JP2015099907A - Insulating resin composition for printed circuit board, and products using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulating resin composition for a printed circuit board with improved characteristics of the glass-transition temperature (Tg), the coefficient of thermal expansion (CTE) and the peel strength, and products using the same.SOLUTION: The insulating resin composition for a printed circuit board comprises an epoxy resin and a curing agent having a bipyridine structure.

Description

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

  With the development of electronic devices, weight reduction, thinning, and miniaturization of printed circuit boards are in progress every day. In order to respond to such a tendency, the wiring of the printed circuit is becoming more complicated and dense. Thus, the electrical, thermal and mechanical properties required for the substrate are acting as more important factors. The printed circuit board is mainly composed of copper that functions as circuit wiring and a polymer that functions as interlayer insulation. The polymer constituting the insulating layer is required to have various characteristics such as a thermal expansion coefficient, a glass transition temperature, and a thickness uniformity as compared with copper. In particular, it is necessary to make the insulating layer thin.

  In recent years, as reinforcing materials other than epoxy resins are used as organic materials for insulating layers used in epoxy molding compounds (EMC) and substrate materials, the interfacial adhesion between circuit layers and insulating layers used as electrodes decreases. Is regarded as a problem.

  Conventionally, the epoxy resin among organic substances constituting the insulating layer has mainly functioned as an adhesive with the circuit layer. However, the adhesive strength between the circuit layer and the insulating layer gradually decreased as the proportion of the epoxy resin in the insulating layer gradually decreased.

  In order to increase the mechanical stability and thermal stability of epoxy resins widely used as epoxy molding compounds and substrate materials, organic reinforcing materials such as bismaleimide and cyanate esters are used. In order to increase the glass transition temperature (Tg) of the material, wholly aromatic curing agents and curing agents having various molecular weight distributions are used.

  However, in the conventional method, it was possible to improve the adhesive strength with the circuit layer by including an epoxy resin in the insulating layer, but by including another organic reinforcing material in the composition of the insulating layer, the epoxy resin As a result, the adhesive strength with the circuit layer gradually decreased.

  On the other hand, Patent Document 1 discloses a photosensitive resin composition containing an epoxy group-containing unsaturated compound, which makes it possible to obtain characteristics of glass transition temperature, coefficient of thermal expansion (CTE), and peel strength (peel strength). There was a limit to improving

Korean Published Patent No. 2012-0089947

  The present invention is for solving the above-mentioned problems of the prior art, and one object of the present invention is to provide an insulating resin composition for a printed circuit board by using an epoxy resin and a curing agent having a bipyridine structure. An object of the present invention is to provide an insulating resin composition for a printed circuit board having improved properties of glass transition temperature (Tg), coefficient of thermal expansion (CTE) and peel strength (peel strength).

  Another object of the present invention is to provide a prepreg containing the insulating resin composition.

  Still another object of the present invention is to provide a printed circuit board manufactured by stacking a buildup layer on a copper clad laminate manufactured by applying the prepreg.

  An insulating resin composition for a printed circuit board for achieving one object of the present invention can include an epoxy resin and a curing agent having a bipyridine structure.

  The insulating resin composition for printed circuit boards may contain 25 to 75 parts by weight of an epoxy resin and 10 to 55 parts by weight of a curing agent having a bipyridine structure with respect to 100 parts by weight of the insulating resin composition. it can.

  In the insulating resin composition for a printed circuit board, the epoxy resin is a naphthalene type epoxy resin, a bisphenol A type epoxy resin, a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, a rubber-modified epoxy resin, a phosphorus type epoxy resin, or a bisphenol. One or more selected from F-type epoxy resins may be used.

  In the insulating resin composition for a printed circuit board, the bipyringin structure may be represented by the following formula.

  Here, a is an integer of 1 to 10, 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, and f is an integer of 1 to 10. And g is an integer of 1-10.

  In the insulating resin composition for a printed circuit board, the curing agent may contain 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 a bismaleimide.

  In the insulating resin composition for a printed circuit board, the inorganic filler may be included in an amount of 82 to 488 parts by weight with respect to 100 parts by weight of the insulating resin composition.

In the insulating resin composition for a printed circuit board, the inorganic filler includes 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 It may be one or more selected from (BaTiO ₃ ) and calcium zirconate (CaZrO ₃ ).

  In the insulating resin composition for a printed circuit board, 10 to 65 parts by weight of the cyanate ester may be contained with respect to 100 parts by weight of the insulating resin composition.

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

  In the insulating resin composition for a printed circuit board, 10 to 43 parts by weight of the bismaleimide may be contained with respect to 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 (1,1 ′-(methylenedi-4,1-phenylene) bismaleimide). There may be.

  A prepreg for achieving another object of the present invention is manufactured by impregnating organic fiber or inorganic fiber into a varnish containing an insulating resin composition for achieving one object of the present invention and drying the varnish. be able to.

  In the prepreg, the inorganic fiber or the organic fiber may be glass fiber, carbon fiber, polyparaphenylene benzobisoxazole fiber, thermotropic liquid crystal polymer fiber, lyotropic liquid crystal polymer fiber, aramid fiber, polypyridobisimidazole. It may be one or more selected from fibers, polybenzothiazole fibers, and polyarylate fibers.

  According to another aspect of the present invention, there is provided a printed circuit board on a copper clad laminate (CCL) obtained by attaching a copper foil to one or both sides of a prepreg for achieving another object of the present invention. It can be manufactured by laminating a buildup layer.

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

  Moreover, the mechanical property of the peeling strength of a metal layer and an insulating layer can be improved by the coordinate bond with a metal layer by including the hardening | curing agent which has a bipyridine structure in the said insulating resin composition.

It is the figure shown roughly in order to demonstrate the structure of the insulating resin composition by one Example of this invention.

  Objects, specific advantages and novel features of the present invention will become more apparent from the following detailed description and preferred embodiments with reference to the accompanying drawings. In this specification, it should be noted that when adding reference numerals to the components of each drawing, the same components are given the same number as much as possible even if they are shown in different drawings. I must. The terms “one side”, “other side”, “first”, “second” and the like are used to distinguish one component from another component, and the component is the term It is not limited by. Hereinafter, in describing the present invention, detailed descriptions of known techniques that may obscure the subject matter of the present invention are omitted.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

  FIG. 1 is a diagram schematically illustrating the structure of an insulating resin composition according to an embodiment of the present invention.

  Referring to FIG. 1, in the present invention, the insulating resin composition includes a curing agent having a bipyridine structure capable of coordinating bonding between an insulating layer and a metal layer, so that a thermal expansion coefficient, a glass transition temperature, and a peel strength can be obtained. Characteristics can be improved.

(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 enhance the handleability of the resin composition after drying as an adhesive film. The epoxy resin means one containing one or more epoxy functional groups in the molecule, and one containing four or more epoxy functional groups is preferable for improving the binding force.

  The epoxy resin is one or more selected from naphthalene type epoxy resin, bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, rubber-modified epoxy resin, phosphorus type epoxy resin and bisphenol F type epoxy resin. However, the present invention is not particularly limited thereto.

  The amount of the epoxy resin used in the insulating resin composition may be 25 to 75 parts by weight with respect to 100 parts by weight of the insulating resin composition. If the amount of the epoxy resin used is less than 25 parts by weight, the adhesive strength with the metal layer may be reduced, making it difficult to use as a substrate material. There is a possibility that the remaining epoxy resin may remain in the composition. As a result, the curing density of the epoxy resin is decreased, the heat resistance of the substrate material is decreased, the thermal expansion coefficient is increased, and the glass transition temperature can be decreased.

(Curing agent having bipyridine 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.

  (Here, a is an integer of 1 to 10, 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, and f is 1 to 10. Integer and g are integers of 1-10.)

  When the curing agent contains two or more functional groups such as phenol, amine, and acid anhydride, a crosslinking reaction with the epoxy resin is possible. In the insulating resin composition, the curing agent may be used in an amount of 10 to 55 parts by weight with respect to 100 parts by weight of the insulating resin composition. When the amount of the curing agent used is less than 10 parts by weight, the degree of cure with the epoxy resin may be reduced and heat resistance may be reduced. When the amount exceeds 55 parts by weight, the epoxy resin in the composition may be used. There is a risk that the chemical resistance will decrease due to a decrease in the amount of.

  Moreover, the said hardening | curing agent can improve the peeling strength of a metal layer and an insulating layer by having the bipyridine structure in which a coordinate bond with a metal layer is possible in a molecule | numerator. The bipyridine structure may be contained in an amount of 30 to 60% by weight in the curing agent. When the bipyridine structure is less than 30% by weight in the curing agent, the effect of improving the peel strength with the metal layer cannot be obtained, and when it exceeds 60% by weight, the crosslinking density with the epoxy resin is reduced. As a result, 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 printed circuit boards, the inorganic filler may be used in an amount of 82 to 488 parts by weight with respect to 100 parts by weight of the insulating resin composition. When the amount of the inorganic filler used is less than 82 parts by weight, the thermal expansion coefficient of the resin composition is increased, and the heat resistance may be reduced, making it difficult to use as a substrate material. When it exceeds the portion, the peel strength from the metal layer may be reduced, making it difficult to apply to the substrate process.

The inorganic filler includes 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 calcium zirconate (CaZrO ₃₎ 1) or more selected from, and not particularly 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 for improving heat resistance.

  In the insulating resin composition for a printed circuit board, the amount of cyanate ester used may be 10 to 65 parts by weight with respect to 100 parts by weight of the insulating resin composition. When the amount of the cyanate ester used is less than 10 parts by weight, the glass transition temperature of the resin composition is increased, heat resistance may be lowered, and it may be difficult to use as a substrate material. If it exceeds 1, the peel strength from the metal layer may be reduced, making it difficult to apply the resin composition to the substrate process.

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

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

  In the insulating resin composition for a printed circuit board, the amount of bismaleimide used may be 10 to 43 parts by weight with respect to 100 parts by weight of the insulating resin composition. When the amount of the bismaleimide used is less than 10 parts by weight, the glass transition temperature of the resin composition may be increased and the heat resistance may be reduced, making it difficult to use as a substrate material. In the case of exceeding, the moisture absorption rate of the resin composition is increased, the reliability of the material is decreased, and the application of the resin composition to the substrate process may be difficult.

  The bismaleimide may be 1,1 ′-(methylenedi-4,1-phenylene) bismaleimide (1,1 ′-(methylenedi-4,1-phenylene) bismaleimide), and is not particularly limited thereto. It is not something.

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

  Thus, the varnish containing the insulating resin composition for printed circuit boards according to one embodiment of the present invention can be impregnated with inorganic fibers or organic fibers and dried to produce a prepreg.

  The inorganic fiber or organic fiber includes glass fiber, carbon fiber, polyparaphenylenebenzobisoxazole fiber, thermotropic liquid crystal polymer fiber, lyotropic liquid crystal polymer fiber, aramid fiber, polypyridobisimidazole fiber, polybenzo It may be one or more selected from thiazole fiber and polyarylate fiber, and is not particularly limited thereto.

  A copper clad laminate (CCL) can be produced by attaching a copper foil to one or both sides of the prepreg. Thereby, the insulation layer containing an epoxy resin and the hardening | curing agent which has a bipyridine structure can improve the peeling strength with a metal layer.

  An insulating film or prepreg comprising an insulating resin composition for a printed circuit board according to an embodiment of the present invention is laminated on a copper-clad laminate used as an inner layer in the production of a printed circuit board. Can be used in the manufacture of For example, an insulating film or prepreg made of the insulating resin composition is laminated on a patterned inner layer circuit board, cured, a desmear process is performed, and then a circuit layer is formed by an electroplating process to form a multilayer printed circuit board Can be manufactured.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, the category of this invention is not limited to the following example.

(Production of curing agent having bipyridine structure)
(Production Example 1)
In a 100 ml round bottom flask equipped with a reflux apparatus, 7.3 g of 2,2′-bipyridine-4,4′-dicarboxylic acid, 8.7 g of 4-aminophenol, 6.6 g of isophthalic acid, 4-hydroxybenzoic acid 6.4 g, 6-hydroxy-2-naphthoic acid 3.1 g, and acetic anhydride 22.4 g were added. The flask was equipped with a sealed mechanical stirrer, nitrogen inlet tube, thermometer and 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 ° C. under the flow of nitrogen gas, and refluxed for about 1 hour while maintaining the temperature inside the flask at that temperature. Next, after further adding 5.6 g of 6-hydroxy-2-naphthoic acid, acetic acid as a reaction byproduct and unreacted acetic anhydride were removed and the temperature was raised to about 300 ° C., and then about 30 A curing agent having a bipyridine structure was synthesized by reacting for minutes.

(Manufacture of curing agent having no bipyridine structure)
(Production Example 2)
In a 100 ml round bottom flask equipped with a reflux apparatus, 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, acetic anhydride 22.4 g was added. Next, the reaction was carried out under the same conditions as in Production Example 1 to synthesize a curing agent having no bipyridine structure.

Example 1
45.0 g of N, N′-dimethylacetamide (33.0 g of the curing agent of Production Example 1 having a bipyridine structure, 22.0 g of an epoxy resin (Araldite MY-721, manufactured by Huntsmann) and 0.22 g of dicyandiamide (DICY) ( The solution was added to DMAc) to produce a mixed solution in a varnish form, impregnated with glass fiber into the varnish, and then dried at about 200 ° C. for 5 minutes to produce a prepreg. The prepreg was cured at a temperature of about 220 ° C. and a pressure of 30 kgf / cm ² for about 60 minutes to prepare a copper clad laminate.

(Example 2)
A varnish was prepared by adding 312 g of spherical silica (manufactured by Admatechs) having a particle size of 500 μm to the mixed solution produced in Example 1, and a copper-clad laminate was produced by the same method as in Example 1.

(Comparative Example 1)
45.0 g of N, N′-dimethylacetamide containing 33.0 g of the curing agent of Production Example 2 having no bipyridine structure, 22.0 g of an epoxy resin (Araldite MY-721, manufactured by Huntsmann) and 0.22 g of dicyandiamide (DICY) (DMAc) was added to produce a mixed solution in a varnish form, and glass fiber was impregnated into the varnish, followed by drying at about 200 ° C. for 5 minutes to produce a prepreg. The prepreg was cured at a temperature of about 220 ° 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 (manufactured by Admatechs) having a particle size of 500 μm was added to the mixed solution produced in Comparative Example 1 to produce a varnish, and a copper-clad laminate was produced by the same method as in Comparative Example 1.

  The thermal expansion coefficient and the glass transition temperature were measured with the samples from which the copper foils of the copper-clad laminates produced in Example 1 and Example 2, Comparative Example 1 and Comparative Example 2 were removed.

  In order to measure the coefficient of thermal expansion, it is measured in a tensile mode using a TMA equipment manufactured by TA, first scanned to about 300 ° C. at 10 ° C. per minute, and after cooling, the secondary Then, the coefficient of thermal expansion was measured at 10 ° C. per minute up to about 310 ° C. and the secondary scanning result value was measured.

  Further, the glass transition temperature was measured using a DSC equipment manufactured by TA, and about 5 mg of each produced sample was put into the equipment and subjected to a primary measurement at 300 ° C. at 10 ° C. per minute and cooled. Thereafter, the glass transition temperature was measured by the secondary measurement up to 300 ° C. at a rate of 10 ° C. per minute.

  Finally, about 1 cm of copper foil was peeled off from the surfaces of the copper clad laminates produced in Example 1 and Example 2 and Comparative Example 1 and Comparative Example 2, and a tensile strength measuring device (universal testing machine, UTM) was used. The peel strength between the copper foil and the insulating layer was measured.

  As can be seen from Table 1, the prepreg of Example 1 composed of an insulating resin composition not containing an inorganic filler according to the present invention has a glass transition temperature, a thermal expansion coefficient and a prepreg of Comparative Example 1 compared with the prepreg produced in Comparative Example 1. This has the effect of improving the peel strength characteristics.

  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 has a glass transition temperature, a coefficient of thermal expansion, and a separation as compared with the prepreg produced in Comparative Example 2. There is an effect of improving strength characteristics.

  As described above, the present invention has been described in detail based on the specific embodiments. However, the present invention is only for explaining the present invention, and the present invention is not limited thereto. It will be apparent to those skilled in the art that modifications and improvements within the technical idea of the present invention are possible.

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

  The present invention is applicable to an insulating resin composition for printed circuit boards and products using the same.

Claims (15)

Epoxy resin,
An insulating resin composition for printed circuit boards, comprising a curing agent having a bipyridine structure.   2. The insulating resin for a printed circuit board according to claim 1, comprising 25 to 75 parts by weight of an epoxy resin and 10 to 55 parts by weight of a curing agent having a bipyridine structure with respect to 100 parts by weight of the insulating resin composition. Composition.   The epoxy resin is one or more selected from naphthalene type epoxy resin, bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, rubber-modified epoxy resin, phosphorus type epoxy resin and bisphenol F type epoxy resin. The insulating resin composition for printed circuit boards according to claim 1, wherein The insulating resin composition for printed circuit boards according to claim 1, wherein the bipyringin structure is represented by the following formula.

(Here, a is an integer of 1 to 10, 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, and f is 1 to 10. Integer and g are integers of 1-10.)   The insulating resin composition for printed circuit boards according to claim 1, wherein the curing agent contains 30 to 60% by weight of a bipyridine structure. An inorganic filler;
Cyanate esters,
The insulating resin composition for printed circuit boards according to claim 1, further comprising bismaleimide.   The insulating resin composition for printed circuit boards of Claim 6 which contains 82-488 weight part of said inorganic fillers with respect to 100 weight part of said insulating resin compositions. The inorganic filler includes 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 calcium zirconate (CaZrO ₃₎ The insulating resin composition for printed circuit boards according to claim 7, which is one or more selected from   The insulating resin composition for printed circuit boards of Claim 6 which contains 10-65 weight part of said cyanate ester with respect to 100 weight part of said insulating resin compositions.   The insulating resin composition for a printed circuit board according to claim 9, wherein the cyanate ester is one or more selected from bisphenol A type cyanate ester, cresol novolac type cyanate ester and phenol novolak type cyanate ester.   The insulating resin composition for printed circuit boards according to claim 6, comprising 10 to 43 parts by weight of the bismaleimide with respect to 100 parts by weight of the insulating resin composition.   The printed circuit board according to claim 11, wherein the bismaleimide is 1,1 ′-(methylenedi-4,1-phenylene) bismaleimide (1,1 ′-(methylenedi-4,1-phenylene) bisaleimide). Insulating resin composition.   A prepreg produced by impregnating and drying organic fibers or inorganic fibers in a varnish containing the insulating resin composition according to claim 1.   The inorganic fiber or organic fiber includes glass fiber, carbon fiber, polyparaphenylenebenzobisoxazole fiber, thermotropic liquid crystal polymer fiber, lyotropic liquid crystal polymer fiber, aramid fiber, polypyridobisimidazole fiber, polybenzo The prepreg according to claim 13, wherein the prepreg is one or more selected from thiazole fibers and polyarylate fibers.   A printed circuit board produced by laminating a build-up layer on a copper clad laminate (CCL) obtained by attaching a copper foil to one or both sides of the prepreg according to claim 13.

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