KR101377356B1 - Epoxy resin composition having an excellent adhesive property and copper foil with resin - Google Patents

Abstract

The present invention provides an epoxy resin composition and a copper foil with resin including a resin layer formed using the epoxy resin composition. The epoxy resin composition comprises a high-epoxy-equivalent-weight first epoxy resin having an epoxy equivalent weight (EEW) of 400 to 1000 g/eq; a low-epoxy-equivalent-weight second epoxy resin having an EEW of 100 to 300 g/eq; an epoxy resin modified with dimer acid; and a curing agent, wherein one or more kinds of the first epoxy resin and the second epoxy resin have polydispersity indexes (PDIs) of 2 or less. The present invention can provide a buildup printed circuit board capable of ensuring an excellent adhesive property and realizing heat resistance and a fine circuit pattern by mixing the high-epoxy-equivalent-weight epoxy, which has narrow molecular weight dispersity due to a low PDI, the low-epoxy-equivalent-weight epoxy, and the curing agent and improving adhesiveness between the copper foil and an insulating layer.

Description

Epoxy resin composition excellent in adhesiveness and resin composite copper foil using same {EPOXY RESIN COMPOSITION HAVING AN EXCELLENT ADHESIVE PROPERTY AND COPPER FOIL WITH RESIN}

The present invention uses a novel epoxy resin composition and the composition which can improve the adhesion between the copper foil and the insulating layer by mixing a high equivalent epoxy, a low equivalent epoxy and a curing agent having a low polydispersity index (PDI) with a narrow molecular weight distribution. The present invention relates to a resin composite copper foil and a laminate for a printed circuit board, which exhibit good adhesion, heat resistance, and fine circuit implementation.

As the low thermal expansion coefficient (LTE CTE) and low dielectric properties of electronic materials become more important, copper foil adhesion of an insulator is also an issue.

In order to realize a low coefficient of thermal expansion, an inorganic resin having a low polarity is used to increase the content of the inorganic filler or to implement a low dielectric constant. In this case, an alternative for improving the adhesive strength is required. In addition, copper foil having a low roughness value is used for low dielectric properties and fine patterns, and thus, a problem of lowering adhesive strength has been raised.

In fact, the copper foil used for conventional printed wiring board manufacture formed the unevenness | corrugation of the copper foil surface, and the unevenness | corrugation of such copper foil was embedded in base resin, and showed the adhesiveness between copper foil and a resin layer. In addition, in order to enhance the adhesive effect, a rust inhibitor, a polyimide (PI) resin, or the like has been used as a surface treatment agent. Such a polyimide (PI) resin is useful in terms of miniaturization of wiring and in terms of heat resistance, but is often problematic in adhesive strength and connection reliability between the polyimide film and the copper foil.

Moreover, in the copper foil which does not surface-treat, the method of applying the primer resin layer which is excellent in adhesive strength is urgently required.

The present invention has been made to solve the above-mentioned problems, a novel epoxy that can improve the adhesion between the insulating layer and the copper foil by mixing a high equivalent epoxy and a low equivalent epoxy having a narrow molecular weight distribution with a low polydispersity index (PDI) It aims at providing the primer resin composite copper foil which can apply | coat thinly the resin composition and the primer layer formed from the said composition, and can ensure favorable adhesiveness with a wiring board and a package board.

The present invention comprises: (a) a high equivalent first epoxy resin having an epoxy equivalent (EEW) in the range of 400 to 1000 g / eq; (b) low equivalent second epoxy resins having an epoxy equivalent weight (EEW) in the range of 100-300 g / eq; (c) dimer acid-modified epoxy resins; And (d) a curing agent, wherein at least one of the first epoxy resin and the second epoxy resin has a polydispersity index (PDI) of 2 or less.

According to a preferred example of the present invention, it is preferable that the weight average molecular weight (Mw) of the first epoxy resin is in the range of 1,000 to 3,000, and the weight average molecular weight (Mw) of the second epoxy resin is in the range of 500 to 2,000.

Moreover, it is preferable that the use ratio of the said 1st epoxy resin and the 2nd epoxy resin is 50-90: 10-10 weight ratio.

According to another preferred embodiment of the present invention, the dimer acid-modified epoxy resin has a modification rate of 5 to 30%, epoxy equivalent of 100 to 500g / eq is preferred.

Here, it is preferable that the said hardening | curing agent is 1 or more types chosen from the group which consists of a cresol novolak, a bisphenol A novolak, a naphthalene type, an amine hardener, and an aminotriazine novolak.

In addition, in the present invention, the curing agent and the epoxy resin is preferably included in a weight ratio of 20 to 50: 50 to 80.

In the present invention, the epoxy resin composition may further comprise a curing accelerator, wherein the curing accelerator is preferably at least one selected from the group consisting of amine-based, phenol-based and imidazole-based curing accelerators.

According to another preferred embodiment of the present invention, the composition comprises 5 to 40 parts by weight of the dimer acid-modified epoxy resin (c) based on 100 parts by weight of the mixture of the epoxy resin and the curing agent, 0.005 to 0.05 parts by weight of the curing accelerator It is preferable to include.

Moreover, this invention is copper foil; And a primer resin layer formed on one or both surfaces of the copper foil using the epoxy resin composition described above.

In addition, the present invention provides a laminate for a printed circuit board comprising a primer resin layer formed on the one surface or both surfaces of the substrate using the epoxy resin composition described above.

Since the epoxy resin composition which concerns on this invention is excellent in the adhesive force between an insulating layer and copper foil, the resin composite copper foil containing the primer resin layer formed using the said composition is excellent in heat resistance and workability, without reducing adhesive force.

In addition, the printed circuit board including the primer resin layer may simultaneously exhibit a low thermal expansion coefficient and a fine circuit pattern implementation effect.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the structure of the resin composite copper foil which concerns on one Example of this invention.
Description of the Related Art
100: resin composite copper foil 110: copper foil
120: primer resin layer

Hereinafter, the present invention will be described in detail.

In the present invention, by using an epoxy resin, a dimer acid-modified epoxy resin, a curing agent and an inorganic filler to provide an adhesive composition that can further improve the adhesive force between the copper foil and the insulating layer, but the low molecular weight index (PDI) as a component It is characterized by mixing a high equivalent first epoxy resin, a low equivalent second epoxy resin, and a hardening | curing agent which have narrow molecular weight distribution (narrow dispersity, ND).

Polydispersity Index (PDI) is a criterion indicating the extent of the molecular weight distribution of the polymer, and is defined as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

In general, when the polymer compound is synthesized, a polymer chain is made, and the polymer has different molecular weights depending on the degree of polymerization. A measure of the width of the molecular distribution is a polydispersity index (PDI). The larger the PDI, the wider the molecular weight distribution. The closer to 1, the closer the polymer is to a single molecular weight polymer having good physical properties.

In the present invention, the resin having a narrow molecular weight distribution (narrow dispersity) (ND resin) is significantly reduced in the content of relatively high high molecular weight material (eg High Mw species) and low molecular weight material (eg Oligomer), The distribution is generally uniform. Since the ND resin has a relatively high content of a high molecular weight material, as the viscosity is lowered, wetting property of the coating surface is excellent. This is good primer resin coating property along the roughness of copper foil, which contributes to the improvement of adhesion.

In addition, under the same temperature conditions, the degree of viscosity decrease of the resin is low, and the filling property is excellent. And low viscosity and gel time increase due to narrow dispersity contribute to stable press formability with primer adhesive copper foil (low adhesive strength) PPG (or product). This means improvement in adhesion.

In addition, the Tg, Td properties are improved by reducing the content of oligomers, which are low molecular weight materials, which contributes to improved heat resistance and reliability. Therefore, in the present invention, by applying the ND resin, it is possible to improve not only the adhesive strength but also the heat resistance and the glass transition temperature (Tg).

Furthermore, the resin composition of the present invention can exhibit excellent adhesiveness by applying to not only copper foil which has not been conventionally treated but also to substrates having low adhesive strength.

<Epoxy resin composition excellent in adhesiveness>

The epoxy resin composition according to the present invention comprises: (a) a high equivalent first epoxy resin having an epoxy equivalent weight (EEW) of 400 to 1000 g / eq; (b) a low equivalent second epoxy resin having an epoxy equivalent weight (EEW) of 100-300 g / eq; (c) dimer acid-modified epoxy resins; And (d) a curing agent, and at least one of the resins (a) and (b) may be configured using an ND resin having a polydispersity index (PDI) of 2 or less. Here, it may further include a curing accelerator. However, it is not particularly limited.

&Lt; Epoxy resin &

The first component of the epoxy resin composition according to the invention is an epoxy resin.

The epoxy resin of the present invention is not particularly limited as long as it contains two or more epoxy groups in the molecule.

Non-limiting examples of the epoxy resins that can be used include bisphenol A, bisphenol F, cresol novolac, dicyclopentazene, trisphenylmethane, naphthalene, biphenyl type and hydrogenated epoxy resins thereof, alone or in combination. More than one species can be used by mixing. In particular, when using a hydrogenated epoxy resin, it is preferable to use bisphenol A or a biphenyl type epoxy resin.

Meanwhile, in the present invention, two or more kinds of epoxy resins having different equivalents are mixed as epoxy resins, and at least one or more of epoxy resins having different equivalents has a polydispersity index (PDI) of ND having a narrow molecular weight distribution of 2.0 or less. (narrow dispersity) It is characterized by using a resin.

When epoxy resins having different equivalents are mixed as described above, an epoxy equivalent weight (EEW) epoxy resin has a good melt property at low melt viscosity and adhesion, and a high equivalent epoxy resin (EEW) has plasticity in itself. It is possible to further improve molding characteristics such as bending property (bending workability) and punching property of the copper foil or laminate for printed circuit board. Therefore, when an epoxy resin having a degree of polymerization (n) or an equivalent difference is mixed as in the present invention, in addition to the effect due to the use of an ND resin having a narrow molecular weight distribution, high adhesiveness, excellent moisture resistance reliability, moldability, and the like can be exhibited. have.

Accordingly, in the present invention, it is preferable to mix and use a high equivalent first epoxy resin having an epoxy equivalent of about 400 to 1000 g / eq and a low equivalent second epoxy resin having an epoxy equivalent of about 100 to 300 g / eq as the epoxy resin. desirable. In this case, the first epoxy resin and the second epoxy resin may be used alone, or two or more kinds of resins having the aforementioned equivalent ranges may be used.

The weight average molecular weight (Mw) of the first epoxy resin is in the range of 1,000 to 3,000, and the weight average molecular weight (Mw) of the second epoxy resin is preferably in the range of 500 to 2,000.

In addition, in the epoxy resin of the present invention, the use ratio of the first epoxy resin and the second epoxy resin may be 50 to 90: 10 to 50 weight ratio, preferably 50 to 70: 30 to 50 range. have.

The first epoxy resin, the second epoxy resin, or both may have a polydispersity index (PDI) of 2 or less, preferably 1 to 1.7, and more preferably 1.1 to 1.5. In addition, the higher the glass transition temperature (T _g ) of the epoxy resin is, the more preferable. For example, it may range from 80 to 250 ° C, or may be from 90 to 200 ° C.

In addition to the first epoxy resin and the second epoxy resin described above, the present invention may further include a conventional epoxy resin known in the art, and is not particularly limited thereto.

In the epoxy resin composition according to the present invention, the content of the epoxy resin may be in the range of 40 to 80 parts by weight relative to 100 parts by weight of the total resin composition, preferably 50 to 70 parts by weight. When the content of the epoxy resin falls within the above range, the curing property, the molding processability and the adhesive force of the resin composition are good.

<Dimer acid modified epoxy resin>

The third component constituting the epoxy resin composition according to the present invention is a dimer acid-modified epoxy resin.

When the dimer acid-modified epoxy resin forms an adhesive composition by a curing reaction, it is easy to form a cured product given flexibility by structural factors of the dimer acid-modified portion, and by imparting elastomeric properties to the adhesive layer (insulator) The adhesiveness, heat resistance, and moisture resistance of the copper base which is a metal base, and an adhesive bond layer (insulator) can be improved.

Non-limiting examples of the dimer acid-modified epoxy resin that can be used are KSR-200 (Kukdo Chemical), SER-200 (Shin-A T & C), etc. These may be used alone or in combination of two or more.

Preferably, examples of the dimer acid-modified epoxy resin include an epoxy resin represented by the following Chemical Formula 1, but are not limited thereto.

When the dimer acid-modified epoxy resin has a modification rate of about 5 to 30%, cracking and peeling phenomena do not occur during punching processing, and thus heat resistance and moisture resistance may be further improved.

In addition, the epoxy equivalent and viscosity of the dimer acid-modified epoxy resin are not particularly limited, but when the epoxy equivalent is about 100 to 500 g / eq and the viscosity is about 5,000 to 30,000 cps, the bending property (bending) is not caused while agglomeration fracture occurs. Processability) and punching processability, such as moldability and heat resistance and moisture resistance can be further improved.

In the epoxy resin composition according to the present invention, the content of the dimer acid-modified epoxy resin may be in the range of about 5 to 40 parts by weight, and preferably in the range of 5 to 30 parts by weight, based on 100 parts by weight of the mixture of the epoxy resin and the curing agent. Can be. When the content of the dimer acid-modified epoxy resin falls within the above-mentioned range, molding processability, heat resistance, adhesiveness and the like of the resin composition are good.

<Curing agent>

The fourth component constituting the epoxy resin composition according to the present invention is a curing agent.

The curing agent may be appropriately selected and used depending on the type of the epoxy resin, and may be used without limitation as long as it is usually used as a curing agent of the epoxy resin.

The polydispersity index (PDI) of the curing agent may be 2 or less, preferably 1 to 1.7, more preferably 1.1 to 1.5 range.

Non-limiting examples of the curing agent that can be used include a phenol-based curing agent, an anhydride-based curing agent, a dicyanamide-based curing agent, among which a phenolic curing agent is preferable because it can further improve the heat resistance and adhesion.

Non-limiting examples of the phenol-based curing agent include phenol novolak, cresol novolak, bisphenol A novolak, naphthalene type, etc. These may be used alone or in combination of two or more.

Non-limiting examples of the acid anhydride curing agent include phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydro phthalic anhydride, and the like. The said hardening | curing agent can be used individually by 1 type, or may use 2 or more types together.

The content of the curing agent may be appropriately adjusted according to the content of the epoxy resin. However, in order to further improve the heat resistance and the adhesive strength, in order to prevent deterioration of molding characteristics such as bending property (bending workability) and punching workability due to the hardening of the insulating layer, the curing agent and the epoxy resin may be reduced from 20 to 50:50 to 50%. It is preferable to mix and use in 80 weight ratio.

<Hardening accelerator>

In the present invention, if necessary, it may further include a conventional curing accelerator known in the art.

In this case, the curing accelerator may be appropriately selected and used depending on the type of the epoxy resin and the curing agent. Examples of curing accelerators that can be used include amine-based, phenol-based, and imidazole-based curing accelerators, and more specific examples thereof include amine complexes of boron trifluoride, imidazole derivatives, organic acids such as phthalic anhydride, and trimellitic anhydride. have.

Preferred non-limiting examples of the curing accelerators include imidazole derivative curing accelerators, specifically 1-methylimidazole, 2-methylimidazole, 2-ethyl 4-methyl imidazole, 2-phenylimidazole. , 2-phenyl4-methyl imidazole, cyanoethylation derivatives thereof, carboxylic acid derivatives, hydroxymethyl group derivatives, and the like, but are not limited thereto. These hardening accelerators can be used individually by 1 type, or can also use 2 or more types together.

The content of the curing accelerator may range from about 0.005 to 0.05 parts by weight, preferably from 0.01 to 0.04, based on 100 parts by weight of the mixture of the epoxy resin and the curing agent.

On the other hand, the epoxy resin composition of the present invention, inorganic fillers, flame retardants, other thermosetting resins and thermoplastic resins not mentioned above, and oligomers thereof, which are generally known in the art as necessary, as long as they do not impair the intrinsic properties of the resin composition. Various polymers such as, solid rubber particles or other additives such as ultraviolet absorbers, antioxidants, polymerization initiators, dyes, pigments, dispersants, thickeners, leveling agents and the like may be further included. For example, flame retardants such as organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants and metal hydroxides; Organic fillers such as silicone-based powder, nylon powder, and fluororesin powder; thickeners such as orthobenzene and benzene; Polymer-based defoaming agents or leveling agents such as silicones and fluororesins; Adhesion-imparting agents such as imidazole-based, thiazole-based, triazole-based and silane-based coupling agents; Phthalocyanine, carbon black, and other coloring agents.

A thermoplastic resin can be mix | blended with the said epoxy resin composition for the purpose of providing suitable flexibility to the resin composition after hardening, etc. Examples of such a thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide, polyamideimide, polyethersulfone, polysulfone and the like. Any one of these thermoplastic resins may be used alone, or two or more of them may be used in combination.

<Resin composite copper foil and manufacturing method thereof>

Hereinafter, with reference to the accompanying drawings will be described in detail with respect to the resin composite copper foil according to an embodiment of the present invention.

Referring to FIG. 1, the resin composite copper foil 100 of the present invention is located on the copper foil 110 and one or both surfaces of the copper foil, and the primer resin layer 120 formed using the epoxy resin composition described above. ).

In the resin composite copper foil according to the present invention, the copper foil 110 may use any conventional copper foil known in the art without limitation, and includes all copper foils produced by a rolling method and an electrolytic method, for example. Here, the copper foil may be subjected to rust prevention treatment in order to prevent the surface from being oxidized and corroded.

The copper foil may have a predetermined surface roughness Rz formed on one surface of the copper foil in contact with the first insulating resin layer, and the surface roughness Rz may be in a range of 0.6 μm to 3.0 μm.

In addition, the thickness of the copper foil is not particularly limited, but may be used less than 10 ㎛ in consideration of the thickness and mechanical properties of the final product, preferably in the range of 1 to 5 ㎛.

Examples of copper foil that can be used include Mitsui 18MT-EX, F2-WS, F1-WS, FWL-WS, T4X, and the like.

In the resin composite copper foil according to the present invention, the primer resin layer 120 is formed on the surface of the copper foil, the copper foil serving as the substrate, and the insulating resin layer or prepreg (PRG) formed on the resin layer. The adhesive force with can be improved more.

The thickness of the primer resin layer 120 may be appropriately adjusted within a range capable of securing the adhesiveness between the copper foil and the insulating layer, for example, may be in the range of 1 to 10 ㎛, preferably 1 to 7 ㎛ More preferably, it may be 1-5 micrometers.

Primer resin layer 120 according to the present invention includes a cured layer formed by curing the above-mentioned epoxy resin composition, wherein the epoxy resin composition does not necessarily need to be completely heat-cured, so that the effect of the present invention is exhibited It should just be hardened.

According to an example of the present invention, the resin composite copper foil 100 may further include a conventional insulating resin layer, a prepreg layer, or both of which are known in the art on the primer resin layer 120.

The resin composite copper foil 100 according to the present invention may be manufactured according to conventional methods known in the art. For example, the epoxy resin composition varnish may be applied to the surface of the copper foil and then heated, dried and cured, or the adhesive sheet or film obtained by heating and drying the resin varnish applied on the support may be coated on the surface of the copper foil. It can also be obtained by arranging in the adhesive.

In this case, when the epoxy resin composition is applied on a substrate, conventional coating methods known in the art, such as dip coating, die coating, roll coating, comma coating, casting or their Various methods such as a mixing method can be used without limitation. In addition, the drying method and drying conditions may be adjusted within the conventional range known in the art, for example, it may be carried out by drying for 1 to 30 minutes at a temperature of 50 to 170 ℃.

Examples of organic solvents that can be used when preparing the epoxy resin composition include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and the like. Carboxols such as acetic acid ester, cellosolve, butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. The organic solvents may be used alone or in combination of two or more.

In the epoxy adhesive composition of the present invention, the organic resin component and the inorganic solid component and organic solvent added as needed may be mixed using a pot mill, a ball mill, a homogenizer, a super mill, and the like.

On the other hand, the present invention provides a laminate for a printed circuit board comprising a primer resin layer formed by using the above-described epoxy resin composition on one side or both sides of the substrate.

In this case, the substrate may be used as a core substrate, and may be an inner layer wiring board.

Since the printed circuit board exhibits excellent performances such as excellent adhesiveness, heat resistance, and the like due to the novel epoxy resin composition, it can contribute to high functionalization and long life of various electronic devices.

Hereinafter, examples and experimental examples of the present invention will be described in detail. However, the following examples correspond only to the preferred embodiments of the present invention, and the present invention is not limited to the following examples and experimental examples.

[Examples 1 to 6]

1-1. Preparation of Epoxy Resin Composition

According to the composition shown in Table 1 below, a first epoxy resin, a second epoxy resin, a curing agent, a dimer acid-modified epoxy resin, a curing accelerator, and the like were mixed to prepare epoxy resin compositions, respectively. In Table 1 below, the amount of each unit used is parts by weight, where "parts by weight" is based on 100 parts by weight of a mixture of a high equivalent epoxy resin, a low equivalent epoxy resin, and a curing agent.

1-2. Fabrication of Resin Composite Copper Foil and Laminates for Printed Circuit Boards

The epoxy resin composition prepared above was coated with 1 to 5 μm on a general 1 / 2Oz copper foil and dried at 160 ° C. for 3 minutes. At this time, the coating method was performed using a casting or gravure coater.

Thereafter, a prepreg (Doosan, DS-7402HFE (PPG)) was applied to the copper foil coated with the primer resin layer to form a laminate, and the improvement effect of the adhesive strength was evaluated.

[Comparative Examples 1 to 3]

Except that according to the composition shown in Table 2, the epoxy resin composition, a resin composite copper foil and a laminate for a printed circuit board were prepared in the same manner as in the above Examples. In Table 2, the amount of each unit used is in parts by weight.

[Comparative Example 4]

On the general copper foil to which the primer resin layer was not applied, prepreg (Doosan, DS-7402HFE (PPG)) was applied to form the laminate of Comparative Example 6, and the improvement effect of the adhesive strength was evaluated.

Experimental Example 1-Property Evaluation

The following experiments were carried out for the laminates for printed circuit boards manufactured in Examples 1 to 6 and Comparative Examples 1 to 4, respectively, and the results are shown in Tables 1 and 2, respectively.

1) Coating property: 1-5 μm resin was coated on a Matt surface of a 12 μm (1 / 3Oz) copper foil which was not surface treated using a Gravure * pilot coater. (* Thin coatable micro coater) It was dried by B-stage for about 3 minutes at 180 degreeC temperature.

2) Peel Strength (P / S); According to the evaluation standard of IPC-TM-650 2.4.8, a circuit pattern was formed on a laminate for printed circuit boards, and the formed circuit pattern was pulled up in a 90 ° direction to measure the time when the circuit pattern (copper layer) was peeled off. It was.

3) Heat resistance: According to the IPC TM-650 2. 4. 13 evaluation standard, it was evaluated by measuring the time until the separation phenomenon between the primer resin layer and the copper foil by floating the laminate for printed circuit board at Solder 288 ℃.

4) Absorption rate: According to the evaluation standard of IPC-TM-650 2.6.2.1.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Dimer Acid Modified Epoxy 5 15 25 5 5 5 Epoxy 1 35 * ND epoxy 1 35 35 35 35 35 Epoxy 2 35 ND epoxy 2 35 35 35 35 35 Curing agent 1 30 ND Curing Agent 1 30 30 30 30 30 Hardening accelerator 0.006 0.006 0.006 0.006 0.006 0.006 Coating property ◎ ◎ ◎ ◎ ◎ ◎ P / S (@ 1/3 Oz-kgf / cm) 1.4 1.35 1.2 1.2 1.3 1.27 Heat Resistance (S / D @ 288) > 10min > 10min > 10min > 10min > 10min > 10min Absorption rate (D-2 / 100) 0.38 0.5 0.7 0.38 0.38 0.38 * ND: Narrow Dispersity

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Dimer Acid Modified Epoxy 5 15 25 Normal copper foil applied Epoxy 1 35 35 35 * ND epoxy 1 Epoxy 2 35 35 35 ND epoxy 2 Curing agent 1 30 30 30 ND Curing Agent 1 Hardening accelerator 0.006 0.006 0.006 Coating property ○ ○ ○ - P / S (@ 1/3 Oz-kgf / cm) 0.9 0.8 0.8 0.65 Heat Resistance (S / D @ 288) > 10min 8 min 7 min 5 min Absorption rate (D-2 / 100) 0.4 0.5 0.7 0.4 * ND: Narrow Dispersity

Company

1) ND epoxy resin 1: PDI: 1.57 / EEW: 600g / eq

2) ND epoxy resin 2: PDI: 1.26 / EEW: 190g / eq

3) Dimer acid modified epoxy resin: Kukdo Chemical KSR-200

4) ND Curing Agent 1: PDI: 1.40 / EEW 106.8

5) Curing accelerator: 2E4Mz (imidazole catalyst)

6) Epoxy Resin 1: PDI: 3.45 / EEW: 600g / eq

7) Epoxy Resin 2: PDI: 2.0 / EEW: 190g / eq

8) Hardener 1: phenol novolac hardener (KOLON KPH-F2003, PDI: 2.3)

As a result of the experiment, the resin composite copper foil using the epoxy resin composition of the present invention showed excellent properties in terms of coating property, adhesiveness, heat resistance, and water absorption (see Table 1).

Therefore, it is possible to manufacture a reliable build-up printed circuit board in the future, and it is judged that it will be usefully used as a constituent material of a small and lightweight new semiconductor package.

Claims (11)

(a) a high equivalent first epoxy resin having an epoxy equivalent (EEW) in the range of 400-1000 g / eq;
(b) low equivalent second epoxy resins having an epoxy equivalent weight (EEW) in the range of 100-300 g / eq;
(c) dimer acid-modified epoxy resins; And
(d) curing agent
Wherein the at least one of the first epoxy resin and the second epoxy resin has a polydispersity index (PDI) of 2 or less. The epoxy resin composition according to claim 1, wherein the weight average molecular weight (Mw) of the first epoxy resin is in the range of 1,000 to 3,000, and the weight average molecular weight (Mw) of the second epoxy resin is in the range of 500 to 2,000. The epoxy resin composition according to claim 1, wherein the use ratio of the first epoxy resin and the second epoxy resin is 50 to 90: 10 to 50 weight ratio. The epoxy resin composition of claim 1, wherein the dimer acid-modified epoxy resin has a modification rate of 5 to 30% and an epoxy equivalent of 100 to 500 g / eq. The epoxy resin composition according to claim 1, wherein the curing agent is at least one selected from the group consisting of cresol novolac, bisphenol A novolac, naphthalene type, amine curing agent and aminotriazine novolac. The epoxy resin composition of claim 1, wherein the curing agent has a polydispersity index (PDI) of 2 or less. The epoxy resin composition of claim 1, wherein the curing agent and the epoxy resin are included in a weight ratio of 20 to 50:50 to 80. The epoxy resin composition of claim 1, wherein the composition comprises 5 to 40 parts by weight of the dimer acid-modified epoxy resin (c) based on 100 parts by weight of the mixture of the epoxy resin and the curing agent. The method of claim 1, wherein the resin composition further comprises one or more curing accelerators selected from the group consisting of amine-based, phenol-based and imidazole-based compounds,
The curing accelerator is 0.005 to 0.05 parts by weight based on 100 parts by weight of the mixture of the epoxy resin and the curing agent epoxy resin composition. Copper foil; And
The resin composite copper foil which contains the primer resin layer formed using the epoxy resin composition of any one of Claims 1-9 on one or both surfaces of the said copper foil. A laminate for printed circuit boards, comprising a primer resin layer formed on one or both surfaces of a substrate using the epoxy resin composition according to any one of claims 1 to 9.

Images