WO2016105051A1 - Thermosetting resin composition for use with high frequencies, and prepreg, laminated sheet and printed circuit board using same - Google Patents

Abstract

The present invention relates to a thermosetting resin composition for use with high frequencies, the composition comprising: (a) a polyphenylene ether having two or more unsaturated substituent groups selected from the group consisting of the vinyl group and the allyl group at both ends of the molecular chain thereof, or an oligomer of said polyphenylene ether; (b) three or more different types of cross-linking curing agents; and (c) a flame-retarding agent. The present invention makes it possible to provide a printed circuit board for use with high frequencies which simultaneously exhibits, inter alia, an outstanding low dielectric loss characteristic and good moisture-absorption heat resistance, low thermal expansion characteristics, thermal stability and outstanding working properties.

Description

Thermosetting resin composition for high frequency, prepreg, laminated sheet and printed circuit board using the same

The present invention relates to a novel high-frequency thermosetting resin composition that can simultaneously exhibit excellent low dielectric loss characteristics, good moisture absorption heat resistance, low thermal expansion characteristics, excellent thermal stability, and the like, and prepregs, functional laminated sheets, and copper foil laminates using the same.

In recent years, signal bands of electronic components such as semiconductor substrates, printed circuit boards, and epoxy molding compounds (EMCs) and information communication devices have increased. The transmission loss of the electrical signal is proportional to the dielectric tangent and frequency. Therefore, the higher the frequency, the greater the transmission loss and the attenuation of the signal, resulting in a lower reliability of the signal transmission. In addition, transmission loss may be converted into heat, which may cause a problem of heat generation. Therefore, in the high frequency region, an insulating material having a very small dielectric tangent is required.

In addition, since the demand for high integration, high microdefinition, high performance, and the like in the semiconductor device and PCB field is increasing, the situation is gradually changing to a situation in which integration of semiconductor devices and high density of printed circuit boards and simplicity of wiring intervals are required. In order to satisfy these characteristics, it is desirable to use a low dielectric constant for increasing the transmission speed and a low dielectric loss material for reducing the transmission loss.

In order to exhibit such low dielectric properties, polyphenylene ether resin having excellent dielectric properties was applied, but it had problems such as high melt viscosity, difficulty in handling, and moldability of prepreg. In addition, there has been no research on a method of effectively crosslinking a thermoplastic resin such as polyphenylene ether resin having excellent dielectric properties.

The present invention has been made to solve the above-described problems, by using a polyphenylene ether resin in which both sides of the molecular chain is modified with an unsaturated bond substituent and three or more specific crosslinking curing agents, thereby improving heat resistance and low dielectric constant characteristics At the same time, a thermosetting resin composition having excellent overall physical properties 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, a laminated sheet and a printed circuit board using the composition.

The present invention (a) a polyphenylene ether having two or more unsaturated substituents selected from the group consisting of vinyl and allyl groups at both ends of the molecular chain or oligomers thereof; (b) at least three different crosslinkable curing agents; And (c) provides a high-frequency thermosetting resin composition comprising a flame retardant.

The high frequency thermosetting resin composition may further include an inorganic filler surface-treated with a vinyl group-containing silane coupling agent.

According to one example, the crosslinkable curing agent may be a mixture of a hydrocarbon-based crosslinking agent (b1), a crosslinking agent (b2) containing three or more functional groups and a rubber of the block structure (b3).

The present invention also provides a fiber substrate surface-treated with a vinyl group-containing silane coupling agent; And it provides a prepreg comprising the above-mentioned thermosetting resin composition impregnated in the fiber substrate.

In addition, the present invention is a metal foil or a polymer film substrate; And a resin layer formed on one or both surfaces of the substrate and including a cured resin layer of the above-mentioned thermosetting resin composition.

In addition, the present invention provides a printed circuit board characterized in that the laminate is formed by including one or more layers of the prepreg.

The thermosetting resin composition according to the present invention simultaneously satisfies the glass transition temperature (Tg) improvement, low coefficient of thermal expansion (CTE), low dielectric properties, low dielectric loss and high heat resistance, excellent processability, the printed circuit board using the high frequency characteristics And good moisture absorption heat resistance and low thermal expansion characteristics can be exhibited.

Accordingly, the thermosetting resin composition of the present invention is a printed circuit board for mobile communication devices that handle high frequency signals of 1 GHz or higher, network-related electronic devices such as base station devices, servers, routers, and various electrical and electronic devices such as large computers. It can be usefully used as a component.

Hereinafter, the present invention will be described in detail.

The present invention seeks to provide a thermosetting resin composition that can be usefully used in printed circuit boards, especially multilayer printed circuit boards for high frequency applications.

Since the dielectric loss of the electrical 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 electrical signal, the higher the frequency of the electrical signal, the larger the dielectric loss. Therefore, in order to be used in an insulating layer of a high frequency printed circuit board, it is required to use a material having low dielectric constant and dielectric loss factor (dielectric loss). Due to these demands, high frequency substrate materials have been developed to reduce the hydroxyl groups of epoxy resins, crosslinking methods of thermoplastic resins, application of liquid crystal polymers or polyimide, etc. to realize low dielectric polymer materials. To satisfy the high frequency characteristics, there is insufficient dielectric characteristics or difficulty in forming a substrate.

Accordingly, in the present invention, in order to satisfy the low dielectric and dielectric loss characteristics described above, polyphenylene ether (poly (phenylene ether), PPE] was used as a component of the thermosetting resin composition, but low heat resistance caused when using PPE And polyphenylene ethers in which both ends of the molecular chain are modified with a vinyl group or allyl group, in which both ends of the molecular chain are unsaturated bond substituents, and three or more specific crosslinking curing agents in combination with the PPE resin melt. Characterized in that.

More specifically, in the present invention, both ends of the polyphenylene ether are modified with a vinyl group, an allyl group, and the like to enable an unsaturated bond. This can cause crosslinking reaction by heat, which contributes to improvement of heat resistance and can suppress deformation and flow of the insulating layer. In addition, the glass transition temperature (Tg), low coefficient of thermal expansion (CTE) and -OH (hydroxy) group not only satisfies the moisture resistance and dielectric properties, but also can be applied in the existing thermal curing system, By studying the dielectric properties according to the crosslinking agent properties, it is possible to secure various physical properties and processability at the same time.

In addition, in the present invention, after modifying the polyphenylene ether (PPE) having excellent dielectric properties to low molecular weight through a redistribution reaction, both ends are treated with a vinyl group to increase the compatibility of the PPE base resin (base) resin, and by using three or more crosslinkable curing agents having excellent dielectric properties, not only low dielectric properties can be realized through radical polymerization, but also excellent heat resistance and mechanical properties can be realized. (See Table 3 below).

According to an example, the three or more types of crosslinkable curing agents may be mixed with a hydrocarbon-based crosslinking agent, a crosslinking agent containing three or more functional groups, and a block structure rubber.

Here, since the hydrocarbon-based crosslinking agent has a low polarization property, not only can implement low dielectric properties, but also has excellent molding processability due to flowability. In addition, since the resin composition of the present invention has elastomeric properties due to the hydrocarbon-based crosslinking agent at the time of curing, it is effective for drill wear during drilling. When such a hydrocarbon-based crosslinking agent is used together with a crosslinking agent containing three or more functional groups (hereinafter, 'three or more functional group-containing crosslinking agents'), the volume skeleton of the resin itself increases due to the three or more functional group-containing crosslinking agents. Synergistic effect with the hydrocarbon-based curing agent can be exerted not only to achieve lower dielectric properties than when using a hydrocarbon-based crosslinking agent alone, but also to increase the crosslinking density to improve heat resistance. In addition, in the case of using a block structure rubber such as styrene-butadiene rubber together with the crosslinking agents, a rigid structure such as styrene in the polymer chain may act as a domain after curing of the resin composition, and in particular, improve mechanical properties. When using a copolymer containing styrene units and butadiene units (eg, styrene-butadiene rubber), it is possible to simultaneously implement the strengths of styrene processability and impact resistance of butadiene and chemical resistance.

<Thermosetting resin composition>

The thermosetting resin composition according to the present invention is a non-epoxy clock thermosetting resin composition, (a) a polyphenylene ether having two or more unsaturated substituents selected from the group consisting of vinyl groups and allyl groups at both ends of the molecular chain, or a Oligomers; (b) three or more crosslinkable curing agents; And (c) flame retardants. In addition, the thermosetting resin composition may further include an inorganic filler surface-treated with a vinyl group-containing silane coupling agent. In this case, a curing accelerator, an initiator (eg, a radical initiator) may be further included as necessary.

(a) polyphenylene ether

The thermosetting resin composition according to the present invention comprises polyphenylene ether (PPE) or an oligomer thereof. The PPE or oligomer thereof has two or more vinyl groups, allyl groups, or both at both ends of the molecular chain, and may be used without particular limitation on its structure.

In this invention, the allylated polyphenylene ether represented by following General formula (1) is preferable. This is because the side has been modified with two or more vinyl groups, it is possible to satisfy the moisture resistance and dielectric properties due to the glass transition temperature, low thermal expansion coefficient, -OH group reduction.

In Chemical Formula 1,

Y is bisphenol A type, bisphenol F type, bisphenol S type, naphthalene type, anthracene type, biphenyl type, tetramethyl biphenyl type, phenol novolak type, cresol novolak type, bisphenol A novolak type, and bisphenol S no. At least one compound selected from the group consisting of

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

Although the present invention mainly uses two or more vinyl groups at both ends of the molecular chain, it is also possible to use conventional unsaturated double-bonding moieties known in the art in addition to the vinyl groups. Belongs to the category.

On the other hand, polyphenylene ether is inherently high in melting point, and therefore, high in melt viscosity of the resin composition, making it difficult to produce a multilayer sheet. Thus, in the present invention, instead of using the conventional high molecular weight polyphenylene ether as it is, it is preferable to use a modified form with a low molecular weight through a redistribution reaction.

In particular, when a high molecular weight polyphenylene ether is modified with a low molecular weight polyphenylene ether resin, a compound such as a phenol-derived compound or bisphenol A is generally used. In this case, the dielectric constant decreases due to the rotation of the molecular structure. Is generated.

Meanwhile, in the present invention, instead of using a conventional high molecular weight polyphenylene ether (PPE) resin as it is, redistribution reaction using specific bisphenol compounds having increased alkyl group (Akyl) content and aromatic ring group (Aromatic) content As a low-molecular weight modified form, a vinyl group (Vinyl group) is introduced at both ends of the resin through redistribution. In this case, the redistribution reaction is carried out in the presence of a radical initiator, a catalyst, or a radical initiator and a catalyst.

Specifically, the conventional polyphenylene ether for copper foil laminates was used by reforming the polymer polyphenylene ether into a low molecular polyphenylene ether having an alcohol group at both terminals through a redistribution reaction using a polyphenol and a radical initiator as a catalyst. Due to the structural characteristics of Bisphenol A, a polyphenol used for, and the high polarity of alcohol groups at both ends formed after redistribution, there was a limit to low dielectric loss characteristics.

In contrast, in the present invention, after redistributing the polyphenol used in the redistribution reaction using specific bisphenol compounds having increased alkyl group content and aromatic aromatic group, aromatic alcohol groups are located at both ends. The polyphenylene ether with low dielectric loss can be obtained even after crosslinking by transforming into a low polar vinyl group. Since the modified polyphenylene ether has a lower molecular weight and higher alkyl group content than the existing polyphenylene-derived compounds, the modified polyphenylene ether has excellent compatibility with existing epoxy resins and the like, and improves processability by increasing flowability in manufacturing laminates. And the dielectric properties are 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 formability, processability, dielectric properties, heat resistance, and adhesive strength.

In this case, the specific bisphenol compound having an increased alkyl content and aromatic ring content may be used without limitation bisphenol-based compounds other than bisphenol A [BPA, 2,2-Bis (4-hydroxyphenyl) propane]. have. Non-limiting examples of bisphenol compounds that can be used include bisphenol AP (1,1-Bis (4-hydroxyphenyl) -1-phenyl-ethane), bisphenol AF (2,2-Bis (4-hydroxyphenyl) hexafluoropropane), bisphenol B ( 2,2-Bis (4-hydroxyphenyl) butane), bisphenol BP (Bis- (4-hydroxyphenyl) diphenylmethane), bisphenol C (2,2-Bis (3-methyl-4-hydroxyphenyl) propane), bisphenol C (Bis (4-hydroxyphenyl) -2,2-dichloroethylene), bisphenol G (2,2-Bis (4-hydroxy-3-isopropyl-phenyl) propane), bisphenol M (1,3-Bis (2- (4-hydroxyphenyl ) -2-propyl) benzene), bisphenol P (Bis (4-hydroxyphenyl) sulfone), bisphenol PH (5,5 '-(1-Methylethyliden) -bis [1,1'-(bisphenyl) -2-ol] propane), bisphenol TMC (1,1-Bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane), bisphenol Z (1,1-Bis (4-hydroxyphenyl) -cyclohexane) or one or more thereof Mixtures and the like.

The polyphenylene ether resin (a) is redistributed to a high molecular weight polyphenylene ether resin having a number average molecular weight ranging from 10,000 to 30,000 in the presence of a bisphenol-based compound (except for bisphenol A), thereby obtaining a number average molecular weight (Mn). This may be modified to a low molecular weight in the range of 1,000 to 10,000, preferably the number average molecular weight (Mn) is in the range of 1000 to 5,000, more preferably may be in the range of 1000 to 3000.

In addition, the molecular weight distribution of the polyphenylene ether is preferably 3 or less (Mw / Mn <3), preferably in the range of 1.5 to 2.5.

In the thermosetting resin composition according to the present invention, the content of the polyphenylene ether resin or oligomer thereof may be about 20 to 50% by weight based on the total weight of the resin composition.

(b) crosslinkable curing agent

The thermosetting resin composition according to the present invention includes three or more different crosslinkable curing agents.

The crosslinkable curing agent crosslinks the polyphenylene ether in three dimensions to form a network structure, and uses a low molecular weight modified polyphenylene ether to increase the fluidity of the resin composition. Even with the use of three or more crosslinking curing agents, the heat resistance of the polyphenylene ether can be improved. In addition, the crosslinkable curing agent may not only realize low dielectric constant and dielectric loss characteristics by crosslinking PPE, but also increase flowability of the curable resin composition and improve peel strength with other substrates (eg, copper foil). You can.

The crosslinkable curing agent may be selected from the group consisting of a hydrocarbon-based crosslinking agent (b1), a crosslinking agent (b2) containing three or more functional groups, and a rubber of a block structure (b3).

According to one example, a hydrocarbon-based crosslinking agent (b1), a crosslinking agent (b2) containing three or more functional groups, and a block structure rubber (b3) may be used as the crosslinkable curing agent.

The hydrocarbon-based crosslinking agent usable in the present invention is not particularly limited as long as it is a hydrocarbon-based crosslinking agent having a double bond or a triple bond, and may preferably be a diene crosslinking agent. Specific examples include butadiene (eg, 1,2-butadiene, 1,3-butadiene, etc.) or polymers thereof, decadiene (eg, 1,9-decadiene, etc.) or polymers thereof, octadiene (eg, 1,7- Octadiene, etc.) or polymers thereof, vinylcarbazole, and the like, which may be used alone or in combination of two or more thereof.

According to an example, polybutadiene represented by the following Chemical Formula 2 may be used as the hydrocarbon-based crosslinking agent.

(In Formula 2, n is an integer of 10 to 30)

The molecular weight (Mw) of the hydrocarbon-based crosslinking agent may be in the range of 500 to 3,000, preferably in the range of 1,000 to 3,000.

Non-limiting examples of crosslinking agents containing three or more (preferably three to four) functional groups usable in the present invention include triallyl isocyanurate (TAIC), 1,2,4-trivinyl cyclo Hexane (1,2,4-trivinyl cyclohexane, TVCH) and the like, these may be used alone or in combination of two or more.

According to an example, triallyl isocyanurate (TAIC) represented by the following formula (3) may be used as a crosslinking agent containing three or more functional groups.

The block structure rubbers usable in the present invention are in the form of block copolymers, preferably in the form of block copolymers containing butadiene units, more preferably styrene units, acrylonitrile units, acrylate units together with butadiene units. Rubber in the form of block copolymers containing units such as the like. Non-limiting examples include styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber, acrylate-butadiene rubber, acrylonitrile-butadiene-styrene rubber, and these may be used alone or in combination of two or more thereof. have.

According to one example, styrene-butadiene rubber represented by the following formula (4) may be used as the rubber of the block structure.

(In Formula 4, n is an integer of 5 to 20, m is an integer of 5 to 20).

In the thermosetting resin composition of the present invention, the content of the crosslinkable curing agent (b) is not particularly limited, but may be in the range of about 5 to 45% by weight based on the total weight of the resin composition, preferably about 10 to 30% by weight Can range from%. When the content of the crosslinkable curing agent falls within the above-described range, the low dielectric properties, curability, molding processability and adhesive strength of the resin composition are good.

According to an example, when the hydrocarbon-based crosslinking agent (b1), the crosslinking agent (b2) containing three or more functional groups, and the block structure rubber are used as the three or more crosslinkable curing agents, the hydrocarbon-based crosslinking agent (b1), 3 The content of the crosslinking agent (b2) and the block structure rubber (b3) containing at least two functional groups are each in the range of about 1.65 to 15% by weight, preferably in the range of about 3.33 to 10% by weight, more preferably based on the total weight of the resin composition. Such as about 5 to 10% by weight.

According to another example, when the hydrocarbon-based crosslinking agent (b1), the crosslinking agent (b2) containing three or more functional groups and the rubber of the block structure as a mixture of the three or more crosslinkable curing agents, the hydrocarbon-based crosslinking agent (b1), The use ratio of the crosslinking agent (b2) and the block structure rubber (b3) containing three or more functional groups is b1: b2: b3 = 1-20: 1-20: 1 weight ratio, Preferably b1: b2: b3 = 1-7: 1-7: 1 may be a weight ratio.

If necessary, the present invention may further include conventional crosslinkable curing agents known in the art, in addition to the above-described hydrocarbon-based curing agent, at least three functional group-containing crosslinking agents and rubbers of block structure. In this case, it is preferable that the crosslinkable curing agent has excellent miscibility with the polyphenylene ether whose side is modified with vinyl group, allyl group or the like.

Non-limiting examples of crosslinkable curing agents that can be used include divinylnaphthalene, divinyldiphenyl, styrene monomer, phenol, triallyl cyanurate (TAC), di-4-vinylbenzyl ether [di- (4-vinylbenzyl) ether] (Formula 5) and the like. At this time, the above-mentioned curing agent may be used alone or in combination of two or more.

In the present invention, not only low dielectric properties, but also various physical properties and processability may be maximized through appropriate mixing and optimized content control of the aforementioned crosslinkable curing agent. In particular, in the present invention, a di-4-vinylbenzyl ether [di- (4-Vinylbenzyl) ether] (formula 5), which exhibits an initiation delaying reaction as a crosslinking agent, is used as another crosslinkable curing agent (hydrocarbon-based curing agent, three or more). Functional groups-containing hardeners and block-structured rubbers) in an optimized amount to facilitate viscosity control. By adjusting the resin flowability based on this, it is possible to overcome the difficulty of handling or forming process of the prepreg.

Specifically, when di-4-vinylbenzyl ether is mixed with a hydrocarbon-based curing agent, three or more functional group-containing curing agents, and a block-type rubber as a crosslinking curing agent, low dielectric properties and flow characteristics due to content control are simultaneously secured. can do. At this time, the hydrocarbon-based curing agent, the at least three functional group-containing curing agent and the rubber of the block structure are each in the range of about 1.65 to 15% by weight, preferably in the range of about 3.33 to 10% by weight, more preferably about It may be used in the range of 5 to 10% by weight, and di-4-vinylbenzyl ether may be used in the range of about 1 to 10% by weight, preferably about 2 to 5% by weight, based on the total weight of the resin composition.

(c) Flame retardant

The thermosetting resin composition according to the present invention includes a flame retardant (c).

The flame retardant may be used without limitation conventional flame retardant known in the art, for example, halogen flame retardant containing bromine or chlorine; Phosphorus flame retardants such as triphenyl phosphate, tricesyl phosphate, trisdichloropropyl phosphate and phosphazene; Antimony flame retardants such as antimony trioxide; Flame retardants of inorganic substances such as metal hydroxides such as aluminum hydroxide and magnesium hydroxide. Additive bromine flame retardants that are not reactive with polyphenylene ether and do not degrade heat and dielectric properties are suitable in the present invention.

The brominated flame retardant in the present invention is bromophthalimide, bromophenyl-added bromine flame retardant, or tetrabromo bisphenol A Allyl ether in the allyl terminated form. By using a flame retardant curing agent in the form of divinylphenol, the characteristics of the curing agent and the flame retardant properties can be simultaneously obtained. In addition, a brominated organic compound may also be used, and specific examples thereof include dicabromodiphenylethane, 4,4-dibromobiphenyl, and ethylene bistetrabromophthalimide.

In the thermosetting resin composition according to the present invention, the content of the flame retardant may be included in about 10 to 30% by weight based on the total weight of the resin composition, preferably in the range of about 10 to 20% by weight. When the flame retardant is included in the above range, it may have a flame resistance of flame retardant 94V-0 level, it may exhibit excellent thermal resistance and electrical properties.

(d) Vinyl -contain Silane With coupling agent  Surface-treated weapons filler

The thermosetting resin composition according to the present invention may further include an inorganic filler surface-treated with a vinyl group-containing silane coupling agent.

The inorganic filler is a surface-treated with a vinyl group-containing silane coupling agent, which is excellent in compatibility with polyphenylene ethers containing vinyl and / or allyl groups at both ends, thereby lowering dielectric properties, Hygroscopic heat resistance and workability can be improved further. In addition, the inorganic filler can effectively improve the warpage characteristics, low expansion, mechanical toughness, low stress of the final product by reducing the difference in the coefficient of thermal expansion (CTE) between the resin layer and other layers.

The inorganic filler (d) usable in the present invention is not particularly limited as long as the surface is treated with a vinyl group-containing silane coupling agent as the inorganic filler known in the art. For example, silicas such as natural silica, fused silica, amorphous silica, crystalline silica, and the like; Boehmite, alumina, talc, spherical glass, calcium carbonate, magnesium carbonate, magnesia, clay, calcium silicate, titanium oxide, antimony oxide, glass fiber, aluminum borate, barium titanate, strontium titanate, calcium titanate , Magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, boron nitride, silicon nitride, talc, mica, and the like, whose surfaces are treated with a vinyl group-containing silane coupling agent. will be. These inorganic fillers may be used alone or in combination of two or more. Of these, fused silica having a low coefficient of thermal expansion is preferable.

The method for producing the inorganic filler surface-treated with the vinyl group-containing silane coupling agent is not particularly limited and may be prepared according to conventional methods known in the art. In one example, the inorganic filler may be added to a solution containing a vinyl group-containing silane coupling agent and then dried.

The size of the inorganic filler (d) is not particularly limited, but is advantageous in dispersibility when the average particle diameter is in the range of about 0.5 to 5 μm.

In addition, the content of the inorganic filler is not particularly limited, and may be appropriately adjusted in consideration of the aforementioned bending characteristics, mechanical properties, and the like. In one example, the range of about 10 to 50% by weight based on the total weight of the thermosetting resin composition is preferred. If the content of the inorganic filler is excessively large, moldability may decrease.

On the other hand, the thermosetting resin composition according to the present invention may further comprise a reaction initiator to enhance the advantageous effect of the crosslinkable curing agent.

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

Non-limiting examples of reaction initiators that can be used include α, α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butyl peroxy) -3 -Hexyne, benzoyl peroxide, 3,3 ', 5,5' '-tetramethyl-1,4-diphenoxyquinone, chloranyl, 2,4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl monocarbonate, azobisisisobutylonitrile, and the like, and further metal carboxylate salts may be further used.

The content of the reaction initiator may be about 2 to 5 parts by weight based on 100 parts by weight of polyphenylene ether, but is not limited thereto.

In addition, the thermosetting resin composition of the present invention may further include a curing accelerator.

Examples of the curing accelerator include an organometallic salt or an organometallic complex including at least one metal selected from the group consisting of iron, copper, zinc, cobalt, lead, nickel, manganese, and tin.

Specific examples of such organometallic salts or organometallic complexes include iron naphthenates, copper naphthenates, zinc naphthenates, cobalt naphthenates, nickel naphthenates, manganese naphthenates, tin naphthenates, Zinc octanoate, tin octanoate, iron octanoate, copper octanoate, zinc 2-ethylhexanate, lead acetylacetonate, cobalt acetylacetonate, or dibutyltin malate, It is not limited to this. In addition, these can be used 1 type or in mixture of 2 or more types.

The amount of the curing accelerator may range from about 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 is a flame retardant generally known in the art as needed, other thermosetting resins or thermoplastic resins and oligomers thereof not described above, as long as they do not impair the intrinsic properties of the resin composition. Various polymers such as, solid rubber particles or other additives such as ultraviolet absorbers, antioxidants, polymerization initiators, dyes, pigments, dispersants, thickeners, leveling agents and the like may be further included. For example, organic fillers such as silicon-based powder, nylon powder, and fluororesin powder, thickeners such as orbene and benton; Polymeric antifoaming agents or leveling agents such as silicone-based and fluorine-based resins; Adhesion imparting agents such as imidazole series, thiazole series, triazole series, and silane coupling agents; Phthalocyanine, carbon black, etc. can be mentioned a coloring agent.

A thermoplastic resin can be mix | blended with the said thermosetting resin composition for the purpose of providing a suitable flexibility to the resin composition after hardening, etc. Examples of such thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyimides, polyamideimides, polyethersulfones, polysulfones and the like. These may be used individually by any 1 type, and may use 2 or more types together.

As said resin additive, Organic fillers, such as a silicone powder, nylon powder, a fluorine powder; Thickeners such as olben and benton; Antifoaming agents or leveling agents based on silicon, fluorine and polymers; Adhesion imparting agents such as imidazole series, thiazole series, triazole series, silane coupling agents, epoxy silanes, aminosilanes, alkylsilanes and mercaptosilanes; Coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow and carbon black; Mold release agents such as higher fatty acids, higher fatty acid metal salts, and ester waxes; Stress relieving agents such as modified silicone oil, silicone powder, silicone resin, and the like. It may also include additives conventionally used in thermosetting resin compositions used in the production of electronic devices (especially printed wiring boards).

According to one embodiment of the present invention, the thermosetting resin composition is based on 100 parts by weight of the composition: (a) about 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) about 5 to 45 parts by weight of three or more crosslinkable curing agents; And (c) may include a flame retardant in the range of about 10 to 30 parts by weight, and may further include a total of 100 parts by weight of an organic solvent or other components. At this time, the basis of the component may be the total weight of the composition, or may be the total weight of the varnish containing the organic solvent.

According to another embodiment of the present invention, the thermosetting resin composition is based on 100 parts by weight of the composition (a) about 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) about 5 to 45 parts by weight of three or more crosslinkable curing agents; (c) about 10 to 30 parts by weight of a flame retardant; And (d) about 10 to about 50 parts by weight of the inorganic filler surface-treated with the vinyl group-containing silane coupling agent, and may further include 100 parts by weight of organic solvent or other components. At this time, the basis of the component may be the total weight of the composition, or may be the total weight of the varnish containing the organic solvent.

Organic solvents usable in the present invention can be used without limitation to conventional organic solvents known in the art, for example acetone, cyclohexanone, methyl ethyl ketone, toluene, xylene, tetrahydrofuran, these alone or Two or more kinds may be mixed and used.

The content of the organic solvent may be in the range of the remaining amount to satisfy the total 100 parts by weight of the varnish using the composition ratio of the above-described composition, it is not particularly limited.

< Prepreg >

The prepreg of the present invention includes a fiber substrate surface treated with a vinyl group-containing silane coupling agent; And the above-mentioned thermosetting resin composition impregnated in the fiber base material. Here, the thermosetting resin composition may be a resin varnish dissolved or dispersed in a solvent.

According to the present invention, when the thermosetting resin composition is impregnated into the fibrous substrate surface-treated with the vinyl group-containing silane coupling agent, the fiber substrate and all the components constituting the composition (ie, resin and optionally inorganic filler) Since it contains this vinyl group, it is excellent in compatibility between these, dielectric property improves, moisture absorption heat resistance, and workability are also improved, and a high frequency material can be developed.

The fibrous substrate usable in the present invention is known in the art as a substrate of prepreg and is not particularly limited as long as the surface is treated with a vinyl group-containing silane coupling agent. For example, there are arbitrarily bendable flexible inorganic fiber substrates, organic fiber substrates, or mixed forms thereof, and the like, whose surfaces are treated with vinyl group-containing silane coupling agents. At this time, the above-mentioned fiber base material can be selected based on the use or performance to be used.

Specific examples of the fiber substrate include inorganic fibers such as glass fibers, carbon fibers, and the like, such as E-glass, D-glass, S-glass, NE-glass, T-glass, and Q-glass; Organic fibers such as polyimide, polyamide, polyester, aramid fiber, aromatic polyester, and fluororesin; And mixtures of the inorganic and organic fibers; Papers, nonwovens, fabrics, papers, etc., made of the inorganic fibers and / or organic fibers, and mats such as roving, chopped strand mats, and surfacing mats. As described above, the surface is treated with a vinyl group-containing silane coupling agent, and may be used alone or in combination of two or more thereof. In addition, when the reinforced fiber substrate is mixed, the stiffness and dimensional stability of the prepreg can be improved.

According to an example of the present invention, the fiber base material is glass fiber, glass paper, glass fiber nonwoven fabric (glass fiber), glass cloth (glass cloth), aramid fiber, aramid paper (aramid paper), polyester fiber, carbon fiber, inorganic Fibers, organic fibers and mixtures thereof can be used.

The thickness of the fibrous substrate is not particularly limited and may be, for example, in the range of about 0.01 to 0.3 mm.

The method for treating the surface of the fibrous base with the vinyl group-containing silane coupling agent may be prepared by conventional methods known in the art, and for example, the inorganic filler surface-treated with the vinyl group-containing silane coupling agent described above. It may be prepared as in the preparation method.

The method for producing the prepreg of the present invention is not particularly limited and may be prepared according to a production method known in the art.

Generally, the prepreg is a sheet-like material obtained by coating or impregnating the above-mentioned thermosetting resin composition on a fiber substrate surface-treated with a vinyl group-containing silane coupling agent, and then curing it to B-stage (semi-cured state) by heating. Refers to. At this time, the heating temperature and time is not particularly limited, for example, the heating temperature may be in the range of about 20 ~ 200 ℃, preferably in the range of about 70 ~ 170 ℃, heating time may be in the range of about 1 to 10 minutes.

In addition to such a method, the prepreg of the present invention may be prepared by a known hot melt method, a solvent method and the like known in the art.

The solvent method is a method in which the resin composition varnish formed by dissolving the thermosetting resin composition for prepreg formation in an organic solvent is impregnated with a fiber base and dried. When employing such a solvent method, a resin varnish is generally used. Examples of the method of impregnating the resin composition into 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, and the like. Can be mentioned. At this time, when the fiber base material is immersed in the resin varnish, since the impregnation property of the resin composition with respect to a fiber base material can be improved, it is preferable.

When preparing the said resin composition varnish, For example, ketones, such as acetone, methyl ethyl ketone, cyclohexanone; Acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; Carbitols such as cellosolve and butyl carbitol; Aromatic hydrocarbons such as toluene and xylene; Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran and the like. The said organic solvent may be used 1 type, or may be used in combination of 2 or more type.

In addition, the hot-melt method may be a method of coating a resin composition and a release paper having excellent peelability without dissolving the resin composition in an organic solvent and then laminating it on a sheet-like fiber base material or coating it directly by a die coater. In addition, it may be produced by continuously laminating an adhesive film made of a thermosetting resin composition laminated on a support under both heating and pressurization conditions from both sides of a sheet-like reinforcing base material.

According to an example of the present invention, the surface is surface-treated with a vinyl group-containing silane coupling agent, and the above-mentioned thermosetting resin composition is coated on a sheet-like fibrous substrate or glass substrate made of fibers, or the substrate is impregnated with the thermosetting resin composition. After preliminary heating and semi-curing at a temperature of about 70 to 170 ° C. for about 1 to 10 minutes, a prepreg, preferably a prepreg for a printed circuit board, may be manufactured. In this case, the thermosetting resin composition may be prepared by a resin varnish.

<Laminated sheet>

Laminated sheet according to the present invention is a metal foil or a polymer film substrate; And a resin layer formed on one or both surfaces of the substrate, and the thermosetting resin composition cured.

For example, metal foil; And copper foil with resin which is formed on one or both surfaces of the metal foil, and includes a resin layer in which the thermosetting resin composition is cured.

The metal foil can be used without limitation those made of conventional metals or alloys known in the art. At this time, when the metal foil is a copper foil, the laminate formed by coating and drying the thermosetting resin composition according to the present invention can be used as a copper foil laminate. Preferably it is copper foil. Examples of copper foil that can be used include CFL (TZA_B, HFZ_B), Mitsui (HSVSP, MLS-G), Nikko (RTCHP), Furukawa, ILSIN and the like.

The said copper foil includes all the copper foils manufactured by the rolling method and the electrolytic method. Here, the copper foil may be subjected to rust prevention treatment in order to prevent the surface from being oxidized and corroded.

The metal foil may have a predetermined surface roughness Rz formed 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 to 3.0 ㎛ for example.

In addition, the thickness of the metal foil is not particularly limited, but may be used less than 5 ㎛ in consideration of the thickness and mechanical properties of the final product, preferably in the range of 1 to 3 ㎛.

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

< Laminate  And Printed Circuit Boards>

The present invention includes a laminate formed by overlapping two or more prepregs described above with each other and then heating and pressing them under normal conditions.

In addition, the present invention includes a copper foil laminate formed by laminating the prepreg and the copper foil, and being formed by heat press molding under ordinary conditions.

For example, the above-mentioned thermosetting resin composition is sufficiently stirred at room temperature using a stirrer, impregnated with a glass substrate, dried, laminated with copper foil and the like, and then subjected to heat and pressure to obtain a desired copper foil laminate. At this time, when forming the copper foil laminate, the heating pressure conditions may be appropriately adjusted according to the thickness of the copper foil laminate to be manufactured or the kind of the thermosetting resin composition according to the present invention.

In addition, the present invention includes a printed circuit board, preferably a multilayer printed circuit board, laminated and molded, including at least one selected from the group consisting of the prepreg, the insulating resin sheet, and the copper foil with resin.

In the present invention, a printed circuit board refers to a printed circuit board laminated by one or more layers by a plating through-hole method, a build-up method, etc., and can be obtained by overlaying the above-described prepreg or insulating resin sheet on an inner wiring board and heating and pressing.

The printed circuit board may be manufactured by conventional methods known in the art. As a preferable example of this, after laminating | stacking and heat-pressing copper foil on the one or both surfaces of the prepreg which concerns on this invention, a copper foil laminated board is produced, opening a hole in a copper foil laminated board, through-hole plating, and then copper foil containing a plating film It can be produced by etching to form a circuit.

As described above, the prepreg and the printed circuit board may be prepared from the thermosetting resin composition according to the present invention. These prepregs and printed circuit boards not only have low dielectric constant and dielectric loss, but also have a low coefficient of thermal expansion (CTE), a high glass transition temperature (Tg), and excellent heat resistance (see Table 1 below). Accordingly, the prepregs and printed circuit boards of the present invention are networks used for mobile communication devices that handle high frequency signals of 1 GHz or higher, network-related electronic devices such as base station devices, servers, routers, and various electrical and electronic devices such as large computers. It can be usefully used as a component part of a printed circuit board.

Hereinafter, the present invention will be described in detail with reference to Examples, but the following Examples and Experimental Examples are merely illustrative of one embodiment of the present invention, and the scope of the present invention is not limited to the following Examples and Experimental Examples. In addition, in the following description, "part" means a "mass part."

[ Example  1 to 3]

1-1. Preparation of Thermosetting Resin Composition

After dissolving the polyphenylene ether in toluene according to the composition shown in Table 1, two or more crosslinkable curing agents, flame retardants and inorganic fillers were mixed, stirred for 3 hours, then an initiator was added, and further 1 hour While stirring to prepare a thermosetting resin composition. In Table 1, the amount of each composition is used in parts by weight.

1-2. Prepreg  And manufacturing of printed circuit boards

The resin composition prepared above was impregnated into a glass fiber surface-treated with a vinyl group-containing silane coupling agent, and then dried at 165 ° C. for about 3 to 10 minutes to prepare a prepreg. Thereafter, 1 ply of the prepreg was laminated and pressed to prepare a laminated thin plate having a thickness of 0.1 mm.

[ Comparative example  1 to 6]

A resin composition, a prepreg, and a printed circuit board were manufactured in the same manner as in the above example, except that the compositions described in Table 2 were followed. In Table 2 below, the amount of each unit used is in parts by weight.

	Example 1	Example 2	Example 3
Alirate PPE	40	40	40
TAIC	8	10	5
1,2-butadiene	8	5	10
1,9-Decadiene	-	-	-
Di- (4-vinylbenzyl) ether	2	2	2
SBR	3	2	2
Flame retardant	9	9	9
Initiator	2	2	2
Inorganic fillers surface-treated with Amino Sliane	-	-	-
Inorganic fillers surface-treated with vinyl silane	30	30	30
Epoxy Silane G / F	-	-	-
Vinyl Silane G / F	○	○	○
1) Allylate PPE: MX-9000 (Number average molecular weight: 2000 ~ 3000) 2) 1,2-Butadiene: B-1000 (NIPPON SODA) 3) 1,9-decadiene: 1,9-decadiene (EVONIC) 4) Styrene -Butadiene: P-1500 (Asahi Kasei Chemical) 5) TAIC: TAIC (NIPPON KASEI CHEMICAL) 6) Di- (4-vinylbenzyl) ether: BPA-DAE (HAOHUA INDUSTRY) 7) Flame retardant: Saytex 8010 (Albemarle Asano Corporation) 8) Initiator: Perbutyl P (Manufacturer NOF Corporation) 9) Inorganic Filler: SC-5200SQ (Admatechs) 10) Glass Fiber (G / F): Ashai Kasei E glass Amino silane

	Comparative example
	One	2	3	4	5	6
Alirate PPE	40	40	40	40	40	40
TAIC	8	5	7	7	10	-
1,2-butadiene	-	-	7	7	5	14
1,9-Decadiene	10	10	-	-	-	-
Di- (4-vinylbenzyl) ether	-	3	2	2	2	2
SBR	-	-	2	2	2	2
Flame retardant	10	10	10	10	9	10
Initiator	2	2	2	2	2	2
Inorganic fillers surface-treated with Amino Sliane	-	-	30	-	-	-
Inorganic fillers surface-treated with vinyl silane	30	30	-	30	30	30
Epoxy Silane G / F	○	○	○	○	-	-
Vinyl Silane G / F	-	-	-	-	○	○
1) Allylate PPE: MX-9000 (Number average molecular weight: 2000 ~ 3000) 2) 1,2-Butadiene: B-1000 (NIPPON SODA) 3) 1,9-decadiene: 1,9-decadiene (EVONIC) 4) Styrene -Butadiene: P-1500 (Asahi Kasei Chemical) 5) TAIC: TAIC (NIPPON KASEI CHEMICAL) 6) Di- (4-vinylbenzyl) ether: BPA-DAE (HAOHUA INDUSTRY) 7) Flame retardant: Saytex 8010 (Albemarle Asano Corporation) 8) Initiator: Perbutyl P (Manufacturer NOF Corporation) 9) Inorganic Filler: SC-5200SQ (Admatechs) 10) Glass Fiber (G / F): Ashai Kasei E glass Amino silane

[ Experimental Example  1]-Properties of printed circuit board

The following experiment was performed on the printed circuit boards prepared in Examples 1 to 3 and Comparative Examples 1 to 6, and the results are shown in Table 3 below.

1) Glass transition temperature Tg ) Measurement

It was measured by DSC 2010 and DSC 2910 of TA Instruments. About 5 mg of the sample was heated to 300 ° C. at a rate of 10 / min by DSC measurement, and then cooled to 30 ° C. at a rate of 10 / min. This first heating / cooling procedure was carried out twice in the same procedure.

2) Coefficient of thermal expansion, CTE )

TMA glass transition temperature measurement: The evaluation board | substrate of each 5 mm was produced from the evaluation board which copper foil laminated board was impregnated with the copper etching liquid, and copper foil was removed, and the thermal expansion characteristic of the evaluation board was observed using the TMA test apparatus (TA Instrument, Q400). It evaluated by doing.

3) heat resistance

According to the IPC TM-650 2. 4. 13 evaluation standard, the printed circuit board was floated in Solder 288 to measure the time until the separation phenomenon between the insulating layer and the copper foil, the insulating layer and the metal core or the insulating layer occurred. .

4) Hygroscopic  Heat resistance rating (PCT)

The copper foil laminated sheet was impregnated with copper etching solution, and the evaluation board | substrate which produced the copper foil was manufactured, and it was left to 121 degreeC and 0.2 MPa conditions for 4 hours using the pressure cooker test apparatus (ESPEC, EHS-411MD), and printed circuit in solder 288. The substrates were evaluated by dipping at intervals of 10 seconds and measuring the time until the separation phenomenon between the insulating layer and the copper foil, the insulating layer and the metal core, or the insulating layer occurred.

5) Relative dielectric constant  And heredity Tangent

The dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured with a dielectric constant measuring instrument (RF Impedence / Material Analyzer; Agilent) using a substrate obtained by impregnating the copper foil laminate with copper liquid and removing the copper foil.

6) Flame retardant

The evaluation board | substrate was produced by 127 mm in length and 12.7 mm in width | variety from the evaluation board which copper foil laminated board was impregnated in copper etching liquid, and copper foil was removed, and evaluated according to the test method (V method) of UL94.

7) Copper 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 when a circuit pattern (copper foil) peels was measured and evaluated.

	Example			Comparative example
	One	2	3	One	2	3	4	5	6
DSC Tg (℃)	195	207	185	205	200	190	193	217	170
CTE (%)	2.0	1.9	2.1	2.6	2.5	2.4	2.2	1.8	2.8
Heat resistance (S / F, (@ 288 ℃)	> 10 min	> 10 min	> 10 min	10 min	10 min	> 10 min	> 10 min	> 12 min	> 15 min
PCT (4hr)	OK	OK	OK	Fail	Fail	OK	OK	OK	Fail
Dielectric constant (Dk @ 1 GHz)	3.60	3.62	3.63	3.77	3.70	3.75	3.70	3.80	3.72
Dielectric Loss (Df @ 1 GHz)	0.0017	0.0019	0.0020	0.0026	0.0026	0.0025	0.0025	0.0027	0.0025
Flame retardant	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0

As a result of the experiment, it was confirmed that the thermosetting resin composition of the present invention not only had excellent low lubrication loss characteristics and low dielectric constant, but also exhibited high glass transition temperature (Tg), excellent heat resistance, low thermal expansion characteristics, high thermal stability, and the like. (See Table 3 above).

Claims (18)

1. (a) polyphenylene ethers or oligomers thereof having at least two unsaturated substituents selected from the group consisting of vinyl and allyl groups at both ends of the molecular chain;

   (b) at least three different crosslinkable curing agents; And

   (c) flame retardants

   High-frequency thermosetting resin composition comprising a.
2. The method of claim 1,

   A thermosetting resin composition for high frequency, further comprising an inorganic filler surface-treated with a vinyl group-containing silane coupling agent.
3. The method of claim 1,

   The crosslinkable curing agent (b) is a high-frequency thermosetting resin composition characterized by mixing a hydrocarbon-based crosslinking agent (b1), a crosslinking agent (b2) containing three or more functional groups, and a rubber of a block structure (b3).
4. The method of claim 3,

   The high frequency content of the hydrocarbon-based crosslinking agent (b1), the crosslinking agent (b2) containing three or more functional groups, and the rubber of the block structure (b3) are in the range of 1.65 to 15% by weight based on the total weight of the resin composition, respectively. Thermosetting resin composition.
5. The method of claim 3,

   The use ratio of the hydrocarbon-based crosslinking agent (b1), the crosslinking agent (b2) containing three or more functional groups, and the block structure rubber (b3) is b1: b2: b3 = 1 to 20: 1 to 20: 1 weight ratio A high frequency thermosetting resin composition.
6. The method of claim 1,

   The polyphenylene ether resin (a) is a high-frequency thermosetting resin composition characterized in that represented by the following formula (1):

   [Formula 1]

   

   In Chemical Formula 1,

   Y is bisphenol A type, bisphenol F type, bisphenol S type, naphthalene type, anthracene type, biphenyl type, tetramethyl biphenyl type, phenol novolak type, cresol novolak type, bisphenol A novolak type, and bisphenol S no. At least one compound selected from the group consisting of

   m and n are each independently a natural number between 3 and 20.
7. The method of claim 1,

   The polyphenylene ether resin (a) is redistributed to 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). Thermosetting resin composition for high frequency, characterized in that modified to a low molecular weight of 10,000 range.
8. The method of claim 1,

   The molecular weight distribution of said polyphenylene ether resin (a) is 3 or less (Mw / Mn <3), The thermosetting resin composition for high frequencies.
9. The method of claim 1,

   The redistribution reaction of the polyphenylene ether resin (a) is a high temperature thermosetting resin composition, characterized in that carried out in the presence of a radical initiator, a catalyst, or a radical initiator and a catalyst.
10. The method of claim 3,

    The hydrocarbon-based crosslinking agent is selected from the group consisting of butadiene or polymer, decadiene or polymer, octadiene or polymer, and vinyl carbazole, thermosetting resin composition for high frequency.
11. The method of claim 3,

    The crosslinking agent containing at least three functional groups is selected from the group consisting of triallyl isocyanurate (TAIC), and 1,2,4-trivinyl cyclohexane (TVCH). Thermosetting resin composition for high frequency, characterized in that selected.
12. The method of claim 3,

    The block structure rubber is a high-temperature thermosetting resin composition, characterized in that selected from the group consisting of styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber, acrylate-butadiene rubber, and acrylonitrile-butadiene-styrene rubber.
13. The method of claim 1,

    The content of the crosslinkable curing agent (b) is a thermosetting resin composition for high frequency, characterized in that 5 to 40% by weight based on the total weight of the resin composition.
14. The method of claim 1,

    The flame retardant (c) is a high-temperature thermosetting resin composition, characterized in that at least one selected from the group consisting of halogen-containing flame retardant, phosphorus flame retardant, antimony flame retardant and metal hydroxide.
15. Fiber substrates surface-treated with vinyl group-containing silane coupling agents; And

    The thermosetting resin composition of any one of Claims 1-14 impregnated in the said fiber base material.

    Prepreg comprising a.
16. The method of claim 15,

    The fiber substrate is a group consisting of glass fiber, glass paper, glass fiber nonwoven fabric (glass web), glass cloth, aramid fiber, aramid paper, polyester fiber, carbon fiber, inorganic fiber and organic fiber Prepreg, characterized in that it comprises at least one selected from.
17. Metal foil or polymer film base material; And

    The resin layer formed on one side or both sides of the said base material, and the thermosetting resin composition in any one of Claims 1-14 hardened | cured.

    Functional laminated sheet comprising a.
18. A printed circuit board comprising a multilayer molded product comprising one or more layers of the prepreg of claim 17.