KR20140074698A - Multi-layered printed circuit board and method of manufacturing the same - Google Patents

Abstract

The present invention provides an insulation resin sheet, a multilayered printed circuit board including the insulation resin sheet, and a manufacturing method for the same. The insulation resin sheet includes a low temperature expansion type first insulation resin layer containing an inorganic filler and a resin and a second insulation resin layer which is formed on one surface of the first insulation resin layer and which is capable of forming illumination intensity by using a desmear process. The present invention reduces the entire laminated thickness and provides a build-up printed circuit board capable of generating minute circuit patterns of high density while lowering expansion coefficient between layers of the board.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a multi-layer printed circuit board

The present invention relates to an insulating resin sheet for forming an insulating layer of a build-up printed circuit board capable of reducing the total stacking thickness and lowering the interlayer thermal expansion coefficient of the substrate while achieving a high density fine circuit pattern, And a method of manufacturing the same.

In recent years, due to the high functionality and miniaturization of electronic devices, high integration has been actively pursued in accordance with Moore's Law. As a result, there is a growing demand for a package substrate on which a semiconductor is mounted, in addition to high functionality and fine wiring, as well as thinness.

In order to meet these demands, a build-up board is used as a package substrate for semiconductor, in which insulating resin is laminated by a build-up method and a circuit is formed by a semi-custom method. . Here, the semi-additive method is one of the methods of forming a circuit of a PCB substrate. The method includes a subtractive method of forming a circuit pattern through etching and a method of forming a circuit by plating only a pattern part There is an advantage that a finer pattern can be formed than the subtractive method by a wiring formation method in which a field method (Additive) is combined.

On the other hand, in the conventional microcircuit build-up printed circuit board, since 100% resin is applied as an interlayer insulating material, there arises a problem that the coefficient of thermal expansion of the substrate increases when the components such as chips are mounted on these substrates, There has been a problem that defects are generated during mounting. In order to solve the above-mentioned problems, attempts have been made to lower the interlayer thermal expansion coefficient by adding a large amount of inorganic filler to the inside of the insulating layer, but the interlayer adhesion strength, heat resistance and long-term reliability are lowered

SUMMARY OF THE INVENTION The present invention has been conceived to solve the above-described problems, and its object is to provide an insulating resin sheet comprising a non-prepreg-type first insulating resin layer having a low thermal expansion coefficient and a second insulating resin layer capable of a fine circuit pattern, When a laminate is formed by laminating with a wiring board and forming a laminate by heating and pressing, a roughness is formed in the circuit forming portion to improve the bonding strength between the rough surface of the insulating layer and the plating layer by the plating process, Reduction and a micro-circuit pattern are realized, thereby completing the present invention

Accordingly, an object of the present invention is to provide an insulating resin sheet of a novel laminate structure capable of lowering the thermal expansion coefficient of a substrate and forming an illuminance by a desmear treatment.

Further, the present invention includes the insulating layer formed using the above-described insulating resin sheet, thereby reducing defects in the circuit formation process and simultaneously achieving reduction in thickness of the laminate, interlaminar bond strength, heat resistance and long- It is another object to provide a substrate and a method of manufacturing the same.

The present invention relates to a low-heat-expandable first insulating resin layer containing an inorganic filler and a resin; And a second insulating resin layer formed on one surface of the first insulating resin layer and capable of forming an illuminance by a desmearing process.

According to another preferred embodiment of the present invention, the microcircuit second insulating resin layer comprises (a) polyphenylene ether in combination with 9,9-bis (hydroxyaryl) fluorene (BCF) or 9,10-dihydro- A polyphenylene ether modified resin obtained by a redistribution reaction in the presence of -oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide (HCA-HQ); (b) an epoxy resin; (c) a curing agent; And (d) at least one modified epoxy resin selected from the group consisting of a dimer acid-modified epoxy resin and a urethane-modified epoxy resin. When the thermosetting resin composition comprises a polyphenylene ether modified resin (a) obtained by redispersing polyphenylene ether in the presence of 9,9-bis (hydroxyaryl) fluorene (BCF), (e) .

Here, the polyphenylene ether-modified resin (a) is obtained by redistributing a high molecular weight polyphenylene ether resin having a number average molecular weight in the range of 10,000 to 30,000 to obtain a modified polyphenylene ether having a number average molecular weight (Mn) of 1,000 to 15,000 It is preferable that the redistribution reaction is carried out in the presence of a radical initiator, a catalyst, or a radical initiator in the presence of a catalyst.

The modified epoxy resin (d) preferably has an epoxy equivalent of 100 to 500 g / eq and a viscosity of 5,000 to 30,000 cps. The epoxy resin (b) preferably contains two or more kinds of epoxy resins different in epoxy equivalent. .

Wherein the resin composition for forming the second insulating resin layer contains, based on 100 parts by weight of the resin composition, (a) 10 to 60 parts by weight of a polyphenylene ether modified resin; (b) 10 to 40 parts by weight of an epoxy resin; (c) 10 to 40 parts by weight of a curing agent; And (d) 5 to 40 parts by weight of a modified epoxy resin, wherein the polyphenylene ether-modified resin (a) contains polyphenylene ether in the presence of 9,9-bis (hydroxyaryl) fluorene (BCF) (E) in the range of 5 to 40 parts by weight based on 10 to 60 parts by weight of the polyphenylene ether modified resin.

According to a preferred embodiment of the present invention, the CTE of the first insulating resin layer is preferably in the range of 5 to 20 ppm / ° C (25 to 150 degC) or 40 to 70 ppm / ° C (150 to 240 degC) . Here, the coefficient of thermal expansion (CTE) of the polymer can be managed by dividing the CTE at a temperature lower than the Tg and the CTE higher than the Tg, starting from the glass transition temperature (Tg).

Preferably, the first insulating resin layer contains 50 to 95 parts by weight of the inorganic filler when the first insulating resin layer is 100 parts by weight, and the average particle diameter of the inorganic filler ranges from 0.5 to 2.0 占 퐉 desirable.

Here, it is preferable that the thickness of the first insulating resin layer is in the range of 20 탆 to 200 탆, and the thickness of the second insulating resin layer is in the range of 1 탆 to 50 탆.

According to a preferred embodiment of the present invention, a support layer may be further included on the second insulating resin layer, and further, a release layer may be further provided between the second insulating resin layer and the support layer.

The present invention also provides a multilayer printed circuit board on which an insulating layer is formed by the above-described insulating resin sheet.

In addition, the present invention provides a method of manufacturing a multilayer printed circuit board using the above-described insulating resin sheet.

According to a preferred embodiment of the present invention, the manufacturing method comprises the steps of: (i) stacking one or more of the above-described insulating resin sheets on one or both surfaces of an inner-layer wiring board, Forming an insulating layer through a heating and pressing process to build up the laminate; (Ii) forming at least one hole in the insulating layer of the laminate; (Iii) desmearing the surface of the insulating layer and the inside of the hole to form an illuminance; (Iv) forming an electroless plating layer on the rough surface and the hole inner surface of the insulating layer; (v) forming a pattern on the formed electroless plating layer using a photoresist; (Vi) forming a circuit layer by electroplating on the pattern; And (iii) peeling the photoresist and removing the exposed electroless plating layer.

In the present invention, since the insulating resin sheet in which the first insulating resin layer capable of lowering the CTE of the substrate and the second insulating resin layer capable of forming the roughness by the desmear treatment are sequentially laminated is used, The micro-crack generation rate of the insulating layer in which the circuit is formed is significantly reduced, thereby realizing more precise circuit implementation.

In addition, the first insulating resin layer overcomes the limitation of the inorganic filler loading (up to 70 wt% level) in the existing micro circuit pattern material, and further forms a first insulating resin layer below the micro circuit layer to form a high- For example, 92 wt% - no reinforcement can be loaded to lower the CTE of the substrate.

Further, the thickness of the printed circuit board can be remarkably reduced, and the structural deflection characteristics of the final product can be minimized, thereby ensuring ease of manufacture.

1 is a cross-sectional view showing a configuration of an insulating resin sheet according to an embodiment of the present invention.
2 is a cross-sectional view illustrating a manufacturing process of a multilayer printed circuit board according to an embodiment of the present invention.
Description of the Related Art
100: insulating resin sheet 110: first insulating resin layer
120: second insulating resin layer 130: release layer
140: support layer

Hereinafter, the present invention will be described in detail.

The present invention relates to an insulating resin sheet capable of forming an insulating layer in the production of a printed circuit board, which is capable of simultaneously exhibiting a reduction in the total thickness of the laminate, a decrease in the CTE of the substrate, and a high- Sheet is provided.

(I) a low thermal expansion non-fibrous base-type first insulating resin layer; And (ii) a second insulating resin layer formed on one surface of the first insulating resin layer and capable of forming roughness by a desmearing process (see FIG. 1).

Here, since the second insulating resin layer is a resin layer that does not contain an inorganic filler or contains a very small amount, a micro crack caused by a high content of inorganic filler contained in the insulating layer in the laser processing step of the printed circuit board manufacturing process -crack) generation rate can be significantly reduced, enabling more precise circuit implementation. Further, since the soluble material capable of forming the roughness by the desmearing process is included, the bonding strength between the rough surface of the insulating layer and the plating layer formed by the subsequent plating process can be improved.

In addition, the insulating resin sheet of the present invention has a structure in which the second insulating resin layer is laminated on the non-prepreg-type low heat-expandable first insulating resin layer, but the second insulating resin layer has a thermal expansion characteristic The effect of reducing the CTE of the substrate by using the first insulating resin layer loaded with a high content of the inorganic filler can be exhibited.

At this time, the coefficient of thermal expansion of the substrate can also be controlled by adjusting the composition of the inorganic filler and the resin constituting the first insulating resin layer and their composition.

≪ Second Insulating Resin Layer-Forming Resin Composition >

In the insulating resin sheet according to the present invention, the second insulating resin layer is formed by curing the thermosetting resin composition.

In this case, the thermosetting resin composition for forming the second insulating resin layer may be prepared by (a) mixing polyphenylene ether with 9,9-bis (hydroxyaryl) fluorene (BCF) or 9,10-dihydro- (Dihydroxyaryl) -10-phosphaphenanthrene 10-oxide (HCA-HQ); (b) an epoxy resin; (c) a curing agent; (d) at least one modified epoxy resin selected from the group consisting of dimeric acid-modified epoxy resins and urethane-modified epoxy resins. When the thermosetting resin composition is a polyphenylene ether modified resin (a) in which polyphenylene ether is redistributed and reacted in the presence of 9,9-bis (hydroxyaryl) fluorene (BCF), the flame retardant (e) As shown in FIG.

(a) a polyphenylene ether (PPE) modified resin

The first component constituting the thermosetting resin composition for forming the second insulating resin layer according to the present invention is the polyphenylene ether modified resin (a).

Conventionally, when modifying a high molecular weight polyphenylene ether with a low molecular weight polyphenylene ether resin, a compound such as a phenol derivative or bisphenol A is generally used. In this case, the molecular structure is rotatable and the dielectric constant is lowered .

However, in the present invention, a 9,9-bis (hydroxyaryl) fluorene (BCF) or 9,10-dihydro-9-oxa-10- (dihydroxyaryl) By modifying a high molecular weight polyphenylene ether with a low molecular weight polyphenylene ether resin using 10-phosphaphenanthrene 10-oxide (HCA-HQ), the solubility is improved and film coating becomes easy, It blocks rotation in the molecular structure and introduces a large number of hydrophobic double ring hydrocarbon groups, thereby reducing the electron polarization and lowering the dielectric constant. In addition, in comparison with conventional phenol derivatives and bisphenol A, 9,9-bis (hydroxyaryl) fluorene (BCF) or 9,10-dihydro-9-oxa-10- (dihydroxyaryl) Since the molecular structure of nhenthrene 10-oxide (HCA-HQ) is bulky and the crystallinity is high, it is possible to improve the properties of the glass transition temperature (Tg) of the low molecular weight modified polyphenylene ether modified resin .

Further, the hygroscopic property can be enhanced by the increase of the hydrophobic group, and the crosslinking property can be strengthened, so that the thermal property and the chemical resistance property can be enhanced. By improving the dielectric properties, low dielectric and low loss substrates can be realized. Particularly, in the case of a desmear process for forming a microcircuit, the chemical resistance of the insulating layer is important because it is mostly composed of an acid / alkali process. In the present invention, the polyphenylene ether-modified resin (PPE) modified with BCF or HCA-HQ has a high degree of crosslinking to enhance the chemical resistance and low surface roughness (Ra).

In addition, the polyphenylene ether (PPE) modified resin having the self-extinguishing property due to the phosphorus (P) component contained in the HCA-HQ molecule has a flame retardant property by itself. As a result, it is possible to develop a microcircuit pattern material having excellent flame retardancy without adding a separate flame retardant.

Accordingly, the insulating resin sheet and the printed circuit board manufactured using the resin composition of the present invention have an advantage of improving physical properties such as moldability, workability, dielectric properties, heat resistance, and adhesive strength.

In the present invention, the polyphenylene ether to be modified may be a high molecular weight polyphenylene ether. For example, a polyphenylene ether having a number average molecular weight (Mn) of 10,000 to 30,000 may be used. Further, it is not particularly limited as long as the main skeleton is polyphenylene ether. The molecular weight of the low molecular weight modified polyphenylene ether modified resin by redistribution of the high molecular weight polyphenylene ether resin is not particularly limited, but may be, for example, in the range of 1,000 to 15,000.

The 9,9-bis (hydroxyaryl) fluorene (BCF) may be at least one compound selected from the group consisting of compounds represented by the following formulas (1) to (3)

In Formula (1), R ¹ to R ³ are each independently a C ₁ to C ₆ alkyl group; p1 is an integer of 1 to 5, q1 is an integer of 0 to 4, and p1 + q1 is an integer of 5 or less; k1 and k2 are each independently an integer of 0 to 4;

In Formula 2, R ⁴ to R ⁶ are each independently a C ₁ to C ₆ alkyl group; p2 is an integer of 1 to 4, q2 is an integer of 0 to 3, and p2 + q2 is an integer of 4 or less; k3 and k4 are each independently an integer of 0 to 4;

In Formula (3), R ⁷ to R ¹⁰ are each independently a C ₁ to C ₆ alkyl group; q3 and q4 are each independently an integer of 0 to 2, p3 + q3 is an integer of 3 or less, p4 + q4 is an integer of 4 or less, p3 is an integer of 1 to 3, p4 is an integer of 0 to 4, ; k5 and k6 are each independently an integer of 0 to 4;

In addition, the 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphapenanthrene 10-oxide (HCA-HQ) May be one or more compounds selected.

In Formula 4, R ¹¹ to R ¹³ are each independently a C ₁ to C ₆ alkyl group; p5 is 2, q5 is an integer of 0 to 3; k7 and k8 are each independently an integer of 0 to 4;

In Formula 5, R ¹⁴ to R ¹⁷ are each independently a C ₁ to C ₆ alkyl group; p6 and p7 are each independently an integer of 0 to 2, p6 + p7 is 2, p6 + q6 is an integer of 3 or less, and p7 + q7 is an integer of 4 or less; k9 and k10 are each independently an integer of 0 to 4;

(BCA) or 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide (HCA-HQ ) Can be carried out in the presence of a radical initiator and / or catalyst.

As the radical initiator and the catalyst, those conventionally known in the art can be used. Examples of the radical initiator include t-butylperoxy isopropylmonocarbonate, t-butylperoxy 2-ethylhexylcarbonate, benzoyl peroxide, acetyl But are not limited to, acetyl peroxide, di-t-butyl peroxide, t-butyl peroxylaurate, t-butylperoxybenzoate, , But is not limited thereto. The radical initiator may be used in an amount of 0.1 to 5 parts by weight based on 10 to 60 parts by weight of the polyphenylene ether.

A non-limiting example of the catalyst is cobalt naphthanate. The catalyst may be used in an amount of 0.001 to 0.5 parts by weight based on 10 to 60 parts by weight of the polyphenylene ether.

The method of synthesizing a modified polyphenylene ether modified resin by redistribution of polyphenylene ether is not particularly limited and a conventional method known in the art can be applied. For example, polyphenylene ether and 9,9-bis (hydroxyaryl) fluorene (BCF) or 9,10-dihydro-9-oxa-10- (dihydroxyaryl ) -10-phosphaphenanthrene 10-oxide (HCA-HQ) and a radical initiator are mixed and heated to obtain a modified polyphenylene ether modified resin. At this time, the solvent may be a hydrocarbon-based solvent such as benzene or toluene, but is not particularly limited thereto. The reaction temperature and the reaction time can be appropriately controlled according to the number average molecular weight of the desired polyphenylene ether resin, and the reaction can be performed at 60 to 200 ° C for 10 minutes to 10 hours, for example.

In the thermosetting resin composition for forming the second insulating resin layer according to the present invention, the content of the polyphenylene ether-modified resin (a) may be in the range of 10 to 60 parts by weight, preferably 20 Lt; / RTI > When the content of the polyphenylene ether-modified resin falls within the above-mentioned range, the curing property, the molding processability and the adhesive force of the resin composition are good.

(b) Epoxy resin

The second component constituting the thermosetting resin composition for forming the second insulating resin layer according to the present invention is the epoxy resin (b).

The epoxy resin may be any conventional epoxy resin known in the art, and it is preferable that two or more epoxy groups are present in one molecule.

Examples of usable epoxy resins include, but are not limited to, bisphenol A type / F type / S type resin, novolak type epoxy resin, alkylphenol novolak type epoxy resin, biphenyl type, aralkyl type, naphthol Naphthol type, dicyclopentadiene type, or mixed form thereof.

More specific examples thereof include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, anthracene epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, Cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol S novolak type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol phenol coaxial novolak type epoxy resin , Naphthol cholizole co-novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, triphenyl methane type epoxy resin, tetraphenyl ethane type epoxy resin, dicyclopentadiene phenol addition reaction type epoxy resin, phenol aral A quarternary epoxy resin, a polyfunctional phenol resin, a naphthol aralkyl type epoxy resin There is. At this time, the above-mentioned epoxy resin may be used alone, or two or more epoxy resins may be used in combination.

Particularly when a hydrogenated epoxy resin is used, it is preferable to use bisphenol A or biphenyl-type epoxy resin. In addition, when a resin having a high molecular weight is used in the epoxy resin, a greater ductility can be imparted to the insulating layer, so that adhesion characteristics between the laminated body and the metal after plating can be improved.

In order to further improve the adhesion properties after plating, two or more epoxy resins having different epoxy equivalents may be used in combination in the present invention. Preferably a first epoxy resin having an epoxy equivalent of 400 to 1,000 g / eq; And a second epoxy resin having an epoxy equivalent of 100 to 300 g / eq at a weight ratio of 50 to 90:10 to 50. For example, YD-011 (epoxy equivalent: 500 g / eq) and YD-128 (epoxy equivalent: 190 g / eq) can be mixed at the above-mentioned weight ratio.

In the thermosetting resin composition for forming the second insulating resin layer according to the present invention, the content of the epoxy resin may be in the range of 10 to 40 parts by weight, preferably 15 to 40 parts by weight, relative to 10 to 60 parts by weight of the polyphenylene ether- 30 parts by weight. When the content of the epoxy resin falls within the above range, the curing property, the molding processability and the adhesive force of the resin composition are good.

(c)

The third component constituting the thermosetting resin composition for forming the second insulating resin layer according to the present invention is the curing agent (c).

The curing agent may be a conventional curing agent known in the art without limitation, and may be appropriately selected depending on the type of epoxy resin to be used. Non-limiting examples of usable curing agents include phenol-based, anhydride-based, dicyanamide-based, and curing agents. Of these, phenolic curing agents are preferred because they can further improve heat resistance and adhesiveness.

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

In the thermosetting resin composition for forming the second insulating resin layer according to the present invention, the content of the curing agent can be appropriately controlled in accordance with the content of the epoxy resin. In order to maintain the surface roughness (Ra) of the insulating layer at a low level while further improving the heat resistance and the adhesive strength, it is preferable to mix the curing agent and the epoxy resin in a weight ratio of 20 to 50:80 to 50.

In the thermosetting resin composition for forming a second insulating resin layer of the present invention, the content of the curing agent may be in the range of 10 to 40 parts by weight, preferably 10 to 30 parts by weight, per 10 to 60 parts by weight of the polyphenylene ether- Weight range. When the content of the curing agent falls within the above-mentioned range, the curing property, strength, heat resistance and fluidity of the resin composition are satisfactory.

In the present invention, the compounding ratio of the epoxy resin and the curing agent may be such that the phenolic hydroxyl group equivalent of the curing agent is in the range of 0.4 to 2.0, preferably 0.5 to 1.0, in terms of the epoxy equivalent of the epoxy resin . ≪ / RTI >

(d) Modified epoxy resin

The fourth component constituting the thermosetting resin composition for forming the second insulating resin layer according to the present invention is the modified epoxy resin (d).

Examples of the usable modified epoxy resin include dimer acid-modified epoxy resin, urethane-modified epoxy resin, and carboxyl-terminated butadiene acrylonitrile (CTBN). These resins may be used alone or in combination of two or more can do.

The dimeric acid-modified epoxy resin is liable to form a cured product which gives flexibility by the structural factors of the dimeric acid-modified part when the insulating layer is formed by the curing reaction. Further, by providing elastomeric properties to the insulator, the plating adhesion, heat resistance, and humidity resistance characteristics can be improved.

Such a dimeric acid-modified epoxy resin is preferable because it has excellent plating adhesion properties and further improved heat resistance and moisture resistance when the modification ratio is about 5 to 30%. Examples of usable dimeric acid-modified epoxy resins include KSR-200 (Kukdo Chemical Co., Ltd.) and the like. The epoxy equivalent weight and viscosity of the dimeric acid-modified epoxy resin are not particularly limited, but when the epoxy equivalent is about 100 to 500 g / eq and the viscosity is about 5,000 to 30,000 cps, the plating adhesion, the heat resistance and the moisture resistance can be further improved desirable.

The urethane-modified epoxy is an insulating layer, which improves the plating adhesion and the ductility of the insulating layer when used, thereby improving heat resistance and moisture resistance.

Examples of the urethane-modified epoxy resin that can be used include UME-315 (Kukdo Chemical), UME-330 (Kukdo Chemical), and the like. These may be used alone or in combination of two or more. In addition, the urethane-modified epoxy resin is preferable because it has excellent plating adhesion properties and further improved heat resistance and moisture resistance when the modification ratio is about 5 to 30%. The epoxy equivalent weight and viscosity of the urethane-modified epoxy resin are not particularly limited. However, when the epoxy equivalent is about 100 to 500 g / eq and the viscosity is about 5,000 to 30,000 cps, the coating adhesion, heat resistance, .

BACKGROUND ART Carboxyl terminated butadiene rubber (CTBN) is a type of rubber-modified epoxy resin added to improve the compatibility of rubber and epoxy. The carboxyl-terminated butadiene rubber (CTBN) Can play a role.

In the thermosetting resin composition for forming the second insulating resin layer according to the present invention, the content of the modified epoxy resin may be in the range of 5 to 40 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the mixture of the epoxy resin and the curing agent By weight, and more preferably from 5 to 15 parts by weight. If the amount of the modified epoxy resin is less than 5 parts by weight, the coating property and the plating adhesion property may be deteriorated. If the amount exceeds 40 parts by weight, the compatibility between the modified epoxy resin and the epoxy resin is poor and coating property and adhesion between the printed circuit board and the insulator And a reduction in heat resistance is expected.

(e) Flame retardant

The thermosetting resin composition for forming the second insulating resin layer according to the present invention may further contain a flame retardant (e) as required.

The flame retardant may be any conventional flame retardant known in the art, but it is preferably an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicon flame retardant, or a metal hydroxide.

The flame retardant may be contained in an amount of 5 to 40 parts by weight, preferably 5 to 30 parts by weight, more preferably 5 to 15 parts by weight, based on 10 to 60 parts by weight of the polyphenylene ether modified resin have. When the content is in the above range, the resin composition has sufficient flame resistance and the heat resistance of the cured product is also preferable.

The thermosetting resin composition for forming the second insulating resin layer of the present invention may further comprise a curing accelerator. The curing accelerator may be an organic metal salt or an organic metal complex containing at least one metal selected from the group consisting of iron, copper, zinc, cobalt, lead, nickel, manganese and tin.

Examples of the organic metal salt or organometallic complex include iron naphthenate, copper naphthenate, zinc naphthenate, cobalt naphthenate, nickel naphthenate, manganese naphthenate, tin naphthenate, zinc Octanoate, tin octanoate, iron octanoate, copper octanoate, zinc 2-ethylhexanate, lead acetylacetonate, cobalt acetylacetonate, or dibutyltin maleate. But is not limited thereto. These may be used singly or in combination of two or more. The curing accelerator may be included in an amount of 0.01 to 1 part by weight based on 10 to 60 parts by weight of polyphenylene ether, but is not limited thereto.

In addition to the above-mentioned components, the thermosetting resin composition for forming the second insulating resin layer of the present invention may further contain an additive such as an inorganic filler. Examples of the inorganic filler include, but are not limited to, silica, alumina, aluminum hydroxide, calcium carbonate, clay, talc, silicon nitride, boron nitride, titanium oxide, barium titanate or titanate.

The resin composition for forming a second insulating resin layer of the present invention may contain a flame retardant generally known in the art or other thermosetting resin or thermoplastic resin not described above as long as the inherent characteristics of the resin composition are not impaired And other additives such as various polymers such as oligomers thereof, solid rubber particles or ultraviolet absorbers, antioxidants, polymerization initiators, dyes, pigments, dispersants, thickeners, leveling agents and the like. For example, flame retardants such as organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants and metal hydroxides; Organic fillers such as silicone-based powder, nylon powder, and fluororesin powder; thickeners such as orthobenzene and benzene; Polymer-based defoaming agents or leveling agents such as silicones and fluororesins; Adhesion-imparting agents such as imidazole-based, thiazole-based, triazole-based and silane-based coupling agents; Phthalocyanine, carbon black, and other coloring agents.

The thermosetting resin composition may be blended with a thermoplastic resin for the purpose of imparting appropriate flexibility to the cured resin composition. Examples of such a thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide, polyamideimide, polyethersulfone, polysulfone and the like. Any one of these thermoplastic resins may be used alone, or two or more of them may be used in combination.

<Composition for forming the first insulating resin layer>

In the insulating resin sheet according to the present invention, the low thermal expansion first insulating resin layer is a non-prepreg type including an inorganic filler and a resin. The first insulating resin layer may be formed by curing the thermosetting resin composition for forming the first insulating resin layer.

The thermosetting resin composition for forming the first insulating resin layer comprises (A) an epoxy resin; (B) a hardener / hardening accelerator; And (C) an inorganic filler, and optionally (D) a bismaleimide resin and / or a cyanate ester resin.

(A) an epoxy resin

The first component constituting the thermosetting resin composition for forming the low thermal expansion first insulating resin layer according to the present invention is an epoxy resin.

The epoxy resin may be any conventional epoxy resin known in the art, and it is preferable that two or more epoxy groups exist in one molecule in order to impart insulation and adhesion to the inner wiring board.

The epoxy resin component may be the same as or different from those of the epoxy resin (b) constituting the above-described second insulating resin layer without limitation. In order to further improve the adhesion property, two or more epoxy resins having different epoxy equivalents may be used in combination.

The weight average molecular weight (Mw) of the epoxy resin is preferably in the range of 90 to 500, but is not limited thereto.

In the thermosetting resin composition for forming a first insulating resin layer according to the present invention, the content of the epoxy resin (A) may range from about 5 to 60 parts by weight based on 100 parts by weight of the resin composition (excluding the curing accelerator and the inorganic filler) And preferably about 15 to 60 parts by weight. When the content of the epoxy resin falls within the above-mentioned range, the resin composition for forming a first insulating resin layer has good curability, moldability and adhesion.

(B) Curing agent / curing accelerator

The thermosetting resin composition for forming the low thermal expansion first insulating resin layer according to the present invention includes a curing agent, a curing accelerator, or both.

The curing agent may be any conventional curing agent known in the art that can undergo a curing reaction with epoxy, and it is preferable to use a curing agent containing a hydroxyl group (-OH).

Non-limiting examples of usable curing agents include phenol-based, anhydride-based, dicyanamide-based, and curing agents. Of these, phenolic curing agents are preferred because they can further improve heat resistance and adhesiveness.

In the thermosetting resin composition for forming a first insulating resin layer of the present invention, the content of the curing agent (B) is not particularly limited and may range from about 10 to 60 parts by weight based on 100 parts by weight of the resin composition, To 50 parts by weight, and more preferably from 20 to 40 parts by weight. When the content of the curing agent falls within the above-mentioned range, the strength and heat resistance of the cured product are excellently exerted and the moldability can be excellently exhibited due to the fluidity.

In the present invention, a curing agent and a curing accelerator may be mixed. In this case, the curing accelerator is a substance that promotes the reaction between the epoxy resin and the curing agent, and any of those known in the art can be used without limitation.

Non-limiting examples of usable curing accelerators include imidazole-based curing accelerators, amine-based curing accelerators, and metal-based curing accelerators. The sum of the content of the curing agent and the curing accelerator may be in the range of 0.01 to 70 parts by weight, preferably in the range of 0.01 to 60 parts by weight, more preferably in the range of 0.01 to 50 parts by weight, Lt; / RTI &gt;

(C) Mineral filler

The thermosetting resin composition for forming the low thermal expansion first insulating resin layer according to the present invention can be used without limitation as a conventional inorganic filler known in the art.

The inorganic filler is used for effectively improving the warpage property, the low expansion, the mechanical properties, and the low stress of the final product by reducing the difference of the CTE between the first insulating resin layer and the inner wiring board.

Nonlimiting examples of usable inorganic fillers include silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, glass fiber, aluminum borate, strontium titanate, calcium titanate , Magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, boron nitride, silicon nitride, talc, mica and the like. Preferably, it is silica. In the present invention, the above-mentioned inorganic fillers may be used singly or in combination of two or more.

In the resin composition for forming a first insulating resin layer of the present invention, the amount of the inorganic filler (C) to be used can be appropriately adjusted in consideration of the flexural characteristics, the mechanical properties, and the like. For example, the content of the inorganic filler may be in the range of 50 to 95 parts by weight based on 100 parts by weight of the composition for forming the first insulating resin layer (epoxy, curing agent, curing accelerator, inorganic filler) , Preferably 70 to 95 parts by weight.

The shape of the inorganic filler is not particularly limited and may be, for example, a sphere, an ellipsoid, a tetrahedron, a hexahedron, a triangular pillar, a quadrangular pillar, a cylinder, an elliptical pillar, a polygonal column or an amorphous shape, and preferably a spherical shape.

In the present invention, the average particle diameter of the inorganic filler may range from 0.1 to 100 mu m, preferably from 0.2 to 2.0 mu m. However, it is not limited thereto. In order to further lower the coefficient of thermal expansion (CTE) of the first insulating resin layer and to improve the rigidity and dimensional stability of the insulating layer, the low thermal expansion first insulating resin layer of the present invention comprises silica having an average particle diameter of 0.5 to 2.0 mu m It is preferable to include an inorganic filler. .

(D) a bismaleimide resin / cyanate ester resin

The thermosetting resin composition for forming the first insulating resin layer of the present invention can use an epoxy resin alone as a main resin or can additionally contain a bismaleimide resin and a cyanate ester resin together with an epoxy resin ester resin, or both.

The bismaleimide resin is a compound having two maleimide groups in the molecule and can be cured by heat to form a crosslinked structure. Specifically, the bismaleimide resin has a crosslinked network structure in which the carbon-carbon double bond of the maleimide group in one molecule reacts with the carbon-carbon double bond of the maleimide group in the other molecule upon thermal curing, And a low coefficient of thermal expansion (CTE).

The bismaleimide resin may be any of those known in the art without limitation, and examples thereof include 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide, bis (3-ethyl-5-methyl (Maleimide-triazine) addition copolymer, N, N'-phenylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N'- Benzophenone bismaleimide, N, N'-diphenylmethane bismaleimide, N, N'-oxy-di-p-phenylene bismaleimide, N, N'- , N, N'-p-diphenylsulfone bismaleimide, N, N '- (3,3'-dimethyl) methylene- Bis (4-phenoxy) benzene-N, N'-bismaleimide, bis -Bis maleimide, 1,3-bis (4-phenoxyphenyl) sulfone-N, N'-bismaleimide, 1,3- And stearamide.

Cyanate ester resins are also resins made up of monomers containing at least one cyanate ester functionality (-O-C? N). Since the cyclotrimerization reaction is initiated by heat and has a crosslinked network structure formed by a triazine group, it can impart a high thermal resistance and a low thermal expansion coefficient (CTE). Since the cyanate ester resin can act as a curing agent for the epoxy resin, only a curing accelerator can be used without using another curing agent when the epoxy resin and the cyanate ester resin are mixed.

Examples of the cyanate ester resin include, but are not limited to, bisphenol A type cyanate ester resin, bisphenol M type cyanate ester resin, bisphenol F type epoxy resin Novolak type cyanate ester resins, dicyclopentadiene bisphenol type (DCPD type) cyanate ester resins, and prepolymers thereof, and the like.

At this time, it is preferable to control the mixing ratio of the epoxy resin, the bismaleimide resin and / or the cyanate resin so that the resin composition for forming the low heat expandable first insulating resin layer has good curability, molding processability and adhesiveness. For example, when used in combination with a bismaleimide resin or a cyanate ester resin, the mixing ratio of these resins may be in the range of 5 to 60: 5 to 60 weight ratio of epoxy resin: bismaleimide resin or cyanate ester resin Preferably in the range of 10 to 50:30 to 60 parts by weight.

On the other hand, when both the bismaleimide resin, the cyanate resin and the epoxy resin are used in combination, the ratio may be in the range of 5 to 40: 5 to 60: 5 to 60 by weight for the bismaleimide resin: cyanate ester resin: epoxy resin, Preferably 5 to 30: 5 to 30: 20 to 60 parts by weight.

The resin composition for forming a first insulating resin layer of the present invention may contain a flame retardant generally known in the art or other thermosetting resin or thermoplastic resin not described above as long as the inherent characteristics of the resin composition are not impaired And other additives such as various polymers such as oligomers thereof, solid rubber particles or ultraviolet absorbers, antioxidants, polymerization initiators, dyes, pigments, dispersants, thickeners, leveling agents and the like.

The composition for forming the first insulating resin layer may be formed by applying it on a substrate and drying / curing it according to a method known in the art, or by forming the resin composition into a film to form a first insulating resin layer Can be prepared. At this time, the surface of the substrate to which the cured layer of the resin composition is attached may be subjected to a release treatment, and the cured layer of the resin composition may be protected with a protective film.

When the resin composition for forming the first insulating resin layer is applied on the substrate, the resin composition for forming the first insulating resin layer may be applied to a substrate such as a roll coater, a bar coater, a coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, , A spray coater or the like, and drying it at a temperature of 50 to 130 캜 for 1 to 30 minutes.

Examples of the organic solvent that can be used in preparing the composition for forming the first insulating resin layer include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate , And carbitol acetate; carbohydrates such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide; dimethylacetamide; and N-methylpyrrolidone. The organic solvents may be used alone or in combination of two or more. If necessary, the resin composition may be appropriately added with a plasticizer, an antioxidant, a flame retarder, a dispersing agent, a viscosity modifier, a leveling agent, or other conventional additives within a range not significantly impairing the objects and effects of the present invention Can be used.

The composition for forming a low heat-expandable first insulating resin layer according to the present invention may contain a laser energy-absorbing component in order to further improve the workability of the hole by a laser. As the laser energy absorbing component, a known one such as carbon powder, metal compound powder, metal powder or black dye can be used. In addition, any one of them or two or more of them may be used in combination.

Examples of the carbon powder include powders of carbon black such as furnace black, channel black, acetylene black, thermal black and anthracene black, graphite powder, and mixtures thereof. Examples of the metal compound include titania such as titanium oxide, magnesia such as magnesium oxide, iron oxide such as iron oxide, nickel oxide such as nickel oxide, zinc oxide such as manganese dioxide and zinc oxide, silicon dioxide, aluminum oxide, Cobalt oxide such as cobalt oxide, tin oxide such as tin oxide, tungsten oxide such as tungsten oxide, silicon carbide, tungsten carbide, boron nitride, silicon nitride, titanium nitride, aluminum nitride, barium sulfate, rare earth oxides, Powder and the like. Examples of the metal powder include powders of silver, aluminum, bismuth, cobalt, copper, iron, magnesium, manganese, molybdenum, nickel, palladium, antimony, silicon, tin, titanium, vanadium, tungsten, zinc, . The laser energy absorbing component is preferably a carbon powder from the viewpoint of conversion efficiency with respect to heat of laser energy, versatility and the like. The upper limit value of the average particle diameter of the laser energy absorbing component is preferably in the range of 0.01 탆 to 20 탆 from the viewpoint of efficiently absorbing the laser energy.

<Insulation resin sheet>

The insulating resin sheet of the present invention comprises the above-described low heat expandable first insulating resin layer; And a second insulating resin layer formed on one surface of the first insulating resin layer.

Hereinafter, an insulating resin sheet according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.

1, the insulating resin sheet 100 of the present invention includes a first insulating resin layer 110 and a second insulating resin layer 120 located on one side of the first insulating resin layer , And these layers are sequentially stacked.

In the insulating resin sheet of the present invention, the first insulating resin layer 110 not only physically supports the insulating resin sheet but also can reduce the coefficient of thermal expansion (CTE) of the substrate because the inorganic filler is included.

The first insulating resin layer is used as a base supporting film and may be in the form of a film or sheet having self-supporting properties. The CTE of the first insulating resin layer of the present invention is preferably in the range of 5 to 20 ppm / ° C (25 to 150 degC) or 40 to 70 ppm / ° C (150 to 240 degC).

In the conventional prepreg or insulating layer, the loading amount of the inorganic filler can be up to 70 wt% in order to be used as a microcircuit pattern material, whereas the first insulating resin layer of the present invention has a maximum of 95 wt% (no-reinforcement) The inorganic filler can be loaded with a high content. Therefore, it is possible to control the coefficient of thermal expansion of the substrate by adjusting the content of the inorganic filler freely.

The first insulating resin layer 110 may have a structure in which the inorganic filler is uniformly arranged in the resin or the resin is contained as a binder depending on the composition ratio of the inorganic filler and the resin and the inorganic filler is fixed and bonded by the resin Lt; / RTI &gt; The first insulating resin layer may contain a range of 50 to 95 parts by weight of the inorganic filler when the first insulating resin layer is 100 parts by weight.

Considering physical stiffness of the insulating resin sheet according to the present invention, handling property of the film, thermal expansion coefficient, thinning of the substrate, high-density wiring, etc., the thickness of the first insulating resin layer 110 may be in the range of 20 탆 to 200 탆 Preferably in the range of 20 to 100 mu m, and more preferably in the range of 20 to 70 mu m.

On the other hand, the first insulating resin layer may be protected by a protective film in order to prevent damage to the surface or adhesion of foreign matter. The protective film may be the same as a conventional plastic film known in the art. The thickness of the protective film may range from 1 to 40 mu m, preferably from 10 to 30 mu m.

In the insulating resin sheet of the present invention, the second insulating resin layer 120 is disposed on the upper surface of the low-thermal-expansion first insulating resin layer 110 and includes a soluble material capable of forming an illuminance by a desmearing process.

The thickness of the second insulating resin layer 120 may range from 1 to 50 mu m, preferably from 1 to 30 mu m, without affecting the thermal expansion characteristics of the substrate. Also, a film which can be peeled off by heating, pressing, and pressing under coating is applied.

The second insulating resin layer 120 includes a cured layer formed by curing the above-mentioned thermosetting resin composition for forming a second insulating resin layer. In this case, the thermosetting resin composition need not necessarily be completely thermally cured, It is sufficient that the curing agent is cured to such an extent that the effects of the invention are exhibited.

The cured layer can be obtained by a method of heating and curing an adhesive sheet coated with a thermosetting resin composition on a support. For example, the adhesive sheet may be formed by applying a thermosetting resin composition varnish for forming a second insulating resin layer on a support, heating and drying the varnish, bonding the same to one surface of the first insulating resin layer, or heating the resin varnish coated on the support , Drying and curing are carried out simultaneously / sequentially to obtain a second insulating resin layer, and the second insulating resin layer is bonded to one surface of the first insulating resin layer to obtain the insulating resin sheet of the present invention.

According to an example of the present invention, the insulating resin sheet 100 may further include a support layer 140 on the second insulating resin layer 120.

As the support, a plastic film may be used, and a metal foil such as a release film, a copper foil, and an aluminum foil may be used as a support. Examples of usable plastic films include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; Polycarbonate, acrylic resin, cyclic polyolefin, triacetyl cellulose, polyether sulfide, polyether ketone, polyimide and the like.

When a polyimide (PI) film is used as the support, high-temperature pressing at about 220 ° C is possible. In the case of a polyethylene terephthalate (PET) film, a low-temperature press of about 180 占 폚 may be used. In this case, when a plastic film is used as the support, it is preferable to use a support having a release layer, in which the surface to be cured of the cured layer of the thermosetting resin composition has been subjected to release treatment, in order to enable release from the cured product of the thermosetting resin composition. In this case, the plastic film may be a matte-treated or corona-treated film, and a release layer may be formed on the treated surface.

Further, since the metal foil can be removed by etching, it is not necessary to further use the release layer when the metal foil is used as a support. It is also possible to use the metal foil as a conductor layer without peeling off. Examples of usable metal foils include aluminum foil and copper foil. When such a metal foil is used as a support layer, a high-temperature press of about 220 캜 is possible.

The thickness of the support layer 140 is not particularly limited, but may be in the range of 10 to 150 占 퐉, and preferably in the range of 25 to 50 占 퐉.

According to another embodiment of the present invention, the insulating resin sheet 100 may further include a release layer 130 between the second insulating resin layer 120 and the support layer 140.

The release layer 130 has a function of easily separating the second insulation resin layer 120 so that the second insulation resin layer 120 can be retained without damage when the support layer 140 is separated from the cured product of the thermosetting resin composition after pressing. Here, the release layer may be a commonly used film-type release material.

The releasing agent used in the releasing layer 130 is not particularly limited to its component as long as the second insulating resin layer can be peeled completely from the support, and conventional releasing agent components known in the art can be used. Non-limiting examples thereof include epoxy-based releasing agents, releasing agents comprising fluororesins, silicone-based releasing agents, alkyd resin-based releasing agents, and water-soluble polymers. The thickness of the release layer 140 is not particularly limited, and may range, for example, from 0.01 to 10 μm, preferably from 0.1 to 5 μm.

The method for forming the release layer 130 is not particularly limited, and known methods such as hot press, thermal roll laminate, extrusion laminate, application of coating liquid, and drying can be employed.

The insulating resin sheet 100 according to the present invention can be obtained by bonding the first insulating resin layer 110 to the cured second insulating resin layer 120 of the thermosetting resin composition. For example, a method may be employed in which the insulating resin layer 120 comprising the support layer 140 and the cured layer of the thermosetting resin composition is laminated on one surface of the first insulating resin layer 110 and the first insulating resin layer The insulating resin layer 120 and the first insulating resin layer 110 are rolled into a roll shape and laminated in a continuous manner to form a laminate. Alternatively, it is also possible to perform lamination after cutting both rolls of the sheet.

In the insulating resin sheet of the present invention, the total thickness of the first insulating resin layer 110 and the insulating resin layer 120 is in the range of 21 탆 to 250 탆, and preferably in the range of 30 to 100 탆. When the thickness of the insulating resin sheet is within the above-mentioned range, the circuit is sufficiently filled, and the multilayer printed circuit board can be made thinner.

<Printed Circuit Board>

The present invention includes a multilayer printed circuit board using the above-described insulating resin sheet as an insulating layer.

The multilayer printed circuit board in the present invention refers to a printed circuit board laminated by two to three or more layers by plating through-hole method, build-up method or the like, and can be obtained by superimposing an insulating resin sheet on an inner wiring board and heating and pressing. The multilayered printed circuit board is obtained by using the insulating resin sheet according to the present invention in which a first insulating resin layer having a low thermal expansion coefficient and a second insulating resin layer capable of forming an illuminance by a desmearing process are sequentially laminated, And a high density fine circuit pattern can be realized while lowering the interlayer thermal expansion coefficient of the substrate.

The printed circuit board of the present invention can be manufactured by a conventional method known in the art, for example, semi-additive, except that the above-described insulating resin sheet is used.

(I) one or more of the above-described insulating resin sheets are laminated on one or both surfaces of the inner-layer wiring board, wherein the low-thermal-expandable first insulating resin layer of the insulating resin sheet is laminated on the wiring board Forming an insulating layer through a heating and pressing process after arranging the metal layer so as to be in contact with the metal surface to build up the laminate; (Ii) forming at least one hole in the insulating layer of the laminate; (Iii) desmearing the surface of the insulating layer and the inside of the hole to form an illuminance; (Iv) forming an electroless plating layer on the rough surface and the hole inner surface of the insulating layer; (v) forming a pattern on the formed electroless plating layer using a photoresist; (Vi) forming a circuit layer by electroplating on the pattern; And (iii) peeling the photoresist and removing the exposed electroless plating layer.

Hereinafter, a manufacturing process of a printed circuit board according to an embodiment of the present invention will be described in detail with reference to FIG. However, the present invention is not limited to the processes illustrated below.

1) A first insulating resin layer of an insulating resin sheet is disposed on one or both surfaces of the inner wiring board so as to be in contact with the metal surface of the wiring board, and then heated and pressed to form a laminate (see FIG.

The inner-layer wiring board is used as a core substrate, and conventional ones known in the art can be used without limitation. For example, a double-sided flexible metal-clad laminate (FCCL) can be used. For example, a double-sided copper plate is drilled to form a hole, and then plating is performed. Then, dry film resistors are laminated on both sides, Lt; RTI ID = 0.0 &gt; a &lt; / RTI &gt;

2, an inner wiring board and an insulating resin sheet are laminated, and the metal surface of the inner wiring board and the first insulating resin layer of the insulating resin sheet are brought into contact with each other. Then, Vacuum heating and pressure molding are performed using an apparatus or the like.

The conditions under which heating and pressure molding is not particularly limited include, for example, a temperature of 60 to 160 DEG C and a pressure of 0.2 to 3 MPa. The conditions for heating are not particularly limited, but for example, the heating can be carried out at a temperature of 140 to 240 캜 for a time of 30 to 120 minutes.

Or the first insulating resin layer of the above-mentioned insulating resin sheet is superimposed on the inner wiring board, and this is heat-pressed with a flat press or the like. Here, the condition under which heating and pressure molding is not particularly limited, but can be carried out at a temperature of 140 to 240 캜 and a pressure of 1 to 4 MPa, for example. In the heat press forming by such a flat press apparatus or the like, an insulating layer is formed simultaneously with the heat press forming.

On the other hand, in the case where the insulating resin sheet includes the release layer 130, the support layer 140, or both, a release layer which is sequentially laminated on each of the upper and lower surfaces of the laminate after the laminate is formed in this step, Layer or both of them are removed, the following 2) step is carried out (see Fig. 2 (b)).

2) One or more holes are formed in the insulating layer of the laminate (see Fig. 2 (c)).

A hole is formed by irradiating the insulating layer of the laminate with a laser. The laser may be an excimer laser, a UV laser, or a carbon dioxide gas (CO ₂ ) laser.

When this step is performed, a hole connected to the inner-layer wiring board is formed.

3) The surface of the insulating layer and the inner surface of the hole are subjected to desmear treatment to form roughness (see Fig. 2 (d)).

The desmear process is a process for removing resin residues (smear) after laser irradiation by an oxidizing agent such as permanganate salt, dichromate, and the like. In this step, the surface of the insulating layer and the inner surface of the hole are processed by laser processing A rough surface having an appropriate roughness (roughness) is formed.

At this time, if the desmear treatment is insufficient and the desmear resistance is not sufficiently secured, even if the metal plating treatment is performed on the hole, the conductivity of the upper layer metal wiring and the lower layer metal wiring can not be sufficiently secured due to the smear. Further, the surface of the smooth insulating layer can be roughened at the same time, and the adhesion of the conductive wiring circuit formed by the subsequent metal plating can be increased.

If necessary, an etching process may be further carried out after the desmearing process to maintain a horizontal roughness surface having an appropriate roughness on the insulating layer.

The surface of the insulating layer after the desmearing process preferably has a desired roughness for forming a fine circuit pattern. For example, the surface roughness of the insulating layer after the desmearing process may range from 50 nm to 1,000 nm, preferably from 100 nm to 500 nm.

4) An electroless plating layer is formed on the rough surface and the inner surface of the hole of the insulating layer (see Fig. 2 (e)).

Electroless plating is performed on the rough surface and the inner surface of the hole to form a comparatively thin plating layer. This electroless plating layer secures adhesion strength to the second insulating resin layer in advance in order to raise the fine circuit pattern layer to be formed thereon.

Generally, the adhesiveness between the formed circuit electrode and the substrate is closely related, and an electroless plating layer is formed between the substrate and the circuit electrode. Here, since the electroless plating layer is formed using the surface-coated catalyst as the active point, ultimately, there is no adhesion with the substrate. Therefore, when the surface roughness of the substrate is large, the adhesion between them is kept good by the anchor effect, but if there is no roughness on the surface of the substrate, the adhesiveness tends to be low. Therefore, it is preferable to adjust the surface roughness to 0.1 times or less of the formed circuit width because a good circuit shape can be obtained.

At this time, the electroless plating layer to be a seed layer of the electroplating layer is preferably in the range of 0.1 to 5 mu m.

5) A pattern is formed on the electroless plating layer formed using a photoresist (see Fig. 2 (f)).

In order to form a desired circuit pattern on the electroless plating layer, a fine circuit pattern is formed through a process of coating a photoresist as a lithography process and forming an opening for forming an outer layer pattern.

Here, the photoresist may be a dry film or the like.

6) A circuit layer is formed by electrolytic plating on the pattern (see Fig. 2 (g)).

Thereafter, a conductor layer for forming the fine circuit pattern is formed on the opening of the photoresist layer by electrolytic plating.

Through this step, the electroplated layer forms a new circuit layer connected to the inner wiring board by the holes. Here, the thickness of the electroplating layer is preferably in the range of about 1 m to 100 m.

7) The photoresist is peeled off and the exposed electroless plating layer is removed.

Finally, the unnecessary photoresist layer is removed and the exposed electroless plating layer is removed to complete the circuit pattern.

Then, if necessary, the production of a printed circuit board is completed by further performing a manufacturing process of a conventional printed circuit board known in the art, such as an electronic element mounting process.

The above-described method for manufacturing a multilayer printed circuit board may be performed by modifying the steps of the respective processes or selectively mixing them according to the design specifications, not by sequentially performing the steps described above.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the scope of the present invention is not limited by the following Examples and Experimental Examples.

[ Example  1 to 4]

1. Preparation of Resin Composition

A composition for forming the first insulating resin layer and a resin composition for forming the second insulating resin layer were prepared according to the compositions shown in Table 1 below. In Table 1, the unit of usage of each composition is parts by weight.

2. Manufacture of insulating resin sheet and printed circuit board

For the evaluation of the present invention, a micro-circuit second insulation resin layer was coated on a 50 탆 polyimide (PI) film having a one-side mold releasing treatment and a double coating technique was applied to form a low- Layer was coated and dried to form a first insulating resin layer in a B-stage type.

With an insulating resin sheet, an inner layer circuit board was prepared in the product was applied with a Mitsubishi Gas Chemical's CCL-HL-832 0.125mm thick, it was molded at a temperature of 180 ℃ at a pressure of 40 kgf / cm ² 120 0.15 bun To prepare a laminate having a thickness of 0.18 mm.

A multilayer printed circuit board was fabricated by performing hole processing, desmear treatment, electroless plating layer, and circuit formation according to a conventional method using the thus prepared laminate.

 [Comparative Examples 1 and 2]

A resin composition, an insulating resin sheet and a printed circuit board were prepared in the same manner as in the above example, except that the composition shown in the following Table 1 was used. In Table 1, the unit of usage of each composition is parts by weight.

division Example Comparative Example One 2 3 4 One 2 The first insulating resin layer Epoxy resin (1) 25 25 25 25 25 25 Epoxy resins (2) 25 25 20 20 25 20 BMI 30 30 20 20 30 20 Cyanate ester 20 20 - - 20 - Hardener - - 35 35 - 35 Hardening accelerator 0.01 0.01 - - 0.01 - Inorganic filler 93 85 93 85 70 70 The second insulating resin layer
(One) PPO  Modified resin Polyphenylene ether
(PPE) 30 30 30 30 30 30 Polyphenylene ether
Resin molecular weight before reforming 24000 24000 24000 24000 24000 24000 Bisphenol A - - - - 0.3 0.3 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene (BCF) 0.3 0.3 0.3 0.3 - - Radical initiator 0.27 0.27 0.27 0.27 0.27 0.27 catalyst 0.008 0.008 0.008 0.008 0.008 0.008 Polyphenylene ether modified resin molecular weight 12500 12500 12500 12500 11000 11000 The second insulating resin layer
(2) Epoxy resin Epoxy resin 1 20 20 20 20 20 20 Epoxy resin 2 20 20 20 20 20 20 The second insulating resin layer
(3) Curing agent Hardener 25 25 25 25 25 25 The second insulating resin layer
(4) Other Modified epoxy resin 1 10 - - 5 10 - Modified Epoxy Resin 2 - 10 - 5 - - Modified Epoxy Resin 3 - - 10 - - 10 The second insulating resin layer
(5)
Flame retardant Flame retardant 10 10 10 10 10 10 evaluation
Item CTE (ppm / ° C - @ 25-150 degC) 5.2 8.7 6.4 10.2 24 27 Plating adhesion (kgf / cm) 0.8 0.8 0.7 0.8 0.5 0.4 Surface roughness-Ra (nm) 240 260 360 252 490 580 Lead heat resistance (@ 288) 600 seconds 600 seconds 600 seconds 600 seconds 120 seconds 120 seconds Flammability V-0 V-0 V-0 V-0 V-0 V-0

Company

&Lt; Low thermal expandable first insulating resin layer >

1) Epoxy resin 1: YX-8800 (JER)

2) Epoxy resin 2: NC-7000L (Nippon Kayaku)

3) BMI: Phenylmethane maleimide

4) Cyanate ester resin: BA-230S

5) Hardener: KPN-2110 (Kangnam Hwaseong)

6) Curing accelerator: Zinc Oxide

&Lt; Fine circuit second insulating resin layer >

1) Epoxy resin 1: YD-011 (epoxy equivalent weight: 500 g / eq)

2) Epoxy resin 2: YD-128 (epoxy equivalent 190 g / eq)

3) Radical initiator: PB-I

4) Catalyst: Cobalt naphthanate

5) Hardener: KTG-105 (OH equivalent: 104 g / eq)

6) Modified Epoxy Resin 1: Dimeric acid-modified epoxy resin (KSR-200)

7) Modified Epoxy Resin 2: Urethane Modified Epoxy Resin (UME-315)

8) Modified Epoxy Resin 3: CTBN Modified Epoxy Resin (KR-207)

9) Flame retardant: phosphorus flame retardant (SPB-100)

Experimental Example  1. Evaluation of physical properties of printed circuit board

The following tests were conducted on the printed circuit boards prepared in Examples 1 to 4 and Comparative Examples 1 and 2, and the results are shown in Table 1 above.

1) CTE: TMA CTE measurement (IPC Method TM-650 2.4.24.5)

2) Plating adhesion strength: The adhesion strength between the plated layer and the insulator was measured according to the test standard of IPC-TM-650 2.4.8.

3) Surface roughness: Ra value was measured using a non-contact 3D Optical Profiler (Bruker Contour GT) to measure the surface roughness. The Ra value is an average value of the height calculated over the entire measurement area, specifically, the absolute value of the height varying in the measurement area is measured from the average line surface and arithmetically averaged. Here, the average roughness It is the value measured according to the obtained.

4) Lead heat resistance: The sample was cut into a size of 5 cm ㅧ 5 cm from a 288 째 C water bath, and the time at which the abnormality started to occur was measured.

5) Flame retardancy: Proceed according to UL 94 VTM test standard.

As a result of the test, the printed circuit board using the insulating resin sheet of the present invention had a surface roughness of less than half of that of the conventional product after the dismear treatment, and exhibited excellent properties in terms of the substrate thermal expansion coefficient, plating adhesion and heat resistance (see Table 1) ).

Accordingly, a multilayer printed circuit board with high reliability can be manufactured in the future, and it is considered to be usefully used as a constituent material of a small and lightweight new semiconductor package.

Claims (21)

A low thermal expansion first insulating resin layer containing an inorganic filler and a resin; And
A second insulating resin layer formed on one surface of the first insulating resin layer and capable of forming an illuminance by a desmearing process,
. The method according to claim 1, wherein the second insulating resin layer
(a) polyphenylene ether is reacted with 9,9-bis (hydroxyaryl) fluorene (BCF) or 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene A polyphenylene ether modified resin obtained by redistribution in the presence of 10-oxide (HCA-HQ);
(b) an epoxy resin;
(c) a curing agent; And
(d) at least one modified epoxy resin selected from the group consisting of a dimer acid-modified epoxy resin, a urethane-modified epoxy resin and a carboxyl-terminated butadiene acrylonitrile (CTBN)
Wherein the thermosetting resin composition is formed by curing the thermosetting resin composition. The thermosetting resin composition according to claim 2, wherein the thermosetting resin composition comprises a polyphenylene ether modified resin (a) in which polyphenylene ether has been redistributed and reacted in the presence of 9,9-bis (hydroxyaryl) fluorene (BCF) (e) a flame retardant. The polyphenylene ether-modified resin (a) according to claim 2, wherein the polyphenylene ether-modified resin (a) is subjected to a redistribution reaction of a high molecular weight polyphenylene ether resin having a number average molecular weight in the range of 10,000 to 30,000, Wherein the insulating resin sheet is made of an insulating resin. The insulating resin sheet according to claim 2, wherein the redistribution reaction of the polyphenylene ether-modified resin (a) is carried out in the presence of a radical initiator, a catalyst, or a radical initiator and a catalyst. The insulating resin sheet according to claim 2, wherein the epoxy resin (b) is a mixture of two or more epoxy resins different in epoxy equivalent. The epoxy resin composition according to claim 6, wherein the epoxy resin (b) is a first epoxy resin having an epoxy equivalent of 400 to 800 g / eq; And a second epoxy resin having an epoxy equivalent of 100 to 300 g / eq at a weight ratio of 50 to 90:10 to 50. The insulating resin sheet according to claim 2, wherein the curing agent (c) is selected from the group consisting of phenol-based, anhydride-based, and dicyanamide-based curing agents. The insulating resin sheet according to claim 2, wherein the modified epoxy resin (d) has an epoxy equivalent of 100 to 500 g / eq and a viscosity of 5,000 to 30,000 cps. The insulating resin sheet according to claim 3, wherein the flame retardant (e) is at least one member selected from the group consisting of organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicon flame retardants, and metal hydroxides. The thermosetting resin composition according to claim 3, wherein the thermosetting resin composition comprises
(a) 10 to 60 parts by weight of a polyphenylene ether modified resin;
(b) 10 to 40 parts by weight of an epoxy resin;
(c) 10 to 40 parts by weight of a curing agent; And
(d) 5 to 40 parts by weight of a modified epoxy resin,
When the polyphenylene ether-modified resin (a) is a polyphenylene ether which has undergone redistribution reaction in the presence of 9,9-bis (hydroxyaryl) fluorene (BCF), the polyphenylene ether- Further comprising a flame retardant (e) in a range of 5 to 40 parts by weight relative to the total weight of the insulating resin sheet. The method of claim 1, wherein the first insulation resin layer has a CTE in the range of 5 to 20 ppm / ° C (25-150 degC), or 40 to 70 ppm / ° C (150-240 degC) Resin sheet. The insulating resin sheet according to claim 1, wherein the first insulating resin layer contains 50 to 95 parts by weight of an inorganic filler when the first insulating resin layer is 100 parts by weight. The insulating resin sheet according to claim 1, wherein an average particle diameter of the inorganic filler ranges from 0.5 to 2.0 mu m. The method according to claim 1, wherein the thickness of the first insulating resin layer is in the range of 20 탆 to 200 탆,
Wherein the thickness of the second insulating resin layer is in the range of 1 占 퐉 to 50 占 퐉. The insulating resin sheet according to claim 1, further comprising a support layer on the second insulating resin layer. The insulating resin sheet according to claim 16, further comprising a release layer between the second insulating resin layer and the support layer. The insulating resin sheet according to claim 16, wherein the support layer is a plastic film or a metal foil. A multilayer printed circuit board in which an insulating layer is formed by the insulating resin sheet according to any one of claims 1 to 18. (i) one or more of the insulating resin sheets according to any one of claims 1 to 18 is laminated on one or both surfaces of the inner-layer wiring board, and the first insulating resin layer of the insulating resin sheet is laminated on the metal surface Forming an insulating layer through a heating and pressing process to build up the laminate;
(Ii) forming at least one hole in the insulating layer of the laminate;
(Iii) dishing the surface and the inside of the insulating layer to form an illuminance;
(Iv) forming an electroless plating layer on the rough surface and the hole inner surface of the insulating layer;
(v) forming a pattern on the formed electroless plating layer using a photoresist;
(Vi) forming a circuit layer by electroplating on the pattern; And
(Iii) peeling the photoresist and removing the exposed electroless plating layer
&Lt; / RTI &gt; 21. The method according to claim 20, wherein, when the insulating resin sheet comprises a release layer, a support layer, or both, between the step (i) and the step (ii) , The support layer, or all of them. &Lt; Desc / Clms Page number 13 &gt;

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