KR102059824B1 - Insulating resin composition for photo curing and printed circuit board using the same - Google Patents

Abstract

The present invention provides a photocurable insulating resin composition and a printed circuit board using the same. More specifically, the photocurable insulating resin composition according to an embodiment of the present invention includes a photocurable liquid crystal oligomer, a photocurable graphene oxide and a photocurable metal alkoxide, it is possible to produce an insulating film using the resin composition, A printed circuit board including the insulating film may be manufactured.

Description

Photocurable insulating resin composition and printed circuit board using the same {INSULATING RESIN COMPOSITION FOR PHOTO CURING AND PRINTED CIRCUIT BOARD USING THE SAME}

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

With the development of electronic devices, the weight, thickness and size of printed circuit boards are increasing day by day, and in order to meet these demands, wiring of printed circuit boards is becoming more complicated and denser. As such, the electrical, thermal, and mechanical stability required in printed circuit boards is considered to be more important. Among them, deformation due to heat is one of important factors that determine reliability in manufacturing printed circuit boards.

The printed circuit board is mainly composed of a metal that acts as a wiring and a polymer that serves as an insulating layer. Compared to the metal, the coefficient of thermal expansion (CTE) of the polymer is very high. To overcome this difference, the polymer is impregnated into woven glass fiber or an inorganic filler is added to the printed circuit. The material which lowered the coefficient of thermal expansion of the polymer which comprises an insulating layer in a board | substrate is used.

In general, increasing the content of the inorganic filler in the insulating layer lowers the coefficient of thermal expansion of the insulating layer, but this has limitations in the manufacturing process of printed circuit boards, and the roughness of the surface in order to meet the demands of densified fine circuit patterns. Is also considered important. In order to secure such surface roughness, the size of the inorganic filler added is getting smaller. However, as the size of the inorganic filler decreases, there is a constraint of uniform dispersibility, and evenly dispersing the nano-sized filler is a big problem.

For example, the thermal expansion coefficient of the metal layer in the printed circuit board is 10 to 20 ppm / ℃ and the thermal expansion coefficient (a ₁ ) of the insulating layer is 50 to 80 ppm / ℃. In particular, the polymer, which is a constituent material of the insulating layer, has a large thermal expansion coefficient higher than the glass transition temperature (Tg), wherein the thermal expansion coefficient (a ₂ ) reaches 150 to 180 ppm / ° C.

In conclusion, there is a need for a metal layer serving as a wiring of a printed circuit board and a polymer material for an insulating layer having the same thermal expansion coefficient as that of a semiconductor chip to be mounted on the substrate.

Patent Document 1: Japanese Unexamined Patent Publication No. 2010-239150

The photocurable insulating resin composition according to an embodiment of the present invention is to provide an effect of lowering the coefficient of thermal expansion by including a photocurable liquid crystal oligomer, a photocurable graphene oxide and a photocurable metal alkoxide.

Moreover, it is providing the insulation film produced using the said photocurable insulation resin composition.

In addition, the present invention provides a printed circuit board including the insulation film, and when processing a via hole in an insulation film existing in the printed circuit board, the process may be performed in a fine size.

The photocurable insulating resin composition according to an embodiment of the present invention includes a photocurable liquid crystal oligomer, a photocurable graphene oxide and a photocurable metal alkoxide.

The photocurable liquid crystal oligomer is represented by the following formula (1),

[Formula 1]

In Formula 1, Ar ₁ is a divalent aromatic organic group having a structural unit selected from one or more selected from esters, amides, ester amides, ester imides and ether imides, the weight average molecular weight is 5000 or less, P ₁ is acrylic At least one is selected from a rate type or methacrylate type resin.

Ar ₁ includes one or more structural units selected from the group represented by Formula 2,

[Formula 2]

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Here, n and m are integers of 1 to 100, Ar ₂ , Ar ₄ , Ar ₅ And Ar _{6 It} is a divalent aromatic organic group, containing at least one structural unit selected from the group represented by the following formula (3),

[Formula 3]

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Ar ₃ is a tetravalent aromatic organic group, and includes one or more structural units selected from the group represented by the following general formula (4).

[Formula 4]

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The acrylate resin is at least one selected from polyester acrylate resin, epoxy acrylate resin, urethane acrylate resin, polyether acrylate resin, polybutadiene acrylate resin, silicone acrylate resin and alkyl acrylate resin, The methacrylate resin is at least one selected from polyester methacrylate resins, epoxy methacrylate resins, urethane methacrylate resins, polyether methacrylate resins and silicone methacrylate resins.

The number average molecular weight of the photocurable liquid crystal oligomer is 500 to 15,000.

The photocurable graphene oxide includes at least one functional group selected from epoxy groups, ketone groups, acrylate groups and methacrylate groups on the surface and at the edges.

The photocurable metal alkoxide includes one or more structures represented by the following Formula 5 or 6,

[Formula 5]

[Formula 6]

R ₁ to R ₃ of Formula 5 and R ₄ to R ₆ of Formula ₆ are each independently an alkyl group having at least one carbon number.

The photocurable metal alkoxide represented by Formula 5 includes an acryl group as a functional group, and the photocurable metal alkoxide represented by Formula 6 includes a methacryl group as a functional group.

The metal of the photocurable metal alkoxide is titanium (Ti), aluminum (Al), germanium (Ge), cobalt (Co), calcium (Ca), hafnium (Hf), iron (Fe), nickel (Ni), niobium ( Nb), molybdenum (Mo), lanthanum (La), rhenium (Re), scandium (Sc), silicon (Si), tantalum (Ta), tungsten (W), yttrium (Y), zirconium (Zr) and vanadium At least one selected from the group consisting of (V).

The photocurable insulating resin composition may further include an epoxy resin, the epoxy resin is contained in 0.01 to 50 parts by weight based on 100 parts by weight of the photocurable liquid crystal oligomer of the composition, naphthalene type epoxy resin, bisphenol A type epoxy resin At least one selected from the group consisting of bisphenol F type epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, rubber modified epoxy resins and phosphorus epoxy resins.

An insulating film may be manufactured using the photocurable insulating resin composition according to the exemplary embodiment of the present invention.

A printed circuit board including the insulating film may be manufactured.

1 is a view schematically illustrating the configuration of a photocurable insulating resin composition according to an embodiment of the present invention.

Before describing the invention in more detail, the terms or words used in the specification and claims are not to be limited to their usual or dictionary meanings, and the concept of terms is appropriately described to best explain the invention. It should be interpreted as meanings and concepts in accordance with the technical spirit of the present invention based on the principle that it can be defined. Therefore, the configuration of the embodiments described herein is only one preferred example of the present invention, and does not represent all of the technical idea of the present invention, various equivalents and modifications that can replace them at the time of the present application It should be understood that there may be

Hereinafter, preferred embodiments of the present invention will be described in detail so that those skilled in the art may easily implement the present invention. In addition, in the description of the present invention, detailed descriptions of related well-known technologies that may unnecessarily obscure the subject matter of the present invention will be omitted.

1 is a view schematically illustrating the configuration of a photocurable insulating resin composition according to an embodiment of the present invention. Referring to FIG. 1, the present invention provides a photocurable insulating resin composition capable of improving the coefficient of thermal expansion and mechanical properties through covalent bonding of a photocurable liquid crystal oligomer, a photocurable graphene oxide, and a photocurable metal alkoxide.

Photocurable  LCD Oligomer

The photocurable insulating resin composition according to an embodiment of the present invention includes a photocurable liquid crystal oligomer. Since the liquid crystal oligomer has a low coefficient of thermal expansion by itself, it can replace an epoxy resin mainly applied to a general insulating resin composition.

The photocurable liquid crystal oligomer may be represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, Ar ₁ is a divalent aromatic organic group having a structural unit selected from one or more selected from esters, amides, ester amides, ester imides and ether imides, the weight average molecular weight of 5000 or less, P ₁ is acrylic At least one is selected from a rate type or methacrylate type resin.

Ar ₁ includes one or more structural units selected from the group represented by Formula 2,

[Formula 2]

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Here, n and m are integers of 1 to 100, Ar ₂ , Ar ₄ , Ar ₅ And Ar _{6 It} is a divalent aromatic organic group, containing at least one structural unit selected from the group represented by the following formula (3),

[Formula 3]

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Ar ₃ is a tetravalent aromatic organic group, and includes one or more structural units selected from the group represented by the following general formula (4).

[Formula 4]

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The number average molecular weight of the photocurable liquid crystal oligomer represented by the formula (1) is preferably 500 to 15,000. When the number average molecular weight of the liquid crystal oligomer is less than 500, the crosslinking density may be increased, thereby causing brittle properties, and when the number average molecular weight of the liquid crystal oligomer is greater than 15,000, the viscosity of the solution may be increased, thereby preventing the flowability of the process.

An example of a photocurable liquid crystal oligomer according to an embodiment of the present invention is shown in Chemical Formula 7.

[Formula 7]

As in Chemical Formula 7, the photocurable liquid crystal oligomer according to an embodiment of the present invention has a soluble structure (A) soluble in one or more solvents in the main chain and a group (B) having excellent processability, which can be dissolved in a general solvent. It may have a functional group (C) capable of realizing liquid crystal (Liquid Crystal) characteristics, and has a functional group (D) that can be cured by light at both ends.

Representatively represented by the formula (7), the soluble structure (A) is 4-aminophenol (4-aminophenol), Grum (B) is excellent in processability isophthalic acid (isophthallc acid) and the functional group (C) that can implement the liquid crystal characteristics 6-hydroxy-2-naphthoic acid and the like can be applied.

P ₁ represented by the formula (1) may be represented by the functional group (D), at least one selected from acrylate resin or methacrylate resin.

The acrylate resin is at least one selected from polyester acrylate resin, epoxy acrylate resin, urethane acrylate resin, polyether acrylate resin, polybutadiene acrylate resin, silicone acrylate resin and alkyl acrylate resin, The methacrylate resin is at least one selected from polyester methacrylate resins, epoxy methacrylate resins, urethane methacrylate resins, polyether methacrylate resins, and silicone methacrylate resins.

The photocurable liquid crystal oligomer may be prepared by reacting compounds capable of preparing a liquid crystal oligomer including a soluble structural unit through polymerization and a compound capable of introducing a photocurable group.

Compounds capable of producing the liquid crystal oligomer including the soluble structural unit are not particularly limited. For example, one or more aromatic, aromatic heterocyclic or aliphatic dicarboxylic acids; Aromatic, aromatic heterocyclic or aliphatic diols; Aromatic, aromatic heterocyclic or aliphatic diamines; Amino phenol: hydroxybenzoic acid; And aminobenzoic acid, and may be selected from the group consisting of aromatic, aromatic heterocyclic or aliphatic diols; Amino phenol; It is suitable to use at least one of amino benzoic acids.

The photocurable liquid crystal oligomer has a significantly lower coefficient of thermal expansion than an epoxy resin used as a conventional insulating polymer, and includes various functional groups, thereby forming a complex structure with other components included in the insulating resin composition. have.

Photocurable Graphene oxide

The photocurable insulating resin composition according to the embodiment of the present invention includes photocurable oxide oxide. Grain oxide has a low coefficient of thermal expansion and has excellent mechanical properties. In order to improve the mechanical stiffness of the insulating resin composition, generally, an inorganic filler made of silica may be added to replace the inorganic filler, which may be used, and a graphene oxide having a photocurable functional group may be applied. You can.

In general, the graphene oxide may be prepared by oxidizing graphite, which has a layered structure in which graphene, which is a plate structure in which carbon atoms are connected by a hexagonal ring, is stacked. In general, the distance between the layers is 3.35 Å and the structure of the carbon nanotubes unfolded in a flat state, which has a high conductivity corresponding to the carbon nanotubes and has excellent mechanical properties.

When the graphite powder is oxidized, each layer of graphite is oxidized to obtain a graphene oxide powder having a hydroxyl group, a carboxyl group, an epoxy group, a ketone group, and the like, which can be represented by the following formula (8).

[Formula 8]

The graphene oxide powder may be prepared by oxidizing the graphite powder by an oxidizing agent or by oxidizing by an electrochemical method. Examples of the oxidizing agent include nitric acid (HNO ₃ ), sodium chlorate (NaClO ₃ ), potassium permanganate (KMnO ₄ ), and the like, and these may be used alone or in combination of two or more thereof.

It is preferable to use the photocurable graphene oxide sufficiently oxidized in order not to deteriorate the characteristic of an insulating resin. That is, it is suitable that it is sufficiently oxidized and shows little or no electrical conductivity characteristics. To this end, the ratio of carbon number to carbon of oxygen (carbon / oxygen) of the graphene oxide may vary depending on the degree of oxidation, for example, 1 to 20 is suitable.

The photocurable graphene oxide is obtained by substituting a hydroxyl group (-OH) of a hydroxyl group and a carboxy group attached to the graphene oxide represented by Chemical Formula 8 with a photocurable functional group.

Therefore, the photocurable graphene oxide is represented by the following formula (9), and includes at least one functional group selected from the epoxy group, ketone group, acrylate group and methacrylate group on the surface and edge.

[Formula 9]

Therefore, when the photocurable graphene oxide represented by the formula (9) is added to the insulating resin composition, it may be physically dispersed in the cured product of the photocurable liquid crystal oligomer, and form a chemical bond with the polymer resin by the functional group. can do. Grain oxide having a photocurable functional group may form a covalent bond by a curing reaction with the photocurable liquid crystal oligomer, thereby forming a complex organically connected with the photocurable liquid crystal oligomer.

The photocurable graphene oxide is preferably included in an amount of 0.01 to 90 parts by weight based on 100 parts by weight of the photocurable liquid crystal oligomer. If the content of the graphene oxide is less than 0.01 parts by weight, the effect of lowering the coefficient of thermal expansion is insignificant, and if it exceeds 90 parts by weight, there is a problem that the thickness becomes too thin due to the low viscosity.

Photocurable Metal alkoxide

The photocurable insulating resin composition according to an embodiment of the present invention includes a photocurable metal alkoxide. The photocurable metal alkoxide may be applied to a metal alkoxide having a photocurable functional group in place of an inorganic filler made of silica, in order to improve the mechanical rigidity of the insulating resin composition like the photocurable graphene oxide. Can be. In addition, the addition of a small amount can improve the coefficient of thermal expansion and mechanical properties, and can be covalently bonded to the photocurable liquid crystal oligomer and the photocurable graphene oxide.

The photocurable metal alkoxide includes one or more structures represented by the following Formula 5 or 6,

[Formula 5]

[Formula 6]

R ₁ to R ₃ of Formula 5 and R ₄ to R ₆ of Formula ₆ are each independently an alkyl group having at least one carbon number.

The photocurable metal alkoxide represented by Formula 5 includes an acryl group as a functional group, and the photocurable metal alkoxide represented by Formula 6 includes a methacryl group as a functional group.

The photocurable metal alkoxide may include a reactor capable of covalent bonding with a photocurable group included in the photocurable liquid crystal oligomer. In addition, each metal compound having one reactor may be used alone, or may be composed of a combination of each metal compound having various reactors.

The metal of the photocurable metal alkoxide is titanium (Ti), aluminum (Al), germanium (Ge), cobalt (Co), calcium (Ca), hafnium (Hf), iron (Fe), nickel (Ni), niobium ( Nb), molybdenum (Mo), lanthanum (La), rhenium (Re), scandium (Sc), silicon (Si), tantalum (Ta), tungsten (W), yttrium (Y), zirconium (Zr) and vanadium At least one selected from the group consisting of (V).

The photocurable metal alkoxide is suitably included in an amount of 0.01 to 90 parts by weight based on 100 parts by weight of the photocurable liquid crystal oligomer. When the content of the metal alkoxide is less than 0.01 part by weight, the effect of lowering the coefficient of thermal expansion is inadequate, and when the content of the metal alkoxide is greater than 90 parts by weight, the insulating resin composition itself may be brittle and cracks may occur.

The photocurable insulating resin composition may further include an epoxy resin in order to improve peel strength, but is not particularly limited, but is not particularly limited to naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol. At least one selected from the group consisting of a novolac epoxy resin, a cresol novolac epoxy resin, a rubber modified epoxy resin and a phosphorus epoxy resin.

As a result, the photocurable insulating resin composition according to an embodiment of the present invention may form a covalent bond with each other by a curing reaction of the photocurable liquid crystal oligomer, the graphene oxide and the metal alkoxide.

The photocurable liquid crystal oligomer is a homogeneous organic-inorganic composite material in which covalent bonds of metal clusters formed by condensation reactions from photocurable oxide and photocurable metal alkoxides are formed.

The covalent bond is formed between the photocurable liquid crystal oligomer-photocurable oxidized photoresist, photocurable liquid crystalline oligomer-photocurable metal alkoxide, photocurable oxidized graphene-photocurable metal alkoxide.

In addition, the photocurable insulating resin composition according to an embodiment of the present invention is not particularly limited in the solvent used in the manufacture, a polar aprotic solvent (Aprotic Solvent) can be used. For example, N, N-dimethylacetamide, N-methylpyrrolidone (NMP), N-methylcaprolactone, N, N-dimethylformamide, N, N-diethylformamide, N, N-di One or more selected from the group consisting of ethyl acetamide, N-methylpropionamide, dimethyl sulfoxide, γ-butyl lactone, dimethylimidazolidinone, tetramethylphosphoric amide and ethyl cellosolve acetate may be used, optionally Among these, two or more types of mixed solvents can be used.

An insulating film or prepreg may be manufactured using the photocurable insulating resin composition according to an exemplary embodiment of the present invention, and a printed circuit board including the insulating film or prepreg may be manufactured. The insulating resin composition is a composite material having an organic-inorganic hybrid structure, and has excellent thermal, mechanical and electrical properties, and thus has high utility as an insulating material of a printed circuit board.

The insulating material may be made of an insulating film by curing the insulating resin composition, or a prepreg prepared by impregnating the insulating resin composition with an organic fiber or an inorganic fiber.

The inorganic fibers or organic fibers include glass fibers, carbon fibers, polyparaphenylene benzobisoxazole fibers, thermotropic liquid crystal polymer fibers, lysotropic liquid crystal polymer fibers, aramid fibers, polypyridobisimidazole fibers, One or more may be selected from polybenzothiazole fibers, and polyarylate fibers, but is not particularly limited thereto.

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

Photocurable  LCD Oligomer  Produce

Molar ratio of aminophenol, isophthalic acid, naphthoic acid, hydroxybenzoic acid, and Nadimido benzoic acid in a 100 ml flask equipped with a condenser and agitator 100 g of liquid crystal oligomer (number average molecular weight 7500) was prepared by mixing and reacting in the range of 2: 1: 2: 2: 2, and 50 g of hydroxylethyl acrylate (HEA), a photocurable functional group, was added thereto. Stirring at the temperature for 12 hours to prepare a photocurable liquid crystal oligomer.

Photocurable Of graphene oxide  Produce

After preparing a three-necked flask and an ice bath, 10 g of graphite and 230 g of sulfuric acid (H ₂ SO ₄ ) were added and dispersed for 2 hours. 6 g of sodium nitrate (Sodium Nitrade, NaNO 3) was added as a catalyst and dispersed for 1 hour. It was prepared to prepare a general graphene oxide.

6 g of the prepared normal oxide of copper was dispersed in 600 g of dimethylformamide (DMF), and further dispersed by ultrasonic wave for 1 hour. Then, prepare a four-necked flask and ice bath, add 143 g of diphenylmethane diisocyanate (DMI), react for 3 hours at a temperature of 70 ° C., and then add 143 g of hydroxyethyl acrylate. Reaction was carried out at a temperature of 50 ℃ for 12 hours to prepare a graphene oxide substituted with an acrylate functional group.

Example 1

100 g of acetone solvent was mixed with 100 g of the photocurable liquid crystal oligomer and 6 g of the photocurable graphene oxide substituted with an acrylate group, and dispersed by ultrasonication for 1 hour. Here, 50 g of methylacryloxypropyltrimethoxysilane, which is a photocurable metal alkoxide, was mixed and dispersed by ultrasonication for 1 hour. Here, 5 g of amine was added as a photoinitiator and dispersed for 30 minutes, followed by degassing at a temperature of 60 ° C. for 5 hours to prepare a photocurable insulating resin composition.

Example 2

A varnish containing the photocurable insulating resin composition was coated on a polyethylene terephthalate (PET) film released by a doctor blade method to a thickness of about 100 μm to prepare a specimen. The specimen was photocured with a 100 W / cm 2 UV irradiator for 30 minutes to prepare an insulating film.

Example 3

The copper foil layer was laminated | stacked on both surfaces of the prepreg, and the circuit pattern was formed. Then, after drying for 30 minutes at a temperature of about 120 ℃, the insulating film prepared in Example 2 was laminated on a substrate on which a circuit pattern was formed and at a condition of about 90 ℃, 2MPa using Morton CVA 725 vacuum laminate The printed circuit board was manufactured by vacuum laminating for about 20 seconds.

Property evaluation

The coefficient of thermal expansion of the specimen prepared using the resin composition according to Example 1 was measured using a thermal analyzer (Thermo Mechanical Analyzer, TMA) in three temperature ranges (α1 (40-80 ° C), α2 (150-200 ° C)). , α 3 (220-240 ° C.).

division Coefficient of thermal expansion (ppm / ℃)
α1 Coefficient of thermal expansion (ppm / ℃)
α2 Coefficient of thermal expansion (ppm / ℃)
α3 Example 1 7.3 2.0 0.7

As can be seen from Table 1, it can be seen that the coefficient of thermal expansion of the specimen prepared using the photocurable insulating resin composition according to an embodiment of the present invention is significantly lower than the coefficient of thermal expansion of the general insulating polymer resin.

In addition, it can be seen that the numerical value of the coefficient of thermal expansion is low in each temperature range section. Through this, the insulating material produced using the photocurable insulating resin composition is suitable for applying to a printed circuit board, it can be seen that the insulating material can minimize the generation of warpage (warpage) with the metal layer in the substrate. .

Therefore, the photocurable insulating resin composition according to an embodiment of the present invention may include a photocurable liquid crystal oligomer, a photocurable graphene oxide, and a photocurable metal alkoxide, thereby lowering the coefficient of thermal expansion and minimizing warpage. In addition, since the photocurable insulating resin composition is cured by light such as UV, the curing speed is short, and thus the process time can be shortened.

In addition, an insulating material such as an insulating film, a prepreg, etc. manufactured using the resin composition may be manufactured, and the prepared insulating material may be applied to a printed circuit board. As a result, when the via hole is processed into the insulating material existing in the substrate, the via hole may be processed to a minute size.

Although the present invention has been described in detail through specific embodiments, it is intended to describe the present invention in detail, and the present invention is not limited thereto, and should be understood by those skilled in the art within the technical spirit of the present invention. It is obvious that modifications and improvements are possible.

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

Claims (13)

A photocurable liquid crystal oligomer comprising at least one or more of an acrylate resin and a methacrylate resin as a functional group;
Photocurable graphene oxide comprising at least one or more of an epoxy group, a ketone group, an acrylate group and a methacrylate group as a functional group; And
Photocurable metal alkoxide containing at least 1 or more of an acryl group and a methylacryl group to a functional group;
Including;
The photocurable liquid crystal oligomer is a photocurable insulating resin composition represented by the following formula (1).
[Formula 1]

In Formula 1, Ar1 is a divalent aromatic organic group having one or more structural units selected from esters, amides, ester amides, ester imides and ether imides, and has a weight average molecular weight of 5000 or less, P1 is the acrylate At least one selected from the group or the methacrylate resin. delete The method according to claim 1,
Ar ₁ includes one or more structural units selected from the group represented by Formula 2,
[Formula 2]

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Here, n and m are integers of 1 to 100, Ar ₂ , Ar ₄ , Ar ₅ And Ar _{6 It} is a divalent aromatic organic group, containing at least one structural unit selected from the group represented by the following formula (3),
[Formula 3]

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Ar ₃ is a tetravalent aromatic organic group, the photocurable insulating resin composition comprising one or more structural units selected from the group represented by the following formula (4).
[Formula 4]

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The method according to claim 1,
The acrylate resin is at least one selected from polyester acrylate resin, epoxy acrylate resin, urethane acrylate resin, polyether acrylate resin, polybutadiene acrylate resin, silicone acrylate resin and alkyl acrylate resin, The methacrylate resin is at least one photocurable insulating resin composition selected from polyester methacrylate resins, epoxy methacrylate resins, urethane methacrylate resins, polyether methacrylate resins, and silicone methacrylate resins. The photocurable insulating resin composition of Claim 1 whose number average molecular weights of the said photocurable liquid crystal oligomer are 500-15,000. delete The method according to claim 1,
The photocurable metal alkoxide has a photocurable insulating resin composition comprising at least one structure represented by the following formula (5) or (6):
[Formula 5]

[Formula 6]

R ₁ to R ₃ of Formula 5 and R ₄ to R ₆ of Formula ₆ are each independently an alkyl group having at least one carbon number. delete The method according to claim 1,
The metal of the photocurable metal alkoxide is titanium (Ti), aluminum (Al), germanium (Ge), cobalt (Co), calcium (Ca), hafnium (Hf), iron (Fe), nickel (Ni), niobium ( Nb), molybdenum (Mo), lanthanum (La), rhenium (Re), scandium (Sc), silicon (Si), tantalum (Ta), tungsten (W), yttrium (Y), zirconium (Zr) and vanadium Photocurable insulating resin composition selected from the group consisting of (V). The method according to claim 1,
The composition is a photocurable insulating resin composition further comprising an epoxy resin. The method according to claim 10,
The epoxy resin is contained in 0.01 to 50 parts by weight based on 100 parts by weight of the photocurable liquid crystal oligomer of the composition, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac epoxy resin, cresol novolac At least one photocurable insulating resin composition selected from the group consisting of an epoxy resin, a rubber modified epoxy resin and a phosphorus epoxy resin. An insulating film using the photocurable insulating resin composition according to claim 1. Printed circuit board comprising an insulating film according to claim 12.

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