KR20220049385A - Phosphorous compound - Google Patents

Abstract

The present invention relates to a phosphorus compound having a structure represented by chemical formula 1, wherein each of R1 and R2 represents an aryl group or substituted aryl group present in an independent or bound structure; X represents a hydrogen atom, methyl or trifluoromethyl group; Y represents a hydrogen atom, methyl, trifluoromethyl, ethyl, cyclohexyl or phenyl group; each n is an integer of 0-1; m is an integer of 1-2; and l is an integer of 0-2.

Description

Phosphorous compound

One aspect of the present invention relates to a phosphorus-based compound, and specifically relates to a phosphorus-based compound that can be used as a flame retardant.

In general, a printed circuit board (PCB) is used to drive electronic products such as computers, cameras, and televisions. A printed circuit board is a circuit connection component that electrically connects and supports the components by attaching a thin film such as copper to an insulating base film such as phenol or epoxy, and then patterning it in a desired shape.

In accordance with the recent trend of light, thin, compact and eco-friendly electronic devices, the demand for high performance such as flame retardancy, heat resistance, moisture resistance, efficiency and thermal conductivity for printed circuit boards is increasing. CCL), Flexible Copper Clad Laminate (FCCL), and Metal Copper Clad Laminate (MCCL) are also required to implement high performance.

A copper clad laminate is a raw material for a printed circuit board, and an insulating plate obtained after heating and pressurizing several layers of sheets combining a compound with an insulating material such as paper or glass is called a laminate. According to recent environmental regulations, the requirements for insulating materials used have increased, such as lead-free, and as the circuit line width is reduced, more parts are mounted per unit area, and considerable heat is generated when high-speed signals are transmitted. is occurring

Such heat can cause problems such as deformation of the board due to the difference in CTE between parts and materials, and the soldering temperature rises from 20℃ to 40℃, so the material has characteristics such as lead free high Tg and high heat resistance is being demanded

Epoxy composition has been widely used for parts of electric and electronic devices due to its excellent properties, but the epoxy/curing agent composition has a disadvantage in that the dielectric constant among electrical properties is lowered due to the generation of secondary alcohol structurally in the curing mechanism.

In addition, in the case of epoxy resins, halogenated flame-retardant epoxy compounds are used to ensure safety against fire, and harmful halogen compounds or polybrominated dibenzodioxins and furans are generated, so there is a limit not to be free from environmental problems. Addition-type flame retardants to improve flame retardant properties have a problem in that they are difficult to utilize because they deteriorate various mechanical properties.

When using such a resin, a flame-retardant curing agent for improving flame-retardant properties is generally used. A flame retardant curing agent is an additive that is physically and chemically added to a resin or compound to slow ignition and prevent the spread of combustion, and is largely divided into reactive and additive types.

The reactive flame-retardant curing agent has a functional group in the molecule and reacts chemically to maintain the flame-retardant effect, and the additive-type flame-retardant curing agent is physically mixed, added, and dispersed.

Since the additive-type flame-retardant curing agent does not cause a chemical reaction with the polymer, it is lost from the substrate and may cause a problem that the flame-retardant effect is lowered, so there is a limit compared to the reactive flame-retardant curing agent. There is a problem in that the heat resistance and adhesive properties of the cured product are deteriorated due to the gelation phenomenon occurring or the curing density being lowered.

Accordingly, in order to solve this problem, it is necessary to study to solve the problem of deterioration of physical properties such as dielectric properties of the cured product by the addition of the flame retardant curing agent while improving the flame retardant properties as a flame retardant that can replace the existing flame retardant curing agents.

Republic of Korea Patent Publication No. 10-2016-0108721

One aspect of the present invention has been devised to solve the problems of the prior art, and provides a phosphorus-based compound that does not deteriorate physical properties such as glass transition temperature and adhesive properties after curing while providing excellent flame retardant properties when mixed in a resin composition It is intended to

In addition, an object of the present invention is to provide a resin composition capable of providing a substrate having low dielectric properties with low dielectric constant and dielectric loss while having excellent flame retardant properties, including phosphorus-based compounds, with excellent productivity and low production price.

One aspect of the present invention is a phosphorus-based compound having a structure of Formula 1 below.

(Formula 1)

(In this case, R1 and R2 are an aryl group or a substituted aryl group, each independently or combined, X is hydrogen, methyl or trifluoromethyl group, Y is hydrogen, methyl, trifluoromethyl, ethyl, cyclo hexyl or phenyl group, n is an integer from 0 to 1, m is an integer from 1 to 2, l is an integer from 0 to 2)

From here,

The phosphorus-based compound may have a structure represented by the following formula (2).

(Formula 2)

구조이며, X는 수소, 메틸 또는 트리플루오로메틸기, Y는 수소, 메틸, 트리플루오로메틸, 에틸, 사이클로헥실 또는 페닐기, n은 0 내지 1 인 정수, m은 1 내지 2 인 정수, l은 0 내지 2 인 정수)(In this case, R3 is

structure, X is hydrogen, methyl or trifluoromethyl group, Y is hydrogen, methyl, trifluoromethyl, ethyl, cyclohexyl or phenyl group, n is an integer from 0 to 1, m is an integer from 1 to 2, l is integer from 0 to 2)

Another aspect of the present invention, a phosphorus compound having a structure of Formula 1; and

polyphenylene-based resin; It is a flame retardant resin composition comprising a.

(Formula 1)

(In this case, R1 and R2 are an aryl group or a substituted aryl group, each independently or combined, X is hydrogen, methyl or trifluoromethyl group, Y is hydrogen, methyl, trifluoromethyl, ethyl, cyclo hexyl or phenyl group, n is an integer from 0 to 1, m is an integer from 1 to 2, l is an integer from 0 to 2)

Here, the phosphorus-based compound may have a structure of the following formula (2).

(Formula 2)

구조이며, X는 수소, 메틸 또는 트리플루오로메틸기, Y는 수소, 메틸, 트리플루오로메틸, 에틸, 사이클로헥실 또는 페닐기, n은 0 내지 1 인 정수, m은 1 내지 2 인 정수, l은 0 내지 2 인 정수)(In this case, R3 is

structure, X is hydrogen, methyl or trifluoromethyl group, Y is hydrogen, methyl, trifluoromethyl, ethyl, cyclohexyl or phenyl group, n is an integer from 0 to 1, m is an integer from 1 to 2, l is integer from 0 to 2)

In this case, the polyphenylene-based resin is preferably a polyphenylene oxide (PPO) resin, and preferably further includes a bismaleimide-based resin, and further includes an initiator.

In addition, with respect to 100 parts by weight of the polyphenylene oxide resin,

It is preferable to include 66.7 to 100 parts by weight of the phosphorus compound,

At this time, with respect to 100 parts by weight of the polyphenylene oxide resin,

22 to 44 parts by weight of the bismaleimide-based resin;

It is preferable to include 2 to 11 parts by weight of the initiator.

In addition, it is preferable that the dielectric constant (Dk) measured at 1 GHz frequency by the JIS-C-6481 method after curing the flame retardant resin composition is 3.30 to 3.60, and the dielectric loss (Df) is 0.0030 to 0.0050.

In addition, a circuit board can be manufactured from the above-described flame retardant resin composition.

The phosphorus-based compound according to an aspect of the present invention has the flame retardant properties of the conventional phosphorus-based flame-retardant curing agent, but reacts with the polyphenylene-based resin of the resin composition due to the vinyl group structure included in the substituent and the terminal, and heat resistance and low dielectric properties after curing has the advantage of maintaining excellent

The phosphorus-based compound according to an aspect of the present invention participates in curing the resin composition by radical polymerization to improve the flame retardancy of the cured resin composition and contribute to improvement of low dielectric properties.

In addition, the flame-retardant resin composition, which is another aspect of the present invention, includes a novel phosphorus-based compound and a polyphenylene-based resin, thereby solving the problem that the conventional resin composition including the phosphorus-based flame-retardant curing agent forms alcohol on the curing mechanism to reduce the dielectric constant. .

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. Hereinafter, embodiments of the present invention and effects thereof will be described with reference to the accompanying drawings.

A first aspect of the present invention is a phosphorus-based compound, which includes phosphorus and has a structure as shown in Formula 1 below.

(Formula 1)

In the structure of Formula 1, R1 and R2 are each an aryl group or an alkyl group or an aryl group substituted with an aryl group, preferably a phenyl group or a substituted phenyl group, R1 and R2 are each an aryl group or a substituted aryl group It is preferable that the structure is independent or combined with each other.

A structure in which an aryl group or a substituted aryl group is bonded to each other means that a bond is formed between R1 and R2 while R1 and R2 each have an aryl group or a substituted aryl group structure, so that one compound is phosphorus or It means to be combined with oxygen bonded to phosphorus, for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) structure corresponds to this.

In Formula 1, X is hydrogen (-H), methyl (-CH ₃ ), or a trifluoromethyl group (-CF ₃ ), Y is hydrogen (-H), methyl (-CH ₃ ), or a trifluoromethyl group (- CF ₃ ), ethyl (—C ₂ H ₅ ), cyclohexyl or a phenyl group.

Also, in Formula 1, n is an integer of 0 to 1, m is an integer of 1 to 2, and l is an integer of 0 to 2.

The phosphorus-based compound is preferably a phosphine-based or phosphite-based compound as a compound containing a phosphorus atom, and specifically, may be a phosphine oxide-based or phosphate-based compound including a phosphorus-oxygen double bond.

More specifically, the phosphorus-based compound is preferably a compound having a structure of the following formula (2).

(Formula 2)

구조이며, X는 수소, 메틸 또는 트리플루오로메틸기, Y는 수소, 메틸, 트리플루오로메틸, 에틸, 사이클로헥실 또는 페닐기, n은 0 내지 1 인 정수, m은 1 내지 2 인 정수, l은 0 내지 2 인 정수.)(In this case, R3 is

structure, X is hydrogen, methyl or trifluoromethyl group, Y is hydrogen, methyl, trifluoromethyl, ethyl, cyclohexyl or phenyl group, n is an integer from 0 to 1, m is an integer from 1 to 2, l is An integer from 0 to 2.)

The following Chemical Formula 3 shows the structure of a compound that can be used as a phosphine-based or phosphite-based compound.

In the present invention, the phosphorus-based compounds to be described later may be used alone or in combination.

A preferred embodiment of the present invention discloses a diphenylphosphine oxide-based compound synthesized from diphenyl phosphine oxide (DPO) having the structure of (a) of Formula 3 below and including the structure, and Another embodiment is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene- A phosphorus-based compound synthesized from 10-oxide, DOPO) and including the structure is disclosed.

(Formula 3)

As such, when using a phosphine-based compound or a phosphite-based compound, two methods are generally understood to exhibit a flame retardant effect. First, the solid phase inhibition method is a method in which the phosphorus-based compound forms Char as a flame retardant to prevent heat from being transferred to the inside, and secondly, the gas phase inhibition method changes the chemical structure during combustion and stops the radical chain reaction by stopping the radical chain reaction. interfere with

The phosphorus-based compound as a preferred embodiment of the present invention is a phosphorus-based vinyl compound.

The phosphorus-based vinyl compound refers to a compound including a phosphorus (P) atom, a compound including a phosphine-based compound, a phosphite-based compound, and derivatives thereof, and a compound including a vinyl (vinyl) functional group.

In this case, the phosphorus-based compound is characterized in that it contains a vinyl (vinyl) group as a functional group, and R3 of Formula 1 is characterized in that it includes a vinyl group at the terminal as in the structure shown in Formula 2.

Due to the inclusion of the vinyl group at the terminal, the phosphorus-based compound can react with other monomers or resins containing a functional group to form a polymer, and the copolymer including the phosphorus-based compound is a flame retardant copolymer due to the flame retardant properties of the phosphorus-based compound. can be utilized, and a flame-retardant resin composition including the copolymer can be obtained.

In order to minimize the phenomenon that the glass transition temperature of the resin composition is lowered or the dielectric constant and dielectric loss of the cured product after curing of the resin composition is increased, such as R3, It is preferred to include a structure.

The structure of the phosphorus compound of the present invention can be obtained by performing the reaction in the following steps.

The method for preparing the phosphorus compound comprises a first step and a second step to be described later.

In the first step, the phosphorus atom of the phosphine or phosphite compound and the carbon of the bisphenol monomer by reacting the phosphine or phosphite compound with a bisphenol monomer using a phosphine or phosphite compound and a bisphenol monomer as reactants As a step of forming a bond between the phosphorus compounds, it is a step in which a phosphorus compound is obtained as a product.

By the reaction of the first step, a hydrogen atom bonded to phosphorus is released from the phosphine-based or phosphite-based compound, the carbon located at the benzyl site is substituted in the bisphenol monomer, and 1 equivalent of a phenol molecule can be removed from the bisphenol monomer. .

The bisphenol-based monomer used as a reactant in the reaction of the first step is not limited, and bisphenol A (BPA), bisphenol F (BPF), bisphenol B (BPB), bisphenol P (BPP), bisphenol Z (BPZ), bisphenol AF One or more bisphenol-based monomers selected from the group consisting of (BPAF) and bisphenol AP (BPAP) may be used.

A preferred embodiment of the present invention uses diphenylphosphine oxide and bisphenol A monomer as reactants in the first step.

When a bisphenol A monomer is used, the reaction of the first step can occur in high yield, there are few side reactions, and the molecular weight of the final product is not high, so that the decrease in dielectric properties or glass transition temperature in the resin composition including the final product is reduced. can

The first step may be carried out by adding 1 equivalent or more of a bisphenol monomer, and may further include a step of synthesizing a compound including a bisphenol dimer or oligomer in which a bond between the bisphenol monomers (monomers) is formed. It is preferable that an equivalent amount of a phenol derivative is bound, which means that m in Formula 2 is 1.

When a product in which a bisphenol monomer is combined with a phosphine or phosphite compound in a dimer or oligomer structure is used, a problem may occur in that the molecular weight of the phosphorus compound increases and side reactions occur.

The second step is a step of performing a reaction for adding a vinyl group to the compound obtained in the first step.

By reacting the phosphorus compound obtained in the first step with a compound having a vinyl group at the terminal, a phosphorus compound having a vinyl group at the terminal can be synthesized.

As a compound containing a vinyl group at the terminal used as a reactant, vinylbenzyl halide (Vinylbenzylic halide or Vinylbenzyl halide) or allyl halide (Allylic halide or Allyl halide) may be used, and preferably vinylbenzyl halide.

As the vinylbenzyl halide, for example, vinylbenzyl chloride, vinylbenzyl bromide, or vinylbenzyl iodide is preferably used.

In this case, the vinyl benzyl halide preferably has a vinyl group and a benzyl group having an ortho- or para- orientation, and in consideration of steric hindrance, it is preferable to use a compound having a para- orientation. .

In the second step, in the phosphorus compound synthesized in the first step, a substitution reaction between phenol oxygen and the carbon to which the halogen atom of vinylbenzyl halide or allyl halide is bonded may proceed.

In this case, when a nucleophilic substitution reaction is to be carried out, it is preferable to proceed under a basic condition in order to proceed the reaction using a phenoxide ion as a nucleophile, and an oxygen-carbon bond is formed by the nucleophilic substitution reaction.

The phosphorus-based compound finally synthesized includes at least one aromatic ring in each of R1, R2 and R3 in the structure of Formula 1, R3 includes a vinyl group at the terminal, and an ether group, more specifically an arylalkylether group It is preferable to include

The following scheme shows the first and second steps of the preparation of the phosphorus compound according to a preferred embodiment of this aspect.

(Scheme 1)

(Scheme 2)

Another aspect of the present invention is a flame retardant resin composition comprising a phosphorus compound. The flame-retardant resin composition is characterized in that it has flame-retardant properties including the aforementioned phosphorus-based compound, and is mixed with other resins or polymers to form a resin composition in order to have additional effects such as low dielectric properties or improved copper foil adhesion.

The flame retardant resin composition includes a polyphenylene-based resin having excellent electrical properties and low dielectric properties in a wide frequency range and a wide temperature range.

The polyphenylene-based resin includes, for example, a polyphenylene oxide (PPO) resin, a polyphenylene ether (PPE) resin, a polyphenylene sulfide resin, or a modified polyphenylene oxide resin, wherein the modified polyphenylene oxide resin The renoxide resin includes a blend of polyphenylene oxide resin and High Impact Polystyrene (HIPS).

A resin composition according to a preferred embodiment of the present invention includes a polyphenylene oxide resin and has a low dielectric constant and dielectric loss upon curing.

The polyphenylene-based resin is preferably included in an amount of 35 to 50 wt%, preferably 40 to 45 wt%, based on the weight of the flame retardant resin composition excluding the solvent.

When the content of the polyphenylene oxide resin is lower than the corresponding range, the glass transition temperature of the flame-retardant resin composition is lowered and there may be a problem that copper foil adhesion is reduced. and problems such as an increase in dielectric loss may occur.

The phosphorus compound is preferably included in an amount of 30 to 45 wt%, preferably 35 to 40 wt%, based on the weight of the flame retardant resin composition excluding the solvent.

In addition, the phosphorus compound is preferably included in an amount of 66.7 to 100 parts by weight based on 100 parts by weight of the total polyphenylene-based resin content, preferably 78 to 90 parts by weight, and more preferably 85 to 89 parts by weight.

If the content of the phosphorus-based compound is lower than the corresponding range, there may be a problem in that the flame retardant properties are lowered during curing of the flame retardant resin composition. of problems may arise.

The phosphorus-based compound has a different molecular weight and three-dimensional structure depending on the X and Y structures of Formula 1 or Formula 2 included in the phosphorus compound when a polyphenylene oxide-based resin is used as the polypennylene-based resin, and the dielectric after curing of the resin composition Constants and dielectric losses may vary.

A preferred embodiment of the present invention includes both methyl groups in the X and Y structures, so that the terminal vinyl group has high flexibility and low steric hindrance, and excellent compatibility with solvents and other resins makes it easy to prepare a resin composition, Since the terminal vinyl group chemically reacts with the composition, there is an advantageous effect of maintaining the low dielectric properties while maintaining the glass transition temperature of the cured product to be cured after manufacturing.

In addition, since the length and flexibility of the chain including a vinyl group at the terminal varies according to the values of m and l in Chemical Formulas 1 and 2, the dielectric properties of the cured product cured after reaction with the polyphenylene oxide resin may vary, A preferred embodiment of the present invention includes a structure in which both m and l have a value of 1, and thus the cured product has an effect of low dielectric loss. In addition, the flame retardant resin composition has, for example, copper foil adhesion when used on a substrate. In order to improve it, it is preferable to include a bismaleimide-based resin. Since the bismaleimide-based resin includes two or more functional groups, it is possible to form a cross-link, and by forming the cross-link, the glass transition temperature of the resin composition can be improved and curing properties can be improved.

The bismaleimide-based resin is preferably included in an amount of 10 to 20 wt%, preferably 12 to 15 wt%, based on the weight of the flame retardant resin composition excluding the solvent.

In addition, the bismaleimide-based resin is preferably included in an amount of 22 to 44 parts by weight, preferably 26 to 33 parts by weight, based on 100 parts by weight of the total polyphenylene-based resin content.

When the content of the bismaleimide-based resin is lower than the corresponding range, the copper foil adhesion of the resin composition is lowered, and thus a problem in which the contacted copper foil is peeled off during the manufacture of a substrate including the resin composition may occur. Otherwise, problems such as an increase in dielectric coefficient and dielectric loss may occur.

In addition, the content of the phosphorus-based compound is preferably 1.5 to 4.5 times the content of the bismaleimide-based resin.

If the content ratio of the phosphorus-based compound and the bismaleimide-based resin is less than the corresponding range, there may be a problem in flame retardant properties.

The initiator is a material for accelerating the polymerization or curing reaction of the flame-retardant resin composition, and the type of the initiator is not limited, but a photoinitiator or a thermal initiator may be used depending on the reaction initiation conditions, preferably a thermosetting agent It is preferable to use, for example, a peroxide-based or dialkyl-based initiator.

The initiator is preferably included in an amount of 1 to 5 wt%, preferably 2 to 4 wt%, based on the weight of the flame retardant resin composition excluding the solvent.

In addition, the initiator is preferably included in an amount of 2 to 11 parts by weight, preferably 4 to 8 parts by weight, based on 100 parts by weight of the total polyphenylene-based resin content.

The content of the initiator does not cause a significant change in the chemical structure of the entire resin composition, etc., but if the content of the initiator is lower than the corresponding range, the flame retardant resin composition may not be sufficiently cured or the curing speed may be slowed. If higher, the curing rate of the flame-retardant resin composition is too fast, so that the physical properties are not uniform or the rate of side reactions increases, which may cause a problem of poor physical properties after curing.

In one embodiment of the present invention, dicumyl peroxide (DCP), which is a peroxide-based compound, is used as an initiator, but the compound type of the initiator is not limited, and a compound generally used as an initiator, those skilled in the art are employed as the initiator Any possible compound can be used as an initiator in the present invention.

According to a preferred embodiment of the present invention, DCP, which is a thermal initiator, is used as an initiator, and the oxygen-oxygen single bond included in the peroxide is broken by heat to obtain two radicals, and the propagation reaction of the radicals Compounds included in the resin composition may cause radical polymerization.

After the radical polymerization reaction, the resin composition is cured, and a cured resin material having low dielectric constant and dielectric loss and flame retardant properties can be obtained.

It is preferable that the flame-retardant resin composition further contain an organic solvent. Even if the organic solvent is included in the flame retardant resin composition, it has little effect on the physical properties, dielectric properties, and flame retardancy of the resin composition. It is easy to express the characteristics of the flame retardant resin composition.

As the organic solvent, it is recommended to use a solvent that can dissolve all of the phosphorus compound, polyphenylene resin, and bismaleimide resin. For example, a solvent such as MEK (Methylethyl ketone) can be used, and the type is not limited. does not

The content of the solvent included in the resin composition is preferably 130 to 190 parts by weight, preferably 150 to 160 parts by weight, based on 100 parts by weight of the total polyphenylene-based resin content.

When the content of the solvent is higher than the corresponding range, there is a problem that the curing speed is slowed or the viscosity is lowered. There may be a problem in that it is difficult to obtain a cured product having uniform properties and coating properties.

By controlling the content of the solvent, the viscosity and curing rate of the resin composition can be controlled, and it is preferable that all of the solvent is removed after the final curing.

The flame-retardant resin composition according to this aspect of the present invention can be used for manufacturing a substrate or a circuit board used for semiconductors or electronic components, and specifically, for manufacturing a prepreg, a sheet, a film, a tape, a laminate or a substrate for printed wiring, etc. It can be used, and it can be used in other technical fields requiring low dielectric constant and low dielectric loss characteristics in a high frequency region.

The flame-retardant resin composition according to one aspect of the present invention can be cured by adding a curing agent, and the cured resin composition is subjected to a frequency condition of 1 GHz using the JIS-C-6481 test method using equipment such as an impedance analyzer. The measured dielectric constant (Dk) is 3.30 to 3.60, and the dielectric loss (Df) value is 0.0030 to 0.0050.

By having a dielectric constant and a dielectric loss within the above range, the flame retardant resin composition has excellent flame retardant properties and at the same time has a low dielectric property in a high frequency region. There is this.

Hereinafter, the present invention will be described with reference to specific examples.

(Production Example)

Preparation Examples 1 to 3 - Preparation of phosphorus-based compounds

Preparation Example 1

After preparing 228 g of bisphenol A, 39 g of bisphenol A novolac resin and 202 g of diphenyl phosphine oxide (DPO), the It was put into the reactor and purged for 30 minutes using nitrogen gas.

The reaction was carried out for 5 hours while the temperature of the reactor was raised to 230° C. to dissolve the materials put into the reactor.

Thereafter, the temperature was increased to 230° C. to sufficiently remove residual phenol.

After dissolving the reactant from which residual phenol was removed by adding 2000 g of toluene, 2000 g of process water and 100 g of sodium hydroxide were added at a temperature of 60°C.

After that, 300 g of VBC (4-vinylbenzeyl chloride) was added, and the reaction was allowed to proceed with reflux for 24 hours.

After the reaction was completed, the supernatant liquid inside the reactor was taken, washed with 700 g of water, and then degassed in vacuum up to 50° C. to remove the remaining water and solvent to obtain a liquid product.

Preparation 2

The reaction was performed in the same manner as in Preparation Example 1, except that 216 g of DPOPO was used instead of 202 g of diphenyl phosphine oxide (DPO) in Preparation Example 1 to obtain a product.

Preparation 3

The reaction was performed in the same manner as in Preparation Example 1, except that 153 g of allyl chloride was added instead of 300 g of 4-vinylbenzeyl chloride (VBC) in Preparation Example 1 to obtain a product.

(Example)

Examples 1 to 8 - Preparation of flame retardant resin composition

Example 1

To 200 g of the phosphorus compound obtained in Preparation Example 1, 225 g of polyphenylene oxide resin (SABIC, SA-9000) and 75 g of bismaleimide-based resin (Daiwa Kasei, BMI-5100) were added to 250 g of a methyl ethyl ketone solvent, 15 g of DCP was added as an initiator and stirred at room temperature for 1 hour to obtain a flame retardant resin composition.

Examples 2 and 3

A flame retardant resin composition was prepared in the same manner as in Example 1, except that 185 g and 270 g of polyphenylene oxide resin were added in Preparation Example 1, respectively.

Examples 4 and 5

A flame retardant resin composition was prepared in the same manner as in Example 1, except that 165 g and 225 g of the phosphorus-based compound obtained in Preparation Example 1 were added, respectively.

Examples 6 and 7

A flame retardant resin composition was prepared in the same manner as in Example 1, except that 60 g and 100 g of the bismaleimide-based resin were added in Preparation Example 1, respectively.

Example 8

A flame retardant resin composition was prepared in the same manner as in Example 1, except that no initiator was added in Preparation Example 1.

Examples 9 to 10

A flame retardant resin composition was prepared in the same manner as in Example 1 using the phosphorus-based compound obtained in Preparation Examples 2 to 3.

The blending amounts of the flame-retardant resin compositions of Examples 1 to 10 are summarized in Table 1 below.

Polyphenylene oxide resin (g) Phosphorus compound (g) BMI-based resin (g) initiator (g) solvent (g) Total (g) Example 1 225 200 75 15 350 865 Example 2 185 200 75 15 350 825 Example 3 270 200 75 15 350 910 Example 4 225 165 75 15 350 830 Example 5 225 225 75 15 350 890 Example 6 225 200 60 15 350 850 Example 7 225 200 100 15 350 890 Example 8 225 200 75 0 350 850 Example 9 225 200 75 15 350 865 Example 10 225 200 75 15 350 865

(Experimental example)

Experimental Example 1 - Dielectric properties test after curing of flame retardant resin composition

After impregnating the flame-retardant resin composition of Examples 1 to 10 into glass fiber, it was dried at a temperature of 80 to 200° C. to prepare a non-stick prepreg, and then the prepared prepreg was placed on both sides of the copper foil and vacuum press A copper clad laminate was prepared by heating and pressing.

Then, the dielectric constant (Dk) and dielectric loss (Df) of the cured copper clad laminate were measured at 1 GHz using an Agilent E4991A RF Impedence/Material analyzer using the JIS-C-6481 method.

Experimental Example 2 - Measurement of Glass Transition Temperature of Flame Retardant Resin Composition

The glass transition temperature (Tg) of the flame-retardant resin compositions of Examples 1 to 10 was measured using a differential thermal analyzer (DSC) under the condition of 20° C./min.

Experimental Example 3 - Moisture absorption heat resistance test

The copper clad laminate of Experimental Example 1 was cut into pieces of 5 cm horizontally and vertically, and the resultant was subjected to moisture absorption treatment in PCT (Pressure cooker test, 121° C.) for 2 hours, and then placed in a solder bath at 288° C. for 10 seconds, and then the state of the surface was measured. When observed with the naked eye, those in which delamination did not occur are indicated by ◎, those with partial surface change are indicated by ○, those with partial delamination are indicated by △, and those with marked delamination are indicated by ×.

Experimental Example 4 - Copper Foil Adhesive Strength Measurement

The obtained flame-retardant resin composition of Examples 1 to 10 was applied to a general 1/20z copper foil to a thickness of 1 to 5 μm and dried for 5 minutes to prepare a copper foil adhesive sheet. After that, two sheets of adhesive sheet with copper foil were laminated, and pressure of 20 kg/cm was applied at a temperature of 190° C. and pressed for 2 hours. Adhesive strength (Copper peel strength, P/S) was measured.

The results of Experimental Examples 1 to 4 are shown in Table 2 below.

Dielectric constant (Dk @1GHz) Dielectric loss (Df @1GHz) Glass transition temperature (℃) Flame retardant properties Copper Foil Adhesive Strength (kgf/cm) Example 1 3.38 0.0038 217 ◎ 1.0 Example 2 3.35 0.0037 200 ◎ 0.8 Example 3 3.51 0.0048 225 △ 1.1 Example 4 3.42 0.0042 220 △ 1.0 Example 5 3.32 0.0035 205 ◎ 0.9 Example 6 3.41 0.0040 215 ○ 0.8 Example 7 3.42 0.0042 219 ○ 1.0 Example 8 not cured not cured 160 not cured not cured Example 9 3.42 0.0040 220 ◎ 1.0 Example 10 3.39 0.0038 210 ◎ 1.0

Features, structures, effects, etc. exemplified in each of the above-described embodiments may be combined or modified for other embodiments by those of ordinary skill in the art to which the embodiments belong. Accordingly, the contents related to such combinations and modifications should be interpreted as being included in the scope of the present invention.

Claims (13)

A phosphorus compound having the structure of Formula 1 below.
(Formula 1)

(In this case, R1 and R2 are an aryl group or a substituted aryl group, each independently or combined, X is hydrogen, methyl or trifluoromethyl group, Y is hydrogen, methyl, trifluoromethyl, ethyl, cyclo hexyl or phenyl group, n is an integer from 0 to 1, m is an integer from 1 to 2, l is an integer from 0 to 2) According to claim 1,
The phosphorus-based compound is a phosphorus-based compound having a structure of the following formula (2).
(Formula 2)

(In this case, R3 is

structure, X is hydrogen, methyl or trifluoromethyl group, Y is hydrogen, methyl, trifluoromethyl, ethyl, cyclohexyl or phenyl group, n is an integer from 0 to 1, m is an integer from 1 to 2, l is integer from 0 to 2) a phosphorus-based compound having the structure of Formula 1 below; and
polyphenylene-based resin; A flame retardant resin composition comprising a.
(Formula 1)

(In this case, R1 and R2 are an aryl group or a substituted aryl group, each independently or combined, X is hydrogen, methyl or trifluoromethyl group, Y is hydrogen, methyl, trifluoromethyl, ethyl, cyclo hexyl or phenyl group, n is an integer from 0 to 1, m is an integer from 1 to 2, l is an integer from 0 to 2) 4. The method of claim 3,
The phosphorus-based compound is a flame retardant resin composition having a structure of the following formula (2).
(Formula 2)

(In this case, R3 is

structure, X is hydrogen, methyl or trifluoromethyl group, Y is hydrogen, methyl, trifluoromethyl, ethyl, cyclohexyl or phenyl group, n is an integer from 0 to 1, m is an integer from 1 to 2, l is integer from 0 to 2) 5. The method of claim 4,
The polyphenylene-based resin is a flame retardant resin composition of a polyphenylene oxide (PPO) resin. 6. The method of claim 5,
The flame-retardant resin composition further comprises a bismaleimide-based resin. 7. The method of claim 6,
The flame-retardant resin composition further comprises an initiator (Initiator). 8. The method of claim 7,
Based on 100 parts by weight of the polyphenylene oxide resin,
A flame retardant resin composition comprising 66.7 to 100 parts by weight of the phosphorus compound. 9. The method of claim 8,
Based on 100 parts by weight of the polyphenylene oxide resin,
A flame retardant resin composition comprising 22 to 44 parts by weight of the bismaleimide-based resin. 10. The method of claim 9,
Based on 100 parts by weight of the polyphenylene oxide resin,
A flame retardant resin composition comprising 2 to 11 parts by weight of the initiator. 11. The method of claim 10,
A flame retardant resin composition having a dielectric constant (Dk) of 3.30 to 3.60 measured at a frequency of 1 GHz by the JIS-C-6481 method after curing the flame retardant resin composition. 12. The method of claim 11,
A flame retardant resin composition having a dielectric loss (Df) of 0.0030 to 0.0050 measured at a frequency of 1 GHz by the JIS-C-6481 method after curing the flame retardant resin composition. A circuit board manufactured from the flame-retardant resin composition of any one of claims 3 to 12.