KR101708146B1 - Thermoplastic resin composition for high frequency having low permittivity, prepreg and copper clad laminate using the same - Google Patents

Abstract

(A) a polyphenylene ether resin or oligomer thereof having at least two unsaturated substituents selected from the group consisting of a vinyl group and an allyl group at both ends of a molecular chain; And (b) a cross-linkable curing agent, a prepreg comprising the composition, and a printed circuit board.
The present invention can provide a high frequency printed circuit board exhibiting excellent low dielectric loss characteristics, good moisture absorption and heat resistance, low thermal expansion characteristics, and thermal stability at the same time.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermosetting resin composition for high frequency use having low dielectric loss characteristics, a prepreg using the same, and a copper-

The present invention relates to a novel high-frequency thermosetting resin composition capable of simultaneously exhibiting excellent low dielectric loss characteristics, good moisture absorption and heat resistance, low thermal expansion characteristics and thermal stability, and a prepreg, a functional laminated sheet and a copper clad laminate using the same.

Recently, the signal band of electronic components such as semiconductor substrates, printed circuit boards, EMC (Epoxy Molding Compound), and information communication devices tends to increase. The transmission loss of an electrical signal is proportional to dielectric tangent and frequency. Therefore, as the frequency is high, the transmission loss becomes large, and signal attenuation is caused, thereby reducing the reliability of the signal transmission. In addition, transmission loss may be converted into heat, which may cause a problem of heat generation. Therefore, an insulating material having a very low dielectric loss tangent is required in a high frequency region.

In addition, demands for high integration, high density, and high performance in the semiconductor devices and PCB fields are increasing, so that integration of semiconductor devices and increasing density of printed circuit boards and simplification of wiring intervals are gradually changing. In order to satisfy such a characteristic, it is preferable to use a low dielectric constant for increasing the transmission speed and a low dielectric loss material for reducing the transmission loss.

Although poly (phenylene ether) resin having excellent dielectric properties has been applied to exhibit such low dielectric properties, it has problems such as high melt viscosity, difficulty in handling, and molding processability of prepreg.

Japanese Patent Application Laid-Open No. 07-090172

Disclosure of the Invention The present invention has been conceived to solve the above-mentioned problems. It is an object of the present invention to provide a poly (phenylene ether) resin in which both sides of a molecular chain are modified with an unsaturated bond substituent group and a crosslinking curing agent in combination, At the same time, an excellent thermosetting resin composition was produced.

Accordingly, an object of the present invention is to provide a thermosetting resin composition exhibiting excellent heat resistance and low dielectric properties, a prepreg using the composition, and a copper-clad laminate.

The present invention relates to (a) polyphenylene ether or an oligomer thereof having at least two unsaturated substituents selected from the group consisting of a vinyl group and an allyl group at both terminals of a molecular chain; And (b) a crosslinkable curing agent. The present invention also provides a thermosetting resin composition for a non-epoxy high frequency wave.

According to a preferred embodiment of the present invention, the polyphenylene ether resin (c) is a resin obtained by redispersing a high molecular weight polyphenylene ether resin having a number average molecular weight of 10,000 to 30,000 in the presence of a bisphenol-based compound (except for bisphenol A) And the number-average molecular weight is modified to a low molecular weight in the range of 1,000 to 10,000.

The molecular weight distribution of the polyphenylene ether resin (a) is preferably 3 or less (Mw / Mn < 3).

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

According to another preferred embodiment of the present invention, it is preferable that the thermosetting resin composition further comprises one selected from the group consisting of a flame retardant, an inorganic filler, 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 characterized by being laminated and formed by including one or more prepregs.

Since the thermosetting resin composition according to the present invention simultaneously satisfies the glass transition temperature (Tg) improvement, the low thermal expansion coefficient (CTE), the low dielectric property and the heat resistance, the printed circuit board using the same has excellent high frequency characteristics, good moisture absorption and heat resistance, Lt; / RTI &gt;

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 realize a low dielectric constant polymer material due to such a demand, substrate materials for high frequency applications have been developed in which epoxy resin is reduced in hydroxyl group, crosslinking of thermoplastic resin, application of liquid crystal polymer or polyimide, and the like. In order to satisfy the high-frequency characteristics, the dielectric properties are insufficient or molding is difficult.

In order to satisfy the above-mentioned low dielectric property and dielectric loss property, the present invention uses poly (phenylene ether) (PPE) as a constituent component of the thermosetting resin composition, but has a low heat resistance, (Phenylene ether) in which both ends of the molecular chain are modified with unsaturated bonding substituent groups and a specific crosslinkable curing agent in consideration of viscosity increase and the like.

More specifically, in the present invention, the side of the poly (phenylene ether) is made to be unsaturated by modification with a vinyl group, an allyl group, or the like. 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, By studying the dielectric properties according to the properties of the crosslinking agent, it is possible to secure various physical properties and workability at the same time.

Therefore, it has been found that di- (4-vinylbenzyl), which is a moiety curing agent having a linear structure of 1,9-decadien, a symmetric structure and a ring structure, inhibiting orientation polarization of poly (phenylene ether) ether curing agent is used in combination, it is possible to secure the flow characteristics by controlling the low dielectric property and the content simultaneously.

&Lt; Thermosetting resin composition >

The thermosetting resin composition according to the present invention is a non-epoxy and non-cyanate ester (CE) thermosetting resin composition, which comprises (a) A polyphenylene ether resin or an oligomer thereof having at least two unsaturated substituents selected from the group consisting of And (b) a cross-linkable curing agent. At this time, if necessary, a flame retardant, an inorganic filler, a curing accelerator, a radical initiator, and the like may be further included.

(a) a poly (phenylene ether)

The first component constituting the thermosetting resin composition according to the present invention is polyphenylene ether (PPE) or an oligomer thereof, provided that it has two or more vinyl groups, allyl groups or both at both ends of the molecular chain, The structure is not particularly limited and can be used.

In the present invention, an allylated poly (phenylene ether) represented by the following general formula (1) is preferable. 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.

Y is at least one selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, naphthalene type epoxy resins, anthracene epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, Cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, and bisphenol S novolac type epoxy resin,

m and n are each independently a natural number of 3 to 20.

In the present invention, those having at least two vinyl groups at both ends of the molecular chain are mainly used. However, it is also possible to use a conventional unsaturated double bond moiety known in the art in addition to the vinyl group Are within the scope of the present invention.

On the other hand, it is difficult to produce a multilayer sheet because the poly (phenylene ether) has a high melting point, and thus the melt viscosity of the resin composition is high. Therefore, in the present invention, it is preferable to use a modified form of low molecular weight through redistribution instead of using high molecular weight polyphenylene ether as it is.

In particular, when modifying a high molecular weight polyphenylene ether with a low molecular weight polyphenylene ether resin, a compound such as a phenol derivative or bisphenol A is generally used. In this case, the molecular structure is rotatable, .

In the present invention, instead of using a conventional high molecular weight polyphenylene ether (PPE) resin as a raw material, a bisphenol derivative having an increased alkyl group (Alkyl) content and aromatic group (aromatic) , A form in which a vinyl group is introduced at both ends of the resin through redistribution is used.

That is, conventionally, polyphenylene ether for copper clad laminate has been modified from low-molecular polyphenylene ether having alcohol groups at both terminals through a redistribution reaction using polyphenol and radical initiator as a catalyst, Due to the structural properties of bisphenol A, which is a polyphenol used, and the high polarity of the alcohol groups at both terminals generated after redistribution, there is a limit to implementation of low dielectric loss characteristics.

In contrast to this, in the present invention, the polyphenol used in the redistribution reaction is redistributed using specific bisphenol derivatives having increased alkyl and alkaline (aromatic) contents, (Vinyl group) having a low polarity, it is possible to obtain a polyphenylene ether having a low dielectric loss even after crosslinking. Such a modified polyphenylene ether has a smaller molecular weight than that of conventional polyphenylene derivatives and 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.

The polyphenylene ether resin is subjected to redistribution reaction of a high molecular weight polyphenylene ether resin having a number average molecular weight in the range of 10,000 to 30,000 in the presence of a bisphenol-based compound (except for bisphenol A) to give a number average molecular weight (Mn) And preferably has a number average molecular weight (Mn) in the range of 1,000 to 5,000, more preferably in the range of 1,000 to 3,000.

The polyphenylene ether resin (a) according to the present invention is obtained by redispersing a high molecular weight polyphenylene ether resin having a number average molecular weight (Mn) of 10,000 to 30,000 under a bisphenol-based compound (except for bisphenol A) It is preferable that the molecular weight is modified to a low molecular weight ranging from 1000 to 10,000. More preferably in the range of 1,000 to 3,000. However, the present invention is not limited thereto.

The molecular weight distribution of the poly (phenylene ether) is preferably 3 or less (Mw / Mn < 3), and preferably 1.5 to 2.5.

(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 three-dimensionally cross-linking the poly (phenylene ether). Even when a poly (phenylene ether) modified with a low molecular weight 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 poly (phenylene ether). 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 miscibility with the polyphenylene ether modified with a vinyl group, an allyl group or the like. Non-limiting examples of crosslinkable curing agents that can be used include allyl (meth) acrylates prepared by the reaction of vinyl benzyl ether compound series divinylbenzene (formula 5), divinyl naphthalene, divinyl diphenyl, styrene monomer, phenol and allyl chloride Ether compounds; (TAIC, formula 4), triallyl cyanurate (TAC), 1,2,4-trivinylcyclohexane, 1,7-octadiene, 1,9-decadiene Diene-4-vinylbenzyl ether (Formula 3), and the like. At this time, the above-mentioned curing agents may be used alone or in combination of two or more.

Specific examples of preferred crosslinking curing agents may be any of the compounds represented by the following formulas (2) to (5). They are not only excellent in compatibility, but also have excellent moldability, low dielectric constant and 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. Particularly, in the present invention, viscosity control can be facilitated by mixing di- (4-vinylbenzyl) ether (Formula 3), which exhibits an initiating delay reaction effect as a crosslinking agent, in an optimal amount with other cross-linkable curing agents. By controlling the resin flowability based on this, it is possible to overcome the difficulty of handling and molding processability of the prepreg

More specifically, when a cross-linking curing agent having a linear structure and a cross-linking curing agent having a cyclic structure are mixed as the cross-linking curing agent, the flow characteristics by controlling the low dielectric constant and the content can be secured at the same time. In this case, the ratio of the linear cross-linking curing agent to the cyclic cross-linking curing agent may be in the range of 10-90: 90-10, preferably 30-70: 70-30 (weight ratio). The crosslinkable curing agent having a linear structure and the crosslinking curing agent having a cyclic structure are not particularly limited. For example, a linear structure of 1,9-decadienes, a mordant having a symmetric structure and a cyclic structure It is preferable to use a di- (4-vinylbenzyl) ether curing agent which is a titanium curing agent.

In the thermosetting resin composition according to the present invention, the content of the cross-linkable curing agent may be 5 to 40 parts by weight, preferably 10 to 25 parts by weight, based on the total weight of the poly (phenyl ether) Lt; / RTI &gt; 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 ether) 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 10 to 30 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of the entire varnish. 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.

(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, it is preferably in the range of 10 to 50 parts by weight based on 100 parts by weight of the entire thermosetting resin composition varnish. 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 ether 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 ether, 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 ether, but is not limited thereto.

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 phenoxy resin, polyvinyl acetal resin, polyimide, polyamideimide, polyethersulfone, 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 embodiment of the present invention, the thermosetting resin composition comprises, based on 100 parts by weight of the composition, (a) 20 to 50 parts by weight of a polyphenylene ether resin having two or more unsaturated substituents at both ends of the molecular chain; (b) 5 to 40 parts by weight of a crosslinkable curing agent (c) 10 to 30 parts by weight of a flame retardant; And (d) 10 to 50 parts by weight of an inorganic filler, and further 100 parts by weight of the total of the organic solvent and other components may be contained. 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, chopped 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 ether 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.

<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. 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 printed circuit boards have low dielectric constant and dielectric loss as well as low thermal expansion coefficient (CTE), high glass transition temperature (Tg) and 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;.

[Examples 1 to 9]

1-1. Preparation of resin composition

The crosslinking curing agent, the curing accelerator, the flame retardant and the inorganic filler were mixed with the polyphenylene ether in toluene according to the composition shown in Table 1 below, stirred for 3 hours, added with an initiator, and further stirred for 1 hour to obtain a resin A composition was prepared. In Table 1, the unit of usage of each composition is parts by weight.

1-2. Preparation of prepreg and printed circuit board

The prepared resin composition was impregnated with glass fiber and dried at 165 ° C for 3 to 10 minutes to prepare a prepreg. 1 ply of the prepreg was laminated and pressed to obtain a laminated thin plate having a thickness of 0.1 mm.

[Comparative Examples 1 and 2]

A resin composition, a prepreg and a printed circuit board were prepared in the same manner as in the above example, except that the composition shown in Table 1 was used. In Table 1, the unit of usage of each composition is parts by weight.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Allyate PPE 40 40 40 40 40 40 40 40 40 40 40 TAIC 10 5 5 5 DVB 10 5 5 5 Di- (4-vinylbenzyl) ether 3 5 7 10 1,9-Decadiene 7 5 3 10 5 5 Naphthalene epoxy 6 BPA epoxy 6 BPM CE 8 8 Flame retardant 10 10 10 10 10 10 10 10 10 10 10 Initiator 2 2 2 2 2 2 2 2 2 2 2 Inorganic filler 30 30 30 30 30 30 30 30 30 30 30 DSC Tg (占 폚) 200 195 190 203 190 210 200 205 200 180 175 CTE (%) 2.5 2.5 2.5 2.7 2.6 2.6 2.5 2.6 2.6 3.4 3.6 R / F (%)
(5 - 10% optimum amount) 6.9 7.4 8.1 5.1 8.8 7.2 6.3 5.2 5.9 9.4 11.4 Solder Folting (@ 288 ^o C) OK OK OK OK OK OK OK OK OK OK OK PCT (4 hr) OK OK OK OK OK OK OK OK OK NG NG Permittivity (Dk @ 1 GHz) 3.64 3.70 3.75 3.60 3.79 3.75 3.78 3.77 3.72 3.95 4.05 Dielectric loss (Df @ 1 GHz) 0.0023 0.0024 0.0026 0.0022 0.0028 0.0026 0.0027 0.0026 0.0026 0.0037 0.0046 Flammability V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 P / S (kgf / cm) 0.8 0.8 0.8 0.7 0.8 0.8 0.8 0.7 0.8 0.8 0.8

^Ltd. 1) Allylate PPE: MX-9000 (number average molecular weight: 2000 to 3000)

2) TAIC: TAIC ^® (NIPPON KASEI CHEMICAL)

3) DVB: DVB (DOW)

4) Di- (4-vinylbenzyl) ether: BPA-DAE (HAOHUA INDUSTRY)

5) 1,9-decadiene: 1,9-decadiene (EVONIC)

6) Naphthalene Epoxy: NC-7000L (Nippon Kayaku)

7) BPA Epoxy: YD-128 (Kukdo Chemical)

8) BPM CE: XU-366 (HUNTSMAN)

10) Flame retardant: Saytex 8010 (Albemarle Asano Corporation)

11) Initiator: Perbutyl P (manufactured by NOF Corporation)

12) Inorganic filler: SC-5200SQ (Manufacturer Admatechs)

Experimental Example 1. Physical properties of printed circuit board

The following tests were conducted on the printed circuit boards prepared in Examples 1 to 9 and Comparative Examples 1 and 2, and the results are shown in Table 1 above.

1) Heat resistance: IPC TM-650 2. 4. 13 According to the evaluation standard, the printed circuit board is floated at solder 288 ° C, and the time from separation of the insulation layer and the copper foil, insulation layer and metal core or insulation layer occurs Were measured and evaluated.

2) Peel Strength (P / S); According to the evaluation standard of IPC-TM-650 2.4.8, the circuit pattern formed on the printed circuit board was pulled up in the 90 ° direction, and the time point at which the circuit pattern (copper foil) peeled off was measured and evaluated.

3) Evaluation of Flame Retardancy: An evaluation board having a length of 127 mm and a width of 12.7 mm was prepared from the evaluation board from which the copper foil was removed by impregnating the copper-clad laminates with a copper etching solution, and evaluated according to the UL94 test method (V method).

4) Measurement of TMA glass transition temperature: An evaluation board of 5 mm in each side was prepared as an evaluation board from which copper foil was removed by impregnating a copper-clad laminate with a copper etching solution, and thermal expansion characteristics of the evaluation board were observed using a TMA testing apparatus (TA Instrument, Q400) Respectively.

5) Moisture absorption heat resistance evaluation (PCT): A copper foil-free evaluation board was prepared by impregnating a copper-clad laminate with a copper etching solution. The evaluation board was subjected to a pressure cooker test (ESPEC, EHS-411MD) After leaving, the printed circuit board was dipped at solder 288 ° C for 10 seconds to measure the time from separation of the insulating layer, the copper foil, and the separation between the insulating layer and the metal core or insulating layer.

6) Measurement of relative dielectric constant and dielectric loss tangent: The relative dielectric constant and dielectric tangent at a frequency of 1 GHz were measured with a relative dielectric constant measuring device (RF Impedence / Material Analyzer; Agilent) using a substrate on which a copper foil was removed by using a copper- Respectively.

7) Measurement of Glass Transition Temperature (Tg): A sample of about 5 mg was heated to 300 DEG C at a rate of 10 DEG C / min by DSC measurement with DSC 2010 and DSC 2910 from TA Instruments, Cool to 30 ℃. This first heating / cooling process was carried out twice in the same process.

8) Measurement of Resin Flowability (R / F): Measured by TECPOS of DAE JIN HYDRAULIC MACHINERY Co., and the weight (W1) was measured by punching 4 pieces of 4 inch × 4 inch semi-hardened prepregs. And pressed for 1 minute, and punched out into a circle corresponding to half the weight of W1, and the weight (W2) was measured. The resin flowability was calculated according to the following equation (1).

[Equation 1]

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 high glass transition temperature (Tg), excellent heat resistance, low thermal expansion property and thermal stability See Table 1 above).

Claims (14)

(a) a polyphenylene ether resin having at least two unsaturated substituents selected from the group consisting of a vinyl group and an allyl group at both ends of a molecular chain; And
(b) a crosslinking curing agent,
The cross-linkable curing agent (b) may be prepared by using 1,9-decadiene, or using a mixture of di-4-vinylbenzyl ether and 1,9-decadiene,
4-vinylbenzyl ether and 1,9-decadiene are in the range of 10-50: 90-50 by weight,
The polyphenylene ether resin (a) is represented by the following formula (1).
[Chemical Formula 1]

In this formula,
Y is at least one selected from the group consisting of bisphenol A type resin, bisphenol F type resin, bisphenol S type resin, naphthalene type resin, anthracene resin, biphenyl type resin, tetramethyl biphenyl type resin, phenol novolac type resin, Novolak type resin, and bisphenol S novolak type resin,
m and n are independently a natural number of 3 to 20. delete The polyphenylene ether resin (a) according to claim 1, wherein the polyphenylene ether resin (a) is redispersed in the presence of a bisphenol-based compound (except bisphenol A) in a high molecular weight polyphenylene ether resin having a number average molecular weight of 10,000 to 30,000 Wherein the modified thermosetting resin composition is modified to have a low molecular weight ranging from 1000 to 10,000 in average molecular weight. The high-frequency thermosetting resin composition according to claim 1, wherein the polyphenylene ether resin (a) has a molecular weight distribution of 3 or less (Mw / Mn <3). The thermosetting resin composition for high frequency use according to claim 1, wherein the redispersion of the polyphenylene ether resin (a) is carried out in the presence of a radical initiator, a catalyst, or a radical initiator and a catalyst. The thermosetting resin composition for high frequency use according to claim 1, wherein the content of the crosslinkable curing agent (b) is in the range of 5 to 40 parts by weight based on 100 parts by weight of the poly (phenylene ether) resin. The thermosetting resin composition for high frequency use according to claim 1, wherein the composition further comprises a flame retardant. The thermosetting resin composition for high frequency use 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 high-frequency thermosetting resin composition according to claim 1, wherein the composition further comprises an inorganic filler. Fiber substrates; And
A prepreg comprising the thermosetting resin composition according to any one of claims 1 to 9 impregnated into the fiber substrate. The prepreg according to claim 10, wherein the fiber substrate comprises at least one 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 9, which is formed on one surface or both surfaces of the substrate,
And the functional laminated sheet. The printed circuit board according to claim 10, wherein one or more prepregs are laminated and formed.