TW201905087A - Curable resin composition, prepreg and printed circuit board using the same - Google Patents

Abstract

The present invention is related to a thermosetting resin composition and a prepreg and a printed circuit board using the same. In particular, the present invention is related to the thermosetting resin composition, the prepreg and the printed circuit board that exhibit excellently low dielectric loss characteristics, good moisture absorption and heat resistance, low thermal expansion characteristics, and good thermal stability.

Description

Curable composition and prepreg and substrate using the same

The present invention relates to a thermosetting resin composition capable of producing a substrate excellent in low dielectric properties, heat resistance and moisture resistance, a prepreg using the same, and a printed circuit board.

Recently, with the miniaturization of mobile communication devices, satellite broadcast receiving devices, computers, etc., electronic components used in the above-mentioned devices have been miniaturized, complicated, highly functional, and highly precise, and electronic circuit components have been required. The substrate wiring pattern responds to high density and high speed of signal transmission.

Further, recently, with the trend toward higher functionality of electronic devices, the frequency band of signals used for communication electronic devices has gradually increased from the MHz region to the GHz band. In the case where the electric signal has a higher frequency, the transmission loss is greater. Therefore, in order to cope with such high frequency, a substrate having a low dielectric loss and a low loss coefficient with a small dielectric loss in the GHz region and excellent transmission characteristics is required. .

Generally, a polymer insulating material is used as a substrate raw material of a printed circuit board (PCB) or the like. Here, various polymer insulating materials such as a polyolefin resin, an epoxy resin, a fluorine-based thermoplastic resin, a polyimide resin, a bismaleimide triazine resin, and the like, and a laminate for a printed circuit board using the above materials have been proposed. It is produced by separately preparing the above polymer material or blending it with glass fiber, non-woven fabric, inorganic filler, or the like.

A method of preparing a laminate by disposing the above-described constituent material in a method in which a polymer insulating material is dissolved in an organic solvent and impregnated into a glass fabric and then dried to obtain a prepreg and a metal foil is heated and pressurized. In the case of a polymer insulating material which is dissolved in an organic solvent, it is processed by a melt injection method to form a plate shape, and then a metal foil such as a copper foil or an aluminum foil is superposed and heated and pressurized.

However, among the various polymer insulating materials previously provided, epoxy resins have the disadvantage of having electrical characteristics, particularly dielectric loss characteristics in a high frequency region.

Therefore, in Korean Patent Publication No. 2015-0060452, a bisphenol M type epoxy resin, a bisphenol M type cyanate resin, a polyphenylene ether, and a crosslinking are proposed as a composition having low dielectric loss characteristics. A thermosetting resin composition of a bonding hardener. However, the thermosetting resin composition proposed in this patent does not sufficiently satisfy the heat resistance although it has a low dielectric property to some extent.

Further, in Korean Patent Publication No. 2016-0032075, a non-epoxy thermoplastic resin which performs crosslinking on a polyphenylene ether resin using 1,9-decadiene and/or di-4-vinylbenzyl ether is proposed. Composition.

When the thermoplastic resin composition proposed in the above patent is used as a substrate, a certain degree of low dielectric loss characteristics can be ensured, but it is produced from the above composition due to the brittleness characteristics of the polyphenylene ether resin itself. The phenomenon that the prepreg is broken during the process or the process does not exhibit sufficient heat resistance.

Therefore, it is an urgent need to develop a thermosetting resin composition which has excellent heat resistance together with low dielectric properties.

[Prior Art Document] [Patent Document] Korean Patent Publication No. 2015-0060452 (2015.06.03), a thermosetting resin composition having heat resistance and low dielectric loss characteristics, a prepreg using the same, and a copper foil laminated plate Korean patent Publication No. 2016-0032075 (2016.03.23), a high-frequency thermosetting resin composition having a low dielectric loss characteristic, a prepreg using the same, and a copper foil laminate

[Question to be solved by the invention]

In order to solve the above problems, the inventors of the present invention applied a benzoxazine compound having a novel structure to a thermosetting resin composition to increase the glass transition temperature of the composition, and as a result, it was confirmed that the above composition was applied to printing. In the case of a circuit board, it exhibits high heat resistance, low dielectric properties, excellent high frequency characteristics, and good hygroscopicity.

Accordingly, an object of the present invention is to provide a thermosetting resin composition which exhibits excellent heat resistance and low dielectric properties, a prepreg using the above composition, and a printed circuit board.

[Means for solving the problem]

In order to achieve the above object, the present invention provides a thermosetting resin composition comprising: (i) a benzoxazine compound having two or more allyl groups at a terminal; (ii) having two or more epoxy resins a ring of epoxy resin; (iii) an active ester modifying hardener; and (iv) a nitrogen hardener.

Further, the present invention provides a prepreg containing the above-mentioned thermosetting resin composition on a fibrous substrate.

Further, the present invention provides a printed circuit board formed by laminating one or more layers of a prepreg comprising the above-mentioned thermosetting resin composition.

[Effects of the Invention]

The thermosetting resin composition of the present invention improves the heat resistance and ensures low dielectric constant characteristics by including a benzoxazine compound in the composition to increase the glass transition temperature of the resin composition.

When a prepreg is produced, such a resin composition does not cause breakage or the like, and the defect rate at the time of producing a component can be reduced, and workability can be improved. Further, since the manufactured printed circuit board has excellent low dielectric loss characteristics, good moisture absorption heat resistance, low thermal expansion characteristics, and thermal stability, it is exhibited even when applied to various parts used in a high frequency region of GHz. Excellent insulation properties, so long-term use without product malfunction.

In this case, the components to be used may be various types of electronic devices such as a mobile communication device that processes high-frequency signals of 1 GHz or higher, or an Internet-related electronic device such as a base station device, a server, a router, and the like, and a large computer.

The present invention proposes a thermosetting resin composition that can be usefully used in printed circuit boards.

A printed circuit board used for various electronic components is made of a thermosetting resin composition. In this case, the heat resistance and dielectric constant of the thermosetting resin itself are lowered to improve the low dielectric loss characteristics of the printed circuit board, and good moisture absorption and heat resistance. , low thermal expansion characteristics, thermal stability. Such physical properties can be achieved to some extent by using an epoxy resin, but heat resistance is insufficient. Therefore, in the present invention, a thermosetting resin composition including a specific composition to improve heat resistance is proposed.

Thermosetting Resin Composition The thermosetting resin composition of the present invention comprises: (i) a benzoxazine compound having two or more allyl groups at the terminal; (ii) an epoxy resin having two or more epoxy rings; (iii) an active ester-modified hardener; and (iv) a nitrogen-based hardener. Hereinafter, each component will be described in detail.

(i) The benzoxazine compound benzoxazine compound has a benzoxazine ring in a molecular structure, and when it is added to a thermosetting resin due to the rigidity of the structure itself, it can exert the following effects: not only an increase in Tg (glass transition temperature), and improve the moisture resistance and lower the dielectric constant. In particular, since the benzoxazine compound proposed in the present invention is polymerized by ring opening of benzoxazine and has two or more allyl groups at the terminal, it is possible to have no by-products (for example, condensation). Self-hardening. Due to the bulky side chain of the above benzoxazine ring, the free volume of the thermoplastic resin composition increases, and the dielectric constant decreases. Further, since the self-hardening by the thermal addition polymerization mechanism increases the hardening density (crosslinking desnsity) and improves the heat resistance. In particular, the above benzoxazine ring is formed in a bilaterally symmetrical manner, whereby the Tg can be further improved along with the above effects.

The benzoxazine-based compound proposed in the present invention is preferably a benzoxazine ring having two or more allyl groups substituted at the terminal as shown in the following Chemical Formula 1 to Chemical Formula 4. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] (In the above Chemical Formula 1 to Chemical Formula 4, Z is -(S)n- or -R'-(S)nR"-, and the above R' and R" are the same or different from each other, and are independently C1 to C5. An alkyl group, n is an integer of 1 to 4, and R ₁ to R ₁₃ are the same or different from each other, and are each independently H, a halogen element, a carboxyl group, a C1 to C20 alkyl group, a C3 to C20 cycloalkyl group, and a C2 to C20. Alkenyl, C2 to C20 alkynyl, C2 to C20 alkoxy, C6 to C20 aryl, C7 to C20 aralkyl or allyl, in which case the above aryl or aralkyl includes a fusion ring R ₁₄ and R ₁₅ are the same or different from each other, and are independently an C6 to C20 aryl group, a C7 to C20 aralkyl group or an allyl group, and o, p and q are each independently an integer of 0 to 5)

The "halogen element" referred to in the specification means F, Cl, Br or I.

The "alkyl group" referred to in the specification includes a linear alkyl group or a dendritic alkyl group, and as an example, includes a methyl group, an ethyl group, a propyl group, a 2-propyl group, a n-butyl group, an isobutyl group, and a third group. Butyl, pentyl, hexyl, dodecyl, etc., and in the case of substitution by a halogen element, more specifically fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl , trichloromethyl, iodomethyl, bromomethyl and the like. In this case, an alkylene group means a divalent linking group in which a hydrogen atom is detached, an alkenyl group is an alkyl group including a double bond in a molecular structure, and an alkynyl group is an alkyl group including a triple bond.

The cycloalkyl group mentioned in the present specification includes a monocyclic ring, a bicyclic ring or a tricyclic ring, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclopentenyl group, a cyclohexyl group, a cyclohexenyl group, and a ring. Heptyl, cyclooctyl, decahydronaphthyl, adamantyl, norbornyl (i.e., bicyclo[2,2,1]hept-5-enyl) and the like.

The alkoxy group referred to in the present specification includes a hydroxyl group (OH) in the molecular structure, and may, for example, be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, or a hexyloxy group. An oxy group, a dodecyloxy group or the like, and, in the case of being substituted by a halogen, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a chloromethoxy group, a dichloromethoxy group may be further exemplified. , trichloromethoxy, iodomethoxy, bromomethoxy, and the like.

The "aryl group" and "extended aryl group" mentioned in the specification have a carbon number of 6 to 60, respectively, as long as nothing else is stated, and are not limited thereto. In the present invention, an aryl group or an aryl group means a monocyclic or polycyclic aromatic group, and includes an aromatic ring which is bonded by an adjacent substituent or which participates in a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, an anthracenyl group, a spirofluorenyl group, or a spirobifluorenyl group.

In this case, the prefix "aryl" or "aralkyl" refers to a radical substituted by an aryl group. For example, an aralkyl group is an alkyl group substituted with an aryl group, an aralkenyl group is an alkenyl group substituted with an aryl group, and a radical substituted with an aryl group has a carbon number as described in the present specification.

Further, the above R ₁ to R ₁₃ may be substituted by one or two or more hydrogens on the benzene ring. When substituted by two or more hydrogens, they may be substituted by the same functional group or by different functional groups. As an example, it may be substituted by dimethyl group, methyl group, bromine or the like, respectively.

In the present specification, all compounds or substituents may be substituted or unsubstituted unless otherwise specified. Here, substituted means that hydrogen is selected from the group consisting of a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amine group, a thio group, a methylthio group, an alkoxy group, a nitrile group, an aldehyde group, an epoxy group, and an ether group. , ester, ester, carbonyl, acetal, keto, alkyl, perfluoroalkyl, cycloalkyl, heterocycloalkyl, allyl, benzyl, aryl, heteroaryl, etc. Any of the populations consisting of a combination of derivatives and the like are substituted.

Preferably, in the above Chemical Formula 1, Z is -(S)n-, in which case n is an integer of 1 to 3, and R' and R" are propyl groups.

Further, R ₁ to R ₁₃ may be H, Br, Cl, C1 to C12 alkyl, C1 to C12 alkoxy, C6 to C12 aryl, allyl, etc., more preferably H, A Base, ethyl, propyl, tert-butyl, hexyl, octyl, octadecyl, dodecyl, cumyl, phenyl, fused phenyl, methoxy, ethoxy, bromomethyl or Allyl.

Further, R ₁₄ and R ₁₅ may be a phenyl group or an allyl group.

The benzoxazine compound represented by the above Chemical Formula 1 to Chemical Formula 4 is more preferably a compound represented by the following Chemical Formula 5 to Chemical Formula 9, respectively. [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] (In the above Chemical Formula 5 to Chemical Formula 10, o, p, and q are the same as above)

The benzoxazine compound represented by the above structure is low in polarity, has excellent heat resistance and low dielectric property, can be rapidly hardened at a low temperature, and has high thermal stability to improve the disadvantages of the existing thermosetting resin. . Further, it is excellent in compatibility with an epoxy resin, and fluidity is increased at the time of producing a laminate, and processability is improved, and dielectric properties are further improved.

In the present invention, the benzoxazine-based compound is used in an amount of from 5% by weight to 50% by weight, preferably from 5% by weight to 40% by weight, based on the total of 100% by weight of the thermosetting resin composition. When the content of the above benzoxazine compound is less than the above range, effects such as low compatibility with an epoxy resin and dielectric properties cannot be ensured, and if it exceeds the above range, the content of other components is not satisfied. It is difficult to manufacture a product having desired physical properties with a relatively small reduction, and therefore it is suitably used within the above range.

(ii) Epoxy Resin In order to achieve curing, the epoxy resin used in the thermosetting resin composition of the present invention may be one having at least two or more epoxy groups.

The epoxy resin preferably includes a benzene structure and a hydrocarbon side chain, and has two or more epoxy groups in one molecule. This is because the main chain of the epoxy resin has a ring structure and a side chain, and has a low melt viscosity and high reactivity. Therefore, heat resistance can be ensured without adding other functional groups. Further, since the main chain has a moiety having a symmetrical structure and a ring structure, it has a structure for suppressing the alignment polarization of the polymer itself, and thus is advantageous in terms of dielectric characteristics.

The epoxy equivalent of such an epoxy resin may range from 200 g/eq to 2,000 g/eq, preferably from 200 g/eq to 1000 g/eq. Further, the above epoxy resin may have a weight average molecular weight (Mw) in the range of 1,000 g/mol to 20,000 g/mol, preferably in the range of 1000 g/mol to 10,000 g/mol, more preferably 1,000 g/ Mol to the range of 5,000 g/mol.

The epoxy resin which can be used is not particularly limited in the present invention, and can be used for a general user in the art.

The epoxy resin of the present invention preferably uses a dicyclopentadiene (DCPD) epoxy resin. The above-mentioned DCPD-based epoxy resin has a hydrophobic bicyclic hydrocarbon group as a polyfunctional resin, and therefore has less electron polarization phenomenon and contributes to lowering the dielectric constant of the copper foil laminate. The above DCPD-based epoxy resin is preferably used in an epoxy equivalent of from 200 g/eq to 500 g/eq. At this time, when the above-described equivalent amount is deviated, there are problems such as insufficient strength of the substrate, deterioration in heat resistance, and problems such as foaming on the surface of the prepreg, which is not preferable.

The DCPD-based epoxy resin is more preferably an epoxy resin represented by the following Chemical Formula 11 and Chemical Formula 12. [Chemical Formula 11] (In the above Chemical Formula 11, s is an integer of 1 to 10) [Chemical Formula 12] (In the above Chemical Formula 12, X is an extended aryl group of C ₆ to C ₄₀ , t and u are integers of 1 to 10, and v and w are integers of 1 to 5)

Such an epoxy resin affects the hardening ability, the moldability, the adhesion force, and the like of the thermosetting resin composition, and the content thereof is limited in order to secure an optimum effect. It is preferred to use 30% by weight to 80% by weight, preferably 30% by weight to 60% by weight, of the epoxy resin in the total 100% by weight of the thermosetting resin composition. When the content of the epoxy resin is less than the above range, the curing ability, the moldability, and the adhesion are lowered, so that the defective rate of the product is high. On the contrary, if it exceeds the above range, the curing degree is higher due to the higher degree of hardening. Since the physical properties are degraded, it is appropriately adjusted within the above range.

A well-known epoxy resin can be used together with the above-mentioned DCPD-based epoxy resin.

Examples include bisphenol A type/bisphenol F type/bisphenol S type resin, novolac type epoxy resin, alkylphenol novolak type epoxy resin, biphenyl type, aralkyl type, and a cyclopentadiene type or a mixed form thereof or the like. More specific examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, fluorene epoxy resin, biphenyl type epoxy resin, and four. Methyl biphenyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol S novolak type epoxy resin, biphenol Aldehyde type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene phenol addition reaction type ring An oxygen resin, a phenol aralkyl type epoxy resin, a polyfunctional phenol type resin, a naphthol aralkyl type epoxy resin, or the like. 50% by weight or less of such an epoxy resin is used with respect to the DCPD-based epoxy resin.

(iii) Active ester-modified hardener The hardener which constitutes one of the compositions of the thermosetting resin composition of the present invention is a substance which undergoes curing by inducing cross-linking.

It is preferred to use an active ester-modified hardener as the above-mentioned hardener. The above "active ester upgrading" relates to the reactivity of an epoxy resin, and means a part of a curing agent substituted with an ester group. It is preferably one or more selected from the group consisting of a phenol ester-based curing agent, a thiophenolic ester-based curing agent, an N-hydroxylamine-based curing agent, and a heterocyclic hydroxy compound ester-based curing agent.

The active ester-modified hardener is excellent in physical properties (that is, heat resistance and dielectric properties) due to high epoxy ring-to-ester hardening reactivity in an epoxy resin. At this time, the curing reactivity is converted to an ester group at the end of the molecular structure after curing as shown in the following Reaction Formula 1, and reacts with the epoxy ring to form an ether group at the terminal.

[Reaction formula 1] (In the above Reaction Scheme 1, R ¹ to R ³ are aliphatic hydrocarbons or aromatic hydrocarbons)

This hardening mechanism differs from known amine hardeners or phenolic hardeners. In other words, the amine-based curing agent or the phenol-based curing agent has a secondary OH group in the molecular structure after curing as in the following Reaction Formula 2, and the OH group exhibits polarity and becomes an element for increasing the dielectric constant. Further, since the secondary OH group reacts again with the epoxy ring, it absorbs moisture due to hydrophilicity, and thus when used as a substrate, physical properties are deteriorated.

[Reaction formula 2] (In the above Reaction Scheme 2, R ¹ to R ³ are aliphatic hydrocarbons or aromatic hydrocarbons)

In this manner, the active ester-modified hardener of the present invention hardens without including an OH group after hardening, that is, forms a network structure, whereby the low dielectric constant property can be activated.

The active ester resin obtained by a condensation reaction of a carboxylic acid compound and/or a sulfuric acid compound with a hydroxy compound and/or a thiol compound is more preferable from the viewpoint of improving heat resistance. Further, an active ester resin obtained by reacting one or two or more compounds selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound with a carboxylic acid compound is preferred. Furthermore, it is more preferably an aromatic resin compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group. Particularly preferred is an aromatic resin compound obtained by reacting a compound having at least two or more carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group, and the aromatic resin An aromatic resin compound having two or more active ester groups in one molecule of the compound. The active ester resin may be linear or may be multi-branched. In addition, when a compound having at least two or more carboxylic acids in one molecule is a compound including an aliphatic chain, compatibility with a resin composition can be improved, and if it is a compound having an aromatic ring, it can be improved. Heat resistance.

Specifically, examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Among them, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and more preferably isophthalic acid or terephthalic acid are preferred. Formic acid. Specifically, examples of the sulfur carboxylic acid compound include thioacetic acid and thiobenzoic acid.

Specifically, examples of the phenol compound or the naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, and methylated double. Phenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene diphenol, Phenolic novolacs and the like. Among them, from the viewpoint of improving heat resistance and improving solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, and methylated bisphenol S are preferred. , catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxydiphenyl Ketone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene diphenol, phenolic novolac, more preferably catechol, 1,5-dihydroxynaphthalene, 1,6 -Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene diphenol a phenolic novolac, further preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxyl Benzophenone, dicyclopentadiene diphenol, phenolic novolac, and more preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentane Alkene diphenol, phenolic novolac, particularly preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene Dicyclopentadiene diphenol, particularly preferably dicyclopentadiene diphenol. Specific examples of the thiol compound include benzenedithiol and triazinedithiol.

The active ester-modified hardener is preferably an active ester resin including a dicyclopentadiene diphenol structure, an active ester resin including a naphthalene structure, an active ester resin including an acetylated phenolic novolac, and a phenolic novolac. An active ester resin of benzamidine compound, more preferably an active ester resin including a naphthalene structure, and an active ester resin including a dicyclopentadiene diphenol structure. As a commercial item, EXB9451, EXB9460, EXB9460S, which is an active ester resin including a dicyclopentadiene diphenol structure, HPC-8000-65T (manufactured by DIC), and an active ester resin including a naphthalene structure are exemplified. EXB9416-70BK (manufactured by DIC), DC808 (manufactured by Mitsubishi Chemical Corporation) as an active ester resin of an acetylated phenolic novolak, and an active ester resin as a benzamidine compound including a phenol novolak YLHl026 (Mitsubishi Chemical Co., Ltd.) and so on.

The active ester-modified hardener of the present invention preferably has a dicyclopentadiene diphenol structure represented by the following Chemical Formula 13 and has an X-group and an XO- group at the terminal (wherein X may also have a substituent) HPC-8000-65T of an active ester resin having a weight average molecular weight of about 2700 g/mol.

[Chemical Formula 13] (In the above Chemical Formula 13, y is 0 or 1, and z is 0.4 to 1.2)

The active ester-modified hardener is used in an amount of from 5% by weight to 30% by weight, preferably from 7% by weight to 25% by weight, based on 100% by weight of the total of the thermosetting resin composition. If the content of the above-mentioned active ester-modified hardener is less than the above range, the effect of minimizing the functional group at the epoxy end and reducing the polar group is small, and the more the content is increased, the more excellent the low dielectric constant loss is exhibited. The characteristics are lower than the dielectric constant effect. However, when it exceeds the above range, there is a problem that the workability is lowered due to the problem that the Tg is low and the reactivity (hardening rate) of the composition is slow.

(iv) Nitrogen-based hardener The thermosetting resin composition of the present invention further includes a nitrogen-based hardener together with the above-mentioned active ester-modified hardener.

The nitrogen-based curing agent may be one or more selected from the group consisting of an amine curing agent, a triazine-phenol curing agent, a carbodiimide curing agent, and a cyanate curing agent.

Examples of the amine-based curing agent include aliphatic amines, polyether polyamines, alicyclic amines, and aromatic amines. Examples of the aliphatic amines include ethylenediamine and 1,3-diamine. Propane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylidenetriamine, iminodipropylamine, bis(six) Methylene)triamine, tri-extension ethyltetramine, tetra-extension ethylpentamine, penta-ethylhexamine, N-hydroxyethylethylenediamine, tetrakis(hydroxyethyl)ethylenediamine, and the like. The polyether polyamine may be selected from the group consisting of triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamine, and the like. One of the mixtures. Examples of the alicyclic amines include isophorone diamine, montan diamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, and bis(amine). Methyl)cyclohexane, 3,9-bis(3-aminopropyl) 2,4,8,10-tetraoxaspiro(5,5)undecane, norbornene diamine, and the like. As the aromatic amine, it may be selected from the group consisting of tetrachloroterephthalamide, m-xylylenediamine, p-xylylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-di Aminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1, 2-diphenylethane, 2,4-diaminodiphenylphosphonium, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, three Ethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyldimethylmethane, α,α One of a mixture of '-bis(4-aminophenyl)p-diisopropylbenzene and the like.

The triazine-phenolic curing agent preferably comprises two or more, three or more or four or more triazine structures per molecule, and preferably comprises two or more and three or more in one molecule. Or 4 or more phenolic hydroxyl groups are suitable. The phenolic hardener containing a triazine structure may be used alone or in combination of two or more.

The phenolic hardener containing a triazine structure is obtained by, for example, a triazine ring containing one or more compounds selected from the group consisting of a phenol compound and a naphthol compound, melamine, benzoguanamine, oxazine, and the like. The compound reacts with formaldehyde. As a commercial item of such a hardening|curing agent, "LA-3018" (the benzene phenol novolak type hardening agent containing a triazine structure) by the DIC ( "LA-7054", "LA-1356" (a phenolic novolak type hardener containing a triazine structure), and the like.

Further, specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

The cyanate-based curing agent is not particularly limited, and examples thereof include a novolac type (phenol novolak type, an alkylphenol type novolak type, etc.) cyanate type curing agent and dicyclopentadiene type cyanate. A hardener, a bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate type hardener, and a prepolymer obtained by triazine-forming a part, etc.. Specific examples include bisphenol A dicyanate and polyphenol cyanate (oligo(3-methylene-1,5-phenylene)) and 4,4'-methylene. Bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4- Cyanate ester) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3 - bis(4-cyanate phenyl-1-(methylethylidene) benzene, bis(4-cyanate phenyl) sulfide, and bis(4-cyanate phenyl) ether a bifunctional cyanate resin, a polyfunctional cyanate resin derived from a phenol novolak and a cresol novolac, a prepolymer obtained by triazine-forming a part of the cyanate resin, etc. Specific examples of the acid ester hardener include "PT30", "PT30S" and "PT60" manufactured by lonza Japan Co., Ltd. (all of which are phenolic novolac type polyfunctional cyanate resins) and "BADcy" (double Phenol A dicyanate), "BA230" (a part or all of bisphenol A dicyanate is triazineized to form a prepolymer of a terpolymer), and the like.

As another form of hardener, a latent amine hardening component is included. The latent hardener means that the hardening component does not react at room temperature, but if it exceeds the initial temperature of the epoxy hardening reaction, it rapidly reacts to cause hardening. Even if the structural adhesive does not activate the hardener, the above-mentioned latent hardener can be easily applied at room temperature or by appropriate heating.

Suitable latent amines include, for example, hydrazine, substituted hydrazine (for example, methyl hydrazine, dimethyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, methyl isoprene, dimethyl isoprene, tetramethyl Isobiguanide, hexamethylisobiguanide, heptamethylisobiguanide and dicyandiamide), melamine resin, guanamine derivatives (for example, alkylated benzoguanamine resin, benzoguanamine resin and methoxymethyl B) Oxymethylbenzamide), cyclic tertiary amine, aromatic amine, substituted urea (for example, p-chlorophenyl-N,N-dimethylurea (methasone), 3-phenyl- 1,1-Dimethylurea (non-oxalon), 3,4-dichlorophenyl-N,N-dimethylurea (diuron), tertiary amide or alkylamine (eg, benzyl) Dimethylamine, tris(dimethylamino)phenol, piperidine and piperidine derivatives), imidazole derivatives (for example, 2-ethyl-2-methylimidazole, N-butylimidazole, benzazole, N-C1 to C12-alkylimidazole and N-arylimidazole) and combinations thereof. Commercially available latent amines include the Asahidized hardener series (EH-3615, EH-3842, and EH-4342S) available from Japan's Adeka Corp., and Ajinomoto from Japan. The Ajicure series (PN-40J) purchased by the company (Ajinomoto Corp.).

In the total 100% by weight of the thermosetting resin composition, 0.0001% by weight to 5% by weight, preferably 0.0005% by weight to 4% by weight, of such an additional hardener is used. When the content of the curing agent exceeds the above range, it is difficult to adjust the curing rate, and it is difficult to produce a product having desired physical properties due to excessive curing. Therefore, it is suitably used within the above range.

The thermosetting resin composition of the present invention can be used in a known composition generally used in the art, in addition to the above components, and various additives can be used as an example.

As an example of the flame retardant, a general flame retardant well known in the art can be used without limitation, and examples thereof include a halogen flame retardant containing bromine or chlorine, triphenyl phosphate, and tricresyl phosphate. Phosphorus flame retardants such as tris(dichloropropyl) phosphate and phosphoric acid, antimony-based flame retardants such as antimony trioxide, and flame retardants for inorganic substances such as aluminum hydride and magnesium hydride.

In the present invention, it is preferred to use an additive type phosphorus-based flame retardant which does not inhibit heat resistance and dielectric properties. The thermosetting resin composition may include a flame retardant in a ratio of 10 parts by weight to 30 parts by weight, preferably 15 parts by weight to 25 parts by weight, based on 100 parts by weight of the total thermosetting resin composition. If the flame retardant is included in the above range, the flame resistance of the flame retardant 94V-0 level can be sufficiently obtained, and excellent heat resistance and electrical properties can be exhibited.

The inorganic filler can reduce the difference in thermal expansion coefficient (CTE) between the resin layer and the other layers, and effectively improve the bending properties, low expansion, mechanical strength, and low stress of the final product.

Non-limiting examples of the inorganic filler which can be used in the present invention include, for example, natural silica, Fused silica, amorphous silica, crystalline cerium oxide (crystalline) Siloxanes such as silica; boehmite, alumina, talc, rectangular glass, calcium carbonate, magnesium carbonate, magnesium oxide, clay, calcium silicate, titanium oxide, cerium oxide, glass fiber, Aluminum borate, barium titanate, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate, calcium zirconate, boron nitride, tantalum nitride, talc (talc), mica (mica )Wait. Such inorganic fillers may be used singly or in combination of two or more.

The hardening accelerator is not particularly limited, and examples thereof include an imidazole-based hardening accelerator, an amine-based hardening accelerator, a phosphorus-based hardening accelerator, an anthraquinone-based hardening accelerator, and a metal-based hardening accelerator. The hardening accelerator may be used singly or in combination of two or more.

As an example, the above-mentioned hardening accelerator can be used in ordinary users in the technical field to which the present invention pertains, for example, imidazole, 2-methylimidazole (2-MI), 2-ethylimidazole, 2-mercaptoimidazole, 2- Hexyl imidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl Imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl-imidazole trimellitate, 1- Cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-(2'-methylimidazolium-(1'))-ethyl-s-triazine, 2,4- Diamino-6-(2'ethyl-4-methylimidazolium-(1'))-ethyl-s-triazine, 2,4-diamino-6-(2'-undecylimidazole- (1'))-Ethyl-s-triazine, 2-phenyl-4,5-dimethylolimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl- 4-benzyl-5-hydroxymethylimidazole, 4,4'-methylene-bis-(2-ethyl-5-methylimidazole), 2-aminoethyl-2-methylimidazole, 1 -cyanoethyl-2-phenyl-4,5- (Cyanoethoxymethyl)imidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, Ethyltriphenylphosphonium Iodide (ETPPI) or imidazole-containing An imidazole compound such as polyamine or a boric acid or the like may be used alone or in combination of two or more.

The hardening accelerator proposed in the present invention is more preferably in the presence of various hardening systems such as an epoxy resin and an amine hardener, an epoxy resin and an active ester hardener, an epoxy resin, and a benzoxazine hardener. It is usually used in an epoxy resin such as 2-ethyl-4-methylimidazole or 2-methylimidazole as an imidazole hardening accelerator, and is selectively used for 4-dimethyl used when an active ester hardener is used. 4-dimethylaminopyridine (DMAP), 3,3'-thiodipropionic acid, 4,4'-thiodiphenol (4) used as a benzoxazine hardening accelerator 4'-thiodiphenol), etc., is not limited thereto.

In order to enhance the advantageous effect of the cross-linking bonding hardener, the thermosetting resin composition of the present invention may further include a reaction initiator.

As non-limiting examples of reaction initiators which can be used, there are α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5- Di(t-butylperoxy)-3-hexyne (hexyne), benzammonium peroxide, 3,3',5,5'-tetramethyl-1,4-diphenoxyfluorene, four Chlorobenzoquinone, 2,4,6-tri-tert-butylphenoxy, tert-butylperoxyisopropylmonocarbonate, azobisisobutyronitrile, and the like. Metal carboxylates can also be used more. The above reaction initiator may be included in an amount of 2 parts by weight to 5 parts by weight based on 100 parts by weight of the thermosetting resin composition, but is not limited thereto.

The thermosetting resin composition of the present invention may further include various polymerizations of other thermosetting resins or thermoplastic resins not described above, and oligomers thereof, etc., in addition to the above-mentioned components, as long as the intrinsic properties of the above-mentioned resin composition are not impaired. Other additives such as solid rubber particles or ultraviolet absorbers, catalysts, antioxidants, dyes, pigments, dispersants, tackifiers, leveling agents, and the like. Examples thereof include organic amine catalysts such as 4-dimethylaminopyridine (DMAP), organic fillers such as anthrone powder, nylon powder, and fluororesin powder; tackifiers such as orben and bentonite; anthrone and fluorine. Polymer antifoaming agent or leveling agent such as resin; adhesion imparting agent such as imidazole coupling agent, thiazole coupling agent, triazole coupling agent, decane coupling agent; coloring agent such as phthalocyanine or carbon black .

The thermoplastic resin can be blended in the thermosetting resin composition for the purpose of imparting appropriate flexibility to the resin composition after curing. Examples of such a thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide, polyamidoximine, polyether oxime, polyfluorene, and the like. These thermoplastic resins may be used alone or in combination of two or more.

Examples of the resin additive include organic fillers such as anthrone powder, nylon powder, and fluorine powder; tackifiers such as orben and bentonite; anthrones, fluorines, polymer defoamers or leveling agents; and imidazole coupling agents. , thiazole coupling agent, triazole coupling agent; decane coupling agent; epoxy decane, amino decane, alkyl decane, decyl decane and other adhesion imparting agents; phthalocyanine blue, phthalocyanine-green, iodine - Coloring agents such as green, disazo yellow, carbon black; mold release agents such as higher fatty acids, higher fatty acid metal salts, and ester waxes; and stress relaxation agents such as ketone oil, anthrone powder, and anthrone resin. Also, an additive which is generally used for a thermosetting resin composition for producing an electronic device (particularly, a printed wiring substrate) may be included.

Preparation of Thermosetting Resin Composition The thermosetting resin composition of the present invention can be prepared by appropriately mixing the above components, and if necessary, using a kneading device such as a three-roll mill, a ball mill, a bead mill, a sand mill, or the like, or Mixing or mixing with a stirring device such as a high-speed rotary mixer, a super mixer, or a planetary mixer. Further, a resin varnish can be prepared by further adding the above organic solvent.

The form of the thermosetting resin composition of the present invention is not particularly limited, and can be applied to a sheet-like laminate material such as an adhesive film or a prepreg, or a circuit board (for laminate use, multilayer printed wiring board use, etc.). The resin composition of the present invention can also be applied to a circuit board in a varnish state to form an insulating layer. However, it is generally industrially preferable to use it in the form of a sheet-like laminate material such as a film or a prepreg. The softening point of the resin composition is preferably from 40 ° C to 150 ° C from the viewpoint of lamination property of the sheet-like laminate material.

Prepreg The prepreg of the present invention comprises a fibrous substrate and the above thermosetting resin composition impregnated with the fibrous substrate. Here, the thermosetting resin composition may be a resin varnish in a form of being dissolved or dispersed in a solvent.

As the fiber base material, a usual inorganic fiber base material, an organic fiber base material, or the like in the form of a mixture which is arbitrarily bendable and flexible can be used. The above fibrous substrate may be selected based on the use or performance to be used.

As non-limiting examples of usable fiber substrates, there are glass fibers (inorganic fibers) such as E-glass, D-glass, S-glass, NE-glass, T-glass, Q-glass, etc.; such as cellophane, Glass web, glass cloth, aromatic polyamide fiber, aramid paper, polyimine, polyamide, polyester, aromatic polyester, An organic fiber such as a fluororesin; a mixed form of one or more of carbon fiber, paper, inorganic fiber, or the like. Examples of the form of the fiber base material include a woven fabric or a non-woven fabric including the above-mentioned fibers; and a woven fabric including a roving, a chopped strand mat, a surfacing mat, a metal fiber, a carbon fiber, a mineral fiber, or the like. Cloth, non-woven fabric, felt, etc. These base materials may be used alone or in combination of two or more. In the case of mixing a reinforced fibrous base material, the rigidity and dimensional stability of the prepreg can be improved. The thickness of such a fibrous base material is not particularly limited and may be, for example, in the range of about 0.01 mm to 0.3 mm.

The above resin composition is used to form a prepreg, and the thermosetting resin composition of the present invention as described above can be used.

In general, the prepreg refers to a sheet-like material obtained by hardening and heating to a B-stage (semi-hardened state) after coating or impregnating a thermosetting resin composition onto a fibrous substrate. In addition to the above methods, the prepreg of the present invention can be produced by a hot melt method, a solvent method or the like which is well known in the art.

The solvent method is a method in which a fiber substrate is impregnated with a resin composition varnish formed by dissolving a thermosetting resin composition for forming a prepreg in an organic solvent, followed by drying. In the case of using such a solvent method, a resin varnish is usually used. An example of a method of impregnating the resin composition with the resin substrate is a method of impregnating a substrate with a resin varnish, a method of applying a resin varnish to a substrate by using various coaters, and spraying a resin varnish with a sprayer. The method to the substrate, and the like. In this case, when the fiber base material is immersed in the resin varnish, the impregnation property of the resin composition to the fiber base material can be improved, which is preferable.

In the case of preparing the above resin composition varnish, examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl ether B. Acetate such as acid ester or carbitol acetate, carbitol such as 赛路苏, butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, and dimethyl Indoleamine, N-methylpyrrolidone, tetrahydrofuran, and the like. The organic solvent may be used alone or in combination of two or more.

Further, the hot-melt method may be a method of applying a release sheet having excellent releasability to a resin composition without dissolving the resin composition in an organic solvent, and then laminating it to a sheet-like fiber substrate or using it. The die coater directly coats. Further, the prepreg may be prepared by continuously heating a bonding film including a thermosetting resin composition laminated on the support from both sides of the sheet-like reinforcing substrate under heating and pressing conditions. Pressure.

The resin composition of the present invention can be prepared into a prepreg by coating or impregnating the resin composition onto a sheet-like fibrous substrate or a glass substrate comprising fibers, which is semi-hardened by heating. A prepreg for a printed circuit board is preferred. At this time, the above resin composition can be adjusted into a resin varnish.

The prepreg of the present invention can be formed by a drying process after coating or staining to the above substrate, and the above drying can be carried out at 20 ° C to 200 ° C. As an example, the prepreg of the present invention can prepare a semi-hardened (B-stage) prepreg by impregnating a substrate with the above-mentioned thermosetting resin composition varnish and drying it at 70 ° C to 170 ° C. Minutes to 10 minutes.

Printed circuit board The present invention includes a printed circuit board in which one or more, preferably two or more of the prepregs are superimposed on each other, and the prepreg is heated and pressurized under normal conditions. And formed.

The above printed circuit board can be manufactured by a usual method well known in the art. As a preferred example of the above printed wiring board, a copper foil laminated board can be produced by heating and pressing one or two-layer copper foil of the prepreg of the present invention, followed by a copper foil laminated board. Through-hole plating is performed by opening a hole, and then the copper foil including the plating film is etched to form an electric circuit.

In this case, the heating and pressing conditions can be appropriately adjusted depending on the thickness of the laminated sheet to be produced, the type of the thermosetting resin composition of the present invention, and the like. As an example, it is preferably carried out under the following pressing conditions: at a temperature of 70 ° C to 250 ° C, preferably 100 ° C to 230 ° C, the pressure reducing degree is usually 0.01 MPa or less, preferably 0.001 MPa or less. The degree of pressure reduction is set to a range of from 0.5 MPa to 4 MPa, and the pressing time is set to 30 minutes to 150 minutes. Heating and pressurization can also be carried out in one step, but from the viewpoint of controlling resin leakage, it is preferably carried out in two or more steps.

It can be seen that the printed circuit board proposed in the present invention not only has a low dielectric constant and dielectric loss, but also has a low coefficient of thermal expansion (CTE), a high glass transition temperature (Tg), and excellent heat resistance ( Refer to Table 2) below. Therefore, the prepreg and the printed circuit board of the present invention can be usefully used as a mobile communication device for processing a high-frequency signal of 1 GHz or higher, or an Internet-related electronic device and a large-sized computer such as a base station device, a server, a router, and the like. A part of a printed circuit board for the Internet of various electronic devices.

Hereinafter, the present invention will be specifically described by way of examples, but the following examples and experimental examples are only intended to illustrate one embodiment of the present invention, and the scope of the present invention is not limited to the following examples and experimental examples. [Examples]

In the examples 1 to 5 and the comparative examples 1 to 3 , the compositions proposed in the following Table 1 were added to the reactor, and uniformly mixed to prepare a thermosetting resin composition.

After the prepared thermosetting resin composition was impregnated into glass fibers, it was dried at 155 ° C for 5 minutes to 30 minutes to prepare a prepreg. Next, after the above prepreg layer 4 is ply, it is pressed to obtain a laminated sheet having a thickness of 0.8 mm to 1.2 mm.

[Table 1] 1) KZH-5031: compound of formula 6, DCPD benzoxazine 2) KZH-5021: compound of formula 8, benzaldehyde novolac benzoxazine 3) TPE BZX: compound of formula 9, tetraphenylbenzene And pyridazine, 4) KZH-5032: compound of formula 7, DCPD benzoxazine 5) KES-7695: DCPD resin with epoxy equivalent of 270 g/eq 6) HPC-8000-65T: activated ester Resin, equivalent 223 g/eq, DIC product 7) DICY: dicyandiamide 8) DMAP: dimethylaminopyridine 9) 2-MI: 2-methyl imidazole 10) TDPA: 3,3'-thiodipropionic acid 11) KGH-3200: KGH-3200 (400 g/eq)

Experimental Example 1 : Physical property measurement and analysis The following experiment was performed on the printed circuit boards produced in the examples and the comparative examples, and the results are shown in Table 2 below.

1) Heat resistance According to the International Institute of Printed Circuit (IPC) TM-650 2.4.13 evaluation standard, the printed circuit board is floated at 288 ° C in solder (Solder) to determine insulation. The time until the point of separation between the layer and the copper foil, the insulating layer and the metal core or the insulating layer was evaluated.

2) Copper foil adhesion (Peel Strength, P/S) According to the evaluation standard of IPC-TM650 2.4.8, the circuit pattern formed on the printed circuit board is pulled in the direction of 90 degrees to determine the circuit pattern (copper) Foil) time point of peeling and evaluation.

3) Evaluation of flame retardancy The evaluation substrate obtained by removing the copper foil by impregnating the copper foil laminate with a copper etching solution was used to fabricate an evaluation substrate having a length of 127 mm and a width of 12.7 mm, according to the American Safety Testing Laboratory ( The test method (V method) of Underwriters Laboratories, UL) 94 was evaluated.

4) Thermomechanical Analysis (TMA) glass transition temperature The evaluation substrate obtained by removing the copper foil by impregnating the copper foil laminate with a copper etching solution was used to fabricate an evaluation substrate having a side of 5 mm on each side, using a TMA test apparatus ( Thermal Analysis (TA) Instrument (Q400) Observed and evaluated the thermal expansion characteristics of the substrate.

5) Evaluation of moisture absorption and heat resistance (Pressure Cooker Test, PCT) The evaluation substrate obtained by removing the copper foil by impregnating the copper foil laminate with a copper etching solution was carried out using a pressure cooker test apparatus (ESPEC, EHS-411MD). After standing at 121 ° C and 0.2 MPa for 4 hours, the printed circuit board was dipped at a temperature of 288 ° C at intervals of 10 seconds until the insulating layer and the copper foil, the insulating layer and the metal core or the insulating layer were produced. The time until the point in time of the separation phenomenon is evaluated.

6) Relative dielectric constant and dielectric loss tangent A substrate obtained by removing a copper foil by impregnating a copper foil laminate with a copper etching solution, by means of a relative dielectric constant measuring device (Radio Frequency (RF) impedance ( Impedence)/Material Analyzer (Agilent) measures the relative dielectric constant and dielectric loss tangent at a frequency of 1 GHz.

7) Glass transition temperature (Tg) A sample of about 5 mg was heated at a rate of 10 ° C/min using a differential scanning calorimeter (DSC) 2010 and DSC 2910 from TA Instruments as a DSC tester. 300 ° C, then cooled to 30 ° C at a rate of 10 ° C / min. This first first heating/cooling process is carried out in accordance with the same procedure.

8) Absorption rate (W/A) Using a test piece cut into 50 mm × 50 mm, the dry weight after drying in an oven at 50 ° C for 24 hours was measured, and then measured in a treatment tank adjusted to 85 ° C / 85% RH Store the weight after 72 hours.

[Table 2]

With reference to the above Table 2, in the case of using the thermosetting resin composition of the benzoxazine-based compound and the active ester-based curing agent of the present invention, all the physical properties exhibited excellent numerical values.

On the other hand, in the case where the benzoxazine compound was not used as in Comparative Example 1, the Tg was low and the hygroscopicity was high, and this case indicates that the dielectric constant was increased.

Further, when a benzoxazine-based compound which does not include an allyl group is used as in Comparative Example 2, Tg tends to rise slightly, but in this case, the dielectric constant is also high.

Further, in the case of using the allyl-containing benzoxazine compound as in Comparative Example 3, when the active ester-based curing agent was not used, the dielectric constant was high.

[Industrial availability]

Since the thermosetting resin composition of the present invention and the substrate produced therefrom have low dielectric constant characteristics, they can be easily applied to electronic parts such as a semiconductor substrate, a printed circuit board, or an epoxy molding compound (EMC). .

no

no

Claims (9)

A thermosetting resin composition comprising: (i) a benzoxazine compound having two or more allyl groups at a terminal; (ii) an epoxy resin having two or more epoxy rings; (iii) an active group An ester-modified hardener; and (iv) a nitrogen-based hardener. The thermosetting resin composition according to claim 1, wherein the benzoxazine compound, 30% by weight to 100% by weight of the total thermosetting resin composition The epoxy resin, 5% by weight to 30% by weight of the active ester-modified hardener, and 0.0001% by weight to 5% by weight of the nitrogen-based hardener. The thermosetting resin composition according to the first aspect of the invention, wherein the benzoxazine compound is at least one selected from the group consisting of the compounds represented by the following Chemical Formulas 1 to 4: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] In the chemical formula 1 to the chemical formula 4, Z is -(S)n- or -R'-(S)nR"-, and R' and R" are the same or different from each other, and are independently C1 to C5. An alkyl group, n is an integer of 1 to 4, and R ₁ to R ₁₃ are the same or different from each other, and are each independently hydrogen, a halogen element, a carboxyl group, a C1 to C20 alkyl group, a C3 to C20 cycloalkyl group, C2 to An alkenyl group of C20, an alkynyl group of C2 to C20, an alkoxy group of C2 to C20, an aryl group of C6 to C20, an aralkyl group or an allyl group of C7 to C20, said aryl or aralkyl group including a fusion ring R ₁₄ and R ₁₅ are the same or different from each other, and are each independently a C6 to C20 aryl group, a C7 to C20 aralkyl group or an allyl group, and o, p and q are each independently an integer of 0 to 5. The thermosetting resin composition according to claim 1, wherein the epoxy resin is a dicyclopentadiene epoxy resin having an epoxy equivalent of from 200 g/eq to 500 g/eq. The thermosetting resin composition according to claim 1, wherein the active ester modifying hardener is selected from the group consisting of a phenol ester hardener, a thiophenol ester hardener, an N-hydroxylamine hardener, and a heterocyclic ring. One or more hardeners in the group consisting of hydroxy compound ester type hardeners. The thermosetting resin composition according to claim 1, wherein the nitrogen hardener is selected from the group consisting of an amine hardener, a triazine-phenol hardener, a carbodiimide hardener, and a cyanate ester. One or more hardeners in the group consisting of hardeners. A prepreg comprising a fibrous substrate, wherein the thermosetting resin composition according to any one of claims 1 to 6 is impregnated into the fibrous substrate. The prepreg according to claim 7, wherein the fibrous substrate comprises a material selected from the group consisting of glass fiber, cellophane, glass fiber nonwoven fabric, glass fabric, aromatic polyamide fiber, aromatic polyamide paper, and poly One or more of the group consisting of ester fibers, carbon fibers, inorganic fibers, and organic fibers. A printed circuit board comprising a laminate of more than one layer of the prepreg as described in claim 7 or 8.