KR101548049B1 - Modified polyphenylene oxide and flexible copper clad having the same - Google Patents

Abstract

The present invention relates to a modified polyphenylene oxide having excellent compatibility with an epoxy resin and processability and having a low genetic characteristic, and a thermosetting resin composition including the modified polyphenylene oxide and exhibiting workability and low dielectric properties, The present invention relates to a prepreg excellent in workability while realizing low dielectric properties by applying polyphenylene oxide, and a copper clad laminate including the prepreg.

Description

TECHNICAL FIELD [0001] The present invention relates to a modified polyphenylene oxide and a copper-clad laminate using the modified polyphenylene oxide,

The present invention relates to a modified polyphenylene oxide having excellent compatibility with an epoxy resin and processability and having a low genetic characteristic, and a thermosetting resin composition including the modified polyphenylene oxide and exhibiting workability and low dielectric properties, To a prepreg excellent in workability while realizing low dielectric properties by applying polyphenylene oxide, and a copper clad laminate including the prepreg.

Recently, a copper clad laminate (CCL) substrate with low dielectric loss and low transmission loss in the GHz region has been demanded in order to cope with higher frequencies of electronic devices. Epoxy resin, which is the main material of CCL material, is disadvantageous in controlling the propagation speed and impedance of high frequency signals. Therefore, researches on application of polyphenylene oxide, which is an engineering plastic of low dielectric properties, have been continuously carried out.

Polyphenylene oxide (PPO), which is a thermoplastic resin, is excellent in mechanical strength, heat resistance, hygroscopicity and genetic characteristics, but has a high melting point due to its high molecular weight, resulting in poor processability and lack of copper foil adhesion and heat resistance have. In addition, it is impossible to apply more than a certain amount due to incompatibility with polar polymers such as epoxy which is the main material of CCL, and degradation of solubility in general-purpose solvents. In addition, there is one alcohol group capable of reacting with epoxy, and there is also a problem in thermosetting property with epoxy.

Therefore, in order to overcome the disadvantages described above, polyphenylene oxide and polyphenol having a weight-average molecular weight as high as about 34,000 to 35,000 are subjected to a redistribution reaction in the presence of a radical initiator to form low-molecular polyphenylene oxide having an alcohol group at both ends Is proposed. Noryl (Sabic), which is a representative example of redistribution polyphenylene oxide actually used, was limited because of its incompatibility with epoxy resin. Commercialized redistributed polyphenylene oxides also have structural characteristics and bisphenol A (4,4 '- (propane-2,2-diyl) diphenol) polyphenols used for redistribution, Lt; RTI ID = 0.0 > dielectric < / RTI >

It is an object of the present invention to provide a modified polyphenylene oxide which is excellent in compatibility with an epoxy resin and processability and has a low genetic property.

Another object of the present invention is to provide a film produced using the modified polyphenylene oxide.

Still another object of the present invention is to provide a thermosetting resin composition, a prepreg, a functional laminated sheet, and a copper clad laminate including the modified polyphenylene oxide.

The present invention provides a modified polyphenylene oxide represented by the following general formula (1).

(In the formula 1,

n is an integer from 1 to 10,000;

a is an integer from 0 to 4, when a is an integer of 1 to 4, R ₁ is C ₁ ~ C ₁₂ alkyl, and C ₁ ~ C ₁₂ alkoxy group is selected from the group consisting of;

m is 0 or 1;

Y ₁ and Y ₂ are either the same or different and each is independently a single bond with each other, or a substituted or unsubstituted arylene group, a C ₆ ~ C _12, wherein arylene of Y ₁ and Y ₂ groups are hydrogen, C ₁ ~ alkyl group of C _12, C ₁ ~ C ₁₂ alkoxy group and a C ₆ ~ C ₁₂ from the group consisting of an aryl group may be substituted with more than one kinds selected substituents, and;

, -C(=O)-R₆,

, -C(=O)-O-R₈ 및

로 이루어진 군에서 선택되며, R ₂ and R ₃ are the same or different and each independently represents -OH, -CR ₄ ═CH ₂ , -C (═O) CR ₅ ═CH ₂ , -NH ₂ ,

, -C (= O) -R ₆ ,

, -C (= O) -OR < ₈ > And

, ≪ / RTI >

R ₄ to R ₈ are the same or different and are each independently selected from the group consisting of hydrogen, a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkoxy group, and a C ₆ to C ₁₂ aryl group,

A plurality of W are the same or different from each other and are each independently selected from the group consisting of hydrogen, a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkoxy group, and a C ₆ to C ₁₂ aryl group;

Ar is a substituent represented by the following formula (2) or (3)

Q ₁ to Q ₃ are the same or different and are independently selected from the group consisting of a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkoxy group and a C ₁ to C ₁₂ haloalkyl group, 0, Q ₁ and Q ₂ are excluded if they are all alkyl groups,

o and p are each independently an integer of 0 to 3).

The present invention also provides a film comprising the above-mentioned modified polyphenylene oxide.

The present invention also relates to the aforementioned modified polyphenylene oxide; And a thermosetting resin composition comprising a crosslinkable curing agent.

In addition, the present invention relates to a fibrous substrate; And a prepreg containing the above-mentioned thermosetting resin composition impregnated in the fiber substrate.

The present invention also relates to a metal foil or a polymer film substrate; And a functional laminated sheet formed on one or both surfaces of the substrate, wherein the thermosetting resin composition comprises a cured resin layer.

The present invention also provides a copper foil comprising: a copper foil; And the above-mentioned prepreg, wherein the one or more layers are laminated and molded.

The modified polyphenylene oxide according to the present invention contains a bisphenol moiety having an increased content of an alkyl group and an aromatic ring group in the main chain, as compared with the conventional modified polyphenylene oxide, and has a vinyl group, an epoxy group, an amine group, Having a low polarity substituent such as an epoxy group, it not only has excellent compatibility with epoxy resin and processability, but also has low genetic properties.

Hereinafter, the present invention will be described.

The modified polyphenylene oxide according to the present invention can be produced by reacting a conventionally modified polyphenylene oxide (for example, Noryl (Sabic)) prepared using bisphenol A [4,4 '- (propane-2,2-diyl) diphenol] A substituent having a low polarity such as an alcohol group, a vinyl group, an epoxy group, an amine group, and an ester group is introduced to both ends while a bisphenol structure having a high alkyl and aromatic content is contained in the main chain Which is characterized by being represented by the above formula (1). These modified polyphenylene oxides are superior to conventional modified polyphenylene oxides in compatibility with epoxy resins and processability, and have low genetic properties.

Specifically, the modified polyphenylene oxide represented by the formula (1) is a polyphenylene oxide obtained by redispersing polyphenylene oxide by a specific bisphenol derivative having an increased alkyl content and aromatic content, Is an alcoholic polymer or a polymer obtained by redistributing the polyphenylene oxide and then modifying both terminals with a substituent having a low polarity (for example, a vinyl group, an epoxy group, an amine group, an ester group, etc.) A bisphenol structure derived from the bisphenol derivative, and an alcohol group, a vinyl group, an epoxy group, an amine group, or an ester group is introduced at both ends.

The bisphenol derivative has a higher content of alkyl group and aromatic ring group than bisphenol A. Since the bisphenol structure derived from such a bisphenol derivative is contained in the main chain, the modified polyphenylene oxide of the present invention can improve the compatibility with the epoxy resin and the processability compared to the conventional modified polyphenylene oxide.

In addition, as the alkyl content and aromatic content of the bisphenol structure are increased, the modified polyphenylene oxide of the above formula (1) may have a reduced dielectric characteristic due to reduced electron polarization.

In addition, the modified polyphenylene oxide of the above formula (1) is modified with a substituent having a low polarity at both ends of the molecular chain, that is, a vinyl group, an epoxy group, an amine group, or an ester group. Therefore, unlike the conventional modified polyphenylene oxide, the modified polyphenylene oxide of the present invention not only improves compatibility with the epoxy resin due to the low polarity substituent at both terminals, but also has a low dielectric property.

≪ Modified Polyphenylene Oxide and its Preparation Method >

In the modified polyphenylene oxide represented by the general formula (1), n is an integer of 1 to 10,000, preferably an integer of 1 to 1,000, more preferably 1 to 100.

A is an integer of 0 to 4, and when a is 0, hydrogen is not substituted by a substituent R ₁ , and when a is an integer of 1 to 4, R ₁ is C ₁ to C ₁₂ An alkyl group, and a C ₁ to C ₁₂ alkoxy group, and is preferably selected from the group consisting of a methyl group, an ethyl group, a propyl group, and a tert-butyl group.

The above-mentioned m may be 0 or 1, preferably 1.

The Y ₁ and Y ₂ may be the same or different and each independently a single bond or a substituted or unsubstituted C ₆ -C ₁₂ arylene group, preferably a single bond or a phenylene group.

The arylene group of Y ₁ and Y ₂ may be substituted with at least one substituent selected from the group consisting of hydrogen, C ₁ to C ₁₂ alkyl groups, C ₁ to C ₁₂ alkoxy groups, and C ₆ to C ₁₂ aryl groups. And may preferably be substituted with at least one substituent selected from the group consisting of a methyl group, a propyl group and a tert-butyl group.

, -C(=O)-R₆,

, -C(=O)-O-R₈ 및

로 이루어진 군에서 선택되며, R ₂ and R ₃ are the same or different and each independently represents -OH, -CR ₄ ═CH ₂ , -C (═O) CR ₅ ═CH ₂ , -NH ₂ ,

, -C (= O) -R ₆ ,

, -C (= O) -OR < ₈ > and

, ≪ / RTI >

Wherein R ₄ to R ₈ are the same or different from each other and each independently selected from the group consisting of hydrogen, a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkoxy group, and a C ₆ to C ₁₂ aryl group,

A plurality of W are the same or different from each other and each independently selected from the group consisting of hydrogen, a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkoxy group, and a C ₆ to C ₁₂ aryl group.

, -C(=O)-CH₃,

, -C(=O)-O-CH₃, 및

로 이루어진 군에서 선택될 수 있다.Preferably, the R ₂ and R ₃ is _{-OH, -CH = CH 2, -C} (-CH 3) = CH 2, -C (= O) CH = CH 2, -C (= O) -C ( -CH ₃ ) = CH ₂ , -NH ₂ ,

_{, -C (= O) -CH 3} ,

, -C (= O) -O- CH 3, and

≪ / RTI >

The above Ar is a substituent derived from a bisphenol derivative other than bisphenol A (BPA) and is a substituent represented by the above formula (2) or (3), preferably a substituent represented by any one of the following formulas And more preferably, it may be a substituent represented by any one of the following general formulas (2a), (2b), (2b) and (3aa).

(2a)

(o = 1~3)

(o = 1 to 3)

(2b)

(o=0~3)

(o = 0 to 3)

[Chemical Formula 2c]

(o=0~3)

(o = 0 to 3)

(2d)

(o=0~3)

(o = 0 to 3)

[Formula 2e]

(o=0~3)

(o = 0 to 3)

[Chemical Formula 3]

(p=1~3)

(p = 1 to 3)

[Formula 2aa]

[Chemical Formula 2ab]

[Chemical Formula 2ba]

[Formula 3aa]

Examples of the modified polyphenylene oxide represented by the above formula (1) include, but are not limited to, modified polyphenylene oxide represented by the following formula (4).

In Formula 4,

n, m, Ar, Y ₁ , Y ₂ , R ₂ , and R ₃ are as defined in Formula 1, respectively.

Specific examples of the modified polyphenylene oxide represented by the formula (1) include modified polyphenylene oxide represented by the following formula (5) to modified polyphenylene oxide represented by the following formula (13), but are not limited thereto.

In the above formulas 5 to 13,

n, Ar, R _6, R ₇ and W are each as defined in formula (1)

W ₁ and W ₂ are the same or different and are each independently selected from the group consisting of hydrogen, a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkoxy group and a C ₆ to C ₁₂ aryl group, May be selected from the group consisting of hydrogen, a methyl group, a propyl group, and a tert-butyl group,

a and b are 0 or 1, respectively.

Representative examples of the modified polyphenylene oxide represented by the above formula (1) include, but are not limited to, the following compounds.

The weight average molecular weight (Mw) of the modified polyphenylene oxide represented by the above formula (1) is not particularly limited and may be, for example, in the range of 5,000 to 100,000, preferably 3,000 to 60,000.

The present invention provides a method for producing the modified polyphenylene oxide represented by the above formula (1).

The modified polyphenylene oxide represented by Formula 1 may be prepared by redispersing polyphenylene oxide using a specific bisphenol derivative having a high alkyl content and an aromatic content.

For example, the method for producing the modified polyphenylene oxide represented by the above formula (1) is a process for producing a polyphenylene oxide by reacting polyphenylene oxide with a specific bisphenol derivative other than bisphenol A (BPA) to form an alcohol- Step < / RTI >

Alternatively, the modified polyphenylene oxide represented by the above formula (1) may be produced by redispersing polyphenylene oxide using a specific bisphenol derivative having a high alkyl and aromatic content, (For example, a vinyl group, an epoxy group, an amine group, an ester group, and the like) having a low polarity.

For example, the method for producing the modified polyphenylene oxide represented by the above formula (1) is a process for producing a polyphenylene oxide by reacting polyphenylene oxide with a specific bisphenol derivative other than bisphenol A (BPA) to form an alcohol- step; And modifying the terminal group of the alcohol-terminated polyphenylene oxide with a vinyl group, an epoxy group, an amine group or an ester group, but the present invention is not limited thereto.

First, polyphenylene oxide is redistributed by using a specific bisphenol derivative (except for bisphenol A (BPA)) having a high alkyl content and aromatic content to form an alcohol-modified polyphenylene oxide (hereinafter, Quot;). The high molecular weight polyphenylene oxide may be redistributed through step S100 to be modified into low molecular weight polyphenylene oxide having an alcohol group at both terminals.

The bisphenol derivative which can be used in the present invention is not particularly limited as long as it contains an alcohol group (-OH) at both ends and is higher in the alkyl content and aromatic content than the bisphenol A (BPA). Examples thereof include bisphenol derivatives represented by the following formula (14) and bisphenol derivatives represented by the following formula (15), but are not limited thereto.

In the above formulas 14 and 15,

Q ₁ to Q ₃ are the same or different and are independently selected from the group consisting of a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkoxy group and a C ₁ to C ₁₂ haloalkyl group, 0, Q ₁ and Q ₂ are excluded if they are all alkyl groups,

o and p are each independently an integer of 0 to 3;

Examples of the bisphenol derivative represented by the above formula (14) or (15) include a bisphenol derivative of the following formula (14a) to a bisphenol derivative of the formula (14e) and a bisphenol derivative of the formula (15a), and more specific examples thereof include bisphenol derivatives of the following formula A bisphenol derivative, a bisphenol derivative of the formula (14b), and a bisphenol derivative of the formula (15aa).

[Chemical Formula 14a]

(o = 1~3)

(o = 1 to 3)

[Chemical Formula 14b]

(o=0~3)

(o = 0 to 3)

[Chemical Formula 14c]

(o=0~3)

(o = 0 to 3)

[Chemical Formula 14d]

(o=0~3)

(o = 0 to 3)

[Chemical Formula 14e]

(o=0~3)

(o = 0 to 3)

[Chemical Formula 15a]

(p=1~3)

(p = 1 to 3)

[Chemical Formula 14aa]

[Chemical Formula 14ab]

[Chemical Formula 14ba]

[Chemical Formula 15aa]

The content of the bisphenol derivative is not particularly limited and is preferably adjusted according to the weight average molecular weight of the polyphenylene oxide used or the target molecular weight of the redispersed polyphenylene oxide. For example, 100 parts by weight of polyphenylene oxide Based on the total weight of the composition.

The polyphenylene oxide which can be used in the present invention is not particularly limited as long as it is a polyphenylene oxide known in the art and may be, for example, polyphenylene oxide represented by the following formula (16), and specific examples thereof include And polyphenylene oxide. More specific examples include, but are not limited to, Noryl, SA-120 from Sabic.

In Formula 16,

a is an integer from 0 to 4, when a is an integer of 1 to 4, R ₁ is selected from the group consisting of alkoxy group of C ₁ ~ C ₁₂ alkyl group and a C ₁ ~ C _12, preferably a methyl group, an ethyl group, A propyl group, and a tert-butyl group,

n is an integer of 1 to 3,000.

[Chemical Formula 16a]

In the above formula (16a)

n is an integer of 1 to 3,000.

The weight average molecular weight (Mw) of the polyphenylene oxide is not particularly limited and may be, for example, 2,000 to 350,000.

The content of the polyphenylene oxide is not particularly limited and is about 1 to 75 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the reaction mixture (including polyphenylene oxide, bisphenol derivative, radical initiator and solvent) .

The redistribution reaction in step S100 may be performed in the presence of a radical initiator and / or a solvent. When the radical initiator is used, the redistribution reaction between the polyphenylene oxide and the bisphenol derivative is initiated and promoted, thereby improving the reaction rate.

The radical initiator usable in the present invention is not particularly limited as long as it is a radical initiator known in the art, and examples thereof include peroxides such as benzoyl peroxide and the like; Quinone compounds such as 3,3 ', 5,5'-tetramethyl-1,4-diphenoquinone and the like; Complexes containing transition metals and amines, and the like, but are not limited thereto.

The content of the radical initiator is not particularly limited, but it is preferable to adjust the content in consideration of the content of the reactant and the rate of redistribution reaction. For example, it may be 0 to 10 parts by weight based on 100 parts by weight of polyphenylene oxide, To 10 parts by weight.

In addition, the solvent usable in the present invention is not particularly limited as long as it is a commonly used solvent in the art. Non-limiting examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, and hexanol; Aromatic hydrocarbon solvents such as benzene, ethylbenzene, chlorobenzene, toluene and xylene. These solvents may be used alone or in combination of two or more. Preferably toluene, or a mixture of toluene and methanol. According to one example, when a mixture of toluene and methanol is used, the mixing ratio of toluene to methanol may be 1: 0.01 to 1: 0.5 by volume of toluene: methanol.

The temperature of the redistribution reaction is not particularly limited, but the reaction rate may be improved at about 20 to 150 ° C, preferably 60 to 80 ° C.

According to an example, when the step S100 is carried out using the reactants, the radical initiator and the solvent described above, the modified polyphenylene oxide represented by the above formula (1) in which both terminals are alcohol groups, that is, the alcohol- Terminal-modified polyphenylene oxide can be obtained.

In Formula 17,

a, R ₁ , Ar, and n are as defined in formula (1).

The weight-average molecular weight of the alcohol-modified polyphenylene oxide represented by Formula 17 varies depending on the weight-average molecular weight of the polyphenylene oxide used, and may range, for example, from 2,000 to 20,000.

Subsequently, both end groups of the alcohol-terminated polyphenylene oxide obtained in the step S100 are modified into a vinyl group, an epoxy group, an amine group or an ester group (hereinafter, step S200). In step S200, a substituent having a low polarity such as a vinyl group, an epoxy group, an amine group or an ester group is introduced in place of the alcohol group located at both ends of the alcohol-terminated polyphenylene oxide, The modified polyphenylene oxide to be displayed can be obtained.

The step S200 may be carried out through various reactions in the art to introduce a vinyl group, an epoxy group, an amine group or an ester group in place of the alcohol group.

According to an example, in step S200, the alcohol-terminated polyphenylene oxide obtained in step S100 is reacted with an acid anhydride in an aromatic hydrocarbon solvent in the presence of a basic catalyst to obtain a poly .

Examples of the aromatic hydrocarbon solvent include, but are not limited to, toluene, benzene, ethylbenzene, chlorobenzene, and xylene.

Examples of the basic catalyst include, but are not limited to, dimethylaminopyridine, triphenylphosphine, triphenylantimony, and the like.

The content of the basic catalyst is not particularly limited, but may be 1 to 20 parts by weight based on 100 parts by weight of the alcohol-modified polyphenylene oxide).

Examples of the acid anhydride include, but are not limited to, methacrylic anhydride, acrylic acid anhydride, and the like.

The mixing ratio of the acid anhydride (a) and the alcohol-terminated polyphenylene oxide (b) is not particularly limited, but is preferably adjusted in consideration of the kind of the acid anhydride. For example, a: b = 10 To 40: 100 weight ratio.

According to another example, in step S200, the alcohol-terminated polyphenylene oxide and epichlorohydrin obtained in step S100 are heated to dissolve, and then reacted in the presence of an alkali metal hydroxide to form an alcohol- And modifying both ends of the phenylene oxide with an epoxy group.

The mixing ratio of the alcohol-terminated polyphenylene oxide (a) and the epichlorohydrin (b) is not particularly limited and may be, for example, a: b = 100: 10 to 40 parts by weight.

Non-limiting examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and the like.

The content of the alkali metal hydroxide is not particularly limited and may be, for example, 1 to 10 parts by weight based on 100 parts by weight of the alcohol-modified polyphenylene oxide.

According to another example, in step S200, the alcohol-modified polyphenylene oxide obtained in step S100 is reacted with 1,3-dinitrobenzene in the presence of potassium carbonate in a dimethylformamide solution to form a first reactant ; Precipitating the first reactant with methanol; And reacting the precipitate with 2-methoxyethanol with Pt / C and triethylamine under a hydrogen atmosphere, wherein the two terminal groups of the alcohol-terminated polyphenylene oxide are modified with an amine group .

According to another example, the step of heating and dissolving the alcohol-terminated polyphenylene oxide obtained in the step S100 together with methyl 4-chlorocarbonyl benzoate to form a reaction solution; And adding triethylamine to the reaction solution to react the two ends of the alcohol-modified polyphenylene oxide with an ester group.

≪ Modified polyphenylene oxide film >

On the other hand, the present invention provides a film comprising the modified polyphenylene oxide represented by the above-mentioned formula (1).

Since the dielectric property of the modified polyphenylene oxide of Formula 1 is low, the film can be used as an insulating layer of a copper clad laminate.

The film may further contain an epoxy resin in addition to the modified polyphenylene oxide of the above formula (1). At this time, since the modified polyphenylene oxide of Formula 1 is excellent in compatibility with epoxy resin, it can be used for various purposes.

≪ Thermosetting resin composition >

On the other hand, the present invention relates to a modified polyphenylene oxide represented by the above-mentioned formula (1); And a thermosetting resin composition comprising a crosslinkable curing agent.

If necessary, the thermosetting resin composition may further contain a cyanate resin, an epoxy resin, a flame retardant, an inorganic filler, a curing accelerator, a radical initiator, a solvent and the like.

The cross-linking curing agent is used for forming a network structure by three-dimensionally cross-linking the modified polyphenylene oxide of Formula 1. Even if the modified polyphenylene oxide modified with a low molecular weight is used to increase the fluidity of the resin composition, it contributes to the improvement of the heat resistance of the modified polyphenylene oxide due to the use of the crosslinkable curing agent. It also has an effect of increasing the fluidity of the resin composition and improving the peel strength with other substrates (e.g., copper foil).

It is preferable that the cross-linkable curing agent usable in the present invention has excellent miscibility with the modified polyphenylene oxide whose terminal is an alcohol group, an vinyl group, an epoxy group, an amine group or an ester group. Non-limiting examples include allyloxide compounds prepared by the reaction of divinylbenzene, divinylbenzene, divinylnaphthalene, divinyldiphenyl, styrene monomer, phenol and allyl chloride, based on vinylbenzyl oxide compounds; Dienes such as triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), 1,2,4-trivinylcyclohexane, 1,7-octadiene and 1,9-decadiene, di- - vinyl benzyl oxide and the like. At this time, the above-mentioned curing agents may be used alone or in combination of two or more. They are preferable not only because they are highly compatible with each other, but also because they have excellent moldability, small dielectric constant, excellent heat resistance and reliability.

In the present invention, it is possible to maximize various physical properties and processability as well as low dielectric properties through proper mixing of the cross-linkable curing agent and control of optimized content.

In the thermosetting resin composition according to the present invention, the content of the cross-linkable curing agent may be in the range of 5 to 50 parts by weight, preferably in the range of 10 to 40 parts by weight, based on 100 parts by weight of the modified polyphenylene oxide resin . When the content of the crosslinkable curing agent falls within the above-mentioned range, the curing property, the molding processability and the adhesive force of the resin composition are good.

The thermosetting resin composition according to the present invention may further contain a flame retardant agent, if necessary.

The flame retardant may be a conventional flame retardant known to those skilled in the art. For example, a halogen flame retardant containing bromine or chlorine, a phosphorus flame retardant such as triphenyl phosphate, trimesylphosphate, trisdicropropyl phosphate, , Antimony flame retardants such as antimony trioxide, inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide, and the like. In the present invention, an additive type bromine flame retardant which is not reactive with the modified polyphenylene oxide and does not deteriorate the heat resistance and dielectric properties is suitable.

In the present invention, the brominated flame retardant is selected from the group consisting of Bromophthalimide, Bromophenyl-added bromine flame retardant or Allyl terminated tetrabromo bisphenol A Allyl ether, Divinylphenol, Flame retardant curing agent can be used to simultaneously obtain the characteristics of the curing agent and the flame retardancy. In addition, brominated organic compounds can also be used. Specific examples thereof include decabromodiphenyl ethane, 4,4-dibromobiphenyl, ethylenbistetrabromophthalimide, and the like.

In the thermosetting resin composition according to the present invention, the content of the flame retardant may be in the range of 5 to 50 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the modified polyphenylene oxide resin. When the flame retardant is included in the above range, flame resistance of the flame retardant 94V-0 level can be sufficiently obtained, and excellent heat resistance and electrical characteristics can be exhibited. The flame retardant is preferably a brominated organic compound.

In addition, the thermosetting resin composition according to the present invention may further comprise a conventional inorganic filler known in the art used for the laminate, if necessary.

The inorganic filler can reduce the difference in thermal expansion coefficient (CTE) between the resin layer and other layers, thereby effectively improving the warping property, the low expansion, the mechanical strength (toughness) and the low stress of the final product.

Non-limiting examples of the inorganic filler usable in the present invention include silicas such as natural silica, fused silica, amorphous silica, crystalline silica and the like; Magnesium oxide, magnesia, clay, calcium silicate, titanium oxide, antimony oxide, glass fiber, aluminum borate, strontium titanate, calcium titanate (calcium titanate), talc , Magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, boron nitride, silicon nitride, talc, mica and the like. These inorganic fillers may be used singly or in combination of two or more. Of these inorganic fillers, fused silica exhibiting a low coefficient of thermal expansion is most preferable.

In the present invention, the size of the inorganic filler is not particularly limited, but an average particle diameter of 0.5 to 5 mu m is advantageous in dispersibility. The content of the inorganic filler is not particularly limited, and can be appropriately adjusted in consideration of the above-described flexural characteristics, mechanical properties, and the like. For example, the modified polyphenylene oxide resin may be in the range of 5 to 90 parts by weight, preferably 30 to 80 parts by weight, based on 100 parts by weight of the modified polyphenylene oxide resin. If the content of the inorganic filler is excessive, the moldability may be deteriorated.

The thermosetting resin composition according to the present invention may further comprise a reaction initiator in order to enhance the favorable effect of the crosslinkable curing agent.

Such a reaction initiator can further accelerate the curing of the modified polyphenylene oxide and the crosslinkable curing agent, and can increase the properties such as heat resistance of the resin.

Non-limiting examples of usable reaction initiators include?,? '-Bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl- Hexyne, benzoyl peroxide, 3,3 ', 5,5'-tetramethyl-1,4-diphenoxyquinone, chloranil, 2,4,6-tri-t-butylphenoxy, t -Butyl peroxyisopropyl monocarbonate, azobisisobutylonitrile, and the like. Further, a metal carboxylate salt may further be used. The reaction initiator may be included in an amount of 2 to 5 parts by weight based on 100 parts by weight of modified polyphenylene oxide, but is not limited thereto.

Further, the thermosetting resin composition of the present invention may further comprise a curing accelerator. The curing accelerator may be an organic metal salt or an organic metal complex containing at least one metal selected from the group consisting of iron, copper, zinc, cobalt, lead, nickel, manganese and tin.

Examples of the organic metal salt or organometallic complex include iron naphthenate, copper naphthenate, zinc naphthenate, cobalt naphthenate, nickel naphthenate, manganese naphthenate, tin naphthenate, zinc Octanoate, tin octanoate, iron octanoate, copper octanoate, zinc 2-ethylhexanate, lead acetylacetonate, cobalt acetylacetonate, or dibutyltin maleate. But is not limited thereto. These may be used singly or in combination of two or more. The curing accelerator may be included in an amount of 0.01 to 1 part by weight based on 10 to 60 parts by weight of modified polyphenylene oxide, but is not limited thereto.

In addition, the thermosetting resin composition of the present invention may further include a conventional rubber known in the art.

In addition to the above-mentioned components, the thermosetting resin composition of the present invention may contain a flame retardant generally known in the art, or other thermosetting resins or thermoplastic resins not described above and oligomers thereof And other additives such as an antioxidant, a polymerization initiator, a dye, a pigment, a dispersant, a thickener, a leveling agent, and the like may be further included. Examples thereof include organic fillers such as silicone-based powder, nylon powder and fluororesin powder, thickeners such as orthobenzene and benzene; Polymer-based defoaming agents or leveling agents such as silicones and fluororesins; Adhesion-imparting agents such as imidazole-based, thiazole-based, triazole-based and silane-based coupling agents; Phthalocyanine, carbon black, and other coloring agents.

The thermosetting resin composition may be blended with a thermoplastic resin for the purpose of imparting appropriate flexibility to the cured resin composition. Examples of such a thermoplastic resin include cyanate resin, epoxy resin, phenoxy resin, polyvinyl acetal resin, polyimide, polyamideimide, polyoxidesulfone, polysulfone and the like. Any one of these thermoplastic resins may be used alone, or two or more of them may be used in combination.

Examples of the resin additive include organic fillers such as silicone powder, nylon powder and fluorine powder; Thickeners such as allven and benton; Silicon-based, fluorine-based, and high-molecular antifoaming agents or leveling agents; Adhesion-imparting agents such as imidazole-based, thiazole-based, triazole-based, silane coupling agent, epoxy silane, aminosilane, alkylsilane and mercaptosilane; Colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow and carbon black; Release agents such as higher fatty acids, higher fatty acid metal salts and ester waxes; Modified silicone oils, silicone powders, and silicone elastomers. In addition, it may contain additives commonly used in thermosetting resin compositions used in the production of electronic devices (particularly, printed wiring boards).

According to a preferred embodiment of the present invention, the thermosetting resin composition comprises (a) a modified polyphenylene oxide resin represented by the formula (1); (B) 5 to 50 parts by weight of a crosslinkable curing agent based on 100 parts by weight of the modified polyphenylene oxide resin; (c) 5 to 50 parts by weight of a flame retardant; And (d) 5 to 90 parts by weight of an inorganic filler Range. ≪ / RTI > At this time, the criterion of the constituent may be the entire weight of the composition or the total weight of the varnish containing the organic solvent.

The organic solvent may be any organic solvent known in the art without limitation. For example, various organic solvents such as acetone, cyclohexanone, methyl ethyl ketone, toluene, xylene, tetrahydrofuran and the like may be arbitrarily used. Here, the content of the organic solvent may be in the range of the residual amount satisfying 100 parts by weight of the entire varnish using the composition ratio of the above-mentioned composition, and is not particularly limited.

<Prepreg>

The prepreg according to the present invention includes a fiber substrate and the aforementioned thermosetting resin composition impregnated in the fiber substrate. Here, the thermosetting resin composition may be a resin varnish in the form of being dissolved or dispersed in a solvent.

The fibrous substrate may be any inorganic fibrous substrate, an organic fiber substrate, or a mixed form thereof, which is flexible and capable of being bent arbitrarily. The above-mentioned fiber substrate may be selected on the basis of the intended use or performance.

Examples of the substrate used in the present invention include inorganic fibers such as E-glass, D-glass, S-glass, NE-glass, T-glass and Q-glass; fibers of organic materials such as polyimide, polyamide, Mixtures, etc., and may be selected on the basis of the application or performance to be used.

Non-limiting examples of the usable fiber substrate include glass fibers (inorganic fibers) such as E-glass, D-glass, S-glass, NE-glass, T-glass and Q-glass; Organic fibers such as glass paper, glass web, glass cloth, aramid fiber, aramid paper, polyimide, polyamide, polyester, aromatic polyester, fluorine resin and the like; Carbon fiber, paper, inorganic fiber, or a mixed form of at least one of these. The form of the fiber substrate may be a woven or nonwoven fabric made of the above-mentioned fibers or the like; Woven fabrics and mats made of roving, choPPOd strand mat, surfacing mat, metal fiber, carbon fiber, mineral fiber and the like. These substrates may be used alone or in combination of two or more. When a reinforced fiber substrate is used in combination, rigidity and dimensional stability of the prepreg can be improved. The thickness of such a fiber substrate is not particularly limited, and may range, for example, from about 0.01 mm to 0.3 mm.

The above-mentioned resin composition is used for forming a prepreg, and the above-mentioned thermosetting resin composition of the present invention can be used.

Generally, prepreg refers to a sheet-like material obtained by coating or impregnating a fiber substrate with a thermosetting resin composition, followed by curing to a B-stage (semi-cured state) by heating. In addition to the above-mentioned methods, the prepreg of the present invention can be produced by a known hot-melt method, a solvent method or the like known in the art.

In the solvent method, a resin composition varnish formed by dissolving a thermosetting resin composition for forming a prepreg in an organic solvent is impregnated with a fiber substrate, followed by drying. When such a solvent method is employed, a resin varnish is generally used. Examples of the method of impregnating the resin composition with the fiber substrate include a method of immersing the substrate in a resin varnish, a method of applying the resin varnish to the substrate by various coaters, a method of spraying the resin varnish onto the substrate by spraying, . At this time, when the fiber substrate is immersed in the resin varnish, impregnability of the resin composition to the fiber substrate can be improved, which is preferable.

When the resin composition varnish is prepared, examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl oxide acetate and carbitol acetate N-methylpyrrolidone, tetrahydrofuran, and the like can be given as examples of the organic solvent used in the present invention. The organic solvents may be used alone or in combination of two or more.

Also, the hot melt method may be a method in which the resin composition is coated on a releasing paper excellent in releasability from the resin composition without dissolving the resin composition in an organic solvent, and then the resin composition is laminated on a sheet-like fiber substrate, or directly coated with a die coater. It may also be produced by continuously laminating an adhesive film comprising a thermosetting resin composition laminated on a support onto both surfaces of a sheet-like reinforcing substrate under heating and pressurizing conditions.

The resin composition of the present invention can be made into a prepreg by coating or impregnating the resin composition on a sheet-like fibrous substrate or glass substrate made of fibers and semi-curing the composition by heating. And is preferably a prepreg for a printed circuit board. At this time, the resin composition may be prepared by using a resin varnish.

The prepreg of the present invention may be formed by coating or impregnating the substrate, followed by further drying, wherein the drying may be performed at 20 to 200 ° C. For example, the prepreg of the present invention can be impregnated with the substrate of the thermosetting resin composition varnish and heated and dried at 70 to 170 ° C for 1 to 10 minutes to prepare a prepreg in a semi-hardened (B-stage) state.

<Functional laminated sheet>

The present invention relates to a metal foil or a polymer film substrate; And a functional laminated sheet formed on one or both surfaces of the substrate, wherein the thermosetting resin composition comprises a cured resin layer.

For example, metal foil; And a resin-coated copper foil formed on one or both surfaces of the metal foil, wherein the thermosetting resin composition includes a cured resin layer.

The metal foil may be of any metal or alloy known in the art without limitation. When the metal foil is a copper foil, a laminate formed by coating and drying the thermosetting resin composition according to the present invention may be used as a copper-clad laminate. It is preferably a copper foil.

The copper foil includes all copper foils produced by a rolling method and an electrolytic method. Here, the copper foil may be rust-proofed to prevent the surface from being oxidized and corroded.

The metal foil may have a predetermined surface roughness (Rz) on one surface of the thermosetting resin composition in contact with the cured resin layer. At this time, the surface roughness Rz is not particularly limited, but may be in the range of 0.6 mu m to 3.0 mu m, for example.

The thickness of the metal foil is not particularly limited, but it may be less than 5 탆 in consideration of the thickness and mechanical properties of the final product, and may preferably be in the range of 1 to 3 탆. Examples of usable copper foils include CFL (TZA_B, HFZ_B), Mitsui (HSVSP, MLS-G), Nikko (RTCHP), Furukawa, and ILSIN.

The polymer film usable in the present invention is not particularly limited as long as it is known in the art as an insulating film. For example, polyimide film, epoxy resin film, and the like, but are not limited thereto.

<Copper-clad laminate and printed circuit board>

The present invention includes a copper-clad laminate formed by laminating two or more of the above-mentioned prepregs together and then heating and pressing them under normal conditions.

Further, the present invention includes a copper-clad laminate formed by laminating the prepreg and the copper foil and heating and pressing under normal conditions.

For example, the above-mentioned resin composition is thoroughly stirred at room temperature with a stirrer, then impregnated with a glass base material, dried, laminated together with a copper foil, and subjected to heat and pressure to obtain a desired copper clad laminate. At this time, at the time of forming the copper clad laminate, the heating and pressing conditions can be appropriately adjusted according to the thickness of the copper clad laminate to be produced, the type of the thermosetting resin composition according to the present invention, and the like.

In addition, the present invention includes a printed circuit board, preferably a multilayer printed circuit board, laminated and formed of at least one member selected from the group consisting of a prepreg, an insulating resin sheet, and a resin-bonded copper foil.

The term &quot; printed circuit board &quot; in the present invention refers to a printed circuit board laminated on one or more layers by plating through-hole method, build-up method or the like, and can be obtained by superimposing the above-mentioned prepreg or insulating resin sheet on the inner-

The printed circuit board can be manufactured by a conventional method known in the art. For example, a copper foil laminate is produced by laminating a copper foil on one side or both sides of a prepreg according to the present invention and heating and pressing the same. After holes are opened in the copper foil laminates to perform through-hole plating, To form a circuit.

As described above, the prepreg and the printed circuit board can be produced from the thermosetting resin composition according to the present invention. These prepregs and the copper-clad laminate had not only low dielectric constant and dielectric loss but also excellent heat resistance (see Table 2 below). Therefore, the prepreg and the printed circuit board of the present invention can be applied to a mobile communication device that handles high frequency signals of 1 GHz or more, network-related electronic devices such as base station devices, servers, routers, The present invention can be effectively used as a component part of a printed circuit board for a display device.

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to these examples.

[Synthesis Example 1] Production of alcohol-terminal modified polyphenylene oxide (alcohol-MPPO-1)

Compound 1 (1.0 Kg, n = about 60), compound 2 (0.1 Kg) and toluene (10 Kg) were added to a 20 L round bottom flask equipped with a thermometer, stirrer and condenser, , And sufficiently dissolved in a nitrogen atmosphere. Then, 75% of Benzoyl peroxide (10 g) was dissolved in Toluene (90 g) and then slowly dropped into the flask. After the dropwise addition, the temperature of the flask was raised to 90 DEG C, and after 8 hours and 30 minutes, the flask was cooled to room temperature. Thereafter, the cooled reaction solution was concentrated to about 50% in toluene, and the concentrate was precipitated in an excess amount of methanol to obtain a precipitate. The precipitate was dried in a vacuum oven at 80 DEG C for 24 hours to obtain alchol- MPPO-1 (0.85 kg, weight average molecular weight: 6500) was obtained.

[Synthesis Example 2] Production of alcohol-terminal modified polyphenylene oxide (alchol-MPPO-2)

The same procedure as in Synthesis Example 1 was carried out except that Compound 2 (0.5 kg) was used instead of Compound 2 (0.1 kg) used in Synthesis Example 1 to obtain alchol-MPPO-2 (0.85 kg, weight average molecular weight : 3500).

[Synthesis Example 3] Production of alcohol-terminated polyphenylene oxide (alchol-MPPO-3)

MPPO-3 (0.8 kg, weight average molecular weight (Mw)) of light brown powder was obtained in the same manner as in Preparation Example 1, except that Compound 3 (0.1 kg) was used instead of Compound 2 : 6300).

[Synthesis Example 4] Production of alcohol-terminated polyphenylene oxide (alchol-MPPO-4)

(0.75 kg, weight average molecular weight (Mw) of alchohol-MPPO-4) was obtained in the same manner as in Preparation Example 1, except that Compound 4 (0.1 kg) : 7200).

[Synthesis Example 5] Production of alcohol-terminated polyphenylene oxide (alchol-MPPO-5)

Except that alchol-MPPO-5 (0.82 kg, weight average molecular weight (Mw)) of light brown powder was obtained in the same manner as in Preparation Example 1, except that Compound 5 (0.1 kg) : 6600).

[Synthesis Example 6] Production of vinyl-terminated polyphenylene oxide (vinyl-MPPO-1)

(700 g), methacrylic anhydride (127 g), and 4-Dimethylaminopyridine (100 g) obtained in Synthesis Example 1 were dissolved in toluene (1400 g, 50 g) in a 5 L round bottom flask equipped with a stirrer, ), The temperature was raised to the reflux temperature, and the reaction was allowed to proceed for 6 hours, and then the reaction solution was cooled to room temperature. Thereafter, the cooled reaction solution was precipitated in an excess amount of methanol to obtain a precipitate, and the precipitate was sufficiently washed with methanol. The washed precipitate was then dried in a vacuum oven at 80 DEG C for 24 hours to give light brown powder of the following vinyl-MPPO-1 (700 g, weight average molecular weight: 6,375).

[Synthesis Example 7] Preparation of epoxy-terminated polyphenylene oxide (epoxy-MPPO-1)

Alchol-MPPO-1 (1 kg) and epichlorohydrin (2.5 kg) obtained in Synthesis Example 1 were added to a 5 L round bottom flask equipped with a thermometer, a stirrer and a condenser and heated to dissolve. Then, sodium hydroxide (50 g) was added slowly to the reaction solution, and the mixture was stirred at 100 캜 for 12 hours, and then cooled to room temperature to obtain a reaction product. Subsequently, the reaction product was precipitated in an excess amount of methanol to obtain a precipitate. The precipitate was thoroughly washed with methanol and then dried in a vacuum oven at 80 DEG C for 24 hours to obtain epoxy-MPPO-1 (900 g, weight average molecular weight: ).

[Synthesis Example 8] Production of amine-terminated polyphenylene oxide (amine-MPPO-1)

The alchol-MPPO-1 (1 kg) and the dimethylformamide solvent (2 L) obtained in Synthesis Example 1 were put in a 5 L round bottom flask equipped with a thermometer, a stirrer and a condenser, Lt; / RTI &gt; Subsequently, 1,3-dinitrobenzene (150 g) and potassium carbonate (300 g) were added to the reaction mixture, followed by stirring at 150 ° C for 8 hours. Thereafter, the reaction product was precipitated in an excess amount of methanol and filtered to obtain a precipitate. The resulting precipitate was added to a 5 L round bottom flask together with 3-methoxyethanol (3 L). Then, Pt / C (30 g) and triethylamine (100 g) were added to the flask under a hydrogen atmosphere and reacted for 20 hours. Then, the catalyst and the separated product were precipitated in methanol through filtering to obtain amine-MPPO -1 (1.1 kg, weight average molecular weight: 6,350).

[ Synthetic example  9] ester-terminated polyphenylene Oxide ( ester - MPPO -1) Manufacturing

To a 5 L round bottom flask equipped with a thermometer, a stirrer and a condenser was added alchol-MPPO-1 (700 g) obtained in Synthesis Example 1 and methyl 4 - (chlorocarbonyl) -benzoate, MCCB) (150 g) was added and dissolved by heating. Then, triethylamine (120 g) was slowly added to the reaction solution, followed by stirring at 70 ° C for 5 hours. Subsequently, the reaction product was precipitated in an excess amount of methanol to obtain a precipitate. The resulting precipitate was sufficiently washed with methanol and then dried in a vacuum oven at 80 캜 for 24 hours to obtain ester-MPPO-1 (600 g, weight average molecular weight: ).

[compare Synthetic example  1] Alcohol-terminated polyphenylene Oxide ( alchol - MPPO - com ) Produce

The procedure of Synthesis Example 1 was repeated except that Compound 6 (0.5 kg) was used instead of Compound 2 (0.1 kg) used in Synthesis Example 1 to obtain alchol-MPPO-com (0.80 kg, weight average molecular weight : 3800).

[Comparative Synthesis Example 2] Production of vinyl-terminated polyphenylene oxide (vinyl-MPPO-com)

MPPO-com (700 g) obtained in Comparative Synthesis Example 1 was used instead of alchol-MPPO-1 (700 g) obtained in Synthesis Example 1 used in Synthesis Example 6, Vinyl-MPPO-com (700 g, weight average molecular weight: 3,700) of light brown powder was obtained.

[ Example  One]

The vinyl-terminated polyphenylene oxide (vinyl-MPPO-1) obtained in Synthesis Example 6 was coated on release paper and dried at 150 ° C for 5 minutes and then peeled off and cured at 210 ° C and 25 kg / cm ² for 150 minutes To prepare a polyphenylene oxide film.

[Example 2]

Except that the alcohol-terminated polyphenylene oxide (alchol-MPPO-1) obtained in Synthesis Example 1 was used instead of the modified polyphenylene oxide used in Example 1, To prepare a phenylene oxide film.

[Example 3]

Except that the amine-terminated polyphenylene oxide (amine-MPPO-1) obtained in Synthesis Example 8 was used in place of the modified polyphenylene oxide used in Example 1, the modified poly To prepare a phenylene oxide film.

[Example 4]

Except that the ester-terminal modified polyphenylene oxide (ester-MPPO-1) obtained in Synthesis Example 9 was used in place of the modified polyphenylene oxide used in Example 1, To prepare a phenylene oxide film.

[Comparative Example 1]

Except that the vinyl-terminated polyphenylene oxide (Vinyl-MPPO-com) obtained in Comparative Synthesis Example 2 was used in place of the modified polyphenylene oxide used in Example 1, To prepare a polyphenylene oxide film.

[Comparative Example 2]

Except that the alcohol-modified polyphenylene oxide (Alcohol-MPPO-com) obtained in Comparative Synthesis Example 1 was used in place of the modified polyphenylene oxide used in Example 1, To prepare a polyphenylene oxide film.

[Example 5]

A glass fiber substrate was impregnated with a resin composition as shown in Table 2 below and then dried at 150 ° C for 5 minutes to obtain a prepreg having a resin content of 50% by weight. After overlapping 8 the prepreg are laminated with copper foil 18 ㎛ the outside on both sides, to 150 minutes with a press 210 ℃, 25 terms of kg / cm ² for copper-clad laminate was produced.

[Example 6]

A prepreg and a copper clad laminate were produced in the same manner as in Example 5, except that the modified polyphenylene oxide of Synthesis Example 1 was used in place of the modified polyphenylene oxide of Synthesis Example 6 used in Example 5.

[Comparative Example 3] - [Comparative Example 5]

A prepreg and a copper-clad laminate were produced in the same manner as in Example 5, except that the resin composition having the composition shown in Table 2 was used. Compound 1 described in Table 2 is polyphenylene oxide (n = 60) represented by the above formula (16a).

[Experimental Example 1]

The following experiments were conducted on the modified polyphenylene oxide films obtained in Examples 1 to 4 and Comparative Examples 1 to 2 in order to confirm the dielectric characteristics and processing characteristics of the modified polyphenylene oxide according to the present invention. The experimental results are shown in Table 1 below.

(1) Dielectric constant (Dk): The dielectric constant (Dk) was measured using a material analyzer according to the test standard of IPC TM-650.2.5.5.1.

(2) Dielectric loss (Df): The dielectric loss (Df) was measured using a material analyzer according to the test standard of IPC TM-650.2.5.5.1.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Dk (@ 1 MHz) 2.45 2.52 2.52 2.5 2.54 2.59 Df (@ 1 MHz) 0.004 0.005 0.005 0.004 0.006 0.007

As can be seen from Table 1, the modified polyphenylene oxides of Examples 1 to 4 were not only low in dielectric constant, but also had a significantly lower dielectric loss than the modified polyphenylene oxide of Comparative Examples 1 and 2.

[Experimental Example 2]

The following tests were performed on the copper clad laminates produced in Examples 5 to 6 and Comparative Examples 3 to 5, and the results are shown in Table 2 below.

(1) Dielectric constant (Dk): The dielectric constant (Dk) was measured using a material analyzer according to the test standard of IPC TM-650.2.5.5.1.

(2) Dielectric loss (Df): The dielectric loss (Df) was measured using a material analyzer according to the test standard of IPC TM-650.2.5.5.1.

(3) Adhesion (P / S): Measured according to the test standard of IPC-TM-650.2.4.8.

(4) Heat resistance: A laminate cut into a size of 5 cm x 5 cm was placed in a 288 ° C water bath, and then the appearance change was visually observed for 10 minutes.

(5) Glass transition temperature (Tg): The copper foil layer of the copper-clad laminate was etched and measured using DSC (Differential Scanning Calorimeter).

As a result of the experiment, it was found that the thermosetting resin composition of the present invention exhibits excellent low dielectric loss characteristics and low dielectric constant, as well as improved adhesion to copper foil, excellent heat resistance, and thermal stability (see Table 2).

In particular, it was confirmed that Example 5 and Example 6 exhibited lower dielectric constant and excellent low dielectric loss characteristics, respectively, as compared with Comparative Example 3 and Comparative Example 4 corresponding to these configurations. Further, it was found that Example 1 using the modified polyphenylene oxide modified with a vinyl group at both terminals exhibited a synergistic effect in terms of heat resistance and adhesion to the copper foil.

Claims (9)

A modified polyphenylene oxide represented by the following formula (1):
[Chemical Formula 1]

(In the formula 1,
n is an integer from 1 to 10,000;
a is an integer from 0 to 4, when a is an integer of 1 to 4, R ₁ is C ₁ ~ C ₁₂ alkyl, and C ₁ ~ C ₁₂ alkoxy group is selected from the group consisting of;
m is 0 or 1;
Y ₁ and Y ₂ are the same or or different and are a direct bond, each independently from each other, or a substituted or unsubstituted arylene group, a C ₆ ~ C _12, wherein arylene of Y ₁ and Y ₂ groups are hydrogen, C ₁ ~ alkyl group of C _12, C ₁ ~ C ₁₂ alkoxy group and a C ₆ ~ C ₁₂ from the group consisting of an aryl group may be substituted with more than one kinds selected substituents, and;
R ₂ and R ₃ are the same or different and each independently represents -OH, -CR ₄ ═CH ₂ , -C (═O) CR ₅ ═CH ₂ , -NH ₂ ,

, -C (= O) -R ₆ ,

, -C (= O) -OR &lt; ₈ &gt; and

, &Lt; / RTI &gt;
R ₄ to R ₈ are the same or different and are each independently selected from the group consisting of hydrogen, a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkoxy group, and a C ₆ to C ₁₂ aryl group,
A plurality of W are the same or different from each other and are each independently selected from the group consisting of hydrogen, a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkoxy group, and a C ₆ to C ₁₂ aryl group;
Ar is a substituent represented by the following formula (2) or (3)
(2)

(3)

Q ₁ to Q ₃ are the same or different and are independently selected from the group consisting of a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkoxy group and a C ₁ to C ₁₂ haloalkyl group, 0, Q ₁ and Q ₂ are excluded if they are all alkyl groups,
o and p are each independently an integer of 0 to 3). The method according to claim 1,
The modified polyphenylene oxide represented by the formula (1) is a modified polyphenylene oxide represented by the following formula (4)
[Chemical Formula 4]

(Wherein,
n, m, Ar, Y ₁ , Y ₂ , R ₂ , and R ₃ are as defined in claim 1, respectively. The method according to claim 1,
The modified polyphenylene oxide represented by the formula (1) is a modified polyphenylene oxide represented by the formula selected from the group consisting of the following formulas (5) to (13):
[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

(Wherein,
n, Ar, R &lt; ₆ &gt; and R &lt; ₇ &gt; are as defined in claim 1,
W ₁ and W ₂ are the same or different and are each independently selected from the group consisting of hydrogen, a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkoxy group, and a C ₆ to C ₁₂ aryl group,
a and b are each 0 or 1). A film comprising the modified polyphenylene oxide according to any one of claims 1 to 3. A modified polyphenylene oxide according to any one of claims 1 to 3; And a thermosetting resin composition comprising a crosslinkable curing agent. Fiber substrates; And
The thermosetting resin composition according to claim 5 impregnated into the fiber substrate
. The method according to claim 6,
The fiber substrate may be one selected from the group consisting of glass fiber, glass paper, glass fiber web, glass cloth, aramid fiber, aramid paper, polyester fiber, Wherein the prepreg comprises: Metal foil or polymer film substrate; And
The thermosetting resin composition according to claim 5, which is formed on one side or both sides of the substrate,
And the functional laminated sheet. Copper foil; And the prepreg according to claim 6, wherein at least one layer of the prepreg is laminated.