KR101614581B1 - Coppor clad laminate using modified polyphenylene oxide - Google Patents

Abstract

The present invention relates to a process for the preparation of (a) a process for redispersion in the presence of a bisphenol compound (except for bisphenol A) and a radical initiator to modify a low molecular weight component having a weight average molecular weight (Mw) in the range of 1,000 to 20,000, A modified polyphenylene oxide resin having at least two functional groups selected from the group consisting of vinyl groups; And (b) a cross-linkable curing agent, a prepreg comprising the composition, and a copper-clad laminate.
The present invention can provide a high frequency printed circuit board exhibiting excellent low dielectric loss characteristics, excellent processability, copper foil adhesion, and thermal stability at the same time.

Description

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

The present invention relates to a copper clad laminate using a modified polyphenylene oxide resin having a low dielectric loss characteristic to a resin composition for a copper clad laminate, and using the prepreg and the prepreg excellent in workability while realizing a low dielectric property.

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, there has been proposed a technique of forming a low molecular weight polyphenylene oxide having an alcohol group introduced at both ends through redistribution reaction of polyphenylene oxide and polyphenol having a high molecular weight in the presence of a radical initiator. SA-90 (SABIC), a commercialized redistributed polyphenylene oxide, has improved compatibility with high-quality epoxy resins and improved melting point. However, the polyphenol bisphenol A (4,4 '- (propane-2 , 2-diyl) diphenol) and the high polarity of the alcohol group at both ends, there was a limit to lowering the dielectric property.

Japan Special Edition 2010-053179

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems.

In the present invention, in order to improve the genetic properties, a low molecular weight polyphenylene oxide resin is obtained by redistributing polyphenylene oxide having a high molecular weight and a specific bisphenol derivative having an increased alkyl content and aromatic content , The both terminals of the low molecular weight polyphenylene oxide were modified with an alcohol group or a vinyl group having a low polarity to obtain a resin having excellent dielectric properties and excellent processability and compatibility.

Accordingly, an object of the present invention is to provide a thermosetting resin composition including the above-mentioned modified polyphenylene oxide and exhibiting excellent processability and low dielectric properties, a prepreg using the composition, and a copper-clad laminate.

The present invention relates to (a) a modified polyphenylene oxide resin; Wherein the modified polyphenylene oxide resin (a) is redispersed in the presence of a bisphenol compound (excluding bisphenol A) and a radical initiator to produce a weight average molecular weight (Mw) Is modified to have a low molecular weight in the range of 1,000 to 20,000 and contains at least two functional groups selected from the group consisting of a hydroxyl group and a vinyl group at both ends of the molecular chain.

At this time, the thermosetting resin composition is preferably a thermosetting resin composition for manufacturing a high-frequency multilayer printed circuit board.

In the present invention, the modified polyphenylene oxide is preferably represented by the following formula (1) or (2).

According to a preferred embodiment of the present invention, the modified polyphenylene oxide resin (a) is obtained by subjecting a high molecular weight polyphenylene oxide resin having a weight average molecular weight (Mw) in the range of 5,000 to 350,000 to redistribution reaction in the presence of a specific bisphenol compound and a radical initiator Modified by a low molecular weight. Here, the specific bisphenol compound is a bisphenol-based compound other than bisphenol A (BPA), which is a compound having higher alkyl group content and aromatic group content than BPA.

Also, the crosslinkable curing agent (b) may be selected from triallyl isocyanurate (TAIC), di-4-vinylbenzyl oxide, divinylbenzene, divinylnaphthalene, divinylphenyl, 1,7- 9-decadiene and 9-decadiene.

According to another preferred embodiment of the present invention, it is preferable that the thermosetting resin composition further comprises a member selected from the group consisting of a flame retardant, an inorganic filler, a rubber, a curing accelerator, and a radical initiator.

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

Here, the fiber substrate may be a fiberglass, a glass paper, a glass fiber, a glass cloth, an aramid fiber, an aramid paper, a polyester fiber, a carbon fiber, And at least one selected from the group consisting of

Further, the present invention provides a printed circuit board comprising the prepreg and the copper foil, wherein the copper foil laminate is formed by laminating at least one of the prepreg and the copper foil, and a printed circuit board comprising the same.

The thermosetting resin composition according to the present invention satisfies low dielectric properties and exhibits excellent processability at the same time, so that the laminate using the laminate can exhibit excellent high frequency characteristics, good moisture absorption and heat resistance, and low thermal expansion characteristics.

Accordingly, the thermosetting resin composition of the present invention is useful as a component of a printed circuit board used in various types of electrical and electronic devices such as mobile communication apparatuses handling high frequency signals of 1 GHz or more, network-related electronic apparatuses such as base station apparatuses, servers, routers, And can be usefully used as an application.

Hereinafter, the present invention will be described in detail.

The present invention is intended to provide a thermosetting resin composition useful for printed circuit boards, particularly multilayer printed circuit boards for high-frequency applications.

Since the dielectric loss of the electric signal is proportional to the product of the square root of the relative dielectric constant of the insulating layer forming the circuit, the dielectric tangent, and the frequency of the electric signal, the higher the frequency of the electric signal, the larger the dielectric loss. Therefore, in order to be used for an insulating layer of a high-frequency printed circuit board, it is required to use a material having a low dielectric constant and a low dielectric loss factor (dielectric loss).

In order to satisfy the above-mentioned low dielectric property and dielectric loss characteristic, it is desired to use polyphenylene oxide (PPO) as a constituent component of the thermosetting resin composition in the present invention, but it is considered that the PPO having a high molecular weight is deteriorated in workability, Polyphenylene oxide having a high molecular weight and a specific bisphenol derivative having an increased alkyl content and aromatic content are redistributed to form a polyphenyleneoxide resin having a low molecular weight in consideration of deterioration and lack of heat resistance . In the present invention, the both ends of the redistributed low-molecular-weight polyphenylene oxide resin are modified into an alcohol group or a vinyl group having a low polarity, so that the resin having excellent dielectric properties and excellent workability and compatibility .

Particularly, the bisphenol derivatives used in the redistribution reaction of polyphenylene oxide in the present invention increase the number of carbon atoms of the alkyl group in the molecule and lower the overall polarity than bisphenol A (BPA) conventionally used. That is, as the alkyl content and the aromatic content are increased, the electron polarization phenomenon can be reduced and the dielectric property can be improved. Therefore, it was confirmed that a laminated board having high heat resistance and dimensional stability can be manufactured by improving low dielectric loss characteristics and improving crosslink density (see Table 1 below).

In the present invention, unsaturated bonds are possible by modifying both ends of a modified polyphenylene oxide molecular chain having excellent dielectric properties with an unsaturated double bond moiety, for example, a vinyl group. This causes a crosslinking reaction due to heat, contributes to improvement of heat resistance, and can suppress deformation and flow of the insulating layer.

In addition to satisfying moisture resistance and dielectric properties due to the improvement of glass transition temperature (Tg), low thermal expansion coefficient (CTE), and reduction of -OH (hydroxy) groups, , Securing various physical properties and processability at the same time.

≪ Thermosetting resin composition >

The thermosetting resin composition according to the present invention is a thermosetting resin composition comprising: (a) a modified polyphenylene oxide resin modified with a low molecular weight and having at least two hydroxyl groups and / or vinyl groups at both ends of the molecular chain; And (b) a cross-linkable curing agent. At this time, if necessary, it 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.

(a) a modified polyphenylene oxide resin

The first component constituting the thermosetting resin composition according to the present invention is a modified polyphenylene oxide (PPO) or an oligomer thereof containing two or more vinyl groups or hydroxyl groups (-OH) at both ends of the molecular chain, But the structure is not particularly limited and can be used.

The modified polyphenylene oxide resin according to the present invention is preferably a modified polyphenylene oxide expressed by the following general formula (1) or (2). This is because the side modified with two or more vinyl groups can satisfy the moisture resistance characteristic and the dielectric property due to the improvement of the glass transition temperature, the low thermal expansion coefficient, and the reduction of the -OH group.

In the above formula (1) or (2)

Ar is a bisphenol derivative compound excluding bisphenol A,

R are the same or different and are each independently an alkyl group having 1 to 12 carbon atoms,

R ₁ and R ₂ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aromatic group having 6 to 12 carbon atoms,

X are the same or different and are each independently a hydroxy group or a vinyl group,

n is a natural number between 1 and 10,000, and a is an integer between 0 and 4.

In the general formulas (1) and (2), Ar represents a bisphenol derivative except for bisphenol A (BPA), and is preferably represented by the general formula (3) or (4).

In the above formula (3) or (4)

R ₁ and R ₂ are the same or different and are each independently an alkyl group having 1 to 12 carbon atoms or a haloalkyl group having 1 to 12 carbon atoms (provided that when n is 0, R ₁ and R ₂ are both alkyl groups Is excluded)

R ₃ is hydrogen or an alkyl group having 1 to 12 carbon atoms,

n is a natural number between 0 and 3, and m is a natural number between 1 and 3.

The modified polyphenylene oxide resin (a) according to the present invention is more preferably a compound represented by any one of the following formulas (5) to (8).

In the above formulas 5 to 8,

R ₁ , R ₂ and n are each as defined in formulas 1 to 2,

Ar is preferably represented by any one of the following formulas (9) to (14).

[Chemical Formula 9]

(n = 1~3)

(n = 1 to 3)

[Chemical formula 10]

(n=1~3)

(n = 1 to 3)

(11)

(n=0~3)

(n = 0 to 3)

[Chemical Formula 12]

(n=0~3)

(n = 0 to 3)

[Chemical Formula 13]

(n=0~3)

(n = 0 to 3)

[Chemical Formula 14]

(n=0~3)

(n = 0 to 3)

In the present invention, those having two or more vinyl groups or hydroxyl groups (-OH) at both ends of the molecular chain are mainly used. In addition to the vinyl group, allyl and the like known in the art such as allyl It is also within the scope of the present invention to use unsaturated double bond moieties.

In the present invention, instead of using the conventional high molecular weight polyphenylene oxide (PPO) resin, the bisphenol derivatives having increased alkyl group content and aromatic group content are used for the redistribution reaction. It is preferable to use a form in which a vinyl group is introduced at both ends of the resin through redistribution.

That is, conventionally, polyphenylene oxide for copper clad laminate has been modified and used by low-molecular polyphenylene oxide having alcohol groups at both terminals through a redistribution reaction using polyphenol and a radical initiator as a catalyst, The structural characteristics of bisphenol A (chemical formula 20) used as a polyphenol used and the high polarity of alcohol groups at both terminals generated after redistribution have a limitation in realizing low dielectric loss characteristics.

In contrast to this, in the present invention, the polyphenol used in the redistribution reaction is redistributed by using an alkyl group (Alkyl) and a bisphenol derivative (except BPA) having an increased aromatic group content, It is possible to obtain a polyphenylene oxide having a low dielectric loss even after crosslinking by modifying an alcohol group located at both ends to a vinyl group having a low polarity. Such a modified polyphenylene oxide has a smaller molecular weight than that of conventional polyphenylene derivatives and also has a high alkyl content and therefore has excellent compatibility with conventional epoxy resins and the like, , The dielectric property is further improved. Therefore, the printed circuit board manufactured using the resin composition of the present invention has an advantage of improving physical properties such as moldability, workability, dielectric properties, heat resistance, and adhesive strength.

At this time, the specific bisphenol derivative compound in which the alkyl content and the aromatic content are increased can be obtained by using a bisphenol-based compound other than bisphenol A [BPA, 2,2-Bis (4-hydroxyphenyl) propane] . Non-limiting examples of usable bisphenol derivatives include bisphenol AP (1,1-bis (4-hydroxyphenyl) -1-phenyl-ethane), bisphenol AF (2,2- Bis (4-hydroxyphenyl) butane, bis- (4-hydroxyphenyl) diphenylmethane, bis (3-methyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) -2,2-dichlorethylene, 2,2-bis (4-hydroxy-3-isopropyl-phenyl) propane, 1,3- Bis (4-hydroxyphenyl) sulfone, 5,5 '- (1-Methylethyliden) -bis [1,1' - (bisphenyl) -2-ol] propane, bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -cyclohexane, And mixtures thereof. Preferably, at least one selected from the group consisting of the bisphenol-based compounds represented by the general formulas (9) to (14) can be used. For example, the bisphenol-based compound may be any one of the following general formulas (16) to (19)

The modified polyphenylene oxide resin (a) according to the present invention is obtained by reacting a high molecular weight polyphenylene oxide resin having a weight average molecular weight (Mw) in the range of 5,000 to 350,000 with a specific bisphenol compound represented by any one of the following general formulas It is preferable to carry out a redistribution reaction in the presence of an initiator to modify the weight average molecular weight (Mw) to a low molecular weight in the range of 1,000 to 20,000. More preferably in the range of 1000 to 10,000. However, the present invention is not particularly limited thereto.

The bisphenol compound may be any one of the following bisphenol compounds represented by the following general formulas (16) to (19).

(b) a crosslinking curing agent

The second component constituting the thermosetting resin composition according to the present invention is a crosslinking curing agent.

Such a cross-linking curing agent is used to form a network structure by cross-linking the polyphenylene oxide three-dimensionally. Even if a low molecular weight modified polyphenylene oxide is used to increase the fluidity of the resin composition, the use of the crosslinkable curing agent contributes to improvement of the heat resistance of the polyphenylene oxide. And 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 according to the present invention has excellent compatibility with polyphenylene oxide whose side is modified with a vinyl group. Non-limiting examples of crosslinkable curing agents that can be used include allyl oxide 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.

(c) Flame retardant

The thermosetting resin composition according to the present invention may further contain a flame retardant (c) as required.

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 poly (phenylene oxide) and does not deteriorate heat resistance characteristics 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.

(d) Inorganic filler

The thermosetting resin composition according to the present invention may further comprise a conventional inorganic filler (d) known in the art for use in a laminate as required.

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

Among the inorganic fillers, fused silica exhibiting a low thermal expansion coefficient 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 to enhance the favorable effect of the crosslinkable curing agent.

Such a reaction initiator can further accelerate the curing of the 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 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 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. It may also contain additives commonly used in thermosetting resin compositions used in the production of electronic devices (particularly printed wiring boards).

According to a preferred example of the present invention, the thermosetting resin composition comprises: (a) a modified polyphenylene oxide resin having two or more hydroxyl groups / vinyl groups at both ends of the molecular chain and modified with a low molecular weight; (B) 5 to 50 parts by weight of a crosslinkable curing agent based on 100 parts by weight of the 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 > The criteria for 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 of the present invention comprises a fiber base material and the aforementioned thermosetting resin composition impregnated in the fiber base material. 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, the impregnability of the resin composition with respect 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.

<Copper with resin>

The present invention relates to a metal foil; And a resin-coated metal foil formed on one or both surfaces of the metal foil, wherein the thermosetting resin composition comprises a cured resin layer.

In the resin-coated metal foil of the present invention, 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.

<Laminates and printed circuit boards>

The present invention includes a laminate formed by superimposing two or more of the above-mentioned prepregs on one another 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 substrate, dried, laminated together with a copper foil, and subjected to heat and pressure to obtain a desired laminated plate. At this time, the heating and pressurizing conditions at the time of forming the laminates can be appropriately adjusted according to the thickness of the laminate to be produced, the kind 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 1 below). Therefore, the prepreg and the printed circuit board of the present invention can be used for a mobile communication device handling a high frequency signal of 1 GHz or higher, a network-related electronic device such as a base station device, a server, a router, And can be usefully used as a component part of a printed circuit board.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the scope of the present invention is not limited by the following Examples and Experimental Examples. In the following description, &quot; part &quot; means &quot; part by mass &quot;.

<Material>

As the alcohol-terminated polyphenylene oxide used in the present invention, commercially available SA-120 (SABIC) was used. In order to secure the characteristics of the other copper-clad laminate, cyanate resin, epoxy resin, curing agent, curing accelerator, The solvent and the like were used without purification.

[Synthesis Example 1]

Preparation of Alcohol-Modified Polyphenylene Oxide Using Formula (16)

In a 20 L round bottom flask equipped with a thermometer, a stirrer and a condenser, 1.0 Kg of the compound of Formula 15, 0.1 Kg of the compound of Formula 16, and 10 kg of Toluene were charged and heated to 60 ° C and sufficiently dissolved in a nitrogen atmosphere. Ten g of Benzoyl peroxide 75% as a catalyst was dissolved in 90 g of toluene, and then slowly dropped into the reactor. After the dropwise addition, the temperature of the reactor was raised to 90 DEG C, and the reaction was continued for 8 hours and 30 minutes and then cooled to room temperature. The cooled reaction solution was concentrated to about 50% in toluene, the concentrate was then precipitated in excess methanol, and the precipitate was dried in a vacuum oven at 80 DEG C for 24 hours. After drying, 0.85 Kg of light reddish brown powdery redispersible polyphenylene oxide resin with a weight average molecular weight (Mw) of 6,500 was obtained. Here, the weight average molecular weight (Mw) of the polyphenylene oxide before the redistribution reaction was 9,000.

[Chemical Formula 15]

[Chemical Formula 16]

[Synthesis Example 2]

Preparation of Alcohol-Modified Polyphenylene Oxide Using Formula (16)

To a 20 L round bottom flask equipped with a thermometer, a stirrer and a condenser, 1.0 Kg of the compound of Formula 15, 0.5 Kg of the compound of Formula 16, and 10 Kg of Toluene were added, and the mixture was heated to 60 캜 and sufficiently dissolved in a nitrogen atmosphere. As a catalyst, 10 g of 75% benzoyl peroxide was dissolved in 90 g of toluene, and then slowly dropped into the reactor. After the dropwise addition, the temperature of the reactor was raised to 90 DEG C, and the reaction was continued for 8 hours and 30 minutes and then cooled to room temperature. The cooled reaction solution was concentrated to about 50% in toluene, the concentrate was then precipitated in excess methanol, and the precipitate was dried in a vacuum oven at 80 DEG C for 24 hours. After drying, 0.85 Kg of light reddish brown powdery redistributed polyphenylene oxide resin with a weight average molecular weight (Mw) of 3,500 was obtained.

[Synthesis Example 3]

Preparation of Alcohol-Modified Polyphenylene Oxide Using Formula (17)

In a 20 L round bottom flask equipped with a thermometer, a stirrer and a condenser, 1.0 Kg of the compound of formula (15), 0.1 kg of the compound of formula (17) and 10 kg of Toluene were added and heated to 60 DEG C and sufficiently dissolved in a nitrogen atmosphere. Ten g of Benzoyl peroxide 75% as a catalyst was dissolved in 90 g of toluene, and then slowly dropped into the reactor. After the dropwise addition, the temperature of the reactor was raised to 90 DEG C, and the reaction was continued for 8 hours and 30 minutes and then cooled to room temperature. The cooled reaction solution was concentrated to about 50% in toluene, the concentrate was then precipitated in excess methanol, and the precipitate was dried in a vacuum oven at 80 DEG C for 24 hours. After drying, 0.8 kg of redistilled polyphenylene oxide resin in the form of light brown powder having a weight average molecular weight (Mw) of 6,300 was obtained.

[Chemical Formula 17]

[Synthesis Example 4]

Preparation of Alcohol-Modified Polyphenylene Oxide Using Formula 18

1.0 Kg of formula (15), 0.1 Kg of formula (18) and 10 Kg of toluene were added to a 20 L round bottom flask equipped with a stirrer, a thermometer, a stirrer and a condenser, and heated to 60 DEG C and sufficiently dissolved in a nitrogen atmosphere. Ten g of Benzoyl peroxide 75% as a catalyst was dissolved in 90 g of toluene, and then slowly dropped into the reactor. After the dropwise addition, the temperature of the reactor was raised to 90 DEG C, and the reaction was continued for 8 hours and 30 minutes and then cooled to room temperature. The cooled reaction solution was concentrated to about 50% in toluene, the concentrate was then precipitated in excess methanol, and the precipitate was dried in a vacuum oven at 80 DEG C for 24 hours. After drying, 0.75 Kg of redistilled polyphenylene oxide resin in the form of light brown powder having a weight average molecular weight (Mw) of 7,200 was obtained.

[Chemical Formula 18]

[Synthesis Example 5]

Preparation of Alcohol-Modified Polyphenylene Oxide Using Formula 19

In a 20 L round bottom flask equipped with a thermometer, a stirrer, and a condenser, 1.0 Kg of Formula 15, 0.1 Kg of Formula 19, and 10 Kg of Toluene were charged and heated to 60 캜 and sufficiently dissolved in a nitrogen atmosphere. Ten g of Benzoyl peroxide 75% as a catalyst was dissolved in 90 g of toluene, and then slowly dropped into the reactor. After the dropwise addition, the temperature of the reactor was raised to 90 DEG C, and the reaction was continued for 8 hours and 30 minutes and then cooled to room temperature. The cooled reaction solution was concentrated to about 50% in toluene, the concentrate was then precipitated in excess methanol, and the precipitate was dried in a vacuum oven at 80 DEG C for 24 hours. After drying, a redistributed polyphenylene oxide resin in the form of light brown powder of 0.82 Kg having a weight average molecular weight (Mw) of 6,600 was obtained.

[Chemical Formula 19]

[Synthesis Example 6]

1-1. Production of vinyl-terminated polyphenylene oxide

700 g of the polyphenylene oxide obtained in Synthesis Example 2, 127 g of methacrylic anhydride, and 100 g of 4-dimethylaminopyridine were dissolved in 1400 g of toluene, and the mixture was heated to reflux temperature for 6 hours to react in a 5 L round bottom flask equipped with a thermometer, And the reaction solution was cooled to room temperature. The cooled reaction solution was allowed to settle in an excess amount of methanol, and the obtained precipitate was washed with sufficient methanol. The obtained precipitate was dried in a vacuum oven at 80 DEG C for 24 hours. After drying, 700 g of a polyphenylene oxide resin having a light brown powdery vinyl group introduced therein having a weight average molecular weight (Mw) of 3,650 was obtained.

[Synthesis Example 7]

Preparation of Alcohol-Modified Polyphenylene Oxide Using Formula 20

In a 20 L round bottom flask equipped with a thermometer, a stirrer and a condenser, 1.0 Kg of the compound of Formula 15, 0.5 Kg of the compound (BPA) of Formula 20 and 10 Kg of Toluene were charged and sufficiently dissolved in a nitrogen atmosphere by heating at 60 ° C. Ten g of Benzoyl peroxide 75% as a catalyst was dissolved in 90 g of toluene, and then slowly dropped into the reactor. After the dropwise addition, the temperature of the reactor was raised to 90 DEG C, and the reaction was continued for 8 hours and 30 minutes and then cooled to room temperature. The cooled reaction solution was concentrated to about 50% in toluene, the concentrate was precipitated in an excess amount of methanol, and the precipitate was dried in a vacuum oven at 80 DEG C for 24 hours. After drying, an alcohol-terminated polyphenylene oxide resin in the form of a pale brown powder having a weight average molecular weight (Mw) of 3,800 and a yield of 0.80 Kg was obtained.

[Chemical Formula 20]

[Synthesis Example 8]

Production of vinyl-terminated polyphenylene oxide

700 g of the polyphenylene oxide obtained in Synthesis Example 7, 127 g of methacrylic anhydride and 100 g of 4-dimethylaminopyridine were dissolved in 1400 g of toluene, and the reaction was allowed to proceed for 6 hours to the reflux temperature in a 5 L round bottom flask equipped with a thermometer, a stirrer and a condenser Then, the reaction solution was cooled to room temperature. The cooled reaction solution was precipitated in an excess amount of methanol and the obtained precipitate was washed with sufficient methanol. The obtained precipitate was dried in a vacuum oven at 80 DEG C for 24 hours. After drying, 700 g of a light brown powdery vinyl group-introduced polyphenylene oxide resin having a weight average molecular weight (Mw) of 3,900 was obtained.

[Example 1: Preparation of resin composition, prepreg and copper-clad laminate]

A glass fiber substrate was impregnated with a resin composition having the composition shown in Table 1 below and then dried at 150 ° C for 5 minutes to obtain a prepreg having a resin content of 50% by weight. After the overlap 8 the prepreg are laminated with copper foil 18 ㎛ the outside on both sides, to 210 ℃, condition of 25kg / cm ² 150 bungan press to prepare a copper-clad laminate.

[Example 2]

A copper-clad laminate was produced in the same manner as in Example 1 except that the polyphenylene oxide of Synthesis Example 2 was used instead of the polyphenylene oxide of Synthesis Example 6.

[ Comparative Example  1-3]

A copper-clad laminate was produced in the same manner as in Example 1, except that the resin composition having the composition shown in Table 1 below was used.

Experimental Example 1. Physical properties of copper clad laminate

The following tests were performed on the copper clad laminates produced in Examples 1 to 2 and Comparative Examples 1 to 3, and the results are shown in Table 1 below.

[Measuring conditions]

1. Permittivity (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): Measured according to the test standard of IPC TM-650.2.5.5.1 using a material analyzer.

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 ㅧ 5 cm from a 288 째 C water bath was placed and 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).

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Polyphenylene oxide
(PPO resin) Synthesis Example 6 100 Synthesis Example 2 100 Synthesis Example 8 100 Synthesis Example 7 100 Formula 15 100 Hardener TAC 40 40 40 40 40 Flame retardant Saytex 8010 40 40 40 40 40 Inorganic filler SC-5200SQ 77 77 77 77 77 Copper clad laminate
Application characteristics 1 GHz Dk 3.63 3.70 3.75 3.82 3.90 Df 0.0025 0.004 0.0045 0.0051 0.0053 P / S
(@ 1 / 2Oz-gf / cm) 1.0 0.9 0.8 0.8 0.6 Heat resistance
(S / F @ 288) > 600 sec > 300 sec > 300 sec > 300 sec > 300 sec Tg 170 160 160 150 130

As a result of the test, 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 improvement in adhesion to a copper foil, excellent heat resistance, and thermal stability (see Table 1 above).

In particular, it was confirmed that Example 1 and Example 2 exhibited lower dielectric constant and excellent low dielectric loss characteristics, respectively, as compared with Comparative Example 1 and Comparative Example 2 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 (14)

(a) a modified polyphenylene oxide resin; And
(b) a cross-linkable curing agent,
The modified polyphenylene oxide resin (a) is obtained by redistributing polyphenylene oxide in the presence of a bisphenol compound (excluding bisphenol A) and a radical initiator and modifying the polyphenylene oxide to a low molecular weight having a weight average molecular weight (Mw)
At least two functional groups selected from the group consisting of a hydroxyl group and a vinyl group at both ends of the molecular chain,
The crosslinkable curing agent (b) is selected from the group consisting of triallyl isocyanurate (TAIC), di-4-vinylbenzyl oxide, divinylbenzene, divinylnaphthalene, divinylphenyl, 1,7-octadiene, -Tecadienes. &Lt; / RTI &gt; The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is a thermosetting resin composition. The thermosetting resin composition according to claim 1, wherein the modified polyphenylene oxide resin (a) is represented by the following formula (1) or (2).
[Chemical Formula 1]

(2)

In this formula,
Ar is a bisphenol-based compound excluding bisphenol A,
R are the same or different and are each independently an alkyl group having 1 to 12 carbon atoms,
R ₁ and R ₂ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aromatic group having 6 to 12 carbon atoms,
X are the same or different and are each independently a hydroxy group or a vinyl group,
n is a natural number between 1 and 10,000, and a is an integer between 0 and 4. The thermosetting resin composition according to claim 2, wherein Ar is represented by the following Chemical Formula 3 or Chemical Formula 4:
(3)

[Chemical Formula 4]

In the above formula (3) or (4)
R ₁ and R ₂ are the same or different and are each independently an alkyl group having 1 to 12 carbon atoms or a haloalkyl group having 1 to 12 carbon atoms (provided that when n is 0, R ₁ and R ₂ are both alkyl groups Is excluded)
R ₃ is hydrogen or an alkyl group having 1 to 12 carbon atoms,
n is a natural number between 0 and 3, and m is a natural number between 1 and 3. 2. The bisphenol compound according to claim 1, wherein the bisphenol compound (excluding bisphenol A) is bisphenol AP (1,1-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxyphenyl) butane, bis- (4-hydroxyphenyl) diphenylmethane and bisphenol C (2,2-bis (3-methyl-4-hydroxyphenyl) propane Bis (4-hydroxyphenyl) -2,2-dichlorethylene, 2,2-bis (4-hydroxy-3-isopropyl-phenyl) propane), bisphenol M 2- (4-hydroxyphenyl) -2-propyl) benzene, Bis (4-hydroxyphenyl) sulfone, 5,5 '- (1-Methylethyliden) -bis [ ) -2-ol] propane, 1,1-Bis (4-hydrophenyl) -3,3,5-trimethyl-cyclohexane, and 1,1-Bis (4-hydroxyphenyl) -cyclohexane Wherein the thermosetting resin composition is a thermosetting resin composition. The polyphenylene oxide resin composition according to claim 1, wherein the modified polyphenylene oxide resin (a) is a high molecular weight polyphenylene oxide resin having a weight average molecular weight (Mw) in the range of 5,000 to 350,000 and a bisphenol compound (excluding bisphenol A) Wherein the thermosetting resin composition is modified to have a low molecular weight by a redistribution reaction in the presence of the thermosetting resin composition. delete The thermosetting resin composition according to claim 1, wherein the composition further comprises a flame retardant. The thermosetting resin composition according to claim 7, wherein the flame retardant is at least one selected from the group consisting of a halogen-containing flame retardant, a phosphorus flame retardant, an antimony flame retardant, and a metal hydroxide. The thermosetting resin composition according to claim 1, wherein the composition further comprises a rubber and an inorganic filler. Fiber substrates; And
A prepreg comprising the thermosetting resin composition according to any one of claims 1 to 5 and 7 to 9 impregnated into the fiber substrate. The prepreg according to claim 10, wherein the fibrous base material is selected from the group consisting of inorganic fibers and organic fibers. The method according to claim 11, wherein the fiber substrate is made of glass fiber, glass paper, glass fiber web, glass cloth, aramid fiber, aramid paper, polyester fiber, Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt; Metal foil or polymer film substrate; And
The thermosetting resin composition according to any one of claims 1 to 5 and 7 to 9, which is formed on one surface or both surfaces of the substrate,
The functional laminated sheet A copper-clad laminate comprising the prepreg and the copper foil according to claim 10, wherein the copper-clad laminate is formed by laminating one or more layers thereof.