KR20140085925A - Low Dielectric Constant Phenolic Resin, Epoxy Resin and Processes for Production thereof - Google Patents

Abstract

The present invention relates to a phenol resin with low dielectric properties, an epoxy resin with low dielectric properties and a manufacturing method thereof and, more specifically, to a phenol resin with low dielectric properties and an epoxy resin with low dielectric properties capable of uniformly realizing low dielectric properties while satisfying physical properties required for a sealing material, a molding material, a casting material, a binding material, a material for an electrical insulation paint and the like used in an electronic part or a copper clad laminate used in a printed circuit board, and to a manufacturing method thereof.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenolic resin, an epoxy resin, and a process for producing the same,

The present invention relates to a phenol resin, an epoxy resin, and a process for producing the same, which have low dielectric properties.

In recent years, with the miniaturization of mobile communication devices, satellite broadcast receiving devices, computers and the like, miniaturization, complexity, high performance, high precision and the like are progressing for electronic components used in them. There is a demand for countermeasures against high-speed signal transmission.

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.

It is a main object of the present invention to provide a resin composition which satisfies physical 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 part, And a method for producing the phenolic resin and the epoxy resin.

The present invention also provides a phenol resin and an epoxy resin having low dielectric properties, which are produced by the above-mentioned production method.

The present invention also provides an epoxy resin composition containing the epoxy resin having the low dielectric property and a cured product thereof.

According to an aspect of the present invention, there is provided a process for producing a phenolic resin, comprising the steps of: (a) reacting a hydroxyl group-containing aromatic compound with an unsaturated cyclic hydrocarbon compound in the presence of a catalyst to produce a phenolic resin; And (b) extracting a phenol resin having a weight average molecular weight of 600 to 2,500 g / mol among the produced phenol resin. The present invention also provides a method for producing a phenol resin having low dielectric properties.

Another embodiment of the present invention provides a phenol resin having low dielectric properties, which is produced by the above production method and has a dielectric constant of 3.5 or less at 1 GHz and a dielectric loss of 0.03 or less at 1 GHz.

Another embodiment of the present invention is a process for producing a phenolic resin, comprising: (a) reacting an aromatic compound containing a hydroxyl group with an unsaturated cyclic hydrocarbon compound in the presence of a catalyst to produce a phenolic resin; (b) extracting a phenol resin having a weight average molecular weight of 600 to 2,500 g / mol among the produced phenol resin; And (c) reacting the extracted phenol resin with epihalohydrin in the presence of a base catalyst. The present invention also provides a process for producing an epoxy resin having low dielectric properties.

Yet another embodiment of the present invention is a low dielectric constant material having a low dielectric constant, which is produced by the above production method and has an epoxy equivalent of 150 to 500 g / eq, a dielectric constant at 1 GHz of 3.5 or less, and a dielectric loss at 1 GHz of 0.03 or less And an epoxy resin.

Another embodiment of the present invention provides an epoxy resin composition, wherein the epoxy resin having the low dielectric property is contained in an amount of 5 to 95% by weight based on the total weight of the composition.

Another embodiment of the present invention provides a cured product of the epoxy resin composition.

The phenolic resin having a low dielectric property according to the present invention satisfies the physical properties such as water resistance and heat resistance and can be used for a sealing material used for a copper-clad laminate used for a printed circuit board or an electronic part, a molding material, a mold material, It is possible to realize balanced low dielectric characteristics suitable for materials.

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.

According to one aspect of the present invention, there is provided a process for producing a phenolic resin, comprising: (a) reacting a hydroxyl group-containing aromatic compound with an unsaturated cyclic hydrocarbon compound in the presence of a catalyst to produce a phenolic resin; And (b) extracting a phenol resin having a weight average molecular weight of 600 to 2,500 g / mol among the produced phenol resin.

More specifically, a phenol resin modified with a conventionally unsaturated cyclic hydrocarbon compound has a limitation of dielectric properties, but the present invention can realize not only water resistance and heat resistance but also excellent low-dielectric property by controlling the molecular weight distribution of the phenol resin .

This can overcome the drawbacks of low water resistance, heat resistance, and high dielectric properties of monomolecular materials by improving the purity by removing the monomolecular substances present in the phenol resin modified with the conventional unsaturated cyclic hydrocarbon compound, Water resistance and heat resistance as well as low dielectric properties.

The hydroxyl group-containing aromatic compound is not particularly limited as long as the aromatic group is directly substituted with an aromatic ring, but examples thereof include phenol, o-cresol, m-cresol, , p-ethylphenol, o-isopropylphenol, m-propylphenol, p-propylphenol, p-sec-butylphenol, p-tert- butylphenol, p- Monovalent phenols such as phenol, m-bromophenol, p-bromophenol,? -Naphthol and? -Naphthol; Bis (4'-hydroxyphenyl) propane, 1,1'-bis (bisphenoxyphenyl) methane, 1,1'-bis (dihydroxynaphthyl Divalent phenols such as methane, tetramethylbiphenol and biphenol; Tris (hydroxyphenyl) methane, and mixtures thereof, and more preferably bisphenol-A [2,2-bis (4'-hydroxyphenyl) propane].

The unsaturated cyclic hydrocarbon compound may be a dicyclopentadiene compound such as dicyclopentadiene, 4-vinylcyclohexene, 5-vinylnonona-2-ene, 3a, 4,7,7a-tetrahydroindene, And it is also possible to use them in a mixture. It is preferable to use dicyclopentadiene in view of the excellent heat resistance, moisture resistance and mechanical properties of the resulting resin.

Although commercial dicyclopentadiene for industrial use contains certain impurities, dicyclopentadiene having a purity of 80 wt% or more, preferably 90 wt% or more can be used without any problem.

In the reaction between the unsaturated cyclic hydrocarbon compound and the aromatic group-containing aromatic compound, the molecular weight and the melt viscosity of the phenol resin obtained by varying the molar ratio of the two components can be appropriately controlled. However, the hydroxyl group-containing aromatic compound and the unsaturated cyclic hydrocarbon compound are usually used in a molar ratio of 1: 0.1 to 1: 1.

If the unsaturated cyclic hydrocarbon compound is used in an amount of less than 0.1 mol based on 1 mol of the hydroxyl group-containing aromatic compound, a large amount of unreacted hydroxyl group-containing aromatic compound remains, which is not effective in controlling the molecular weight distribution and the yield is low If the amount of the unsaturated cyclic hydrocarbon compound exceeds 1 mol, the double bond that can react with the unsaturated cyclic hydrocarbon compound may remain, so that the produced phenolic resin may be insufficient in hygroscopicity.

The catalyst used in the reaction between the unsaturated cyclic hydrocarbon compound and the hydroxyl group-containing aromatic compound may be selected from inorganic acids such as sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid and the like; Organic acids such as para-toluenesulfonic acid, benzenesulfonic acid and the like; And at least one member selected from the group consisting of Lewis acids such as tin tetrachloride, boron trifluoride, boron trichloride, zinc chloride, trichloride, trimethylsilyl trifluoromethanesulfonate, phosphoryl chloride, aluminum chloride and the like And Lewis acids can be used in view of their ease of activity and catalyst removal.

The catalyst may be used in an amount of 0.05 to 1 part by weight based on 100 parts by weight of the hydroxyl group-containing aromatic compound. When the amount of the catalyst is less than 0.05 part by weight, If it exceeds the weight part, the heat generation during the reaction is severe, so that the runaway reaction may occur and safety problems may occur.

Further, in the present invention, it is preferable to use the reaction substrate itself as a solvent as the reaction mode, 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 thereof include 1-methoxy-2-propanol, 2-methoxyethanol, Xylene, toluene and the like can be used, and the content thereof can be 20 to 60 parts by weight based on 100 parts by weight of the aromatic group-containing aromatic compound.

The reaction can be carried out either batchwise or continuously. In the batch method, the order and the method for adding the reaction substrate are not particularly limited, but a method of slowly adding at least an unsaturated cyclic hydrocarbon into the reaction system can be employed as mentioned later. A method in which an unsaturated cyclic hydrocarbon is slowly added to a reactor in which a hydroxyl group-containing aromatic hydrocarbon and, if necessary, a solvent are preliminarily charged, may be employed. The catalyst may be added slowly as in the case of the unsaturated cyclic hydrocarbon, or the whole amount may be added in advance.

In the present invention, the reaction of the unsaturated cyclic hydrocarbon compound and the aromatic group-containing aromatic compound can be carried out at 60 to 150 ° C for 1 to 10 hours. If the reaction temperature is higher than 150 ° C, volatilization of the unsaturated cyclic hydrocarbon compound may change the reaction molar ratio and the desired physical properties can not be realized. When the reaction is conducted at a temperature lower than 60 ° C, the reaction rate is slow, .

As described above, the phenol resin produced by reacting the unsaturated cyclic hydrocarbon compound and the hydroxyl group-containing aromatic compound has a weight average molecular weight of about 500 to 1,500 g / mol. Since the phenol resin having a weight average molecular weight in the above range contains an aromatic compound having an unreacted hydroxyl group and is superior in physical properties such as solvent solubility and impregnation property but contains an unreacted hydroxyl group-containing aromatic compound There is a limit to the dielectric properties.

Therefore, in the present invention, phenol resin having low dielectric properties (dielectric constant and dielectric loss) can be produced by extracting only phenol resin having a weight average molecular weight of 600 to 2,500 g / mol among the phenol resins obtained by the above-described method.

The method of extracting the phenol resin having the specific molecular weight can be carried out by using a high vacuum distillation apparatus capable of easily separating and extracting only water having a specific molecular weight.

The phenol resin obtained as described above is melted by heating to a temperature above the softening point so as to be easily injected into a high vacuum distillation apparatus, and is then introduced into a high vacuum distillation apparatus. The softening point above or below was measured using a FP90 instrument from METTLER TOLEDO at a heating rate of 2 DEG C / min.

In the high-vacuum distillation apparatus, the temperature and the pressure of the main body of the high vacuum distillation apparatus can be appropriately set so that only a number of phenols having a specific weight average molecular weight can be taken out. At this time, the temperature and the pressure of the high vacuum distillation apparatus are 200 to 280 DEG C and 0.001 to 0.5 mbar, respectively. When the temperature of the high vacuum distillation apparatus is lower than 200 DEG C, only the phenol number of the proper molecular weight can not be efficiently extracted, The phenol resin may be thermally deformed or deteriorated due to the high temperature. When the pressure of the high-vacuum distillation apparatus is less than 0.001 mbar, the phenol resin in the high-molecular region is also separated to separate only the phenol resin having an appropriate molecular weight. If the pressure exceeds 0.5 mbar, the manufacturing cost is excessively high, Only the number of phenols having a molecular weight can not be efficiently extracted and the separation efficiency is lowered.

The process for producing a phenol resin having low dielectric properties according to the present invention can easily and easily produce a phenol resin which can realize a low dielectric property in a balanced manner while satisfying water resistance and heat resistance by controlling the molecular weight of the phenol resin.

In another aspect, the present invention relates to a phenol resin having a low dielectric property, which is produced by the above production method and has a dielectric constant of 3.5 or less at 1 GHz and a dielectric loss of 0.03 or less at 1 GHz.

The phenol resin having a low dielectric property of the present invention effectively removes an aromatic compound containing an unreacted hydroxyl group to have a lower dielectric property, a good moisture resistance, a softening point of 90 to 140 캜, Is useful as a raw material for epoxy resin production, and is useful as an electrical insulating material, particularly as a curing agent for epoxy resin for semiconductor encapsulant or laminate. If the dielectric constant exceeds 3.5 or the dielectric loss exceeds 0.03, the application is limited due to the high dielectric property, and when the softening point is out of the range of 90 to 140 캜, the solvent solubility may be poor.

The phenol resin having low dielectric properties obtained by the above production method is superior in solvent solubility compared with the phenolic resin having the same structure prepared by the conventional method and has characteristics such as lower low dielectric constant, high heat resistance and low hygroscopicity Balanced implementation.

According to another aspect of the present invention, there is provided a process for producing a phenolic resin, comprising the steps of: (a) reacting a hydroxyl group-containing aromatic compound with an unsaturated cyclic hydrocarbon compound in the presence of a catalyst to produce a phenolic resin; (b) extracting a phenol resin having a weight average molecular weight of 600 to 2,500 g / mol among the produced phenol resin; And (c) reacting the extracted phenol resin with epihalohydrin in the presence of a base catalyst. The present invention also relates to a process for producing an epoxy resin having low dielectric properties.

More specifically, a method for producing an epoxy resin having low dielectric properties according to an embodiment of the present invention includes reacting a phenol resin having low dielectric properties prepared by the above-described method in the presence of an epihalohydrin and a base catalyst, Can be prepared by hydrating.

First, a method for producing an epoxy resin having low dielectric properties according to an embodiment of the present invention will be described. A phenol resin having low dielectric properties, that is, a phenol resin taken out to a specific molecular weight, An epoxy resin having low dielectric properties can be produced by reacting with a halohydrin.

In the present invention, the production of the epoxy resin is not particularly limited as long as it can be produced by reacting a phenolic resin with an epihalohydrin. Preferably, the epoxy resin is produced by reacting a phenol resin with epihalohydrin, Condensation reaction of a phenol resin and an epihalohydrin monomer. At this time, the heavy / condensation reaction can be carried out at 40 to 100 ° C for 2 to 6 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 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 30 to 60% Is suitable for minimizing the production of by-products of the resin and for the reaction rate. On the other hand, the content of phenol resin, epihalohydrin and basic catalyst having low dielectric properties can be used in a weight ratio of 1: 1 to 6: 0.1 to 1.0.

According to another aspect of the present invention, there is provided a method for producing an epoxy resin composition, which is produced by the above process and has an epoxy equivalent of 150 to 500 g / eq, a dielectric constant at 1 GHz of 3.5 or less, Or less and a softening point of 60 to 120 ° C.

In addition, the epoxy resin having low dielectric properties of the present invention can have lower dielectric properties by effectively removing unreacted hydroxyl group-containing aromatic compounds, and thus can be used as an electrical insulating material, particularly an epoxy resin composition raw material for semiconductor encapsulant or laminate .

According to another aspect of the present invention, there is provided an epoxy resin composition comprising the epoxy resin having the low dielectric property 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 having low dielectric properties 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 hygroscopicity, heat resistance and dielectric properties. If an epoxy resin having a low dielectric property 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, heat resistance may be deteriorated.

The epoxy resin composition having the low dielectric property has low dielectric properties (low dielectric constant and low dielectric loss) while satisfying the water resistance, heat resistance, and the like, and is useful as a sealing material used for a printed circuit board, It is possible to provide a cured product capable of realizing balanced low dielectric properties suitable for ashes, adhesives, electric insulation paint materials, and the like.

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.

[ Comparative Example  One]

1000 g (4.39 mol) of bisphenol-A and 500 g of xylene were charged into the reactor and the temperature was raised to 75 캜. When a catalyst to reach _{75 ℃ BF 3 -Phenol (26%} ) solution was added to 7.18g stirred for 30 minutes, and the mixture warmed to 80 ℃, dicyclopentadiene a diene (dicyclopentadiene) 72.5g (0.55mol) 1 Over a period of time. After completion of the addition, the temperature was raised to 140 ° C and the reaction was carried out for 3 hours. After completion of the reaction, 14.73 g of KW-1000 (manufactured by Japan Kagaku Kogyo Co., Ltd.) was added, and while stirring for 1 hour, BF ₃ The catalyst was neutralized. After neutralization, KW-1000 used for neutralization was removed using a 100 micrometer bag filter. Subsequently, degassing was carried out at 175 ° C under a degree of vacuum of 40 torr, maintained at 175 ° C for 1 hour, and then solid phase was removed to obtain 742.5 g of a phenol resin. The yield was 69.2%. The softening point of the phenol resin was found to be 76.0 ° C. The gel permeation chromatography (GPC) showed a weight average molecular weight of 589 g / mol and a liquid chromatography (LC) analysis The content of unreacted bisphenol-A was found to be 38.09% by weight.

[ Comparative Example  2]

1000 g (4.39 mol) of bisphenol-A and 500 g of xylene were charged into the reactor and the temperature was raised to 75 캜. When the temperature reached 75 ° C., 14.36 g of a BF ₃ -phenol (26%) solution was added and stirred for 30 minutes. Then, the temperature was raised to 80 ° C. and 145.0 g (1.10 mol) of dicyclopentadiene was dropped Respectively. After completion of the addition, the temperature was raised to 140 ° C and the reaction was carried out for 3 hours. After completion of the reaction, 29.46 g of KW-1000 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was added, and the BF ₃ catalyst was neutralized while stirring for 1 hour. After neutralization, KW-1000 used for neutralization was removed using a 100 micrometer bag filter. The mixture was degassed at 175 ° C under a degree of vacuum of 40 torr, maintained at 175 ° C for 1 hour, and then taken out of the solid phase to obtain 784.2 g of a phenol resin. The yield was 68.5%. The softening point of the phenol resin was found to be 85.7 ° C. The gel permeation chromatography (GPC) measurement showed a weight average molecular weight of 719 g / mol and was analyzed by liquid chromatography (LC) The content of the reaction bisphenol-A was found to be 24.20% by weight.

[ Comparative Example  3]

500 g of the phenol resin obtained in Comparative Example 2 and 1500 g of epichlorohydrin were put into a 5 L four-necked flask and thoroughly mixed. Then 360 g of NaOH was added dropwise uniformly at 60 DEG C over 2 hours and the unreacted epichlorohydrin was vacuum- Degassed and completely removed. The mixture was diluted by adding methyl isobutyl ketone (MIBK) to the mixture in which unreacted epichlorohydrin was completely removed. The unreacted hydrolysable chlorine was subjected to a purification reaction by uniformly dropping NaOH, and then washed twice with 200 g of water. After the completion of the reaction, an epoxy resin having a weight average molecular weight of 958 g / mol and a softening point of 63.7 DEG C was produced through a MIBK degassing process.

[ Example  One]

The phenol resin prepared in Comparative Example 1 was heated to 76 DEG C to melt and then flowed at a constant rate into a high vacuum distillation apparatus having a wall temperature of 250 DEG C and a pressure of 0.2 mbar at a high vacuum distillation apparatus, Only the unreacted low molecular weight bisphenol-A was taken out, and the phenol resin of the polymer was taken out as another take-out line. As a result of gel permeation chromatography (GPC) measurement, the weight average molecular weight was 1,214 g / mol, and it was confirmed by liquid chromatography (LC) analysis that the softening point of the polymer phenol resin was 96.1 ° C. The content of unreacted bisphenol-A was found to be 4.01% by weight.

[ Example  2]

The phenol resin obtained in Comparative Example 2 was heated to 85.7 ° C to be molten and then flowed at a constant rate into a high vacuum distillation apparatus in which the wall temperature of the high vacuum distillation apparatus was 250 ° C and the pressure was set at 0.2 mbar. Only the unreacted low molecular weight bisphenol-A was taken out, and the phenol resin of the polymer was taken out to other take-out lines. As a result of gel permeation chromatography (GPC), the weight average molecular weight was 1492 g / mol, and the liquid phenol resin (LC) From the analysis, it was found that the content of unreacted bisphenol-A was 2.25% by weight.

[ Example  3]

500 g of the phenol resin synthesized in Example 2 and 1500 g of epichlorohydrin were put into a 5 L four-necked flask and thoroughly mixed. Then 360 g of NaOH was added dropwise uniformly at 60 DEG C for 2 hours, and unreacted epichlorohydrin was distilled off under vacuum Degassed and completely removed. The mixture was diluted by adding methyl isobutyl ketone (MIBK) to the mixture in which unreacted epichlorohydrin was completely removed. The unreacted hydrolysable chlorine was subjected to a purification reaction by uniformly dropping NaOH, and then washed twice with 200 g of water. After completion of the reaction, an epoxy resin having a weight average molecular weight of 1,680 g / mol and a softening point of 84.2 ° C was produced through a MIBK deaeration process.

≪ Property evaluation method &

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

The resins obtained in Comparative Examples 1 to 3 and Examples 1 to 3 were dissolved in Tetra Hydro Furan (THF) at a concentration of 4000 ppm and gel permeation chromatography (GPC (0 to 100,000 g / mol) was used And the weight average molecular weight was measured.

(2) Measurement of unreacted hydroxyl group-containing aromatic compound content

The resin obtained in Comparative Examples 1 to 3 and Examples 1 to 3 was measured for unreacted Bisphenol-A content by liquid chromatography (Agilent 1200 series) .

(3) varnish manufacturing

The varnishes were prepared from the resins prepared in Comparative Examples 1 to 3 and Examples 1 to 3 (indicated as "samples" in Table 1 below) in the formulations shown in Table 1 below. The phenol novolac hardener was a phenol novolak (PN) resin (KPH-F2004, manufactured by Kolon Industries) having a hydroxyl equivalent of 106, Mn = 1200 (n = 11 to 12) and a softening point of 120 ° C, 2-Ethyl-4-methyl imidazole (2E4MZ) was used as the curing accelerator, and the phenol novolac epoxy resin was used in an equivalent weight of 184 g / mol (KEP-1138, manufactured by Kolon Industries, 0.14 phr of the solid epoxy was used.

(4) Production of copper clad laminate

The varnish prepared in (3) was impregnated with glass fiber, air dried at room temperature for 1 hour, and then dried in an oven at 155 ° C for 5 minutes to prepare a prepreg. The prepared prepregs were prepared by pressing the prepregs with a copper foil (1 once) at the front and back and at a pressure of 40 kgf / cm ² at 195 캜 for 120 minutes.

(5) Measurement of dielectric constant and dielectric loss

The dielectric constant and dielectric loss of the copper-clad laminate under 1 GHz were measured using RF Impedance (Agilent E4991A).

(6) DSC (Differential Scanning Calorimeters) measurement

Was measured at a heating rate of 20 占 폚 / min from 30 占 폚 to 250 占 폚 using a TA Instruments DSC Q2000.

(7) Measurement of water absorption rate

The weight increase ratio of the copper-clad laminate after removal of the copper foil at 100 占 폚 and 2 atm vapor pressure using PCT (Pressure Cooker Test) before and after moisture absorption was measured by the following formula 1.

[Formula 1]

Item Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 Varnish manufacturing sample 125 125 100 125 125 100 Phenol novolac hardener (g) - - 80 - - 80 Phenol novolak epoxy (g) 100 100 - 100 100 - 2E4MZ (g) 0.14 0.14 0.14 0.14 0.14 Methyl ethyl ketone (g) 67.5 67.5 54 67.5 67.5 54 Varnish solids content (wt%) 70 70 70 70 70 70 permittivity 3.04 3.01 3.09 2.87 2.83 2.88 Dielectric loss 0.025 0.024 0.028 0.021 0.019 0.022 Glass transition temperature (캜) 131.56 135.36 135.01 153.27 156.73 155.56 Hygroscopicity (%) 0.24 0.20 0.25 0.15 0.12 0.18

As shown in Table 1, Examples 1 to 3 were found to have not only dielectric properties but also excellent glass transition temperature and hygroscopicity as compared with Comparative Examples 1 to 3.

Accordingly, the phenolic resin and the epoxy resin according to the present invention satisfy the water resistance and heat resistance 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 part , It was confirmed that the low dielectric characteristics can be realized in a balanced manner.

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 (26)

(a) reacting a hydroxyl group-containing aromatic compound with an unsaturated cyclic hydrocarbon compound in the presence of a catalyst to produce a phenolic resin; And
(b) extracting a phenol resin having a weight average molecular weight of 600 to 2,500 g / mol among the produced phenol resin.
The process for producing a phenolic resin according to claim 1, wherein the aromatic group-containing aromatic compound is at least one selected from the group consisting of monovalent phenols, bivalent phenols, and trivalent phenols.
The method according to claim 1, wherein the unsaturated cyclic hydrocarbon compound is selected from the group consisting of dicyclopentadiene, 4-vinylcyclohexene, 5-vinylnonona-2-ene, 3a, 4,7,7a-tetrahydroindene, And limonene, wherein the phenol resin is at least one selected from the group consisting of ethylene, propylene, butylene, and limonene.
The method for producing a phenolic resin according to claim 1, wherein the unsaturated cyclic hydrocarbon compound is dicyclopentadiene.
The process for producing a phenol resin according to claim 1, wherein the content of the hydroxyl group-containing aromatic compound and the unsaturated cyclic hydrocarbon compound is 1: 0.1 to 1: 1.
The method for producing a phenolic resin according to claim 1, wherein the catalyst is at least one selected from the group consisting of inorganic acids, organic acids and Lewis acids.
The method for producing a phenolic resin according to claim 1, wherein the catalyst is used in an amount of 0.05 to 1 part by weight based on 100 parts by weight of the hydroxyl group-containing aromatic compound.
The method of claim 1, wherein the reaction of step (a) is performed at 60 to 150 ° C for 1 to 10 hours.
The method for producing a phenol resin according to claim 1, wherein the step (b) is carried out using a high vacuum distillation apparatus.
The high vacuum distillation apparatus according to claim 9, wherein the high-vacuum distillation apparatus is set at 200 to 280 DEG C under a pressure of 0.001 to 0.5 mbar to take out a phenol resin having a weight average molecular weight of 600 to 2,500 g / mol. A method for producing a phenolic resin.
11. A phenol resin having low dielectric constant, which is produced by the production method of any one of claims 1 to 10, characterized in that the dielectric constant at 1 GHz is 3.5 or less and the dielectric loss at 1 GHz is 0.03 or less.
12. The phenol resin according to claim 11, wherein the phenol resin has a softening point of 90 to 140 占 폚.
(a) reacting a hydroxyl group-containing aromatic compound with an unsaturated cyclic hydrocarbon compound in the presence of a catalyst to produce a phenolic resin;
(b) extracting a phenol resin having a weight average molecular weight of 600 to 2,500 g / mol among the produced phenol resin; And
(c) reacting said phenol resin taken out with epihalohydrin in the presence of a base catalyst to prepare an epoxy resin having low dielectric properties.
14. The method for producing an epoxy resin according to claim 13, wherein the aromatic group-containing aromatic compound is at least one selected from the group consisting of monovalent phenols, divalent phenols, and trivalent phenols.
14. The method according to claim 13, wherein the unsaturated cyclic hydrocarbon compound is selected from the group consisting of dicyclopentadiene, 4-vinylcyclohexene, 5-vinylnonona-2-ene, 3a, 4,7,7a-tetrahydroindene, And limonene. The method for producing an epoxy resin according to claim 1,
14. The method for producing an epoxy resin according to claim 13, wherein the unsaturated cyclic hydrocarbon compound is dicyclopentadiene.
14. The method of claim 13, wherein the content of the hydroxyl group-containing aromatic compound and the unsaturated cyclic hydrocarbon compound is 1: 0.1 to 1: 1.
14. The method for producing an epoxy resin according to claim 13, wherein the catalyst is at least one selected from the group consisting of inorganic acid, organic acid and Lewis acid.
14. The method according to claim 13, wherein the catalyst is used in an amount of 0.05 to 1 part by weight based on 100 parts by weight of the hydroxyl group-containing aromatic compound.
14. The method of claim 13, wherein the reaction of step (a) is performed at 60 to 150 DEG C for 1 to 10 hours.
14. The method according to claim 13, wherein the step (b) is carried out using a high vacuum distillation apparatus.
The high vacuum distillation apparatus according to claim 21, wherein the high vacuum distillation apparatus is set at 200 to 280 DEG C under a pressure of 0.001 to 0.5 mbar to take out a phenol resin having a weight average molecular weight of 600 to 2,500 g / mol. A method for producing an epoxy resin.
The epoxy resin composition according to any one of claims 13 to 22, which has an epoxy equivalent of 150 to 500 g / eq, a dielectric constant at 1 GHz of 3.5 or less, and a dielectric loss at 1 GHz of 0.03 or less Epoxy resin having dielectric properties.
The epoxy resin according to claim 23, wherein the epoxy resin has a softening point of 60 to 120 캜.
An epoxy resin composition comprising an epoxy resin having low dielectric properties according to claim 23 or 24 in an amount of 5 to 95% by weight based on the total weight of the composition.
26. A cured product of the epoxy resin composition of claim 25.