KR20140080182A - Resin composition for printed circuit board, insulating film, prepreg and printed circuit board - Google Patents

Abstract

The present invention provides a resin composition for a printed circuit board including a liquid crystal oligomer, an epoxy resin, and a tetraphenylethane curing agent; an insulating film and a prepreg manufactured using the resin composition; and a printed circuit board including the insulating film or the prepreg. The resin composition for the printed circuit board according to the present invention, and the insulating film and the prepreg manufactured using the same have low coefficient of thermal expansion, excellent heat resistance and a high glass transition temperature.

Description

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

The present invention relates to a resin composition for a printed circuit board, an insulating film, a prepreg, and a printed circuit board.

Background Art [0002] With the development of electronic devices and the demand for complex functions, the weight, thickness, and miniaturization of printed circuit boards have been progressively increasing. In order to meet such a demand, the wiring of the printed circuit becomes more complicated, the density becomes higher, and the function becomes higher. Further, in the case of a printed circuit board, the build-up layer is required to be made into a multilayer structure, so that miniaturization and densification of wiring are required. Thus, the electrical, thermal and mechanical properties required of the substrate are more important factors.

The structure of the printed circuit board consists mainly of copper, which acts as a circuit wiring, and a polymer, which acts as an interlaminar insulation. Compared to copper, the polymer constituting the insulating layer is required to have various characteristics such as a thermal expansion coefficient, a glass transition temperature, and a thickness uniformity, and in particular, the thickness of the insulating layer must be made thinner.

As the circuit board is made thinner, the stiffness of the substrate itself is lowered, and defects may be caused by warpage at the time of component mounting at a high temperature. For this purpose, the thermal expansion characteristics and heat resistance of the thermosetting polymer resin are important factors, and the polymer structure and the network and curing density between the polymer resin chains constituting the substrate composition closely influence the thermosetting property.

On the other hand, Patent Document 1 discloses an epoxy resin composition containing a liquid crystal oligomer. However, since a network between a curing agent and a polymer resin can not be sufficiently formed, a thermal expansion coefficient suitable for a printed circuit board can not be sufficiently lowered, The temperature can not be raised sufficiently.

Patent Document 1: Korean Patent Publication No. 2011-0108198

Accordingly, the present invention provides a resin composition for a printed circuit board, which comprises a liquid crystal oligomer, preferably a liquid crystal oligomer having a specific structure, an epoxy resin, preferably an epoxy resin having at least four epoxy functional groups, and a tetraphenyl ethane curing agent And a product manufactured using the same exhibit improved thermal expansion coefficient and excellent thermal characteristics, and the present invention has been completed on the basis thereof.

Accordingly, one aspect of the present invention is to provide a resin composition for a printed circuit board having a low thermal expansion coefficient and improved heat resistance and glass transition temperature.

Another aspect of the present invention is to provide an insulating film produced from the resin composition, having a low thermal expansion coefficient, and improved heat resistance and glass transition temperature.

Another aspect of the present invention is to provide a prepreg having a low coefficient of thermal expansion of a substrate impregnated with the resin composition and having improved heat resistance and glass transition temperature.

Another aspect of the present invention is to provide a printed circuit board having the insulating film or the prepreg.

A resin composition (first invention) for a printed circuit board according to the present invention for achieving the above-mentioned one aspect comprises: a liquid crystal oligomer; Epoxy resin; And a tetraphenyl ethane curing agent represented by the following formula (1).

[Chemical Formula 1]

In the first invention, the resin composition further comprises an inorganic filler (hereinafter referred to as "second invention").

In the first invention, the liquid crystal oligomer is characterized by being represented by the following general formula (2), (3), (4) or (5)

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

A represents an integer of 13 to 26; b represents an integer of 13 to 26; c represents an integer of 9 to 21; d represents an integer of 10 to 30; and e represents an integer of 10 to 30.

In the first invention, the resin composition comprises 39 to 60% by weight of the liquid crystal oligomer, 39 to 60% by weight of an epoxy resin, and 0.1 to 1% by weight of a tetraphenyl ethane curing agent.

In the second invention, the resin composition is characterized by containing 9 to 30% by weight of a liquid crystal oligomer, 9 to 30% by weight of an epoxy resin, 0.01 to 0.5% by weight of a tetraphenyl ethane curing agent, and 50 to 80% by weight of an inorganic filler do.

In the first invention, the liquid crystal oligomer has a number average molecular weight of 2,000 to 10,000.

In the first aspect of the invention, the liquid crystal oligomer has a polydispersity index of 1.5 to 3.

In the first invention, the epoxy resin is at least one selected from naphthalene-based epoxy resin, bisphenol A-type epoxy resin, phenol novolak epoxy resin, cresol novolac epoxy resin, rubber modified epoxy resin, and phosphorus-based epoxy resin .

In the first invention, the epoxy resin is characterized by having four or more epoxy functional groups.

In the second invention, the inorganic filler is at least one selected from the group consisting of silica, alumina, barium sulfate, talc, mud, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, calcium titanate , Magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate.

In the first invention, the resin composition further comprises a curing accelerator selected from at least one of a metal-based curing accelerator, an imidazole-based curing accelerator, and an amine-based curing accelerator.

In the first invention, the resin composition may be at least one selected from the group consisting of a phenoxy resin, a polyimide resin, a polyamideimide (PAI) resin, a polyetherimide (PEI) resin, a polysulfone (PS) resin, a polyether sulfone The thermoplastic resin further comprises at least one thermoplastic resin selected from phenylene ether (PPE) resin, polycarbonate (PC) resin, polyetheretherketone (PEEK) resin and polyester resin.

An insulating film (third invention) for attaining another aspect of the present invention is made of the resin composition.

A prepreg (fourth invention) for achieving still another aspect of the present invention is prepared by impregnating a base material with the resin composition.

A printed circuit board (fifth invention) for attaining another aspect of the present invention comprises the insulating film according to the third invention.

A printed circuit board (sixth invention) for achieving still another aspect of the present invention comprises the prepreg according to the fourth invention.

INDUSTRIAL APPLICABILITY The resin composition for a printed circuit board according to the present invention, and the insulating film and prepreg produced therefrom have a low thermal expansion coefficient, excellent heat resistance, and high glass transition temperature.

The features and advantages of the present invention will become more apparent from the following detailed description based on the accompanying drawings.

1 is a cross-sectional view of a general printed circuit board to which the resin composition according to the present invention is applicable.

Before describing the invention in more detail, it is to be understood that the words or words used in the specification and claims are not to be construed in a conventional or dictionary sense, It should be interpreted as meaning and concept consistent with the technical idea of the present invention. Therefore, the constitution of the embodiments described in the present specification is merely a preferred example of the present invention, and does not represent all the technical ideas of the present invention, so that various equivalents and variations And the like.

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

1 is a cross-sectional view of a general printed circuit board to which the resin composition according to the present invention is applicable. Referring to FIG. 1, the printed circuit board 100 may be an embedded substrate having electronic components built therein. Specifically, the printed circuit board 100 includes an insulator or prepreg 110 having a cavity, an electronic component 120 disposed inside the cavity, an insulator including the electronic component 120, or a top surface of the prepreg 110 And a build-up layer 130 disposed on at least one side of the lower surface. The buildup layer 130 may include an insulating layer 131 disposed on at least one of the upper and lower surfaces of the insulator 110 and a circuit layer 132 disposed on the insulating layer 131 and forming an interlayer connection.

Here, the electronic component 120 may be an active element such as a semiconductor element. In addition, the printed circuit board 100 may not contain only one electronic component 120 but may further include at least one additional electronic component such as the capacitor 140 and the resistor element 150 And the type and number of electronic components are not limited in the embodiments of the present invention. Here, the insulator or prepreg 110 and the insulating layer 131 serve to provide insulation between the circuit layers or the electronic components, and at the same time, serve as structural members for maintaining the rigidity of the package.

At this time, when the wiring density of the printed circuit board 100 is increased, the insulating material or the prepreg 110 and the insulating layer 131 have a low permittivity to reduce the noise between the circuit layers and simultaneously reduce the parasitic capacitance. And the insulator or prepreg 110 and the insulating layer 131 also require low dielectric loss characteristics in order to increase the insulating property.

At least one of the insulator or the prepreg 110 and the insulating layer 131 should have a low dielectric constant and dielectric loss and a high rigidity. In the present invention, in order to lower the coefficient of thermal expansion of the insulating layer and increase the glass transition temperature, the insulating layer may include a liquid crystal oligomer, preferably a liquid crystal oligomer represented by the following Chemical Formulas 2 to 5; Epoxy resin; And a tetraphenylethane curing agent represented by the following formula (1).

Further, the insulating layer or prepreg may be a liquid crystal oligomer, preferably a liquid crystal oligomer represented by the following general formulas (2) to (5); Epoxy resin; A tetraphenyl ethane curing agent represented by the following formula (1); And an inorganic filler.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

A represents an integer of 13 to 26; b represents an integer of 13 to 26; c represents an integer of 9 to 21; d represents an integer of 10 to 30; and e represents an integer of 10 to 30.

Liquid crystal Oligomer

Liquid crystal oligomers (LCO), preferably liquid crystal oligomers represented by the general formulas (2) to (5), contain ester groups at both ends of the main chain for improving dielectric tangent and dielectric constant, and include naphthalene groups for crystallization , And may contain a phosphorus component imparting flame retardancy.

The number average molecular weight of the liquid crystal oligomer is preferably 2,000 to 10,000 g / mol, more preferably 3,000 to 6,000 g / mol, and still more preferably 4,500 to 5,500 g / mol. When the number average molecular weight of the liquid crystal oligomer is less than 2,000 g / mol, the mechanical properties are poor. When the number average molecular weight is more than 10,000 g / mol, the solubility is decreased.

The polydispersity index of the liquid crystal oligomer is preferably 1.5 to 3. When the polydispersity index is less than 1.5 in the LCO single synthesis process, the synthesis time is prolonged and the number average molecular weight is increased to 10,000 or more, so that the solubility in a polar solvent such as DMAc is lowered and it is difficult to ensure the fairness. In addition, when the polydispersity index is more than 3 in the LCO single synthesis process, the number average molecular weight is less than 2,000, and when the low molecular weight LCO is used as the substrate material, the glass transition temperature of the cured product decreases to 200 ° C or less.

On the other hand, when a resin composition containing no inorganic filler is prepared, the amount of the liquid crystal oligomer used is preferably 39 to 60% by weight, and more preferably 45 to 55% by weight. When the amount is less than 39% by weight, the thermal expansion coefficient is decreased and the glass transition temperature is not improved. When the amount is more than 60% by weight, the mechanical properties tend to decrease.

On the other hand, when preparing a resin composition containing an inorganic filler, the amount of the liquid crystal oligomer to be used is preferably 9 to 30% by weight. If the amount is less than 9 wt%, the thermal expansion coefficient decreases and the glass transition temperature does not improve. If the amount is more than 30 wt%, mechanical properties tend to deteriorate.

Epoxy resin

The resin composition according to the present invention includes an epoxy resin in order to improve the handleability of the resin composition after drying as an adhesive film. The epoxy resin is not particularly limited but means that one or more epoxy groups are contained in the molecule, preferably two or more epoxy groups are contained in the molecule, more preferably four or more epoxy groups are contained in the molecule .

The epoxy resin used in the present invention may contain a naphthalene group as shown in the following formula (6), or an aromatic amine type as shown in the following formula (7).

[Chemical Formula 6]

In Formula 6, R is an alkyl group having 1 to 20 carbon atoms, and n is an integer of 0 to 20.

(7)

However, the epoxy resin used in the present invention is not particularly limited to the epoxy resin represented by the above formula 6 or 7, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, Naphthalene type epoxy resins, phenols and phenolic hydroxyl groups, phenolic hydroxyl group-containing epoxy resins, phenol novolak type epoxy resins, biphenyl type epoxy resins, aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, A biphenylaralkyl type epoxy resin, a fluorene type epoxy resin, a xanthene type epoxy resin, a triglycidyl isocyanurate, a rubber modified epoxy resin, and a phosphorous type epoxy resin Resins, and examples thereof include naphthalene-based epoxy resins, bisphenol-A-type epoxy resins, phenol novolac epoxy Kinds, cresol novolak epoxy resins, rubber metamorphic type epoxy resin, and a (phosphorous) based epoxy resin is preferred. One or more epoxy resins may be used in combination.

In the case of producing a resin composition not containing an inorganic filler, the amount of the epoxy resin is preferably from 39 to 60% by weight, and if the amount is less than 39% by weight, the handling property is poor. If the amount is more than 60% by weight, The addition amount of the component is decreased, and the dielectric tangent, the dielectric constant and the thermal expansion coefficient hardly improve.

On the other hand, when a resin composition containing an inorganic filler is prepared, the amount of the epoxy resin is preferably 9 to 30% by weight, and if the amount is less than 9% by weight, handling is inferior. When the amount is more than 30% by weight, The addition amount of the other components is reduced, and the dielectric tangent, the dielectric constant and the thermal expansion coefficient hardly improve.

Tetraphenyl ethane  Hardener

Meanwhile, the resin composition according to the present invention includes a tetraphenyl ethane curing agent represented by the following formula (1) to further improve thermal expansion coefficient and thermal properties.

[Chemical Formula 1]

The hydroxy group of the tetraphenyl ethane curing agent reacts with the epoxy group of the epoxy resin in the thermosetting reaction to form a network in which the liquid crystal oligomer, the epoxy resin and the tetraphenyl ethane curing agent are interconnected in the resin composition according to the present invention do. That is, in the present invention, a liquid crystal oligomer having a specific structure as described above and a tetraphenylethane curing agent having excellent reactivity with an epoxy resin are selected from among various curing agents to form interconnected networks, thereby lowering the thermal expansion rate of the resin composition, Heat resistance could be exhibited. The tetraphenyl ethane curing agent has been used as a curing agent in various resin compositions, but there has been no report to improve the heat resistance property.

When a resin composition containing no inorganic filler is prepared, the amount of the tetraphenylethane curing agent is preferably from 0.1 to 1% by weight, and if it is less than 0.1% by weight, the curing rate is poor, The curing rate is too fast to be applied to the process, and the unreacted curing agent is present after the reaction, and the moisture absorption rate of the insulating film or prepreg is increased, and the electrical characteristics tend to be deteriorated.

On the other hand, when a resin composition containing an inorganic filler is prepared, the amount of the tetraphenylethane curing agent is preferably 0.01 to 0.5 wt%, and if it is less than 0.01 wt%, the curing rate is poor or the curing rate is poor, , The curing rate is too fast and the process is difficult to apply. After the reaction, the unreacted curing agent is present and the moisture absorption rate of the insulating film or the prepreg is increased, and the electrical characteristics tend to be lowered.

Inorganic filler

The resin composition according to the present invention further includes an inorganic filler to lower the coefficient of thermal expansion (CTE) of the epoxy resin. The inorganic filler lowers the coefficient of thermal expansion. The content of the inorganic filler in the resin composition varies depending on the properties required in consideration of the use of the resin composition and the like, but is preferably 50 to 80% by weight. If it is less than 50% by weight, the dielectric loss tangent is low and the thermal expansion rate is high. If it exceeds 80% by weight, the adhesive strength tends to decrease.

Specific examples of the inorganic filler used in the present invention include silica, alumina, barium sulfate, talc, mud, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, Calcium, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc. may be used alone or in combination of two or more. Particularly, silica having low dielectric loss tangent is preferable.

In addition, when the inorganic filler has an average particle diameter exceeding 5 mu m, it is difficult to stably form a fine pattern when a circuit pattern is formed on the conductor layer, and therefore, the average particle diameter is preferably 5 mu m or less. The inorganic filler is preferably surface-treated with a surface treatment agent such as a silane coupling agent in order to improve moisture resistance. More preferably silica having a diameter of 0.2 to 2 mu m is preferable.

Hardening accelerator

The resin composition of the present invention can be efficiently cured by selectively containing a curing accelerator. The curing accelerator used in the present invention includes metal curing accelerators, imidazole curing accelerators and amine curing accelerators. These can be used alone or in combination of two or more in the usual amounts used in the art have.

The metal-based curing accelerator is not particularly limited, and examples thereof include organometallic complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese and tin. Specific examples of the organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, free copper complexes such as copper (II) acetylacetonate, zinc (II) acetylacetonate 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 organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. As the metal curing accelerator, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, zinc naphthenate and iron (III) acetylacetonate are preferable from the viewpoints of curability and solvent solubility Cobalt (II) acetylacetonate, and zinc naphthenate are particularly preferred. Based curing accelerators may be used alone or in combination of two or more.

The imidazole-based curing accelerator is not particularly limited, and examples thereof include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2- 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- 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenyl Imidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- -s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl- Phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole isocyanuric acid adduct, Methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenyl-2-methylimidazolium chloride, 2- Imidazole compounds such as imidazoline, and adducts of imidazole compounds and epoxy resins. The imidazole curing accelerator may be used alone or in combination of two or more.

Examples of the amine curing accelerator include, but are not limited to, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) , And 8-diazabicyclo (5,4,0) -undecene (hereinafter referred to as DBU). One or more amine-based curing accelerators may be used in combination.

Thermoplastic resin

The resin composition of the present invention may optionally contain a thermoplastic resin to improve the film properties of the resin composition or to improve the mechanical properties of the cured product. Examples of the thermoplastic resin include phenoxy resin, polyimide resin, polyamideimide (PAI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyphenylene ether PPE resin, polycarbonate (PC) resin, polyetheretherketone (PEEK) resin, and polyester resin. These thermoplastic resins may be used alone or in combination of two or more. The weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000. If it is less than 5,000, the effect of improving film formability and mechanical strength tends not to be sufficiently exhibited. If it is more than 200,000, compatibility with liquid crystal oligomer and epoxy resin is not sufficient, surface unevenness after curing becomes large, There is a problem that it becomes difficult. Specifically, the weight average molecular weight was measured using Shimadzu Seisakusho LC-9A / RID-6A as a measuring device and Shodex K-800P / K-804L / K-804L as a column. , And the mobile phase was measured at a column temperature of 40 ° C using chloroform (CHCl ₃ ) or the like and calculated using a calibration curve of standard polystyrene.

When a thermoplastic resin is blended in the resin composition of the present invention, the content of the thermoplastic resin in the resin composition is not particularly limited, but is preferably 0.1 to 10% by weight, more preferably 0.1 to 10% by weight based on 100% By weight is 1 to 5% by weight. If the content of the thermoplastic resin is less than 0.1% by weight, the effect of improving film formability and mechanical strength tends not to be exhibited. If the content is more than 10% by weight, the increase of the melt viscosity and the surface roughness of the insulating layer after the wet- .

The insulating resin composition according to the present invention is mixed in the presence of an organic solvent. As the organic solvent, in consideration of the solubility and miscibility of the resin and other additives used in the present invention, it is preferable to use 2-methoxyethanol, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, But are not limited to, methyl ether acetate, ethylene glycol monobutyl ether acetate, cellosolve, butyl cellosolve, carbitol, butyl carbitol, xylene, dimethyl formamide and dimethylacetamide.

The viscosity of the resin composition according to the present invention is preferably 1000 to 2000 cps when the inorganic filler is not contained and is preferably 700 to 1500 cps when the inorganic filler is contained, It has the characteristic of maintaining tenacity. The viscosity of the resin composition can be controlled by varying the content of the solvent. The resin composition contains the non-volatile component excluding the solvent in an amount of 30 to 70% by weight. If the viscosity of the resin composition is out of the above range, it is difficult to form an insulating film or it may be difficult to form a member even if it is formed.

The peel strength is 1.0 kN / m or more when a copper foil of 12 mu m is used in the state of an insulating film. The insulating film made of the resin composition according to the present invention has a coefficient of thermal expansion (CTE) of 15 to 50 ppm / 占 폚 when the inorganic filler is not contained. Further, the glass transition temperature (Tg) is 210 占 폚 or higher, preferably 220 to 270 占 폚.

In addition, the present invention may further include other leveling agents and / or flame retardants and the like, which are known to those skilled in the art by those skilled in the art within the technical scope of the present invention.

The insulating resin composition of the present invention can be produced in a semi-solid state dry film by any general method known in the art. For example, a roll coater or a curtain coater may be used to produce a film, followed by drying and applying the same to a substrate to form an insulating layer Or an insulating film) or a prepreg. Such an insulating film or prepreg has a low thermal expansion coefficient (CTE) of 50 ppm / DEG C or less.

As described above, the resin composition according to the present invention is obtained by impregnating a substrate such as glass fiber or the like, and then curing the prepreg to prepare a copper clad laminate (CCL) by laminating a copper foil thereon. In addition, the insulating film made of the resin composition according to the present invention is used for manufacturing a multilayer printed circuit board by laminating the CCL used as an inner layer in the manufacture of a multilayer printed circuit board. For example, an insulating film made of the insulating resin composition is laminated on a patterned inner-layer circuit board, cured at a temperature of 80 to 110 ° C for 20 to 30 minutes, subjected to a desmearing process, It is possible to manufacture a multilayer printed circuit board by forming it through an electroplating process.

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

Production Example 1

Preparation of liquid crystal oligomer

(2.0 mol) of 4-aminophenol, 415.33 g (2.5 mol) of isophthalic acid, 276.24 g (2.0 mol) of 4-hydroxybenzoic acid and 282.27 g ), 648.54 g (2.0 mol) of 9,10-dihydroxy-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO; And 1531.35 g (15.0 mol) of acetic anhydride were added. After sufficiently replacing the inside of the reactor with nitrogen gas, the temperature in the reactor was raised to 230 deg. C under a nitrogen gas flow, and refluxed for 4 hours while maintaining the temperature inside the reactor. After addition of 188.18 g (1.0 mol) of 6-hydroxy-2-naphthoic acid for end capping, the reaction by-products acetic acid and unreacted acetic anhydride were removed to obtain a liquid crystal oligomer having a molecular weight of about 4,500, .

Example 1

1400 g of silica having a size distribution of 0.2 to 1 mu m in average particle diameter was dispersed in 2-methoxyethanol to prepare a silica slurry having a concentration of 70% by weight. Thereafter, a bisphenol F type tetrafunctional epoxy (N, N, N ', N'-tetraglycidyl-4,4'-methylenebisbenzamine (N, N, N ', N'-Tetraglycidyl-4,4'-methylenebisbenzenamine)) was added, and the mixture was stirred at 300 rpm at room temperature to dissolve the mixture. Then, 5 g of tetraphenylethane represented by the above formula (1) and 500 g of the liquid crystal oligomer prepared in Preparation Example 1 dissolved in dimethylacetamide were added to the mixture, followed by further stirring at 300 rpm for 1 hour to prepare a resin composition . This is coated on a copper foil shiny side with a doctor blade method to a thickness of 100 mu m to produce a film. The resulting film is dried at room temperature for 2 hours, dried in a vacuum oven at 80 ° C for 1 hour, and then dried at 110 ° C for 1 hour to form a semi-cured state (B-stage). This is fully cured using a vacuum press. At this time, the maximum temperature was 230 DEG C and the maximum pressure was 2 MPa.

Example 2

The procedure of Example 1 was repeated except that no silica was used.

Comparative Example 1

1400 g of silica having a size distribution of 0.2 to 1 mu m in average particle diameter was dispersed in 2-methoxyethanol to prepare a silica slurry having a concentration of 70% by weight. Thereafter, 500 g of a bisphenol F type tetrafunctional epoxy (N, N, N ', N'-tetraglycidyl-4,4'-methylenebisbenzamine) having an average epoxy equivalent of 100 to 300 was added to the prepared silica slurry And the mixture was stirred at room temperature and 300 rpm to prepare a mixture. Then, 5 g of dicyandiamide curing agent and 500 g of the liquid crystal oligomer prepared in Preparation Example 1 dissolved in dimethylacetamide were added to the mixture, followed by further stirring at 300 rpm for 1 hour to prepare a resin composition. This is coated on a copper foil shiny side with a doctor blade method to a thickness of 100 mu m to produce a film. The resulting film is dried at room temperature for 2 hours, dried in a vacuum oven at 80 ° C for 1 hour, and then dried at 110 ° C for 1 hour to form a semi-cured state (B-stage). This is fully cured using a vacuum press. At this time, the maximum temperature was 230 DEG C and the maximum pressure was 2 MPa.

Comparative Example 2

1400 g of silica having a size distribution of 0.2 to 1 mu m in average particle diameter was dispersed in 2-methoxyethanol to prepare a silica slurry having a concentration of 70% by weight. Thereafter, 500 g of a bisphenol F type tetrafunctional epoxy (N, N, N ', N'-tetraglycidyl-4,4'-methylenebisbenzamine) having an average epoxy equivalent of 100 to 300 was added to the prepared silica slurry And the mixture was stirred at room temperature and 300 rpm to prepare a mixture. Then, 5 g of the tetrafluoroethane curing agent represented by the above formula (1) was added to the mixture and further stirred at 300 rpm for 1 hour to prepare a resin composition. This is coated on a copper foil shiny side with a doctor blade method to a thickness of 100 mu m to produce a film. The resulting film is dried at room temperature for 2 hours, dried in a vacuum oven at 80 ° C for 1 hour, and then dried at 110 ° C for 1 hour to form a semi-cured state (B-stage). This is fully cured using a vacuum press. At this time, the maximum temperature was 230 DEG C and the maximum pressure was 2 MPa.

Evaluation of thermal properties

The thermal expansion coefficient (CTE) of the specimen of the insulating film prepared according to Example 1 and Comparative Examples 1 and 2 was measured using a thermomechanical analyzer (TMA), and the glass transition temperature (Tg) (First cycle) and 300 占 폚 (second cycle) in a nitrogen atmosphere by heating a thermal analyzer (TA Instruments TMA 2940) with a differential scanning calorimeter (DSC) at 10 ° C / Respectively.

Evaluation of peel strength of copper foil

The peel strength of the copper foil was measured by peeling a copper foil having a width of 1 cm from the surface of the copper foil laminates and measuring the peel strength of the copper foil using a universal testing machine (UTM) (KTW100). The results are shown in Table 1 Deg.] Peel test, crosshead speed: 50 mm / min).

Thermal Expansion Coefficient (ppm / ° C) Glass transition temperature (캜) Peel strength (T) (kN / m) Example 1 49.2 228 1.0 or higher Example 2 50.0 222 1.0 or higher Comparative Example 1 54.8 207 0.92 Comparative Example 2 65.0 170 0.91

The results of Table 1 show that the insulating films according to Examples 1 and 2 using the tetraphenylethane curing agent have a lower coefficient of thermal expansion (CTE) than the insulating film according to Comparative Example 1 using the dicyandiamide curing agent and have a glass transition temperature Tg) is high. The peel strength can also be improved. In addition, it can be seen that the insulating film according to Example 1 exhibits more improved thermal characteristics than the insulating film according to Comparative Example 2 except for the liquid crystal oligomer and the tetraphenylethane curing agent.

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

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

100: printed circuit board 110: insulator
120: Electronic component 130: Buildup layer
131: insulating layer 132: circuit layer
140: capacitor 150: resistive element
160: solder resist 170: external connection means
180: Pad

Claims (16)

Liquid crystal oligomers;
Epoxy resin; And
1. A resin composition for a printed circuit board comprising a tetrafluoroethane curing agent represented by the following formula (1).
[Chemical Formula 1]

The method according to claim 1,
The resin composition for a printed circuit board according to claim 1, further comprising an inorganic filler.
The method according to claim 1,
Wherein the liquid crystal oligomer is represented by the following general formula (2), (3), (4), or (5)
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

B is an integer of 13 to 26, c is an integer of 9 to 21, d is an integer of 10 to 30, and e is an integer of 10 to 30, in the formulas 2 to 5, a is an integer of 13 to 26, b is an integer of 13 to 26,
The method according to claim 1,
Wherein the resin composition comprises 39 to 60% by weight of the liquid crystal oligomer, 39 to 60% by weight of an epoxy resin, and 0.1 to 1% by weight of a tetraphenyl ethane curing agent.
The method of claim 2,
Wherein the resin composition comprises 9 to 30% by weight of a liquid crystal oligomer, 9 to 30% by weight of an epoxy resin, 0.01 to 0.5% by weight of a tetraphenyl ethane curing agent, and 50 to 80% by weight of an inorganic filler.
The method according to claim 1,
Wherein the liquid crystal oligomer has a number average molecular weight of 2,000 to 10,000.
The method according to claim 1,
Wherein the liquid crystal oligomer has a polydispersity index of 1.5 to 3.
The method according to claim 1,
Wherein the epoxy resin is at least one selected from naphthalene type epoxy resin, bisphenol A type epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, rubber modified epoxy resin, and phosphorous epoxy resin Resin composition.
The method according to claim 1,
Wherein the epoxy resin has at least four epoxy functional groups.
The method of claim 2,
The inorganic filler may be selected from the group consisting of silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, calcium titanate, Titanium oxide, barium zirconate, and calcium zirconate. The resin composition according to claim 1,
The method according to claim 1,
Wherein the resin composition further comprises at least one curing accelerator selected from metal-based curing accelerators, imidazole-based curing accelerators, and amine-based curing accelerators.
The method according to claim 1,
The resin composition may be at least one selected from the group consisting of phenoxy resin, polyimide resin, polyamideimide (PAI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyphenylene ether Wherein the thermoplastic resin further comprises at least one thermoplastic resin selected from a resin, a polycarbonate (PC) resin, a polyetheretherketone (PEEK) resin, and a polyester resin.
An insulating film made from the resin composition according to claim 1.
A prepreg produced by impregnating a substrate with a resin composition according to claim 1.
A printed circuit board comprising the insulating film of claim 13.
A printed circuit board comprising the prepreg of claim 14.

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