KR100771331B1 - Epoxy resin composition and printed circuit board using the same - Google Patents

Abstract

An epoxy resin composition for a printed circuit board is provided to satisfy an adequate level of modulus and elongation required as a build-up insulation material, and to impart physical and mechanical properties suitable for carrying out imprint lithography to a printed circuit board. An epoxy resin composition comprises: (a) a composite epoxy resin including a bisphenol A epoxy resin, a phenol novolac epoxy resin, a cresol novolac epoxy resin, a rubber-modified epoxy resin, a phosphorus-containing epoxy resin and a naphthalene-based epoxy resin; (b) 0.5-2 eq. of a curing agent containing both of a phenol novolac type curing agent and a xylol type curing agent per equivalent of the composite epoxy resin, wherein the equivalent ratio of the phenol novolac type curing agent to the xylol type curing agent is 1:0.5-2; (c) 0.1-1 parts by weight of a curing accelerator per 100 parts by weight of the composite epoxy resin; and (d) 10-50 parts by weight of inorganic fillers per 100 parts by weight of the composite epoxy resin combined with the curing agent.

Description

Epoxy resin composition and printed circuit board using the same}

The present invention relates to an epoxy resin composition and a printed circuit board using the same. More specifically, the present invention uses a phenol novolak-type curing agent and a xylox-type curing agent together as a curing agent, and at the same time adjusts the composition and composition ratio of the resin to achieve the appropriate level of modulus and elongation (as the build-up insulation material). The present invention relates to an epoxy resin composition capable of satisfying both elongation and a printed circuit board using the same.

FCBGA, which acts as a medium between semiconductors and main boards, is increasingly required for thin substrates and high density circuits. Accordingly, build-up insulating materials require corresponding mechanical and thermal properties, and there is a need to optimize the composition of the insulating materials.

Build-up insulation materials generally consist of various types of epoxy resins, various additives, solvents, inorganic fillers, and curing agents that will cause a curing reaction. The mechanical and thermal properties of the insulating material vary depending on the amount of each composition. In particular, an insulating material having a certain modulus while maintaining an appropriate elongation among mechanical properties is ideal.

Epoxy resins are one of the most important thermosetting resins. Advanced composites are characterized by high stiffness, high strength, good chemical resistance and dimensional stability. It is widely used in coatings, structural adhesives, microelectronics, and the like. However, epoxy resins have a critical weakness of lack of toughness, which limits their use in more applications.

The build-up insulation material used for FCBGA is also composed of epoxy-based thermosetting polymer, and the composition should be optimized to show the appropriate modulus and elongation value.

In this regard, there are a number of factors that affect the mechanical properties of the insulating material. There are a method of adding a large number of epoxy resins having excellent mechanical properties, a method of properly adjusting the amount of the inorganic filler, and a method of selectively using an appropriate curing agent.

As a prior art in which such methods are introduced, for example, Korean Patent Laid-Open Publication No. 2004-70877 discloses an epoxy resin composition containing a bisphenol A-type epoxy resin and a circuit board using the same, and Korean Patent Laid-Open Publication No. 2004-36219 Epoxy / thermoplastic resin blend compositions are disclosed.

However, in the case of a substrate obtained from such a resin composition, the modulus and percent elongation (%) of the mechanical properties are in a trade off relationship in which the other decreases as one increases, and by controlling any one factor, Increasing the physical properties will cause another property to decrease.

In particular, in order to use as a build-up insulating material for a substrate, only one physical property should not be high, and all the required physical properties must be satisfied within an appropriate level range so that there is no restriction in use. There is an urgent need to develop a resin composition for insulating materials that can impart suitable mechanical properties to the resin.

Accordingly, in the present invention, as a result of extensive research to solve the above problems, in the epoxy resin composition containing the epoxy resin, the curing agent, the curing accelerator and the inorganic filler as the main components, each component is adjusted to a specific composition and composition ratio, Phenol novolac-type hardener with excellent modulus and thermal stability but relatively low elongation (%) to obtain the mechanical properties, and Tg or modulus slightly decreased but elongation (%) to compensate By simultaneously using a xylock type curing agent having a co-curing system (co-curing system) by introducing a hardening resin composition having a mechanical property suitable for use as a build-up insulating material, the present invention was based on It is finished.

Accordingly, it is an object of the present invention to provide an epoxy resin composition and a printed circuit board using the same that can satisfy both modulus and elongation of an appropriate level required as a build-up insulating material.

Another object of the present invention is to provide an epoxy resin composition capable of providing an insulating material for a substrate having both physical and mechanical properties suitable for performing an imprint lithography process, and a printed circuit board using the same.

The epoxy resin composition according to the present invention for achieving the above and other objects are:

(a) a composite epoxy resin comprising a bisphenol A epoxy resin, a phenol novolac epoxy resin, a cresol novolac epoxy resin, a rubber modified epoxy resin, a phosphorus epoxy resin and a naphthalene epoxy resin;

(b) a curing agent comprising 0.5 to 2 equivalents of a phenol novolak type curing agent and a xylock type curing agent based on 1 equivalent of the composite epoxy resin;

(c) 0.1 to 1 part by weight of a curing accelerator based on 100 parts by weight of the composite epoxy resin; And

(d) 10 to 50 parts by weight of an inorganic filler based on 100 parts by weight of the total amount of the composite epoxy resin and the curing agent;

Characterized in that it comprises a.

Here, the composite epoxy resin is preferably 1 to 40 parts by weight of bisphenol A epoxy resin, 1 to 30 parts by weight of phenol novolac epoxy resin, 1 to 40 parts by weight of cresol novolac epoxy resin, based on 100 parts by weight of composite epoxy resin. 1 to 20 parts by weight of a rubber-modified epoxy resin, 1 to 50 parts by weight of a phosphorous epoxy resin and 1 to 40 parts by weight of a naphthalene epoxy resin.

Moreover, the said (bis) bisphenol-A epoxy resin, (ii) phenol novolak epoxy resin, (iv) cresol novolak epoxy resin, (iv) rubber modified epoxy resin, (iv) phosphorus epoxy resin, and (iv) naphthalene The average epoxy resin equivalents of the epoxy resins are (i) 100 to 1000, (ii) 100 to 500, (iii) 100 to 600, (iii) 100 to 500, (iii) 400 to 800 and (iii) 100 to 500, respectively. It is preferable that it is 600.

On the other hand, the equivalent ratio of the said phenol novolak-type hardening | curing agent and a xyloic hardening | curing agent becomes like this. Preferably it is 1: 0.5-2. It is preferable that the said phenol novolak-type hardening | curing agent and the xyloic-type hardening | curing agent have 100-130 equivalent (g / eq) and the softening point of 45-150 degreeC, respectively. The curing agent may also further comprise a bisphenol A based (BPA) novolac curing agent.

The curing accelerator is an imidazole compound, more preferably 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 1- (2-cyanoethyl) -2-alkyl imidazole, 2-phenyl Imidazole, 2-phenyl-4-phenyl imidazole and mixtures thereof.

The inorganic filler may preferably be selected from the group consisting of graphite, carbon black, silica, clay and mixtures thereof, and may be surface treated with a silane coupling agent. The inorganic fillers also preferably have an average particle diameter of 0.5-5 μm, where the inorganic fillers may be mixtures of spherical fillers of different sizes.

The printed circuit board according to the present invention is characterized in that it is manufactured using the epoxy resin composition of the present invention described above.

Hereinafter, the present invention will be described in more detail.

The epoxy resin composition of this invention contains an epoxy resin, a hardening | curing agent, a hardening accelerator, and an inorganic filler.

The epoxy resin used in the present invention is a bisphenol A type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a rubber It is a composite epoxy resin containing a modified epoxy resin and a phosphorus epoxy resin.

The bisphenol A type epoxy resin imparts excellent peel strength, and the novolak epoxy resin serves to provide excellent thermal stability. In addition, the rubber-modified epoxy resin serves to give flexibility, and phosphorus-based epoxy resin is used to impart flame retardancy to an insulating material. The naphthalene-based epoxy resin serves to impart low thermal expansion coefficient (CTE) and high Tg.

Preferably, the composite epoxy resin is a bisphenol A epoxy resin having an average epoxy resin equivalent of 100 to 1000, a phenol novolac epoxy resin having an average epoxy resin equivalent of 100 to 500, and a cresol furnace having an average epoxy resin equivalent of 100 to 600 It is insulated that a volac epoxy resin, a rubber modified epoxy resin having an average epoxy resin equivalent of 100 to 500, a phosphorous epoxy resin having an average epoxy resin equivalent of 400 to 800, and a naphthalene epoxy resin having an average epoxy resin equivalent of 100 to 600 is insulated. It is more suitable for use as a material.

The composite epoxy resin is also 1 to 40 parts by weight of bisphenol A epoxy resin, 1 to 30 parts by weight of phenol novolac epoxy resin, 1 to 40 parts by weight of cresol novolac epoxy resin, rubber modified based on 100 parts by weight of composite epoxy resin. It is preferable that it is comprised by the composition of 1-20 weight part of epoxy resins, 1-50 weight part of phosphorus epoxy resins, and 1-40 weight part of naphthalene type epoxy resins.

Each of the epoxy resins described above may be used by dissolving in an appropriate ratio of solvent as needed and blending them in solution.

The curing agent used in the present invention is a mixture of a phenol novolak type curing agent and a xylock type curing agent. The curing agent should theoretically be used in an equivalent of 1: 1 with the composite epoxy resin, but is typically used in an amount of 0.5 to 2 equivalents relative to 1 equivalent of the composite epoxy resin.

In general, in order to use as a substrate insulating material, mechanical, thermal, and electrical characteristics must be satisfied at the same time. In addition, among the mechanical properties, modulus, elongation and tensile strength must be satisfied at the same time to have an appropriate value.

In the process of pursuing high Tg, low CTE, and high modulus value, the material itself may be stiff and the elongation (%) value may drop. In order to improve the elongation rate by giving flexibility to the curing agent rather than), the xylox type curing agent is mixed with the phenol novolac type curing agent.

In general, the mechanical properties of the epoxy resin are also affected by the type of curing agent. Among them, when only xylox type curing agent is used, Tg or modulus is slightly decreased, but elongation (%) is increased. Accordingly, in the present invention, a phenol novolak type curing agent having excellent modulus or thermal stability but relatively low elongation in order to obtain an appropriate level of mechanical properties is used in combination with a xylock type curing agent having the above-described characteristics. The present invention provides a resin composition exhibiting mechanical properties suitable for use as an insulating material for build-up printed circuit boards by introducing a curing agent of a co-curing system. That is, the modulus value or Tg value may be slightly lowered due to the addition of the xylock type curing agent. However, when the phenol novolac type curing agent is mixed in an appropriate amount, the physical properties required as the buildup material may be satisfied as compared to the case where the mixing agent is not mixed. Will be.

In the case of the insulating material using the resin composition whose physical properties are controlled through the mixed use of a specific curing agent, in particular, during the imprint process, the insulating material itself affects flowability and flexibility, thereby reducing defects between molds. It also helps to apply uniform pressure throughout the area imprint.

In the case of the curing agent, the molecular weight is defined using the equivalent weight (g / eq) divided by the number of functional groups, rather than the molecular weight. As the phenol novolac type curing agent and xylloc type curing agent used in the present invention, Preferably, those having an equivalent weight (g / eq) of about 100 to 130 and a softening point of 45 to 150 ° C are better for expressing the desired properties such as high Tg and high toughness properties.

Here, it is preferable that the equivalence ratios of the said phenol novolak-type hardening | curing agent and a xyloic hardening | curing agent are 1: 0.5-2.

In addition, bisphenol A-based (BPA-based) novolak curing agents may be further added as necessary to improve the curing performance and the adhesive strength.

As a hardening accelerator used by this invention, Preferably an imidazole compound is mentioned. Examples of the imidazole compound include 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 1- (2-cyanoethyl) -2-alkyl imidazole, 2-phenyl imidazole and 2 Any one of -phenyl-4-phenyl imidazole can be used or two or more can be used in combination. In this case, the amount of the curing accelerator is preferably 0.1 to 1 parts by weight based on 100 parts by weight of the composite epoxy resin.

The inorganic filler used in the present invention is not particularly limited, but any one of graphite, carbon black, silica and clay may be used or two or more may be used in combination. Preferably the inorganic filler is more preferably surface treated with a silane coupling agent. It is more preferable that the average particle diameter of the said inorganic filler is 0.5-5 micrometers in adhesiveness, dispersibility, and flow property with resin. In addition, it is better to use a mixture of spherical fillers of different sizes to increase the filler filling rate.

At this time, the amount of the inorganic filler is preferably 10 to 50 parts by weight based on 100 parts by weight of the total amount of the composite epoxy resin and the curing agent in order to express the appropriate mechanical properties and flow properties.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto.

<Example 1>

9 g of bisphenol A epoxy resin, 10 g of phenol novolac epoxy resin, 20 g of cresol novolac epoxy resin, 4 g of rubber modified epoxy resin, 30 g of phosphorus flame retardant epoxy resin and 27 g of naphthalene epoxy resin at 45 ° C. Dissolved in. After stirring at 300 rpm for 1 hour while maintaining the temperature, 88.05 g of spherical silica having a particle size distribution of 0.6 to 1.2 µm was added, followed by stirring at 400 rpm for 3 hours. Thereafter, 13.10 g of a phenol novolak type curing agent and 30.56 g of a xyloic type curing agent were added, followed by further stirring for 1 hour. After the temperature was lowered to room temperature, 0.5 g of 2-methyl imidazole was added thereto, followed by stirring for 30 minutes to prepare a resin composition for insulating materials. The resin composition thus prepared was film cast on a PET film and then completely cured by heat treatment at 90 ° C. for 30 minutes and at 120 ° C. for 120 minutes, and then a dog bone was prepared to measure elongation and CTE. Tg (DSC) used a commonly used method, and adopted the value at the second scanning. The measurement results are summarized in Table 1 below.

<Example 2>

9 g of bisphenol A epoxy resin, 10 g of phenol novolac epoxy resin, 20 g of cresol novolac epoxy resin, 4 g of rubber modified epoxy resin, 30 g of phosphorus flame retardant epoxy resin and 27 g of naphthalene epoxy resin at 45 ° C. Dissolved in. After stirring at 300 rpm for 1 hour while maintaining the temperature, 88.05 g of spherical silica having a particle size distribution of 0.6 to 1.2 µm was added, followed by stirring at 400 rpm for 3 hours. Thereafter, 21.83 g of a phenol novolak type curing agent and 22.04 g of a xyloic type curing agent were added, followed by further stirring for 1 hour. After the temperature was lowered to room temperature, 0.5 g of 2-methyl imidazole was added, followed by stirring for 30 minutes to prepare a resin composition. The resin composition thus prepared was film cast on a PET film and then completely cured by heat treatment at 90 ° C. for 30 minutes and at 180 ° C. for 120 minutes, and then a dog bone was prepared to measure elongation and CTE. Tg (DSC) used a commonly used method, and adopted the value at the second scanning. The measurement results are summarized in Table 1 below.

<Example 3>

9 g of bisphenol A epoxy resin, 10 g of phenol novolac epoxy resin, 20 g of cresol novolac epoxy resin, 4 g of rubber modified epoxy resin, 30 g of phosphorus flame retardant epoxy resin, and 27 g of naphthalene epoxy resin at 45 ° C. Dissolved in. After stirring at 300rpm for 1 hour while maintaining the temperature, 88.05g of spherical silica having a particle size distribution of 0.6 to 1.2㎛ was added, followed by stirring at 400rpm for 3 hours. Thereafter, 30.56 g of a phenol novolac type curing agent and 13.10 g of a xyloic type curing agent were added, followed by further stirring for 1 hour. After the temperature was lowered to room temperature, 0.5 g of 2-methyl imidazole was added, followed by stirring for 30 minutes to prepare a resin composition. The resin composition thus prepared was film cast on a PET film, heat treated at 90 ° C. for 30 minutes, and then heated at 180 ° C. for 120 minutes to completely cure the dog bone, thereby measuring elongation and CTE. Tg (DSC) used a commonly used method, and adopted the value at the second scanning. The measurement results are summarized in Table 1 below.

Comparative Example 1

9 g of bisphenol A epoxy resin, 10 g of phenol novolac epoxy resin, 20 g of cresol novolac epoxy resin, 4 g of rubber modified epoxy resin, 30 g of phosphorus flame retardant epoxy resin and 27 g of naphthalene epoxy resin at 45 ° C. Dissolved in. After stirring at 300 rpm for 1 hour while maintaining the temperature, spherical silica having a particle size distribution of 0.6 to 1.2 µm was added by 88.05 g, followed by stirring at 400 rpm for 3 hours. Thereafter, 43.66 g of a phenol novolak-type curing agent was added, and further stirred for 1 hour. No xyl hardener was added. After the temperature was lowered to room temperature, 0.5 g of 2-methyl imidazole was added, followed by stirring for 30 minutes to prepare an insulating material composition. The insulating material composition thus prepared was film cast on a PET film, heat treated at 90 ° C. for 30 minutes, and then heated at 180 ° C. for 120 minutes to completely cure the dog bone, thereby measuring elongation and CTE. Tg (DSC) used a commonly used method, and adopted the value at the second scanning. The measurement results are summarized in Table 1 below.

Epoxy resin (g) Curing agent (g) (i) (ii) (iii) (iv) (v) (vi) (i) (ii) MI ^{* 1} ME ^{* 2} Silica Example 1 9 10 20 4 30 27 13.10 30.56 0.5 45 88.05 Example 2 9 10 20 4 30 27 21.83 22.04 0.5 45 88.05 Example 3 9 10 20 4 30 27 30.56 13.10 0.5 45 88.05 Comparative Example 1 9 10 20 4 30 27 43.66 - 0.5 45 88.05 Elongation (%) Tg (DSC / ℃) CTE (25-150 ° C) (ppm) Example 1 5.9 159.10 55.9 Example 2 5.1 165.50 54.7 Example 3 4.3 172.93 53.9 Comparative Example 1 3.7 178.70 53.4

Note) Epoxy resin: (i) Bisphenol A epoxy resin, (ii) Phenolic novolac epoxy resin, (iii) Cresol novolac epoxy resin, (iv) Rubber modified epoxy resin, (v) Phosphorus epoxy resin, (vi Naphthalene epoxy resin

Curing agent: (i) phenol novolac type hardener, (ii) xylox type hardener

^{* 1} MI: 2-methyl imidazole (g) / ^{* 2} ME: 2-methoxy ethanol (ml)

As shown in Table 1 above, in the case of the insulating material produced using the resin composition according to the present invention (Examples 1 to 3), the insulating material prepared using the resin composition without using a xylock type curing agent (Comparative Example) Compared with 1), it was found to be excellent in terms of elongation rate and various physical properties such as Tg and CTE.

Although the present invention has been described in detail with reference to specific examples, it is intended to describe the present invention in detail, and the epoxy resin composition and the printed circuit board using the same according to the present invention are not limited thereto, and the technical spirit of the present invention is limited thereto. It is apparent that modifications and improvements are possible by those skilled in the art.

As described above, according to the present invention, by using a phenol novolak-type curing agent and a xylox-type curing agent together as a curing agent, by adjusting the composition and composition ratio of the resin to have a specific composition, an appropriate level of modulus required as a build-up insulating material The present invention provides an epoxy resin composition capable of satisfying both the elongation and elongation and a printed circuit board using the same.

As described above, in the case of an insulating material manufactured by using a resin composition whose physical properties are controlled through a mixed use of a specific curing agent, in particular, during the imprint process, the insulating material itself affects flowability and flexibility, thereby reducing defects between molds. In addition, it helps to apply a uniform pressure throughout large area imprint, and it is possible to realize a fine circuit with high reliability.

All simple modifications and variations of the present invention fall within the scope of the present invention, and the specific scope of protection of the present invention will be apparent from the appended claims.

Claims (13)

(a) a composite epoxy resin comprising a bisphenol A epoxy resin, a phenol novolac epoxy resin, a cresol novolac epoxy resin, a rubber modified epoxy resin, a phosphorus epoxy resin and a naphthalene epoxy resin; (b) a curing agent comprising 0.5 to 2 equivalents of a phenol novolak type curing agent and a xylox type curing agent based on 1 equivalent of the composite epoxy resin, wherein the equivalent ratio of the phenol novolak type curing agent and the xylloc type curing agent is 1: 0.5 to 2 being; (c) 0.1 to 1 part by weight of a curing accelerator based on 100 parts by weight of the composite epoxy resin; And (d) 10 to 50 parts by weight of an inorganic filler based on 100 parts by weight of the total amount of the composite epoxy resin and the curing agent; Epoxy resin composition comprising a. According to claim 1, wherein the composite epoxy resin is 1 to 40 parts by weight of bisphenol A epoxy resin, 1 to 30 parts by weight of phenol novolac epoxy resin, 1 to 40 parts by weight of cresol novolac epoxy resin with respect to 100 parts by weight of composite epoxy resin An epoxy resin composition comprising 1 to 20 parts by weight of a rubber-modified epoxy resin, 1 to 50 parts by weight of a phosphorous epoxy resin and 1 to 40 parts by weight of a naphthalene epoxy resin. 2. The bisphenol A epoxy resin of claim 1, (ii) phenol novolac epoxy resin, (iv) cresol novolac epoxy resin, (iv) rubber modified epoxy resin, and (iv) phosphorus epoxy resin. And (iii) the average epoxy resin equivalent of the naphthalene epoxy resin is (i) 100 to 1000, (ii) 100 to 500, (iii) 100 to 600, (iii) 100 to 500, (iii) 400 to 800, and (Iii) 100 to 600, the epoxy resin composition characterized by the above-mentioned. delete The epoxy resin composition according to claim 1, wherein the phenol novolak type curing agent and the xyllock type curing agent each have an equivalent weight (g / eq) of 100 to 130 and a softening point of 45 to 150 ° C. The epoxy resin composition of claim 1, wherein the curing agent further comprises a bisphenol A (BPA) novolak curing agent. The epoxy resin composition of claim 1, wherein the curing accelerator is an imidazole compound. The method of claim 7, wherein the imidazole compound is 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 1- (2-cyanoethyl) -2-alkyl imidazole, 2-phenyl imidazole, Epoxy resin composition, characterized in that it is selected from the group consisting of 2-phenyl-4-phenyl imidazole and mixtures thereof. The epoxy resin composition of claim 1, wherein the inorganic filler is selected from the group consisting of graphite, carbon black, silica, clay, and mixtures thereof. The epoxy resin composition of claim 1 wherein the inorganic filler is surface treated with a silane coupling agent. The epoxy resin composition of claim 1, wherein the inorganic filler has an average particle diameter of 0.5 to 5 탆. 12. The epoxy resin composition of claim 11 wherein the inorganic filler is a mixture of spherical fillers of different sizes. Printed circuit board manufactured using the epoxy resin composition according to claim 1.