KR102656211B1 - Poly phenylene ether resin mixture - Google Patents

Abstract

One aspect of the present invention is,
It is acrylated 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 formula (1),
It is characterized as a polyphenylene ether (meth)acrylate resin mixture with a total content of benzene, toluene, and xylene of less than 500 ppm.
(Formula 1)

(Here, R is each independently methyl (CH ₃ ) or hydrogen (H),
Y is sulfur _{( S )} or oxygen (O ₎ , and 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, if m=0, n=0, and if m=1, n is an integer from 1 to 100.)

Description

Polyphenylene ether resin mixture {Poly phenylene ether resin mixture}

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

In accordance with the recent trend of high integration, high miniaturization, flexibility, and high functionality in electronic devices, copper clad laminates have excellent transmission characteristics due to low dielectric loss in the GHz range and a low thermal expansion coefficient to ensure component design, processability, and reliability. (CCL, copper clad laminate) or semiconductor encapsulant (EMC, Epoxy Molding Compound) materials are required. Organic materials with low dielectric constant include epoxy resin, Teflon resin, and polyphenylene ether (PPE), and among them, Teflon material is known to have 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, and flexible display substrates. There is a disadvantage in that the adhesive properties are significantly poor, and in the case of cyanate resin, high energy is required when curing at a temperature of 230°C and it is easily gelled by alcoholic hydroxy such as moisture, which limits its use. In addition, polyphenylene ether (PPE) is a polymer that does not have hydrolyzable bonds or polar groups, and has significantly superior low dielectric constant and low dielectric loss factor compared to other resins. Combining PPE with other resins provides chemical resistance, high strength, and high fluidity. However, blending PPE with other resins is hampered by lack of compatibility between the resins, often resulting in delamination and/or poor physical properties such as low ductility. It represents the characteristics.

For this reason, epoxy resins, which have high adhesive properties, a certain degree of low dielectric constant and low dielectric loss factor, and are easy to use, are increasingly being used as materials for CCL or EMC materials. However, epoxy resins have polar groups such as hydroxyl groups after curing. Therefore, it is difficult to realize an insulating layer with sufficiently excellent dielectric properties when manufacturing an insulating layer using an epoxy resin. One useful method of improving compatibility between resins known in the PPE art is to create a reaction product between the polymers that acts as a compatibilizer for the resins. The reaction product is often thought of as a copolymer of resins. One challenge in preparing the reaction product is the need for reactive sites on 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 primarily phenolic end groups and are generally not reactive enough to produce the above reaction products in a commercially feasible process, so methods and processes for introducing functionality into PPE have been extensively studied. there is.

The present invention was devised to solve the above-mentioned problems, and a (meth)acrylate having excellent electrical properties while obtaining the desired heat resistance, curing reactivity, adhesion, and thermal expansion coefficient required for CCL or EMC was introduced. The object is to provide a method for producing a radically curable polyphenylene ether-based resin.

Republic of Korea Patent No. 10-0595771

One aspect of the present invention is that it does not contain BTX (benzene, toluene, xylene)-based compounds, which are environmentally regulated substances, or contains trace amounts, so it has a low moisture absorption rate and excellent electrical properties without using a BTX-based organic solvent. The purpose of the present invention is to provide a polyphenylene ether resin mixture and a method for producing the same.

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

Furthermore, the present invention provides a resin mixture that can be used as a low-dielectric material that can be used in 5th generation wireless communication (5G) technology with low dielectric and heat resistance properties that can be used even in the high frequency range of hundreds of MHz or several GHz. The purpose is 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 formula (1),

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

(Formula 1)

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

Y is sulfur _{( S )} or oxygen (O ₎ , and 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, if m=0, n=0, and if 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, R is each independently methyl (CH ₃ ) or hydrogen (H).

In addition, it is preferable to contain less than 0.7 wt% of (meth)acrylic acid, which is a by-product of the acrylation reaction of the (meth)acrylic 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 preferably has the structure of Formula 10 below.

(Formula 10)

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

In addition, a polyphenylene ether compound of the following formula (2) and (meth)acrylic acid anhydride of the formula (3) having a (meth)acrylate terminal provided by acrylation reaction in a first solvent, which is a non-aromatic organic solvent. Contains polyphenylene ether (meth)acrylate resin,

It is preferred 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 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, if m=0, n=0, and if 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 anhydride is less than 0.7 wt%,

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

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

The method for producing a polyphenylene ether-based resin mixture according to one aspect of the present invention is to perform an acrylation reaction of the resin using an aprotic solvent having a dielectric constant of about 5 to 25 at a temperature of 20° C. as a first solvent to produce benzene, It has a higher reaction efficiency compared to organic solvents such as toluene or xylene, and has the advantage of reducing the amount of alcohol used and shortening the time during work-up and separation after reaction.

Additionally, unreacted monomers and (meth)acrylic acid can be easily removed and the amount of catalyst used can be reduced.

In addition, when washing and drying the product, a second solvent mixed with water and alcohol is used, which has the advantage of high cleaning and drying efficiency.

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

When a resin composition is manufactured using the polyphenylene ether resin mixture of the present invention, the content of BTX contained in the overall resin composition can be lowered, so it can be safely manufactured and used within strict environmental regulation conditions.

The above resin composition has a low moisture absorption rate after curing, can have low dielectric properties, and has the advantage of excellent heat resistance.

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

Before describing the present invention in detail below, it is understood that the terms used in this specification are only for describing specific embodiments and are not intended to limit the scope of the present invention, which is limited only by the scope of the appended claims. shall. All technical and scientific terms used in this specification have the same meaning as generally understood by those skilled in the art, unless otherwise specified.

Throughout this specification and claims, unless otherwise stated, the terms comprise, comprises, and comprise mean to include the mentioned article, step, or group of articles, and steps, and any other article. , it is not used in the sense of excluding a step, a group of objects, or a group of steps.

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

The polyphenylene ether (meth)acrylate resin of the present invention is a polyphenylene ether (meth)acrylic having the 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 polyphenylene ether (meth)acrylate compound and can be obtained as a solid crystalline resin.

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

At this time, Y is preferably oxygen (O), and X is preferably a structure containing sp3 hybridized carbon. _{For example , ​ ​ ​ ​ ​} It is preferable to have a structure in which the aromatic rings are connected by sp3 hybridized carbon or sulfur, such as ₂ CH ₃ )-, preferably -CH ₂ -, -(C)(CH ₃ ) ₂ - or -(CH) It is better to select a hydrocarbon with 3 or less carbon atoms, such as (CH ₂ CH ₃ )-.

If an sp2 hybridized carbon is located at the position connecting the aromatic ring in the structure of There may be a problem that crosslinks are less formed.

If a sulfur atom is included in the structure of

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

At this time, the organic compound is an organic solvent used in the synthesis of polyphenylene ether (meth)acrylate resin. Some of the first solvent may be included in the resin mixture, and after the resin synthesis reaction, the product is crystallized, washed, or separated (isolated). ) The second solvent or alcohol-based compound used 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 can dissolve 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 low polarity compound may be used as the first solvent. For example, a compound having a dielectric constant measured at 20°C of 25 or less, specifically 5 to 25, may be used.

If the dielectric constant is greater than 25, the polarity of the solvent may increase, which may worsen the solubility of the organic compounds used in the reaction. Side reactions may occur, resulting in reduced yield, and polymerization, which reduces cured properties. If the dielectric constant is less than 5, the polarity of the solvent may become too low, which may worsen the solubility of materials such as catalysts, and reactivity may be significantly reduced, causing problems such as increased reaction time and reaction temperature.

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

The above-mentioned first solvent is a solvent such as toluene or benzene that has the advantage of not significantly increasing the dielectric constant or dielectric loss even if it contains an aromatic ring and remains, making it easy to remove due to its high solubility in polyphenylene ether polymer and low boiling point. Compared to the case of using , it provides not low polyphenylene ether solubility, the efficiency of the acrylation reaction is high, and the amount of alcohol used is reduced, helping to maintain the low dielectric properties of the resin.

In addition, the resin mixture containing polyphenylene ether (meth)acrylate resin has a high content of BTX (Benzene, Toluene, Xylene)-based compounds, which collectively refer to benzene, toluene, and xylene, which are aromatic organic compounds that cause environmental pollution. It is characterized by 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 the BTX-based compounds is less than 500 ppm, preferably. may be 300 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less.

The polyphenylene ether (meth)acrylate resin mixture of the present invention has the advantage of having less environmental pollution or negative effects on the human body due to its low content of BTX-based compounds, and has excellent reaction efficiency without using BTX-based solvents. When manufacturing, the product 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 poor, so the content of (meth)acrylic acid anhydride in the resin mixture is preferably 500 ppm or less, and more preferably 300 ppm. or less, more preferably 100 ppm or less.

In this 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 the situation in which charged particles enter the solvent. For example, when (+) charged particles enter the solvent. Once introduced, cancellation occurs in such a way that the δ- portion of the solvent surrounds the particle. At this time, if cancellation occurs well and the electric field strength of the (+) charged particles is greatly reduced, the solvent can be said to have a high dielectric constant.

In other words, if the degree to which the electric charge is reduced is large, the dielectric constant is large. Conversely, if the electric charge is not well offset, the solvent has a low dielectric constant.

Polar solvents and non-polar solvents described in this specification can be distinguished based on the dielectric constant value of 5. This value can be derived using the dipole moment, because a solvent in which δ+ and δ- are clearly divided within the molecule can well cancel out the charge intensity.

However, the tendency and magnitude of the dipole moment and dielectric constant may not completely match, and unless there are exceptional circumstances, such tendency can be maintained in most cases. More specifically, a dispersion medium with a dielectric constant ε value lower than 3 is referred to as a non-polar solvent, a dispersion medium with a dielectric constant ε value of 3 to 6 is referred to as a neutral solvent, and a dispersion medium with a dielectric constant ε value greater than 6 is referred to as a polar solvent. can be distinguished.

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

As a manufacturing method for producing a polyphenylene ether (meth)acrylate resin mixture containing polyphenylene ether (meth)acrylate resin and a trace amount of the first solvent, benzene-based and toluene-based resins, which have become difficult to use due to recent environmental regulations, Provides a method for producing a radically 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, when the dielectric constant, which indicates the polarity of the material, was measured for the first solvent used, the dielectric constant at 20°C was 5 to 25, and it reacted with (meth)acrylic anhydride, which can be used as a reactant during the reaction. A method for producing a radically curable polyphenylene ether-based resin mixture into which (meth)acrylate is introduced using a non-aromatic, aprotic solvent is disclosed, and the production method includes the following reactant preparation steps: , mixture creation step, and by-product removal step.

The reactant preparation step includes a polyphenylene ether compound represented by the following (Formula 2) or a resin containing the same, (Meth)Acrylic acid anhydride having the same structure as (Formula 3), and 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 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 the reaction to be described later, and includes reactive -OH terminals at both ends, which have a structure similar to that of a phenol derivative.

(Formula 3)

In Formula 3 above,

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

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

In Formula 3, R is preferably a methyl group, and (meth)acrylate is preferably obtained as a functional group after reaction.

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

The reaction catalyst used in 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 type selected from the group consisting of compounds containing ammonium ions formed by can be used.

The reaction catalyst may be a compound represented by the following formulas 4 to 9, for example, 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-tert-Butyl-1,1,3,3-tetramethylguanidine (2-tert-Butyl-1,1,3,3-tetramethylguanidine), 9-azazuloridine ( 9-Azajulolidine), 1ㅡ8-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 contains 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 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 independently C ₁ to C ₆ It is an 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 the reaction catalyst is used above the above range, the amount of catalyst remaining in the final product, polyphenylene ether (meth)acrylate resin, may increase, increasing the dielectric constant of the resin. There is a problem.

The mixture creation step is an acrylation reaction of the polyphenylene ether compound of Formula 2 and the (meth)acrylic acid anhydride of Formula 3 under the conditions of the first solvent, which is an aprotic, non-aromatic organic solvent, to produce polyphenylene ether of Formula 1 ( This is the step of synthesizing a resin mixture containing meth)acrylate resin.

According to this manufacturing method, the aprotic first solvent may be an organic solvent having a dielectric constant ε of 5 to 25 at 20°C. When using an aprotic organic solvent with a dielectric constant in the corresponding range, it is easier to remove (meth)acrylic acid obtained as a reaction by-product than when using organic solvents such as benzene, toluene, or xylene, and it is less likely to cause environmental pollution or human toxicity. This has the advantage of reducing problems such as lowering the moisture absorption rate (or moisture absorption rate) of the resin in the atmosphere by lowering the content of (meth)acrylic acid contained in the resin containing polyphenylene ether (meth)acrylate obtained through the reaction. ) is lowered, and there is an advantage that the dielectric constant of the resin can be maintained low.

More specifically, when using an aprotic organic solvent with a dielectric constant ε of 5 to 25 at 20°C, the efficiency of the synthesis reaction increases, the content of the BTX-based compound contained in the resin decreases, and the reaction progresses. During subsequent work-up and isolation, the process progress time is reduced, the amount of alcohol used during washing is reduced, the removal of unreacted monomers or by-product (meth)acrylic acid is easy to remove, and the amount of catalyst used is reduced. There is an advantage in being able to lower .

The acrylation reaction that proceeds in this step involves the reaction of 1 equivalent of a polyphenylene ether compound having a hydroxyl group bonded to a phenyl group at the end with 1 equivalent of (meth)acrylic acid anhydride, and (meth)acrylic acid added to the hydroxyl group bonded to a phenyl group. An ester bond is formed through a condensation reaction of anhydride under catalytic conditions, and (meth)acrylate or (meth)acrylic acid fails to form a bond with the hydroxy group of the (meth)acrylate that forms the (meth)acrylic acid anhydride molecule and is separated as a leaving group. This 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 added as a reactant is esterified with (meth)acrylate, and single (meth)acrylated polyphenylene ether resin and double (meth)acrylated polyphenylene ether resin are obtained. Here, it is preferable that the ratio of a resin in which all 1 or 2 terminal hydroxy groups participate in the reaction is esterified, preferably a (meth)acrylated polyphenylene ether resin in which both hydroxy groups participate in the reaction, is high. .

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

Specifically, the cured product of the resin mixture preferably has a dielectric constant of 2.0 to 4.0, and 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 the structure of Formula 10 below as an example of polyphenylene ether (meth)acrylate resin.

(Formula 10)

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

According to Formula 10, (meth)acrylic acid anhydride is used as a (meth)acrylic acid anhydride that reacts with the polyphenylene ether compound in the first solvent to produce a polyphenylene ether (meth)acrylate resin having a (meth)acrylate terminal. can be obtained.

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

In the process of washing the reaction product using a second solvent, (meth)acrylic acid or (meth)acrylate salt produced by the reaction and the reaction catalyst added for the reaction may be washed and removed. At this time, 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, so it is difficult to separate and remove as much as possible. In order to proceed with the reaction to increase the yield of the product and minimize the yield of mono-substituted polyphenylene ether (meth)acrylate resin, which is an unreacted product or intermediate product, a larger amount of (meth)acrylic acid anhydride than the reaction equivalent was added to produce polyphenyl. It is desirable to allow the lene ether compound to react completely.

The polyphenylene ether (meth)acrylate resin mixture may contain some residual (meth)acrylic acid, which may not be completely removed even after washing and may remain trapped or remain inside the high molecular weight polymer chain. At this time, the (meth)acrylic acid content of the resin mixture can be calculated by calculating the acid value (acid value or acid number) of the resin using the formula below.

The acid value of the resin is a value that represents the amount of acidic substance obtained from 1g of polymer, and refers to 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 the molecular weight of KOH, 56.1 g/mol, and the molecular weight of (meth)acrylic acid to obtain the 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 0.7wt%, and preferably less than 0.6wt%.

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

Additionally, since (meth)acrylic acid is a polar molecule, in the final polyphenylene ether (meth)acrylate resin mixture, it forms a (meth)acrylic acid dimer structure by hydrogen bonding and can be included inside the polymer chain with low polarity. It is also possible for oxygen and (meth)acrylic acid contained in polyphenylene ether (meth)acrylate resin to form hydrogen bonds and 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 can be any compound containing a hydroxy group bonded to carbon, but preferably at least one selected from the group consisting of methanol, ethanol, normal propanol, and isopropanol is used, which is advantageous in terms of economic efficiency and handling. , more preferably 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 when absolute alcohol is used, and the quality of the resin finally obtained after washing is superior. .

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

It is recommended that the by-product removal step further include drying the washed polyphenylene ether (meth)acrylate resin after washing the product. The drying method is not greatly limited. For example, a drying process may be performed in a convection oven, or a method of removing volatile solvents by reducing pressure may be used.

According to one 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 increase, and if the drying temperature is higher than the corresponding range, the (meth)acrylate functional group contained in polyphenylene ether (meth)acrylate reacts due to the high temperature to obtain a by-product or the final product. Problems may arise where the yield decreases.

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 containing polyphenylene ether (meth)acrylate resin with (meth)acrylic groups esterified at both ends, and reaction by-products (BTX-based compounds) that are not completely removed during the washing process remain. ) or other unintended impurities or reaction catalysts may be present in the resin mixture. By-products or impurities may remain trapped within the three-dimensional structure of the polymer resin chain, and in addition, water or alcohol remaining after washing and not completely removed during the drying process may be included in the resin mixture.

In the present invention, in addition to the resin mixture containing polyphenylene ether (meth)acrylate resin with a (meth)acrylic group introduced at the terminal as described above and the method for producing the same, a resin composition having low dielectric properties including the resin is manufactured. Discloses a method for doing so.

The resin composition includes a polyphenylene ether (meth)acrylate resin mixture prepared by the above-described production method, a resin or resin mixture containing a 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 the resin mixture 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. It is preferably contained in an amount of 65 to 90 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 corresponding range, the low dielectric and heat resistance characteristics may deteriorate, and if it is more than the corresponding range, the content of the BTX-based compound in the resin composition increases, and the bending characteristics may decrease. There is a problem that it falls off and breaks easily.

The resin containing a vinyl functional group includes a resin compound containing a vinyl functional group. Here, the compound containing a vinyl functional group is a compound with high heat resistance, and preferably contains a vinyl functional group excluding an acrylic group, for example, bismaleimide. It is preferable that it is a vinyl compound derived from the (Bismaleimide) structure or the Isocyanurate structure.

When using a vinyl compound derived from a bismaleimide structure or an isocyanurate structure, it has a high glass transition temperature and a high thermal decomposition temperature, so it has the advantage of being applied to parts materials that require heat resistance.

The resin mixture containing a vinyl functional group can form crosslinks through reaction with the polyphenylene ether (meth)acrylate resin mixture in the resin composition, and can have excellent curing properties through crosslinking.

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

(Formula 11)

(Formula 12)

In Formula 11 and Formula 12,

M is an atomic group selected from the group consisting of C ₀ to C ₆ alkyl, C ₂ to C ₆ alkane, C ₂ to C ₆ alkyne, oxygen, hydrogen and benzene,

Q independently includes 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 .

(Formula 13)

An initiator is a substance used to initiate a chain reaction such as a radical reaction, and a substance that can easily generate radicals by heat or light may be used.

The resin composition of the present invention preferably includes a peroxide-based initiator as an initiator. Peroxide-based initiators include, for example, Dicumyl peroxide, Benzoyl peroxide, Lauryl peroxide, t-butyl cumyl peroxide, D. (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, One or more compounds selected from the group consisting of 5-di(tert-butyl peroxy)hexane) and di-t-butyl peroxide may be used.

The initiator may be included in the resin mixture 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.

If the content of the initiator is less than the range, the curing speed may be slowed due to the slow chain reaction, which may reduce productivity. The degree of curing may decrease and heat resistance may deteriorate. If the content of the initiator is higher than the range, the curing heat may cause appearance problems. This may occur, and the curing reaction speed of the mixture is fast during curing, which lowers the curing density and lowers heat resistance. Also, due to poor flowability, the surface of the cured product becomes uneven, which can lead to problems with partial physical properties being distorted.

The third solvent included in the resin composition can be used without limitation as long as it can dissolve polyphenylene ether (meth)acrylate resin and a compound containing a vinyl functional group well, and may be an organic solvent that does not contain a BTX-based compound. A solvent is preferred, and examples include 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 containing at least one selected substance may be used.

The third solvent may be included in the resin mixture 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.

If the content of the third solvent is less than the corresponding range, the viscosity of the composition may increase, which may reduce processability and make it difficult to wet glass fiber. If the content of the third solvent is higher than the corresponding range, the adhesive strength of the resin composition may decrease. Alternatively, problems with lowered heat resistance may occur.

Meanwhile, the resin composition of the present invention is characterized by low BTX content, moisture absorption rate, dielectric material, and dielectric loss rate in the composition, and the above physical properties can be measured after curing the resin composition.

The physical properties of the resin composition were measured by measuring the cured product obtained by impregnating glass fibers with the resin composition in the examples of the present invention, then laminating the impregnated glass fibers and curing them for 2 hours at a pressure of 2.9 MPa and a temperature of 230°C. can be obtained.

The BTX content of the resin composition is preferably less than 550 ppm, preferably less than 500 ppm, in order to meet strict environmental regulations.

The moisture absorption rate 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 is 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 utilizing the resin composition It is desirable because it can be suitable for.

Resin compositions with such low BTX and moisture content, low dielectric and low dielectric loss properties have excellent electrical properties and have excellent heat resistance and bending properties, making them less brittle.

The manufactured resin composition has the advantage of low dielectric properties and excellent heat resistance, and has a very low content of BTX-based compounds harmful to the human body, ensuring safety, while hardly deteriorating physical properties such as low dielectric properties and heat resistance.

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

Hereinafter, 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 formula 14 below was placed in a 1 L 3-neck round glass reactor equipped with a magnetic stirrer, cooling pipe, thermometer, and heating mantle. ) (Number average molecular weight (Mn) 1,600, product name SA-90 manufacturer Sabic) 100g (0.12g/eq) and methacrylic anhydride (hereinafter referred to as MAA) 27.5g (0.24g/eq) were mixed with the first solvent, methyl isobutyl ketone ( Add to 190g of MIBK (hereinafter referred to as MIBK) and dissolve at 50°C. After dissolution, 1.5 g of 4-(dimethylamino)pyridine (AHA, DMAP) was added as a reaction catalyst, and the reaction proceeded while heating to 100°C and stirring for 8 hours.

(Formula 14)

(Where x and y are each integers from 1 to 100.)

Afterwards, it was cooled to room temperature to obtain a MIBK solution of methacrylate-terminated polyphenylene ether methacrylate resin.

A second solvent, which is a mixture of 200 g of methanol and 20 g of water, was added dropwise to the MIBK solution of the polyphenylene ether methacrylate resin at the methacrylate end while stirring for 30 minutes, and after completion of the dropwise addition, stirred for an additional 60 minutes to obtain crystals. did. The generated crystals were filtered under reduced pressure and additionally washed twice in a solvent mixed with 200 g of methanol and 20 g of water. The washed resin was dried in a convection oven at 90°C for 12 hours to produce 102 g of methacrylate-terminated polyphenyl. A resin mixture containing lene ether methacrylate resin was obtained.

Example 2

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

Example 3

A resin mixture containing 104 g of methacrylate-terminated polyphenylene ether methacrylate resin was obtained in the same manner as in Example 1 except that the first solvent was changed from MIBK to propylene glycol monoethyl acetate (PGMEA).

Example 4

92 g of meta was prepared in the same manner as in Example 1 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 acrylate-terminated polyphenylene ether methacrylate resin was obtained.

Examples 5 to 8

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

Example 9

After performing the reaction in the same manner as in Example 1, except that a material having the structure of the following formula 15 was used as the PPE, a resin mixture containing a methacrylate-terminated polyphenylene ether methacrylate resin was obtained, Resin compositions were prepared in the same manner as Examples 5 to 8.

(Formula 15)

Example 10

After performing the reaction in the same manner as in Example 9, except that a material having the structure of the following formula 16 was used as the PPE, a resin mixture containing a methacrylate-terminated polyphenylene ether methacrylate resin was obtained, Resin compositions were prepared in the same manner as Examples 5 to 8.

(Formula 16)

Example 11

After performing the reaction in the same manner as in Example 9, except that a material having the structure of Formula 17 below was used as the PPE, a resin mixture containing a methacrylate-terminated polyphenylene ether methacrylate resin was obtained, Resin compositions were prepared in the same manner as Examples 5 to 8.

(Formula 17)

Example 12

The reaction was performed in the same manner as in Example 9, except that a material having the structure of Formula 18 below was used as the PPE to obtain a resin mixture containing a methacrylate-terminated polyphenylene ether methacrylate resin, Resin compositions were prepared in the same manner as Examples 5 to 8.

(Formula 18)

Example 13

After performing the reaction in the same manner as in Example 9, except that a material having the structure of the following formula (19) was used as the PPE, a resin mixture containing methacrylate-terminated polyphenylene ether methacrylate resin was obtained, Resin compositions were prepared in the same manner as Examples 5 to 8.

(Formula 19)

Example 14

After performing the reaction in the same manner as in Example 9, except that a material having the structure of the following formula (20) was used as the PPE, a resin mixture containing a methacrylate-terminated polyphenylene ether methacrylate resin was obtained, Resin compositions were prepared in the same manner as Examples 5 to 8.

(Formula 20)

Example 15

After performing the reaction in the same manner as in Example 9, except that a material having the structure of the following formula (21) was used as the PPE, a resin mixture containing a methacrylate-terminated polyphenylene ether methacrylate resin was obtained, Resin compositions were prepared in the same manner as Examples 5 to 8.

(Formula 21)

Comparative example

Comparative Example 1

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

After dissolution, 1.46 g of DMAP was added, the temperature was raised to 100°C, the reaction was stirred for 8 hours, and the mixture was cooled to room temperature. The reactant was added dropwise to the second solvent, which was a mixture of 400 g of methanol and 40 g of water, while stirring for 30 to 60 min, and stirred for an additional 60 min after the dropwise addition was completed.

The resulting crystals are filtered under reduced pressure and further washed twice with a second solvent containing 400 g of methanol and 40 g of water. The washed resin was dried in an oven at 80~90℃ for 12 hours to obtain 72g of crystalline resin mixture.

Comparative Example 2

In Comparative Example 1, the first solvent was changed from toluene to xylene, and the washing was performed with 440 g of methanol alone. In the same manner as in Comparative Example 1, 80 g of methacrylate-terminated polyphenylene ether methacrylate resin was used. 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 A resin composition was prepared by dissolving 6g of 3,5-Triallylisocyanurate, Sigma-Aldrich) and 1g of DCP (Dicumyl peroxide, Sigma-Aldrich) in 83g of MEK.

Comparative Example 5

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

Comparative Example 6

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

Comparative Example 7

A resin composition was prepared by dissolving 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) in 83 g of MEK.

Comparative Example 8

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

Comparative Example 9

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

Experiment 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

The resin compositions of Examples 5 to 8, 10, 11, and 14, and Comparative Examples 3 to 9 were impregnated into glass fibers (Hankook Carbon #2116 (100㎛)), and the impregnated glass fibers were stacked in 6 sheets and subjected to a pressure of 2.9 MPa. After curing at 230°C for 2 hours, the BTX content, thermal decomposition rate, dielectric constant, dielectric loss rate, glass transition temperature, mass loss 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
Methacrylic acid amount (%) 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
BTX total (ppm) 300 450 490 320 350 350 330 moisture absorption rate 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 (°C) 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
BTX total (ppm) 570 680 780 480 509 330 460 moisture absorption rate 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 (°C) 222.81 210.69 267.05 214.20 212.81 221.55 209.79 T _d
( ℃) -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 experimental method for each experimental item is as follows.

[Assessment Methods]

1. (Meth)acrylic acid content

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

(Formula 1)

2. BTX solvent content

Using GC (gas chromatography) equipped with a headspace, the contents of benzene, toluene, and xylene were each determined and the total was displayed.

3. Moisture absorption rate

The specimen cured in water at 25°C was left for 24 hours and then measured as weight increase (wt%).

4. Dielectric constant (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. 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 was created using TA DSC Q200. At this time, the temperature increase rate was 10℃/min. Measurements were made in a nitrogen atmosphere.

6. Mass loss temperature (T _d )

Using Mettler Tolrdo's STAR System TGA, the temperatures at which weight loss due to thermal change was 1wt%, 3wt%, and 5wt% were measured. At this time, the temperature increase rate was 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 greater the peel strength, the better the adhesion to copper.

Claims (10)

Poly phenylene ether compound of the following formula (2) and (meth)acrylic acid anhydride of the formula (3) are acrylated in a first solvent, which is an aprotic and non-aromatic organic solvent with a dielectric constant of 5 to 25 at 20°C. By reacting, a mixture containing a polyphenylene ether (meth)acrylate resin of the following formula (1) and other by-products is prepared, and the mixture is mixed with a second mixed solvent in which 1 to 50 parts by weight of water is mixed with 100 parts by weight of alcohol. A crystalline solid polyphenylene ether (meth)acrylate resin mixture prepared by washing with a solvent, drying the washed resin, and solidifying the mixture, and having a total content of benzene, toluene, and xylene in the mixture of less than 100 ppm. .

(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 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, if m=0, n=0, and if m=1, n is an integer from 1 to 100.) delete According to paragraph 1,
A polyphenylene ether (meth)acrylate resin mixture containing less than 0.7 wt% of (meth)acrylic acid, a by-product of the acrylation reaction of the (meth)acrylic anhydride.
According to paragraph 3,
A polyphenylene ether (meth)acrylate resin mixture in which the content of (meth)acrylic acid is calculated from the acid value of the polyphenylene ether (meth)acrylate resin having the structure of Formula 1.
delete According to paragraph 1,
The polyphenylene ether (meth)acrylate resin is a polyphenylene ether (meth)acrylate resin mixture having the structure of Formula 10 below.
(Formula 10)

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


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