JP2015199905A - Insulating resin compositions for printed circuit board, and products using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: insulating resin compositions for a printed circuit board using resin compositions containing polyether sulfone resins as curative agents so as to improve glass transformation temperature (Tg), coefficient of thermal expansion (CTE) and tensile strength properties; and products using the same.SOLUTION: An insulating resin composition for a printed circuit board contains a naphthalene-based epoxy resin, a cyanate ester resin, a polyethersulfone resin, a bismaleimide resin, and an inorganic filler.

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, printed circuit boards are becoming lighter, thinner, and smaller. In order to meet such a demand, the wiring of the printed circuit is further complicated and densified. As described above, the electrical, thermal, and mechanical properties required for the substrate are further important factors.

  The printed circuit board is mainly composed of copper serving as circuit wiring and a polymer serving as interlayer insulation. Compared to copper, the polymer constituting the insulating layer requires many characteristics such as thermal expansion coefficient, glass transition temperature, and uniformity of thickness. In particular, the insulating layer must be made thin. .

  Further, since the rigidity of the board itself decreases as the circuit board becomes thinner, there is a possibility that a defect due to a warp phenomenon may occur when a component is mounted at a high temperature. Therefore, the thermal expansion characteristics and heat resistance of the thermosetting polymer resin act as important factors, but the network structure and the curing density between the polymer chains constituting the polymer structure and the substrate composition are close at the time of thermosetting. Influence.

  Conventionally, attempts have been made to lower the thermal expansion coefficient and glass transition temperature using an insulating resin composition for a printed circuit board containing a general-purpose epoxy resin and an inorganic filler such as silica. However, according to the above method, although the characteristics of the coefficient of thermal expansion and the glass transition temperature are improved, there arises a problem that the modulus and the thermal stability are lowered. In addition, there is a limit to improving the characteristics of the thermal expansion coefficient and the glass transition temperature.

  On the other hand, Patent Document 1 discloses a resin composition for a printed circuit board. However, there is a limit to sufficiently forming a mutual network between the compositions, and the thermal expansion coefficient and glass transition of the printed circuit board are limited. There was a problem that the temperature characteristics could not be improved.

Korean Published Patent No. 2011-0108782

In order to solve the above-described problems of the prior art, the object of the present invention is to use a resin composition containing a polyethersulfone resin as a curing agent, so that the glass transition temperature (Tg), the coefficient of thermal expansion (CTE), An object of the present invention is to provide an insulating resin composition for a printed circuit board having improved tensile strength characteristics.
Another object of the present invention is to provide an insulating film or prepreg containing the insulating resin composition.
Still another object of the present invention is to provide a copper clad laminate produced by laminating copper foil on both sides of the prepreg and a printed circuit board including the same.

  An insulating resin composition for a printed circuit board according to one aspect of the present invention includes a naphthalene epoxy resin, a cyanate ester resin, a polyethersulfone resin, a bismaleimide resin, and an inorganic filler.

  The insulating resin composition comprises 5 to 30% by weight naphthalene-based epoxy resin, 5 to 40% by weight cyanate ester resin, 3 to 15% by weight polyethersulfone resin, and 1 to 10% by weight bismaleimide. Resin and 50-80 wt% inorganic filler.

  The naphthalene-based epoxy resin may be an ester-type naphthalene-based epoxy resin represented by the following chemical formulas 1 and 2 or a mixture thereof.

  The cyanate ester resin may be a phenol novolac type cyanate ester resin represented by the following chemical formula 3.

  In formula, n is an integer of 0-3.

  The polyethersulfone resin includes a phenolic hydroxyl group and may be represented by the following chemical formula 4.

  In the formula, n is an integer of 1 to 3.

  The bismaleimide resin may be a compound represented by the following chemical formula 5, chemical formula 6, or chemical formula 7, or a mixture thereof.

  In the formula, n is an integer of 1 to 3.

  The inorganic filler may have an average particle size of 0.05 to 1 μm.

The inorganic filler is silica (SiO ₂ ), alumina (Al ₂ O ₃ ), barium sulfate (BaSO ₄ ), talc, aluminum hydroxide (AlOH ₃ ), magnesium hydroxide (Mg (OH) ₂ ), calcium carbonate (CaCO _3), magnesium carbonate (MgCO _3), selected of magnesium oxide (MgO), boron nitride (BN), aluminum borate (alBO _3), barium titanate (BaTiO _3), and calcium zirconate (CaZrO ₃₎ Can be one or more.

  The resin composition may further include a curing accelerator.

  The curing accelerator may be one or more selected from a metal curing accelerator, an imidazole curing accelerator, and an amine curing accelerator.

  According to another aspect of the present invention, a prepreg can be produced by impregnating a glass fiber into a varnish containing the insulating resin composition.

  The glass fiber may be one or more selected from E glass, T glass, NE glass, and S glass.

  According to another aspect of the present invention, one or more circuit layers or insulating layers are laminated on one side or the other side of a copper clad laminate (CCL) manufactured by laminating copper foil on both sides of the prepreg. Thus, a printed circuit board can be manufactured.

  An insulating resin composition for a printed circuit board according to an embodiment of the present invention includes a polyethersulfone resin capable of maintaining heat resistance, a low coefficient of thermal expansion, and a high glass transition temperature. The coefficient and tensile strength characteristics can be improved.

  The insulating resin composition according to an embodiment of the present invention uses a polyethersulfone resin as a curing agent, so that the hydroxyl group at the terminal of the polyethersulfone resin is effective as an epoxy resin, a bismaleimide resin, and a cyanate ester resin. Can be cured.

  In addition, an insulating film using the resin composition and a prepreg produced by impregnating glass fiber into a varnish containing the composition can improve the characteristics of glass transition temperature, thermal expansion coefficient, and tensile strength. it can.

  Moreover, the copper clad laminated board manufactured by laminating | stacking copper foil on both surfaces of the said insulating film or prepreg can improve the characteristic of a glass transition temperature, a thermal expansion coefficient, and tensile strength.

  The printed circuit board manufactured by laminating one or more circuit layers or insulating layers on one surface or the other surface of the insulating film, prepreg, or copper clad laminate has a glass transition temperature, a thermal expansion coefficient, and a tensile strength. The characteristics can be improved.

1 is a schematic view illustrating a configuration of an insulating resin composition for a printed circuit board according to an embodiment of the present 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 schematic view illustrating a configuration of an insulating resin composition for a printed circuit board according to an embodiment of the present invention.

  Referring to FIG. 1, an insulating resin composition including a polyethersulfone resin capable of maintaining heat resistance, a low coefficient of thermal expansion, and a high glass transition temperature, and a product using the insulating resin composition include a glass transition temperature and a thermal expansion coefficient. And tensile strength 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 a naphthalene-based epoxy resin that can achieve high heat resistance, low moisture absorption, and low thermal expansion. The epoxy resin contains two or three functional groups (epoxide groups) in the molecule, and can improve the bonding strength with other compositions.

  The epoxy resin is for improving the heat resistance of the resin composition, and the functional group introduced at the terminal can be easily packed when the resin composition is cured. In addition, since a phenomenon in which planar chromophores such as aromatic rings are stacked by dispersion force or hydrophobic interaction, that is, a stacking structure is formed, deformation due to heat can be minimized.

  The naphthalene-based epoxy resin may be an ester naphthalene-based epoxy resin represented by the following chemical formulas 1 and 2 or a mixture thereof.

  The naphthalene-based epoxy resin represented by the chemical formula 1 and the chemical formula 2 is rigid and thus has thermal stability. In addition, a network interconnected with the bismaleimide resin can be formed, and high heat resistance can be realized.

  In the insulating resin composition according to an embodiment of the present invention, the amount of the epoxy resin used is not particularly limited, but it is appropriate to use 5 to 30% by weight. More specifically, when the amount of the epoxy resin used is 5 to 15% by weight, the optimum condition can be obtained. If the amount of the epoxy resin used is less than 5% by weight, the adhesive strength of the resin composition may be weakened. If it exceeds 30% by weight, the thermal expansion coefficient of the resin composition increases. obtain.

(Cyanate ester resin)
The insulating resin composition for a printed circuit board according to an embodiment of the present invention may contain a cyanate ester resin in order to reduce the melt viscosity of the resin composition. Low melt viscosity ensures the flowability of the resin composition even when the inorganic filler content is high, and prevents product defects such as voids and delamination, and is reliable. Can be realized. Moreover, heat resistance and a low thermal expansion coefficient are realizable because the resin composition contains the said cyanate ester resin.

  The cyanate ester resin may be a phenol novolac type cyanate ester resin represented by the following chemical formula 3.

  In formula, n is an integer of 0-3.

  In the insulating resin composition according to one embodiment of the present invention, the amount of cyanate ester resin used is not particularly limited, but it is appropriate to use 5 to 40% by weight. More specifically, when the amount of the cyanate ester resin used is 5 to 20% by weight, the optimum condition can be obtained. When the amount of the cyanate ester resin used is less than 5% by weight, the heat resistance may be lowered, and when it exceeds 40% by weight, a curing degree suitable as a printed circuit board material is realized. Since there is a limit to the reliability, the reliability can be lowered.

(Polyethersulfone resin)
An insulating resin composition for a printed circuit board according to an embodiment of the present invention includes a polyethersulfone resin in order to maintain heat resistance, a low coefficient of thermal expansion, a high glass transition temperature, and improve brittleness. be able to. The polyethersulfone resin has an effect of promoting the formation of a triazine ring of a cyanate ester resin and realizing high heat resistance and a low coefficient of thermal expansion. Moreover, even when the content of the inorganic filler in the resin composition is large, it is possible to prevent the brittleness of the cured product from increasing.

  The polyethersulfone resin includes a phenolic hydroxyl group and may be represented by the following chemical formula 4.

式中、ｎは１〜３の整数である。この際、ｎが１未満である場合には、脆性が低下する恐れがあり、ｎが３を超過する場合には、熱膨張係数が増加し、ガラス転移温度が低くなって、熱的特性が低下し得る。

In the formula, n is an integer of 1 to 3. At this time, when n is less than 1, brittleness may be reduced, and when n exceeds 3, the thermal expansion coefficient is increased, the glass transition temperature is lowered, and the thermal characteristics are reduced. Can be reduced.

  Since the polyethersulfone resin contains a phenolic hydroxyl group in the molecule, it can undergo a curing reaction with a resin such as epoxy, bismaleimide, and cyanate ester. Therefore, heat resistance and brittleness can be improved by using the polyethersulfone resin of the present invention as a curing agent without using a conventional curing agent conventionally used.

  In addition, the polyethersulfone resin may have a bisphenol A type structure represented by the following chemical formula 8.

式中、ｎは１〜３の整数である。

In the formula, n is an integer of 1 to 3.

  In the insulating resin composition according to an embodiment of the present invention, the amount of the polyethersulfone resin used is not particularly limited, but it is appropriate to use 3 to 15% by weight. More specifically, when the amount of the polyethersulfone resin used is 3 to 10% by weight, the optimum condition can be obtained. If the amount of the polyethersulfone resin used is less than 3% by weight, the tensile strength may decrease, and if it exceeds 15% by weight, the crosslinking density is lowered and the glass transition temperature is lowered. Thus, the thermal expansion coefficient can be increased.

(Bismaleimide resin)
The insulating resin composition for a printed circuit board according to an embodiment of the present invention may include a bismaleimide resin in order to improve glass transition temperature characteristics. The bismaleimide resin may be cured by a Michael reaction with the hydroxyl group of the polyethersulfone resin or may be homopolymerized.

  The bismaleimide resin may be a compound represented by the following chemical formula 5, chemical formula 6, or chemical formula 7, or a mixture thereof.

  In the formula, n is an integer of 1 to 3.

  In the insulating resin composition according to one embodiment of the present invention, the amount of bismaleimide resin used is not particularly limited, but it is appropriate to use it at 1 to 10% by weight. More specifically, when the amount of bismaleimide resin used is 2 to 8% by weight, the optimum condition can be obtained. If the amount of the bismaleimide resin used is less than 1% by weight, the glass transition temperature may be lowered. If it exceeds 10% by weight, the solubility is lowered and high temperature curing conditions are required. Therefore, processability may be reduced.

(Inorganic filler)
The insulating resin composition for a printed circuit board according to an embodiment of the present invention may include an inorganic filler in order to realize a low thermal expansion coefficient of the resin composition.

  The inorganic filler is not particularly limited, but may have an average particle size of 0.05 to 1 μm, and the same or different inorganic fillers can be used.

The inorganic filler is silica (SiO ₂ ), alumina (Al ₂ O ₃ ), barium sulfate (BaSO ₄ ), talc, aluminum hydroxide (AlOH ₃ ), magnesium hydroxide (Mg (OH) ₂ ), calcium carbonate (CaCO _3), magnesium carbonate (MgCO _3), selected of magnesium oxide (MgO), boron nitride (BN), aluminum borate (alBO _3), barium titanate (BaTiO _3), and calcium zirconate (CaZrO ₃₎ When silica or alumina is used, the optimum effect for achieving a low coefficient of thermal expansion can be obtained.

  In the insulating resin composition according to one embodiment of the present invention, the amount of the inorganic filler used is not particularly limited, but it is appropriate to use it at 50 to 80% by weight. More specifically, when the amount of the inorganic filler used is 60 to 75% by weight, the optimum condition can be obtained. If the amount of the inorganic filler used is less than 50% by weight, the thermal expansion coefficient may increase. If it exceeds 80% by weight, the adhesive strength may be reduced.

  The insulating resin composition according to an embodiment of the present invention may further include a curing accelerator in order to improve the curing rate.

  The curing accelerator may be one or more selected from a metal curing accelerator, an imidazole curing accelerator, and an amine curing accelerator.

  Although it does not restrict | limit especially as said metal type hardening accelerator, The organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetyl. Organic zinc complexes such as acetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate .

  Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. As the metal-based curing accelerator, in terms of curability and solvent solubility, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, zinc naphthenate, iron (III) Acetylacetonate is preferable, and cobalt (II) acetylacetonate and zinc naphthenate are particularly preferable. Moreover, a metal type hardening accelerator can be used 1 type or in combination of 2 or more types.

  The imidazole curing accelerator is not particularly limited, but 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl. Imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1- Cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4 - Mino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ′)]-Ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2, 3-dihydroxy-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methyli Dazorin, additive of 2-phenyl imidazoline imidazole compounds such as and imidazole compound and an epoxy resin. Moreover, an imidazole hardening accelerator can be used 1 type or in combination of 2 or more types.

  The amine curing accelerator is not particularly limited, but trialkylamine such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1, And amine compounds such as 8-diazabicyclo (5,4,0) -undecene. Moreover, an amine hardening accelerator can be used 1 type or in combination of 2 or more types.

  An insulating film, a prepreg, a copper clad laminate, and a printed circuit board can be manufactured using the insulating resin composition according to an embodiment of the present invention.

  The insulating film according to an embodiment of the present invention can be manufactured into a semi-cured dry film by a conventional method known in this technical field. For example, a roll coater, a curtain coater, a comma coater, or the like is used to form a film, and after drying, it is applied on a substrate to form a multilayer by a build-up method. When manufacturing a printed circuit board, it can be used as an insulating layer (insulating film) or a prepreg. With this insulating film or prepreg, the characteristics of thermal expansion coefficient, glass transition temperature, and tensile strength can be improved.

  As described above, a prepreg can be produced by impregnating glass fiber into a varnish containing an insulating resin composition according to an embodiment of the present invention.

  The glass fiber may be one or more selected from E glass, T glass, NE glass, and S glass. More specifically, for example, E2116 and T2116 manufactured by Nitto Boseki Co., Ltd., E2116 and S2116 manufactured by Asahi Kasei E-Materials Co., Ltd. and the like can be mentioned.

  Also, a printed circuit board is manufactured by laminating an insulating film or prepreg manufactured with an insulating resin composition according to an embodiment of the present invention on a copper clad laminate (CCL) used as an inner layer of the printed circuit board. be able to. For example, an insulating film or prepreg manufactured with the insulating resin composition is laminated and cured on a patterned inner layer circuit board, and after performing a desmear process, a circuit layer is formed by an electroplating process. A printed circuit board can be manufactured.

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

(Manufacture of polyethersulfone resin)
(Production Example 1)
38.5 g of a naphthalene phenol curing agent represented by the following chemical formula 9, 25.16 g (bis- (4-chlorophenyl) sulfone, Sigma-Aldrich) represented by the following chemical formula 10, potassium carbonate (K ₂ CO ₃ , Sigma-Aldrich) 25.39 g, dimethylacetamide (DMAc, Samchun Pure Chemical Co.) 400 ml, and toluene (toluene, JT Baker) 50 ml in a two-neck round bottom flask (2 neck round blot) Added and stirred. The reaction conditions were performed while refluxing at about 150 ° C. for 4 hours. Thereafter, after further reaction for about 2 hours, the temperature was lowered to room temperature. A solution in which methanol and water were mixed at a ratio of 4: 1 was added to the reacted mixture, and when a precipitate was formed, it was first washed with water and finally washed with methanol. Finally, it was dried in a vacuum oven at 60 ° C. for 24 hours, thereby producing a polyethersulfone resin represented by the chemical formula 4.

(Example 1)
10.8 g of naphthalene type epoxy (HP-6000, EEW250) and 15 g of phenol novolac type cyanate ester (PT-30) were mixed together with 5 g of MEK (methyl ethyl ketone) solvent. To this, 101.1 g of a filler slurry (SC2050-MTE, Admatech) having a solid content of 69.2% containing 70 g of an inorganic filler surface-treated with GPTMS (Glyoxypropyl trimethylsilane) was added and stirred for about 30 minutes. . To the stirred mixture, 4.2 g of the polyethersulfone resin prepared in Preparation Example 1 and 0.081 g of 2-ethyl-4-methylimidazole (2E4MZ) were added, and the mixture was further stirred for about 30 minutes. A test piece was manufactured by applying this to a shiny surface of copper foil to a thickness of 80 μm by a doctor blade method. The manufactured test piece was dried in an oven at about 80 ° C. for 30 minutes and further at about 120 ° C. for 10 minutes so as to be in a semi-cured (B-stage) state. This was completely cured by a vacuum press (maximum temperature 230 ° C., maximum pressure 2 MPa).

(Example 2)
10.8 g of naphthalene type epoxy (HP-6000, EEW250) and 7.5 g of phenol novolac type cyanate ester (PT-30) were mixed together with 4 g of MEK (methyl ethyl ketone). To this, 101.1 g of a filler slurry (SC2050-MTE, Admatech) having a solid content of 69.2% containing 70 g of an inorganic filler surface-treated with GPTMS (Glyoxypropyl trimethylsilane) was added and stirred for about 30 minutes. . After 7.5 g of bismaleimide (BMI-2300) was added to the stirred mixture and stirred for 30 minutes, 4.2 g of the polyethersulfone resin prepared in Preparation Example 1 and 2-ethyl-4-methylimidazole ( 2E4MZ) (0.081 g) and DTBP (Di-tert-butyl peroxide) (0.075 g) were added, and the mixture was further stirred for 30 minutes. A test piece was manufactured by applying this to a shiny surface of copper foil to a thickness of 80 μm by a doctor blade method. The manufactured test piece was dried in an oven at about 80 ° C. for 30 minutes and further at about 120 ° C. for 10 minutes so as to be in a semi-cured (B-stage) state. This was completely cured by a vacuum press (maximum temperature 230 ° C., maximum pressure 2 MPa).

(Example 3)
10.8 g of naphthalene epoxy (HP-6000, EEW250) and 12 g of phenol novolac cyanate ester (PT-30) were mixed together with 5 g of MEK (methyl ethyl ketone). To this, 101.1 g of a filler slurry (SC2050-MTE, Admatech) having a solid content of 69.2% containing 70 g of an inorganic filler surface-treated with GPTMS (Glyoxypropyl trimethylsilane) was added and stirred for about 30 minutes. . After adding 3 g of bismaleimide (BMI-2300) to the stirred mixture and stirring for 30 minutes, 4.2 g of the polyethersulfone resin prepared in Preparation Example 1, 2-ethyl-4-methylimidazole (2E4MZ) 0.081 g and 0.03 g of DTBP (Di-tert-butyl peroxide) were added and further stirred for 30 minutes. A test piece was manufactured by applying this to a shiny surface of copper foil to a thickness of 80 μm by a doctor blade method. The manufactured test piece was dried in an oven at about 80 ° C. for 30 minutes and further at about 120 ° C. for 10 minutes so as to be in a semi-cured (B-stage) state. This was completely cured by a vacuum press (maximum temperature 230 ° C., maximum pressure 2 MPa).

Example 4
A varnish containing the insulating resin composition according to Example 2 was impregnated with glass fiber (E2116, Nitto Boseki Co., Ltd.), dried at 80 ° C., and then a prepreg was produced based on a basis weight of 210 g / m ² .

(Example 5)
A copper foil was applied to both sides of the prepreg produced in Example 4, and a copper-clad laminate was produced using a vacuum press at a temperature of 230 ° C. and a pressure of 2 MPa.

(Example 6)
After forming a circuit pattern on the copper clad laminate produced in Example 5 and drying at 120 ° C. for 30 minutes, the test piece produced in Example 2 was placed on a Morton CVA725 vacuum on both sides of the copper clad laminate. A printed circuit board was produced by vacuum laminating for 20 seconds under the conditions of a temperature of 90 ° C. and a pressure of 2 MPa using a laminator.

(Comparative Example 1)
8 g of cresol novolac epoxy (YD-128, EEW190, Kukdo Chemical) and 15 g of phenol novolac type cyanate ester (PT-30) were mixed with 5 g of MEK (methyl ethyl ketone) solvent. To this, 101.1 g of a filler slurry (SC2050-MTE, Admatech) having a solid content of 69.2% containing 70 g of an inorganic filler surface-treated with GPTMS (Glyoxypropyl trimethylsilane) was added and stirred for about 30 minutes. . To the stirred mixture, 4.2 g of the polyethersulfone resin prepared in Preparation Example 1 and 0.081 g of 2-ethyl-4-methylimidazole (2E4MZ) were added, and the mixture was further stirred for about 30 minutes. Thereafter, a test piece was manufactured under the same conditions as in Example 1.

(Comparative Example 2)
10.8 g of naphthalene type epoxy (HP-6000, EEW250) and 15 g of phenol novolac type cyanate ester (PT-30) were mixed together with 5 g of MEK (methyl ethyl ketone) solvent. To this, 101.1 g of a filler slurry (SC2050-MTE, Admatech) having a solid content of 69.2% containing 70 g of an inorganic filler surface-treated with GPTMS (Glyoxypropyl trimethylsilane) was added and stirred for about 30 minutes. . To the stirred mixture, 4.2 g of phenol novolac type curing agent (TD2090-60M, DIC) and 0.081 g of 2-ethyl-4-methylimidazole (2E4MZ) were added and further stirred for about 30 minutes. Thereafter, a test piece was manufactured under the same conditions as in Example 1.

(Comparative Example 3)
8 g of cresol novolac epoxy (YD-128, EEW190, Kukdo Chemical) and 15 g of phenol novolac type cyanate ester (PT-30) were mixed with 5 g of MEK (methyl ethyl ketone) solvent. To this, 101.1 g of a filler slurry (SC2050-MTE, Admatech) having a solid content of 69.2% containing 70 g of an inorganic filler surface-treated with GPTMS (Glyoxypropyl trimethylsilane) was added and stirred for about 30 minutes. . To the stirred mixture, 4.2 g of phenol novolac type curing agent (TD2090-60M, DIC) and 0.081 g of 2-ethyl-4-methylimidazole (2E4MZ) were added and further stirred for about 30 minutes. Thereafter, a test piece was manufactured under the same conditions as in Example 1.

(Measuring method)
The physical properties of the test pieces manufactured according to Examples 1 to 3 and Comparative Examples 1 to 3 were measured as follows. The glass transition temperature (Tg) and the tensile strength (Tensile strength) were measured in a temperature range of 30 to 350 ° C. using a DMA (Dynamic mechanical analyzer, TA Instruments, Q800 model). The glass transition temperature was calculated by the maximum value of the Tan delta value (maximum peak).

  The coefficient of thermal expansion (CTE) was measured at a primary scan of 30 to 310 ° C., a secondary scan of 310 to 10 ° C., and a tertiary scan of 10 to 300 ° C. using TMA (Thermal mechanical analyzer, TA Instruments, Q400 model). Thereafter, the thermal expansion coefficient at 50 to 100 ° C. was further measured by a third scan.

  Referring to Table 1, the test pieces manufactured with the insulating resin compositions according to Examples 1 to 3 of the present invention have a glass transition temperature and a thermal expansion coefficient as compared with the test pieces manufactured according to Comparative Examples 1 to 3. It can be seen that the properties of the tensile strength are remarkably excellent. For this reason, when the polyethersulfone resin produced in Production Example 1 is used as a curing agent like the test pieces produced with the insulating resin compositions according to Examples 1 to 3 of the present invention, the polyether It can be seen that the terminal hydroxyl group (OH) of the sulfone resin effectively cures with the epoxy resin, bismaleimide resin, and cyanate ester resin.

  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 a printed circuit board and a product using the same.

Claims (13)

Naphthalene epoxy resin,
A cyanate ester resin;
Polyethersulfone resin,
Bismaleimide resin,
An insulating resin composition for a printed circuit board, comprising an inorganic filler.   5-30 wt% naphthalene epoxy resin, 5-40 wt% cyanate ester resin, 3-15 wt% polyethersulfone resin, 1-10 wt% bismaleimide resin, 50-80 wt% The insulating resin composition for printed circuit boards according to claim 1, comprising: 2. The insulating resin composition for a printed circuit board according to claim 1, wherein the naphthalene-based epoxy resin is an ester-type naphthalene-based epoxy resin represented by the following chemical formulas 1 and 2 or a mixture thereof.

The insulating resin composition for a printed circuit board according to claim 1, wherein the cyanate ester resin is a phenol novolac-type cyanate ester resin represented by the following chemical formula 3.

In formula, n is an integer of 0-3. The insulating resin composition for a printed circuit board according to claim 1, wherein the polyethersulfone resin contains a phenolic hydroxyl group and is represented by the following chemical formula 4.

In the formula, n is an integer of 1 to 3. The insulating resin composition for a printed circuit board according to claim 1, wherein the bismaleimide resin is a compound represented by the following chemical formula 5, chemical formula 6, or chemical formula 7 or a mixture thereof.

In the formula, n is an integer of 1 to 3.

  The insulating resin composition for a printed circuit board according to claim 1, wherein the inorganic filler has an average particle diameter of 0.05 to 1 μm. The inorganic filler is silica (SiO ₂ ), alumina (Al ₂ O ₃ ), barium sulfate (BaSO ₄ ), talc, aluminum hydroxide (AlOH ₃ ), magnesium hydroxide (Mg (OH) ₂ ), calcium carbonate (CaCO _3), magnesium carbonate (MgCO _3), selected of magnesium oxide (MgO), boron nitride (BN), aluminum borate (alBO _3), barium titanate (BaTiO _3), and calcium zirconate (CaZrO ₃₎ The insulating resin composition for printed circuit boards according to claim 1, wherein the insulating resin composition is one or more.   The insulating resin composition for a printed circuit board according to claim 1, further comprising a curing accelerator.   The insulating resin composition for a printed circuit board according to claim 9, wherein the curing accelerator is at least one selected from a metal curing accelerator, an imidazole curing accelerator, and an amine curing accelerator.   A prepreg produced by impregnating glass fiber into a varnish containing the insulating resin composition according to claim 1.   The prepreg according to claim 11, wherein the glass fiber is one or more selected from E glass, T glass, NE glass, and S glass.   Printing produced by laminating one or more circuit layers or insulating layers on one side or the other side of a copper clad laminate (CCL) produced by laminating copper foil on both sides of the prepreg according to claim 11. Circuit board.

Images