KR102287602B1 - Phosphorus containing flame-retardant polymer and flame-retardant resin composition comprising the same - Google Patents

Abstract

The present invention relates to a phosphorus-based flame-retardant polymer and a flame-retardant resin composition comprising the same, and more particularly, by including a carbonyl group having an ester structure in the molecular structure, flame retardancy and dielectric properties can be secured at the same time, so that an insulating material for electrical and electronic parts, printing It can be widely applied to various composite materials such as circuit boards and insulating plates, adhesives, coatings, and paints.

Description

Phosphorus-based flame-retardant polymer and flame-retardant resin composition comprising the same

The present invention relates to a phosphorus-based flame retardant polymer and a flame retardant resin composition comprising the same.

A printed circuit board (PCB) on which a specific electronic circuit is printed is used in various electronic products such as computers, semiconductors, displays, and communication devices. Signal lines for signal transmission, insulating layers for preventing a short circuit between the wires, and a switching element may be formed on the substrate.

The printed circuit board may be formed by laminating a prepreg in which glass cloth is impregnated with an epoxy resin and semi-cured on an inner circuit board on which a circuit is formed. Alternatively, it may be manufactured by a build-up method in which the substrate is manufactured by alternately stacking insulating layers on the circuit pattern of the inner-layer circuit board on which the circuit is formed. In this case, the build-up method has an advantage in densification and thinning of the printed circuit board because it forms a via hole to increase the wiring density, and forms a circuit by laser processing or the like.

As printed circuit boards are also highly integrated and dense due to the recent trend of light, thin, compact and miniaturized electronic devices, electrical, thermal, and mechanical stability of printed circuit boards is becoming an important factor for stability and reliability of electronic devices.

Since epoxy resins exhibit excellent electrical and thermal properties, they are widely used as semiconductor encapsulants or insulating materials for printed circuit boards.

BACKGROUND ART In printed circuit boards, the implementation of high-density wiring by narrowing the wiring pitch is required with the flow of miniaturization, thinning, and high performance of electronic devices. For this purpose, a flip-chip connection method in which a semiconductor device and a wiring board are joined by a solder ball is mainly used instead of the conventional wire bonding method.

In the flip-chip connection method, since solder balls are disposed between a wiring board and a semiconductor device and the solder is reflowed by heating the whole, and bonding is performed, an insulating material with higher flammability resistance is required.

In addition to this, in response to the demand for higher performance of electronic devices as described above, there is a tendency to increase the speed and high frequency of signals inside the electronic device. The transmission loss of an electrical signal is _{proportional to the dielectric dissipation factor (D f} ) and frequency. Therefore, the higher the frequency, the greater the transmission loss, and the attenuation of the signal causes a decrease in the reliability of the signal transmission. In addition, the transmission loss is converted into heat, which may cause a problem of heat generation. Accordingly, there is a need for an insulating material having a smaller dielectric constant and dielectric loss factor than conventional insulating materials.

However, it is not easy to lower the dielectric constant and the dielectric loss factor due to the inherent characteristics of the epoxy resin composition and its cured product, which are widely used as insulating materials in the prior art.

Therefore, there is a demand for a polymer material that can be used together with the epoxy resin composition to exhibit excellent flammability resistance and low dielectric properties for high-speed and high-frequency signals.

In this regard, Korean Patent Registration No. 10-1596992 discloses a non-halogen flame retardant polymer having excellent impregnation, adhesion, flame retardancy and compatibility with other polymers and a method for manufacturing the same.

In addition, Korean Patent Application Laid-Open No. 2016-0018507 discloses an active ester resin containing a phosphorus atom that is used in an epoxy resin composition to improve flame retardancy, heat resistance and dielectric properties.

In the case of the flame retardant polymer or active ester resin presented in these patents, the flame retardant properties of the final cured product are improved to some extent, but the effect is not sufficient, and in particular, in the former case, dielectric properties are not considered at all. Therefore, there is a need for further research on flame-retardant compounds capable of securing high flame retardancy and low dielectric properties at the same time.

Republic of Korea Patent No. 10-1596992 (2016.02.17), non-halogen flame retardant polymer and flame retardant polymer composition containing the same Korean Patent Laid-Open No. 2016-0018507 (2016.02.17), phosphorus atom-containing active ester resin, epoxy resin composition, cured product thereof, prepreg, circuit board, and build-up film

Accordingly, the present inventors have conducted various studies to solve the above problems, and as a result, when the hydroxyl group present in the phosphorus-based flame-retardant polymer is substituted with a carbonyl group of an ester structure, it is found that flame retardancy and dielectric properties can be satisfied at the same time. was completed.

Accordingly, it is an object of the present invention to provide a phosphorus-based flame retardant polymer having high flame retardancy and low dielectric properties.

In order to achieve the above object, the present invention provides a phosphorus-based flame-retardant polymer comprising at least one of the repeating units represented by the following Chemical Formulas 1 and 2, wherein _{at least one of R 1 in the entire repeating unit is a carbonyl group:}

[Formula 1]

[Formula 2]

(In Formulas 1 and 2, R ₁ to R ₄ , R _a , m and n are as described in the specification).

The repeating unit may be at least one selected from repeating units represented by the following Chemical Formulas 3 to 9:

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

(In Formulas 3 to 9, R ₁ to R ₄ , R _a and m are as described in the specification).

_{The ratio of carbonyl groups in the total R 1} in the phosphorus-based flame-retardant polymer may be 20 to 100%.

The phosphorus-based flame retardant polymer may have a phosphorus content of 5.0 to 9.0 wt% based on the total weight of the polymer.

The phosphorus-based flame retardant polymer may have a dielectric constant (D _k ) of less than 3.8 at 1 GHz, and a dielectric loss coefficient (D _f ) of 0.015 or less at 1 GHz.

In addition, the present invention provides a flame-retardant resin composition comprising the phosphorus-based flame-retardant polymer.

In addition, the present invention provides a printed circuit board comprising the flame-retardant resin composition.

The phosphorus-based flame-retardant polymer according to the present invention includes a carbonyl group having an ester structure in a certain ratio or more instead of a hydroxyl group in the repeating unit, thereby reducing the dielectric constant and the dielectric loss factor while the cured product finally produced exhibits a flame retardancy equivalent to that of the existing one. . Therefore, the phosphorus-based flame retardant polymer of the present invention can be applied to various electrical and electronic components such as semiconductor encapsulants or printed circuit boards requiring high reliability, excellent flame retardancy and low dielectric properties.

1 is a graph showing the GPC measurement results of the phosphorus-based flame-retardant polymer prepared in Example 1 and Comparative Example 1 of the present invention.
2 is a graph showing the GPC measurement results of the phosphorus-based flame-retardant polymer prepared in Examples 3 and 4 of the present invention.
3 is a graph showing the IR measurement results of the phosphorus-based flame-retardant polymer prepared in Example 1 and Comparative Example 1 of the present invention.

Hereinafter, the present invention will be described in detail.

The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

The terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present invention, terms such as 'comprise' or 'have' designate the existence of features, numbers, steps, operations, components, parts, or a combination thereof described in the specification, but one or more other It is to be understood that this does not preclude the possibility of addition or presence of features or numbers, steps, operations, components, parts, or combinations thereof.

As used in the present invention, the terms “flame-retardant property”, “flame retardancy” or “flammability resistance” refer to properties of a material that is difficult to combust between incombustibility and non-combustibility, and is flame-retardant, flame-retardant, and flame-retardant. sex) have the same meaning.

As used herein, the term “alkyl group” means a linear or branched saturated monovalent hydrocarbon group of 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms. The alkyl group may encompass not only unsubstituted ones but also those that are further substituted by certain substituents to be described later. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a 2-propyl group, an n-butyl group, an iso-butyl group, a t-butyl group, a pentyl group, a hexyl group, a dodecyl group, a fluoromethyl group, a difluoromethyl group, A trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, an iodomethyl group, a bromomethyl group, etc. are mentioned.

As used herein, the term “alkoxy group” refers to an alkyl group having 1 to 20 carbon atoms including an oxygen radical, unless otherwise specified, and is not limited thereto. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentoxy group, a hetoxy group, a dodecy group, and the like. oxy, trifluoromethoxy, chloromethoxy, dichloromethoxy, trichloromethoxy, iodomethoxy, bromomethoxy and the like.

As used herein, the term “alkenyl group” refers to a linear or branched monovalent hydrocarbon of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms containing at least one carbon-carbon double bond. it means gear The alkenyl group may be bonded through a carbon atom comprising a carbon-carbon double bond or through a saturated carbon atom. The alkenyl group may include not only unsubstituted ones but also those that are further substituted by certain substituents to be described later. Examples of the alkenyl group include an ethenyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, pentenyl group, 5-hexenyl group, dodecenyl group, and the like.

As used herein, the term “alkynyl group” refers to a linear or branched monovalent hydrocarbon of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms containing at least one carbon-carbon triple bond. it means gear The alkynyl group may be bonded through a carbon atom comprising a carbon-carbon triple bond or through a saturated carbon atom. The alkynyl group may be referred to as encompassing those further substituted by certain substituents to be described later. For example, an ethynyl group, a propynyl group, etc. are mentioned as said alkynyl group.

As used herein, the term “cycloalkyl group” means a saturated or unsaturated monovalent monocyclic, bicyclic or tricyclic non-aromatic hydrocarbon group of 3 to 20, preferably 3 to 12 ring carbons, It may also be referred to as encompassing those further substituted by certain substituents to be described later. For example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclohexyl group, cyclohexenyl group, cycloheptyl group, cyclooctyl group, decahydronaphthalenyl group, adamantyl group, norbornyl group (ie, bicyclo [2,2,1] hept-5-enyl) and the like.

As used herein, the term “aryl group” refers to a monovalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon group having 6 to 40, preferably 6 to 30 ring atoms, and certain substituents described later It can also be referred to as encompassing those further substituted by . Examples of the aryl group include a phenyl group, a biphenyl group, and a fluorene group.

As used herein, the term “heteroaryl group” has 5 to 40, preferably 5 to 30 ring atoms, and at least one carbon in the ring is nitrogen (N), oxygen (O), sulfur ( S), or phosphorus (P) means substituted. means a monocyclic or bicyclic or higher aromatic group containing, for example, 1 to 4 heteroatoms. Examples of the monocyclic heteroaryl group include a thiazolyl group, an oxazolyl group, a thiophenyl group, a furanyl group, a pyrrolyl group, an imidazolyl group, an isoxazolyl group, a pyrazolyl group, a triazolyl group, a thiadiazolyl group, tetra Zolyl group, oxadiazolyl group, pyridinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group and similar groups are possible, but are not limited thereto. Examples of the bicyclic heteroaryl group include indolyl group, benzothiophenyl group, benzofuranyl group, benzimidazolyl group, benzoxazolyl group, benzisoxazolyl group, benzthiazolyl group, benzthiadiazolyl group, benztriazole diary, a quinolinyl group, an isoquinolinyl group, a purinyl group, a furopyridinyl group, and a group similar thereto, but is not limited thereto.

As used herein, the term “alkylene group” means a linear or branched saturated divalent hydrocarbon group of 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms. The alkylene group may be referred to as encompassing those further substituted by certain substituents to be described later. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and the like.

As used herein, the term “alkenylene group” refers to a linear or branched group of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms containing at least one carbon-carbon double bond. It means a divalent hydrocarbon group. The alkenylene group may be bonded through a carbon atom including a carbon-carbon double bond and/or a saturated carbon atom, and may be further substituted by a specific substituent to be described later.

As used herein, the term “cycloalkylene group” means a saturated or unsaturated divalent monocyclic, bicyclic or tricyclic non-aromatic hydrocarbon group of 3 to 20, preferably 3 to 12 ring carbons, , may be further substituted by certain substituents to be described later. Examples of the cycloalkylene group include a cyclopropylene group and a cyclobutylene group.

As used herein, the term “arylene group” refers to a divalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon group having 6 to 40, preferably 6 to 30 ring atoms, and a certain substituent group described later can be further substituted by For example, the arylene group includes, but is not limited to, phenylene, biphenylene, naphthylene, anthracenylene, and the like.

The term “halogen element” used in the present invention is fluorine (F), chlorine (Cl), bromine (Br) or iodine (I), and the term “halo” used in the present invention refers to a group substituted with the aforementioned halogen element. it means.

All compounds or substituents in the present invention may be substituted or unsubstituted unless otherwise specified. Here, substituted means that a hydrogen atom is a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amino group, a thio group, a methyl thio group, an alkoxy group, a nitrile group, an aldehyde group, an epoxy group, an ether group, an ester group, a carbonyl group, Substituted with any one selected from the group consisting of acetal group, ketone group, alkyl group, perfluoroalkyl group, cycloalkyl group, heterocycloalkyl group, allyl group, benzyl group, aryl group, heteroaryl group, derivatives thereof, and combinations thereof means that

The present invention provides a phosphorus-based flame retardant polymer exhibiting excellent flame retardancy and dielectric properties.

According to the recent trend of miniaturization and high performance of electronic and communication devices, the signal transmission speed of these products is increasing, and the frequency band of the signal used is moving from MHz to GHz. However, when the frequency of the signal increases as described above, it is difficult to secure the reliability of signal transmission because the amount of lost signal increases as well as noise increases, and the transmission loss is converted into heat, which may cause a heat problem. However, since epoxy resin, which is widely used as an insulating material for conventional printed circuit boards, has a high dielectric constant and dielectric loss coefficient, there is a limit to its application to miniaturized and highly integrated printed circuit boards. Accordingly, there is a need for an insulating material having both low dielectric properties and excellent flame retardant properties in line with technological trends such as the exclusion of halogen-based flame retardants as well as high-speed and high-frequency of electronic devices.

In the case of an epoxy resin composition for a printed circuit board, a phosphorus-based flame retardant polymer is mixed to increase flame retardancy. Accordingly, the present invention provides a phosphorus-based flame-retardant polymer having both high flame retardancy and low dielectric properties by introducing a carbonyl group having an ester structure into the phosphorus-based flame-retardant polymer in a certain ratio or more.

The phosphorus-based flame-retardant polymer according to the present invention includes at least one type of repeating units represented by the following Chemical Formulas 1 and 2:

[Formula 1]

[Formula 2]

(In Formulas 1 and 2,

또는

이고;R ₁ is each independently hydrogen,

or

ego;

R ₂ is each independently a C1-C20 alkyl group or a C6-C20 aryl group;

이되, 상기 반복단위 내의 A 중 적어도 하나 이상은

이고;R ₃ is each independently —CH ₂ —A, wherein A is a hydroxyl group, a C1-C10 alkoxy group, or

However, A in the repeating unit at least one or more of

ego;

R ₄ is each independently a simple bond, -CH ₂ - or -CH ₂ -O-CH ₂ -,

R ₅ is a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, or a C5-C20 heteroaryl group;

R ₆ is a C1-C20 alkylene group, a C2-C20 alkenylene group, a C3-C20 cycloalkylene group, or a C6-C20 arylene group;

R ₇ is a carboxyl group (-C(=O)OH) or a haloformyl group (-C(=O)X), wherein X is a halogen element;

R _a is a simple bond or a C1-C10 alkylene group, a C6-C20 arylene group, a C3-C20 cycloalkylene group, or a sulfonyl group (-SO ₂ -, sulfonyl group);

each m is independently an integer from 0 to 2;

n is each independently an integer of 0 or 1, but at least two or more of n in the repeating unit is 1.).

In the present invention, the repeating units represented by Chemical Formulas 1 and 2 are formed by converting a hydrogen atom of a hydroxyl group located on a benzene ring in the repeating unit to a carbonyl group using an esterification reaction. By substituting with C = O), the dielectric constant and dielectric loss coefficient of the cured product finally obtained by reacting the secondary alcohol in the epoxy generated during the curing reaction with the epoxy resin with the carbonyl group of the ester structure can be lowered to ensure low dielectric properties. . Therefore, the phosphorus-based flame-retardant polymer including the repeating unit according to the present invention can simultaneously secure high flame retardancy and low dielectric properties by including the ester structure in the molecular structure.

또는

로 표시되는 카보닐기일 수 있다.As described above, in the present invention, R ₁ is

or

It may be a carbonyl group represented by .

Preferably, R ₅ is a C1-C10 alkyl group or a C6-C20 aryl group, and R ₆ is a C1-C10 alkylene group or a C6-C20 arylene group.

The carbonyl group represented by Chemical Formulas as described above may be at least one of _{R 1} in each of the repeating units represented by Chemical Formulas 1 and 2 above. For example, in the case of Formula 1, when all R _{1 in} Formula 1 is a carbonyl group, when _{at least one of R 1} in Formula 1 is a carbonyl group, and when all R _{1 in} Formula 1 are hydrogen. Each repeating unit according to the invention has three main types. The form of such a repeating unit is equally applied to Chemical Formula 2, and has three types of repeating units. In the finally obtained phosphorus-based flame retardant polymer of the present invention, the repeating units of the above-described form may be alternately arranged in block form or irregularly, and at least one of a _{form in which all R 1 in the} repeating unit is a carbonyl group and R _{1 in the repeating unit.} and at least one form in which is a carbonyl group. _{Preferably, at least one of R 1} in all repeating units constituting the phosphorus-based flame retardant polymer may be a carbonyl group.

In addition, in Formula 2, when n is 0, there is no bond with other adjacent repeating units.

In one embodiment of the present invention, the repeating unit may be at least one selected from repeating units represented by the following Chemical Formulas 3 to 9.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

(In Formulas 3 to 9,

또는

이고;R ₁ is each independently hydrogen,

or

ego;

R ₂ is each independently a C1-C20 alkyl group or a C6-C20 aryl group;

이되, 상기 반복단위 내의 A 중 적어도 하나 이상은

이고;R ₃ is each independently —CH ₂ —A, wherein A is a hydroxyl group, a C1-C10 alkoxy group, or

However, A in the repeating unit at least one or more of

ego;

R ₄ is each independently a simple bond, -CH ₂ - or -CH ₂ -O-CH ₂ -, _{except that R 4} is a simple bond;

R ₅ is a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, or a C5-C20 heteroaryl group;

R ₆ is a C1-C20 alkylene group, a C2-C20 alkenylene group, a C3-C20 cycloalkylene group, or a C6-C20 arylene group;

R ₇ is a carboxyl group (-C(=O)OH) or a haloformyl group (-C(=O)X), wherein X is a halogen element;

R _a is a simple bond or a C1-C10 alkylene group, a C6-C20 arylene group, a C3-C20 cycloalkylene group, or a sulfonyl group (-SO ₂ -, sulfonyl group);

m is each independently an integer from 0 to 2.).

Preferably, the R ₂ may each independently be a C1-C10 linear or branched alkyl group.

일 수 있다.Also, preferably, each of R ₃ is independently —CH ₂ —A, wherein A is each independently a C1-C5 alkoxy group or

can be

Also, preferably, each of R ₄ is independently -CH ₂ - or -CH ₂ -O-CH ₂ -, and in the repeating unit represented by the above formula, R ₄ is -CH ₂ - and -CH ₂ -O-CH ₂ - may include both.

The phosphorus-based flame-retardant polymer of the present invention may include 50 to 100%, preferably 75 to 100%, of the repeating unit represented by the above formula based on the total number of repeating units in the polymer.

In another embodiment of the present invention, the phosphorus-based flame retardant polymer may be any one of compounds represented by the following Chemical Formulas 10 to 16:

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

(In Formulas 10 to 16,

또는

이고;R ₁ is each independently hydrogen,

or

ego;

이되, 상기 반복단위 내의 A 중 적어도 하나 이상은

이고;R ₃ is each independently —CH ₂ —A, wherein A is a hydroxyl group, a C1-C10 alkoxy group, or

However, A in the repeating unit at least one or more of

ego;

R ₄ is each independently a simple bond, -CH ₂ - or -CH ₂ -O-CH ₂ -, _{except that R 4} is a simple bond;

R ₅ is a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, or a C5-C20 heteroaryl group;

R ₆ is a C1-C20 alkylene group, a C2-C20 alkenylene group, a C3-C20 cycloalkylene group, or a C6-C20 arylene group;

R ₇ is a carboxyl group (-C(=O)OH) or a haloformyl group (-C(=O)X), wherein X is a halogen element;

R′ and R″ are the same as or different from each other and are each independently hydrogen, a C1-C10 alkyl group, a C3-C20 cycloalkyl group, or a C6-C20 aryl group;

이며;A ₁ to A ₁₄ are the same as or different from each other, and each independently a hydroxyl group, a C1-C10 alkoxy group, or

is;

each m is independently an integer from 0 to 2;

p to z are rational numbers from 0 to 4.).

Preferably, in Formulas 10 to 16, R ₁ is the same as described above, and in the phosphorus-based flame retardant polymer of the present invention, the _{proportion of carbonyl groups among the total R 1} in the repeating unit is 20 to 100%, preferably 50 to 100%, more preferably from 70 to 100%. When the ratio of the carbonyl group is within the above-described range, a sufficient effect of improving dielectric properties may be obtained. At this time, not all R _{1 in} the phosphorus-based flame retardant polymer is substituted with the above-described carbonyl group, and at least one of _{all R 1 in the polymer may be hydrogen.}

일 수 있다.As described above, R ₃ is preferably, each independently -CH ₂ -A, wherein A is each independently a C1-C5 alkoxy group or

can be

Also, preferably, each of R ₄ is independently —CH ₂ — or —CH ₂ —O—CH ₂ —, and in each compound represented by Formulas 10 to 16, —CH ₂ — and —CH ₂ — O-CH ₂ - may be mixed.

Also, preferably, R′ and R″ are the same as or different from each other, and each independently may be hydrogen, a C1 to C5 alkyl group, a C3 to C12 cycloalkyl group, or a C6 to C12 aryl group. More preferably, R′ and R″ are the same as or different from each other, and each independently may be a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a phenyl group, or a methylphenyl group.

일 수 있다.Also, preferably, the A ₁ to A ₈ are the same as or different from each other, and each independently a C1-C5 alkoxy group or

can be

Also preferably, p to z are rational numbers from 1 to 4.

In Formula 12, when all of _{R 4 are -CH 2} -, A in -CH _{2 -A, which is R 3} , may each independently be a hydroxy group or a C1-C10 alkoxy group.

The phosphorus-based flame-retardant polymer of the present invention represented by the above formula may exhibit a low dielectric property by including a carbonyl group instead of a hydroxyl group, thereby introducing an ester structure. In addition, the phosphorus-based flame-retardant polymer of the present invention is intended to improve flame retardancy by necessarily including an aromatic ring containing a phosphorus atom.

The phosphorus-based flame retardant polymer may have a phosphorus content of 5.0 to 9.0 wt%, preferably 7 to 8.5 wt%, based on the total weight of the polymer. When the phosphorus content is less than the above range, the flame retardant effect is insufficient and the input amount is increased when the resin is mixed.

The phosphorus-based flame retardant polymer according to the present invention may have a weight average molecular weight (M _w ) of 1000 to 2000 g/mol, preferably 1,000 to 1,600 g/mol. When the weight average molecular weight of the phosphorus-based flame-retardant polymer is less than the above range, the effect of improving dielectric properties cannot be obtained. In addition, the phosphorus-based flame retardant polymer of the present invention may have a glass transition temperature (T _g ) in the range of 150 to 170 ℃.

The phosphorus-based flame-retardant polymer according to the present invention may have a dielectric constant (D _k ) of less than 3.8 at 1 GHz, preferably 2.7 to 3.5. In addition, the phosphorus-based flame retardant polymer may have a dielectric loss coefficient (D _f ) of 0.015 or less at 1 GHz, preferably 0.0050 to 0.010.

In addition, the present invention provides a method for preparing the above-described phosphorus-based flame retardant polymer.

For example, the phosphorus-based flame-retardant polymer according to the present invention may be prepared by reacting a polymer represented by the following Chemical Formula 15 with a compound represented by Chemical Formula 16 or 17 in the presence of a catalyst to prepare a polymer represented by Chemical Formula 11:

[Formula 11]

[Formula 17]

[Formula 18]

[Formula 19]

(In Formulas 11 and 17 to 19,

R ₁ , R ₃ , R ₄ to R ₇ , A ₃ , A ₄ , m and s are as mentioned above;

R ₈ is hydrogen or a halogen element.)

In the method for producing the phosphorus-based flame-retardant polymer according to the present invention, the polymer represented by Chemical Formula 17 as a starting material may be formed through various known methods, and the present invention is not particularly limited.

For example, the polymer represented by Formula 17 is obtained by polymerizing a monomer containing a bisphenol structure such as bisphenol A and bisphenol F with an aldehyde compound, and then reacting the intermediate product obtained therewith with an organophosphorus compound having a phosphine structure and It can be prepared by sequentially reacting. In this case, when the phosphorus-based flame retardant polymer finally prepared has an alkyl phenol structure, the starting material may be a monomer including an alkyl phenol structure, for example, para-tert-butylphenol (PTBP) and para-tert-octylphenol (PTOP). can

In this case, the aldehyde compound may be used without limitation as long as it is a compound capable of substituting a methylol group at the end of each monomer through reaction with a monomer having a bisphenol structure, preferably formaldehyde, acetaldehyde, alkyl aldehyde, benz At least one selected from the group consisting of aldehydes, alkyl-substituted aldehydes, hydroxy benzaldehyde, naphthoaldehyde and glutaraldehyde may be used, and formaldehyde may be preferably used.

In the reaction with the aldehyde compound, the reaction may be carried out in the presence of a catalyst to increase reactivity, and the catalyst is, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, etc. It may be an alkali catalyst.

In addition, since the intermediate product obtained by the reaction with the aldehyde compound having a terminal substituted with a methyl group is an unstable substance that easily undergoes self-polymerization, it can inhibit the self-polymerization of the methyl group by reacting it with an alcohol prior to the reaction with the organophosphorus compound. there is. In this case, the usable alcohol may be any one or more selected from the group consisting of methanol, ethanol, butanol, propanol, glycol, 2-methoxy ethanol, ether and phenol, preferably butanol is very advantageous for improving physical properties. do.

The organophosphorus compound is for imparting flame retardancy, for example, phenylphosphine, diphenyl phosphate, diethyl phosphate, dimethyl phosphite, phenylphosphinic acid, phenylphosphonic acid, dimethylphosphinic acid and 9,10-dihydro- At least one selected from the group consisting of 9-oxa-10-phosphaphenanthrene-10-oxide may be used, and preferably 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- It may be an oxide.

The polymer of Formula 17 obtained through the above is reacted with the compound represented by Formula 18 or 19 in the presence of a catalyst.

The catalyst serves to improve reactivity so that the introduction of the carbonyl group derived from Chemical Formula 18 or 19 into the polymer of Chemical Formula 17 can proceed more easily.

An amine-based compound may be used as the catalyst, for example, methyl diethanol amine, triethylamine, tributylamine, dimethyl benzylamine, triphenylamine, tricyclohexyl amine, pyridine, quinoline and 1,8-dia It may include at least one selected from the group consisting of zabicyclo(5.4.0)undec-7-ene. Preferably, it may include at least one selected from the group consisting of triethylamine, tributylamine, and pyridine.

The catalyst may be used in an amount of 0.1 to 0.5% by weight, preferably 0.1 to 0.2% by weight, based on 100% by weight of the polymer of Formula 17. If the catalyst is used in less than the above range, the effect of improving the reactivity cannot be obtained.

The compound represented by Formula 18 or 19 is for introducing a carbonyl group into the polymer of Formula 17, and any compound containing a carbonyl group may be used without limitation.

Preferably, in Formulas 18 or 19, R ₅ to R ₇ may be the same as described above, R ₈ may _{be hydrogen when R 7} is a carboxyl group, and may be the same halogen element when _{R 7 is a haloformyl group.}

For example, the compound represented by Formula 18 or 19 is benzoyl chloride, isophthaloyl dichloride, terephthaloyl dichloride, benzoic acid, as shown in the figure below. acid), isophthalic acid, terephthalic acid, etc., preferably benzoyl chloride:

The compound of Formula 18 or 19 may be used in an amount of 0.01 to 0.5% by weight, preferably 0.04 to 0.3% by weight, based on 100% by weight of the polymer of Formula 13. If the compound of Formula 18 or 19 is used below the above range, there is a slight problem in the change in the glass transition temperature.

In addition, the present invention provides a flame-retardant resin composition comprising the phosphorus-based flame-retardant polymer.

As an example, the flame-retardant resin composition includes an epoxy resin, an epoxy curing agent, a curing accelerator and a non-halogen flame retardant. In particular, in the present invention, excellent flame retardant properties and low dielectric properties can be secured by including a phosphorus-based flame retardant polymer as the non-halogen flame retardant. there is.

Unlike the flame-retardant resin composition including the existing phosphorus-based flame-retardant polymer, the flame-retardant resin composition of the present invention includes the phosphorus-based flame-retardant polymer represented by the above-described chemical formula, thereby having flame retardant properties equivalent to or higher than that of the existing phosphorus-based flame-retardant polymer, while having a dielectric constant And by lowering the dielectric loss coefficient, it is possible to further reduce the dielectric properties of the finally obtained cured product.

The epoxy resin is not particularly limited in the present invention, and those used in the art may be used without limitation. Non-limiting examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, anthracene epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, Alicyclic epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, dicyclopentadiene type epoxy resin, polyfunctional phenol type epoxy resin, Biphenyl novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol phenol coaxial novolak type epoxy resin, naphthol choresol coaxial novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, triphenyl methane type There are epoxy resins, tetraphenylethane type epoxy resins, dicyclopentadiene phenol addition reaction type epoxy resins, phenol aralkyl type epoxy resins, and naphthol aralkyl type epoxy resins, and these may be used alone or in combination of two or more types.

The epoxy curing agent can be used without any particular limitation as long as it is a conventional curing agent known in the art as a curing reaction with the epoxy resin can proceed. For example, an amine curing agent, an acid anhydride curing agent, an isocyanuric acid curing agent, a phenol-based curing agent, etc. may be used, and these may be used alone or in combination of two or more.

The amine curing agent includes dicyandiamide, diethylenetriamine, tetraethylenetriamine, tetraethylenepentaamine, isopropyldiamine, bis(aminomethyl)cyclohenic acid, 1,4-butanediol bis(3-aminopropyl)ether, xylenediamine, 1,4-phenylenediamine, or the like can be used.

Acid anhydride curing agents include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethyl glutaric anhydride, Diethyl glutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like can be used.

As the isocyanuric acid curing agent, 1,3,5-tris(1-carboxymethyl)isocyanurate, 1,3,5-tris(2-carboxyethyl)isocyanurate, 1,3,5-tris (3-carboxypropyl) isocyanurate, 1, 3-bis (2-carboxyethyl) isocyanurate, etc. are mentioned.

Phenolic curing agents include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol and aminophenol, and/or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and form a novolak-type phenol resin obtained by condensing or co-condensing a compound having an aldehyde group such as aldehyde, benzaldehyde, and salicylaldehyde under an acidic catalyst; phenol/aralkyl resin synthesized from phenols and/or naphthols and dimethoxyparaxylene or bis(methoxy)biphenyl; aralkyl-type phenol resins such as biphenylene-type phenol/aralkyl resins and naphthol/aralkyl resins; dicyclopentadiene type phenol resins such as dicyclopentadiene type phenol novolac resin and dicyclopentadiene type naphthol novolak resin synthesized by copolymerization of phenols and/or naphthols with dicyclopentadiene; triphenylmethane type phenol resin; terpene-modified phenolic resin; para-xylene and/or meta-xylene-modified phenolic resins; melamine-modified phenolic resin; Alternatively, a cyclopentadiene-modified phenol resin may be used.

In addition, other epoxy curing agents such as isocyanate-based, mercaptan-based, and melamine may be used.

The curing accelerator is a material that promotes the reaction between the epoxy resin and the curing agent, and for example, an imidazole-based curing accelerator, an amine-based curing accelerator, and a metal-based curing accelerator, but is not limited thereto.

Non-limiting examples of imidazole-based curing accelerators that can be used include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-decylimidazole, 2-hexylimidazole, 2-isopropyl Imidazole, 2-undecyl imidazole, 2-heptanedecyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenylimidazole, 2-phenyl-4-methyl imidazole, 1-benzyl-2 -Methyl imidazole, 1-benzyl-2-phenyl imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl -2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl-imidazole trimellitate, 1-cyanoethyl-2-phenyl imidazole trimellitate, 2,4-diamino-6-(2'-methylimidazole-(1')-ethyl-s-triazine, 2-pecyl-4,5-dihydroxymethylimidazole; 2-Pesyl-4-methyl-5-hydroxymethylimidazole, 2-pecyl-4-benzyl-5-hydroxymethylimidazole, 4,4'-methylene-bis-(2-ethyl-5- methylimidazole), 2-aminoethyl-2-methyl imidazole, 1-cyanoethyl-2-phenyl-4,5-di(cyanoethoxymethyl)imidazole, 1-dodecyl-2-methyl -3-benzylimidazolinium chloride, imidazole-containing polyamide, mixtures thereof, etc. In addition, tertiary amines, organometallic compounds, organophosphorus compounds, boron compounds, etc. may be additionally used.

Non-limiting examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine; amine compounds such as 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecel (DBU), or and mixtures of one or more thereof.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Examples of the organometallic complex include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, zinc(II) acetylacetonate, and the like. an organic zinc complex, an organic iron complex such as iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex such as manganese (II) acetylacetonate. not limited Examples of the organometallic salt include, but are not limited to, zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. The metal-based curing accelerator as described above may be used alone or in combination of two or more.

The flame retardant resin composition according to the present invention preferably contains 30 to 70 parts by weight of the epoxy curing agent, 0.1 to 1 parts by weight of the curing accelerator, and 10 to 150 parts by weight of the phosphorus-based flame retardant polymer based on 100 parts by weight of the epoxy resin. . If the phosphorus-based flame-retardant polymer is included in an amount of less than 10 parts by weight based on 100 parts by weight of the epoxy resin, there is a problem that flame retardancy cannot be ensured due to insufficient phosphorus content in the entire formulation, and when it exceeds 150 parts by weight, the reactivity is lowered There is a problem in that solubility with other resins is lowered.

The flame retardant resin composition comprising the phosphorus-based flame retardant polymer according to the present invention is excellent as an additive of engineering plastics such as polycarbonate, acrylonitrile butadiene styrene (ABS), and high impact polystyrene (HIPS). It has properties and physical and chemical properties, and can be used as a raw material for epoxy resins, cyanate resins and acrylate resins, and as a curing agent for epoxy resins. Therefore, the flame-retardant resin composition according to the present invention is a high-reliability insulating material for electric and electronic components such as an epoxy molding compound (EMC), a halogen-free compound, and a printed circuit board (PCB) requiring excellent flame retardancy and thermal stability; It can be widely applied to various composite materials such as insulating plates, adhesives, coatings, and paints.

Hereinafter, Examples, Comparative Examples, and Experimental Examples are described to help understanding of the effects of the present invention. However, the following description is only an example of the content and effect of the present invention, and the scope and effect of the present invention are not limited thereto.

Example 1 and comparative example 1: Preparation of phosphorus-based flame retardant polymer

[Example 1]

800 g of bis(4-hydroxyphenyl)methane, 1580.7 g of an aqueous formaldehyde solution (40%), 31.98 g of a 50% aqueous solution of sodium hydroxide and 650 g of butanol were put into the reactor, and then heated and reacted with stirring at 80 °C. Then, 650 g of butanol was added, and an alcohol addition reaction was performed while draining the water generated at 140° C. for 32 hours. After completion of the reaction, 250 g of water and 60 g (2 mol) of carbonyl diamine were added to the reactor to remove unreacted formaldehyde and washed with water. The resin layer of the upper layer from which unreacted formaldehyde was removed was separated and washed with water two times with an additional 100 g of water. 540 g (2.5 mol) of 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxice was added to the resin layer, and the reaction mixture was reacted at 170° C. for 12 hours while removing butanol and water present in the reaction mixture. . After completion of the reaction, it was degassed under reduced pressure to obtain a solid polymer A.

Based on 500 parts by weight of the obtained polymer A, 1.2 parts by weight of triethylamine, 1.2 parts by weight of benzoyl chloride, and 0.65 parts by weight of chloroform were added, followed by heating and reacting at 80° C. for 4 hours with stirring.

After completion of the reaction, 250 g of water was added to the reactor to remove the salt produced after the reaction. After completion of the water washing process, 590 g of a solid phosphorus-based flame retardant polymer was obtained by degassing under reduced pressure. A liquid resin containing 65% of a solid phosphorus-based flame retardant polymer was obtained by using 1-methyl-2-propanol as a solvent mixing method.

[Example 2]

It was prepared in the same manner as in Example 1, except that 0.96 parts by weight of benzoyl chloride was used.

[Example 3]

800 g of para-tert-octylphenol (PTOP), 728.16 g of an aqueous formaldehyde solution (40%), 96 g of a 50% aqueous solution of sodium hydroxide and 431.07 g of butanol were put into a reactor, and then heated and reacted with stirring at 80°C. Then, 431.07 g of butanol was added, and then, an alcohol addition reaction was performed while draining the water produced at 140° C. for 32 hours. After completion of the reaction, 250 g of water and 60 g (2 mol) of carbonyl diamine were added to the reactor to remove unreacted formaldehyde and washed with water. The resin layer of the upper layer from which unreacted formaldehyde was removed was separated and washed with water two times with an additional 100 g of water. 540 g (2.5 mol) of 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxice was added to the resin layer, and the reaction mixture was reacted at 170° C. for 12 hours while removing butanol and water present in the reaction mixture. . After completion of the reaction, solid polymer B was obtained by degassing under reduced pressure.

It was prepared in the same manner as in Example 1, except that 300 parts by weight of Polymer B was used instead of Polymer A.

[Example 4]

Para-tert-butylphenol (PTBP) 400 g, para-tert-octylphenol (PTOP) 400 g, formaldehyde aqueous solution (40%) 864.08 g, sodium hydroxide 50% aqueous solution 96 g, and butanol 511.53 g were put into the reactor. Then, it was heated and reacted with stirring at 80 °C. Then, 511.53 g of butanol was added, and then an alcohol addition reaction was performed at 140° C. for 32 hours while draining the water produced. After completion of the reaction, 250 g of water and 60 g (2 mol) of carbonyl diamine were added to the reactor to remove unreacted formaldehyde and washed with water. The resin layer of the upper layer from which unreacted formaldehyde was removed was separated and washed with water twice more with 100 g of water. 540 g (2.5 mol) of 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxice was added to the resin layer and reacted at 170° C. for 12 hours while removing butanol and water present in the reaction mixture. After completion of the reaction, solid polymer C was obtained by degassing under reduced pressure.

It was prepared in the same manner as in Example 1, except that Polymer C was used instead of Polymer A.

[Comparative Example 1]

Polymer A was used.

Experimental example 1: Physical property evaluation

The physical properties of the phosphorus-based flame-retardant polymers prepared in Examples and Comparative Examples were measured, and the results are shown in Table 1 and FIGS. 1 to 3 below. The property evaluation method is as follows.

(1) Measurement of weight average molecular weight

The phosphorus-based flame retardant polymer prepared in Examples and Comparative Examples was dissolved in Tetra Hydro Furan (THF) at a concentration of 4000 ppm, and a weight average molecular weight using Gel Permeation Chromatography (GPC (0 to 100,000 g/mol)) was measured.

(2) FT-IR (Fourier Transform-Infrared Spectrometer) measurement

The phosphorus-based flame-retardant polymer prepared in Example 1 and Comparative Example 1 was measured using an FT-IR measuring instrument (Perkin Elmer, Spectrum 100).

(3) Measurement of phosphorus content

The phosphorus content of the phosphorus-based flame-retardant polymers prepared in Examples and Comparative Examples was measured using an ICP device and Equation 1 below:

[Equation 1]

Phosphorus content (% by weight) = (W ₁ x P ₁ ) / W ₂

(In Equation 1 above,

W ₁ is the weight (g) of Comparative Example 1,

W ₂ is the weight (g) of the sample to be measured,

P ₁ is the phosphorus content (% by weight) of Comparative Example 1.)

(4) Viscosity measurement

Viscosity was measured using the phosphorus-based flame retardant polymer Rheometer (TA Instruments AR2000) prepared in Examples and Comparative Examples.

(5) Differential Scanning Calorimeters (DSC) measurement

50 g of the phosphorus-based flame retardant polymer prepared in Examples and Comparative Examples, 100 g of phenol novolac epoxy resin (KEP-1138, manufactured by Kolon Industries Co., Ltd.), 2-Ethyl-4-methyl imidazole (2E4MZ) as a curing accelerator A varnish was prepared by mixing 0.14 phr of solid epoxy with the remainder, 1-methoxy-2-propanol as a solvent. The varnish thus prepared was impregnated with glass fibers, dried naturally at room temperature for 1 hour, and then dried in an oven at 155° C. for 5 minutes to prepare a prepreg. The prepreg thus prepared was prepared by laminating copper foil on the front and back of 8 layers, and ^{pressing at 195° C. under 40 kgf/cm 2} pressure for 120 minutes. The copper clad laminate thus obtained was measured at a temperature increase rate of 20°C per minute at 30-250°C using a TA Instruments DSC Q2000.

(6) Measurement of dielectric properties

The dielectric properties of the copper clad laminate prepared in (5) were measured using a split post dielectric resonance (SPDR) method, and the dielectric constant and dielectric loss factor at 1 GHz were measured using an Agiletn E5071B ENA device at 25°C and 50%RH. measured.

(7) flame retardancy measurement

It was measured by the UL-94 method.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Weight average molecular weight (g/mol) 1570 1200 665 663 1280 Phosphorus content (wt%) 8.0 7.4 8.0 8.0 8.8 Viscosity (cps, 25℃) 1100 850 1000 950 1270 Glass transition temperature (℃) 158 164 154 157 171 dielectric properties permittivity 3.12 3.78 3.36 3.12 3.80 dielectric loss factor 0.0076 0.0150 0.020 0.0150 0.0160 flame retardant V-0 V-0 V-0 V-0 V-0

As shown in Table 1, the phosphorus-based flame-retardant polymer according to the present invention has a flame retardancy equivalent to that of the phosphorus-based flame-retardant polymer of Comparative Example 1, and at the same time exhibits a lower dielectric constant and dielectric loss coefficient than Comparative Example 1, thereby having low dielectric properties. can be checked

Specifically, referring to FIG. 3 , in the case of the phosphorus-based flame-retardant polymer of Example 1 according to the present invention, the hydroxyl group peak present at ^{3,247 cm -1} was reduced compared to Comparative Example 1, and the carbonyl group present at ^{1,700 cm -1} has a C=O peak of From these results, it was confirmed that, in the phosphorus-based flame retardant polymer of Example 1, the hydroxyl group in the molecular structure was substituted with a functional group including a carbonyl group, and thus, the dielectric properties were improved.

Claims (9)

It includes one or more of the repeating units represented by the following Chemical Formulas 1 and 2, wherein _{at least one of R 1} in the entire repeating unit is a carbonyl group,
A phosphorus-based flame-retardant polymer in which the ratio of the carbonyl group in the _{total R 1} in the entire repeating unit is 20 to 100%:
[Formula 1]

[Formula 2]

(In Formulas 1 and 2,
R ₁ is each independently hydrogen,

or

ego;
R ₂ is each independently a C1-C20 alkyl group or a C6-C20 aryl group;
R ₃ is each independently —CH ₂ —A, wherein A is a hydroxyl group, a C1-C10 alkoxy group, or

However, A in the repeating unit at least one or more of

ego;
R ₄ is each independently a simple bond, -CH ₂ - or -CH ₂ -O-CH ₂ -,
R ₅ is a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, or a C5-C20 heteroaryl group;
R ₆ is a C1-C20 alkylene group, a C2-C20 alkenylene group, a C3-C20 cycloalkylene group, or a C6-C20 arylene group;
R ₇ is a carboxyl group (-C(=O)OH) or a haloformyl group (-C(=O)X), wherein X is a halogen element;
R _a is a simple bond or a C1-C10 alkylene group, a C6-C20 arylene group, a C3-C20 cycloalkylene group, or a sulfonyl group (-SO ₂ -, sulfonyl group);
each m is independently an integer from 1 to 2;
n is each independently an integer of 0 or 1, but at least two or more of n in the repeating unit is 1.). According to claim 1,
The repeating unit is at least one selected from repeating units represented by the following Chemical Formulas 3 to 9, a phosphorus-based flame retardant polymer:
[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

(In Formulas 3 to 9,
R ₁ is each independently hydrogen,

or

ego;
R ₂ is each independently a C1-C20 alkyl group or a C6-C20 aryl group;
R ₃ is each independently —CH ₂ —A, wherein A is a hydroxyl group, a C1-C10 alkoxy group, or

However, A in the repeating unit at least one or more of

ego;
R ₄ is each independently a simple bond, -CH ₂ - or -CH ₂ -O-CH ₂ -, _{except that R 4} is a simple bond;
R ₅ is a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, or a C5-C20 heteroaryl group;
R ₆ is a C1-C20 alkylene group, a C2-C20 alkenylene group, a C3-C20 cycloalkylene group, or a C6-C20 arylene group;
R ₇ is a carboxyl group (-C(=O)OH) or a haloformyl group (-C(=O)X), wherein X is a halogen element;
R _a is a simple bond or a C1-C10 alkylene group, a C6-C20 arylene group, a C3-C20 cycloalkylene group, or a sulfonyl group (-SO ₂ -, sulfonyl group);
m is each independently an integer of 1 to 2.). According to claim 1,
The phosphorus-based flame-retardant polymer is any one of the compounds represented by the following formulas 10 to 16, phosphorus-based flame-retardant polymer:
[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

(In Formulas 10 to 16,
R ₁ is each independently hydrogen,

or

ego;
R ₃ is each independently —CH ₂ —A, wherein A is a hydroxyl group, a C1-C10 alkoxy group, or

However, A in the repeating unit at least one or more of

ego;
R ₄ is each independently a simple bond, -CH ₂ - or -CH ₂ -O-CH ₂ -, _{except that R 4} is a simple bond;
R ₅ is a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, or a C5-C20 heteroaryl group;
R ₆ is a C1-C20 alkylene group, a C2-C20 alkenylene group, a C3-C20 cycloalkylene group, or a C6-C20 arylene group;
R ₇ is a carboxyl group (-C(=O)OH) or a haloformyl group (-C(=O)X), wherein X is a halogen element;
R′ and R″ are the same as or different from each other, and each independently represents hydrogen, a C1 to C10 alkyl group, a C3 to C20 cycloalkyl group, or a C6 to C20 aryl group;
A ₁ to A ₁₄ are the same as or different from each other, and each independently a hydroxyl group, a C1-C10 alkoxy group, or

is;
each m is independently an integer from 1 to 2;
p to z are rational numbers from 0 to 4.). delete According to claim 1,
The phosphorus-based flame-retardant polymer has a phosphorus content of 5.0 to 9.0% by weight based on the total weight of the polymer. According to claim 1,
The phosphorus-based flame-retardant polymer has a dielectric constant (D _k ) of less than 3.8 at 1 GHz, a phosphorus-based flame-retardant polymer. According to claim 1,
The phosphorus-based flame-retardant polymer has a dielectric loss coefficient (D _f ) of 0.015 or less at 1 GHz, a phosphorus-based flame-retardant polymer. A flame retardant resin composition comprising the phosphorus-based flame retardant polymer according to any one of claims 1 to 3 and 5 to 7. A printed circuit board manufactured using the flame-retardant resin composition according to claim 8.

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