KR20150078859A - Epoxy Resin and Method for Preparing the Same - Google Patents

Abstract

The present invention relates to an epoxy resin and a manufacturing method thereof and, more specifically, an epoxy resin which meets a condition like resistance to high heat that a copper-clad laminate substrate used in a printed circuit substrate, a sealing material, a molding material, a casting material, an adhesive and a material for an electrical insulating paint used in electronic parts while properly implementing a low dielectric property, and a manufacturing method thereof.

Description

EPOXY RESIN AND METHOD FOR PREPARING THE SAME [0002]

More particularly, the present invention relates to an epoxy resin having excellent dielectric properties and high heat resistance, and a method for producing the same.

In recent years, with the miniaturization of mobile communication devices, satellite broadcast receiving devices, computers, etc., miniaturization, complexity, high performance, and high precision are progressing for electronic components used for them, and also for high density and signal transmission A demand for high-speed response is required.

In addition, the frequency band of signals used in telecommunication equipment is shifting from the MHz to the GHz band. Since the electrical signal has a characteristic that the transmission loss increases as the frequency increases, development of an electrically insulating material having excellent high frequency transmission characteristics and a substrate using the same is indispensable.

Generally, a polymer insulating material is used as a substrate material for a printed circuit board (PCB) or the like. Various polymer insulating materials such as a polyolefin resin, an epoxy resin, a fluorine-based thermoplastic resin, a polyimide resin, and a bismaleimide triazine resin have been proposed. In the laminate for a printed circuit board using these materials, Non-woven fabric, inorganic filler and so on.

A method of preparing a laminate by mixing the above components includes a method of melting the polymer insulating material in an organic solvent, impregnating the glass cloth with a glass cloth, drying the prepreg, and heating and pressing the metal laminate, In the case of a material, it is melted and processed by a melt injection method, and a metal foil such as a copper foil or an aluminum foil is rolled up after being formed into a plate form.

However, in the case of an epoxy resin, various electrical insulating properties, particularly dielectric loss characteristics in a high frequency range, are disadvantageous as a variety of conventionally provided polymeric insulating materials. On the other hand, the fluorine-based thermoplastic resin typified by PTFE has high frequency characteristics, but since it is a thermoplastic resin, it expands and shrinks greatly during molding processing, and its workability is inferior so that its use area is extremely limited.

Further, in the case of a polyolefin thermoplastic resin, when the laminate is formed into a laminate, even if adhesion with a metal foil is secured, the lead heat resistance is generally poor. In the case of a polyolefin-based resin, since it has no polar group, it has a disadvantage in that it has excellent electrical characteristics, particularly dielectric loss characteristics, but low heat resistance. In addition, since the coefficient of linear expansion is large, when used as a laminated board for a wiring board, there is a problem that reliability of connection and reliability of plated through-hole are insufficient when the component is mounted. The bismaleimide triazine resin and the polyimide resin are inferior in utility as a general-purpose resin due to their high cost.

Accordingly, development of a resin capable of realizing a balance of various physical properties and low dielectric properties required for a sealing material, a molding material, a mold material, an adhesive, and an electric insulating paint material used for a copper-clad laminate used for a printed circuit board or an electronic component This is desperate.

The main object of the present invention is to provide a resin composition which satisfies the high heat resistance required for a copper clad laminate used for a printed circuit board, a sealing material used for an electronic part, a molding material, a mold material, an adhesive, And a method for manufacturing the same.

In order to achieve the above object, an embodiment of the present invention provides an epoxy resin comprising a repeating unit represented by the following formula (1) and having a weight average molecular weight of 560 to 5,600 g / mol.

≪ Formula 1 >

In the above formula (1), R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 10.

In one preferred embodiment of the present invention, the epoxy resin has a softening point of 50 to 110 ° C and an epoxy equivalent of 240 to 320 g / eq.

Another embodiment of the present invention is a process for preparing a copolymer comprising: (a) polymerizing a dicyclopentadiene and a bisphenol compound in the presence of a first acid catalyst to produce a copolymer; (b) condensing the resulting copolymer with an aldehyde compound in the presence of a second acid catalyst to produce a novolak resin; And (c) reacting the resulting novolak resin with epihalohydrin under base catalyst to produce an epoxy resin having a weight average molecular weight of 560 to 5,600 g / mol, Wherein the epoxy resin is a resin.

≪ Formula 1 >

In the above formula (1), R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 10.

In another preferred embodiment of the present invention, the polymerization in step (a) may be performed at 80 to 140 ° C for 1 to 10 hours.

In another preferred embodiment of the present invention, the bisphenol compound used in step (a) may be used in an amount of 1.0 to 10.0 moles per mole of dicyclopentadiene.

In another preferred embodiment of the present invention, the condensation reaction is performed at 80 to 120 ° C for 1 to 10 hours in the step (b).

In another preferred embodiment of the present invention, the aldehyde compound in the step (b) may be used in an amount of 0.1 to 0.99 mol based on 1 mol of the copolymer.

In another preferred embodiment of the present invention, the first acid catalyst is a Lewis acid catalyst.

In another preferred embodiment of the present invention, the second acid catalyst is selected from the group consisting of oxalic acid, sulfuric acid, phosphoric acid, hydrochloric acid and acetic acid; And at least one organic acid selected from the group consisting of para-toluenesulfonic acid, benzenesulfonic acid, phenolsulfonic acid, lactic acid, acetic acid, and formic acid.

In another preferred embodiment of the present invention, the epihalohydrin in the step (c) is used in an amount of 1.0 to 10.0 mol based on 1 mol of the novolak resin.

In another preferred embodiment of the present invention, the reaction of step (c) is performed at 20 to 80 ° C for 5 to 15 hours.

Another embodiment of the present invention provides an epoxy resin composition comprising the epoxy resin in an amount of 5 to 95% by weight based on the total weight of the composition, and a cured product of the epoxy resin composition.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a resin composition which can achieve a balance of low-dielectric property and thermal stability required for a copper-clad laminate used for a printed circuit board, a sealing material used for electronic parts, a molding material, a mold material, an adhesive, An epoxy resin can be provided.

1 is a FT-IR measurement graph of an epoxy resin prepared in Example 1 of the present invention.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

In one aspect, the present invention relates to an epoxy resin comprising a repeating unit represented by the following formula (1) and having a weight average molecular weight of 560 to 5,600 g / mol.

≪ Formula 1 >

In the above formula (1), R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 10.

Particularly, in the above formula (1), n represents an average value of degree of polymerization and is an integer of 1 to 10, and is an integer of 2 to 4 in view of solvent solubility and viscosity in varnish production. The average value of the degree of polymerization is a value calculated from the weight average molecular weight measured by gel permeation chromatograph (GPC).

In the above formula (1), R is preferably a hydrogen atom or a methyl group in terms of heat resistance.

The epoxy resin containing the repeating unit represented by the formula (1) has a weight average molecular weight of 560 to 5,600 g / mol. If the weight average molecular weight is less than 560 g / mol, the heat resistance of the epoxy resin is low and the weight average molecular weight is 5,600 g / mol, the viscosity is It may be elevated or gelled to lower the workability and lower the compatibility with other resins.

The epoxy resin containing the repeating unit represented by the above formula (1) has a softening point of 50 ° C or higher, which causes a phenomenon that the resin is blocked in the resin, that is, a phenomenon in which the resin becomes lumpy in an environment of high temperature and humidity, Can be prevented and high thermal stability at a high temperature can be ensured. By setting the temperature at 110 DEG C or less, the resin can be easily melted and workability can be improved.

The epoxy resin containing the repeating unit represented by the formula (1) has an epoxy equivalent of 240 to 320 g / eq, and has an optional ease when mixed with a curing agent.

The epoxy resin containing the repeating unit represented by formula (1) according to the present invention has a main chain length extended due to the methylene linkage of the intermediate, and the molecular weight can be increased to secure thermal stability, and the dicyclopentadiene and bisphenol The low dielectric properties expressed in the compound structure can be balanced with the thermal stability.

In another aspect, the present invention provides a process for producing a copolymer, comprising: (a) polymerizing a dicyclopentadiene and a bisphenol compound in the presence of a first acid catalyst to produce a copolymer; (b) condensing the resulting copolymer with an aldehyde compound in the presence of a second acid catalyst to produce a novolak resin; And (c) reacting the resulting novolak resin with epihalohydrin under base catalyst to produce an epoxy resin having a weight average molecular weight of 560 to 5,600 g / mol, To a process for producing an epoxy resin.

≪ Formula 1 >

In the above formula (1), R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 10.

Conventionally, a copolymer obtained by polymerizing dicyclopentadiene and a bisphenol compound to prepare an epoxy resin that realizes a low dielectric property is epoxidized. However, when epoxidized using only dicyclopentadiene and a bisphenol compound, The reaction was not proceeded smoothly due to the failure, and thus it had limitations on heat resistance and dielectric properties.

Accordingly, in the present invention, by copolymerizing dicyclopentadiene and a bisphenol compound followed by making it novolac, heat resistance and dielectric properties far superior to those of a copolymer epoxy resin of a conventionally prepared dicyclopentadiene and a bisphenol compound can be realized have.

Specifically, as shown in the following Reaction Scheme 1, the epoxy resin according to the present invention is obtained by polymerizing dicyclopentadiene (A) and bisphenol compound (B) in the presence of a first acid catalyst to produce a copolymer (step a) The resulting copolymer (C) and an aldehyde compound (D) are subjected to a condensation reaction in the presence of a second acid catalyst to produce a novolac resin (step b), and the resulting novolak resin (E) and epihalohydrin F) is reacted under a base catalyst to prepare an epoxy resin containing the repeating unit of the formula (1).

[Reaction Scheme 1]

In the above Reaction Scheme 1, R and n are as described above.

The polymerization of the dicyclopentadiene and the bisphenol compound can be carried out at 80 to 140 ° C for 1 to 10 hours. If the reaction is carried out at a temperature lower than the reaction temperature range described above, the reaction does not proceed smoothly and the conversion is lowered. When the reaction is carried out in a temperature range exceeding the above-mentioned temperature range, dicyclopentadiene- It may be difficult to easily adjust the distribution.

The bisphenol compound may be bisphenol A, bisphenol B, bisphenol F, bisphenol E or the like as long as it is a compound having phenol bonded to both carbon atoms. Specific examples thereof include bisphenol A, have.

The bisphenol compound may be used in an amount of 1.0 to 10.0 moles, preferably 2.0 to 5.0 moles, per 1 mole of dicyclopentadiene. If the amount of the bisphenol compound added is less than 1.0 mole based on 1 mole of the dicyclopentadiene, the reaction may not proceed smoothly, resulting in a problem that the molecular weight of the product is reduced. When the addition exceeds 10 moles, There may be a problem that a large amount of unreacted bisphenol compound is present in the resin.

The first acid catalyst used in the polymerization of the dicyclopentadiene and the bisphenol compound includes tin tetrachloride, boron trifluoride, boron trichloride, zinc chloride, trichloride, trimethylsilyl trifluoromethanesulfonate, phosphoryl chloride, Aluminum chloride, and the like.

In this case, the content of the first acid catalyst is 0.1 to 2.0 parts by weight based on 100 parts by weight of the bisphenol compound. When the amount of the first acid catalyst is less than 0.1 parts by weight, the reaction may not proceed well, If the amount exceeds the above range, heat generation during the reaction is severe, so that a runaway reaction may occur and safety problems may occur.

The copolymer of the dicyclopentadiene and the bisphenol compound prepared as described above is subjected to a condensation reaction in the presence of an aldehyde compound and a second acid catalyst to prepare a novolak resin containing the repeating unit of the above formula (1).

The copolymer of the dicyclopentadiene and the bisphenol compound prepared as described above is subjected to a condensation reaction in the presence of an aldehyde compound and a second acid catalyst to prepare a novolak resin containing the repeating unit of the above formula (1).

The aldehyde compound may be at least one selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, salicylic aldehyde, benzaldehyde, glyoxal and butylaldehyde, though not particularly limited. As the formaldehyde, Formaldehyde, which is a polymer thereof, and formalin, which is in the form of an aqueous solution.

The aldehyde compound may be added in an amount of 0.1 to 0.99 mole, preferably 0.7 to 0.9 mole, per mole of the copolymer. If the aldehyde compound is added in an amount of less than 0.1 moles per mole of the copolymer, the degree of polymerization is low and the methylene bond is not properly formed. When the aldehyde compound is added in excess of 0.99 mole, the reaction proceeds excessively, It can be difficult.

The second acid catalyst used in the condensation reaction of the copolymer and the aldehyde compound includes inorganic acids selected from oxalic acid, sulfuric acid, phosphoric acid, hydrochloric acid and acetic acid; And at least one organic acid selected from the group consisting of para-toluenesulfonic acid, benzenesulfonic acid, phenolsulfonic acid, lactic acid, acetic acid and formic acid, and oxalic acid may be used because it is easy to remove the activity and catalyst.

In this case, the content of the second acid catalyst is 0.1 to 3.0 parts by weight based on 100 parts by weight of the copolymer. When the amount of the second acid catalyst is less than 0.1 parts by weight, the activation energy is low, If the amount is more than 3.0 parts by weight, heat generation during the reaction is severe, and congestion reaction may occur, which may cause safety problems.

In the present invention, the first and second acid catalysts can be added together with the reactants, or after the reactants are mixed, they can be introduced in the reaction step.

Further, in the present invention, as another form of the reaction, it is preferable to use the reaction substrate itself as a solvent, but it is also possible to use another reaction solvent. The reaction solvent is not particularly limited as long as it does not inhibit the reaction. Examples of the reaction solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, 1-methoxy- -Methoxyethanol and the like, and the content thereof may be 20 to 80 parts by weight based on 100 parts by weight of the total reaction product.

After completion of the condensation reaction, water produced by the reaction, an acid catalyst, a reaction solvent, unreacted dicyclopentadiene, a bisphenol compound, an aldehyde compound and the like are removed through vacuum suction, heating and the like. In addition, the ion exchange water may be added to remove the impurities, and the water washing process may proceed. In this case, the amount of the ion-exchange water may be about 10% to 100% by weight of the total weight of the reaction product, and the washing step by ion-exchange water may be performed once or several times.

Further, the reaction product may be dehydrated under normal pressure or reduced pressure of 0 to 160 mmHg. The dehydration may be performed at a temperature in the range of 150 to 200 ° C, and the steam blow distillation process may be further performed.

The novolac resin produced in this manner can be produced by glycidylating the epihalohydrin in the presence of a base catalyst.

In the present invention, the glycidylation of the novolak resin can be carried out without particular limitation as long as it can be produced by reacting with epihalohydrin. Preferably, the novolak resin and the epihalohydrin Condensation reaction of the monomers. At this time, the heavy / condensation reaction can be carried out at 20 to 80 ° C for 5 to 15 hours.

The epihalohydrin may be epichlorohydrin, epi-iodohydrin, epibromohydrin, methyl epichlorohydrin, methyl epibromohydrin, methyl epi-iodohydrin, etc., Lt; RTI ID = 0.0 > epichlorohydrin. ≪ / RTI >

The epihalohydrin is used in an amount of 1.0 to 10.0 mol based on 1 mol of the novolac resin. When epihalohydrin is used in an amount less than 1.0 mol, the epoxidation reaction does not take place properly, and 10.0 mol There is a problem that the cost of recovering the epihalohydrin is increased and the production amount is decreased.

The base catalyst may be any catalyst as long as it can be used in the glycidylation reaction. The base catalyst may be a base catalyst such as sodium hydroxide or potassium hydroxide, more preferably a sodium hydroxide having a concentration of 20 to 60% Is suitable for minimizing the production of by-products of the resin and for the reaction rate.

The content of the base catalyst is in the range of 0.3 to 3.0 mol per mol of the novolac resin. When the content of the base catalyst is out of the range, the epoxy ring does not proceed smoothly or the reaction proceeds excessively, It is difficult to generate heat, so that a runaway reaction occurs, which may cause safety problems.

The epoxy resin obtained by such a production method can realize a lower dielectric property and heat resistance than conventional epoxy resin for a copper clad laminate, and is suitable for high speed and high frequency signal, a sealing material used for electronic parts, a molding material, , Adhesives, and materials for electrical insulation paints.

In another aspect, the present invention relates to an epoxy resin composition comprising the epoxy resin in an amount of 5 to 95% by weight based on the total weight of the composition, and a cured product of the epoxy resin composition.

The epoxy resin according to the present invention may be added in an amount of 5 to 95% by weight based on the total weight of the composition in consideration of heat resistance, dielectric properties, and the like. If the epoxy resin is added in an amount of less than 5% by weight based on the total weight of the composition, the effect is insufficient. If the epoxy resin is added in an amount exceeding 95% by weight, the heat resistance may be lowered.

The above-mentioned epoxy resin composition has excellent low dielectric properties and high heat resistance to balance low dielectric properties suitable for a sealing material, a molding material, a mold material, an adhesive, and an electric insulation paint material used for a copper-clad laminate used for a printed circuit board or an electronic component A cured product can be provided.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the present invention is not limited to these examples.

[ Example  One]

1-1: Synthesis of Copolymer

2,800 g (12.27 mol) of bisphenol A (BPA, Kumho P & B) and 1,600 g of xylene were placed in a flask equipped with a thermometer, a cooling tube, and a stirrer and charged with BF ₃ -phenolate (Stella Chemifa Corp. 26% Boron Trifluoride Phenol) was charged, the temperature was raised to 100 ° C, and 770 g (5.83 mol) of dicyclopentadiene was uniformly added dropwise over 3 hours. After the homogeneous dropwise addition, the mixture was heated to 140 ° C and reacted for 3 hours. When the reaction was completed, KW-1000 (Kyowa Chemical) was added as a neutralizing agent and neutralized at 95 ° C for 2 hours. When the neutralization was completed, 2,040 g of a copolymer was obtained through diatomaceous earth filtering.

1-2: Novolac  Resin synthesis

300 g (3.73 mol) of 40% by weight formaldehyde was added to 2,40 g (3.83 mol) of the copolymer prepared in Example 1-1, and 16 g of oxalic acid was added as a second acid catalyst. The reaction was carried out for 5 hours under a reflux circuit. The condensed water, unreacted material and solvent were removed by vacuum dehydration for 1 hour at a temperature of 175 ° C and a vacuum degree of 0 mmHg or higher to obtain 2,600 g of novolak resin .

The obtained novolak resin had a softening point of 107.1 ° C, a phenolic hydroxyl group equivalent of 187 g / eq, and a weight average molecular weight of 1,011 g / mol by GPC.

1-3: Epoxy resin manufacturing

600 g (3.21 mol) of the novolac resin obtained in Example 1-2 and 1800 g (19.46 mol) of epichlorohydrin were put into a 5 L four-necked flask and sufficiently mixed. Then, 60 g of KOH (45 wt% Lt; 0 > C for 5 hours. Subsequently, 350 g of NaOH (50 wt%) was added and reacted for 5 hours. After the reaction was completed, 650 g of water was added to remove the salt formed during the reaction, and the unreacted epichlorohydrin was completely removed by vacuum degassing. The mixture was diluted by adding methyl isobutyl ketone (MIBK) to the mixture which had been completely removed from the unreacted epichlorohydrin, and then washed twice with 350 g of water and purified to obtain a salt and hydrolyzable chlorine And neutralized and degassed by adding 0.5 g of phosphoric acid to prepare an epoxy resin having a weight average molecular weight of 1,210 g / mol, a softening point of 76.6 DEG C and an epoxy equivalent of 282 g / eq (wherein R is a methyl group, n is 3).

The novolak resin thus obtained was confirmed to have an epoxy ring peak in the region of 913 cm ^-1 by confirming the structure using FT-IR (FIG. 1). At this time, the instrument used for FT-IR measurement is PerkinElmer Spectrum 100 product.

[ Comparative Example  One]

1-1: Synthesis of Copolymer

Add 2,800 g (12.27 mol) of phenol (Kumho P & B) to a flask equipped with a thermometer, a cooling tube and a stirrer, and add 30 g of BF ₃ -phenolate (Stella Chemifa Corp. 26% Boron Trifluoride Phenol) Thereafter, the temperature was raised to 100 ° C, and 1,000 g (7.58 mol) of dicyclopentadiene was uniformly added dropwise over 3 hours. After the homogeneous dropwise addition, the temperature was raised to 140 ° C and reacted for 3 hours. When the reaction was completed, KW-1000 (Kyowa Chemical) was added as a neutralizing agent and neutralized at 95 ° C for 2 hours. When the neutralization was completed, 2,070 g of dicyclopentadiene-phenol copolymer was obtained through diatomaceous earth filtering.

1-2: Epoxy resin production

600 g (3.59 mol) of the dicyclopentadiene-phenol copolymer obtained in Comparative Example 1-1 and 2498 g (27 mol) of epichlorohydrin were put into a 5 L four-necked flask, and sufficiently mixed. Then, 85 g of KOH (45 wt% And the mixture was reacted at 60 DEG C for 5 hours. Subsequently, 500 g of NaOH (50 wt%) was added and reacted for 5 hours. After the completion of the reaction, 700 g of water was added to remove the salt formed during the reaction, and the unreacted epichlorohydrin was completely removed by vacuum degassing. The mixture was diluted by adding methyl isobutyl ketone (MIBK) to the mixture which had been completely removed from the unreacted epichlorohydrin, and then washed twice with 350 g of water and purified to obtain a salt and hydrolyzable chlorine 0.5 g of phosphoric acid was added to neutralize and degassed to prepare 800 g of an epoxy resin having a weight average molecular weight of 628 g / mol, a softening point of 65 캜, and an epoxy equivalent of 279.6 g / eq.

[ Comparative Example  2]

2-1: Synthesis of copolymer

2,800 g (12.27 mol) of bisphenol A (BPA, Kumho P & B) and 1,600 g of xylene were placed in a flask equipped with a thermometer, a cooling tube, and a stirrer and charged with BF ₃ -phenolate (Stella Chemifa Corp. 26% Boron Trifluoride Phenol) was charged, the temperature was raised to 100 ° C, and 770 g (5.83 mol) of dicyclopentadiene was uniformly added dropwise over 3 hours. After the homogeneous dropwise addition, the temperature was raised to 140 ° C and reacted for 3 hours. When the reaction was completed, KW-1000 (Kyowa Chemical) was added as a neutralizing agent and neutralized at 95 ° C for 2 hours. When the neutralization was completed, 2,040 g of dicyclopentadiene-bisphenol A copolymer was obtained through diatomaceous earth filtering.

2-2: Production of epoxy resin

600 g (3.08 mol) of the dicyclopentadiene-bisphenol A copolymer obtained in Comparative Example 2-1 and 1400 g (15.14 mol) of epichlorohydrin were put into a 5 L four-necked flask and thoroughly mixed. Then, KOH (45 wt% And the mixture was reacted at 60 DEG C for 5 hours. Subsequently, 300 g of NaOH (50 wt%) was added and reacted for 5 hours. After completion of the reaction, 600 g of water was added to remove the salt formed during the reaction, and the unreacted epichlorohydrin was completely removed by vacuum degassing. The mixture was diluted by adding methyl isobutyl ketone (MIBK) to the mixture which had been completely removed from the unreacted epichlorohydrin, and then washed twice with 350 g of water and purified to obtain a salt and hydrolyzable chlorine And 0.5 g of phosphoric acid was added to neutralize and degassed to obtain 700 g of an epoxy resin having a weight average molecular weight of 775 g / mol, a softening point of 64.2 캜, and an epoxy equivalent of 283 g / eq

≪ Property evaluation method &

(1) Measurement of molecular weight (g / mol)

The polystyrene reduced weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by gel permeation chromatography (GPC) (Waters: Waters 707). The measurement resin was dissolved in tetrahydrofuran so as to have a concentration of 4000 ppm, and 100 μl was injected into GPC. The mobile phase of GPC was run at a flow rate of 1.0 mL / min using tetrahydrofuran and the assay was performed at 35 < 0 > C. The column was connected in series with four Waters HR-05, 1, 2, and 4E. Detector was measured at 35 ℃ using RI and PAD Detector. At this time, the PDI (polydispersity index) was calculated by dividing the measured weight average molecular weight by the number average molecular weight.

(2) Softening point (° C) measurement

Was measured using a Mettler Toledo FP90 / FP83HT instrument at a heating rate of 2 [deg.] C / min.

(3) Measurement of epoxy equivalent (g / eq)

The excess amount of HCl solution was added to 7 g of the measurement resin, and the epoxy ring was broken in an oil bath at 70 ° C for 30 minutes. Then, the equivalent amount was determined by reversing with NaOH.

(3) Measurement of hydrolyzable chlorine (Hy-Cl) content

0.5 g of the measuring resin was dissolved in toluene, the KOH solution was added in an excess amount, the reaction was carried out in an oil bath for 30 minutes, and then the hydrolyzable chlorine was measured by reversing with HCl solution.

(5) Manufacture of copper clad laminates

A DICY curing agent (Samchun Pure Chemicla, dicyandiamide) having an active hydrogen equivalent (AHEW) of 10.5 g / eq was mixed with an epoxy resin (epoxy resin of each of Examples and Comparative Examples) in an equivalent ratio of 1: 2-methylimidazole) was added and the gel-time was adjusted to be about 260 sec. The gel-time was measured by dropping 0.2 cc of varnish on a hot plate and stirring the gelation. The glass fibers were cut into a size of 30 cm x 30 cm and impregnated with the varnish. The impregnated glass fibers were dried at room temperature for 1 hour and then dried in an oven at 155 ° C to set the drying time such that the prepreg gel time was about 110 sec. The prepreg dried at the set drying time was laminated together with the copper foil, and pressed under high temperature and pressure to prepare a copper clad laminate. At this time, the press condition was maintained at 190 占 폚 under 0 mmHg vacuum for 2 hours.

(6) Glass transition temperature (캜) measurement

The glass transition temperature of the copper-clad laminate (300 mm x 300 mm x 300 mm) obtained in (5) was measured with a differential scanning calorimeter (DSC, Q2000 manufactured by TA Instrument Co., Ltd.) Lt; / RTI > at a rate of temperature rise of < RTI ID = 0.0 >

(7) Measurement of dielectric constant

The dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product were measured using an impedance analyzer (Agilent E4991A 1 MHz to 3GHz) manufactured by Agilent under the following conditions.

Measuring frequency: 1GHz

Measuring temperature: 25 ~ 27 ℃

Measuring humidity: 45 ~ 55%

Measurement sample: thickness 1.5 mm (1.3-1.7 mm)

Softening point
(° C) EEW
(g / eq) Hy-Cl
(ppm) Mn
(g / mol) Mw
(g / mol) PDI Tg
(° C) Dk Df Comparative Example 1 65 258 50 475 628 1.32 176.2 3.5 0.018 Comparative Example 2 64.2 283 80 470 775 1.65 166.5 3.08 0.0115 Example 1 76.6 282 92 560 1210 2.37 180.1 3.03 0.0105

As shown in Table 1, it was confirmed that Comparative Example 2 had better dielectric properties than Comparative Example 1, but deteriorated in heat resistance characteristics. Example 1 shows that the dielectric characteristics of Comparative Example 1 and Comparative Example 1 were maintained, 1 and 2, respectively.

Therefore, the epoxy resin according to the present invention balances the low dielectric properties and thermal stability required for a copper-clad laminate used in a printed circuit board, a sealing material used for electronic parts, a molding material, a mold material, an adhesive, It can be realized that

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (14)

An epoxy resin having a repeating unit represented by the following formula (1) and having a weight average molecular weight of 560 to 5,600 g / mol:
≪ Formula 1 >

In the above formula (1), R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 10.
The epoxy resin according to claim 1, wherein the epoxy resin has a softening point of 50 to 110 캜 and an epoxy equivalent of 240 to 320 g / eq.
(a) polymerizing a dicyclopentadiene and a bisphenol compound in the presence of a first acid catalyst to produce a copolymer;
(b) condensing the resulting copolymer with an aldehyde compound in the presence of a second acid catalyst to produce a novolak resin; And
(c) reacting the resulting novolak resin with epihalohydrin under base catalyst to produce an epoxy resin having a weight average molecular weight of 560 to 5,600 g / mol, : ≪ / RTI >
≪ Formula 1 >

In the above formula (1), R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 10.
4. The method according to claim 3, wherein the polymerization is carried out at 80 to 140 ° C for 1 to 10 hours in the step (a).
4. The method for producing an epoxy resin according to claim 3, wherein the bisphenol compound used in step (a) is used in an amount of 1.0 to 10.0 moles relative to 1 mole of dicyclopentadiene.
4. The method for producing an epoxy resin according to claim 3, wherein the condensation reaction is carried out at 80 to 120 DEG C for 1 to 10 hours in the step (b).
4. The method for producing an epoxy resin according to claim 3, wherein the aldehyde compound in step (b) is used in an amount of 0.1 to 0.99 mol based on 1 mol of the copolymer.
The method for producing an epoxy resin according to claim 3, wherein the first acid catalyst is a Lewis acid catalyst.
4. The process of claim 3, wherein the second acid catalyst is selected from the group consisting of oxalic acid, sulfuric acid, phosphoric acid, hydrochloric acid and acetic acid; And at least one organic acid selected from the group consisting of para-toluenesulfonic acid, benzenesulfonic acid, phenolsulfonic acid, lactic acid, acetic acid and formic acid.
4. The method for producing an epoxy resin according to claim 3, wherein the epihalohydrin in step (c) is used in an amount of 1.0 to 10.0 mol based on 1 mol of the novolak resin.
The method of claim 3, wherein the reaction of step (c) is performed at 20 to 80 ° C for 5 to 15 hours.
An epoxy resin composition comprising the epoxy resin according to claim 1 or 2.
13. The epoxy resin composition according to claim 12, wherein the epoxy resin composition comprises 5 to 95% by weight based on the total weight% of the composition of the epoxy resin.
A cured product of the epoxy resin composition of claim 12.

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