JP2015005712A - Insulator film for printed-circuit board, and product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulator film for a printed-circuit board having low thermal expansion coefficient and high peel strength characteristics, and a product using the same.SOLUTION: An insulator film 131 for a printed-circuit board comprises: a core layer 10; and primer layers 20 laminated on opposite sides of the core layer 10 and containing a polyamide-imide resin.

Description

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

  As electronic devices become smaller and higher performance, multilayer printed circuit boards are also required to have higher density, higher functionality, smaller size, and thinner film. In particular, a build-up layer of a multilayer printed circuit board is made into a multi-layer, and development for miniaturization and high density of wiring is being performed.

  Also in the insulating layer of the multilayer printed circuit board, thermal characteristics, mechanical characteristics, and electrical characteristics are important. In order to minimize warpage caused by reflow during the mounting process of electronic devices and electrical devices, characteristics of low thermal expansion coefficient, high glass transition temperature and modulus are required.

  In recent years, with the development of electronic devices, various build-up layers used in multilayer printed circuit boards used in the electronic devices have various types to improve the thermal properties, mechanical properties, and electrical properties of the insulating layer. Methods are being studied.

  In order to realize high peel strength, low dielectric constant, and low thermal expansion coefficient, resin compositions characterized by containing specific epoxy resins have been studied. However, the effect of improving the physical properties is not sufficient.

  On the other hand, Patent Document 1 discloses an insulating composition containing an epoxy resin and a maleimide resin as thermosetting resins and a polyamideimide resin as a thermoplastic resin. However, the thermosetting resin and the thermoplastic resin are disclosed as follows. In addition, it is difficult to realize the peel strength between the metal layer and the insulating layer in that the thermoplastic resin contains an inorganic filler, and the thermal expansion of the insulating layer is difficult. There was a problem that the coefficient could not be reduced sufficiently.

JP 2007-092072 A

  In the insulating film for printed circuit boards, the inventors have an insulating film comprising a core layer and a primer layer that is laminated on both surfaces of the core layer and includes a polyamideimide resin, and a product manufactured using the insulating film. Based on this finding, the present invention was completed.

  Accordingly, a first object of the present invention is to provide an insulating film for a printed circuit board having characteristics of a low thermal expansion coefficient and a high peel strength.

  The second object of the present invention is to provide a resin with a copper foil (RCC) or a flexible copper clad laminate (FCCL) made of the insulating film.

  A third object of the present invention is to provide a prepreg for a printed circuit board having characteristics of a low thermal expansion coefficient and a high peel strength.

  The fourth object of the present invention is to provide a copper clad laminate (CCL) comprising the prepreg.

  A fifth object of the present invention is to provide a printed circuit board comprising the resin with copper foil or a flexible copper clad laminate.

  The sixth object of the present invention is to provide a multilayer printed circuit board comprising the prepreg.

  In order to achieve the first object of the present invention, the printed circuit board insulating film (hereinafter referred to as "first invention") is a core layer and a primer laminated on both surfaces of the core layer and containing a polyamideimide resin And a layer.

  In the first invention, the core layer includes a liquid crystal oligomer, an epoxy resin, a bismaleimide resin, and an inorganic filler, and the primer layer includes a polyamideimide resin and an epoxy resin. And

  1st invention WHEREIN: The said core layer is 2-20 weight% liquid crystal oligomer, 5-20 weight% epoxy resin, 2-20 weight% bismaleimide resin, and 40-90 weight% inorganic filler. It is characterized by including these.

  1st invention WHEREIN: The said primer layer is characterized by including 50-80 weight% polyamide imide resin and 20-50 weight% epoxy resin.

  In the first invention, the liquid crystal oligomer has a number average molecular weight of 3000 to 5000 g / mol, and is a compound represented by the following chemical formula 1, chemical formula 2, chemical formula 3, or chemical formula 4, or a mixture thereof: And

(In said chemical formulas 1-4, a is an integer of 13-26, b is an integer of 13-26, c is an integer of 9-21, d is an integer of 10-30, e is It is an integer of 10-30.)

  In the first invention, the epoxy resin contained in the core layer or the primer layer includes naphthalene type epoxy resin, bisphenol A type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, rubber-modified epoxy resin, phosphorus type epoxy resin and It is one or more selected from bisphenol F type epoxy resins.

  In the first invention, the bismaleimide resin is a compound represented by the following chemical formula 5, chemical formula 6, or chemical formula 7, or a mixture thereof.

(Here, n is an integer of 1 to 3.)

In the first invention, the inorganic filler is silica (SiO ₂ ), alumina (Al ₂ O ₃ ), silicon carbide (SiC), barium sulfate (BaSO ₄ ), talc, clay, mica powder, aluminum hydroxide (AlOH) _3), magnesium hydroxide (Mg _(OH) 2), calcium carbonate (CaCO _3), magnesium carbonate (MgCO _3), magnesium oxide (MgO), boron nitride (BN), aluminum borate (albo _3), titanate It is at least one selected from barium (BaTiO ₃ ) and calcium zirconate (CaZrO ₃ ), and has an average particle size of 0.05 to 2 μm.

  In the first invention, the polyamideimide resin is a compound represented by the following chemical formula 8, chemical formula 9, or chemical formula 10, or a mixture thereof.

(Here, n is an integer of 1 to 50.)

(Here, n is an integer of 1 to 50.)

  In the first invention, the core layer has a thickness of 80 to 94 μm, and the primer layer has a thickness of 3 to 10 μm.

  In the first invention, each of the core layer and the primer layer further includes a curing agent, a curing accelerator, or a combination thereof.

  In the first invention, the curing agent is selected from an amine curing agent, an acid anhydride curing agent, a polyamine curing agent, a polysulfate curing agent, a phenol novolac curing agent, a bisphenol A curing agent and a dicyandiamide curing agent. It is characterized by being one or more.

  In the first invention, the curing accelerator is one or more selected from a metal curing accelerator, an imidazole curing accelerator, and an amine curing accelerator.

  A resin with a copper foil (RCC) or a flexible copper clad laminate (FCCL) (hereinafter referred to as “second invention”) for achieving the second object of the present invention is a copper foil on one side or both sides of the insulating film. Are laminated and pressure-bonded.

  A prepreg for achieving the third object of the present invention (hereinafter referred to as “third invention”) is a mixture of a resin composition containing a liquid crystal oligomer, an epoxy resin, a bismaleimide resin, and an inorganic filler. A primer layer containing a polyamideimide resin is laminated on both surfaces of a core layer obtained by impregnating and drying organic fibers or inorganic fibers in the varnish.

  A copper-clad laminate (CCL) (hereinafter referred to as “fourth invention”) for achieving the fourth object of the present invention is formed by laminating and pressing a copper foil on one or both surfaces of the prepreg.

  A printed circuit board for achieving the fifth object of the present invention is obtained by laminating and laminating a resin with a copper foil or a flexible copper-clad laminate according to the second invention on a substrate on which a circuit pattern is formed.

  A printed circuit board for achieving the sixth object of the present invention is obtained by laminating an insulating film on a copper clad laminate (CCL) obtained by laminating copper foil on one or both sides of a prepreg according to the third invention. Become.

  In an insulating film for a printed circuit board according to a typical embodiment of the present invention, an insulating film including a core layer and a primer layer that is laminated on both surfaces of the core layer and includes a polyamide-imide resin, and the insulating film is manufactured using the insulating film. The product can exhibit a low coefficient of thermal expansion and a high peel strength.

  The features and advantages of the present invention will become more apparent from the following detailed description taken in conjunction with the accompanying drawings.

It is sectional drawing of the insulating film which concerns on this invention. It is sectional drawing of general resin with copper foil (RCC) which can apply the insulating film which concerns on this invention. It is sectional drawing of the general flexible copper clad laminated board (FCCL) which can apply the insulating film which concerns on this invention. It is sectional drawing of the general prepreg (PPG) which can apply the insulating film which concerns on this invention. It is sectional drawing of the general copper clad laminated board (CCL) which can apply the insulating film which concerns on this invention. It is sectional drawing of the general printed circuit board which can apply the insulating film which concerns on 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.

  The present invention includes, for example, a printed circuit board insulating film as shown in FIG. 1, and includes a core layer 10 and a primer layer 20 laminated on both surfaces of the core layer 10 and containing polyamideimide (PAI). Using the insulating film 131 for printed circuit boards, a resin with copper foil (RCC), a flexible copper-clad laminate (FCCL), a prepreg (PPG), a copper-clad laminate (CCL), and a printed circuit board are provided.

(Core layer)
The core layer of the insulating film according to the exemplary embodiment of the present invention includes a liquid crystal oligomer, an epoxy resin, a bismaleimide resin, and an inorganic filler.

  The core layer has a thickness of 80 to 94 μm, preferably 86 to 94 μm. If the thickness of the core layer is less than 80 μm, the thermal expansion coefficient in the insulating film may increase, and if it exceeds 94 μm, it may be difficult to implement a fine circuit pattern.

  The liquid crystal oligomer is preferably a compound represented by the following chemical formula 1, the following chemical formula 2, the following chemical formula 3, or the following chemical formula 4, or a mixture thereof.

(In said chemical formulas 1-4, a is an integer of 13-26, b is an integer of 13-26, c is an integer of 9-21, d is an integer of 10-30, e is It is an integer of 10-30.)

  The liquid crystal oligomers represented by the chemical formulas 1 to 4 include an ester group at both ends of the main chain for improving the dielectric loss tangent and the dielectric constant, and include a naphthalene group for crystallinity. The liquid crystal oligomer represented by Formula 4 may contain a phosphorous component that imparts flame retardancy. In addition, the liquid crystal oligomer represented by the chemical formula 1 and the chemical formula 2 includes a hydroxy group at a terminal, and the liquid crystal oligomer represented by the chemical formula 3 and the chemical formula 4 includes a nadimide at a terminal. A thermosetting reaction can be performed with an epoxy resin or a bismaleimide resin.

  In the core layer in the insulating film according to a typical embodiment of the present invention, the amount of the liquid crystal oligomer used is not particularly limited, but is preferably 2 to 20% by weight. When the amount of the liquid crystal oligomer used is less than 2% by weight, the thermal expansion coefficient tends to increase, and when it exceeds 20% by weight, the chemical resistance may be lowered.

  The number average molecular weight of the liquid crystal oligomer is preferably 3000 to 5000 g / mol, and more preferably 3500 to 5500 g / mol. When the number average molecular weight of the liquid crystal oligomer is less than 3000 g / mol, there may be a problem that the mechanical properties are inferior, and when it exceeds 5000 g / mol, there may be a problem that the solubility is lowered.

  The epoxy resin is one or more selected from naphthalene type epoxy resin, bisphenol A type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, rubber-modified epoxy resin, phosphorus type epoxy resin and bisphenol F type epoxy resin. Preferably, it is a naphthalene type epoxy resin or a bisphenol F type epoxy resin.

  In the core layer in the insulating film according to the representative embodiment of the present invention, the amount of the epoxy resin used is not particularly limited, but is preferably 5 to 20% by weight. If the amount of the epoxy resin used is less than 5% by weight, the peel strength tends to decrease, and if it exceeds 20% by weight, the thermal expansion coefficient can be increased.

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

(Here, n is an integer of 1 to 3.)

  The bismaleimide resins represented by the chemical formulas 5 to 7 exhibit high glass transition temperature (Tg) characteristics, thereby minimizing printed circuit board warpage and increasing reliability. And the hydroxy group of the compound can be linked by a Michael reaction.

  In the core layer in the insulating film according to the typical embodiment of the present invention, the amount of the bismaleimide resin used is not particularly limited, but is preferably 2 to 20% by weight. If the amount of the bismaleimide resin used is less than 2% by weight, the glass transition temperature tends to decrease, and if it exceeds 20% by weight, the solubility is lowered and curing conditions at high temperatures are required. May be reduced.

The inorganic filler includes silica (SiO ₂ ), alumina (Al ₂ O ₃ ), silicon carbide (SiC), barium sulfate (BaSO ₄ ), talc, clay, mica powder, aluminum hydroxide (AlOH ₃ ), and hydroxide. magnesium (Mg _(OH) 2), calcium carbonate (CaCO _3), magnesium carbonate (MgCO _3), magnesium oxide (MgO), boron nitride (BN), aluminum borate (alBO _3), barium titanate (BaTiO ₃₎ And calcium zirconate (CaZrO ₃ ) may be used alone or in combination of two or more.

  The inorganic filler is not particularly limited, but the average particle size is preferably 0.05 to 2 μm, and the same or different inorganic fillers may be used.

  In the core layer in the insulating film according to a typical embodiment of the present invention, the amount of the inorganic filler used is 40 to 90% by weight, preferably 60 to 90% by weight, more preferably 70 to 90% by weight, Preferably it is 75 to 85 weight%. When the amount of the inorganic filler used is less than 40% by weight, the dielectric loss tangent is low and the thermal expansion coefficient tends to increase, and when it exceeds 90% by weight, the peel strength tends to decrease.

  The core layer is composed of a liquid crystal oligomer-epoxy resin (reaction between the hydroxyl group of the liquid crystal oligomer and the epoxide group of the epoxy resin), a liquid crystal oligomer-bismaleimide resin (reaction between the hydroxy group of the liquid crystal oligomer and the double bond of the bismaleimide resin). ), Bismaleimide resin-curing agent (reaction of bismaleimide resin double bonds with amine or hydroxy group of curing agent) and epoxy resin-curing agent (epoxide group of epoxy resin and amine or hydroxy group of curing agent) In this case, they are connected to each other by a Michael reaction to form a network connected to each other, and can exhibit high heat resistance characteristics.

(Primer layer)
The primer layer of the insulating film according to a typical embodiment of the present invention includes a polyamideimide resin and an epoxy resin, and is laminated on both surfaces of the core layer.

  The primer layer has a thickness of 3 to 10 μm, preferably 3 to 7 μm. If the thickness of the primer layer is less than 3 μm, the primer layer itself may be lost by the desmear process, the peel strength may be reduced, and it may be difficult to implement a fine circuit. May increase.

  The polyamideimide resin is preferably a compound represented by the following chemical formula 8, the following chemical formula 9, or the following chemical formula 10, or a mixture thereof.

(Here, n is an integer of 1 to 50.)

(Here, n is an integer of 1 to 50.)

  The polyamideimide resin represented by the chemical formulas 8 to 10 has characteristics of high heat resistance and low thermal expansion coefficient, and does not need to include an inorganic filler. Therefore, this can increase the peel strength from the copper foil, and can advantageously act in forming a fine circuit.

  In the primer layer in the insulating film according to a typical embodiment of the present invention, the amount of the polyamideimide resin used is 50 to 80% by weight, preferably 70 to 80% by weight. If the amount of the polyamideimide resin used is less than 50% by weight, the coefficient of thermal expansion tends to increase, and if it exceeds 80% by weight, the viscosity in the solution state becomes high and the workability may decrease. .

  In the primer layer in the insulating film according to a typical embodiment of the present invention, the epoxy resin includes a naphthalene-based epoxy resin, a bisphenol A-type epoxy resin, a phenol novolac epoxy resin, a cresol novolac epoxy resin, a rubber-modified epoxy resin, phosphorus One or more selected from a bisphenol F epoxy resin and a bisphenol F epoxy resin may be used, and a naphthalene epoxy resin or a bisphenol F epoxy resin is preferable.

  Moreover, the usage-amount of an epoxy resin in the said primer layer is although it does not restrict | limit in particular, 20 to 50 weight% is preferable. If the amount of the epoxy resin used is less than 20% by weight, the workability tends to decrease, and if it exceeds 50% by weight, the thermal expansion coefficient can be increased.

  In the insulating film for a printed circuit board according to a typical embodiment of the present invention, a curing agent, a curing accelerator, or a combination thereof can be selectively used for each of the core layer and the primer layer.

  Any curing agent can be used as long as it contains a reactive group capable of reacting with an epoxide ring contained in an epoxy resin, and is not particularly limited. Specific examples include amine curing agents, acid anhydride curing agents, polyamine curing agents, polysulfate curing agents, phenol novolac curing agents, bisphenol A curing agents, dicyandiamide curing agents, and the like. You may use it in combination of seed | species or 2 or more types. The curing agent may be used by appropriately selecting a use amount that does not lower the physical properties within a range of 0.1 to 1 part by weight with respect to 100 parts by weight of the core layer or the primer layer in view of the curing speed. it can.

  Examples of the curing accelerator include metal-based curing accelerators, imidazole-based curing accelerators, and amine-based curing accelerators, and these may be used alone or in combination.

  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 organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, glass 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 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. You may use a metal type hardening accelerator 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, 1,2 -Dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 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- Anoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-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-benzyl-imidazolium chloride, 2-methyl-imidazoline, 2-phenyl-imidazoline imidazole compounds such as and imidazole compounds and additives epoxy resins. One or more imidazole curing accelerators may be used in combination.

  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. You may use an amine hardening accelerator 1 type or in combination of 2 or more types.

  The insulating film for a printed circuit board according to a typical embodiment of the present invention is obtained by laminating and pressing a copper foil on one side or both sides, and for example, as shown in FIG. 2, the insulating film 131 is attached on the copper foil layer 50. Resin with copper foil (RCC) or a flexible copper-clad laminate (FCCL) in which the copper foil layers 50 are laminated on both surfaces of the insulating film 131 can be manufactured as shown in FIG.

  In addition, the resin composition forming the core layer in the insulating film according to a typical embodiment of the present invention is impregnated with a base material such as organic fiber or inorganic fiber and then cured, and a primer is formed on both surfaces of the core layer. For example, as shown in FIG. 4, a prepreg in which a primer layer 20 is laminated on both surfaces of a core layer 10 impregnated with organic fibers or inorganic fibers 5 can be manufactured. As shown in FIG. 5, a copper clad laminate (CCL) can be manufactured by pressing a copper foil layer 50 on one or both sides of the prepreg.

  The inorganic fiber is glass fiber, and the organic fiber is carbon fiber, polyparaphenylene benzobisoxazole fiber, thermotropic liquid crystal polymer fiber, lyotropic liquid crystal polymer fiber, aramid fiber, polypyridobisimidazole fiber, polybenzothiazole. You may use a fiber and a polyarylate fiber 1 type or in combination of 2 or more types.

  The insulating film of the present invention and a resin with a copper foil, a flexible copper clad laminate, and a prepreg produced using the insulating film are formed on a copper clad laminate (CCL) used as an inner layer when producing a multilayer printed circuit board. Laminated and used in the manufacture of multilayer printed circuit boards.

  FIG. 5 is a general cross-sectional view showing a printed circuit board manufactured in this manner.

  That is, the printed circuit board 100 is roughly divided into an insulating layer and a circuit layer. Referring to FIG. 6, circuit layers 132 are formed on both sides of the insulator 110, and a build-up film is formed on the circuit layer. Insulating layer 131 is formed, and circuit layer 132 is formed thereon to form continuous buildup layer 130.

  Such a printed circuit board may include a capacitor 140, a resistance element 150, or other electronic components 120 as necessary, and a solder resist 160 layer is provided on the outermost side to protect the circuit board. ing.

  Further, such a printed circuit board may be provided with an external connection means 170 according to the electronic product to be mounted, and may be provided with a pad 180 layer when necessary. The printed circuit board manufactured according to the representative embodiment of the present invention not only has excellent thermal expansion coefficient characteristics but also has excellent peel strength between the insulating layer and the metal layer.

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

(Manufacture of core layer)
[Production Example 1]
A liquid crystal oligomer solution was prepared by adding 6 g of a liquid crystal oligomer containing a hydroxyl group at the end to 6 g of N, N′-dimethylacetamide (DMAc), and 102.41 g of a silica (SiO ₂ ) slurry was added thereto. Stir for 30 minutes. 8 g of epoxy resin Araldite MY-721 (manufactured by Huntsman) and 6 g of bismaleimide (BMI-2300) were added thereto and stirred for 1 hour. Next, 0.08 g of dicyandiamide (DICY) and 0.09 g of azobisisobutyronitrile (AIBN) were added, and the mixture was further stirred for 30 minutes to produce a resin composition. The resin composition is applied to a smooth surface of copper foil by a doctor blade method to a thickness of about 80 μm to produce a film, and the film is dried in an oven at 80 ° C. and 120 ° C. for 30 minutes, A semi-cured (B-stage) core layer was produced.

(Manufacture of insulation film)
[Example 1]
Add 4 g of N, N′-dimethylacetamide (DMAc) to 43.64 g of polyamideimide resin containing a carboxyl group at the end and dissolved in N, N′-dimethylacetamide (DMAc). 3 g of epoxy resin (HP-4710, DIC) was added and stirred for 1 hour. This was applied to a smooth surface of copper foil by a doctor blade method at a thickness of about 10 μm to produce a film, and the film was dried in an oven at 80 ° C. and 120 ° C. for 30 minutes, respectively, and semi-cured (B-stage) ) State of the primer layer. Next, the primer layers were laminated on top and bottom with the core layer obtained from Production Example 1 interposed therebetween, and were completely cured using a vacuum press to produce an insulating film (maximum temperature 230 ° C., Maximum pressure 2 MPa).

[Example 2]
Add 6g of N, N'-dimethylacetamide (DMAc) to 36.36g of polyamideimide resin containing carboxyl group at the end and dissolved in N, N'-dimethylacetamide (DMAc), 4-functional naphthylene series Epoxy resin (HP-4710, DIC) 5 g was added and stirred for 1 hour to produce a semi-cured film under the same conditions as in Example 1. Next, the primer layers were laminated on top and bottom with the core layer obtained from Production Example 1 interposed therebetween, and were completely cured using a vacuum press to produce an insulating film (maximum temperature 230 ° C., Maximum pressure 2 MPa).

[Example 3]
N-N′-dimethylacetamide (DMAc) 9 g is added to 29.09 g of polyamideimide resin containing a carboxyl group at the end and dissolved in N, N′-dimethylacetamide (DMAc), and a tetrafunctional naphthylene system 8 g of epoxy resin (HP-4710, DIC) was added and stirred for 1 hour, and a semi-cured film was produced under the same conditions as in Example 1. Next, the primer layers were laminated on top and bottom with the core layer obtained from Production Example 1 interposed therebetween, and were completely cured using a vacuum press to produce an insulating film (maximum temperature 230 ° C., Maximum pressure 2 MPa).

[Comparative Example 1]
A liquid crystal oligomer solution is prepared by adding 8.1 g of a liquid crystal oligomer containing a hydroxyl group at a terminal to 48.1 g of N, N′-dimethylacetamide (DMAc), and 93.4 g of a silica (SiO ₂ ) slurry is added thereto. And stirred for 30 minutes. 10.8 g of epoxy resin Araldite MY-721 (manufactured by Huntsman) and 8.1 g of bismaleimide resin (BMI-2300) were added thereto and stirred for 1 hour. Next, 0.108 g of dicyandiamide (DICY) and 0.122 g of azobisisobutyronitrile (AIBN) were added and further stirred for 30 minutes. This is applied to the smooth surface of copper foil by a doctor blade method to a thickness of about 100 μm to produce a film, and the film is dried in an oven at 80 ° C. and 120 ° C. for 30 minutes, respectively, and is semi-cured The film was manufactured. Next, the film was completely cured using a vacuum press to produce an insulating film (maximum temperature 230 ° C., maximum pressure 2 MPa).

[Comparative Example 2]
A liquid crystal oligomer solution was prepared by adding 6 g of a liquid crystal oligomer containing a hydroxyl group at the end to 6 g of N, N′-dimethylacetamide (DMAc), and 102.41 g of a silica (SiO ₂ ) slurry was added thereto. Stir for 30 minutes. 8 g of epoxy resin Araldite MY-721 (manufactured by Huntsman) and 6 g of bismaleimide resin (BMI-2300) were added thereto and stirred for 1 hour. Next, 0.08 g of dicyandiamide (DICY) and 0.09 g of azobisisobutyronitrile (AIBN) were added and further stirred for 30 minutes. This is applied to the smooth surface of copper foil by a doctor blade method to a thickness of about 100 μm to produce a film, and the film is dried in an oven at 80 ° C. and 120 ° C. for 30 minutes, respectively, and is semi-cured The film was manufactured. Next, the film was completely cured using a vacuum press to produce an insulating film (maximum temperature 230 ° C., maximum pressure 2 MPa).

(Manufacture of resin with copper foil and flexible copper-clad laminate)
[Example 4]
A copper foil was laminated on one side or both sides of the insulating film produced in Example 1, and thermocompression bonded to produce a resin with copper foil and a flexible copper-clad laminate.

(Manufacture of prepreg)
[Example 5]
The varnish mixed with the resin composition of Production Example 1 was impregnated with glass fiber (manufactured by Baotek, 1078). The glass fiber impregnated with the resin composition passes through a heating zone at 200 ° C. and is semi-cured (B-stage), and the primer layers manufactured according to Example 1 are stacked on top and bottom, respectively. Thus, a prepreg was obtained.

(Manufacture of copper-clad laminate)
[Example 6]
A copper foil of about 12 μm was laminated on one side or both sides using the prepreg of Example 6 and laminated by thermocompression bonding under a vacuum of about 250 ° C. and 1 MPa to produce a copper-clad laminate.

(Manufacturing printed circuit boards)
[Example 7]
After the inner layer circuit board having copper foil laminated on both sides was dried at 120 ° C. for 30 minutes, the insulating film of Example 1 was placed on both sides for 20 seconds at 90 ° C. under 2 MPa using Morton CVA 725 vacuum laminate. Vacuum printed lamination produced a printed circuit board.

  Table 1 below shows the evaluation of physical properties of the insulating films prepared according to the examples and comparative examples.

  The thermal expansion coefficient was measured and evaluated using a thermomechanical analyzer (Thermo Mechanical Analysis, TMA) in a temperature range of 50 to 100 ° C., and thermomechanical analysis was performed by a tensile load method. After mounting the test piece on the apparatus, the measurement was performed under the measurement conditions of a heating rate of 5 ° C./min. The coefficient of thermal expansion (α1, Tg or less) in the measurement was calculated as the average linear thermal expansion coefficient (ppm) from 50 ° C. to 100 ° C. The peel strength was measured and evaluated by measuring the peel strength between the copper foil layer and the insulating layer using a tensile strength measuring device (Universal Testing Machine, UTM).

  As can be seen from Table 1, the thermal expansion coefficients and peel strengths of Examples 1 to 3 are superior to those of Comparative Examples 1 and 2, and the results of Example 1 are the best. Moreover, it was because content of the inorganic filler in the said insulating film generate | occur | produced exceeding 80 weight% that the peeling strength of the insulating film manufactured by the comparative example 2 was not able to be measured. Therefore, it can confirm that the insulating film which concerns on this invention is a level suitable as a material of a board | substrate.

  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 film for a printed circuit board and a product using the same.

5 Organic fiber or inorganic fiber 10 Core layer 20 Primer layer 50 Copper foil layer 100 Printed circuit board 110 Insulator 120 Electronic component 130 Build-up layer 131 Insulating film 132 Circuit layer 140 Capacitor 150 Resistive element 160 Solder resist 170 External connection means 180 Pad

(Manufacture of core layer)
[Production Example 1]
A liquid crystal oligomer solution is prepared by adding 6 g of a liquid crystal oligomer represented by Chemical Formula 2 containing a hydroxyl group at the terminal to 6 g of N, N′-dimethylacetamide (DMAc), and a silica (SiO ₂ ) slurry 102 is added thereto. .41 g was added and stirred for 30 minutes. To this, 8 g of epoxy resin Araldite MY-721 (manufactured by Huntsman) and 6 g of bismaleimide (BMI-2300) represented by Chemical Formula 5 were added and stirred for 1 hour. Next, 0.08 g of dicyandiamide (DICY) and 0.09 g of azobisisobutyronitrile (AIBN) were added, and the mixture was further stirred for 30 minutes to produce a resin composition. The resin composition is applied to a smooth surface of copper foil by a doctor blade method to a thickness of about 80 μm to produce a film, and the film is dried in an oven at 80 ° C. and 120 ° C. for 30 minutes, A semi-cured (B-stage) core layer was produced.

(Manufacture of insulation film)
[Example 1]
4 g of N, N′-dimethylacetamide (DMAc) is added to 43.64 g of polyamideimide resin represented by the chemical formula 9 containing a carboxyl group at the terminal and dissolved in N, N′-dimethylacetamide (DMAc). 3 g of tetrafunctional naphthylene epoxy resin (HP-4710, DIC) was added and stirred for 1 hour. This was applied to a smooth surface of copper foil by a doctor blade method at a thickness of about 10 μm to produce a film, and the film was dried in an oven at 80 ° C. and 120 ° C. for 30 minutes, respectively, and semi-cured (B-stage) ) State of the primer layer. Next, the primer layers were laminated on top and bottom with the core layer obtained from Production Example 1 interposed therebetween, and were completely cured using a vacuum press to produce an insulating film (maximum temperature 230 ° C., Maximum pressure 2 MPa).

Claims (18)

The core layer,
An insulating film for a printed circuit board, comprising: a primer layer that is laminated on both surfaces of the core layer and includes a polyamideimide resin.   The core layer includes a liquid crystal oligomer, an epoxy resin, a bismaleimide resin, and an inorganic filler, and the primer layer includes a polyamideimide resin and an epoxy resin. The insulating film for printed circuit boards described in 1.   The core layer includes 2 to 20 wt% liquid crystal oligomer, 5 to 20 wt% epoxy resin, 2 to 20 wt% bismaleimide resin, and 40 to 90 wt% inorganic filler. The insulating film for printed circuit boards according to claim 2.   3. The insulating film for a printed circuit board according to claim 2, wherein the primer layer includes 50 to 80 wt% polyamideimide resin and 20 to 50 wt% epoxy resin. 4. The number average molecular weight of the liquid crystal oligomer is 3000 to 5000 g / mol, and the liquid crystal oligomer is a compound represented by the following chemical formula 1, chemical formula 2, chemical formula 3, or chemical formula 4, or a mixture thereof. The insulating film for printed circuit boards described in 1.
(In said chemical formulas 1-4, a is an integer of 13-26, b is an integer of 13-26, c is an integer of 9-21, d is an integer of 10-30, e is It is an integer of 10-30.)   The epoxy resin contained in the core layer or primer layer includes naphthalene type epoxy resin, bisphenol A type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, rubber-modified epoxy resin, phosphorus type epoxy resin and bisphenol F type epoxy resin. The insulating film for a printed circuit board according to claim 2, wherein the insulating film is one or more selected from the group consisting of: The insulating film for a printed circuit board according to claim 2, 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.
(Here, n is an integer of 1 to 3.)
The inorganic filler includes silica (SiO ₂ ), alumina (Al ₂ O ₃ ), silicon carbide (SiC), barium sulfate (BaSO ₄ ), talc, clay, mica powder, aluminum hydroxide (AlOH ₃ ), and hydroxide. magnesium (Mg _(OH) 2), calcium carbonate (CaCO _3), magnesium carbonate (MgCO _3), magnesium oxide (MgO), boron nitride (BN), aluminum borate (alBO _3), barium titanate (BaTiO ₃₎ The insulating film for printed circuit boards according to claim 2, wherein the insulating film is one or more selected from calcium zirconate (CaZrO ₃ ) and has an average particle size of 0.05 to 2 μm. The insulating film for a printed circuit board according to claim 2, wherein the polyamide-imide resin is a compound represented by the following chemical formula 8, chemical formula 9, or chemical formula 10, or a mixture thereof.
(Here, n is an integer of 1 to 50.)
(Here, n is an integer of 1 to 50.)   2. The insulating film for a printed circuit board according to claim 1, wherein the core layer has a thickness of 80 to 94 μm and the primer layer has a thickness of 3 to 10 μm.   The insulating film for a printed circuit board according to claim 1, wherein each of the core layer and the primer layer further includes a curing agent, a curing accelerator, or a combination thereof.   The curing agent is at least one selected from amine curing agents, acid anhydride curing agents, polyamine curing agents, polysulfate curing agents, phenol novolac curing agents, bisphenol A curing agents and dicyandiamide curing agents. The insulating film for a printed circuit board according to claim 11.   The insulating film for a printed circuit board according to claim 11, wherein the curing accelerator is at least one selected from a metal curing accelerator, an imidazole curing accelerator, and an amine curing accelerator.   Resin with copper foil (RCC) or flexible copper clad laminated board (FCCL) formed by laminating | stacking and crimping | bonding copper foil on the single side | surface or both surfaces of the insulating film for printed circuit boards as described in any one of Claims 1-13. A core layer obtained by impregnating and drying organic fibers or inorganic fibers in a varnish obtained by mixing a resin composition containing a liquid crystal oligomer, an epoxy resin, a bismaleimide resin, and an inorganic filler;
A prepreg comprising a primer layer laminated on both surfaces of the core layer and containing a polyamideimide resin.   The copper clad laminated board (CCL) formed by laminating | stacking and crimping | bonding copper foil on the single side | surface or both surfaces of the prepreg of Claim 15.   The printed circuit board formed by laminating | stacking and laminating | stacking the resin with a copper foil of Claim 14, or a flexible copper clad laminated board on the board | substrate with which the circuit pattern was formed.   The multilayer printed circuit board formed by laminating | stacking an insulating film on the copper clad laminated board (CCL) obtained by laminating | stacking copper foil on the single side | surface or both surfaces of the prepreg of Claim 15.