KR102600976B1 - Phosphorous compound - Google Patents

Abstract

The phosphorus-based compound, which is one aspect of the present invention, is characterized by having the structure of the following formula (1).
(Formula 1)

(In this case, R1 and R2 are an aryl group or a substituted aryl group, each independent or combined structure, hexyl or phenyl group, n is each an integer from 0 to 1, m is an integer from 1 to 2, l is an integer from 0 to 2)

Description

Phosphorous compound}

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

Generally, 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 attaches a thin film, such as copper, to an insulating base film, such as phenol or epoxy, and then patterns it into a desired shape to electrically connect and support the components.

Recently, with the trend of making electronic devices lighter, thinner, shorter, and more eco-friendly, the demand for high performance such as flame retardancy, heat resistance, moisture resistance, efficiency, and thermal conductivity for printed circuit boards is increasing. Copper Clad Laminate, the basic material of printed circuit boards, is increasing. High-performance implementation is also required for CCL), Flexible Copper Clad Laminate (FCCL), and Metal Copper Clad Laminate (MCCL).

Copper-clad laminate is a raw material for printed circuit boards. An insulating plate obtained after heating and pressing several layers of sheets that combine a compound with an insulating material such as paper or glass is called a laminate. Copper foil is attached to one or both sides of this laminate. Requirements for the insulating materials used, such as being lead-free, have increased in accordance with recent environmental regulations, and as circuit line widths have decreased, more components are mounted per unit area, generating significant heat when transmitting high-speed signals. It is happening.

This heat can cause problems such as deformation of the board due to the difference in CTE between the component and the material, and the soldering temperature increases by 20℃ to 40℃, so the material has characteristics such as Lead Free High Tg and high heat resistance. It is being demanded.

Epoxy compositions have been widely used in electrical and electronic device components due to their excellent properties, but epoxy/curing agent compositions have the disadvantage of lowering dielectric constant among electrical properties due to the structural production of secondary alcohol in the curing mechanism.

In addition, in the case of epoxy resins, halogenated flame-retardant epoxy compounds were used to ensure safety against fire, creating harmful halogen compounds, polybrominated dibenzodioxins and furans, which created limitations in environmental problems, and polymers Addition-type flame retardants that were added to improve flame retardant properties had the problem of deteriorating various mechanical properties, making them difficult to utilize.

Flame retardant curing agents are generally used to improve flame retardant properties when using these resins. Flame retardant hardeners are additives that are added physically and chemically to resins or compounds to slow ignition and prevent the spread of combustion. They are largely divided into reactive and additive types.

Reactive flame retardant hardeners work by chemically reacting with functional groups within the molecule to sustain the flame retardant effect, while additive flame retardant hardeners work by physically mixing, adding, and dispersing.

Addition-type flame retardant curing agents do not cause chemical reactions with polymers, so they may be lost from the substrate and have a lower flame retardant effect, so there are limitations compared to reactive flame retardant curing agents. In the case of reactive flame retardant curing agents, when a large amount is added, the molecular weight of the polymer increases. There is a problem in that the heat resistance and adhesive properties of the cured product deteriorate due to gelation phenomenon or lowered cured density.

Accordingly, in order to solve this problem, research is needed to solve the problem of improving the flame retardant properties with a flame retardant that can replace existing flame retardant curing agents, but also deteriorating the physical properties such as dielectric properties of the cured product due to the addition of the flame retardant curing agent.

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

One aspect of the present invention was devised to solve the problems of the prior art described above, and provides a phosphorus-based compound that provides excellent flame retardant properties when mixed with a resin composition and does not deteriorate physical properties such as glass transition temperature and adhesive properties after curing. The purpose is to do this.

In addition, the purpose is to provide a resin composition that contains a phosphorus compound and can provide a substrate with low dielectric properties, low dielectric constant and low dielectric loss, while having excellent flame retardant properties, with excellent productivity and low production price.

One aspect of the present invention is a phosphorus-based 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 independent or combined structure, hexyl or phenyl group, n is each 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 preferably has the structure of the following formula (2).

(Formula 2)

(At this time, R3 is It is a structure, integer from 0 to 2)

Another aspect of the present invention is a phosphorus-based compound having the structure of Formula 1 below; and

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

(Formula 1)

(In this case, R1 and R2 are an aryl group or a substituted aryl group, each independent or combined structure, hexyl or phenyl group, n is each 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 preferably has the structure of the following formula (2).

(Formula 2)

(At this time, R3 is It is a structure, integer from 0 to 2)

At this time, the polyphenylene-based resin is preferably a polyphenylene oxide (PPO) resin, preferably includes a bismaleimide-based resin, and preferably 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-based 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, after curing the flame retardant resin composition, it is preferable that the dielectric constant (Dk) measured at a frequency of 1 GHz using the JIS-C-6481 method is 3.30 to 3.60, and the dielectric loss (Df) is 0.0030 to 0.0050.

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

The phosphorus-based compound according to one aspect of the present invention has the flame retardant properties of conventional phosphorus-based flame retardant curing agents, but due to the vinyl group structure included in the substituents and terminals, it reacts with the polyphenylene-based resin of the resin composition and exhibits heat resistance and low dielectric properties after curing. It has the advantage of being able to maintain excellent quality.

The phosphorus-based compound according to one aspect of the present invention participates in curing the resin composition through radical polymerization, improves the flame retardancy of the cured resin composition, and contributes to improving low dielectric properties.

In addition, the flame-retardant resin composition, which is another aspect of the present invention, contains a novel phosphorus-based compound and a polyphenylene-based resin, thereby solving the problem of a resin composition containing a conventional phosphorus-based flame retardant curing agent forming alcohol in the curing mechanism and lowering the dielectric constant. .

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

The first aspect of the present invention is a phosphorus-based compound, which contains phosphorus and has a structure shown in the following formula (1).

(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, and R1 and R2 are each an aryl group or a substituted aryl group. It is better to have an independent or combined structure.

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

_{In Formula} 1 _, CF ₃ ), ethyl (-C ₂ H ₅ ), cyclohexyl or phenyl group.

Additionally, in Formula 1, n is an integer from 0 to 1, m is an integer from 1 to 2, and l is an integer from 0 to 2.

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

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

(Formula 2)

(At this time, R3 is It is a structure, An integer from 0 to 2.)

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

In the present invention, it is also possible to use the phosphorus-based compounds described later alone or in combination.

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

(Formula 3)

When using a phosphine-based or phosphite-based compound, it is generally understood that there are two ways to achieve a flame retardant effect. First, the solid-state inhibition method is a method in which phosphorus compounds form char as a flame retardant to prevent heat from being transferred internally, and the second method is the gas-phase inhibition method, which changes the chemical structure during combustion and stops the radical chain reaction. interfere with

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

A phosphorus-based vinyl compound refers to a compound containing a phosphorus (P) atom, a phosphine-based compound, a phosphite-based compound, and their derivatives, and a compound containing a vinyl (vinyl) functional group.

At this time, the phosphorus compound is characterized by including a vinyl group as a functional group, and R3 in Formula 1 is characterized by including a vinyl group at the terminal as in the structure shown in Formula 2.

Because it contains a vinyl group at the end, the phosphorus-based compound can react with other monomers or resins containing functional groups to form a polymer, and the copolymer polymerized with the phosphorus-based compound is a flame-retardant copolymer due to the flame-retardant properties of the phosphorus-based compound. It can be used as a flame retardant resin composition containing the copolymer can be obtained.

The phosphorus compound contains a vinyl group at the terminal and is used as R3 to minimize the phenomenon of lowering the glass transition temperature of the resin composition or increasing the dielectric constant and dielectric loss of the cured product after curing. It is desirable to include a structure.

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

The method for producing a phosphorus-based compound includes first and second steps, which will be described later.

The first step is to react the phosphine or phosphite compound and the bisphenol monomer using a phosphine or phosphite compound and a bisphenol monomer as reactants to form a phosphorus atom of the phosphine or phosphite compound and a carbon of the bisphenol monomer. This is the step of forming bonds between livers, and is the step where a phosphorus-based compound is obtained as a product.

Through the first step reaction, the hydrogen atom bonded to phosphorus in the phosphine or phosphite compound is removed, the carbon located at the benzyl position in the bisphenol monomer is replaced, and 1 equivalent of the phenol molecule can be removed from the bisphenol monomer. .

The bisphenol-based monomer used as a reactant in the first step reaction is not limited, and includes bisphenol A (BPA), bisphenol F (BPF), bisphenol B (BPB), bisphenol P (BPP), bisphenol Z (BPZ), and 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 using bisphenol A monomer, the first step reaction can occur in high yield, there are few side reactions, and the molecular weight of the final product is not high, so the decrease in dielectric properties or glass transition temperature in the resin composition containing the final product can be reduced. You can.

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

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

The second step is to carry out a reaction to add a vinyl group to the compound obtained in the first step.

A phosphorus-based compound containing a vinyl group at the terminal can be synthesized by reacting the phosphorus-based compound obtained in the first step with a compound containing a vinyl group at the terminal.

The compound containing a vinyl group at the terminal used as a reactant may be vinylbenzylic halide or vinylbenzyl halide or allyl halide, and vinylbenzyl halide is preferable.

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

At this time, the vinylbenzyl halide preferably has an ortho- or para-orientation of the vinyl and benzyl groups, and when considering steric hindrance, etc., it is preferable to use a compound with a para-orientation. .

The second step may be carried out by a substitution reaction between the carbon to which the phenol oxygen and the halogen atom of vinylbenzyl halide or allyl halide are bonded in the phosphorus-based compound synthesized in the first step.

At this time, when attempting to proceed with a nucleophilic substitution reaction, it is preferable to proceed under basic conditions in order to proceed with the reaction using a phenoxide ion as a nucleophile, and an oxygen-carbon bond is formed through the nucleophilic substitution reaction.

The finally synthesized phosphorus compound is composed of at least one aromatic ring in each of R1, R2, and R3 in the structure of Formula 1, and R3 contains a vinyl group at the terminal, and an ether group, more specifically, an arylalkyl ether group. It is desirable to include it.

The following reaction equation shows the first and second steps of the reaction in the production step of the phosphorus-based 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 containing a phosphorus-based compound. The flame-retardant resin composition is characterized by having flame-retardant properties by including the above-described phosphorus-based compound, and is mixed with other resins or polymers to form a resin composition to have additional effects such as low dielectric properties or improved copper foil adhesion.

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

Polyphenylene-based resins include, for example, polyphenylene oxide (PPO) resin, polyphenylene ether (PPE) resin, polyphenylene sulfide resin, or modified polyphenylene oxide resin, wherein the modified polyphenylene Len oxide resin includes a resin blended with polyphenylene oxide resin and High Impact Polystyrene (HIPS).

The resin composition, which is a preferred embodiment of the present invention, contains polyphenylene oxide resin and has a low dielectric coefficient and dielectric loss when cured.

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

If the content of polyphenylene oxide resin is lower than the corresponding range, the glass transition temperature of the flame retardant resin composition may be lowered and the copper foil adhesion may be reduced, and if it is higher than the corresponding range, the flame retardant properties of the flame retardant resin composition may deteriorate, and the dielectric coefficient may decrease. Problems such as increased dielectric loss may occur.

The phosphorus compound is preferably contained in an amount of 30 to 45 wt%, preferably 35 to 40 wt%, of 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, preferably 78 to 90 parts by weight, and more preferably 85 to 89 parts by weight, based on 100 parts by weight of the total polyphenylene resin content.

If the content of the phosphorus compound is lower than the corresponding range, a problem may occur in which the flame retardant properties are deteriorated during curing of the flame retardant resin composition, and if it is higher than the corresponding range, the glass transition temperature of the flame retardant resin composition decreases, the copper foil adhesion strength decreases, etc. problems may occur.

When a polyphenylene oxide-based resin is used as a polyphenylene-based resin, the phosphorus-based compound has a different molecular weight and three-dimensional structure depending on the Constants and dielectric losses may vary.

A preferred embodiment of the present invention includes both methyl groups in the Since the composition reacts chemically with the terminal vinyl group, there is an advantageous effect of maintaining low dielectric properties while maintaining the glass transition temperature of the cured product that is cured after manufacture.

In addition, the length and flexibility of the chain containing a vinyl group at the end vary depending on the values of m and l in Formula 1 and Formula 2, so the dielectric properties of the cured product after reaction with polyphenylene oxide resin may vary, A preferred embodiment of the present invention has a structure in which both m and l have a value of 1, which has the effect of lowering the dielectric loss of the cured product. In addition, the flame-retardant resin composition has copper foil adhesion when used for, for example, a substrate. In order to improve it, it is preferable to include a bismaleimide-based resin. Since the bismaleimide-based resin contains two or more functional groups, it can form crosslinks, and by forming crosslinks, it can improve the glass transition temperature of the resin composition and improve curing characteristics.

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

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.

If the content of the bismaleimide resin is lower than the corresponding range, the adhesion of the resin composition to the copper foil may be lowered, which may cause a problem of peeling of the copper foil in contact when manufacturing a substrate containing the resin composition. If the content is higher than the corresponding range, the flame retardant properties may deteriorate. Alternatively, problems such as increased dielectric coefficient and dielectric loss may occur.

Additionally, the content of the phosphorus compound is preferably 1.5 to 4.5 times the content of the bismaleimide resin.

If the content ratio of the phosphorus compound and bismaleimide resin is less than the corresponding range, there may be a problem with flame retardant properties, and if it is greater than the corresponding range, there may be a problem with the glass transition temperature being lowered.

An initiator is a substance that promotes the polymerization or curing reaction of a flame-retardant resin composition. The type of initiator is not limited, but a photoinitiator or a thermal initiator may be used depending on the reaction initiation conditions, and a thermal curing agent is preferable. It is good, for example, to use 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%, of 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 resin content.

The content of the initiator does not cause a significant change in the chemical structure of the overall resin composition, but if the content of the initiator is lower than the corresponding range, problems may occur such as insufficient curing of the flame retardant resin composition or slowing of the curing speed. If it is higher, the curing speed of the flame retardant resin composition may be too fast, and the physical properties may not be uniform, or the rate of side reactions may increase, causing problems with deterioration of the physical properties after curing.

One embodiment of the present invention uses Dicumyl peroxide (DCP), a peroxide-based compound, as an initiator. However, the type of compound of the initiator is not limited, and a compound commonly used as an initiator is adopted as an initiator by those skilled in the art. Any possible compound can be used as an initiator in the present invention.

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

After the radical polymerization reaction, the resin composition is cured, and a cured resin product with low dielectric coefficient and dielectric loss and flame retardant properties can be obtained.

It is recommended that the flame retardant resin composition additionally 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. Therefore, when calculating the percentage of other components included in the flame retardant resin composition, the percentage is calculated from the weight excluding the organic solvent. It is easy to express the characteristics of the flame retardant resin composition.

As an organic solvent, it is recommended to use a solvent that can dissolve all phosphorus compounds, polyphenylene resins, and bismaleimide resins. For example, solvents such as MEK (Methylethyl ketone) can be used, and the type is not limited. No.

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 resin content.

If the solvent content is higher than the corresponding range, there is a problem that the curing speed is slowed or the viscosity is lowered, and if the solvent content is lower than the corresponding range, uniform mixing between the resins is not achieved, making it difficult to handle the flame retardant resin composition and making it uniform. Problems may arise where it is difficult to apply and obtain a cured product with uniform physical properties.

The viscosity and curing speed of the resin composition can be controlled by adjusting the solvent content, and it is preferable that all solvent is removed after final curing.

The flame-retardant resin composition according to this aspect of the present invention can be used in the production of substrates or circuit boards used in semiconductors or electronic components, and specifically, in the production of prepregs, sheets, films, tapes, laminates, or printed wiring boards, etc. It can be used in other technical fields that require characteristics of low dielectric constant and low dielectric loss in the 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 can be tested under a frequency condition of 1 GHz using equipment such as an impedance analyzer and the JIS-C-6481 test method. The measured dielectric constant (Dk) was 3.30 to 3.60, and the dielectric loss (Df) value was 0.0030 to 0.0050.

By having a dielectric constant and dielectric loss in the above range, the flame retardant resin composition has excellent flame retardant properties and at the same time has low dielectric properties in the high frequency region, which has the advantage of minimizing transmission loss between the base station and terminal in 5G 5th generation mobile communication. There is.

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

(Manufacturing example)

Preparation Examples 1 to 3 - Preparation of phosphorus compounds

Manufacturing Example 1

After preparing 228 g of Bisphenol A, 39 g of Bisphenol A Novolac resin, and 202 g of diphenyl phosphine oxide (DPO), a thermometer, a stirring device, and a reflux condenser were prepared. It was put into the reactor and purged for 30 minutes using nitrogen gas.

The temperature of the reactor was raised to 230°C and the reaction proceeded for 5 hours while dissolving the materials added to the reactor.

Afterwards, the temperature was increased to 230°C to sufficiently remove remaining phenol.

2000 g of toluene was added to dissolve the reactant from which the remaining phenol was removed, and then 2000 g of process water and 100 g of sodium hydroxide were added at a temperature of 60°C.

Afterwards, 300 g of VBC (4-vinylbenzeyl chloride) was added, and the reaction proceeded with reflux for 24 hours.

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

Production example 2

Preparation Example 1, except that 216 g of DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) was used instead of 202 g of diphenyl phosphine oxide (DPO). The reaction was performed in the same manner to obtain the product.

Production example 3

The reaction was performed in the same manner as Preparation Example 1, except that 153 g of Allyl chloride was added instead of 300 g of VBC (4-vinylbenzeyl chloride) 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 resin (Daiwa kasei, BMI-5100) were added to 250 g of 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, 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 bismaleimide-based resin were added in Preparation Example 1, respectively.

Example 8

A flame-retardant resin composition was prepared in the same manner as Example 1, except that the initiator was not added in Preparation Example 1.

Examples 9 to 10

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

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

Polyphenylene oxide resin (g) Phosphorus compounds (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

The flame-retardant resin compositions of Examples 1 to 10 were impregnated into glass fibers and then dried at a temperature of 80 to 200°C to prepare non-adhesive prepregs. The prepared prepregs were then placed on both sides of the copper foil and used a vacuum press. A copper clad laminate was manufactured by heating and pressing.

Afterwards, 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 at 20°C/min using a differential thermal analyzer (DSC).

Experimental Example 3 - Hygroscopic heat resistance experiment

The copper clad laminate of Experimental Example 1 was cut into pieces measuring 5cm horizontally and vertically, subjected to moisture absorption treatment in a PCT (Pressure cooker test, 121°C) for 2 hours, placed in a lead bath at 288°C for 10 seconds, and then examined for surface condition. When observed with the naked eye, those in which no delamination occurred are indicated with ◎, those with some surface changes observed are indicated with ○, those with some delamination are indicated with △, and those in which delamination clearly occurred are indicated with ×.

Experimental Example 4 - Measurement of copper foil adhesion strength

The obtained flame-retardant resin compositions of Examples 1 to 10 were applied to a general 1/20z copper foil to a thickness of 1 to 5 ㎛ and dried for 5 minutes to prepare a copper foil adhesive sheet. Afterwards, the two manufactured copper foil-attached adhesive sheets were laminated and heated and compressed for 2 hours at a temperature of 190℃ under a pressure of 20kg/cm. At room temperature, the copper foil was pulled vertically using a tensile strength meter to peel off the copper foil. Adhesion 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 characteristics 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

The features, structures, effects, etc. illustrated in each of the above-described embodiments can be combined or modified for other embodiments by those skilled in the art. Therefore, contents related to such combinations and modifications should be construed as being included in the scope of the present invention.

Claims (13)

A phosphorus-based compound having the structure of Formula 2 below.
(Formula 2)

(At this time, R3 is It is a structure, integer from 0 to 2) delete A phosphorus-based compound having the structure of Formula 2 below; and
polyphenylene-based resin; and
A flame-retardant resin composition containing an initiator.
(Formula 2)

(At this time, R3 is It is a structure, integer from 0 to 2) delete According to paragraph 3,
A flame retardant resin composition wherein the polyphenylene-based resin is polyphenylene oxide (PPO) resin. According to clause 5,
The flame retardant resin composition further includes a bismaleimide-based resin. delete According to clause 6,
With respect to 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-based compound. According to clause 8,
With respect to 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. According to clause 9,
With respect to 100 parts by weight of the polyphenylene oxide resin,
A flame-retardant resin composition comprising 2 to 11 parts by weight of the initiator. According to clause 10,
A flame retardant resin composition having a dielectric constant (Dk) of 3.30 to 3.60 measured at a frequency of 1 GHz using the JIS-C-6481 method after curing the flame retardant resin composition. According to clause 11,
A flame retardant resin composition having a dielectric loss (Df) of 0.0030 to 0.0050 measured at a frequency of 1 GHz using the JIS-C-6481 method after curing the flame retardant resin composition. A circuit board manufactured from the flame retardant resin composition of claim 3.