JP2014051640A - Printed circuit board composition, and printed circuit board containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printed circuit board composition with excellent thermal characteristics, and a printed circuit board containing the same.SOLUTION: A printed circuit board composition having a low thermal expansion coefficient and high heat resistance comprises: 5-49 wt.% of a liquid crystal oligomer which includes, at least at one end, a functional group of the specified chemical formula E; 5-42 wt.% of an epoxy resin; and 14-90 wt.% of a filler. (In the chemical formula E, Z4 represents a substituted or unsubstituted C3-C30 heteroatom-containing alicyclic group, and n4 represents an integer of 0-3.)

Description

  The present invention relates to a composition for a printed circuit board excellent in thermal characteristics and a printed circuit board containing the composition.

  Various electronic products such as computers, semiconductors, displays, and communication devices use a substrate on which a specific electronic circuit is printed. On the substrate, signal lines (signal lines), insulating layers for preventing a short circuit between the wires, a switching element, and the like can be formed.

  Recently, with the development of electronic devices that are miniaturized, increased in frequency, and digitized, higher integration and higher density of components and substrates are required.

  The printed circuit board may be formed by laminating a prepreg obtained by impregnating a glass fiber with an epoxy resin and semi-curing the prepreg on the inner circuit board on which the circuit is formed.

  Alternatively, it can be manufactured by a build-up method in which a substrate is manufactured by alternately laminating insulating layers on a circuit pattern of an inner layer circuit board on which a circuit is formed. In the build-up method, a via hole is formed to increase the wiring density, a circuit is formed by laser processing or the like, and the printed circuit board can be densified and thinned.

  Recently, with the development of electronic devices that are reduced in weight, thickness, and size, such printed circuit boards have also been highly integrated and densified. Accordingly, the electrical, thermal and mechanical stability of the printed circuit board is an important factor for the stability and reliability of the electronic equipment.

Korean Patent Publication No. 10-2011-0108782

  The present invention provides a composition for a printed circuit board having excellent thermal characteristics and a printed circuit board including the composition.

  One embodiment of the present invention includes a structural unit of the following chemical formula 1, a structural unit of the following chemical formula 2, and a structural unit of the following chemical formula D, and a liquid crystal oligomer having a functional group of the following chemical formula E at at least one terminal. And a composition for a printed circuit board comprising 5 to 42 wt% of an epoxy resin and 30 to 90 wt% of a filler.

（化２）

（化Ｄ）

（化Ｅ）

(Chemical formula 1)

(Chemical formula 2)

(Chemical D)

(Chemical E)

In the above chemical formulas 1, 2, D and E,
X _{1 to} X ₄ are the same or different from each other, and C (═O) O, O, C (═O) NR, NR ′, or CO (wherein R and R ′ are the same or different from each other, hydrogen, substituted or non-substituted A substituted C1-C20 alkyl group, or a substituted or unsubstituted C6-C30 aryl group).
Z ₁ and Z ₂ are each independently a hydroxy group, a substituted or unsubstituted C3-C30 alicyclic group, and Z ₃ and Z ₄ are substituted or unsubstituted C3-C30 heteroatom-containing alicyclic rings. Family group,
N _{1 to} n ₄ are each independently an integer of 0 to 3, and n ₁ + n ₂ + n ₃ + n ₄ may be 1 or more,
_{A 1} in Formula 1 is one of the functional group represented by the following chemical formula 4-1 to 4-7.

（化４−２）

（化４−３）

（化４−４）

（化４−５）

（化４−６）

（化４−７）

(Chemical 4-1)

(Chemical 4-2)

(Chemical 4-3)

(Chemical 4-4)

(Chemical 4-5)

(Chemical 4-6)

(Chemical 4-7)

In Chemical Formula 4-7, L ₁ is a divalent organic functional group. In Chemical Formula 4-1 to Chemical Formula 4-7, at least one hydrogen of each aromatic ring is halogen, substituted or unsubstituted. C1-C20 alkyl group, substituted or unsubstituted C1-C20 alkoxy group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C7 -C30 arylalkyl group, substituted or unsubstituted C6-C30 aryloxy group or Z ₁ (Z ₁ is as defined in Chemical Formula 1 above),
A ₂ in the chemical formula ₂ is a C2 to C20 alkylene group having one of the functional groups represented by the following chemical formulas 5-1 to 5-6 or the functional group of the following chemical formula 6.

(Chemical 5-1)

In the chemical formula 5-1, Y ^{1 to} Y ³ are the same or different and are hydrogen, a C1 to C10 alkyl group, or a functional group of the following chemical formula 6, provided that at least one of Y ^{1 to} Y ³ is represented by the following chemical formula 6 P1 is an integer of 0 to 4, m1 and m2 are the same or different, and are an integer of 0 to 3, p1, m1 and m2 are not simultaneously 0 and R and R ′ are hydrogen or C1 Is a C10 alkyl group.

(Chemical 5-2)

In the above chemical formula 5-2, Y ⁴ and Y ⁵ are the same or different and are hydrogen, a C1-C10 alkyl group or a functional group of the following chemical formula 6, and at least one of Y ⁴ and Y ⁵ is a function of the following chemical formula 6 P2 and p3 are integers of 0 to 3, and are not 0 at the same time.

(Chemical formula 5-3)

In the above chemical formula 5-3, Y ^{6 to} Y ⁸ are the same or different and are hydrogen, a C1 to C10 alkyl group, or a functional group of the following chemical formula 6, and at least one of Y ^{6 to} Y ⁸ is a function of the following chemical formula 6 P4 and p6 are integers of 0 to 3, p5 is an integer of 0 to 2, and p4, p5 and p6 are not 0 at the same time.

(Chemical formula 5-4)

In the above chemical formula 5-4, Y ⁹ and Y ¹⁰ are the same or different and are hydrogen, a C1-C10 alkyl group or a functional group of the following chemical formula 6, and at least one of Y ⁹ and Y ¹⁰ is the function of the following chemical formula 6 P7 and p8 are integers of 0 to 2 and are not 0 at the same time.

上記化学式５−５において、Ｙ^１１及びＹ^１２は同一または異なり、水素、Ｃ１〜Ｃ１０のアルキル基または下記化学式６の作用基であり、Ｙ^１１及びＹ^１２の少なくとも一つは下記化学式６の作用基であり、ｐ９及びｐ１０は０〜４の整数で、同時に０ではない。 (Chemical 5-5)

In Formula 5-5, Y ¹¹ and Y ¹² are the same or different and are hydrogen, a C1-C10 alkyl group, or a functional group of the following Chemical Formula 6, and at least one of Y ¹¹ and Y ¹² is the function of Chemical Formula 6 below. P9 and p10 are integers of 0 to 4, and are not 0 at the same time.

(Chemical 5-6)

In the above chemical formula 5-6, Y ¹³ and Y ¹⁴ are the same or different and are hydrogen, a C1-C10 alkyl group or a functional group of the following chemical formula 6, and at least one of Y ¹³ and Y ¹⁴ is the functional formula of the following chemical formula 6. a group, pi 1 and p12 is an integer from 0 to 4, _{L 2} is an ether group, sulfide group, ketone group, an amide group, a sulfoxide, a sulfone group, an azo group, cyanide group, a substituted or unsubstituted C1~C20 An alkylene group, a substituted or unsubstituted C2-C20 alkenylene group, a substituted or unsubstituted C6-C30 arylene group, a divalent organic functional group that is not substituted or substituted with at least one functional group of the following chemical formula 6, or a divalent organic functional groups of the following formula 7-1 to 7-3, _{when L 2} is not substituted with a functional group of the following formula 6, pi 1 and p12 All instead of 0,
In the above chemical formulas 5-1 to 5-6, at least one hydrogen of each aromatic ring is a halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted Or an unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, a substituted or unsubstituted C6-C30 aryloxy group, or Z ₁ (Z ₁ is the same as defined in Chemical Formula 1) can be substituted.

(Chemical formula 6)

In Formula 6, Ar ₁ and Ar ₂ are C4-C30 substituted or unsubstituted aromatic ring groups, and R and R ′ are the same or different from each other, and are hydrogen, C1-C20 alkyl group, or C6-C30 An aryl group, m is an integer of 0 to 3;

(Chemical 7-1)

  In Formula 7-1, R is hydrogen, halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C3-C20 cycloalkyl group, A substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, or a substituted or unsubstituted C6-C30 aryloxy group.

(Chemical Formula 7-2)

  In the above chemical formula 7-2, R is hydrogen, halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C3-C20 cycloalkyl group, A substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, or a substituted or unsubstituted C6-C30 aryloxy group.

(Chemical Formula 7-3)

According to one embodiment of the present invention, L _{1 in} Formula 4-7 is an ether group, a sulfide group, a ketone group, a sulfoxide, a sulfone group, an azo group, a cyanide group, a substituted or unsubstituted C1-C20 alkylene group. A substituted or unsubstituted C2-C20 alkenylene group or a substituted or unsubstituted C6-C30 arylene group.

In addition, L _{2 in} Formula 5-6 is an ether group, a sulfide group, a ketone group, an amide group, a sulfoxide, a sulfone group, an azo group, a cyanide group, a substituted or unsubstituted C1-C20 alkylene group, a substituted or non-substituted group A substituted C2-C20 alkenylene group, a substituted or unsubstituted C6-C30 arylene group, a divalent organic functional group that is not substituted or substituted with at least one functional group of Formula 6, or the above Formulas 7-1-7 -3, a divalent organic functional group.

  Formula 6 may be represented by Formula 11 below.

(Chemical Formula 11)

In Formula 11, R ¹ and R ² are the same or different and are hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl group, substituted or unsubstituted C1-C20 alkoxy group, substituted or unsubstituted C3- C20 cycloalkyl group, a substituted or unsubstituted C6~C30 aryl group, a substituted or unsubstituted C7~C30 arylalkyl group, an aryloxy group, or _{Z 1} of C6~C30 substituted or unsubstituted (formula 1 P1 and p2 are integers of 0 to 4, and R and R ′ are the same or different from each other, and are hydrogen, a C1 to C20 alkyl group or a C6 to C30 aryl group. , M is an integer of 0-3.

  According to an embodiment of the present invention, the liquid crystal oligomer may be represented by the following Formula 12.

(Chemical formula 12)

  In the chemical formula 12, the structural units of a, b, c, d and e mean molar ratios, and can be determined within the number average molecular weight of the liquid crystal oligomer.

  According to an exemplary embodiment of the present invention, the liquid crystal oligomer may be represented by the following chemical formula 13.

(Chemical Formula 13)

  In the above chemical formula 13, the structural units of a, b, c, d and e mean a molar ratio and can be determined within the number average molecular weight of the liquid crystal oligomer.

  The ratio of the liquid crystal oligomer and the epoxy resin (liquid crystal oligomer / epoxy resin) may be 0.66 or more and 2.33 or less.

  In addition, the structural unit of the chemical formula D and the functional group of the chemical formula E may be included in an amount of 5 to 40 mol% with respect to the total amount of the liquid crystal oligomer.

  The above epoxy resins are phenolic novolac type epoxy resins, cresol novolac type epoxy resins, naphthol modified novolak type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, triphenyl type epoxy resins, etc. Glycidyl ether type epoxy resins, dicyclopentadiene type epoxy resins having a dicyclopentadiene skeleton, naphthalene type epoxy resins having a naphthalene skeleton, dihydroxybenzopyran type epoxy resins, glycidyl amine type epoxy resins made from polyamines such as diaminophenylmethane , One or more selected from the group consisting of a triphenolmethane type epoxy resin and a tetraphenylethane type epoxy resin.

The filler can be an inorganic filler, an organic filler, or a mixture thereof.

  The inorganic filler is not particularly limited, and may be one or more selected from the group consisting of alumina, aluminum nitride, boron nitride, fused silica, silicon nitride, and Teflon, for example.

  The organic filler is not particularly limited, and may be, for example, one or more selected from the group consisting of thermoplastic liquid crystal polymer resin, cellulose, carbon nanotube, graphene, and graphite.

  The composition for a printed circuit board according to the present invention may further include 0.1 to 0.5 wt% of a curing agent.

  Still another embodiment of the present invention includes an insulating layer and a circuit pattern formed on the insulating layer, and the insulating layer includes a structural unit represented by the following chemical formula 1, a structural unit represented by the following chemical formula 2, and a structure represented by the following chemical formula D. Provided is a printed circuit board comprising a composition containing 5 to 49 wt% of a liquid crystal oligomer containing a unit and having a functional group of the following chemical formula E at at least one end, 5 to 42 wt% of an epoxy resin, and 14 to 90 wt% of a filler can do.

（化２）

（化Ｄ）

（化Ｅ）

(Chemical formula 1)

(Chemical formula 2)

(Chemical D)

(Chemical E)

  In another embodiment of the present invention, a liquid crystal oligomer having a structural unit represented by the following chemical formula 1, a structural unit represented by the following chemical formula 2, and a structural unit represented by the following chemical formula D and having a functional group represented by the following chemical formula E at at least one end: % And an epoxy resin of 5 to 42 wt% can be provided.

  ADVANTAGE OF THE INVENTION According to this invention, the composition for printed circuit boards which has a low thermal expansion coefficient and has high heat resistance, and the printed circuit board which applied this can be provided.

1 is a cross-sectional view schematically illustrating a printed circuit board according to an embodiment of the present invention.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings.

  However, the embodiments of the present invention can be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.

  In addition, the embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.

  Accordingly, the shape and size of elements in the drawings may be exaggerated for a clearer description, and elements denoted by the same reference numerals in the drawings are the same elements.

  In addition, the same reference numerals are used throughout the drawings for parts having similar functions and operations.

  Further, in all the specifications, “comprising” a certain component means that the component can further include other components rather than excluding other components unless specifically stated to the contrary. .

  Unless otherwise specified herein, “substituted” means that a hydrogen atom in a compound or a functional group is halogen (F, Cl, Br, I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, Azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C1-C20 alkyl group, C2-C16 alkynyl group, C6-C20 aryl group, C7-C13 arylalkyl group, C1-C4 oxyalkyl group, C1-C20 heteroalkyl group, C3-C20 heteroarylalkyl group, C3-C20 A cycloalkyl group, a C3-C15 cycloalkenyl group, a C6-C15 cycloalkynyl group, B means that has been substituted with a cycloalkyl group or a combination of substituents thereof.

  Unless otherwise specified herein, “hetero” means that 1 to 3 hetero atoms of N, O, S, Si, or P are present in the ring.

  Unless otherwise specified in this specification, the “alicyclic group” means a C3-C30 cycloalkyl group, a C3-C30 cycloalkenyl group, a C3-C30 cycloalkynyl group, a C3-C30 heterocycloalkyl group. , C3-C30 heterocycloalkenyl group, C3-C30 heterocycloalkynyl group and the like.

  Unless otherwise specified in this specification, an “aromatic ring group” means a ring structure in which unsaturated bonds, unpaired electron pairs, etc. are mixed, and electrons are non-localized. A functional group in the form of delocalization or resonance structure means a C6-C30 aryl group, a C2-C30 heteroaryl group and a C2-C30 heterocycloalkenyl group.

  FIG. 1 is a cross-sectional view schematically illustrating a printed circuit board according to an embodiment of the present invention.

  Referring to FIG. 1, the printed circuit board according to the present embodiment includes a circuit formed on one side or both sides of first to third insulating layers 11, 12, 13 and first to third insulating layers 11, 12, 13. Horizontal wirings 21 as patterns and via electrodes 22 can be included.

  For example, the first insulating layer 11 as an intermediate layer may be provided, and the second insulating layer 12 and the third insulating layer 13 may be stacked on the upper surface and the lower surface of the first insulating layer 11 to form the main body of the substrate.

  At least one horizontal wiring 21 is formed on one or both surfaces of the first to third insulating layers 11, 12, and 13, and the via electrode 22 penetrates the first to third insulating layers 11, 12, and 13 vertically. By being connected, each horizontal wiring 21 is electrically connected.

  On the other hand, in the present embodiment, a printed circuit board having a four-layer structure is illustrated, but the present invention is not limited to this, and a single layer or two or more layers depending on the number of insulating layers to be stacked and a circuit pattern to be formed. A multilayer wiring board may be used.

  The first to third insulating layers 11, 12, and 13 of such a printed circuit board can be formed of the composition according to an embodiment of the present invention described in detail below.

  At this time, the first to third insulating layers 11, 12, and 13 may be made of a prepreg in which a composition according to an embodiment of the present invention is impregnated with a reinforcing material.

  As described above, when the printed circuit board is composed of the composition according to the present embodiment, the electrical, thermal and mechanical stability can be ensured even if the printed circuit board is reduced in weight, thickness and size. I can look forward to it.

  Hereinafter, the components of the composition for a printed circuit board according to an embodiment of the present invention and the characteristics thereof will be described more specifically.

  The composition for a printed circuit board according to an embodiment of the present invention may include (A) a liquid crystal oligomer, (B) an epoxy resin, and (C) a filler.

(A) Liquid Crystal Oligomer The liquid crystal oligomer contained in the composition for a printed circuit board according to the present embodiment includes a structural unit represented by the following chemical formula 1, a structural unit represented by the following chemical formula 2, and a structural unit represented by the following chemical formula D. The functional group of the following chemical formula E can be included.

（化２）

（化Ｄ）

（化Ｅ）

(Chemical formula 1)

(Chemical formula 2)

(Chemical D)

(Chemical E)

In the above chemical formulas 1, 2, D and E,
X _{1 to} X ₄ are the same or different from each other, and C (═O) O, O, C (═O) NR, NR ′, or CO (wherein R and R ′ are the same or different from each other, hydrogen, substituted or non-substituted A substituted C1-C20 alkyl group or a substituted or unsubstituted C6-C30 aryl group).

Z ₁ and Z ₂ are each independently a hydroxy group, a substituted or unsubstituted C3-C30 alicyclic group, and Z ₃ and Z ₄ are substituted or unsubstituted C3-C30 heteroatom-containing alicyclic rings. It can be a group.

N _{1 to} n ₄ are each independently an integer of 0 to 3, and n ₁ + n ₂ + n ₃ + n ₄ may be 1 or more.

_{A 1} in Formula 1 can be one of the functional group represented by the following chemical formula 4-1 to 4-7.

In the above A ₁ , both bonding groups of the aromatic ring bonded to the main chain may be in the ortho or meta position.

  An aromatic structural unit having such a kink structure can be repeatedly introduced into the main chain of the liquid crystal oligomer.

  That is, the linearity of the main chain of the liquid crystal oligomer decreases due to the introduction of the twisted structure. Thereby, the interaction between the main chains and the crystallinity are reduced, and the solubility in the solvent can be improved.

（化４−２）

（化４−３）

（化４−４）

（化４−５）

（化４−６）

（化４−７）

(Chemical 4-1)

(Chemical 4-2)

(Chemical 4-3)

(Chemical 4-4)

(Chemical 4-5)

(Chemical 4-6)

(Chemical 4-7)

In Chemical Formula 4-7, L ₁ is a divalent organic functional group. In Chemical Formula 4-1 to Chemical Formula 4-7, at least one hydrogen of each aromatic ring is halogen, substituted or unsubstituted. C1-C20 alkyl group, substituted or unsubstituted C1-C20 alkoxy group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C7 It can be substituted with a -C30 arylalkyl group, a substituted or unsubstituted C6-C30 aryloxy group or Z ₁ (Z ₁ is as defined in Chemical Formula 1 above).

In the chemical formula 2, A ₂ may be one of the functional groups represented by the following chemical formulas 5-1 to 5-6 or a C2 to C20 alkylene group having the functional group of the following chemical formula 6.

(Chemical 5-1)

In the chemical formula 5-1, Y ^{1 to} Y ³ may be the same or different, and are hydrogen, a C1 to C10 alkyl group, or a functional group of the following chemical formula 6. However, at least one of Y ^{1 to} Y ³ is a functional group of the following chemical formula 6, p1 is an integer of 0 to 4, m1 and m2 are the same or different, and are an integer of 0 to 3, p1, m1 And m2 are not simultaneously 0 and R and R ′ can be hydrogen or a C1-C10 alkyl group.

(Chemical 5-2)

In the above chemical formula 5-2, Y ⁴ and Y ⁵ are the same or different and are hydrogen, a C1-C10 alkyl group or a functional group of the following chemical formula 6, and at least one of Y ⁴ and Y ⁵ is a function of the following chemical formula 6 Can be a group. p2 and p3 are integers of 0 to 3, and are not 0 at the same time.

(Chemical formula 5-3)

In the above chemical formula 5-3, Y ^{6 to} Y ⁸ are the same or different and are hydrogen, a C1 to C10 alkyl group, or a functional group of the following chemical formula 6, and at least one of Y ^{6 to} Y ⁸ is a function of the following chemical formula 6 Can be a group. p4 and p6 are integers of 0 to 3, p5 is an integer of 0 to 2, and p4, p5 and p6 are not 0 at the same time.

(Chemical formula 5-4)

In the above chemical formula 5-4, Y ⁹ and Y ¹⁰ are the same or different and are hydrogen, a C1-C10 alkyl group or a functional group of the following chemical formula 6, and at least one of Y ⁹ and Y ¹⁰ is the function of the following chemical formula 6 Can be a group. p7 and p8 are integers of 0 to 2, and are not 0 at the same time.

(Chemical 5-5)

In Formula 5-5, Y ¹¹ and Y ¹² are the same or different and are hydrogen, a C1-C10 alkyl group, or a functional group of the following Chemical Formula 6, and at least one of Y ¹¹ and Y ¹² is the function of Chemical Formula 6 below. Can be a group. p9 and p10 are integers of 0 to 4, and are not 0 at the same time.

(Chemical 5-6)

In the above chemical formula 5-6, Y ¹³ and Y ¹⁴ are the same or different and are hydrogen, a C1-C10 alkyl group or a functional group of the following chemical formula 6, and at least one of Y ¹³ and Y ¹⁴ is the functional formula of the following chemical formula 6. a group, pi 1 and p12 is an integer from 0 to 4, _{L 2} is an ether group, sulfide group, ketone group, an amide group, a sulfoxide, a sulfone group, an azo group, cyanide group, a substituted or unsubstituted C1~C20 An alkylene group, a substituted or unsubstituted C2-C20 alkenylene group, a substituted or unsubstituted C6-C30 arylene group, a divalent organic functional group that is not substituted or substituted with at least one functional group of the following chemical formula 6, or It can be a divalent organic functional group of the following chemical formulas 7-1 to 7-3. When L ₂ is not substituted with the functional group of the following chemical formula 6, p11 and p12 are not all 0.

In the above chemical formulas 5-1 to 5-6, at least one hydrogen of each aromatic ring is a halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted Or an unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, a substituted or unsubstituted C6-C30 aryloxy group, or Z ₁ (Z ₁ is the same as defined in Chemical Formula 1) can be substituted.

(Chemical formula 6)

In Formula 6, Ar ₁ and Ar ₂ are C4-C30 substituted or unsubstituted aromatic ring groups, and R and R ′ are the same or different from each other, and are hydrogen, C1-C20 alkyl group, or C6-C30 It can be an aryl group, and m is an integer of 0-3.

(Chemical 7-1)

  In Formula 7-1, R is hydrogen, halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C3-C20 cycloalkyl group, It can be a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, or a substituted or unsubstituted C6-C30 aryloxy group.

(Chemical Formula 7-2)

  In the above chemical formula 7-2, R is hydrogen, halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C3-C20 cycloalkyl group, It can be a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, or a substituted or unsubstituted C6-C30 aryloxy group.

(Chemical Formula 7-3)

  Formula 7-3 is still another embodiment of the present invention, and R may not be present.

  The number average molecular weight of the liquid crystal oligomer may be 500 to about 10,000 g / mol. When the liquid crystal oligomer has a number average molecular weight in the above range, it has an appropriate crosslinking density, excellent solubility characteristics in a solvent, and when impregnated into a network structure for prepreg production, the solid content is sufficient and excellent The physical properties can be secured.

  The structural unit of the chemical formula D and the functional group of the chemical formula E may be included in an amount of 5 to 40 mol% with respect to the total amount of the liquid crystal oligomer. When the content is less than 5 mol%, the effect of reducing the thermal expansion coefficient is not clear, and the thermal expansion coefficient tends to decrease from 5 mol% to 40 mol%. When it exceeds 40 mol%, the tendency for the thermal expansion coefficient to decrease does not appear, and the mechanical properties of the liquid crystal oligomer may decrease.

L _{1 in} Formula 4-7 is an ether group, a sulfide group, a ketone group, a sulfoxide, a sulfone group, an azo group, a cyanide group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20. It may be an alkenylene group, a substituted or unsubstituted C6-C30 arylene group, and the like. Specifically, L ₁ may be any one of those represented by the following chemical formulas 9-1 to 9-10.

（化９−２）

(Chemical Formula 9-1)

(Chemical 9-2)

In the chemical formula 9-2, R _a and R _b are each independently hydrogen, halogen, a C1-C5 alkyl group, a C1-C5 haloalkyl group, or Z ₁ (same as defined in the chemical formula 1). Can be.

（化９−４）

（化９−５）

(Chemical 9-3)

(Chemical 9-4)

(Chemical 9-5)

In the chemical formula 9-5, R _a is hydrogen, halogen, a C1-C5 alkyl group, a C1-C5 haloalkyl group, or Z ₁ (Z ₁ is the same as defined in the chemical formula 1).

(Chemical 9-6)

In Formula 9-6, R _a and R _b are each independently hydrogen, halogen, a C1-C5 alkyl group, a C1-C5 haloalkyl group, or Z ₁ (same as defined in Formula 1 above). is there.

(Chemical 9-7)

In the chemical formula 9-7, R _a and R _b are each independently hydrogen, halogen, a C1-C5 alkyl group, a C1-C5 haloalkyl group, or Z ₁ (same as defined in the chemical formula 1). is there.

(Chemical 9-8)

In the chemical formula 9-8, E ₁ and E ₂ are the same or different from each other and are a linking group selected from the group consisting of a single bond, an ether group, an ester group, a ketone group, a sulfide group, a sulfoxide and a sulfone group.

(Chemical 9-9)

In Chemical Formula 9-9, R _a and R _b are each independently hydrogen, halogen, a C1-C5 alkyl group, a C1-C5 haloalkyl group, or Z ₁ (same as defined in Chemical Formula 1 above). E ₁ and E ₂ are the same or different from each other, and are a linking group selected from the group consisting of a single bond, an ether group, an ester group, a ketone group, a sulfide group, a sulfoxide and a sulfone group.

(Chemical 9-10)

In the chemical formulas 9-10, E ₁ and E ₂ are each independently a linking group selected from the group consisting of a single bond, an ether group, an ester group, a ketone group, a sulfide group, a sulfoxide, and a sulfone group.

In the above chemical formulas 9-8 to 9-10, at least one hydrogen of each aromatic ring is halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, substituted or Unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C7-C30 arylalkyl group, substituted or unsubstituted C6-C30 aryloxy group or Z ₁ (same as defined in Chemical Formula 1 above).

L _{2 in} Formula 5-6 is an ether group, a sulfide group, a ketone group, an amide group, a sulfoxide, a sulfone group, an azo group, a cyanide group, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C2 ~ C20 alkenylene group, substituted or unsubstituted C6 to C30 arylene group, divalent organic functional group not substituted or substituted with at least one functional group of Chemical Formula 6 above, or Chemical Formulas 7-1 to 7-3 above It is a divalent organic functional group.

The L ₂ may be any one of those represented by the chemical formulas 9-1 to 9-10, for example. In the chemical formulas 9-2, 9-5, 9-6, 9-7 and 9-9, R _a and R _b are each independently hydrogen, halogen, a C1-C5 alkyl group, or a C1-C5 haloalkyl group. , Z ₁ (similar to the definition in Chemical Formula 1 above) or the functional group of Chemical Formula 6 in which at least one hydrogen of each aromatic ring is a halogen atom, a substituted group in Chemical Formulas 9-8 to 9-10 Or an unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted arylalkyl group C7 to C30, substituted or unsubstituted aryloxy group C6 to C30, (which is the same as defined in formula 1) _{Z 1} or the chemical formula It may be substituted with functional groups.

  As a specific example of the chemical formula 6, the chemical formula 11 can be given.

(Chemical Formula 11)

In Formula 11, R ¹ and R ² are the same or different and are hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl group, substituted or unsubstituted C1-C20 alkoxy group, substituted or unsubstituted C3- C20 cycloalkyl group, a substituted or unsubstituted C6~C30 aryl group, a substituted or unsubstituted C7~C30 arylalkyl group, an aryloxy group, or _{Z 1} of C6~C30 substituted or unsubstituted (formula 1 P1 and p2 are integers of 0 to 4, and R and R ′ are the same or different from each other, and are hydrogen, a C1 to C20 alkyl group or a C6 to C30 aryl group. , M is an integer of 0-3.

  According to an embodiment of the present invention, the liquid crystal oligomer may include a functional group that is curable not only in the chain or terminal but also in the main chain. The functional group can include a hydroxy group, a carbon-carbon double bond, and a carbon-carbon triple bond. In particular, by including a curable functional group in the main chain, curing may occur between the liquid crystal oligomers, thereby providing a composition for a substrate having a low thermal expansion coefficient.

  Moreover, the flame retardance of an insulating resin composition can be improved more, when the functional group containing phosphorus is included in the principal chain or measuring chain of a liquid crystal oligomer.

  In addition, the liquid crystal oligomer according to an embodiment of the present invention may be represented by the following chemical formula 12.

(Chemical formula 12)

  In the above chemical formula 12, a, b, c, d and e mean the molar ratio of structural units and can be determined by the content of the starting material.

  The liquid crystal oligomer represented by the chemical formula 12 contains a hydroxyl group at both ends, a functional group containing phosphorus in the chain, and a ferulic acid group having an ethylene structure in the main chain. The double bond of the ethylene structure contained in the main chain enables a curing reaction between the oligomers contained in the composition.

  The liquid crystal oligomer according to another embodiment of the present invention may be represented by the following chemical formula 13.

(Chemical 13)

  The liquid crystal oligomer represented by the chemical formula 13 contains a hydroxyl group at both ends, a functional group containing phosphorus in the chain, and a ferulic acid group having an acetylene structure in the main chain. The triple bond of the acetylene structure contained in the main chain enables a curing reaction between the oligomers contained in the composition.

  The liquid crystal oligomer of the above chemical formula 12 or 13 has a feature that it can be cured between the liquid crystal oligomers by photocuring.

(B) Epoxy Resin The resin composition for a printed circuit board according to the present embodiment can contain an epoxy resin.

The epoxy resin is not particularly limited. For example, phenol novolac epoxy resin, cresol novolac epoxy resin, naphthol modified novolac epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, triphenyl Phenolic glycidyl ether type epoxy resin such as epoxy resin; dicyclopentadiene type epoxy resin having dicyclopentadiene skeleton; naphthalene type epoxy resin having naphthalene skeleton; dihydroxybenzopyran type epoxy resin; polyamine such as diaminophenylmethane Glycidylamine type epoxy resin; triphenolmethane type epoxy resin; tetraphenylethane type epoxy resin; or a mixture thereof. Rukoto can.

  More specifically, the epoxy resin is N, N, N ′, N′-tetraglycidyl-4,4′-methylenebisbenzenamine (N, N, N ′, N′-tetragylcydyl-4,4 ′. -Methylenebisbenzenamine), glycidyl ether type o-cresol-formaldehyde novolac, or a mixture thereof.

  The epoxy resin may be included such that the ratio of the liquid crystal oligomer to the epoxy resin (liquid crystal oligomer / epoxy resin) is 0.66 or more and 2.33 or less. As the epoxy resin increases, the thermal expansion coefficient decreases. However, when the ratio of the liquid crystal oligomer to the epoxy resin (liquid crystal oligomer / epoxy resin) is less than 0.66, the effect of reducing the thermal expansion coefficient is remarkably reduced, and the dielectric constant. Is not suitable for use as a thin-layer substrate material. Further, if the content of the epoxy resin is reduced so that the ratio of the liquid crystal oligomer to the epoxy resin (liquid crystal oligomer / epoxy resin) exceeds 2.33, it is difficult to form a cured structure, and thus the thermal expansion coefficient is remarkably increased.

(C) Filler The printed circuit board composition according to the present invention may contain an inorganic filler, an organic filler, or a mixture thereof.

  The inorganic filler is not particularly limited, but may include one or more selected from the group consisting of alumina, aluminum nitride, boron nitride, fused silica, silicon nitride, and Teflon, for example.

  The inorganic filler may be included in the printed circuit board composition in an amount of 30 to 90 wt%. If the inorganic filler is contained in an amount of less than 30 wt%, the effect of reducing the thermal expansion coefficient is small and is not suitable for use as an ultrathin layer substrate material. If the inorganic filler is contained in an amount exceeding 90 wt%, the liquid crystal oligomer and the epoxy resin are added. In some cases, it may be difficult to produce the composition, and the adhesive strength of the composition may be reduced, making interlayer bonding difficult.

  The organic filler is not particularly limited, and may include, for example, one or more fillers selected from the group consisting of thermoplastic liquid crystal polymer resins, cellulose, carbon nanotubes, graphene, and graphite, or mixed fillers.

  The organic filler may be included in the printed circuit board composition in an amount of 30 to 90 wt%. If the organic filler is contained in an amount of less than 30 wt%, the effect of reducing the thermal expansion coefficient is small and is not suitable for use in an ultra-thin layer substrate material. If the organic filler is contained in an amount of more than 90 wt%, the organic filler has a high dielectric constant. Depending on the characteristics, the insulating properties may be deteriorated, it may be difficult to produce a composition containing a liquid crystal oligomer and an epoxy resin, and the adhesive strength of the composition may be reduced, making interlayer bonding difficult.

(D) Other Reinforcing Material The printed circuit board composition according to the present invention may contain other reinforcing material. The other reinforcing material is not particularly limited, and can include, for example, a reinforcing material selected from the group consisting of glass fiber, thermoplastic liquid crystal polymer fiber such as aramid, quartz fiber and the like.

  The reinforcing material may be included in an amount of 25 to 150 parts by weight with respect to 100 parts by weight of the resin composition including the liquid crystal oligomer and the epoxy resin. If the reinforcing material is less than 25 parts by weight, the effect of reducing the thermal expansion coefficient is small and it is difficult to use it as a printed circuit board. If the reinforcing material exceeds 150 parts by weight, the insulating properties of the material are lowered and the substrate material is reduced. Difficult to use.

  In another embodiment of the present invention, a liquid crystal oligomer having a structural unit of the above chemical formula 1, a structural unit of the above chemical formula 2, and a structural unit of the above chemical formula D and having a functional group of the above chemical formula E at at least one terminal is used. % And an epoxy resin of 5 to 42 wt% can be provided.

  Example 1 Production of a liquid crystal oligomer of formula 12 and a film using the same.

(Chemical formula 12)

  In a 1 L glass reactor, 21.826 g (0.2 mol) of 4-aminophenol, 39.871 g (0.24 mol) of isophthalic acid, 12.873 g (0.09 mol) of 4-hydroxybenzoic acid, 6-hydroxy-2-naphtho Acid 12.495 g (0.07 mol), ferulic acid 18.100 g (0.09 mol), 2- (6-oxide-6H-dibenz [c, e] [1,2] oxaphospholin-6-yl)- Add 1,9.8-benzenediol 39.871 g (0.12 mol) 99.575 g (0.975 mol) of acetic anhydride and mix.

  The glass reactor is sealed with a mechanical stirrer, nitrogen injection tube, thermometer and reflux condenser. After sufficiently replacing the inside of the reactor with nitrogen gas, the temperature inside the reactor is raised to 140 ° C. under the flow of nitrogen gas, and then refluxed for 3 hours while maintaining the temperature.

  Next, the temperature inside the reactor is increased to 250 ° C., and 22.5822 g (0.12 mol) of 6-hydroxy-2-naphthoic acid is further added, followed by reaction for 2 hours.

  After the reaction, while removing the by-product aceto acid and unreacted aceto anhydride, the temperature was raised to 300 ° C. and reacted for 1 hour 30 minutes, and then the by-product was further removed for 30 minutes in a vacuum at the same temperature, The liquid crystal oligomer of the above chemical formula 12 is manufactured.

  The oligomer produced by the above method has a number average molecular weight of 3000 to 7000 g / mol, includes a ferulic acid group having an ethylene structure in the main chain, and has a characteristic that curing between oligomers is possible by exposure to ultraviolet rays. .

  4.23 g of the liquid crystal oligomer of the above chemical formula 12, 2.82 g of Araldite MY-721 (Huntsmann) as an epoxy resin, 0.03 g of dicyandiimide (DICY) as a curing catalyst, N, N′-dimethylacetamide (DMAc) 5. Add to 77 g to make a mixed solution.

  The mixed solution is applied to a copper foil having a thickness of 12 μm, and a film having a thickness of 100 μm is manufactured using a doctor blade method. After the film was dried at room temperature for 2 hours, it was exposed to an ultraviolet light amount of 691.94 mJ for 0 minute (Example 1-1), 5 minutes (Example 1-2), and 10 minutes (Example 1-3). To induce curing between the oligomers.

  After the UV exposure step, a curing reaction between the epoxy resin and the oligomer is allowed to proceed at 80 ° C. for 1 hour and at 120 ° C. for 1 hour to form a semi-cured film.

  The produced semi-cured films are laminated one above the other and reacted at 230 ° C. and 3 MPa for 2 hours under vacuum to produce a cured film. The coefficient of thermal expansion of the cured film was analyzed through a thermomechanical analyzer (TMA).

  Example 2 Production of Prepreg Using Liquid Crystalline Oligomer of Chemical Formula 12

  33.0 g of the liquid crystal oligomer obtained in Example 1, 22.0 g of Araldite MY-721 (Huntsmann) and 0.22 g of dicyandiimide (DICY) as a curing catalyst were 45.0 g of N, N′-dimethylacetamide (DMAc). To prepare a mixed solution. A slurry is prepared by mixing 55 g of silica filler (manufactured by Admatech) with the mixed solution. Glass fiber (manufactured by Baotek 1078) was impregnated with the above slurry uniformly. The glass fiber impregnated with the slurry is exposed to an ultraviolet light amount of 691.94 mJ for 10 minutes and then passed through a 200 ° C. heating zone to be semi-cured to obtain a prepreg. The prepreg is cured by applying a pressure of 2.3 Mpa and a temperature of 230 ° C. for 2 hours in a vacuum press to evaluate the properties.

  Comparative Example 1) Production of a film using a liquid crystal oligomer (chemical formula 14) having no curable functional group in the main chain.

(Chemical Formula 14)

  4.23 g of the liquid crystal oligomer of the above chemical formula 14, 2.82 g of Araldite MY-721 (Huntsmann) as the epoxy resin, and 0.03 g of dicyandiimide (DICY) as the curing catalyst, N, N′-dimethylacetamide (DMAc) 5. Add to 77 g to make a mixed solution. The mixed solution is applied to a copper foil having a thickness of 12 μm, and a film having a thickness of 100 μm is manufactured using a doctor blade method.

  After the film is dried at room temperature for 2 hours, a curing reaction between the epoxy resin and the oligomer is allowed to proceed at 80 ° C. for 1 hour and 120 ° C. for 1 hour to obtain a semi-cured film.

  The produced semi-cured films are laminated one above the other and reacted at 230 ° C. and 3 MPa for 2 hours under vacuum to produce a cured film. The coefficient of thermal expansion of the cured film was analyzed through a thermomechanical analyzer (TMA).

  Comparative Example 2) Manufacture of prepreg using liquid crystal oligomer of formula 14

  45.0 g of N, N′-dimethylacetamide (DMAc) 33.0 g of liquid crystal oligomer of the above chemical formula 14, 22.0 g of Araldite MY-721 (Huntsmann) and 0.22 g of dicyandiimide (DICY) as a curing catalyst To produce a mixed solution. A slurry is prepared by mixing 55 g of silica filler (manufactured by Admatech) with the mixed solution. Glass fiber (manufactured by Baotek 1078) was impregnated with the above slurry uniformly. The glass fiber impregnated with the slurry is passed through a heating zone at 200 ° C. and semi-cured to obtain a prepreg. The prepreg is cured by applying a pressure of 2.3 Mpa and a temperature of 230 ° C. for 2 hours in a vacuum press to evaluate the properties.

[Evaluation]
Table 1 below shows data obtained by measuring the thermal expansion coefficients of the cured films of Example 1 and Comparative Example 1 through a thermomechanical analyzer.

  Referring to Table 1 above, the thermal expansion coefficient of Example 1 from Comparative Example 1 is about 5 ppm / ° C-13 ppm / ° C when measured at 50-100 ° C, and about 200 ppm when measured at 200-230 ° C. It turns out that it decreased by 40 ppm / ° C.-80 ppm / ° C. Therefore, when the main chain contains a curable functional group (double bond), a film having a lower thermal expansion coefficient than that can be produced. Moreover, when Example 1-1 is compared with Example 1-2 and Example 1-3, it turns out that a thermal expansion coefficient further reduces with the irradiation time of an ultraviolet-ray. Considering that the double bond is a functional group capable of photocuring by irradiation with ultraviolet rays, it can be seen that the decrease in the thermal expansion coefficient is caused by the double bond introduced into the main chain.

  Accordingly, the films according to the examples have a low coefficient of thermal expansion and high heat resistance, and therefore can be applied to ultra-thin printed circuit boards.

  Table 2 below shows data obtained by measuring the thermal expansion coefficients of the prepregs of Example 2 and Comparative Example 2 through a thermomechanical analyzer.

  Referring to Table 2 above, the thermal expansion coefficient of Example 2 from Comparative Example 2 is about 4 ppm / ° C. when measured at 50-100 ° C. and about 7 ppm / ° C. when measured at 200-230 ° C. I understand that. Therefore, when the main chain contains a curable functional group (double bond), a prepreg having a lower thermal expansion coefficient than that can be produced.

  Therefore, since the prepreg according to the embodiment of the present invention has a low thermal expansion coefficient and high heat resistance, it can be applied to an ultrathin printed circuit board.

  The present invention is not limited by the above-described embodiments and the accompanying drawings, but is limited by the appended claims.

  Accordingly, various forms of substitution, modification, and alteration can be made by persons having ordinary knowledge in the art without departing from the technical idea of the present invention described in the claims. Belongs to a range.

11, 12, 13 Insulating layer 21 Horizontal wiring 22 Via electrode

Claims (14)

5 to 49 wt% of a liquid crystal oligomer containing a structural unit of the following chemical formula 1, a structural unit of the following chemical formula 2 and a structural unit of the following chemical formula D, and having a functional group of the following chemical formula E at at least one end;
5 to 42 wt% epoxy resin,
30-90 wt% filler,
A printed circuit board composition comprising:
(Chemical formula 1)

(Chemical formula 2)

(Chemical D)

(Chemical E)

In the chemical formulas 1, 2, D and E,
X _{1 to} X ₄ are the same or different from each other, and C (═O) O, O, C (═O) NR, NR ′, or CO (wherein R and R ′ are the same or different from each other, hydrogen, substituted or non-substituted A substituted C1-C20 alkyl group, or a substituted or unsubstituted C6-C30 aryl group).
Z ₁ and Z ₂ are each independently a hydroxy group, a substituted or unsubstituted C3-C30 alicyclic group, and Z ₃ and Z ₄ are substituted or unsubstituted C3-C30 heteroatom-containing alicyclic rings. Family group,
N _{1 to} n ₄ are each independently an integer of 0 to 3, and n ₁ + n ₂ + n ₃ + n ₄ may be 1 or more,
_{A 1} in Formula 1 is one of the functional group represented by the following chemical formula 4-1 to 4-7.
(Chemical 4-1)

(Chemical 4-2)

(Chemical 4-3)

(Chemical 4-4)

(Chemical 4-5)

(Chemical 4-6)

(Chemical 4-7)

In Formula 4-7, L ₁ is a divalent organic functional group, and in Formula 4-1 to Formula 4-7, at least one hydrogen of each aromatic ring is halogen, substituted or unsubstituted. C1-C20 alkyl group, substituted or unsubstituted C1-C20 alkoxy group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C7 -C30 arylalkyl group, substituted or unsubstituted C6-C30 aryloxy group or Z ₁ (Z ₁ is the same as defined in Formula 1),
A ₂ in the chemical formula ₂ is a C2 to C20 alkylene group having one of the functional groups represented by the following chemical formulas 5-1 to 5-6 or the functional group of the following chemical formula 6.
(Chemical 5-1)

In Formula 5-1, Y ^{1 to} Y ³ are the same or different and are hydrogen, a C1 to C10 alkyl group, or a functional group of Formula 6 below, provided that at least one of Y ^{1 to} Y ³ is Formula 6 P1 is an integer of 0 to 4, m1 and m2 are the same or different, and are an integer of 0 to 3, p1, m1 and m2 are not simultaneously 0 and R and R ′ are hydrogen or C1 Is a C10 alkyl group.
(Chemical 5-2)

In the chemical formula 5-2, Y ⁴ and Y ⁵ are the same or different and are hydrogen, a C1-C10 alkyl group or a functional group of the following chemical formula 6, and at least one of Y ⁴ and Y ⁵ is a function of the following chemical formula 6. P2 and p3 are integers of 0 to 3, and are not 0 at the same time.
(Chemical formula 5-3)

In Formula 5-3, Y ^{6 to} Y ⁸ are the same or different and are hydrogen, a C1 to C10 alkyl group, or a functional group of the following Chemical Formula 6, and at least one of Y ^{6 to} Y ⁸ is a function of the following Chemical Formula 6: P4 and p6 are integers of 0 to 3, p5 is an integer of 0 to 2, and p4, p5 and p6 are not 0 at the same time.
(Chemical formula 5-4)

In Formula 5-4, Y ⁹ and Y ¹⁰ are the same or different and are hydrogen, a C1-C10 alkyl group, or a functional group of the following Chemical Formula 6, and at least one of Y ⁹ and Y ¹⁰ is the function of Chemical Formula 6 below. P7 and p8 are integers of 0 to 2 and are not 0 at the same time.
(Chemical 5-5)

In Formula 5-5, Y ¹¹ and Y ¹² are the same or different and are hydrogen, a C1-C10 alkyl group, or a functional group of the following Chemical Formula 6, and at least one of Y ¹¹ and Y ¹² is the function of the following Chemical Formula 6 P9 and p10 are integers of 0 to 4, and are not 0 at the same time.
(Chemical 5-6)

In Formula 5-6, Y ¹³ and Y ¹⁴ are the same or different and are hydrogen, a C1-C10 alkyl group, or a functional group of the following Chemical Formula 6, and at least one of Y ¹³ and Y ¹⁴ is the function of Chemical Formula 6 below. a group, pi 1 and p12 is an integer from 0 to 4, _{L 2} is an ether group, sulfide group, ketone group, an amide group, a sulfoxide, a sulfone group, an azo group, cyanide group, a substituted or unsubstituted C1~C20 An alkylene group, a substituted or unsubstituted C2-C20 alkenylene group, a substituted or unsubstituted C6-C30 arylene group, a divalent organic functional group that is not substituted or substituted with at least one functional group of the following chemical formula 6, or a divalent organic functional groups of the following formula 7-1 to 7-3, _{when L 2} is not substituted with a functional group of the following formula 6, pi 1 and p12 All instead of 0,
In the chemical formulas 5-1 to 5-6, at least one hydrogen of each aromatic ring is a halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted group. Or an unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, a substituted or unsubstituted C6-C30 aryloxy group, or Z ₁ (Z ₁ is the same as defined in Chemical Formula 1) can be substituted.
(Chemical formula 6)

In Formula 6, Ar ₁ and Ar ₂ are C4-C30 substituted or unsubstituted aromatic ring groups, and R and R ′ are the same or different from each other, and are hydrogen, C1-C20 alkyl group, or C6-C30 An aryl group, m is an integer of 0 to 3;
(Chemical 7-1)

In Formula 7-1, R is hydrogen, halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C3-C20 cycloalkyl group, A substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, or a substituted or unsubstituted C6-C30 aryloxy group.
(Chemical Formula 7-2)

In Formula 7-2, R is hydrogen, halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C3-C20 cycloalkyl group, A substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, or a substituted or unsubstituted C6-C30 aryloxy group.
(Chemical Formula 7-3)

L _{1 in} Formula 4-7 represents an ether group, a sulfide group, a ketone group, a sulfoxide, a sulfone group, an azo group, a cyanide group, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C2-C20. The composition for a printed circuit board according to claim 1, wherein the alkenylene group is a substituted or unsubstituted C 6 -C 30 arylene group. L _{2 in} Formula 5-6 is an ether group, sulfide group, ketone group, amide group, sulfoxide, sulfone group, azo group, cyanide group, substituted or unsubstituted C1-C20 alkylene group, substituted or unsubstituted. A C2-C20 alkenylene group, a substituted or unsubstituted C6-C30 arylene group, a divalent organic functional group that is not substituted or substituted with at least one functional group of Formula 6, or the Formulas 7-1 to 7-3 The composition for a printed circuit board according to claim 1, which is a divalent organic functional group. The printed circuit board composition according to claim 1, wherein the chemical formula 6 is represented by the following chemical formula 11:
(Chemical Formula 11)

In Formula 11, R ¹ and R ² are the same or different and are hydrogen, halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C3-C3. A C20 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, a substituted or unsubstituted C6-C30 aryloxy group, or Z ₁ (formula 1 P1 and p2 are integers of 0 to 4, and R and R ′ are the same or different from each other, and are hydrogen, a C1 to C20 alkyl group or a C6 to C30 aryl group. , M is an integer of 0-3. The composition for a printed circuit board according to claim 1, wherein the liquid crystal oligomer is represented by the following chemical formula 12.
(Chemical formula 12)

The composition for a printed circuit board according to claim 1, wherein the liquid crystal oligomer is represented by Chemical Formula 13 below.
(Chemical Formula 13)

  2. The composition for a printed circuit board according to claim 1, wherein a ratio of the liquid crystal oligomer to the epoxy resin (liquid crystal oligomer / epoxy resin) is 0.66 or more and 2.33 or less.   The composition for a printed circuit board according to claim 1, wherein the structural unit of the chemical formula D and the functional group of the chemical formula E are contained in an amount of 5 to 40 mol% based on the total amount of the liquid crystal oligomer.   The epoxy resin is a phenolic type such as phenol novolac type epoxy resin, cresol novolak type epoxy resin, naphthol modified novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, triphenyl type epoxy resin, etc. Glycidyl ether type epoxy resins, dicyclopentadiene type epoxy resins having a dicyclopentadiene skeleton, naphthalene type epoxy resins having a naphthalene skeleton, dihydroxybenzopyran type epoxy resins, glycidyl amine type epoxy resins made from polyamines such as diaminophenylmethane 2. The printing times according to claim 1, wherein the printing times are at least one selected from the group consisting of triphenolmethane type epoxy resins and tetraphenylethane type epoxy resins. Board composition.   The filler is at least one selected from the group consisting of alumina, aluminum nitride, boron nitride, fused silica, silicon nitride, Teflon, thermoplastic liquid crystal polymer resin, cellulose, carbon nanotube, graphene, and graphite. Item 4. The printed circuit board composition according to Item 1.   The printed circuit board composition according to claim 1, further comprising 0.1 to 0.5 wt% of a curing agent. 5 to 49 wt% of a liquid crystal oligomer containing a structural unit of the following chemical formula 1, a structural unit of the following chemical formula 2 and a structural unit of the following chemical formula D, and having a functional group of the following chemical formula E at at least one end;
5 to 42 wt% epoxy resin,
A printed circuit board composition comprising:
(Chemical formula 1)

(Chemical formula 2)

(Chemical D)

(Chemical E)

In the chemical formulas 1, 2, D and E,
X _{1 to} X ₄ are the same or different from each other, and C (═O) O, O, C (═O) NR, NR ′, or CO (wherein R and R ′ are the same or different from each other, hydrogen, substituted or non-substituted A substituted C1-C20 alkyl group, or a substituted or unsubstituted C6-C30 aryl group).
Z ₁ and Z ₂ are each independently a hydroxy group, a substituted or unsubstituted C3-C30 alicyclic group, and Z ₃ and Z ₄ are substituted or unsubstituted C3-C30 heteroatom-containing alicyclic rings. Family group
N _{1 to} n ₄ are each independently an integer of 0 to 3, and n ₁ + n ₂ + n ₃ + n ₄ may be 1 or more,
_{A 1} in Formula 1 is one of the functional group represented by the following chemical formula 4-1 to 4-7.
(Chemical 4-1)

(Chemical 4-2)

(Chemical 4-3)

(Chemical 4-4)

(Chemical 4-5)

(Chemical 4-6)

(Chemical 4-7)

In Formula 4-7, L ₁ is a divalent organic functional group, and in Formula 4-1 to Formula 4-7, at least one hydrogen of each aromatic ring is halogen, substituted or unsubstituted. C1-C20 alkyl group, substituted or unsubstituted C1-C20 alkoxy group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C7 -C30 arylalkyl group, substituted or unsubstituted C6-C30 aryloxy group or Z ₁ (Z ₁ is the same as defined in Formula 1),
A ₂ in the chemical formula ₂ is a C2 to C20 alkylene group having one of the functional groups represented by the following chemical formulas 5-1 to 5-6 or the functional group of the following chemical formula 6.
(Chemical 5-1)

In Formula 5-1, Y ^{1 to} Y ³ are the same or different and are hydrogen, a C1 to C10 alkyl group, or a functional group of Formula 6 below, provided that at least one of Y ^{1 to} Y ³ is Formula 6 P1 is an integer of 0 to 4, m1 and m2 are the same or different, and are an integer of 0 to 3, p1, m1 and m2 are not simultaneously 0 and R and R ′ are hydrogen or C1 Is a C10 alkyl group.
(Chemical 5-2)

In the chemical formula 5-2, Y ⁴ and Y ⁵ are the same or different and are hydrogen, a C1-C10 alkyl group or a functional group of the following chemical formula 6, and at least one of Y ⁴ and Y ⁵ is a function of the following chemical formula 6. P2 and p3 are integers of 0 to 3, and are not 0 at the same time.
(Chemical formula 5-3)

In Formula 5-3, Y ^{6 to} Y ⁸ are the same or different and are hydrogen, a C1 to C10 alkyl group, or a functional group of the following Chemical Formula 6, and at least one of Y ^{6 to} Y ⁸ is a function of the following Chemical Formula 6: P4 and p6 are integers of 0 to 3, p5 is an integer of 0 to 2, and p4, p5 and p6 are not 0 at the same time.
(Chemical formula 5-4)

In Formula 5-4, Y ⁹ and Y ¹⁰ are the same or different and are hydrogen, a C1-C10 alkyl group, or a functional group of the following Chemical Formula 6, and at least one of Y ⁹ and Y ¹⁰ is the function of Chemical Formula 6 below. P7 and p8 are integers of 0 to 2 and are not 0 at the same time.
(Chemical 5-5)

In Formula 5-5, Y ¹¹ and Y ¹² are the same or different and are hydrogen, a C1-C10 alkyl group, or a functional group of the following Chemical Formula 6, and at least one of Y ¹¹ and Y ¹² is the function of the following Chemical Formula 6 P9 and p10 are integers of 0 to 4, and are not 0 at the same time.
(Chemical 5-6)

In Formula 5-6, Y ¹³ and Y ¹⁴ are the same or different and are hydrogen, a C1-C10 alkyl group, or a functional group of the following Chemical Formula 6, and at least one of Y ¹³ and Y ¹⁴ is the function of Chemical Formula 6 below. a group, pi 1 and p12 is an integer from 0 to 4, _{L 2} is an ether group, sulfide group, ketone group, an amide group, a sulfoxide, a sulfone group, an azo group, cyanide group, a substituted or unsubstituted C1~C20 An alkylene group, a substituted or unsubstituted C2-C20 alkenylene group, a substituted or unsubstituted C6-C30 arylene group, a divalent organic functional group that is not substituted or substituted with at least one functional group of the following chemical formula 6, or a divalent organic functional groups of the following formula 7-1 to 7-3, _{when L 2} is not substituted with a functional group of the following formula 6, pi 1 and p12 All instead of 0,
In the chemical formulas 5-1 to 5-6, at least one hydrogen of each aromatic ring is a halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted group. Or an unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, a substituted or unsubstituted C6-C30 aryloxy group, or Z ₁ (Z ₁ is the same as defined in Chemical Formula 1) can be substituted.
(Chemical formula 6)

In Formula 6, Ar ₁ and Ar ₂ are C4-C30 substituted or unsubstituted aromatic ring groups, and R and R ′ are the same or different from each other, and are hydrogen, C1-C20 alkyl group, or C6-C30 An aryl group, m is an integer of 0 to 3;
(Chemical 7-1)

In Formula 7-1, R is hydrogen, halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C3-C20 cycloalkyl group, A substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, or a substituted or unsubstituted C6-C30 aryloxy group.
(Chemical Formula 7-2)

In Formula 7-2, R is hydrogen, halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C3-C20 cycloalkyl group, A substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, or a substituted or unsubstituted C6-C30 aryloxy group.
(Chemical Formula 7-3)

An insulating layer;
A circuit pattern formed on the insulating layer,
The insulating layer includes a structural unit of the following chemical formula 1, a structural unit of the following chemical formula 2, and a structural unit of the following chemical formula D, and a liquid crystal oligomer having a functional group of the following chemical formula E at at least one terminal, and an epoxy resin The printed circuit board which consists of a composition containing 5-42 wt% and 14-90 wt% of fillers.
(Chemical formula 1)

(Chemical formula 2)

(Chemical D)

(Chemical E)

5 to 49 wt% of a liquid crystal oligomer containing a structural unit of the following chemical formula 1, a structural unit of the following chemical formula 2 and a structural unit of the following chemical formula D, and having a functional group of the following chemical formula E at at least one end;
5 to 42 wt% epoxy resin,
A sheet-like film including:
(Chemical formula 1)

(Chemical formula 2)

(Chemical D)

(Chemical E)

In the chemical formulas 1, 2, D and E,
X _{1 to} X ₄ are the same or different from each other, and C (═O) O, O, C (═O) NR, NR ′, or CO (wherein R and R ′ are the same or different from each other, hydrogen, substituted or non-substituted A substituted C1-C20 alkyl group, or a substituted or unsubstituted C6-C30 aryl group).
Z ₁ and Z ₂ are each independently a hydroxy group, a substituted or unsubstituted C3-C30 alicyclic group, and Z ₃ and Z ₄ are substituted or unsubstituted C3-C30 heteroatom-containing alicyclic rings. Family group
N _{1 to} n ₄ are each independently an integer of 0 to 3, and n ₁ + n ₂ + n ₃ + n ₄ may be 1 or more,
_{A 1} in Formula 1 is one of the functional group represented by the following chemical formula 4-1 to 4-7.
(Chemical 4-1)

(Chemical 4-2)

(Chemical 4-3)

(Chemical 4-4)

(Chemical 4-5)

(Chemical 4-6)

(Chemical 4-7)

In Formula 4-7, L ₁ is a divalent organic functional group, and in Formula 4-1 to Formula 4-7, at least one hydrogen of each aromatic ring is halogen, substituted or unsubstituted. C1-C20 alkyl group, substituted or unsubstituted C1-C20 alkoxy group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C7 -C30 arylalkyl group, substituted or unsubstituted C6-C30 aryloxy group or Z ₁ (Z ₁ is the same as defined in Formula 1),
A ₂ in the chemical formula ₂ is a C2 to C20 alkylene group having one of the functional groups represented by the following chemical formulas 5-1 to 5-6 or the functional group of the following chemical formula 6.
(Chemical 5-1)

In Formula 5-1, Y ^{1 to} Y ³ are the same or different and are hydrogen, a C1 to C10 alkyl group, or a functional group of Formula 6 below, provided that at least one of Y ^{1 to} Y ³ is Formula 6 P1 is an integer of 0 to 4, m1 and m2 are the same or different, and are an integer of 0 to 3, p1, m1 and m2 are not simultaneously 0 and R and R ′ are hydrogen or C1 Is a C10 alkyl group.
(Chemical 5-2)

In the chemical formula 5-2, Y ⁴ and Y ⁵ are the same or different and are hydrogen, a C1-C10 alkyl group or a functional group of the following chemical formula 6, and at least one of Y ⁴ and Y ⁵ is a function of the following chemical formula 6. P2 and p3 are integers of 0 to 3, and are not 0 at the same time.
(Chemical 5-3)

In Formula 5-3, Y ^{6 to} Y ⁸ are the same or different and are hydrogen, a C1 to C10 alkyl group, or a functional group of the following Chemical Formula 6, and at least one of Y ^{6 to} Y ⁸ is a function of the following Chemical Formula 6: P4 and p6 are integers of 0 to 3, p5 is an integer of 0 to 2, and p4, p5 and p6 are not 0 at the same time.
(Chemical formula 5-4)

In Formula 5-4, Y ⁹ and Y ¹⁰ are the same or different and are hydrogen, a C1-C10 alkyl group, or a functional group of the following Chemical Formula 6, and at least one of Y ⁹ and Y ¹⁰ is the function of Chemical Formula 6 below. P7 and p8 are integers of 0 to 2 and are not 0 at the same time.
(Chemical 5-5)

In Formula 5-5, Y ¹¹ and Y ¹² are the same or different and are hydrogen, a C1-C10 alkyl group, or a functional group of the following Chemical Formula 6, and at least one of Y ¹¹ and Y ¹² is the function of the following Chemical Formula 6 P9 and p10 are integers of 0 to 4, and are not 0 at the same time.
(Chemical 5-6)

In Formula 5-6, Y ¹³ and Y ¹⁴ are the same or different and are hydrogen, a C1-C10 alkyl group, or a functional group of the following Chemical Formula 6, and at least one of Y ¹³ and Y ¹⁴ is the function of Chemical Formula 6 below. a group, pi 1 and p12 is an integer from 0 to 4, _{L 2} is an ether group, sulfide group, ketone group, an amide group, a sulfoxide, a sulfone group, an azo group, cyanide group, a substituted or unsubstituted C1~C20 An alkylene group, a substituted or unsubstituted C2-C20 alkenylene group, a substituted or unsubstituted C6-C30 arylene group, a divalent organic functional group that is not substituted or substituted with at least one functional group of the following chemical formula 6, or a divalent organic functional groups of the following formula 7-1 to 7-3, _{when L 2} is not substituted with a functional group of the following formula 6, pi 1 and p12 All instead of 0,
In the chemical formulas 5-1 to 5-6, at least one hydrogen of each aromatic ring is a halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted group. Or an unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, a substituted or unsubstituted C6-C30 aryloxy group, or Z ₁ (Z ₁ is the same as defined in Chemical Formula 1) can be substituted.
(Chemical formula 6)

In Formula 6, Ar ₁ and Ar ₂ are C4-C30 substituted or unsubstituted aromatic ring groups, and R and R ′ are the same or different from each other, and are hydrogen, C1-C20 alkyl group, or C6-C30 An aryl group, m is an integer of 0 to 3;
(Chemical 7-1)

In Formula 7-1, R is hydrogen, halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C3-C20 cycloalkyl group, A substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, or a substituted or unsubstituted C6-C30 aryloxy group.
(Chemical Formula 7-2)

In Formula 7-2, R is hydrogen, halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C3-C20 cycloalkyl group, A substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, or a substituted or unsubstituted C6-C30 aryloxy group.
(Chemical Formula 7-3)

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