KR20150057460A - Insulating resin composition for printed circuit board and products having the same - Google Patents

Abstract

The present invention provides an insulaton resin composition for a printed circuit board, a prepreg, a copper clad laminate, and a printed circuit board which are manufactured by using the same composition. More specifically, according to an embodiment of the present invention, a curing agent including a bipyridine structure is included in the insulaton resin composition. Therefore, heat-resistant properties, including the glass transition temperature and a coefficient of thermal expansion, and mechanical properties, including separation strength between a metal layer and an insulation layer, are increased.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an insulating resin composition for a printed circuit board,

The present invention relates to an insulating resin composition for a printed circuit board and a product using the same.

Background Art [0002] With the development of electronic devices, the weight, thickness, and miniaturization of printed circuit boards have been progressively increasing. In order to meet such a demand, the wiring of a printed circuit is becoming more complicated and densified. As such, the electrical, thermal and mechanical properties required of substrates are becoming more important. The structure of the printed circuit board consists mainly of copper, which acts as a circuit wiring, and a polymer, which acts as an interlaminar insulation. Compared to copper, the polymer constituting the insulating layer is required to have various characteristics such as a coefficient of thermal expansion, a glass transition temperature and uniformity of thickness, and in particular, it is required to make the thickness of the insulating layer thin

BACKGROUND ART [0002] In recent years, as an organic material for an insulating layer used for an epoxy molding compound (EMC) or a substrate material, a reinforcing material other than an epoxy resin is widely used, and a decrease in interfacial adhesion between a circuit layer and an insulating layer used as an electrode is a problem.

Among the organic materials constituting the conventional insulating layer, the epoxy resin has played a main role as an adhesive with the circuit layer. However, the proportion of the epoxy resin in the insulating layer gradually decreased, and the bonding strength between the circuit layer and the insulating layer gradually decreased.

Organic stiffeners such as bismaleimide and cyanate ester have been used to increase the mechanical and thermal stability of epoxy resins widely used as epoxy molding compounds and substrate materials and the glass transition temperature Tg), a curing agent having various molecular weight distributions and the like have been used. However, in the conventional method, the adhesive strength to the circuit layer can be improved by including the epoxy resin in the insulating layer. However, when the other organic stiffener is included in the composition of the insulating layer, the addition amount of the epoxy resin is decreased, .

On the other hand, Patent Document 1 discloses a photosensitive resin composition containing an epoxy group-containing unsaturated compound, but there is a limit to improve the properties of glass transition temperature, CTE and peel strength.

Patent Document 1: Korean Patent Publication No. 2012-0089947

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide an insulating resin composition for a printed circuit board, which comprises a curing agent comprising an epoxy resin and a bipyridine structure, And to provide an insulating resin composition for a printed circuit board having improved CTE and peel strength characteristics.

Another aspect of the present invention is to provide a prepreg including the insulating resin composition.

Another aspect of the present invention is to provide a printed circuit board manufactured by laminating a buildup layer on a copper-clad laminate produced by applying the prepreg.

An insulating resin composition for a printed circuit board according to one aspect of the present invention comprises:

Epoxy resin; And

A curing agent comprising a bipyridine structure;

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In the insulating resin composition for a printed circuit board, 25 to 75 parts by weight of an epoxy resin and 10 to 55 parts by weight of a curing agent containing a bipyridine structure may be included relative to 100 parts by weight of the insulating resin composition.

In the insulating resin composition for a printed circuit board, the epoxy resin may be at least one selected from the group consisting of naphthalene type epoxy resin, bisphenol A type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, rubber modified epoxy resin, phosphorus epoxy resin and bisphenol F type One or more epoxy resins may be selected.

In the insulating resin composition for a printed circuit board, the bipyridine structure may be represented by the following formula (1)

[Chemical Formula 1]

B is an integer of 1 to 13, c is an integer of 1 to 13, d is an integer of 1 to 21, e is an integer of 1 to 21, f is an integer of 1 to 10, g is an integer of 1 to 10;

In the insulating resin composition for a printed circuit board, the curing agent may include 30 to 60% by weight of a bipyridine structure.

In the insulating resin composition for a printed circuit board, the insulating resin composition may further include an inorganic filler, a cyanate ester, and bismaleimide.

In the insulating resin composition for a printed circuit board, the inorganic filler may include 82 to 488 parts by weight based on 100 parts by weight of the insulating resin composition.

In the printed circuit insulating resin composition for the substrate, the inorganic filler is silica (SiO _2), alumina (Al ₂ O _3), barium sulfate (BaSO _4), aluminum hydroxide (AlOH _3), magnesium hydroxide (Mg (OH) ₂ ), calcium carbonate (CaCO _3), magnesium carbonate (MgCO _3), magnesium oxide (MgO), boron nitride (BN), silicon carbide (SiC), aluminum borate (AlBO _3), barium titanate (BaTiO ₃₎ and zirconate It may be selected from one or more of calcium (CaZrO _3).

In the insulating resin composition for a printed circuit board, the cyanate ester may be included in an amount of 10 to 65 parts by weight based on 100 parts by weight of the insulating resin composition.

In the insulating resin composition for a printed circuit board, the cyanate ester may be selected from one or more of bisphenol A type, cresol novolak type and phenol novolac type.

In the insulating resin composition for a printed circuit board, the bismaleimide may be included in an amount of 10 to 43 parts by weight based on 100 parts by weight of the insulating resin composition.

In the insulating resin composition for a printed circuit board, the bismaleimide is 1,1'- (methylenedi-4,1-phenylene) bismaleimide ).

A prepreg according to another aspect of the present invention comprises:

The varnish containing the insulating resin composition according to one aspect of the present invention may be impregnated with organic or inorganic fibers and dried.

In the prepreg, the inorganic fibers or the organic fibers may be formed of glass fibers, carbon fibers, polyparaphenylene benzobisoxazole fibers, thermotropic liquid crystal polymer fibers, lyotropic liquid crystal polymer fibers, aramid fibers, Bismigidazole fibers, polybenzothiazole fibers, and polyarylate fibers.

A printed circuit board according to another aspect of the present invention includes:

The present invention can be manufactured by laminating a buildup layer on a copper clad laminate (CCL) obtained by attaching a copper foil to one side or both sides of a prepreg according to another aspect of the present invention.

The insulating resin composition for a printed circuit board according to the present invention and the prepreg, the copper clad laminate, and the printed circuit board using the same can improve the heat resistance characteristics of the glass transition temperature and the thermal expansion coefficient.

Further, by including a bipyridine structure in the insulating resin composition, there is an effect of improving the mechanical properties of the peel strength between the metal layer and the insulating layer through coordination bonding with the metal layer.

FIG. 1 is a schematic view for explaining the constitution of an insulating resin composition according to an embodiment of the present invention.

Before describing the invention in more detail, it is to be understood that the words or words used in the present specification and claims should not be construed in a conventional or dictionary sense, It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined. Therefore, the constitution of the embodiment described in this specification is merely an example of the present invention, and not all of the technical ideas of the present invention are described. Therefore, various equivalents and modifications It should be understood.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.

FIG. 1 is a schematic view for explaining the constitution of an insulating resin composition according to an embodiment of the present invention. Referring to FIG. 1, the present invention can improve the thermal expansion coefficient, glass transition temperature, and peel strength characteristics by including a curing agent including a bipyridine structure capable of coordinate bonding between an insulating layer and a metal layer in an insulating resin composition .

Epoxy resin

The insulating resin composition for a printed circuit board according to an embodiment of the present invention may include an epoxy resin in order to improve handleability of the resin composition after drying as an adhesive film. The epoxy resin means that at least one epoxy functional group is contained in the molecule, and it is preferable that the epoxy resin contains at least four epoxy functional groups to improve the bonding strength.

The epoxy resin may be at least one selected from naphthalene type epoxy resin, bisphenol A type epoxy resin, phenol novolac epoxy resin, cresol novolak epoxy resin, rubber modified epoxy resin, phosphorus epoxy resin and bisphenol F type epoxy resin, But is not limited thereto.

The amount of the epoxy resin used in the insulating resin composition may be 25 to 75 parts by weight based on 100 parts by weight of the insulating resin composition. If the amount of the epoxy resin is less than 25 parts by weight, the adhesive strength with the metal layer may be lowered, which may be difficult to use as a substrate material. If the amount exceeds 75 parts by weight, an uncured epoxy resin may remain in the composition. As a result, the curing density of the epoxy resin is reduced, the heat resistance of the substrate material is reduced, the thermal expansion coefficient is increased, and the glass transition temperature is lowered.

Bipyridine  Hardener containing structure

The insulating resin composition for a printed circuit board according to an embodiment of the present invention may include a curing agent having a bipyridine structure represented by the following formula (1).

[Chemical Formula 1]

B is an integer of 1 to 13, c is an integer of 1 to 13, d is an integer of 1 to 21, e is an integer of 1 to 21, f is an integer of 1 to 10, g is an integer of 1 to 10;

The curing agent may include a crosslinking reaction with an epoxy resin by containing two or more functional groups such as phenol, amine, and anhydrous acid. The amount of the curing agent used in the insulating resin composition may be 10 to 55 parts by weight based on 100 parts by weight of the insulating resin composition. If the amount of the curing agent is less than 10 parts by weight, the degree of curing with the epoxy resin may be lowered and the heat resistance may be decreased. If the amount of the curing agent is more than 55 parts by weight, the amount of the epoxy resin in the composition may be decreased and the chemical resistance may be decreased.

In addition, the curing agent may include a bipyridine structure capable of coordinating with the metal layer in the molecule, thereby improving the peeling strength between the metal layer and the insulating layer. The bipyridine structure may comprise 30 to 60 wt% in the curing agent. If the bipyridine structure is less than 30% by weight in the curing agent, the effect of improving the peeling strength with the metal layer can not be obtained. If the bipyridine structure is more than 60% by weight, the crosslinking density with the epoxy resin decreases and the thermal strength may decrease.

Inorganic filler

The insulating resin composition for a printed circuit board according to an embodiment of the present invention may further include an inorganic filler for improving the thermal expansion coefficient.

In the insulating resin composition for a printed circuit board, the amount of the inorganic filler to be used may be 82 to 488 parts by weight based on 100 parts by weight of the insulating resin composition. If the amount of the inorganic filler used is less than 82 parts by weight, the thermal expansion coefficient of the resin composition may be high, and the heat resistance may be low to be difficult to use as a substrate material. If the amount is more than 488 parts by weight, It can be difficult.

The inorganic fillers include silica (SiO _2), alumina (Al ₂ O _3), barium sulfate (BaSO _4), aluminum hydroxide (AlOH _3), magnesium hydroxide (Mg (OH) _2), calcium carbonate (CaCO _3), acid magnesium (MgCO _3), magnesium oxide (MgO), boron nitride (BN), silicon carbide (SiC), aluminum borate (AlBO _3), is selected at least one from barium titanate (BaTiO ₃₎ and zircon calcium (CaZrO ₃₎ But is not limited thereto.

Cyanate  Ester

The insulating resin composition for a printed circuit board according to an embodiment of the present invention may further include a cyanate ester to improve heat resistance.

In the insulating resin composition for a printed circuit board, the cyanate ester may be used in an amount of 10 to 65 parts by weight based on 100 parts by weight of the insulating resin composition. If the amount of the cyanate ester is less than 10 parts by weight, the glass transition temperature of the resin composition becomes high and the heat resistance of the resin composition tends to be low, which may be difficult to use as a substrate material. If the amount exceeds 65 parts by weight, It may be difficult to apply it to a substrate process.

The cyanate ester may be selected from one or more of bisphenol A type, cresol novolak type and phenol novolak type cyanate ester, but is not limited thereto.

Bismaleimide

The insulating resin composition for a printed circuit board according to an embodiment of the present invention may further include bismaleimide to improve heat resistance.

The amount of bismaleimide used in the insulating resin composition for a printed circuit board may be 10 to 43 parts by weight based on 100 parts by weight of the insulating resin composition. When the amount of the bismaleimide is less than 10 parts by weight, the glass transition temperature of the resin composition becomes high and the heat resistance of the resin composition decreases. When the amount of the bismaleimide is more than 43 parts by weight, the moisture absorption rate of the resin composition increases, The reliability is reduced and it may be difficult to apply the resin composition to the substrate process.

The bismaleimide may be 1,1'- (methylenedi-4,1-phenylene) bismaleimide, but is not limited thereto. It is not.

The insulating resin composition according to one embodiment of the present invention can be manufactured into a semi-solid state dry film by any general method known in the art. For example, it is manufactured in a film form using a roll coater, a curtain coater, or a comma coater, and then dried and applied to a substrate to form a multi-layer printed circuit May be used as an insulating layer (or an insulating film) or a prepreg in manufacturing a substrate. Such an insulating film or prepreg can improve the characteristics of the thermal expansion coefficient and the glass transition temperature.

As described above, the varnish containing the insulating resin composition for a printed circuit board according to an embodiment of the present invention may be impregnated with inorganic fibers or organic fibers and dried to prepare prepregs.

The inorganic fiber or the organic fiber may be a fiber such as glass fiber, carbon fiber, polyparaphenylene benzobisoxazole fiber, thermotropic liquid crystal polymer fiber, lysotropic liquid crystal polymer fiber, aramid fiber, polypyridobisimidazole fiber, A polybenzothiazole fiber, and a polyarylate fiber, but is not limited thereto.

The copper clad laminate (CCL) can be manufactured by attaching a copper foil to one side or both sides of the prepreg. Through this, an insulating layer containing a curing agent containing an epoxy resin and a bipyridine structure can improve the peeling strength with the metal layer.

In addition, an insulating film or prepreg made from an insulating resin composition for a printed circuit board according to an embodiment of the present invention may be laminated on a copper-clad laminate used as an inner layer in the production of a printed circuit board to be used for manufacturing a multilayer printed circuit board . For example, an insulating film or a prepreg made of the insulating resin composition is laminated on an inner layer circuit board patterned and then cured, followed by a desmearing process, and then a circuit layer is formed through an electroplating process, A printed circuit board can be manufactured.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited to the following examples.

Bipyridine  Manufacture of hardener containing

Production Example 1

7.3 g of 2,2'-bipyridine-4,4'-dicarboxylic acid, 8.7 g of 4-aminophenol, 6.6 g of isophthalic acid, 6.4 g of 4-hydroxybenzoic acid, 3.1 g of hydroxy-2-naphthoic acid and 22.4 g of acetic anhydride were added. The flask was equipped with a mechanical stirrer, a nitrogen injection tube, a thermometer and a reflux condenser. After sufficiently replacing the inside of the flask with nitrogen gas, the temperature inside the flask was raised to a temperature of about 140 캜 under a nitrogen gas flow, and refluxed for about 1 hour while maintaining the temperature inside the flask at that temperature. Then, 5.6 g of 6-hydroxy-2-naphthoic acid was further added, and then the temperature was raised to about 300 ° C. while removing acetic acid and unreacted acetic anhydride, which are byproducts of the reaction, Were synthesized.

Bipyridine  Preparation of non-containing curing agent

Production Example 2

8.7 g of 4-aminophenol, 10.0 g of isophthalic acid, 6.4 g of 4-hydroxybenzoic acid, 3.1 g of 6-hydroxy-2-naphthoic acid and 22.4 g of acetic anhydride were added to a 100 ml round bottom flask equipped with a reflux condenser. Then, the reaction was carried out under the same conditions as in Preparation Example 1 to synthesize a curing agent containing no bipyridine.

Example 1

22.0 g of an epoxy resin (Araldite MY-721, Huntsmann) and 0.22 g of dicyandiamide (DICY) were dissolved in 45.0 g of N, N'-dimethylacetamide (DMAc) To prepare a mixed solution in a varnish state. The glass fiber was impregnated in the varnish and then dried at about 200 DEG C for 5 minutes to prepare a prepreg. Then, the prepreg was cured at a temperature of about 220 DEG C and a pressure of 30 kgf / cm < 2 > for about 60 minutes to prepare a copper clad laminate.

Example 2

312 g of spherical silica having a particle diameter of 500 탆 (Admatech Corp.) was added to the mixed solution prepared in Example 1 to prepare a varnish, and a copper-clad laminate was produced in the same manner as in Example 1.

Comparative Example 1

22.0 g of an epoxy resin (Araldite MY-721, Huntsmann) and 0.22 g of dicyandiamide (DICY) were dissolved in 45.0 g of N, N'-dimethylacetamide DMAc) to prepare a mixed solution. The glass fiber was impregnated with the varnish and then dried at about 200 DEG C for 5 minutes to prepare a prepreg. Then, the prepreg was cured at a temperature of about 220 DEG C and a pressure of 30 kgf / cm < 2 > for about 60 minutes to prepare a copper clad laminate.

Comparative Example 2

312 g of spherical silica having a particle diameter of 500 탆 (Admatech Corp.) was added to the mixed solution prepared in Comparative Example 1 to prepare a varnish, and a copper-clad laminate was prepared in the same manner as in Comparative Example 1.

The thermal expansion coefficient and the glass transition temperature of the copper clad laminate prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were measured through the copper foil-free specimens.

The thermal expansion coefficient was measured in Tensile mode using TA's TMA equipment. The temperature was scanned up to about 300 ° C. at a rate of 10 ° C. per minute, followed by cooling to about 310 ° C. at a rate of 10 ° C. per second, The thermal expansion coefficients of the scanned results were measured.

The glass transition temperature was measured using TA DSC equipment. About 5 mg of the prepared sample was placed in the equipment, and the sample was firstly measured at 10 ° C / min up to 300 ° C, cooled, and then cooled to 10 ° C / The glass transition temperature was measured by the second measurement and the second measurement.

Finally, about 1 cm of copper foil was peeled from the surface of the copper clad laminate prepared in Examples 1 and 2 and Comparative Examples 1 and 2, and the peel strength between the copper foil and the insulating layer was measured using a universal testing machine (UTM) Were measured.

division Glass transition temperature (캜) Thermal Expansion Coefficient (ppm / ° C) Peel strength (kgf / cm) Example 1 250 10 2.5 Comparative Example 1 237 18 1.5

As can be seen from Table 1, the prepreg of Example 1, which was made from an insulating resin composition containing no inorganic filler according to the present invention, had a glass transition temperature, a thermal expansion coefficient And the effect of improving the peel strength.

division Glass transition temperature (캜) Thermal Expansion Coefficient (ppm / ° C) Peel strength (kgf / cm) Example 2 235 5 1.6 Comparative Example 2 220 11 0.6

As can be seen from Table 2, the prepreg of Example 2 made of an insulating resin composition containing an inorganic filler according to the present invention had a glass transition temperature, a coefficient of thermal expansion and a coefficient of thermal expansion The effect of improving the peel strength can be obtained.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, the same is by way of illustration and example only and is not to be construed as limiting the present invention. It is obvious that it can be modified or improved.

It is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

Claims (15)

Epoxy resin; And
A curing agent comprising a bipyridine structure;
And an insulating resin composition for a printed circuit board.
The method according to claim 1,
And a curing agent comprising 25 to 75 parts by weight of an epoxy resin and 10 to 55 parts by weight of a bipyridine structure based on 100 parts by weight of the insulating resin composition.
The method according to claim 1,
The epoxy resin may be at least one selected from the group consisting of naphthalene type epoxy resin, bisphenol A type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, rubber modified epoxy resin, phosphorus epoxy resin and bisphenol F type epoxy resin Insulated resin composition.
The method according to claim 1,
Wherein the bipyridine structure is represented by the following Formula 1:
[Chemical Formula 1]

B is an integer of 1 to 13, c is an integer of 1 to 13, d is an integer of 1 to 21, e is an integer of 1 to 21, f is an integer of 1 to 10, g is an integer of 1 to 10;
The method according to claim 1,
Wherein the curing agent comprises 30 to 60% by weight of a bipyridine structure.
The method according to claim 1,
Wherein the insulating resin composition further comprises an inorganic filler, a cyanate ester, and bismaleimide.
The method of claim 6,
Wherein the inorganic filler comprises 82 to 488 parts by weight based on 100 parts by weight of the insulating resin composition.
The method of claim 7,
The inorganic fillers include silica (SiO _2), alumina (Al ₂ O _3), barium sulfate (BaSO _4), aluminum hydroxide (AlOH _3), magnesium hydroxide (Mg (OH) _2), calcium carbonate (CaCO _3), acid magnesium (MgCO _3), magnesium oxide (MgO), boron nitride (BN), silicon carbide (SiC), aluminum borate (AlBO _3), barium titanate (BaTiO ₃₎ and zircon calcium print the selected one or more from the (CaZrO ₃₎ Insulating resin composition for circuit board.
The method of claim 6,
Wherein the cyanate ester is contained in an amount of 10 to 65 parts by weight based on 100 parts by weight of the insulating resin composition.
The method of claim 9,
Wherein the cyanate ester is at least one selected from the group consisting of bisphenol A type, cresol novolak type and phenol novolac type.
The method of claim 6,
Wherein the bismaleimide is contained in an amount of 10 to 43 parts by weight based on 100 parts by weight of the insulating resin composition.
The method of claim 11,
Wherein the bismaleimide is 1,1'- (methylenedi-4,1-phenylene) bismaleimide. 2. The insulating resin composition for a printed circuit board according to claim 1, wherein the bismaleimide is 1,1'- (methylenedi-4,1-phenylene) bismaleimide.
A prepreg produced by impregnating organic fibers or inorganic fibers with a varnish containing the insulating resin composition according to claim 1 and drying the varnish.
14. The method of claim 13,
The inorganic fiber or the organic fiber may be a fiber such as glass fiber, carbon fiber, polyparaphenylene benzobisoxazole fiber, thermotropic liquid crystal polymer fiber, lysotropic liquid crystal polymer fiber, aramid fiber, polypyridobisimidazole fiber, Polybenzothiazole fibers, and polyarylate fibers.
A printed circuit board manufactured by laminating a buildup layer on a copper clad laminate (CCL) obtained by attaching a copper foil to one side or both sides of a prepreg of claim 13.

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