JP2022539763A - End-capped phosphorus-containing resin with unsaturated group, method for producing the same, and resin composition containing phosphorus-containing resin end-capped with unsaturated group - Google Patents

Abstract

A terminal-capped phosphorus-containing resin, a method for producing the same, and a resin composition containing a terminal-capped phosphorus-containing resin, wherein the unsaturated group contained in the terminal reduces the dielectric constant And the dielectric loss factor can be reduced, but also shows an excellent level of flame retardancy based on the high phosphorus content.

Description

TECHNICAL FIELD The present invention relates to a terminal-capped phosphorus-containing resin, a method for producing the same, and a resin composition containing the terminal-capped phosphorus-containing resin.

Printed circuit boards (PCBs) on which specific electronic circuits are printed are used in various electronic products such as computers, semiconductors, displays, and communication devices. A wiring for signal transmission, an insulating layer for preventing a short circuit between wirings, a switching element, and the like are also formed on the substrate.

The printed circuit board can also be formed by laminating a prepreg, which is made by impregnating glass fiber with epoxy resin and forming a radius, on an inner layer circuit board on which a circuit is formed. Alternatively, it may be manufactured by a build-up method of manufacturing a board by stacking insulating layers on a circuit pattern of an inner layer circuit board on which a circuit is formed. Here, the build-up method forms via holes, increases the wiring density, and forms circuits by laser processing or the like, which is advantageous in increasing the density and thinning of the printed circuit board.

Recently, due to the trend toward lightness, thinness, shortness and miniaturization of electronic equipment, the printed circuit board has also been highly integrated and densified. Mechanical stability is an important factor.

In printed circuit boards, with the trend toward smaller, thinner, and higher performance electronic devices, there is a demand for realization of high-density wiring by narrowing the wiring pitch. Therefore, instead of the existing wire bonding method, a flip-chip connection method is mainly used in which the semiconductor device and the wiring substrate are joined by solder balls.

In the flip-chip connection method, solder balls are placed between the wiring board and the semiconductor device, and the whole is heated to cause the solder to reflow for bonding. ing.

In addition, due to the above-mentioned demand for high performance electronic equipment, there is a tendency for signals inside the electronic equipment to increase in speed and frequency. A transmission loss of an electric signal is proportional to a dielectric dissipation factor (D _f ) and frequency. The higher the frequency, the greater the transmission loss, causing signal attenuation and reduced reliability of signal transmission. In addition, transmission loss is converted into heat, causing a problem of heat generation. Therefore, there is a need for an insulating material with a smaller dielectric constant and dielectric loss factor than existing insulating materials.

However, it is not easy to reduce the dielectric constant and the dielectric loss factor of the epoxy resin composition and its cured product, which are often used as conventional insulating materials, due to their unique properties.

In relation to this, Korean Patent No. 10-1596992 discloses a halogen-free flame-retardant polymer having excellent impregnability, adhesive strength, flame retardancy, and compatibility with other polymers, and a method for producing the same. ing.

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

In the case of the flame-retardant polymers or active ester resins presented by them, the flame-retardant properties of the final cured product were improved to a certain level, but the effect was not sufficient, and the dielectric properties were not considered.

Accordingly, the technical problem to be solved by the present invention includes a resin that simultaneously satisfies flame retardancy and dielectric properties by capping the end of a phosphorus-based flame-retardant resin with an unsaturated group, a method for producing the same, and the same. It is to provide a resin composition.

One aspect of the present invention relates to a terminal-capped phosphorus-containing resin containing a compound represented by Formula 1 below.

<Chemical Formula 1>

In Formula 1, X ₁ and X ₂ are the same or different from each other and are each independently represented by hydrogen, a hydroxy group, or Chemical Formula 2 or Chemical Formula 3 below,
At least one of X ₁ and X ₂ is represented by the following chemical formula 2 or the following chemical formula 3,
Y ₁ and Y ₂ are the same as or different from each other and are represented by any one of the following chemical formulas 4 to 8,
R ₁ ′ is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
n1 is an integer from 1 to 15;

<Chemical Formula 2>

であり、 In Formula 2, R ₂ ' is hydrogen, C ₁ -C ₈ alkyl, or

and

said R ₃ ' is hydrogen or C ₁ -C ₈ alkyl;
m1 is an integer of 0 or 1, m2 is an integer of 0 to 5,
when m2 is 2 or more, two or more R ₃ ′ are the same or different,

<Chemical Formula 3>

<Chemical Formula 4>

In Formula 4, R ₁ to R ₄ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ —C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
said a1 and said b1 are each independently an integer of 0 to 4;
When said a1 is 2 or more, two or more _R1 are the same or different,
When said b1 is 2 or more, two or more _R2 are the same or different from each other,

<Chemical Formula 5>

wherein R ₉ to R ₁₄ are the same or different from each other and are hydrogen or C ₁ -C ₃ alkyl;

<Chemical Formula 6>

In Formula 6, R ₁₅ and R ₁₆ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ —C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
said a2 and said b2 are each independently an integer of 0 to 4;
When said a2 is 2 or more, two or more R ₁₅ are the same or different from each other,
When said b2 is 2 or more, two or more R ₁₆ are the same or different from each other,

<Chemical formula 7>

In Formula 7, R ₂₁ and R ₂₂ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ —C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
said a3 and said b3 are each independently an integer of 0 to 3;
When said a3 is 2 or more, two or more R ₂₁ are the same or different from each other,
When said b3 is 2 or more, two or more R ₂₂ are the same or different from each other,

<Chemical Formula 8>

wherein R ₂₅ is hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
a4 is an integer of 0 to 4;
When said a4 is 2 or more, two or more R ₂₅ are the same or different from each other.

Another aspect of the present invention is the step of providing a hydroxyl-terminated oligomeric phosphonate (S1) and reacting said hydroxyl-terminated oligomeric phosphonate with a reactant comprising an unsaturated group, the terminally unsaturated and (S2) preparing a phosphorus-containing resin capped with a group, wherein the unsaturated group is an acrylate or vinylbenzyl group. .

Yet another aspect of the present invention relates to a terminal-capped phosphorus-containing resin composition comprising a compound represented by Formula 1 below, a curing agent and a curing accelerator.

<Chemical Formula 1>

In Formula 1, X ₁ and X ₂ are the same or different from each other and are each independently hydrogen, a hydroxy group, or a compound represented by Chemical Formula 2 or Chemical Formula 3 below;
at least one of X ₁ and X ₂ is a compound represented by the following chemical formula 2 or the following chemical formula 3;
Y ₁ and Y ₂ are the same as or different from each other and are compounds represented by any one of the following chemical formulas 4 to 8;
R ₁ ′ is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
n1 is an integer from 1 to 15;

<Chemical Formula 2>

であり、
前記Ｒ_３’は、水素またはＣ_１－Ｃ_８アルキルであり、
前記ｍ１は、０または１の整数であり、ｍ２は、０ないし５の整数であり、
前記ｍ２が２以上である場合、２つ以上のＲ_３’は、互いに同一であるか、あるいは異なっており、 In Formula 2, R ₂ ' is hydrogen, C ₁ -C ₈ alkyl, or

and
said R ₃ ' is hydrogen or C ₁ -C ₈ alkyl;
m1 is an integer of 0 or 1, m2 is an integer of 0 to 5,
when m2 is 2 or more, two or more R ₃ ′ are the same or different,

<Chemical Formula 3>

<Chemical Formula 4>

In Formula 4, R ₁ to R ₄ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ —C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
said a1 and said b1 are each independently an integer of 0 to 4;
When said a1 is 2 or more, two or more _R1 are the same or different,
When said b1 is 2 or more, two or more _R2 are the same or different from each other,

<Chemical Formula 5>

wherein R ₉ to R ₁₄ are the same or different from each other and are hydrogen or C ₁ -C ₃ alkyl;

<Chemical Formula 6>

In Formula 6, R ₁₅ and R ₁₆ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ —C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
said a2 and said b2 are each independently an integer of 0 to 4;
When said a2 is 2 or more, two or more R ₁₅ are the same or different from each other,
When said b2 is 2 or more, two or more R ₁₆ are the same or different from each other,

<Chemical formula 7>

In Formula 7, R ₂₁ and R ₂₂ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ —C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
said a3 and said b3 are each independently an integer of 0 to 3;
When said a3 is 2 or more, two or more R ₂₁ are the same or different from each other,
When said b3 is 2 or more, two or more R ₂₂ are the same or different from each other,

<Chemical Formula 8>

wherein R ₂₅ is hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
a4 is an integer of 0 to 4;
When said a4 is 2 or more, two or more R ₂₅ are the same or different from each other.

Yet another aspect of the present invention provides a copper clad laminate manufactured using a phosphorus-containing resin composition capped with an unsaturated group at its ends.

The terminal-capped phosphorus-containing resin according to the present invention can not only reduce the dielectric constant and the dielectric loss factor due to the unsaturated groups contained in the terminal, but also, based on the high phosphorus content, Exhibits an excellent level of flame resistance.

1 is a graph showing the results of GPC (gel permeation chromatography) measurement of a terminally unsaturated group-capped phosphorus-containing resin produced in Example 1 of the present invention. 1 is a graph showing NMR (nuclear magnetic resonance) results of a terminal-capped phosphorus-containing resin prepared in Example 1 of the present invention;

Various aspects and various implementations of the present invention are described in greater detail below.

Terms and words used in the specification and claims are not to be construed as being limited to their general or lexical meaning, and the inventors intend to use their invention in the best possible manner. According to the principle that the concepts of terms can be properly defined for the purpose of explanation, they are interpreted to have meanings and concepts consistent with the technical idea of the present invention.

The terminology used in the present invention is merely used to describe particular embodiments and is not intended to limit the invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In the present invention, terms such as "including" or "having" designate that the features, numbers, steps, acts, components, parts, or combinations thereof described in the specification are present. and does not a priori exclude the possibility of the presence or addition of one or more other features, numbers, steps, acts, components, parts, or combinations thereof.

The terms "flame-retardant properties", "flame-retardant" or "flammable-resistant" as used in the present invention are intermediate between combustible and non-combustible, and refer to the properties of a material that is difficult to burn, resistant to It has the same meaning as flammability, flame resistance, smoke resistance, etc.

The term "alkyl group" as used herein refers to a linear or branched saturated monovalent radical of 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms. means a valent hydrocarbon group. The above alkyl group can be comprehensively referred to not only as unsubstituted one but also as a group further substituted with certain substituents described below. Examples of the alkyl group include methyl group, ethyl group, propyl group, 2-propyl group, n-butyl group, iso-butyl group, t-butyl group, pentyl group, hexyl group, dodecyl group, fluoromethyl group, difluoro A methyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, an iodomethyl group, a bromomethyl group and the like can be mentioned.

The term "alkenyl group" used in the present invention includes 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon-carbon double bonds containing one or more carbon-carbon double bonds. It means a linear or branched monovalent hydrocarbon radical of carbon atoms. The alkenyl group may be bonded via a carbon atom containing a carbon-carbon double bond or via a saturated carbon atom. The alkenyl group can be comprehensively referred to as not only unsubstituted alkenyl groups but also those further substituted with certain substituents described below. Examples of the alkenyl group include ethenyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, pentenyl group, 5-hexenyl group and dodecenyl group.

The term "alkynyl group" used in the present invention includes 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms containing one or more carbon-carbon triple bonds. means a linear or branched monovalent hydrocarbon radical of The alkynyl group may be attached through a carbon atom containing a carbon-carbon triple bond or through a saturated carbon atom. The alkynyl group can be collectively referred to as those further substituted with certain substituents described later. Examples of the alkynyl group include an ethynyl group and a propynyl group.

The term "cycloalkyl group" as used herein refers to a monovalent monocyclic, bicyclic or tricyclic non- It means an aromatic hydrocarbon group, and can be comprehensively referred to as those further substituted with certain substituents described later. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantyl, norbornyl (i.e., piccyclo[2, 2,1]hept-5-enyl) and the like.

The term "aryl group" as used in the present invention refers to a monovalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon group having 6 to 40, preferably 6 to 20 ring atoms. and those further substituted by certain substituents described later can be collectively referred to. Examples of the aryl group include a phenyl group, a biphenyl group, and a fluorene group.

In the present invention all compounds or substituents are also substituted or unsubstituted unless otherwise stated. Here, substituted means that a hydrogen atom is a halogen atom, a hydroxy group, a carboxyl group, a cyano group, a nitro group, an amino group, a thio group, a methylthio group, an alkoxy group, a nitrile group, an aldehyde group, an epoxy group, ether group, ester group, carbonyl group, acetal group, ketone group, alkyl group, perfluoroalkyl group, cycloalkyl group, heterocycloalkyl group, allyl group, benzyl group, aryl group, heteroaryl group, derivatives thereof, and It means one substituted with any one selected from the group consisting of combinations thereof.

Recently, due to the trend of miniaturization and high performance of electronic devices and communication devices, the signal transmission speed in these products has increased, and the frequency band of signals used has moved from the MHz range to the GHz range. However, when the signal frequency increases, not only does the amount of signal loss increase, but also noise increases, making it difficult to ensure reliability of signal transmission, and transmission loss is converted into heat. , causing a heat problem. However, epoxy resin, which is widely used as an insulating material for existing printed circuit boards, has a high dielectric constant and dielectric loss factor, so it is difficult to apply to miniaturized and highly integrated printed circuit boards. ,There is a limit. Therefore, there is a need for an insulating material that simultaneously has low dielectric properties and excellent flame retardant properties in keeping with the technical trend of eliminating halogen-based flame retardants as the speed and frequency of electronic devices increase.

Therefore, in the present invention, by substituting the terminals of a phosphorus-based flame-retardant resin with an unsaturated group, a resin that secures high flame retardancy and low dielectric properties is presented.

One aspect of the present invention provides a terminal-capped phosphorus-containing resin comprising a compound represented by Formula 1 below.

<Chemical Formula 1>

In Formula 1, X ₁ and X ₂ are the same or different from each other and are each independently represented by hydrogen, a hydroxy group, or Chemical Formula 2 or Chemical Formula 3 below,
At least one of X ₁ and X ₂ is represented by the following chemical formula 2 or the following chemical formula 3,
Y ₁ and Y ₂ are the same as or different from each other and are represented by any one of the following chemical formulas 4 to 8,
R ₁ ′ is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
n1 is an integer from 1 to 15;

<Chemical Formula 2>

であり、
前記Ｒ_３’は、水素またはＣ_１－Ｃ_８アルキルであり、
前記ｍ１は、０または１の整数であり、ｍ２は、０ないし５の整数であり、
前記ｍ２が２以上である場合、２つ以上のＲ_３’は、互いに同一であるか、あるいは異なっており、 In Formula 2, R ₂ ' is hydrogen, C ₁ -C ₈ alkyl, or

and
said R ₃ ' is hydrogen or C ₁ -C ₈ alkyl;
m1 is an integer of 0 or 1, m2 is an integer of 0 to 5,
when m2 is 2 or more, two or more R ₃ ′ are the same or different,

<Chemical Formula 3>

<Chemical Formula 4>

In Formula 4, R ₁ to R ₄ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ —C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
said a1 and said b1 are each independently an integer of 0 to 4;
When said a1 is 2 or more, two or more _R1 are the same or different,
When said b1 is 2 or more, two or more _R2 are the same or different from each other,

<Chemical Formula 5>

wherein R ₉ to R ₁₄ are the same or different from each other and are hydrogen or C ₁ -C ₃ alkyl;

<Chemical Formula 6>

In Formula 6, R ₁₅ and R ₁₆ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ —C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
said a2 and said b2 are each independently an integer of 0 to 4;
When said a2 is 2 or more, two or more R ₁₅ are the same or different from each other,
When said b2 is 2 or more, two or more R ₁₆ are the same or different from each other,

<Chemical Formula 7>

In Formula 7, R ₂₁ and R ₂₂ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ —C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
said a3 and said b3 are each independently an integer of 0 to 3;
When said a3 is 2 or more, two or more R ₂₁ are the same or different from each other,
When said b3 is 2 or more, two or more R ₂₂ are the same or different from each other,

<Chemical Formula 8>

wherein R ₂₅ is hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
a4 is an integer of 0 to 4;
When said a4 is 2 or more, two or more R ₂₅ are the same or different from each other.

In Chemical Formulas 2 to 8, * indicates a bonding position with an adjacent atom.

The terminal-capped phosphorus-containing resin of the present invention not only has the inherent flame retardancy exhibited by the phosphorus-containing resin, but also has a reactive terminal unsaturated group, which makes the resin composition It has the advantage of being able to participate in curing through a cross-linking reaction with other products added for manufacturing. In addition, the acrylate group of Chemical Formula 2 and the vinylbenzyl group of Chemical Formula 3, which are end-capping unsaturated groups, have shorter chain lengths than other unsaturated groups, and are therefore advantageous in forming crosslinks. be.

Furthermore, in the case of a phosphonate having a general structure, since it acts as a simple additive, there is a problem that heat resistance and dielectric properties are deteriorated after curing. , since it can participate in the role of cross-linking, it has the advantage of no loss of heat resistance and dielectric properties after curing.

For example, Formula 4 can be represented by Formula 4-1 below.

<Chemical Formula 4-1>

In Formula 4-1, R ₃ to R ₈ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ —C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl.

Also, Formula 6 can be represented by Formula 6-1 below.

<Chemical Formula 6-1>

In Formula 6-1, R ₁₇ to R ₂₀ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ - C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl.

The chemical formula 7 can be represented, for example, by the following chemical formula 7-1.

<Chemical Formula 7-1>

In Formula 7-1, R ₂₃ to R ₂₄ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ —C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl.

In Formula 1, R ₁ ′ is also preferably C ₁ -C ₆ alkyl, C ₂ -C ₅ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl or C ₆ -C ₁₂ aryl. , more preferably a methyl group, an ethyl group, a methylene group, an ethylene group, a cyclohexane group, a phenyl group, and _a naphthyl group, and most preferably a methyl group and a phenyl group. This is because when it corresponds to the functional groups described above, it has excellent compatibility with other resins and solvents used in forming the composition.

In one embodiment, Y ₁ and Y ₂ in Formula 1 are the same or different, and are also compounds represented by any one of Formulas 9 to 16 below.

<Chemical Formula 9>

<Chemical Formula 10>

<Chemical Formula 11>

<Chemical Formula 12>

<Chemical Formula 13>

<Chemical Formula 14>

<Chemical formula 15>

<Chemical Formula 16>

Preferably, in Formula 1, R ₁ ' is C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl. , n1 is an integer of 1 to 8; in Formula 2, R ₂ ' is hydrogen or C ₁ -C ₈ alkyl; and in Formula 4, R ₁ to R ₄ are the same , or different and is hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl, in Formula 5 above , R ₉ to R ₁₄ are the same or different from each other and are hydrogen or methyl; in Formula 6, R ₁₅ and R ₁₆ are the same or different from each other, hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C _{6 alkynyl} , C ₃ -C ₁₂ cycloalkyl or C ₆ -C _{20 aryl} ; are the same or different from each other and are hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl; , wherein R ₂₅ is also hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ arylaryl .

In particular, n1 is preferably an integer of 1 to 8. If n1 exceeds 8, the molecular weight is relatively large, the viscosity is high, and the composition cannot have sufficient fluidity. This is because the moldability of the cured product is hindered.

As described above, the compound represented by Formula 1 has a high phosphorus content, and can impart flame retardancy like existing phosphorus-based compounds. However, general phosphorus-based flame retardants have no reactivity or low reactivity, which may cause a decrease in cured crosslink density and a significant decrease in the physical properties of the final cured product. In addition, the unsaturated group present in the compound represented by Chemical Formula 1 has excellent reactivity and can improve heat resistance.

In addition, X ₁ and X ₂ in Chemical Formula 1 are preferably compounds represented by Chemical Formula 2 or Chemical Formula 3 above. When both ends are compounds represented by the chemical formula 2 or the chemical formula 3, the low dielectric properties expressed by the unsaturated groups at the terminals are improved, and the reactivity is improved. A commercially viable gel time can be expected during the composition molding process.

The phosphorus content of the compound represented by Formula 1 is also 7 to 15% by weight based on the total weight of the compound. If the phosphorus content is less than 7% by weight, there are problems that flame retardancy and heat resistance are deteriorated, and there is a disadvantage that a large amount of flame retardant additive is required when blending the resin. If it exceeds, the reactivity will decrease, and there will be problems with compatibility and solubility in solvents and other products.

The compound represented by Formula 1 has a weight average molecular weight of 1,000 to 7,000 g/mol, preferably 1,500 to 4,000 g/mol. If the weight-average molecular weight is less than 1,000 g/mol, the effect of improving heat resistance and dielectric properties is insufficient, and if it exceeds 7,000 g/mol, the compatibility with solvents decreases, making application difficult. becomes.

The compound represented by Formula 1 also has a glass transition temperature of 170 to 210°C. It has excellent heat resistance in the glass transition temperature range.

According to a preferred embodiment, the terminal-capped phosphorus-containing resin is also represented by Formula 17-1, Formula 17-2, or Formula 17-3 below.

<Chemical Formula 17-1>

<Chemical Formula 17-2>

<Chemical Formula 17-3>

In Formula 17-1, Formula 17-2 or Formula 17-3, each R is independently C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl;
Each n2 is independently an integer from 1 to 8.

According to another preferred embodiment, the terminal-capped phosphorus-containing resin is also represented by Formula 18-1, Formula 18-2, or Formula 18-3 below.

<Chemical Formula 18-1>

<Chemical Formula 18-2>

<Chemical Formula 18-3>

In Formula 18-1, Formula 18-2 or Formula 18-3, each R is independently C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl;
Each n3 is independently an integer from 1 to 8.

According to another preferred embodiment, the terminal-capped phosphorus-containing resin is also represented by Formula 19-1, Formula 19-2, or Formula 19-3 below.

<Chemical Formula 19-1>

<Chemical Formula 19-2>

<Chemical formula 19-3>

In Formula 19-1, Formula 19-2 or Formula 19-3, each R is independently C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl;
Each n4 is independently an integer from 1 to 8.

According to another preferred embodiment, the terminal-capped phosphorus-containing resin may also be represented by Formula 20-1, Formula 20-2, or Formula 20-3 below.

<Chemical Formula 20-1>

<Chemical Formula 20-2>

<Chemical Formula 20-3>

In Formula 20-1, Formula 20-2 or Formula 20-3, each R is independently C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl;
Each n5 is independently an integer from 1 to 8.

As described above, the compounds represented by Chemical Formulas 17 to 20 have excellent reactivity due to the unsaturated groups present in the compounds and can improve heat resistance. In some cases, it has been found to have good compatibility with other resins and solvents used to form the composition.

The end-capped phosphorus-containing resin also has a dielectric constant (D _k ) at 1 GHz of less than 3.6. In addition, the terminal-capped phosphorus-containing resin has a dielectric loss factor (D _f ) at 1 GHz of less than 0.0050.

As described above, the end-capped phosphorus-containing resin of the present invention exhibits excellent low dielectric properties due to the structural features of introducing an acrylate group or a vinylbenzyl group into the end. can be shown. In addition, flame retardancy is greatly improved by including a phosphonate containing phosphorus in the repeating unit. In particular, as described above, the terminal-unsaturated group-capped phosphorus-containing resin of the present invention has a high phosphorus content of 7 to 15% by weight. It has the advantage of being able to satisfy the required phosphorus content even with a relatively small composition compared to other low resins.

Another aspect of the present invention is the step of providing a hydroxyl-terminated oligomeric phosphonate (S1) and reacting said hydroxyl-terminated oligomeric phosphonate with a reactant comprising an unsaturated group, the terminally unsaturated and (S2) preparing a phosphorus-containing resin capped with a group, wherein the unsaturated group is an acrylate or vinylbenzyl group. The manufacturing method is introduced into the purification process without a solidification process, and can effectively remove by-products and salts, so that it is easy to apply to industrial processes.

The reaction of step S2 is carried out in the presence of a catalyst, and the catalyst is an amine compound such as 4-dimethylaminopyridine, pyridine, triethylamine, aqueous ammonia, or an alkali metal oxide such as NaOH.KOH.LiOH.K. ₂ CO ₃ , tetramethylammonium hydroxide which is an ammonium compound, and AlCl ₃ which is an aluminum compound, or a mixture of two or more. In particular, when an alkali metal oxide is used, its suitable concentration is 0 to 50% by mass.

When using a catalyst containing water, the reaction is preferably performed in the presence of a phase transfer catalyst. In particular, when using an alkali metal hydroxide, it is desirable to carry out the reaction under a phase transfer catalyst. The phase transfer catalyst serves to bring the alkali metal hydroxide from the polar solvent to the non-polar solvent when reacting in a polar solvent phase such as water and a non-polar solvent phase.

Specifically, when an aqueous solution of sodium hydroxide is used as a catalyst for an organic solvent such as toluene as an alkali metal hydroxide, it becomes difficult to contribute to the acceleration of the reaction without a phase transfer catalyst.

The phase transfer catalyst may be, but is not limited to, quaternary ammonium salts such as tetra-n-butylammonium chloride (TBAC) and tetra-n-butylammonium bromide (TBAB).

The unsaturated group-containing reactant includes methacryloyl halide, methacrylic anhydride (MAAH), acrylic anhydride, methacrylic acid, acrylic acid, 4-vinylbenzyl halide, and a mixture of 4-vinylbenzyl alcohol and 2-vinylbenzyl alcohol. any one, or a mixture of two or more. The methacryloyl halide can be selected from the group consisting of methacryloyl fluoride, methacryloyl chloride, methacryloyl bromide, methacryloyl iodide, and combinations thereof, and the 4-vinylbenzyl halide or 2-vinylbenzyl halide can be a vinyl It can be selected from the group consisting of benzyl fluoride, vinylbenzyl chloride, vinylbenzyl bromide, vinylbenzyl iodide, and combinations thereof.

The reactant containing the unsaturated group may desirably be methacrylic anhydride or a mixture of 4-vinylbenzyl chloride and 2-vinylbenzyl chloride, but is presented This is because it has the effect of making the reaction proceed more easily than other reactants.

In the step S2, the reactant containing the unsaturated group may be added at a content of 0.5 to 5 equivalents based on 1 equivalent of the hydroxyl group of the oligomeric phosphonate. If it is less than the above range, the amount of unsaturated groups is remarkably small, and if it exceeds the above range, the surplus unreacted product deteriorates the quality of the resin to be produced, unnecessarily increasing the production cost, which is desirable. do not have.

In the step S2, the reaction may be performed at a temperature of 50°C to 90°C. If the temperature is less than 50° C., the reaction rate is too slow, requiring a long period of time to prepare the resin.

The solvent for the step S2 reaction is not particularly limited as long as it does not inhibit the reaction with the compound. In particular dimethylaniline, acetonitrile, dimethylformamide (DMF), toluene, xylene, methylene chloride, chlorobenzene, cyclohexane, cyclohexanol, tetrahydrofuran (THF), acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK), if enumerated. It can be any one selected from or a mixture of two or more. Among them, a non-polar solvent such as toluene or xylene is preferable because it can improve the efficiency of a smooth purification process of the polymer.

A purification step (S3) may be included for removing unreacted substances from the unsaturated group-capped phosphorus-containing resin in step S2 using an alkali compound. The purification step may vary slightly depending on the type of reactants, but is mainly performed to remove the generated salt and its by-products. For example, an aqueous NaOH solution may be used as the alkaline compound. can.

The hydroxyl-terminated oligomeric phosphonate is also represented by Formula 21 below.

<Chemical Formula 21>

Y ₁ and Y ₂ in Chemical Formula 21 are the same or different and are compounds represented by any one of Chemical Formulas 4 to 8 below;
R4′ is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
n6 is an integer from 1 to 15;

<Chemical Formula 4>

In Formula 4, R ₁ to R ₄ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ —C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
said a1 and said b1 are each independently an integer of 0 to 4;
When said a1 is 2 or more, two or more _R1 are the same or different,
When said b1 is 2 or more, two or more _R2 are the same or different from each other,

<Chemical Formula 5>

wherein R ₉ to R ₁₄ are the same or different from each other and are hydrogen or C ₁ -C ₃ alkyl;

<Chemical Formula 6>

In Formula 6, R ₁₅ and R ₁₆ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ —C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
said a2 and said b2 are each independently an integer of 0 to 4;
When said a2 is 2 or more, two or more R ₁₅ are the same or different from each other,
When said b2 is 2 or more, two or more R ₁₆ are the same or different from each other,

<Chemical formula 7>

In Formula 7, R ₂₁ and R ₂₂ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ —C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
said a3 and said b3 are each independently an integer of 0 to 3;
When said a3 is 2 or more, two or more R ₂₁ are the same or different from each other,
When said b3 is 2 or more, two or more R ₂₂ are the same or different from each other,

<Chemical Formula 8>

wherein R ₂₅ is hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
a4 is an integer of 0 to 4;
When said a4 is 2 or more, two or more R ₂₅ are the same or different from each other.

In addition, Y ₁ and Y ₂ in Formula 21 are the same or different from each other, and are also compounds represented by any one of Formulas 9 to 16 below.

<Chemical Formula 9>

<Chemical Formula 10>

<Chemical Formula 11>

<Chemical Formula 12>

<Chemical Formula 13>

<Chemical Formula 14>

<Chemical formula 15>

<Chemical Formula 16>

Yet another aspect of the present invention provides a terminal-capped phosphorus-containing resin composition comprising the compound represented by Formula 1, a curing agent and a curing accelerator.

Preferably, in Formula 1, R ₁ ' is C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl. , n1 is an integer of 1 to 8; in Formula 2, R ₂ ' is hydrogen or C ₁ -C ₈ alkyl; and in Formula 4, R ₁ to R ₄ are the same , or different and is hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl, in Formula 5 above , R ₉ to R ₁₄ are the same or different from each other and are hydrogen or methyl; in Formula 6, R ₁₅ and R ₁₆ are the same or different from each other, hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C _{6 alkynyl} , C ₃ -C ₁₂ cycloalkyl or C ₆ -C _{20 aryl} ; are the same or different from each other and are hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl; , wherein R ₂₅ is also hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl.

0.1 to 50 parts by weight of a curing agent and 0.0001 to 0.05 parts by weight of a curing accelerator may be included with respect to 100 parts by weight of the compound represented by Formula 1 above.

When the curing agent is within the above range, it has the advantage of having a suitable curing speed. If the amount of the curing accelerator is less than 0.0001 parts by weight, the curing reaction may not proceed smoothly.

The curing agent may be one commonly used in the field to which the present invention belongs, such as triallyl isocyanurate (TAIC) and bismaleimide. Although it is also triallyl isocyanurate, it is preferable because it contains two or more unsaturated groups in its structure, and effective cross-linking reaction can be carried out through the introduction of multi-functional groups.

As the curing accelerator, those commonly used in the field to which the present invention belongs can be used. For example, dicumyl peroxide (DCP), peroxides such as benzoyl peroxide, It can have common radical initiators such as nitriles.

The terminal-capped phosphorus-containing resin composition may further include a modified PPO (modified polyphenylene oxide) resin. Examples of the modified PPO resin include SA-9000 (manufactured by SABIC), which is a modified polyphenylene ether known to have excellent dielectric constant and dielectric properties, and to have excellent properties even in the ultra-high frequency range. , contained in the phosphorus-containing resin whose terminal is capped with an unsaturated group, not only assists the cross-linking reaction, but also has the effect of improving dielectric properties and heat resistance.

Yet another aspect of the present invention provides a copper clad laminate manufactured using the phosphorus-containing resin composition capped with an unsaturated group.

Hereinafter, the present invention will be described in more detail through examples. Those examples are merely for the purpose of more specifically describing the present invention, and the scope of the present invention is not limited by those examples. It will be obvious to those skilled in the art.

<Example 1: Production of a phosphorus-containing resin capped with a metal acrylic group (diphenyl P-methylphosphonate polymer with 4,4'-(1-methylethylidene)bis[phenol])>
Diphenyl P-methylphosphonate polymer with 4,4'-(1-methylethylidene)bis[phenol] was added to a nitrogen purged 3 L 3-necked flask. [phenol]) and 1,300.5 g of toluene, and 10 g of DMAP (4-dimethylaminopyridine; 4-dimethylaminopyridine) were added, and the temperature was raised to 75°C.

Then, 128.48 g of MAAH (methacrylic anhydride) was slowly added for 4 hours. After the addition was completed, the mixture was reacted at 75° C. for 20 hours and then cooled. After cooling, in order to remove unreacted raw materials, 1,938.98 g of water and 107.42 g of 50% NaOH were added as a purification reaction and stirred at 75° C. for 1 hour.

After the stirring was completed, the mixture was allowed to stand and liquid separation was performed. After removing water from the lower layer, 517 g of water was added and stirred. After stirring, phosphoric acid was added to set the pH to 5-6 level. After removing the neutralized water-washed layer, the toluene solvent was removed by degassing under vacuum pressure. At 70° C., the system was degassed to a degree of vacuum of 200 to 300 Torr to remove the reaction solvent, and then 214 g of MEK solvent was added.

The terminal-capped phosphorus-containing resin obtained as described above has a phosphorus content of 8.5% by mass and a molecular weight of 28.78 g/mol as a result of GPC (gel permeation chromatography) measurement. and the structure was confirmed using nuclear magnetic resonance (NMR) spectroscopy. FIG. 1 shows the GPC measurement results of Example 1 of the present invention, and FIG. 2 shows the NMR measurement results.

<Example 2: Production of phosphorus-containing resin capped with vinylbenzyl group (diphenyl P-methylphosphonate polymer with 4,4'-(1-methylethylidene)bis[phenol]) >
Diphenyl P-methylphosphonate polymer with 4,4'-(1-methylethylidene)bis[phenol] was added to a nitrogen purged 3 L 3-necked flask. [phenol]) 500 g (0.66 mol) and toluene 1300.5 g, TBAB (tetra-n-butylammonium bromide) 2.5 g, vinyl benzyl chloride mixture (2-vinylbenzyl chloride / 4-vinylbenzyl After adding 111 g of chloride=2/8 (2-vinylbenzyl chloride/4-vinylbenzyl chloride=2/8), the temperature was raised to 75.degree.

Next, 69 g of a 50% sodium hydroxide aqueous solution was gradually added for 1 hour. After the addition was completed, the mixture was reacted at 75° C. for 20 hours and then cooled. After cooling, in order to remove unreacted raw materials, 1,938.98 g of water and 107.42 g of 50% NaOH were added as a purification reaction and stirred at 75° C. for 1 hour.

After the stirring was completed, the mixture was allowed to stand and liquid separation was performed. After removing water from the lower layer, 517 g of water was added and stirred. After stirring, phosphoric acid was introduced and the pH was set to a level of 5-6. After removing the neutralized water-washed layer, the toluene solvent was removed by degassing under vacuum pressure. After degassing at 70° C. to a degree of vacuum of 200 to 300 Torr to remove the reaction solvent, 214 g of toluene solvent was added.

The terminal-capped phosphorus-containing resin obtained as described above had a phosphorus content of 8.0 mass % and a molecular weight of 3,100 g/mol as a result of GPC measurement. The structure was confirmed using nuclear magnetic resonance spectroscopy and FT-IR (Fourier transform infrared spectroscopy).

<Example 3: Production of phosphorus-containing resin capped with methacrylic group (poly(m-phenylene methylphosphonate)>
A nitrogen-purged 3 L three-ball flask was charged with 500 g (0.66 mol) of poly(m-phenylene methylphosphonate) and 1,300.5 g of toluene, and DMAP (4 -dimethylaminopyridine; 4-dimethylaminopyridine) was added, and then the temperature was raised to 75°C.

Then 113.48 g of MAAH was slowly introduced for 2 hours. After the addition was completed, the mixture was reacted at 75° C. for 20 hours and then cooled. After cooling, in order to remove unreacted raw materials, 1,938.98 g of water and 107.42 g of 50% NaOH were added as a purification reaction and stirred at 75° C. for 1 hour.

After the stirring was completed, the mixture was allowed to stand and liquid separation was performed. After removing water from the lower layer, 517 g of water was added and stirred. After stirring, phosphoric acid was added to set the pH to 5-6 level. After removing the neutralized water-washed layer, the toluene solvent was degassed and removed under reduced pressure. After degassing at 70° C. to a degree of vacuum of 200 to 300 Torr to remove the reaction solvent, 214 g of MEK solvent was added.

The terminal-capped phosphorus-containing resin obtained as described above had a phosphorus content of 10.5% by weight, a molecular weight of 2,127 g/mol as determined by GPC, and a nuclear magnetic resonance The structure was confirmed using analytical methods and FT-IR.

<Example 4: Production of phosphorus-containing resin capped with vinylbenzyl group (poly(m-phenylene methylphoshponate)>
A nitrogen purged 3 L 3-ball flask was charged with 500 g (0.66 mol) of poly(m-phenylene methylphosphonate) and 1,300.5 g of toluene, followed by TBAB. After adding 5 g and 111 g of a vinylbenzyl chloride mixture (2-vinylbenzyl chloride/4-vinylbenzyl chloride = 2/8 (2-vinylbenzyl chloride/4-vinylbenzyl chloride = 2/8)), the temperature was raised to 75°C. rice field.

Next, 69 g of a 50% sodium hydroxide aqueous solution was gradually added for 1 hour. After the addition was completed, the mixture was reacted at 75° C. for 20 hours and then cooled. After cooling, in order to remove unreacted raw materials, 1,938.98 g of water and 107.42 g of 50% NaOH were added as a purification reaction and stirred at 75° C. for 1 hour.

After the stirring was completed, the mixture was allowed to stand and liquid separation was performed. After removing water from the lower layer, 517 g of water was added and stirred. After stirring, phosphoric acid was introduced and the pH was set to a level of 5-6. After removing the neutralized water-washed layer, the toluene solvent was degassed and removed under reduced pressure. After degassing at 70° C. to a degree of vacuum of 200 to 300 Torr to remove the reaction solvent, 214 g of toluene solvent was added.

The terminal-capped phosphorus-containing resin obtained as described above had a phosphorus content of 9.5 mass % and a molecular weight of 2,442 g/mol as a result of GPC measurement. The structure was confirmed using nuclear magnetic resonance spectroscopy and FT-IR.

<Comparative Example 1: Use of commercial phosphorus-containing resin>
A commercial phosphorus-containing resin, SPV-100 (Otsuka Chemical Co., Ltd.) was used.

<Production of Phosphorus-Containing Resin Composition End Capped with an Unsaturated Group>
The phosphorus content in the terminal-capped phosphorus-containing resin composition of Examples 1 to 4 was adjusted to 2.5% by mass, and the terminal-capped phosphorus-containing resin composition (varnish ) were mixed in the amounts shown in Table 1 below.

The specific contents of manufacturing the varnish are as follows.

TAIC (triallyl isocyanurate), which is a polyfunctional group, is used as the curing agent, and SA-9000 (SABIC Co., Ltd.), a polyphenylene ether resin known to have excellent dielectric constant and dielectric properties, is used. and the SA-9000 (SABIC) weight was adjusted to match the phosphorus content in the varnish. DCP (dicumylperoxide) was used as a curing accelerator, and its amount was injected to SA-9000 at 5,000 ppm. In addition, MEK (methyl ethyl ketone) was added to adjust the solid content of the varnish to 60% by weight.

<Production of commercial phosphorus-containing resin composition>
, except that the commercial (commercially available) phosphorus-containing resin of Comparative Example 1 was used instead of the end-capped phosphorus-containing resin composition of Examples 1-4. As part of the preparation of an end-capped phosphorus-containing resin composition, a commercial phosphorus-containing resin composition was prepared in the same manner as described. Table 1 below shows the compounding ratios of the resin compositions including Examples 1 to 4 and Comparative Example 1.

<Test example: physical property evaluation method>
(1) Measurement of Weight Average Molecular Weight (Mw) Polystyrene conversion weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) (Waters: Waters 707). The polymer to be measured was dissolved in tetrahydrofuran so as to have a concentration of 4,000 ppm, and 100 μl of the solution was injected into GPC. The GPC mobile phase used tetrahydrofuran, flowed in at a flow rate of 1.0 mL/min, and the analysis was performed at 35°C. The columns were Waters HR-05, 1, 2 and 4E connected in series. As a detector, an RI and PAD detector was used, and measurements were made at 35°C.

(2) Phosphorus content measurement The phosphorus content in the resin is determined by acid decomposition with an ICP emission spectrometer (ICP-OES), referring to US EPA 3052 (requested by Intertec Testing Services Korea Ltd., US EPA 3052) ( With reference to US EPA 3052, by acid digestion and determined by ICP-OES)). The phosphorus content of the varnish was calculated and derived based on the resin content in the varnish.

(3) NMR measurement
Measurements were taken using Avance 500 (Brucker) equipment.

(4) Preparation of prepreg A varnish was impregnated with glass fibers, air-dried at room temperature for 1 hour, and then dried in an oven at 155°C to prepare a prepreg.

(5) Manufacture of copper clad laminate 6 sheets of the prepreg manufactured as described above were piled up, covered with copper foil (1 ounce) on both sides, and pressed at 195°C under a pressure of 40 kgf/ ^cm2 for 120 minutes. manufactured by

(6) Dielectric constant measurement After cutting the produced copper clad laminate into 1 cm × 1 cm, peel off the copper foil, using Agilent E4991A RF Impedance / Material Analyzer under the condition of 1 GHz, the dielectric constant ( _Dk ) and dielectric loss (D _f ) were measured. Specific measurement conditions are as follows.

Measurement frequency: 1GHz
Measurement temperature: 25-27°C
Measurement humidity: 45-55%
Measurement sample thickness: 1.5 mm

(7) Glass transition temperature (Tg) measurement The copper foils produced in Examples 1 to 4 and Comparative Example 1 above were subjected to DSC measurement using a TA Instruments DSC Q2000 at 30°C to 350°C at 20°C per minute. It was measured at the rate of temperature increase.

(8) Flame retardancy measurement Measured according to the UL-94 method.

The physical properties measured by the above method are shown in Table 2 below.

As can be seen from Table 2, the resins of Examples 1 to 4 have a shorter gelation time than Comparative Example 1, which indicates that they participate in curing more than Comparative Example 1 through a cross-linking reaction. means. It was confirmed that the glass transition temperature and dielectric properties, which are important physical properties, are excellent. Therefore, the terminal-capped phosphorus-containing resin according to the present invention can not only reduce the dielectric constant and dielectric loss factor due to the unsaturated groups contained in the terminal, but also has a high phosphorus content. shows an excellent level of flame retardancy.

The aforementioned examples and comparative examples are examples for explaining the present invention, and the present invention is not limited to them. A person skilled in the art to which the present invention pertains can implement the present invention with various modifications, so the technical protection scope of the present invention is defined by the claims.

The terminal-capped phosphorus-containing resin according to the present invention can not only reduce the dielectric constant and the dielectric loss factor due to the unsaturated groups contained in the terminal, but also, based on the high phosphorus content, Exhibits an excellent level of flame resistance.

Claims (27)

A terminal-capped phosphorus-containing resin containing a compound represented by the following chemical formula 1:
<Chemical Formula 1>

In Chemical Formula 1, X ₁ and X ₂ are the same or different, and are each independently represented by hydrogen, a hydroxy group, Chemical Formula 2 or Chemical Formula 3 below,
At least one of X ₁ and X ₂ is represented by the following chemical formula 2 or the following chemical formula 3,
Y ₁ and Y ₂ are the same or different from each other and are represented by any one of the following chemical formulas 4 to 8,
R ₁ ′ is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
n1 is an integer from 1 to 15;
<Chemical Formula 2>

In Formula 2, R ₂ ' is hydrogen, C ₁ -C ₈ alkyl, or

and
said R ³ ' is hydrogen or C ₁ -C ₈ alkyl;
m1 is an integer of 0 or 1, m2 is an integer of 0 to 5,
when m2 is 2 or more, two or more R3′ are the same or different,
<Chemical formula 3>

<Chemical Formula 4>

In Formula 4, R ₁ to R ₄ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ —C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
said a1 and said b1 are each independently an integer of 0 to 4;
When said a1 is 2 or more, two or more _R1 are the same or different,
When said b1 is 2 or more, two or more _R2 are the same or different from each other,
<Chemical Formula 5>

wherein R ₉ to R ₁₄ are the same or different from each other and are hydrogen or C ₁ -C ₃ alkyl;
<Chemical Formula 6>

In Formula 6, R ₁₅ and R ₁₆ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ - _C20 cycloalkyl or C6 _{- C20} aryl;
said a2 and said b2 are each independently an integer of 0 to 4;
When said a2 is 2 or more, two or more R ₁₅ are the same or different from each other,
When said b2 is 2 or more, two or more R ₁₆ are the same or different from each other,
<Chemical formula 7>

In Formula 7, R ₂₁ and R ₂₂ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ - _C20 cycloalkyl or C6 _{- C20} aryl;
said a3 and said b3 are each independently an integer of 0 to 3;
When said a3 is 2 or more, two or more R ₂₁ are the same or different from each other,
When said b3 is 2 or more, two or more R ₂₂ are the same or different from each other,
<Chemical Formula 8>

wherein R ₂₅ is hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
a4 is an integer of 0 to 4;
When said a4 is 2 or more, two or more R ₂₅ are the same or different from each other. [Claim ₁ ] wherein Y1 and Y2 in Chemical Formula ₁ are the same or different from each other and are compounds represented by any one of Chemical Formulas 9 to 16 below; An end-capped phosphorus-containing resin according to:
<Chemical Formula 9>

<Chemical Formula 10>

<Chemical Formula 11>

<Chemical Formula 12>

<Chemical Formula 13>

<Chemical Formula 14>

<Chemical Formula 15>

<Chemical Formula 16>

wherein R ₁ ′ is C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl;
n1 is an integer from 1 to 8;
wherein R ₂ ' is hydrogen or C ₁ -C ₈ alkyl;
In Formula 4, R ₁ to R ₄ are the same or different, hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ - C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl;
wherein R ₉ to R ₁₄ are the same or different from each other and are hydrogen or methyl;
In Formula 6, R ₁₅ and R ₁₆ are the same or different, hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ - C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl;
In Formula 7, R ₂₁ and R ₂₂ are the same or different, hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ - C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl;
wherein R ₂₅ is hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl; The end-capped phosphorus-containing number according to claim 1 with an unsaturated group. The phosphorus content of the compound represented by Formula 1 is 7 to 15% by weight based on the total weight of the compound, and the phosphorus content is end-capped with an unsaturated group according to claim 1. The terminal-unsaturated group-capped phosphorus-containing compound according to claim 1, wherein the compound represented by Formula 1 has a weight average molecular weight of 1,000 to 7,000 g/mol. The compound represented by Formula 1 is the terminal unsaturated group-capped phosphorus compound according to claim 1, having a glass transition temperature of 170 to 210°C. [Claim 1] [Chemical Formula 1] [Chemical Formula 1] [Chemical Formula 1] [Chemical Formula 1] [Chemical Formula 1] [Chemical Formula 1] [Chemical Formula 1] [Chemical Formula 1] [Chemical Formula 1]
<Chemical Formula 17-1>

<Chemical Formula 17-2>

<Chemical Formula 17-3>

In Formula 17-1, Formula 17-2, or Formula 17-3, each R is independently C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl;
Each n2 is independently an integer from 1 to 8. 2. The terminal-capped phosphorus-containing resin according to claim 1, wherein the chemical formula 1 is represented by the following chemical formula 18-1, the following chemical formula 18-2, or the following chemical formula 18-3:
<Chemical Formula 18-1>

<Chemical Formula 18-2>

<Chemical Formula 18-3>

In Formula 18-1, Formula 18-2 or Formula 18-3, each R is independently C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl;
Each n3 is independently an integer from 1 to 8. The terminal-capped phosphorus-containing resin according to claim 1, wherein the chemical formula 1 is represented by the following chemical formula 19-1, the following chemical formula 19-2, or the following chemical formula 19-3:
<Chemical Formula 19-1>

<Chemical Formula 19-2>

<Chemical formula 19-3>

In Formula 19-1, Formula 19-2, or Formula 19-3, each R is independently C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl;
Each n4 is independently an integer from 1 to 8. The terminal-capped phosphorus-containing resin according to claim 1, wherein the chemical formula 1 is represented by the following chemical formula 20-1, the following chemical formula 20-2, or the following chemical formula 20-3:
<Chemical Formula 20-1>

<Chemical Formula 20-2>

<Chemical Formula 20-3>

In Formula 20-1, Formula 20-2 or Formula 20-3, each R is independently C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl;
Each n5 is independently an integer from 1 to 8. 2. The terminally unsaturated group-capped phosphorus-containing number of claim 1, wherein the terminally unsaturated group-capped phosphorus-containing resin has a dielectric constant ( _Dk ) at 1 GHz of less than 3.6. be. 2. The end-unsaturated group-capped phosphorus-containing number of claim 1, wherein the end-unsaturated group-capped phosphorus-containing resin has a dielectric loss factor (D _f ) at 1 GHz of less than 0.0050. is. providing a hydroxyl-terminated oligomeric phosphonate (S1);
reacting the hydroxyl-terminated oligomeric phosphonate with a reactant containing unsaturated groups to produce an end-capped phosphorus-containing resin (S2);
A method for producing an end-capped phosphorus-containing resin, wherein the unsaturated group is an acrylate or vinylbenzyl group. The step S2 reaction is carried out in the presence of a catalyst,
The catalyst is any one or two selected from ₄ -dimethylaminopyridine, pyridine, triethylamine, aqueous ammonia, NaOH, KOH, LiOH, _{K2CO3 ,} tetramethylammonium hydroxide and AlCl3. 14. The method for producing a terminal-capped phosphorus-containing resin according to claim 13, which is a mixture of the above. Reactants containing unsaturated groups include methacryloyl halide, methacrylic anhydride, acrylic anhydride, methacrylic acid, acrylic acid, 4-vinylbenzyl halide, 4-vinylbenzyl alcohol, 2-vinylbenzyl halide and 2-vinylbenzyl alcohol. 14. The method for producing a terminal-unsaturated group-capped phosphorus-containing resin according to claim 13, which is any one selected from or a mixture of two or more thereof. [Claim 14] The terminally unsaturated group according to claim 13, wherein in the step S2, the reactant containing the unsaturated group is added in a content of 0.5 to 5 equivalents based on 1 equivalent of the hydroxyl group of the oligomeric phosphonate. A method for producing a phosphorus-containing resin capped with saturated groups. [Claim 14] The method of claim 13, wherein in the step S2, the reaction is performed at a temperature of 50 to 90[deg.]C. Solvents for the step S2 reaction are dimethylaniline, acetonitrile, dimethylformamide (DMF), toluene, xylene, methylene chloride, chlorobenzene, cyclohexane, cyclohexanol, methylhydrofuran (THF), acetone, methyl ethyl ketone (MEK) and methyl isobutyl. 14. The method for producing a terminal-unsaturated group-capped phosphorus-containing resin according to claim 13, which is any one or a mixture of two or more selected from ketones (MIBK). [Claim 14] The end-capped unsaturated group according to claim 13, comprising a purification step (S3) of removing unreacted substances from the unsaturated group-capped phosphorus-containing resin in step S2 using an alkali compound. A method for producing a phosphorus-containing resin. 14. The method for preparing an end-capped phosphorus-containing resin according to claim 13, wherein the hydroxyl-terminated oligomeric phosphonate is represented by Formula 21 below:
<Chemical formula 21>

In Chemical Formula 21, Y ₁ and Y ₂ are the same or different and are compounds represented by any one of Chemical Formulas 4 to 8 below;
R ₄ ′ is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
n6 is an integer from 1 to 15;
<Chemical Formula 4>

In Formula 4, R ₁ to R 4 are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ —C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
said a1 and said b1 are each independently an integer of 0 to 4;
When said a1 is 2 or more, two or more _R1 are the same or different,
When said b1 is 2 or more, two or more _R2 are the same or different from each other,
<Chemical Formula 5>

wherein R ₉ to R ₁₄ are the same or different from each other and are hydrogen or C ₁ -C ₃ alkyl;
<Chemical Formula 6>

In Formula 6, R ₁₅ and R ₁₆ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ - _C20 cycloalkyl or C6 _{- C20} aryl;
said a2 and said b2 are each independently an integer of 0 to 4;
When said a2 is 2 or more, two or more R ₁₅ are the same or different from each other,
When said b2 is 2 or more, two or more R ₁₆ are the same or different from each other,
<Chemical formula 7>

In Formula 7, R ₂₁ and R ₂₂ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ - _C20 cycloalkyl or C6 _{- C20} aryl;
said a3 and said b3 are each independently an integer of 0 to 3;
When said a3 is 2 or more, two or more R ₂₁ are the same or different from each other,
When said b3 is 2 or more, two or more R ₂₂ are the same or different from each other,
<Chemical Formula 8>

wherein R ₂₅ is hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
a4 is an integer of 0 to 4;
When said a4 is 2 or more, two or more R ₂₅ are the same or different from each other. According to claim ₂₀ , Y1 and Y2 in Chemical Formula 21 _are the same as or different from each other and are compounds represented by any one of Chemical Formulas 9 to 16 below. Methods for producing the described end-capped phosphorus-containing resins:
<Chemical Formula 9>

<Chemical Formula 10>

<Chemical Formula 11>

<Chemical Formula 12>

<Chemical Formula 13>

<Chemical Formula 14>

<Chemical formula 15>

<Chemical Formula 16>

A phosphorus-containing resin composition end-capped with an unsaturated group, comprising a compound represented by the following chemical formula 1, a curing agent and a curing accelerator:
<Chemical Formula 1>

In Chemical Formula 1, X ₁ and X ₂ are the same or different, and are each independently represented by hydrogen, a hydroxy group, Chemical Formula 2 or Chemical Formula 3 below,
At least one of X ₁ and X ₂ is represented by the following chemical formula 2 or the following chemical formula 3,
Y ₁ and Y ₂ are the same as or different from each other and are represented by any one of the following chemical formulas 4 to 8,
R ₁ ′ is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
n1 is an integer from 1 to 15;
<Chemical Formula 2>

In Formula 2, R ₂ ' is hydrogen, C ₁ -C ₈ alkyl, or

and
said R ₃ ' is hydrogen or C ₁ -C ₈ alkyl;
m1 is an integer of 0 or 1, m2 is an integer of 0 to 5,
when m2 is 2 or more, two or more R ₃ ′ are the same or different,
<Chemical formula 3>

<Chemical Formula 4>

In Formula 4, R ₁ to R ₄ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ - _C20 cycloalkyl or C6 _{- C20} aryl;
said a1 and said b1 are each independently an integer of 0 to 4;
When said a1 is 2 or more, two or more _R1 are the same or different,
When said b1 is 2 or more, two or more _R2 are the same or different from each other,
<Chemical Formula 5>

wherein R ₉ to R ₁₄ are the same or different from each other and are hydrogen or C ₁ -C ₃ alkyl;
<Chemical Formula 6>

In Formula 6, R ₁₅ and R ₁₆ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ - _C20 cycloalkyl or C6 _{- C20} aryl;
said a2 and said b2 are each independently an integer of 0 to 4;
When said a2 is 2 or more, two or more R ₁₅ are the same or different from each other,
When said b2 is 2 or more, two or more R ₁₆ are the same or different from each other,
<Chemical formula 7>

In Formula 7, R ₂₁ and R ₂₂ are the same or different, hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ - _C20 cycloalkyl or C6 _{- C20} aryl;
said a3 and said b3 are each independently an integer of 0 to 3;
When said a3 is 2 or more, two or more R ₂₁ are the same or different from each other,
When said b3 is 2 or more, two or more R ₂₂ are the same or different from each other,
<Chemical Formula 8>

wherein R ₂₅ is hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl or C ₆ -C ₂₀ aryl;
a4 is an integer of 0 to 4;
When said a4 is 2 or more, two or more R ₂₅ are the same or different from each other. 23. The compound according to claim 22, wherein Y1 and Y2 in Chemical Formula _{1 are} the same as or different from each other and are represented by any one of Chemical Formulas 9 to 16 below. Phosphorus-containing resin compositions end-capped with unsaturated groups as described:
<Chemical Formula 9>

<Chemical Formula 10>

<Chemical Formula 11>

<Chemical Formula 12>

<Chemical Formula 13>

<Chemical Formula 14>

<Chemical formula 15>

<Chemical Formula 16>

wherein R ₁ ′ is C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl;
n1 is an integer from 1 to 8;
In Formula 2, R ₂ ' is hydrogen or C ₁ -C ₈ alkyl;
In Formula 4, R ₁ to R ₄ are the same or different, hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ - C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl;
wherein R ₉ to R ₁₄ are the same or different from each other and are hydrogen or methyl;
In Formula 6, R ₁₅ and R ₁₆ are the same or different, hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ - C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl;
In Formula 7, R ₂₁ and R ₂₂ are the same or different, hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ - C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl;
wherein R ₂₅ is hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl; The phosphorus-containing resin composition according to claim 22, the end of which is capped with an unsaturated group. 23. The terminally unsaturated compound according to claim 22, comprising 0.1 to 50 parts by weight of a curing agent and 0.0001 to 0.05 parts by weight of a curing accelerator for 100 parts by weight of the compound represented by Formula 1. A phosphorus-containing resin composition capped with a group. 23. The end-capped phosphorus-containing resin composition of claim 22, wherein the end-capped phosphorus-containing resin composition further comprises a modified PPO (modified polyphenylene oxide) resin. A copper clad laminate manufactured using the phosphorus-containing resin composition terminal-capped with an unsaturated group according to any one of claims 22 to 26.

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