is a solvent used in the synthesis of polyphenylene ether (meth)acrylate resin, and is not limited as long as it is a solvent capable of dissolving the reactants well in the synthesis of polyphenylene ether (meth)acrylate resin. It can be used, but it is preferable to use an aprotic solvent.

More specifically, a compound having a low polarity may be used as the first solvent, and for example, a compound having a dielectric constant of 25 or less, specifically 5 to 25 measured at 20°C, is preferably used.

When the dielectric constant is greater than 25, the polarity of the solvent is increased, there is a problem in that the solubility of the organic compound used for the reaction may deteriorate, the yield is reduced due to the generation of side reactions, and the cured properties are reduced due to polymerization. If the dielectric constant is less than 5, the polarity of the solvent may be too low, and the solubility of a material such as a catalyst may deteriorate, and the reactivity may be remarkably lowered, which may cause problems in that the reaction time and reaction temperature increase.

As the first solvent, an ester solvent, a ketone solvent, or a mixture thereof may be used, and specifically, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, methyl ethyl ketone, diethyl ketone, methanepropyl ketone , methyl isobutyl ketone, benzyl phenyl ketone, benzyl methyl ketone, methyl phenethyl ketone, or a mixture thereof, an organic solvent, more preferably a non-aromatic ketone solvent, methyl ethyl ketone, diethyl ketone, methane propyl ketone, Methylisobutylketone and mixtures thereof may be used.

The above-described first solvent is a solvent such as toluene or benzene, which has the advantage of not significantly increasing the dielectric constant or dielectric loss even if the first solvent has a high solubility in the polyphenylene ether polymer and a low boiling point, while it is easy to remove, even if it contains an aromatic ring. Compared to the case of using polyphenylene ether, it provides low polyphenylene ether solubility, high acrylate reaction efficiency, and reduces the amount of alcohol used, which helps to maintain low dielectric properties of the resin.

In addition, the resin mixture containing the polyphenylene ether (meth) acrylate resin contains benzene, toluene, and xylene, which are aromatic organic compounds that cause environmental pollution, and contains BTX (Benzene, Toluene, Xylene) compounds. It is characterized as low, and specifically, the content of at least one selected from benzene-based, toluene-based or xylene-based compounds (BTX-based compounds) is less than 500 ppm, and the total content of BTX-based compounds is less than 500 ppm, preferably may be 300 ppm or less, more preferably 100 ppm or less, and more preferably 50 ppm or less.

The polyphenylene ether (meth)acrylate resin mixture of the present invention has the advantage that the content of the BTX-based compound is low, so it has less negative effects on the environment or the human body, and the reaction efficiency is excellent without using a BTX-based solvent During the manufacture of the product, it has the advantage of high thermal stability and low moisture absorption.

On the other hand, if the content of unreacted (meth)acrylic acid anhydride contained in the resin mixture is large, there is a disadvantage in that thermal stability is lowered, and the content of (meth)acrylic acid anhydride in the resin mixture is preferably 500 ppm or less, more preferably 300 ppm or less, more preferably 100 ppm or less.

In the present specification, embodiments using a first solvent having a dielectric constant within a specific range are disclosed. The dielectric constant may vary depending on the degree of polarity of the compound, and the dielectric constant of the first solvent is determined based on a situation in which charged particles enter the solvent. If it does, offsetting occurs in such a way that the δ- portion of the solvent wraps around the (+) particles. At this time, if the offset occurs well and the electric field strength of the (+) charged particles is greatly reduced, it can be said that the solvent has a large dielectric constant.

That is, if the degree of reducing the intensity of the charge is large, the dielectric constant is large, and conversely, if the charge is not well offset, the solvent has a small dielectric constant.

The polar solvent and the non-polar solvent described herein may be divided based on a dielectric constant value of 5. This value can be derived using the dipole moment, because the solvent, in which δ+ and δ- are clearly divided in the molecule, can cancel the charge intensity well.

However, the tendency and magnitude of dipole moment and dielectric constant may not completely coincide, and unless there is an exception, most of the tendency can be maintained. More specifically, a dispersion medium having a dielectric constant ε value lower than 3 is a non-polar solvent, a dispersion medium having a dielectric constant ε value of 3 to 6 is a medium polar solvent, and a dispersion medium having a dielectric constant ε value greater than 6 is a polar solvent. can be distinguished.

Hereinafter, a method and synthesis of the polyphenylene ether (meth)acrylate resin and the resin mixture will be described.

As a manufacturing method for preparing a polyphenylene ether (meth)acrylate resin mixture containing a polyphenylene ether (meth)acrylate resin and a trace amount of a first solvent, benzene-based, toluene-based, which have become difficult to use due to recent environmental regulations , a method for preparing a radical-curable polyphenylene ether resin into which (meth)acrylate is introduced without using an organic solvent containing an aromatic compound such as a xylene-based BTX-based compound.

At this time, with respect to the first solvent used, when the dielectric constant indicating the polarity of the material is measured, the dielectric constant at 20° C. is 5 to 25, and reacts with (meth)acrylic anhydride that can be used as a reactant during the reaction Disclosed is a method for preparing a radical-curable polyphenylene ether-based resin mixture into which (meth)acrylate is introduced using a non-aromatic, aprotic solvent that does not do, and the preparation method includes the following reactant preparation step , a mixture generation step, and a by-product removal step are provided.

The reactant preparation step is a polyphenylene ether compound represented by the following (Formula 2) used as a reactant or a resin containing the same, (Meth) acrylic acid anhydride having the same structure as (Formula 3) and (Meth) Acrylic acid anhydride) This is the step of preparing the reaction catalyst.

(Formula 2)

In Formula 2,

R is each independently methyl (CH ₃ ) or hydrogen (H),

Y is sulfur (S) or oxygen (O),

X is a direct connection, -CH ₂ -, -(C)(CH ₃ ) ₂ -, -CO-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, -(C)(CH ₂ CH ₃ ) ₂ - or -(CH)(CH ₂ CH ₃ )-,

l is an integer from 1 to 100, m is 0 or 1, when m=0, n=0, and when m=1, n is an integer from 1 to 100.

The reactive polyphenylene ether compound of Formula 2 acts as a reactant in a reaction to be described later, and includes a reactive -OH end having a structure similar to that of a phenol derivative at both ends.

(Formula 3)

In Formula 3,

each R is independently methyl (CH ₃ ) or hydrogen (H).

(meth)acrylic anhydride of Formula 3 is a compound that provides (meth)acrylate as a functional group, participates in the reaction as a reactant, provides a (meth)acrylate end, and can be converted to (meth)acrylic acid and removed.

In Chemical Formula 3, R is preferably a methyl group, and it is preferable that (meth)acrylate be obtained as a functional group after the reaction.

At this time, the methyl group has a higher free volume than hydrogen and thus shows low dielectric properties, and thermal stability is improved when the resulting resin mixture is used.

The reaction catalyst used for the reaction is tertiary alkylamine, tertiary mixed alkyl-aryl amine, tertiary mixed alkyl-aryl amine, heterocyclic amine and proton reaction of organic amine. At least one selected from the group consisting of compounds containing ammonium ions formed by

The reaction catalyst may be a compound represented by the following Chemical Formulas 4 to 9, for example, 4-(dimethylamino)pyridine (4-(Dimethylamino)pyridine), 1,5-diazabicyclo[4,3, 0]5-non-5-ene (1,5-Diazabicyclo[4.3.0]non-5-ene), diazabicyclo[5,4,0]undeca-7-ene (Diazabicyclo[5.4.0] undec-7-ene), 2-t-butyl-1,1,3,3,-tetramethylguanidine (2-tert-Butyl-1,1,3,3-tetramethylguanidine), 9-azazulolidine ( 9-Azajulolidine), 1-8-bis(tetramethylguanidino)naphthalene (1,8-Bis(tetramethylguanidino)naphthalene), 6-(dibutylamino)-1,8-diazabicyclo[5,4, 0]undeca-7-ene (6-(Dibutylamino)-1,8-diazabicyclo[5.4.0]undec-7-ene), 4-piperidinopyridine and 4-pyrrolidinopyridine It is preferable that the catalyst comprises at least one compound selected from the group consisting of (4-Pyrrolidinopyridine).

(Formula 4)

(Formula 5)

(Formula 6)

(Formula 7)

(Formula 8)

(Formula 9)

From here,

R ₁₀ to R ₁₉ are each independently hydrogen or C ₁ to C ₆ alkyl, R ₂₀ is C ₁ to C ₆ alkyl, benzene or naphthalene, and R ₂₁ to R ₂₅ are each independently C ₁ to C ₆ alkyl in the ring structure of

The reaction catalyst is preferably used in an amount of 0.1 to 3.0 parts by weight, preferably 1.0 to 2.0 parts by weight, based on 100 parts by weight of the polyphenylene ether compound as a reactant. If the reaction catalyst is used below the above range, the reaction may not proceed smoothly, and if used above the above range, the amount of catalyst remaining in the polyphenylene ether (meth)acrylate resin, which is the final product, increases, increasing the dielectric constant of the resin. there is a problem

In the mixture generation step, the polyphenylene ether compound of Formula 2 and the (meth)acrylic anhydride of Formula 3 are acrylated under the first solvent condition, which is an aprotic, non-aromatic organic solvent, to form a polyphenylene ether of Formula 1 ( It is a step of synthesizing a resin mixture including a meth) acrylate resin.

According to the present manufacturing method, an organic solvent having a dielectric constant ε of 5 to 25 at 20° C. may be used as the aprotic first solvent. When an aprotic organic solvent with a dielectric constant within the corresponding range is used, it is easier to remove (meth)acrylic acid obtained as a reaction by-product than when an organic solvent such as benzene, toluene, or xylene is used, and environmental pollution or human toxicity There is an advantage in that problems such as such are lowered, and because the content of (meth)acrylic acid contained in the resin containing polyphenylene ether (meth)acrylate obtained by the reaction is lowered, the moisture absorption rate (or moisture absorption rate) in the atmosphere of the resin ) is lowered, and the dielectric constant of the resin can be kept low.

More specifically, when an aprotic organic solvent having a dielectric constant ε of 5 to 25 is used at 20° C., the efficiency of the synthesis reaction is increased, the content of the BTX-based compound included in the resin is reduced, and the reaction proceeds. After work-up and isolation (Isolation), the process time is reduced, the amount of alcohol used during washing is reduced, and the removal of unreacted monomers or (meth)acrylic acid as a by-product is easy, and the amount of catalyst is used. It has the advantage of lowering

In the acrylate reaction proceeding in this step, 1 equivalent of a polyphenylene ether compound having a hydroxyl group bonded to a phenyl group at the terminal reacts with 1 equivalent of (meth)acrylic anhydride, and (meth)acrylic acid added to a hydroxyl group bonded to a phenyl group An ester bond is formed by the condensation reaction of the anhydride under catalytic conditions, and (meth)acrylate or (meth)acrylic acid that is separated from the leaving group without forming a bond with the hydroxyl group among the (meth)acrylates constituting the (meth)acrylic anhydride molecule It is a reaction in which 1 equivalent is obtained as a by-product.

As a result of the reaction, the terminal hydroxyl group of the polyphenylene ether compound introduced as a reactant is esterified with (meth)acrylate to obtain a single (meth)acrylated polyphenylene ether resin and a double (meth)acrylated polyphenylene ether resin. In this case, it is preferable that the ratio of the (meth)acrylated polyphenylene ether resin in which all one or two terminal hydroxyl groups participate in the reaction is esterified, preferably in the (meth)acrylated polyphenylene ether resin in which both hydroxyl groups participate in the reaction. .

At this time, the polyphenylene ether (meth)acrylate resin mixture obtained by the reaction can be mixed with other resins and measured after curing, and the cured product of the resin mixture is characterized in that the dielectric constant and dielectric loss are low.

Specifically, the cured product of the resin mixture preferably has a dielectric constant of 2.0 to 4.0, preferably 2.6 to 3.5. In addition, the cured product of the resin mixture preferably has a dielectric loss of 0.002 to 0.009, preferably 0.003 to 0.005.

A preferred embodiment of the present invention discloses a compound having a structure of the following formula (10) as an example of a polyphenylene ether (meth)acrylate resin.

(Formula 10)

where x and y are each an integer from 1 to 100.

According to Chemical Formula 10, (meth)acrylic anhydride is used as (meth)acrylic acid anhydride reacting with polyphenylene ether compound in the first solvent, so that polyphenylene ether (meth)acrylate resin having (meth)acrylate ends is formed. can be obtained

The by-product removal step is a step of washing and drying the resin mixture including the polyphenylene ether (meth)acrylate resin obtained in the above-mentioned mixture production step with a second solvent, which is a mixed solvent of water and alcohol.

In the process of washing the reaction product using the second solvent, (meth)acrylic acid or (meth)acrylate salt generated by the reaction, and the reaction catalyst added for the reaction may be washed and removed. At this time, the polyphenylene ether (meth)acrylate polymer in which only one end is (meth)acrylated has similar physical properties to the product and has a relatively large molecular weight, so it is difficult to separate and remove it using a second solvent. In order to increase the yield of the product by advancing the reaction and minimize the yield of the unreacted or intermediate monosubstituted polyphenylene ether (meth)acrylate resin, (meth)acrylic anhydride in an amount greater than the reaction equivalent is added to polyphenylene. It is preferable to completely react the ren ether compound.

Some (meth)acrylic acid may remain in the polyphenylene ether (meth)acrylate resin mixture, and may not be completely removed even after washing, and may be trapped or remain inside a high molecular weight polymer chain. At this time, the (meth)acrylic acid content of the resin mixture may be calculated by the following formula by obtaining the acid value (acid value, acid value or acid number) of the resin.

The acid value of the resin is a number indicating the amount of acidic substances obtained from 1 g of polymer, and it means the number of mg of KOH required to neutralize the sample. Measure the acid value, which is the weight (mg) of KOH required for neutralization per unit weight of the sample, and convert it using 56.1 g/mol, the molecular weight of KOH, and the molecular weight value of (meth)acrylic acid to acrylic acid contained per unit weight of the entire sample The weight fraction of can be obtained.

According to a preferred embodiment of the present invention, the (meth)acrylic acid content of the polyphenylene ether (meth)acrylate resin is preferably less than 0.7 wt%, preferably less than 0.6 wt%.

When the content of (meth)acrylic acid is 0.7wt% or more, the moisture absorption rate of the polyphenylene ether (meth)acrylate resin and the composition prepared using the same increases, and there is a problem that dielectric properties may deteriorate after curing.

Additionally, (meth)acrylic acid is a polar molecule, so in the finally obtained polyphenylene ether (meth)acrylate resin mixture, it forms a (meth)acrylic acid dimer structure by hydrogen bonding and can be included in the low polarity polymer chain. In addition, oxygen and (meth)acrylic acid included in the polyphenylene ether (meth)acrylate resin form a hydrogen bond and may be included in the resin mixture.

The second solvent of the present invention is a solvent used for crystallization and washing of the resin mixture in the by-product removal step, and is preferably a polar protic solvent containing water and alcohol. The alcohol may be any compound containing a hydroxy group bonded to carbon, but it is advantageous in terms of economy and handleability that at least one selected from the group consisting of methanol, ethanol, normal propanol and isopropanol is preferably used. , More preferably, it is good to use ethanol or methanol mixed with water.

At this time, when a mixture of alcohol and water is used as the second solvent, it is easier to remove the above-mentioned reaction by-products and reaction catalyst compared to the case of using anhydrous alcohol, and the quality of the resin finally obtained after washing has the advantage of being superior. .

The second solvent may be a solution in which 1 to 50 parts by weight of water is mixed with respect to 100 parts by weight of alcohol, and preferably, it is preferable to use a second solvent in which 5 to 20 parts by weight of water is mixed with respect to 100 parts by weight of alcohol. If the ratio of water in the mixing ratio of water and alcohol in the second solvent is less than the corresponding range, the washing efficiency is lowered and the content of (meth)acrylic acid, a reaction by-product or reaction catalyst, may increase in the final product after washing, and the ratio of water is too high If it is high, the moisture content of the final product increases due to the water not completely removed after drying, which may cause a problem in that the dielectric constant of the resin is increased.

The by-product removal step may further include drying the polyphenylene ether (meth)acrylate resin after washing the product. The drying method is not particularly limited, and for example, a process of drying in a convection oven may be performed, and a method of removing the volatile solvent by reducing the pressure may be used.

According to an embodiment of the present invention, a method of drying at a temperature of 50 to 120° C. using a convection oven is disclosed. When the drying temperature is lower than the corresponding range, the water contained in the second solvent is not sufficiently removed. The dielectric constant of the final product resin may be increased, and if the drying temperature is higher than the corresponding range, the (meth)acrylate functional group contained in the polyphenylene ether (meth)acrylate reacts with the high temperature to obtain a by-product or the final product There may be a problem in that the yield of

The product crystallized, washed and dried in the by-product removal step after the reaction is a crystalline solid resin. The final product is a resin mixture including polyphenylene ether (meth)acrylate resin in which (meth)acryl groups are esterified at both ends, and the reaction by-product (BTX-based compound) that is not completely removed in the washing process ) or other unintended impurities and reaction catalysts may be present in the resin mixture. By-products or impurities may remain trapped inside the three-dimensional structure of the polymer resin chain. In addition, water or alcohol remaining after washing and drying may be included in the resin mixture.

In the present invention, in addition to the resin mixture containing the polyphenylene ether (meth)acrylate resin having a (meth)acrylic group introduced at the terminal as described above and the method for preparing the same, a resin composition having low dielectric properties is prepared by including the resin discloses a method to

The resin composition includes a polyphenylene ether (meth)acrylate resin mixture prepared by the above-described manufacturing method, a resin or resin mixture containing a vinyl (Vinyl) functional group, an initiator, and a third solvent.

The resin containing a vinyl functional group includes a compound containing a vinyl functional group, and may be included in an amount of 12.5 to 100 parts by weight, preferably 50 parts by weight, based on 100 parts by weight of the polyphenylene ether (meth)acrylate resin mixture in the resin mixture. to 95 parts by weight, more preferably 65 to 90 parts by weight.

If the content of the polyphenylene ether (meth)acrylate resin mixture is less than the range, the low dielectric and heat resistance properties may be reduced. There is a problem that it falls off and breaks easily.

A resin containing a vinyl functional group includes a resin compound containing a vinyl functional group, wherein the compound containing a vinyl functional group is a compound with high heat resistance, and preferably includes a vinyl functional group other than an acryl group, for example, bismaleimide (Bismaleimide) structure or isocyanurate (Isocyanurate) structure-derived vinyl compound is preferable.

When a vinyl compound derived from a bismaleimide structure or an isocyanurate structure is used, the glass transition temperature is high and the thermal decomposition temperature is high, so it is advantageous to apply it to a component material requiring heat resistance.

The resin mixture including a vinyl functional group may form a crosslink by reacting with the polyphenylene ether (meth)acrylate resin mixture in the resin composition, and may have excellent curing properties through crosslinking.

Specifically, the compound containing a vinyl functional group is preferably a compound represented by the following Chemical Formulas 11 to 13, and more specifically, as a compound containing a vinyl functional group, Daiwa-Kasei's BMI-5100, BMI-2300, A BMI-3000, BMI-1000, BMI-4000 or BMI-7000 may be used.

(Formula 11)

(Formula 12)

In the above formulas 11 and 12,

M is an atomic group selected from the group consisting of C ₀ ~ C ₆ alkyl, C ₂ ~ C ₆ alkanes, C ₂ ~ C ₆ alkynes, oxygen, hydrogen and benzene,

Q is hydrogen or an atomic group selected from the group consisting of C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkane, C ₂ -C ₁₀ alkyne, C ₂ -C ₁₀ hydroxyalkyl and phenyl, each independently .

(Formula 13)

The initiator is a material used to initiate a chain reaction such as a radical reaction, and a material capable of easily generating radicals by heat or light may be used.

The resin composition of the present invention preferably contains a peroxide (peroxide)-based initiator as an initiator. As a peroxide-based initiator, for example, dicumyl peroxide, benzoyl peroxide, lauryl peroxide, tert-butyl cumyl peroxide, di (t-butyl peroxy isopropyl) benzene (di (tert-butyl peroxy isopropyl) benzene), 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane (2,5-dimethyl-2, At least one compound selected from the group consisting of 5-di(tert-butyl peroxy)hexane) and di-tert-butyl peroxide may be used.

The initiator may be included in an amount of 0.25 to 13 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polyphenylene ether (meth)acrylate resin mixture in the resin mixture.

If the content of the initiator is less than the range, the rate of the chain reaction is slow and the curing speed is slowed, so productivity may deteriorate, the degree of curing may be poor, and the heat resistance may deteriorate. During curing, the curing reaction speed of the mixture is fast, so the curing density is lowered, resulting in poor heat resistance, and poor flowability, which may cause problems in partial physical properties due to uneven surface of the cured product.

The third solvent included in the resin composition can be used without any limitation as long as it can dissolve the polyphenylene ether (meth)acrylate resin and the compound containing the vinyl functional group well, and it is an organic solvent that does not contain a BTX-based compound. Preferably, the solvent is, for example, from the group consisting of isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, acetone, methyl cellosolve, butyl cellosolve and propylene glycol methyl ether acetate. A solvent comprising at least one selected may be used.

The third solvent may be included in an amount of 75 to 800 parts by weight, preferably 100 to 350 parts by weight, based on 100 parts by weight of the polyphenylene ether (meth)acrylate resin mixture in the resin mixture.

If the content of the third solvent is less than the corresponding range, the viscosity of the composition may increase, resulting in poor processability and difficulty in wetting the glass fiber. Otherwise, there may be a problem of lowering heat resistance.

On the other hand, the resin composition of the present invention is characterized in that the BTX content, moisture absorption, dielectric material and dielectric loss factor in the composition are low, and the physical properties can be measured after curing the resin composition.

The physical properties of the resin composition are measured by measuring the cured product obtained by impregnating the resin composition in the glass fiber in the embodiments of the present invention, then by overlapping the impregnated glass fiber in a laminated manner and curing at a pressure of 2.9 MPa and a temperature of 230° C. for 2 hours. can be obtained

The BTX content of the resin composition is preferably less than 550 ppm, preferably having a value of 500 ppm or less in order to satisfy strict environmental regulation conditions.

The moisture absorption of the resin composition is preferably 0.40 or less, preferably 0.35 or less because it can provide both chemical stability and low dielectric properties.

The dielectric constant of the resin composition has a value of 2.0 to 4.0, preferably 2.6 to 3.5, and the dielectric loss factor is 0.002 to 0.009, preferably 0.003 to 0.005. Materials such as high-frequency circuits and packages using the resin composition It is preferable because it can be suitable for

The resin composition having such low BTX and moisture content, low dielectric and low dielectric loss characteristics has very good electrical properties and is not easily broken due to excellent heat resistance and warpage properties.

The prepared resin composition has advantages of excellent low dielectric properties and heat resistance, and has a very low content of BTX-based compounds that are harmful to the human body, so that safety is secured while physical properties such as low dielectric properties and heat resistance are hardly deteriorated.

In addition, due to these characteristics, it is possible to transmit/receive a high-frequency signal of 3.5 GHz or higher that can be utilized in 5G mobile communication, and preferably, it can be used as a polymer resin and material suitable for transmitting/receiving a high-frequency signal of 28 GHz or higher.

Hereinafter, the contents of the present invention will be described in detail through examples.

Example

Example 1

Polyphenylene ether (hereinafter referred to as PPE) containing phenolic hydroxy-end capped oligo (2,6-dimethyl phenylene oxide) having the structure of the following formula 14 in a 1L three-neck round glass reactor equipped with a magnetic stirrer, cooling tube, thermometer, and heating mantle ) (number average molecular weight (Mn) 1,600, product name SA-90 manufacturer Sabic) 100 g (0.12 g/eq) and methacrylic anhydride (hereinafter MAA) 27.5 g (0.24 g/eq) were mixed with methyl isobutyl ketone ( Hereinafter, MIBK) is added to 190 g and dissolved at 50°C. After dissolution, 1.5 g of 4-(dimethylamino)pyridine (Aha, DMAP) was added as a reaction catalyst, and the temperature was raised to 100° C. and the reaction was performed while stirring for 8 hours.

(Formula 14)

(Here, x and y are integers from 1 to 100, respectively.)

After cooling to room temperature, a MIBK solution of polyphenylene ether methacrylate resin with methacrylate ends was obtained.

A second solvent obtained by mixing 200 g of methanol and 20 g of water in the MIBK solution of the polyphenylene ether methacrylate resin at the methacrylate terminal was added dropwise to the reaction product while stirring for 30 min, and after completion of the dropping, further stirred for 60 min to obtain a crystal did. The resulting crystals were filtered under reduced pressure and washed twice in a solvent mixed with 200 g of methanol and 20 g of water. A resin mixture containing a ren ether methacrylate resin was obtained.

Example 2

In Example 1, except that the first solvent was changed from MIBK to methyl ethyl ketone (hereinafter MEK), a resin mixture containing 97 g of methacrylate-terminated polyphenylene ether methacrylate resin was obtained in the same manner.

Example 3

In Example 1, except for changing the first solvent from MIBK to propylene glycol monoethyl acetate (hereinafter PGMEA), 104 g of a resin mixture containing methacrylate-terminated polyphenylene ether methacrylate resin was obtained in the same manner.

Example 4

In Example 1, 92 g of meta-method was used in the same manner except that the first solvent was changed from MIBK to ethyl acetate (hereinafter referred to as EA) and the reaction catalyst was changed to 7.39 g of 1,5-diazabicyclo [4.3.0] nonene-5 (DBN). A resin mixture containing polyphenylene ether methacrylate resin with acrylate ends was obtained.

Examples 5 to 8

24 g of the crystalline resin mixture obtained in Examples 1 to 4, BMI-5100 (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, Daiwa-kasei) 6 g, TAIC (1 ,3,5-Triallylisocyanurate, Sigma-Aldrich) 6g and DCP (Dicumyl peroxide, Sigma-Aldrich) 1g were dissolved in MEK 83g to prepare a resin composition.

Example 9

After the reaction was performed in the same manner as in Example 1, except that a material having a structure of the following formula (15) was used as PPE, a resin mixture containing a polyphenylene ether methacrylate resin at the methacrylate end was obtained, A resin composition was prepared in the same manner as in Examples 5 to 8.

(Formula 15)

Example 10

In Example 9, the reaction was performed in the same manner except that a material having the structure of the following formula (16) was used as PPE to obtain a resin mixture comprising a polyphenylene ether methacrylate resin at the methacrylate end, A resin composition was prepared in the same manner as in Examples 5 to 8.

(Formula 16)

Example 11

In Example 9, the reaction was performed in the same manner except that a material having a structure of the following formula 17 was used as PPE to obtain a resin mixture including a polyphenylene ether methacrylate resin at the methacrylate end, A resin composition was prepared in the same manner as in Examples 5 to 8.

(Formula 17)

Example 12

In Example 9, the reaction was performed in the same manner except that a material having the structure of the following formula (18) was used as PPE to obtain a resin mixture including a polyphenylene ether methacrylate resin at the methacrylate end, A resin composition was prepared in the same manner as in Examples 5 to 8.

(Formula 18)

Example 13

In Example 9, the reaction was performed in the same manner except that a material having a structure of the following formula (19) was used as PPE to obtain a resin mixture comprising a polyphenylene ether methacrylate resin at the methacrylate end, A resin composition was prepared in the same manner as in Examples 5 to 8.

(Formula 19)

Example 14

In Example 9, the reaction was performed in the same manner except that a material having a structure of the following formula 20 was used as PPE to obtain a resin mixture comprising a polyphenylene ether methacrylate resin at the methacrylate end, A resin composition was prepared in the same manner as in Examples 5 to 8.

(Formula 20)

Example 15

In Example 9, the reaction was performed in the same manner except that a material having a structure of the following formula (21) was used as PPE to obtain a resin mixture including a polyphenylene ether methacrylate resin at the methacrylate end, A resin composition was prepared in the same manner as in Examples 5 to 8.

(Formula 21)

comparative example

Comparative Example 1

In a 1L 3-neck round glass reactor equipped with a magnetic stirrer, cooling tube, thermometer, and heating mantle, 100 g of PPE and 27.5 g of MAA as in Example 1 were dissolved in 190 g of Toluene as the first solvent at 50 to 60 ° C.

After dissolution, 1.46 g of DMAP was added, the temperature was raised to 100° C., stirred for 8 hours, and then cooled to room temperature. The reactant was added dropwise to a second solvent in which 400 g of methanol and 40 g of water were mixed with stirring for 30 to 60 min, and after completion of the dropping, the mixture was further stirred for 60 min.

The resulting crystals are filtered under reduced pressure, and additional washing is performed twice in a second solvent in which 400 g of methanol and 40 g of water are mixed. The washed resin was dried in an oven at 80-90° C. for 12 hours to obtain 72 g of a crystalline resin mixture.

Comparative Example 2

In Comparative Example 1, the first solvent was changed from toluene to xylene, and 80 g of methacrylate-terminated polyphenylene ether methacrylate resin was included in the same manner as in Comparative Example 1, except that washing was performed with 440 g of methanol alone. A resin mixture was obtained.

Comparative Examples 3 to 4

24 g of the crystalline resin mixture obtained in Comparative Examples 1 and 2, 6 g of BMI-5100 (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, Daiwa-Kasei), TAIC (1 ,3,5-Triallylisocyanurate, Sigma-Aldrich) 6g and DCP (Dicumyl peroxide, Sigma-Aldrich) 1g were dissolved in MEK 83g to prepare a resin composition.

Comparative Example 5

18 g of the crystalline resin mixture obtained in Example 1, BMI-5100 (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, Daiwa-Kasei) 12 g, TAIC (1,3) A resin composition was prepared by dissolving 6 g of ,5-Triallylisocyanurate, Sigma-Aldrich) and 1 g of DCP (Dicumyl peroxide, Sigma-Aldrich) in 83 g of MEK.

Comparative Example 6

29 g of the crystalline resin mixture obtained in Example 1, BMI-5100 (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, Daiwa-Kasei) 1 g, TAIC (1,3) A resin composition was prepared by dissolving 6 g of ,5-Triallylisocyanurate, Sigma-Aldrich) and 1 g of DCP (Dicumyl peroxide, Sigma-Aldrich) in 83 g of MEK.

Comparative Example 7

30 g of the crystalline resin mixture obtained in Example 1, 6 g of TAIC (1,3,5-Triallylisocyanurate, Sigma-Aldrich), and 1 g of DCP (Dicumyl peroxide, Sigma-Aldrich) were dissolved in 83 g of MEK to prepare a resin composition.

Comparative Example 8

24 g of the crystalline resin mixture obtained in Example 1, BMI-5100 (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, Daiwa-Kasei) 6 g, TAIC (1,3) A resin composition was prepared by dissolving 6 g of ,5-Triallylisocyanurate, Sigma-Aldrich) and 2 g of DCP (Dicumyl peroxide, Sigma-Aldrich) in 83 g of MEK.

Comparative Example 9

24 g of the crystalline resin mixture obtained in Example 1, BMI-5100 (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, Daiwa-Kasei) 6 g, TAIC (1,3) A resin composition was prepared by dissolving 6 g of ,5-Triallylisocyanurate, Sigma-Aldrich) and 0.2 g of DCP (Dicumyl peroxide, Sigma-Aldrich) in 83 g of MEK.

Experimental example

Experimental Example 1

The contents of methacrylic acid and BTX solvent, which are by-products contained in the resins obtained in Examples 1 to 4 and Comparative Examples 1 to 2, were measured and shown in Table 1 below.

Experimental Example 2

Glass fibers (Hankook Carbon #2116 (100㎛)) were impregnated with the resin compositions of Examples 5 to 8, 10, 11, 14, and Comparative Examples 3 to 9, and the impregnated glass fibers were overlapped with 6 sheets at a pressure of 2.9 MPa After curing for 2 hours at 230 ° C., BTX content, thermal decomposition rate, dielectric constant, dielectric loss factor, glass transition temperature, mass reduction temperature and 90° adhesion were measured, respectively, and the results are shown in Tables 2 and 3.

measurement sample Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 in the resin mixture
Amount of methacrylic acid (%) 0.1 0.5 0.2 0.4 0.7 1.2 Total BTX solvent in resin mixture (ppm) 30 30 35 40 500 700

measurement sample Example 5 Example 6 Example 7 Example 8 Example 10 Example 11 Example 14 in the resin composition
Total BTX (ppm) 300 450 490 320 350 350 330 moisture absorption 0.26 0.34 0.29 0.31 0.30 0.30 0.32 D _K 3.18 3.35 3.23 3.24 3.20 3.21 3.25 D _f 0.0043 0.0045 0.0043 0.0044 0.0047 0.0045 0.0048 T _g (℃) 254.01 236.95 240.6 245.81 244.5 248.0 250.5 T _d -1wt% 429.99℃ 412.76℃ 420.54 ℃ 409.07℃ 410.1 412.2 433.8 -3wt% 454.85℃ 450.24℃ 451.43 ℃ 450.39℃ 449.8 450.3 458.6 -5wt% 460.57℃ 460.64℃ 460.66℃ 457.38 ℃ 458.1 457.8 462.6 Peel strength (kgf/cm) 0.51 0.53 0.54 0.55 0.52 0.52 0.55

measurement sample Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 in the resin composition
Total BTX (ppm) 570 680 780 480 509 330 460 moisture absorption 0.42 0.62 0.34 0.27 0.31 0.38 0.49 D _K 3.64 3.97 3.75 3.14 3.15 3.54 3.52 D _f 0.0054 0.0067 0.0082 0.0041 0.0039 0.0052 0.0062 T _g (℃) 222.81 210.69 267.05 214.20 212.81 221.55 209.79 T _d
( °C) -1wt% 391.76 372.54 429.76 404.17 404.02 428.16 385.21 -3wt% 448.24 435.43 453.14 434.11 432.32 447.32 431.33 -5wt% 455.64 442.66 460.45 454.26 451.48 455.62 440.61 Peel strength (kgf/cm) 0.49 0.38 0.54 0.51 0.49 0.49 0.38

The test method of each test item is as follows.

[Assessment Methods]

One. (meth)acrylic acid content

The acid value of the resin was obtained and the (meth)acrylic acid content was calculated in the same manner as in Equation 1.

(Formula 1)

2. Content of BTX solvent

The contents of benzene, toluene, and xylene were respectively calculated using GC (gas chromatography) with a headspace, and the total was displayed.

3. Moisture absorption

After the specimen cured in 25°C water was left for 24 hours, the weight increase rate (wt%) was measured.

4. Permittivity (D _k ) and dielectric loss factor (D _f )

It was measured using an Agilent E4991A RF Impedance/Material analyzer according to the JIS-C-6481 method, and the lower this value, the better the electrical properties of the cured product.

5. Glass transition temperature (T _g )

The glass transition temperature was obtained by interpolating the temperature at which the inflection point of the cured product is generated using DSC Q200 from TA. At this time, the temperature increase rate is 10 ℃ / min. Measurements were made in a nitrogen atmosphere.

6. Mass loss temperature (T _d )

Mettler Tolrdo's STAR System TGA was used to measure the temperature at which the weight loss with respect to thermal change becomes 1wt%, 3wt%, and 5wt%. At this time, the temperature increase rate is 10 ℃ / min. Measurements were made in a nitrogen atmosphere.

7. Peel strength (1/2 oz copper peel strength)

Peel strength was measured by the JIS C-6417 method. The higher the peel strength, the better the adhesion to copper.

Claims (10)

It is synthesized in a first solvent that is an ester-based solvent, a ketone-based solvent, or a mixture thereof, and includes a polyphenylene ether-based resin having the structure of the following Chemical Formula 1,
Polyphenylene ether (meth)acrylate resin mixture having a total content of benzene, toluene and xylene of less than 500 ppm.

(Formula 1)

Here, each R is independently methyl (CH ₃ ) or hydrogen (H),
Y is sulfur (S) or oxygen (O), X is a direct connection, -CH ₂ -, -(C)(CH ₃ ) ₂ -, -CO-, -S-, -SO ₂ -, -C( CF ₃ ) ₂ -, -(C)(CH ₂ CH ₃ ) ₂ - or -(CH)(CH ₂ CH ₃ )-,
l is an integer from 1 to 100, m is 0 or 1, when m=0, n=0, and when m=1, n is an integer from 1 to 100.
According to claim 1,
The (meth)acrylate end of the polyphenylene ether (meth)acrylate resin is a polyphenylene ether (meth)acrylate resin mixture derived from (meth)acrylic acid anhydride of the following formula (3).
(Formula 3)

In Formula 3, each R is independently methyl (CH ₃ ) or hydrogen (H).
3. The method of claim 2,
A polyphenylene ether (meth)acrylate resin mixture comprising less than 0.7 wt% of (meth)acrylic acid, which is a by-product of the acrylate reaction of the (meth)acrylic acid anhydride.
4. The method of claim 3,
The content of the (meth)acrylic acid is a polyphenylene ether (meth)acrylate resin mixture calculated from the acid value of the polyphenylene ether (meth)acrylate resin having the structure of Formula 1 above.
According to claim 1,
The first solvent is an aprotic solvent having a dielectric constant of 5 to 25 at 20°C, a polyphenylene ether (meth)acrylate resin mixture.
6. The method of claim 5,
The polyphenylene ether (meth)acrylate resin is a polyphenylene ether (meth)acrylate resin mixture having a structure of the following Chemical Formula 10.
(Formula 10)

Here, x and y are integers from 1 to 100.
Having the structure of Formula 1 below,
A polyphenylene having a (meth) acrylate end, which is provided by acrylated reaction of a polyphenylene ether compound of Chemical Formula 2 and (meth)acrylic anhydride of Chemical Formula 3 in a first solvent which is a non-aromatic organic solvent Lene ether (meth) acrylate resin,
Polyphenylene ether (meth)acrylate resin mixture having a total content of benzene, toluene and xylene of less than 500 pmm.

(Formula 1)

(Formula 2)

(Formula 3)

(In Formulas 1 to 3, R is each independently methyl (CH ₃ ) or hydrogen (H),
Y is sulfur (S) or oxygen (O),
X is a direct connection, -CH ₂ -, -(C)(CH ₃ ) ₂ -, -CO-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, -(C)(CH ₂ CH ₃ ) ₂ - or -(CH)(CH ₂ CH ₃ )-,
l is an integer from 1 to 100, m is 0 or 1, when m=0, n=0, and when m=1, n is an integer from 1 to 100.)
8. The method of claim 7,
A polyphenylene ether (meth)acrylate resin mixture having a content of (meth)acrylic acid produced after the reaction of the (meth)acrylic acid anhydride of less than 0.7 wt%.
9. The method of claim 8,
The first solvent is an aprotic solvent having a dielectric constant of 5 to 25 at 20°C, a polyphenylene ether (meth)acrylate resin mixture.
10. The method of claim 9,
The polyphenylene ether (meth)acrylate resin is a polyphenylene ether (meth)acrylate resin mixture solidified by washing with a second solvent, which is a mixed solvent containing water and alcohol.