KR20100075383A - Thermoset resin composition and board using the same - Google Patents

Abstract

PURPOSE: A thermoset resin composition and a substrate using thereof are provided to apply the composition for manufacturing a prepreg or a printed circuit board without the strength degradation. CONSTITUTION: A thermoset resin composition contains a thermoset aromatic oligomer marked with chemical formula 1, a hollow particle, and a solvent. In the chemical formula 1, B is a backbone including a recurring unit marked with chemical formula 2. L1 and L2 are linkers. Z1 and Z2 are a thermosetting functional group with a multi bond at the end, or a hydroxyl group. A substrate contains a cured material of the thermoset resin composition and a reinforcing material. The cured material of the thermoset resin composition is either penetrated to the reinforcing material, or placed on the reinforcing material.

Description

Thermosetting resin composition and substrate using the same {THERMOSET RESIN COMPOSITION AND BOARD USING THE SAME}

The present substrate relates to a thermosetting resin composition and a substrate using the same.

With the development of information and communication technology, it is becoming a highly communication informatization society in which a computer and a communication device are integrated. In addition, as electronic devices such as mobile phones and personal computers are miniaturized and high-performance, printed circuit boards basically used for them are multi-layered, reduced board thickness, reduced through-hole diameter, and reduced hole spacing. As the density increases, the substrate material of higher performance is required.

One aspect of the present invention is to provide a thermosetting resin composition having a low coefficient of thermal expansion and a dielectric constant.

Another aspect of the present invention is to provide a cured resin using the thermosetting resin composition.

Another aspect of the present invention is to provide a substrate using the thermosetting resin composition.

One aspect of the invention provides a thermosetting resin composition comprising a thermosetting aromatic oligomer, hollow particles and a solvent represented by the following formula (1).

[Formula 1]

(In the formula 1,

B is a main chain including a repeating unit of Formula 2,

L ₁ and L ₂ are linking groups,

Z ₁ and Z ₂ are thermosetting functional groups or hydroxy groups having multiple bonds at the terminals.)

[Formula 2]

(In Formula 2,

A ₁ is an aromatic ring group including any one or more of arylene groups represented by the following Chemical Formulas 3-1 to 3-5,

X ₁ and Y ₁ are each independently COO, O, CNR ′, CONR '', NR '''or CO, wherein R', R '' and R '''are each independently a hydrogen atom, a substitution or Unsubstituted C1 to C20 alkyl group, or substituted or unsubstituted C6 to C30 aryl group,

k ₁ is an integer from 1 to 50.)

A ₁ in Chemical Formula 2 may include any one or more of arylene groups represented by the following Chemical Formulas 3-1 to 3-5, and any one or more of arylene groups represented by the following Chemical Formulas 5-1 to 5-4. have.

[Formula 3-1]

 [Formula 3-2]

(In Chemical Formulas 3-1 and 3-2,

n ₁₅ is an integer of 0 to 4,

R ₁₅ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C6 to C30 is an aryloxy group which is a substituent, when n ₁₅ is 2 or more, the substituents may be the same or different from each other,

The aromatic ring may contain a hetero atom of N, O, S or P in the ring.)

[Formula 3-3]

[Formula 3-4]

(In Chemical Formulas 3-3 and 3-4,

n ₁₆ and n ₁₈ are each independently an integer of 0 to 3, n ₁₇ is an integer of 0 to 2,

R ₁₆ , R ₁₇ and R ₁₈ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 An aryl group or a substituted or unsubstituted C6 to C30 aryloxy group, and when n ₁₆ to n ₁₈ are each 2 or more, the substituents may be the same or different from each other,

l is an integer from 0 to 3,

The aromatic ring may contain a hetero atom of N, O, S or P in the ring.)

[Formula 3-5]

(In Chemical Formula 3-5,

n ₁₉ and n ₂₀ are each independently an integer of 0 to 4,

R ₁₉ and R ₂₀ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituent which is a substituted or unsubstituted C6 to C30 aryloxy group, when n ₁₉ and n ₂₀ are each 2 or more, the substituents may be the same or different from each other,

W is a single bond or O, S, CO, SO ₂ , N ₂ , substituted or unsubstituted C1 to C20 alkylene group, substituted or unsubstituted C1 to C20 alkoxylene group, substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted C6 to C30 oxyarylene group, substituted or unsubstituted C6 to C30 heteroarylene group, substituted or unsubstituted C6 to C30 oxyheteroarylene group, CONR ', or Any one of the linking groups represented by the formula 4-1 to 4-7,

 Wherein R and R 'are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or Unsubstituted C6 to C30 aryloxy group,

The aromatic ring may contain a hetero atom of N, O, S or P in the ring.)

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

[Formula 4-7]

(In Chemical Formulas 4-3, 4-5, 4-6 and 4-7,

R, R 'and R' 'each independently represent a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy, a substituted or unsubstituted C6 to C30 aryl group, or A substituted or unsubstituted C6 to C30 aryloxy group.)

[Formula 5-1]

[Formula 5-2]

(In Chemical Formula 5-2,

n ₁₅ is an integer from 0 to 4, n ₃₀ is an integer from 0 to 5,

R ₁₅ and R ₃₀ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituent which is a substituted or unsubstituted C6 to C30 aryloxy group, when n ₁₅ and n ₃₀ is 2 or more, the substituents may be the same or different from each other,

The aromatic ring may contain a hetero atom of N, O, S or P in the ring.)

[Formula 5-3]

[Formula 5-4]

(In Chemical Formulas 5-1, 5-3, and 5-4, n ₁₅ to n ₂₀ , n ₃₀ , R ₁₅ to R ₂₀ , R ₃₀ , and W are each defined in Chemical Formulas 3-1 to 3-5, respectively. As shown.)

In Formula 1, B may include a structural unit represented by Formula 6 below.

[Formula 6]

(In Chemical Formula 6,

A ₁ may be selected from any one or more of the arylene groups represented by Formulas 3-1 to 3-5, A ₁₁ is selected from any one or more of the arylene groups represented by Formulas 5-1 to 5-4 Can be,

X ₁ and X ₁₁ and Y ₁ and Y ₁₁ are each independently COO, O, CNR ', CONR'',NR''' or CO, wherein R ', R''andR''' are each independently A hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

k ₁ and k ₁₁ are each an integer of 1 to 50.)

In Formula 1, Z ₁ and Z ₂ are each independently a hydroxy group, a maleimide group, a namidide group, a phthalimide group, an alkenyl group, an alkynyl group, a propagyl ether group, a benzocyclobutene group, and a cyanate A substituted or unsubstituted C3 to C30 alicyclic group having a group, a double bond or a triple bond, a C6 to C30 aryl group having a C2 to C30 alkenyl group or a C2 to C30 alkynyl group, or a C6 to C30 having a cyanide group It may be an aryl group, and may also be any one of the thermosetting functional groups represented by the formulas 8-1 to 8-11 independently.

[Formula 8-1]

(In Chemical Formula 8-1,

n ₁ is an integer of 0 to 6,

R ₁ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted A substituent which is an aryloxy group of C6 to C30, and when n ₁ is 2 or more, the substituents may be the same or different from each other.)

[Formula 8-2]

(In Chemical Formula 8-2,

n ₂ is 1, n ₃ is an integer of 0 to 3,

R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituted or unsubstituted C6 to C30 aryloxy group, and when n ₃ is 2 or more, the substituents may be the same or different.)

[Formula 8-3]

(In Chemical Formula 8-3,

n ₄ is an integer of 0 to 2,

R ₄ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted A substituent which is an aryloxy group of C6 to C30, and when n ₄ is 2 or more, the substituents may be the same or different from each other.)

[Formula 8-4]

(In Chemical Formula 8-4,

n ₅ is an integer of 0 to 8,

R ₅ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted A substituent which is an aryloxy group of C6 to C30, and when n ₅ is 2 or more, the substituents may be the same or different from each other.)

[Formula 8-5]

(In Chemical Formula 8-5,

n ₆ is an integer of 0 to 7,

R ₆ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted A substituent which is an aryloxy group of C6 to C30, and when n ₆ is 2 or more, the substituents may be the same or different from each other.)

[Formula 8-6]

(In Chemical Formula 8-6,

n ₈ and n ₉ are each independently an integer of 0 to 6,

R ₈ and R ₉ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituted or unsubstituted C6 to C30 aryloxy group, and when n ₈ and n ₉ are each 2 or more, the substituents may be different from each other,

Q ₁ and Q ₂ are each independently a methylene group, O or S,

m ₁ is an integer of 1-3. )

[Formula 8-7]

(In Chemical Formula 8-7,

n ₁₀ is an integer from 0 to 7, n ₁₁ is an integer from 0 to 6,

R ₁₀ and R ₁₁ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituent which is a substituted or unsubstituted C6 to C30 aryloxy group, when n ₁₀ and n ₁₁ are each 2 or more, the substituents may be different from each other,

Q ₃ and Q ₄ are each independently a methylene group, O or S,

m ₂ is an integer of 1 to 3.)

[Formula 8-8]

(In Chemical Formula 8-8,

n ₁₂ is an integer from 0 to 7, n ₁₃ is an integer from 0 to 6, n ₁₄ is an integer from 0 to 8,

R ₁₂ to R ₁₄ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituted or unsubstituted C6 to C30 aryloxy group, and when n ₁₂ to n ₁₄ are each 2 or more, the substituents may be different from each other,

Q ₅ and Q ₆ are each independently a methylene group, O or S,

m ₃ and m ₄ are each independently an integer of 1 to 3.)

[Formula 8-9]

(In Chemical Formula 8-9,

n ₁₅ is an integer of 0 to 2,

R ₁₅ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted A substituent which is an aryloxy group of C6 to C30, and when n ₁₅ is 2, the substituents may be the same or different from each other.)

[Formula 8-10]

[Formula 8-11]

The repeating unit of Formula 2 may be included in more than 5 mol% to 70 mol% based on the total number of moles of the main chain of the thermosetting aromatic oligomer.

The number average molecular weight of the thermosetting aromatic oligomer may be 500 to 15,000, and may be included in 10 to 75% by weight based on the total amount of the thermosetting resin composition.

The hollow particles may be a porous inorganic material, a porous polymer or a combination thereof. The porous inorganic material may be alumina, silica, fused silica, glass, or a combination thereof, and the porous polymer may be urea resin, phenol resin, or a combination thereof.

The hollow particle may be an airgel. The airgel can be obtained from silica, organic polymer, alumina, platinum, nickel, titania, zirconia, ruthenium, cobalt or combinations thereof.

The hollow particles may be included in 0.5 to 70% by volume relative to the total volume of the thermosetting aromatic oligomer and the hollow particles, the size of the hollow particles may be 0.1 to 100 um.

The thermosetting resin composition may further include a maleimide compound.

Another aspect of the present invention provides a cured resin using the thermosetting resin composition.

Another aspect of the invention the cured resin; And a reinforcing material, wherein the cured resin is infiltrated with the reinforcing material or positioned on the reinforcing material surface.

The substrate may further include a metal foil, and the metal foil may be combined with at least one surface of the cured resin.

Other details of aspects of the invention are included in the following detailed description.

Prepregs and substrates using a thermosetting resin composition having a low coefficient of thermal expansion and a dielectric constant can be improved in signal delay, strength degradation, and the like.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is only defined by the scope of the claims to be described later.

Unless stated otherwise in the specification, "substituted" means a halogen atom, an alkyl group of C1 to C20, a haloalkyl group of C1 to C20, an alkoxy group of C1 to C20, an aryl group of C6 to C30 or an aryloxy group of C6 to C30 It means substituted.

Unless stated otherwise in the specification, "alkyl group", "alkenyl group", "alkynyl group", "alkylene group", "alkenylene group", "alkynylene group", "cycloalkylene group", "cycloalkenyl "Alkyl group", "cycloalkynylene group", "alkoxy group" and "alkoxy group" are each C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C1 to C20 alkylene group, C2 C20 to C20 alkenylene group, C2 to C20 alkynylene group, C3 to C20 cycloalkylene group, C3 to C20 cycloalkenylene group, C3 to C20 cycloalkynylene group, C1 to C20 alkoxy group and C1 to C20 C20 means an alkoxylene group, wherein "aryl group", "arylene group", "aryloxy group" and "oxyarylene group" are each C6 to C30 aryl group, C6 to C30 arylene group, C6 to C30 aryl Oxyarylene group of oxy group and C6 to C30.

Unless otherwise specified herein, "heteroarylene group" and "oxyheteroarylene group" are each a heteroarylene group and an oxyheteroarylene group containing a hetero atom of N, O, S or P in the ring of the arylene group "Heterocycloalkyl group" "heterocycloalkylene group", "heterocycloalkenyl group", "heterocycloalkenylene group", "heterocycloalkynyl group" and "heterocycloalkynylene group" are each a cycloalkyl group, a cyclo Heterocycloalkyl group, heterocycloalkylene group, heterocycloalkenyl group, containing a hetero atom of N, O, S or P in the ring of the alkylene group, cycloalkenyl group, cycloalkenylene group, cycloalkynyl group and cycloalkynylene group, It means a heterocycloalkenylene group, a heterocycloalkynyl group, and a heterocycloalkynylene group.

Unless stated otherwise in the present specification, "(meth) acrylate" may be both "acrylate" and "methacrylate", and "epoxy (meth) acrylate" may be "epoxyacrylate" and "epoxymeta". Acrylates "are possible," di (meth) acryloxy-bisphenol "is both" diacryloxy-bisphenol "and" dimethacryloxy-bisphenol ", and" poly (meth) acrylate "is" Acrylate "and" methacrylate "are both possible.

Unless stated otherwise in the specification, an "alicyclic group" is a C3 to C30 cycloalkyl group, C3 to C30 cycloalkynyl group, C3 to C30 cycloalkenyl group, C3 to C30 heterocycloalkyl group, C3 to C30 hetero Cycloalkynyl group, C3-C30 heterocycloalkenyl group, etc. are mentioned.

Unless stated otherwise in the specification, an “aromatic ring group” has a ring structure in which unsaturated bonds, lone pairs, and the like are mixed, and electrons are delocalized or resonated. Refers to the functional group in the form.

The thermosetting resin composition according to one embodiment includes a thermosetting aromatic oligomer, hollow particles and a solvent. Hereinafter, each component is demonstrated in detail.

Thermosetting aromatic oligomers

The thermosetting aromatic oligomer is an oligomer including an aromatic ring in the main chain, it may be represented by the formula (1).

[Formula 1]

(In the formula 1,

B is a main chain including a repeating unit of Formula 2,

L ₁ and L ₂ are linking groups,

Z ₁ and Z ₂ are thermosetting functional groups or hydroxy groups having multiple bonds at the terminals.)

[Formula 2]

(In Formula 2,

A ₁ is a substituted or unsubstituted aromatic ring group,

X ₁ and Y ₁ are each independently COO, O, CNR ′, CONR '', NR '''or CO, wherein R', R '' and R '''are each independently a hydrogen atom, a substitution or Unsubstituted C1 to C20 alkyl group, or substituted or unsubstituted C6 to C30 aryl group,

k ₁ is an integer from 1 to 50.)

Specific examples of the aromatic ring group A ₁ in the formula (2), C5 to C20 cycloalkenylene group, C4 to C20 heterocycloalkenylene group, C6 to C30 arylene group, C2 to C30 heteroarylene group, C2 To C30 heteroaryloxyylene group; and the like. In addition, the main chain may include two or more aromatic ring groups different from each other.

As a more specific example of the aromatic ring group, A ₁ in Formula 2 may be selected from any one or more of the arylene groups represented by the following Formulas 3-1 to 3-5. In addition, any one or more of the arylene groups represented by the following Chemical Formulas 3-1 to 3-5 and any one or more of the arylene groups represented by the following Chemical Formulas 5-1 to 5-4 may be simultaneously selected.

In this case, the arylene groups represented by the following Chemical Formulas 3-1 to 3-5 may be included in an amount of about 5 to about 60 mol%, and specifically, about 10 to about 50 mol%, based on the total moles of the thermosetting aromatic oligomer. .

When included in the content range solubility in the solvent is improved, the viscosity can be properly maintained.

[Formula 3-1]

 [Formula 3-2]

(In Chemical Formulas 3-1 and 3-2,

n ₁₅ is an integer of 0 to 4,

R ₁₅ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C6 to C30 is an aryloxy group which is a substituent, when n ₁₅ is 2 or more, the substituents may be the same or different from each other,

The aromatic ring may contain a hetero atom of N, O, S or P in the ring.)

[Formula 3-3]

[Formula 3-4]

(In Chemical Formulas 3-3 and 3-4,

n ₁₆ and n ₁₈ are each independently an integer of 0 to 3, n ₁₇ is an integer of 0 to 2,

R ₁₆ , R ₁₇ and R ₁₈ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 An aryl group or a substituted or unsubstituted C6 to C30 aryloxy group, and when n ₁₆ to n ₁₈ are each 2 or more, the substituents may be the same or different from each other,

l is an integer from 0 to 3,

The aromatic ring may contain a hetero atom of N, O, S or P in the ring.)

[Formula 3-5]

(In Chemical Formula 3-5,

n ₁₉ and n ₂₀ are each independently an integer of 0 to 4,

R ₁₉ and R ₂₀ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituent which is a substituted or unsubstituted C6 to C30 aryloxy group, when n ₁₉ and n ₂₀ are each 2 or more, the substituents may be the same or different from each other,

W is a single bond or O, S, CO, SO ₂ , N ₂ , substituted or unsubstituted C1 to C20 alkylene group, substituted or unsubstituted C1 to C20 alkoxylene group, substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted C6 to C30 oxyarylene group, substituted or unsubstituted C6 to C30 heteroarylene group, substituted or unsubstituted C6 to C30 oxyheteroarylene group, CONR ', or Any one of the linking groups represented by the formula 4-1 to 4-7,

 Wherein R and R 'are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or Unsubstituted C6 to C30 aryloxy group,

The aromatic ring may contain a hetero atom of N, O, S or P in the ring.)

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

[Formula 4-7]

(In Chemical Formulas 4-3, 4-5, 4-6 and 4-7,

R, R 'and R' 'each independently represent a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy, a substituted or unsubstituted C6 to C30 aryl group, or A substituted or unsubstituted C6 to C30 aryloxy group.)

[Formula 5-1]

[Formula 5-2]

(In Chemical Formula 5-2,

n ₁₅ is an integer from 0 to 4, n ₃₀ is an integer from 0 to 5,

R ₁₅ and R ₃₀ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituent which is a substituted or unsubstituted C6 to C30 aryloxy group, when n ₁₅ and n ₃₀ is 2 or more, the substituents may be the same or different from each other,

The aromatic ring may contain a hetero atom of N, O, S or P in the ring.)

[Formula 5-3]

[Formula 5-4]

(In Chemical Formulas 5-1, 5-3, and 5-4, n ₁₅ to n ₂₀ , n ₃₀ , R ₁₅ to R ₂₀ , R ₃₀ , and W are each defined in Chemical Formulas 3-1 to 3-5, respectively. As shown.)

In addition, the main chain represented by B in Chemical Formula 1 may include a structural unit represented by Chemical Formula 6.

[Formula 6]

(In Chemical Formula 6,

A ₁ may be selected from any one or more of the arylene groups represented by Formulas 3-1 to 3-5, A ₁₁ is selected from any one or more of the arylene groups represented by Formulas 5-1 to 5-4 Can be,

X ₁ and X ₁₁ and Y ₁ and Y ₁₁ are each independently COO, O, CNR ', CONR'',NR''' or CO, wherein R ', R''andR''' are each independently A hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

k ₁ and k ₁₁ are each an integer of 1 to 50.)

As a specific example, the repeating unit of Formula 2 may be selected from repeating units represented by the following Formulas 7-1 to 7-3.

[Formula 7-1]

[Formula 7-2]

[Formula 7-3]

(In Chemical Formulas 7-1 to 7-3,

A ₁ and k _l are each as mentioned above.)

The repeating unit of Formula 2 may be included in more than about 5 mol% to less than about 70 mol% based on the total number of moles of the main chain of the thermosetting aromatic oligomer, specifically, it may be included in more than about 10 mol% to less than about 70 mol% And more specifically, greater than about 10 mol% up to about 50 mol%. When the repeating unit of Formula 2 is included in the content range, solubility in a solvent is increased.

Specific examples of L ₁ and L _{2 as} the linking group in Chemical Formula 1 may be each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 alkoxylene group, a substituted or Unsubstituted C6 to C30 arylene group, substituted or unsubstituted C6 to C30 oxyarylene group, O, COO or CONR ', wherein R' is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, A substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C6 to C30 aryloxy group.

Specific examples of Z ₁ and Z ₂ , which are thermosetting functional groups in Chemical Formula 1, may each independently be a hydroxy group, a maleimide group, a nadimide group, a phthalimide group, an alkenyl group, an alkynyl group, a propagyl ether group, or a benzo. C6 to C30 aryl group having a cyclobutene group, a cyanate group, a substituted or unsubstituted C3 to C30 alicyclic group having a double bond or a triple bond, a C2 to C30 alkenyl group or a C2 to C30 alkynyl group, or cyanide C6 thru | or C30 aryl group which has group is mentioned. Among these, thermosetting aromatic oligomers having different kinds of thermosetting functional groups may be mixed and used.

At this time, an acetylene group etc. are mentioned as a specific example of the said alkynyl group.

Specific examples of the alicyclic group include C3 to C30 cycloalkyl group, C3 to C30 cycloalkynyl group, C3 to C30 cycloalkenyl group, C3 to C30 heterocycloalkyl group, C3 to C30 heterocycloalkynyl group, C3 to C30 C30 heterocycloalkenyl group, etc. are mentioned.

As a more specific example of Z ₁ and Z ₂ in the formula (1), any one of the thermosetting functional groups represented by the following formula (8-1 to 8-11) may be selected independently.

[Formula 8-1]

(In Chemical Formula 8-1,

n ₁ is an integer of 0 to 6,

R ₁ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted A substituent which is an aryloxy group of C6 to C30, and when n ₁ is 2 or more, the substituents may be the same or different from each other.)

[Formula 8-2]

(In Chemical Formula 8-2,

n ₂ is 1, n ₃ is an integer of 0 to 3,

R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituted or unsubstituted C6 to C30 aryloxy group, and when n ₃ is 2 or more, the substituents may be the same or different.)

[Formula 8-3]

(In Chemical Formula 8-3,

n ₄ is an integer of 0 to 2,

R ₄ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted A substituent which is an aryloxy group of C6 to C30, and when n ₄ is 2 or more, the substituents may be the same or different from each other.)

[Formula 8-4]

(In Chemical Formula 8-4,

n ₅ is an integer of 0 to 8,

R ₅ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted A substituent which is an aryloxy group of C6 to C30, and when n ₅ is 2 or more, the substituents may be the same or different from each other.)

[Formula 8-5]

(In Chemical Formula 8-5,

n ₆ is an integer of 0 to 7,

R ₆ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted A substituent which is an aryloxy group of C6 to C30, and when n ₆ is 2 or more, the substituents may be the same or different from each other.)

[Formula 8-6]

(In Chemical Formula 8-6,

n ₈ and n ₉ are each independently an integer of 0 to 6,

R ₈ and R ₉ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituted or unsubstituted C6 to C30 aryloxy group, and when n ₈ and n ₉ are each 2 or more, the substituents may be different from each other,

Q ₁ and Q ₂ are each independently a methylene group, O or S,

m ₁ is an integer of 1-3. )

[Formula 8-7]

(In Chemical Formula 8-7,

n ₁₀ is an integer from 0 to 7, n ₁₁ is an integer from 0 to 6,

R ₁₀ and R ₁₁ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituent which is a substituted or unsubstituted C6 to C30 aryloxy group, when n ₁₀ and n ₁₁ are each 2 or more, the substituents may be different from each other,

Q ₃ and Q ₄ are each independently a methylene group, O or S,

m ₂ is an integer of 1 to 3.)

[Formula 8-8]

(In Chemical Formula 8-8,

n ₁₂ is an integer from 0 to 7, n ₁₃ is an integer from 0 to 6, n ₁₄ is an integer from 0 to 8,

R ₁₂ to R ₁₄ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituted or unsubstituted C6 to C30 aryloxy group, and when n ₁₂ to n ₁₄ are each 2 or more, the substituents may be different from each other,

Q ₅ and Q ₆ are each independently a methylene group, O or S,

m ₃ and m ₄ are each independently an integer of 1 to 3.)

[Formula 8-9]

(In Chemical Formula 8-9,

n ₁₅ is an integer of 0 to 2,

R ₁₅ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted A substituent which is an aryloxy group of C6 to C30, and when n ₁₅ is 2, the substituents may be the same or different from each other.)

[Formula 8-10]

[Formula 8-11]

The thermosetting functional groups undergo crosslinking reactions between the thermosetting functional groups while undergoing high temperature curing to form a stable liquid crystal alignment structure in the form of a solid net film. Accordingly, the printed circuit board manufactured by using the thermosetting aromatic oligomer including the thermosetting functional group may improve mechanical properties.

The thermosetting aromatic oligomer may have a number average molecular weight of about 500 to about 15,000, specifically about 1000 to about 4000. When the number average molecular weight of the thermosetting aromatic oligomer is within the above range, the solid content may be increased.

The thermosetting aromatic oligomer may be included in an amount of about 10 wt% to about 75 wt%, and specifically, about 30 wt% to about 65 wt%, based on the total amount of the thermosetting resin composition. When the thermosetting aromatic oligomer is included within the above range, the impregnation amount of the thermosetting aromatic oligomer is increased in the reinforcing material such as glass fiber during the preparation of the prepreg, thereby eliminating the need for an additional impregnation process.

The method for preparing the thermosetting aromatic oligomer is not particularly limited, and specifically, the method may be prepared by melt polymerization, solution polymerization, or bulk polymerization.

As an example of a method for producing a thermosetting aromatic oligomer by the melt polymerization method, a monomer that provides a repeating unit of Formula 2 by a reaction of a diamine compound with a monocarboxylic acid compound (for example, represented by Formula 9 below) Compound), and a mixture containing such monomers can be heated to prepare a thermosetting aromatic oligomer by a polycondensation reaction.

[Formula 9]

(In Formula 9,

A ₁ is the same as the definition of A ₁ in Formula 2,

X and Y are each a reactive group for inducing X ₁ and Y ₁ in Formula 2.

As an example of the method for producing a thermosetting aromatic oligomer by the solution polymerization method, first, isophthaloyl chloride, aminophenol, 2,6-dihydroxynaphthalene and triethylamine After putting (triethylamine) in the reactor, the reaction proceeds while stirring at room temperature. After a certain time, a thermosetting aromatic oligomer can be synthesized by further adding a compound capable of adding a thermosetting functional group, such as maleimide, nadimide, acetylene, and the like to react to obtain a thermosetting aromatic oligomer, and then separating and purifying it.

As an example of a method for producing a thermosetting aromatic oligomer by the bulk polymerization method, isophthalic acid, aminophenol, 2-hydroxy-6-naphthoic acid and acetic anhydride are added to the reactor, and then the temperature is gradually increased to 150 ° C while stirring. After raising, the mixture is reacted for a certain time while refluxing. Subsequently, the by-product acetic acid and acetic anhydride which were generated are removed, 4-hydroxy benzoic acid is further added, and it heated up to 320 degreeC and makes it react. In this way, an aromatic oligomer having an alcohol group at at least one of both ends of the main chain is synthesized. Thereafter, the aromatic oligomer having an alcohol group is dissolved in a solvent (for example, DMF) and then reacted by adding a compound capable of adding a thermosetting functional group. Then, the thermosetting aromatic oligomer having a thermosetting functional group added to at least one of both terminals of the main chain is reacted. Can be obtained.

Hollow particles

The hollow particles may be a composite material which is a porous inorganic material, a porous polymer or a combination thereof.

The porous inorganic material and the porous polymer mean inorganic and organic compounds each having pores therein and may include air. The porous inorganic material may be alumina, silica, fused silica, glass, or a combination thereof, and the porous polymer may be urea resin, phenol resin, or a combination thereof. Among them, a porous inorganic material of glass may be preferably used as the hollow particles.

 The porous inorganic materials and porous polymers can be easily obtained as a product, for example, alumina bubble (pacific random yarn), scotch bubble (Sumitomo 3M company), cell star (Tokai Industries Co., Ltd.), hollow glass beads, etc. are mentioned. The size of the hollow particles may be about 0.1 to about 100 um, specifically about 0.1 to about 50 um. When the size of the hollow particles is in the above range, it is possible to uniformly disperse and to manufacture a thin film.

In addition, the hollow particles may use an airgel.

The airgel is a low-density solid material having fine pores filled in most of the volume, and has a low dielectric constant and a coefficient of thermal expansion. Specifically, the dielectric constant of the airgel is about 1.1 to about 2.5, and when the porosity is high, the dielectric constant is almost 1, which is the lowest value among the existing solid materials. In addition, the thermal expansion coefficient of the airgel is about 2 to about 4 ppm / ℃.

The airgel can be obtained from silica, organic polymer, alumina, platinum, nickel, titania, zirconia, ruthenium, cobalt or combinations thereof.

The airgel may itself be hydrophilic, in which case it may be made hydrophobic through chemical treatment. Absorption of water causes structural changes, such as shrinkage or decomposition, which can be prevented by making them hydrophobic. In addition, the hydrophobic treatment to the inside can prevent the decomposition of the airgel even if deep cracks occur.

The pore size of the airgel may be about 1 to about 100 nm, specifically about 10 to about 80 nm. If the pore size of the airgel is in the above range it may have a low dielectric constant.

The porosity of the airgel may be about 30 to about 99.9% by volume, specifically, about 50 to about 99.9% by volume. If the porosity of the airgel is within the above range, the mechanical strength of the airgel is excellent and may have a low dielectric constant.

The hollow particles may be included in about 0.5 to about 70% by volume relative to the total volume of the thermosetting aromatic oligomer and the hollow particles, specifically about 30 to about 60% by volume. When the hollow particles are included in the above range, the effect of using the hollow particles is optimized and the mechanical strength is also excellent.

In addition, the mixture of the thermosetting aromatic oligomer and the hollow particles may be included in about 70% by weight or less, specifically about 30% by weight or less based on the total amount of the thermosetting resin composition. When the mixture of the thermosetting aromatic oligomer and the hollow particles is included in the above range, it is possible to maintain the appropriate viscosity required for impregnation with a reinforcing material such as glass fiber in the preparation of the prepreg.

menstruum

The solvent is an aprotic solvent, halogen-based solvent such as 1-chlorobutane, chlorobenzene, 1,1-dichloroethane, 1,2-dichloroethane, chloroform, 1,1,2,2-tetrachloroethane; Ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane; Ketone solvents such as methyl ethyl ketone (MEK), acetone and cyclohexanone; Acetate solvents such as propylene glycol monomethyl ether acetate (PGMEA); Ester solvents such as ethyl acetate; lactone solvents such as γ-butyrolactone; Carbonate solvents such as ethylene carbonate and propylene carbonate; Amine solvents such as triethylamine and pyridine; Nitrile solvents such as acetonitrile; Amide solvents such as N, N'-dimethylformamide (DMF), N, N'-dimethylacetamide (DMAc), tetramethylurea and N-methylpyrrolidone (NMP); Nitro solvents such as nitromethane and nitrobenzene; Sulfide solvents such as dimethyl sulfoxide (DMSO) and sulfolane; Phosphoric acid solvents such as hexamethyl phosphate amide and tri-n-butyl phosphate; Or a combination thereof can be used, but is not necessarily limited thereto.

Among them, N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N, N'-dimethylformamide (DMF), N, N'-dimethylacetamide (DMAc), methyl ethyl ketone (MEK ), Propylene glycol monomethyl ether acetate (PGMEA), or a combination thereof can be used.

The solvent may be included in the remainder, that is, about 30 to about 95% by weight based on the total amount of the thermosetting resin composition according to one embodiment, the viscosity may be properly maintained when included in the content.

The thermosetting resin composition according to an embodiment may further include a polymer such as a thermosetting resin and a thermoplastic resin other than the aforementioned thermosetting aromatic oligomer.

Specific examples of the polymer include phosphorous compounds such as phosphate esters and melamine phosphate, nitrogen-containing compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, silicone compounds, polyimides, polyvinyl acetals, phenoxy resins, Acrylic resins, alkyd resins, polyurethane resins, polybutadiene, butadiene-acrylonitrile copolymers, polychloroprene, butadiene-styrene copolymers, polyisoprene, butyl rubber, fluoro rubbers and the like Elastomers such as natural rubber, styrene-isoprene rubber, acrylic rubber, epoxidized butadiene, maleated butadiene, polyethylene, polypropylene, polyethylene-propylene copolymers, polyvinyl chloride, polyvinylidene chloride, polystyrene , Polyvinyl toluene, polyvinyl phenol, acryloni Reel-styrene resin, acrylonitrile-butadiene-styrene resin, acrylate-butadiene-styrene resin, poly-4-fluoroethylene, fluoroethylene-propylene, 4-fluoroethylene-6 -Fluoroethylene, vinylidene fluoride, polycarbonate, polyester carbonate, polyphenylene ether, polysulfone, polyester, polyether sulfone, polyamide, polyamide imide, polyester imide, poly Phenylene sulfite, (meth) acrylate, epoxy (meth) acrylate, di (meth) acryloxy-bisphenol, poly (meth) acrylate, styrene, vinylpyrrolidone, diacryl phthalate, divinyl Benzene, diallylbenzene, diallyl ether bisphenol, trialkenyl isocyanurate, dicyclopentadiene, phenol resin, polyisocyanate, and the like.

The polymer may be included in an amount of about 1 to about 50 parts by weight based on 100 parts by weight of the thermosetting resin composition including a thermosetting aromatic oligomer, hollow particles, and a solvent. When the polymer is included in the above range, the inherent properties of the thermosetting resin composition according to the embodiment are not impaired.

In addition, the thermosetting resin composition according to an embodiment may further include a maleimide compound in addition to the polymer.

The maleimide compound is used as a crosslinking agent in the thermosetting resin composition and is a compound containing two or more maleimide groups. As a specific example of the maleimide-based compound, any one of bismaleimide compounds represented by the following Chemical Formula 10 and trimaleimide compounds represented by the following Chemical Formulas 13 and 14 may be used.

[Formula 10]

(In Chemical Formula 10,

U is a C1 to C20 alkylene group, C6 to C30 arylene group or a linking group represented by the following formula (11-1),

R ₂₁ to R ₂₄ are each independently a hydrogen atom or an alkyl group of C1 to C20.)

[Formula 11-1]

(In Chemical Formula 11-1,

G is O, S, CO, SO, SO ₂ , substituted or unsubstituted C2 to C20 alkylene group, substituted or unsubstituted C2 to C20 alkoxylene group, substituted or unsubstituted C2 to C20 oxyalkoxylene A group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C6 to C30 oxyarylene group, a substituted or unsubstituted C6 to C30 heteroarylene group, a substituted or unsubstituted C6 to C30 oxy Heteroarylene group or a linking group represented by the following formula (11-2).)

[Formula 11-2]

(In Chemical Formula 11-2,

Ar is any one selected from arylene groups represented by the following formulas 11-3 to 11-9,

T ₁ and T ₂ are each independently O, S, CO, SO, SO ₂ , CONH or COO.)

[Formula 11-3]

[Formula 11-4]

[Formula 11-5]

[Formula 11-6]

[Formula 11-7]

[Formula 11-8]

[Formula 11-9]

(In Chemical Formulas 11-6 and 11-9,

R and R 'are each C1 to C20 alkyl groups.)

Specific examples of the U in Formula 10 may include any one selected from the linking groups represented by the following Formulas 11-10 to 11-18.

[Formula 11-10]

[Formula 11-11]

[Formula 11-12]

[Formula 11-13]

[Formula 11-14]

[Formula 11-15]

[Formula 11-16]

[Formula 11-17]

[Formula 11-18]

Specific examples of the bismaleimide compound are any one selected from compounds represented by the following Chemical Formulas 12-1 to 12-18, and are not necessarily limited thereto.

[Formula 12-1]

[Formula 12-2]

[Formula 12-3]

[Formula 12-4]

[Formula 12-5]

[Formula 12-6]

[Formula 12-7]

[Formula 12-8]

[Formula 12-9]

[Formula 12-10]

[Formula 12-11]

[Formula 12-12]

[Formula 12-13]

[Formula 12-14]

[Formula 12-15]

[Formula 12-16]

[Formula 12-17]

[Formula 12-18]

[Formula 13]

[Formula 14]

The maleimide compound may be prepared by a method of reacting an aromatic diamine with maleic anhydride and replacing the resulting aromatic bismaleamic acid with an aromatic bismaleimide compound by a ring-closing reaction. Can be.

In addition, the thermosetting resin composition according to an embodiment may include an epoxy compound instead of or in addition to the maleimide compound. Thereby, the adhesive force of a thermosetting resin composition and copper etc. can be improved.

Specific examples of the epoxy compound include a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, a naphthol modified novolak type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a biphenyl type epoxy resin, and a tree Phenolic glycidyl ether type epoxy resins such as phenyl type epoxy resins; Alcohol-based glycidyl ether type epoxy resins such as polypropylene glycol glycidyl ether and hydrogenated bisphenol A type epoxy resins; Dicyclopentadiene type epoxy resins having a dicyclopentadiene skeleton; Naphthalene-type epoxy resins having a naphthalene skeleton; Dihydroxy benzopyran type epoxy resin; Dihydroxy dinaphthalene type epoxy resins; Glycidyl ester type epoxy resins using hexahydrophthalic anhydride, dimer acid or the like as a raw material; Glycidylamine type epoxy resins using polyamines such as diaminophenylmethane as a raw material; Alicyclic epoxy resins; Brominated epoxy resins or combinations thereof.

Another example of the epoxy compound may include a structural unit represented by the following Formula 15, and an epoxy equivalent weight may be about 100 to about 400 g / eq. An example thereof may include two structural units represented by Formula 15, and an epoxy equivalent may be about 100 to about 150 g / eq. Another example thereof may include two or more structural units represented by Formula 15, and an epoxy equivalent weight of about 150 to about 200 g / eq, about 200 to about 250 g / eq, or about 250 to about 300 g / may be eq.

[Formula 15]

(In Chemical Formula 15,

V is O, S, P or N, n is 1 when V is O or S, and n is 1 or 2 when V is P or N.)

The maleimide compound and the epoxy compound may be included in an amount of about 5 to about 100 parts by weight based on 100 parts by weight of the solvent. When the maleimide compound and the epoxy compound are included in the above ranges, the coefficient of thermal expansion may be reduced, thereby improving heat resistance, and the mechanical and physicochemical properties of the printed circuit board manufactured therefrom may be improved.

Although the mixing weight ratio of the thermosetting aromatic oligomer and the maleimide compound or the epoxy compound is not particularly limited, it may be specifically mixed in a weight ratio of 1: 9 to 9: 1.

The thermosetting resin composition according to one embodiment has a thermosetting aromatic oligomer of about 20 to about 80 parts by weight of the total solids content, the maleimide compound is about 5 to about 30 parts by weight of the total solids content, the epoxy compound is the total solids The content may be about 5 to about 30 parts by weight.

In addition, the thermosetting resin composition according to one embodiment includes additives such as fillers, softeners, plasticizers, antioxidants, flame retardants, flame retardant aids, lubricants, antistatic agents, colorants, heat stabilizers, light stabilizers, UV absorbers, coupling agents or antisettling agents. It may further include more.

The filler is an organic filler and an inorganic filler. Examples of the organic filler include epoxy resin powder, melamine resin powder, urea resin powder, benzoguanamine resin powder, styrene resin, and the like. Examples of the inorganic filler include natural silica, fused silica, and amorphous silica. , Hollow silica, aluminum hydroxide, boehmite, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, aluminum Borate, potassium titanate, magnesium sulfate, silicon carbide, zinc oxide, silicon nitride, silicon dioxide, aluminum titanate, barium titanate, barium strontium titanate, aluminum oxide, alumina, clay, kaolin, talc, calcined ) Clay, calcined kaolin, calcined talc, mica, short glass fibers, etc. There. These may be used alone or in mixture of two or more.

Examples of the plasticizer include polyethylene glycol, polyamide oligomer, ethylenebisstearoamide, phthalic acid ester, polystyrene oligomer, liquid paraffin, polyethylene wax, silicone oil and the like. These may be used alone or in mixture of two or more.

Examples of the antioxidants include phosphorus-containing antioxidants, phenolic antioxidants, sulfur-containing antioxidants, and the like. These may be used alone or in mixture of two or more.

Examples of the flame retardant include brominated polystyrene, brominated syndiotactic polystyrene, brominated polyphenylene ether, bromine-containing diphenylalkanes, bromine-containing diphenyl ethers, and the like. These may be used alone or in mixture of two or more.

Examples of the flame retardant adjuvant include antimony trioxide and the like.

The thermosetting resin composition according to the above-described embodiment may be prepared by blending constituents such as thermosetting aromatic oligomers, hollow particles, and solvents according to various methods such as room temperature mixing and melt mixing.

Another embodiment of the present invention provides a cured resin using the above-mentioned thermosetting resin composition. The said cured resin means the state which the said thermosetting resin composition hardened | cured.

Another embodiment of the present invention provides a prepreg including the cured resin and the reinforcing material.

The prepreg can be produced by applying or impregnating the cured resin on the reinforcing material, followed by drying to remove the solvent. Specifically, the hollow particles may be dispersed in a solvent and then dissolved by adding a thermosetting aromatic oligomer, and the solution may be impregnated with a reinforcing material, followed by drying to prepare a prepreg, or after the thermosetting aromatic oligomer is dissolved in a solvent, The particles may be added and dispersed and then dried to prepare a prepreg.

Examples of the reinforcing material are glass fiber, woven glass fiber, woven alumina glass fiber, glass fiber nonwoven fabric, silica glass fiber, woven carbon fiber, carbon fiber, cellulose nonwoven fabric, polymer fabric, alumina fiber, silicon carbide fiber, asbestos, rock wool, mineral Cotton, gypsum whistle, woven or nonwoven fabrics thereof, aromatic polyamide fibers, polyimide fibers, liquid crystalline polyesters, polyester fibers, fluorine fibers, polybenzoxazole fibers, glass fibers with polyamide fibers, Glass fibers with carbon fibers, glass fibers with polyimide fibers, glass fibers with aromatic polyesters, glass paper, mica paper, alumina paper, paper kraft, cotton paper, paper-glass bonded paper, and the like. These may be used by mixing one or more of them.

The dispersion can be carried out using a homogenizer, ultrasonic waves or a stirrer.

In order to evaporate the solvent, a method such as heating under reduced pressure or ventilation may be used.

The impregnated amount of the cured resin may be about 40 to about 70 wt% based on the total amount of the prepreg. When the impregnation amount is within the above range, the adhesion between the prepregs is improved, and the mechanical strength and the dimensional stability of the prepregs are improved. The impregnated amount of the cured resin refers to the total amount of the cured resin and the cured resin positioned on the surface of the reinforcement. The resin cured product located on the surface of the reinforcing material is meant to include being laminated on the surface of the reinforcing material.

Yet another embodiment of the present invention provides a substrate including the prepreg.

The substrate is not particularly limited, and may be, for example, each layer of a multilayer substrate, a laminate form combined with a metal foil, a printed board, and the like. In addition, the prepreg may include a form combined with a metal foil.

The substrate may be in various forms, for example in the form of a film. The film may be prepared by curing the thermosetting resin composition and thinning the film. Examples of such a method include a cast molding method of cast molding a thermosetting composition into a film; There is a dip molding method in which an inorganic substrate such as glass or a substrate in the form of a fabric is immersed in a varnish of the thermosetting resin composition, and then the substrate is formed into a film, but is not limited thereto. In this substrate, the thermosetting resin composition is in a cured state.

The substrate may be in a form combined with a metal foil. Copper foil, aluminum foil, etc. are used as said metal foil. Although the thickness of a metal foil changes with a use, the thing of 5-100 micrometers is used suitably. The metal foil may be bonded to the cured resin surface. The metal foil on the surface of the laminate may be a pattern formed. For example, the metal foil can be fabricated into a printed circuit board by circuit processing (for example, an etching process). The metal foil-coated laminate may be laminated on the surface of the printed laminate and processed in the same manner to produce a multilayer printed circuit board.

The form combined with the metal foil may be prepared by a method in which the thermosetting composition is applied onto the metal foil (eg, copper foil) or cast on the metal foil (eg, copper foil), and the heat treatment is performed after the solvent is removed. Solvent removal is specifically carried out by evaporating the solvent. Examples of the method for evaporating the solvent include heating under reduced pressure, ventilation, and the like.

Examples of the method of applying the thermosetting resin composition may include a roller coating method, a dip coating method, a spray coating method, a spinner coating method, a curtain coating method, a slot coating method, a screen printing method, and the like, but are not limited thereto. It is not. Before being applied or cast on the copper foil, the thermosetting resin composition is preferably filtered through a filter or the like to remove fine foreign substances contained in the solution.

In addition, a printed circuit board may be manufactured by laminating an inner layer substrate, a prepreg, and a metal foil on which a circuit is made according to design specifications, and then putting the prepreg into a press machine to melt / cure the prepreg by pressing and heating. . In addition, the printed circuit board may have a conductive pattern formed on one side or both sides of the prepreg, and may be a laminate of a plurality of prepregs.

The shape combined with the metal foil may be used as one component of a printed circuit board, and may be, for example, a resin coated copper (RCC) or a copper clad laminate (CCL).

The printed circuit board may be employed in various devices using a printed circuit board or a storage medium such as a hard disk drive (HDD), a solid state drive (SSD), a memory stick, and the like. Can be. For example, the printed circuit board may be electrically connected to the memory chip by mounting a memory chip through or without a lead.

With the demand for slimming storage media and improving driving speeds, printed circuit boards are required to have higher densities due to multilayering, substrate thickness reduction, miniaturization of through-hole diameters, and hole spacing. For example, an SSD may use a flash memory chip to achieve a faster driving speed compared to a general HDD. To this end, printed circuit boards should be thinner and denser than conventional HDDs. When reducing the thickness of the printed circuit board, it is difficult to secure low dielectric properties and low thermal expansion rate to an appropriate level. However, the printed circuit board according to various embodiments of the present invention may have a low thermal expansion and dielectric properties, and thus may be usefully employed in next-generation storage media such as SSDs.

The solid state device (SSD) may be a CMOS device, a MOS device, a conductor-insulator-semiconductor (CIS) device, an electro-optical device, a monoatomic device, a monomolecule device, a single hole device, a monoatomic PN junction device, a monomolecular PN junction Devices, single-electron devices, one-dimensional solid state devices, two-dimensional solid state devices, or three-dimensional solid state devices.

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

Example # 1

In a 1000 ml flask, 32.83 g (0.2 mol) of 5-norbornene-2,3-dicarboxylic anhydride (nadic anhydride) was added to 400 ml of acetic acid (glacial) at 110 ° C. After dissolving by heating, 41.1 g (0.3 mol) of excess 4-aminobenzoic acid is added thereto. After the reaction, the reaction was stirred for 2 hours and then precipitated at room temperature. The precipitate was washed with acetic acid and water and dried in a vacuum oven at 60 ° C. to obtain 4-nadimidobenzoic acid with a yield of 95%.

500 ml flask equipped with a condenser and a mechanical stirrer, 10.798 g (0.065 mol) isophthalic acid, 23.974 g (0.127 mol) 6-hydroxy-2-naphthoic acid, 17.60 g (4-hydroxy-benzoic acid) 0.127 mol), 14.187 g (0.130 mol) of 4-aminophenol, and 58.396 g (9.5 mol) of acetic anhydride were added, and the temperature was gradually increased to 140 ° C. under a nitrogen atmosphere, followed by reaction for 3 hours while maintaining the temperature. Complete the acetylation reaction. Subsequently, after adding 36.79 g (0.130 mol) of 4-namidimide benzoic acid prepared above, the reaction by-products acetic acid and unreacted acetic anhydride were removed, and the temperature was raised to 215 ° C. at a rate of 1 to 2 ° C. per minute, followed by 4 at that temperature. The reaction is carried out for a time to prepare a thermosetting aromatic oligomer having a thermosetting functional group at the terminal (number average molecular weight Mn = 3300). ¹ H-NMR data of the thermosetting aromatic oligomer as a product is shown in FIG. 1. In the graph of FIG. 1, F1 on the horizontal axis represents a frequency domain with respect to the time axis.

10 g of the thermosetting aromatic oligomer powder is added to 90 g of N-methyl-2-pyrrolidone, and heated to 60 ° C. to completely dissolve to obtain a brown solution. 0.015 g of aerosol silica gel having a porosity of 90% by volume was added to 10 g of the solution, followed by stirring at room temperature to obtain a thermosetting resin composition in which airgel was mixed.

Example # 2

A thermosetting resin composition was obtained in the same manner as in Example 1, except that 0.053 g of silica airgel was added in Example 1.

Example # 3

A thermosetting resin composition was obtained in the same manner as in Example 1, except that 0.125 g of silica airgel was added in Example 1.

Example # 4

A thermosetting resin composition was obtained in the same manner as in Example 1, except that 0.833 g of silica airgel was added in Example 1.

Comparative Example 1

A thermosetting resin composition was obtained in the same manner as in Example 1 except that the silica airgel was not added in Example 1.

Comparative Example 1

The thermosetting aromatic oligomer prepared in Example 1 was placed in a molder, heated to 50 ° C., and melted and molded to prepare a film having a diameter of 2 cm and a thickness of 300 μm.

Experimental Example 1 Measurement of Thermal Expansion Coefficient

The thermosetting resin compositions prepared according to Examples 1 to 4 and Comparative Example 1 were each coated on a silicon wafer, dried at 200 ° C. and then heated to 290 ° C. to cure for 1 hour. The thermal expansion coefficient of each specimen obtained at this time was measured, and the measurement results are shown in Table 1 below. The coefficient of thermal expansion was measured under nitrogen, with the temperature increasing at a rate of 5 ° C./min.

Experimental Example 2: Dielectric Constant Measurement

The thermosetting resin compositions prepared according to Examples 1 to 4 and Comparative Example 1 were each coated on copper foil, dried at 200 ° C. and then heated to 290 ° C. to cure for 1 hour. Since the copper foil was peeled off and the dielectric constant was measured, the measurement results are shown in Table 1 below. The dielectric constant was measured at 1 GHz.

In addition, for comparison thereof, the dielectric constant of the film prepared in Comparative Example 1 was measured under 1 GHz, and the dielectric constant was 2.8.

TABLE 1

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Thermal expansion coefficient (ppm / ℃) 33 25 16 6 35 Dielectric constant 2.5 2.1 1.7 1.25 2.9

Through Table 1, Examples 1 to 4 including the hollow particles as the thermosetting resin composition according to the embodiment can be confirmed that both the thermal expansion coefficient and the dielectric constant are low compared to Comparative Example 1 without the hollow particles. Accordingly, it can be seen that it is possible to manufacture prepregs and printed circuit boards with improved signal delay, reduced strength, and the like.

Example # 5

A thermosetting aromatic oligomer prepared in Example 1, that is, a thermosetting aromatic oligomer having a nadimide group at its terminal as a thermosetting functional group is prepared.

In a three neck 500 ml flask equipped with a condenser and a mechanical stirrer, 29.9 g (0.18 mol) of isophthalic acid, 16.9 g (0.09 mol) of 6-hydroxy-2-naphthoic acid, 4- 18.6 g (0.135 mol) of hydroxy-benzoic acid, 24.6 g (0.225 mol) of 4-aminophenol, and 68.9 g (0.675 mol) of acetic anhydride are added, and the temperature is gradually increased to 140 ° C. under a nitrogen atmosphere, and the temperature is maintained. 3 hours to complete the acetylation reaction. Subsequently, after further adding 8.5 g (0.045 mol) of 6-hydroxy-2-naphthoic acid prepared above, the reaction product was heated to 270 ° C. for 30 minutes while removing acetic acid and unreacted acetic anhydride. The liquid crystalline amide-ester oligomer which is a thermosetting aromatic oligomer which has a hydroxyl group at the terminal is prepared. The thermosetting aromatic oligomer obtained has a structure represented by the following formula (16).

[Formula 16]

3 g of the thermosetting aromatic oligomer having the prepared nadimide group at the terminal, 3 g of the thermosetting aromatic oligomer having the hydroxy group at the terminal, 2 g of the bismaleimide compound (Daiwakasei Industry Co., LTD, BMI-100) and an epoxy compound (Huntsman, MY 721) 2 g are added to 90 g of N-methyl-2-pyrrolidone and heated to 60 ° C. to complete dissolution to give a brown solution. 0.39 g of the silica airgel having a porosity of 90% by volume was added to 10 g of the solution, followed by stirring at room temperature to obtain a thermosetting resin composition in which the airgel was mixed. After impregnating the prepared thermosetting resin composition into the glass fiber (impregnation rate: 55% by weight), the glass fiber impregnated with the thermosetting resin composition was applied on the copper foil, and then cured at about 300 degrees Celsius for 1 hour in a high temperature electric furnace Then, copper foil is removed with an aqueous nitric acid solution to prepare a prepreg.

Example # 6

A thermosetting resin composition and a prepreg using the same were prepared in the same manner as in Example 5, except that 0.75 g of silica airgel was added in Example 5.

Example # 7

A thermosetting resin composition and a prepreg using the same were prepared in the same manner as in Example 5 except that 1 g of fused silica was added instead of silica airgel in Example 5.

Example # 8

A thermosetting resin composition and a prepreg using the same were prepared in the same manner as in Example 5, except that 2g of fused silica was added instead of silica airgel in Example 5.

Comparative Example 2

Except not containing the silica airgel in Example 5 was carried out in the same manner as in Example 5 to prepare a thermosetting resin composition and a prepreg using the same.

Experimental Example 3: Measurement of the coefficient of thermal expansion

For the prepregs prepared according to Examples 5 to 8 and Comparative Example 2 using a thermo-mechanical analyzer to calculate the coefficient of thermal expansion between 50 ℃ to 150 ℃ is shown in Table 2 below. Thermal hysteresis may remain for hot cured samples, so two thermal scans yielded primary and secondary coefficients of thermal expansion.

TABLE 2

Thermal expansion coefficient (ppm / ℃) 1st scan 2nd scan Example 5 10.9 8.4 Example 6 12.1 15.9 Example 7 12.5 17.2 Example 8 12.1 15.0 Comparative Example 2 15.8 17.4

Through Table 2, Examples 5 to 8 including the hollow particles as the thermosetting resin composition according to the embodiment can be confirmed that the coefficient of thermal expansion is low compared to Comparative Example 2 without the hollow particles. Accordingly, it can be seen that it is possible to manufacture prepregs and printed circuit boards with improved signal delay, reduced strength, and the like.

In particular, Examples 5 and 6 used an airgel as hollow particles, and Examples 7 and 8 used fused silica. Thus, even when only a small amount of the airgel was used, it could have a better or equivalent effect than that of fused silica. It can be seen that.

Example # 9

A thermosetting resin composition and a prepreg using the same were prepared in the same manner as in Example 5 except that the impregnation rate of the thermosetting resin composition impregnated with the glass fiber in Example 5 was 40 wt%.

Comparative Example 3

A thermosetting resin composition and a prepreg using the same were prepared in the same manner as in Comparative Example 2 except that the impregnation rate of the thermosetting resin composition impregnated with the glass fiber in Comparative Example 2 was 50% by weight.

Experimental Example 4: dielectric constant measurement

The dielectric constants of the prepregs prepared in Example 9 and Comparative Example 3 were measured, and the results are shown in Table 3 below. The dielectric constant was measured at 1 GHz.

[Table 3]

Example 9 Comparative Example 3 Dielectric constant 2.62 3.5

Through Table 3, Example 9 including the hollow particles as the thermosetting resin composition according to an embodiment can be confirmed that the dielectric constant is low compared to Comparative Example 3 does not include the hollow particles. Accordingly, it can be seen that it is possible to manufacture prepregs and printed circuit boards with improved signal delay, reduced strength, and the like.

The present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications may be made by those skilled in the art within the scope of the technical idea of the present invention. It is possible.

1 is ¹ H-NMR data of a thermosetting aromatic oligomer prepared according to Example 1. FIG.

Claims (18)

A thermosetting aromatic oligomer represented by Formula 1 below; Hollow particles; And Thermosetting resin composition containing a solvent. [Formula 1]

(In the formula 1, B is a main chain including a repeating unit of Formula 2, L ₁ and L ₂ are linking groups, Z ₁ and Z ₂ are thermosetting functional groups or hydroxy groups having multiple bonds at the terminals.) [Formula 2]

(In Formula 2, A ₁ is an aromatic ring group including any one or more of arylene groups represented by the following Chemical Formulas 3-1 to 3-5, X ₁ and Y ₁ are each independently COO, O, CNR ′, CONR '', NR '''or CO, wherein R', R '' and R '''are each independently a hydrogen atom, a substitution or Unsubstituted C1 to C20 alkyl group, or substituted or unsubstituted C6 to C30 aryl group, k ₁ is an integer from 1 to 50.) [Formula 3-1]

 [Formula 3-2]

(In Chemical Formulas 3-1 and 3-2, n ₁₅ is an integer of 0 to 4, R ₁₅ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C6 to C30 is an aryloxy group which is a substituent, when n ₁₅ is 2 or more, the substituents may be the same or different from each other, The aromatic ring may contain a hetero atom of N, O, S or P in the ring.) [Formula 3-3]

[Formula 3-4]

(In Chemical Formulas 3-3 and 3-4, n ₁₆ and n ₁₈ are each independently an integer of 0 to 3, n ₁₇ is an integer of 0 to 2, R ₁₆ , R ₁₇ and R ₁₈ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 An aryl group or a substituted or unsubstituted C6 to C30 aryloxy group, and when n ₁₆ to n ₁₈ are each 2 or more, the substituents may be the same or different from each other, l is an integer from 0 to 3, The aromatic ring may contain a hetero atom of N, O, S or P in the ring.) [Formula 3-5]

(In Chemical Formula 3-5, n ₁₉ and n ₂₀ are each independently an integer of 0 to 4, R ₁₉ and R ₂₀ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituent which is a substituted or unsubstituted C6 to C30 aryloxy group, when n ₁₉ and n ₂₀ are each 2 or more, the substituents may be the same or different from each other, W is a single bond or O, S, CO, SO ₂ , N ₂ , substituted or unsubstituted C1 to C20 alkylene group, substituted or unsubstituted C1 to C20 alkoxylene group, substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted C6 to C30 oxyarylene group, substituted or unsubstituted C6 to C30 heteroarylene group, substituted or unsubstituted C6 to C30 oxyheteroarylene group, CONR ', or Any one of the linking groups represented by Formulas 4-1 to 4-7,  Wherein R and R 'are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substitution Or an unsubstituted C6 to C30 aryloxy group, The aromatic ring may contain a hetero atom of N, O, S or P in the ring.) [Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

[Formula 4-7]

(In Chemical Formulas 4-3, 4-5, 4-6 and 4-7, R, R 'and R' 'each independently represent a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy, a substituted or unsubstituted C6 to C30 aryl group, or A substituted or unsubstituted C6 to C30 aryloxy group.) The method of claim 1, A ₁ in Formula 2 includes any one or more of arylene groups represented by Formulas 3-1 to 3-5, and at least one of arylene groups represented by Formulas 5-1 to 5-4. Phosphorus thermosetting resin composition. [Formula 5-1]

[Formula 5-2]

(In Chemical Formula 5-2, n ₁₅ is an integer from 0 to 4, n ₃₀ is an integer from 0 to 5, R ₁₅ and R ₃₀ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituent which is a substituted or unsubstituted C6 to C30 aryloxy group, when n ₁₅ and n ₃₀ is 2 or more, the substituents may be the same or different from each other, The aromatic ring may contain a hetero atom of N, O, S or P in the ring.) [Formula 5-3]

[Formula 5-4]

(In Chemical Formulas 5-1, 5-3, and 5-4, n ₁₅ to n ₂₀ , n ₃₀ , R ₁₅ to R ₂₀ , R ₃₀ , and W are each defined in Chemical Formulas 3-1 to 3-5, respectively. As shown.) The method of claim 2, In Formula 1, B is a thermosetting resin composition comprising a structural unit represented by the following formula (6). [Formula 6]

(In Chemical Formula 6, A ₁ may be selected from any one or more of the arylene groups represented by the formulas 3-1 to 3-5, A ₁₁ may be any one or more selected from the arylene groups represented by the formulas 5-1 to 5-4. Formulas 3-1 to 3-5 and Formulas 5-1 to 5-4 are the same as mentioned above. X ₁ and X ₁₁ and Y ₁ and Y ₁₁ are each independently COO, O, CNR ', CONR'',NR''' or CO, wherein R ', R''andR''' are each independently A hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, k ₁ and k ₁₁ are each an integer of 1 to 50.) The method of claim 1, In Formula 1, Z ₁ and Z ₂ are each independently a hydroxy group, a maleimide group, a namidide group, a phthalimide group, an alkenyl group, an alkynyl group, a propagyl ether group, a benzocyclobutene group, and a cyanate A substituted or unsubstituted C3 to C30 alicyclic group having a group, a double bond or a triple bond, a C6 to C30 aryl group having a C2 to C30 alkenyl group or a C2 to C30 alkynyl group, or a C6 to C30 having a cyanide group A thermosetting resin composition which is an aryl group. The method of claim 1, Z ₁ and Z ₂ in Chemical Formula 1 are each independently any one of the thermosetting functional groups represented by the following Chemical Formulas 8-1 to 8-11. [Formula 8-1]

(In Chemical Formula 8-1, n ₁ is an integer of 0 to 6, R ₁ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted A substituent which is an aryloxy group of C6 to C30, and when n ₁ is 2 or more, the substituents may be the same or different from each other.) [Formula 8-2]

(In Chemical Formula 8-2, n ₂ is 1, n ₃ is an integer of 0 to 3, R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituted or unsubstituted C6 to C30 aryloxy group, and when n ₃ is 2 or more, the substituents may be the same or different.) [Formula 8-3]

(In Chemical Formula 8-3, n ₄ is an integer of 0 to 2, R ₄ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted A substituent which is an aryloxy group of C6 to C30, and when n ₄ is 2 or more, the substituents may be the same or different from each other.) [Formula 8-4]

(In Chemical Formula 8-4, n ₅ is an integer of 0 to 8, R ₅ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted A substituent which is an aryloxy group of C6 to C30, and when n ₅ is 2 or more, the substituents may be the same or different from each other.) [Formula 8-5]

(In Chemical Formula 8-5, n ₆ is an integer of 0 to 7, R ₆ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted A substituent which is an aryloxy group of C6 to C30, and when n ₆ is 2 or more, the substituents may be the same or different from each other.) [Formula 8-6]

(In Chemical Formula 8-6, n ₈ and n ₉ are each independently an integer of 0 to 6, R ₈ and R ₉ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituted or unsubstituted C6 to C30 aryloxy group, and when n ₈ and n ₉ are each 2 or more, the substituents may be different from each other, Q ₁ and Q ₂ are each independently a methylene group, O or S, m ₁ is an integer of 1-3. ) [Formula 8-7]

(In Chemical Formula 8-7, n ₁₀ is an integer from 0 to 7, n ₁₁ is an integer from 0 to 6, R ₁₀ and R ₁₁ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituent which is a substituted or unsubstituted C6 to C30 aryloxy group, when n ₁₀ and n ₁₁ are each 2 or more, the substituents may be different from each other, Q ₃ and Q ₄ are each independently a methylene group, O or S, m ₂ is an integer of 1 to 3.) [Formula 8-8]

(In Chemical Formula 8-8, n ₁₂ is an integer from 0 to 7, n ₁₃ is an integer from 0 to 6, n ₁₄ is an integer from 0 to 8, R ₁₂ to R ₁₄ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, Or a substituted or unsubstituted C6 to C30 aryloxy group, and when n ₁₂ to n ₁₄ are each 2 or more, the substituents may be different from each other, Q ₅ and Q ₆ are each independently a methylene group, O or S, m ₃ and m ₄ are each independently an integer of 1 to 3.) [Formula 8-9]

(In Chemical Formula 8-9, n ₁₅ is an integer of 0 to 2, R ₁₅ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted A substituent which is an aryloxy group of C6 to C30, and when n ₁₅ is 2, the substituents may be the same or different from each other.) [Formula 8-10]

[Formula 8-11]

The method of claim 1, The repeating unit of Chemical Formula 2 is contained in more than 5 mol% to 70 mol% based on the total number of moles of the main chain of the thermosetting aromatic oligomer. The method of claim 1, Thermosetting resin composition of the number average molecular weight of the thermosetting aromatic oligomer is 500 to 15,000. The method of claim 1, The thermosetting aromatic oligomer is 10 to 75% by weight based on the total amount of the thermosetting resin composition. The method of claim 1, The hollow particles are a porous inorganic material, a porous polymer or a combination thereof thermosetting resin composition. 10. The method of claim 9, The porous inorganic material is alumina, silica, fused silica, glass or a combination thereof, The porous polymer is a urea resin, a phenol resin or a combination thereof thermosetting resin composition. The method of claim 1, The hollow particle is an airgel thermosetting resin composition. The method of claim 11, The airgel is a thermosetting resin composition obtained from silica, organic polymer, alumina, platinum, nickel, titania, zirconia, ruthenium, cobalt or a combination thereof. The method of claim 1, The hollow particles are thermosetting resin composition that comprises 0.5 to 70% by volume relative to the total volume of the thermosetting aromatic oligomer and the hollow particles. The method of claim 1, The size of the hollow particles is 0.1 to 100 um thermosetting resin composition. The method of claim 1, The thermosetting resin composition is a thermosetting resin composition further comprising a maleimide compound. The resin cured material using the thermosetting resin composition of any one of Claims 1-15. The cured resin of claim 16; And Including reinforcement, Wherein the cured resin is permeately attached to the reinforcement or is located on the surface of the reinforcement. The method of claim 17, The substrate further comprises a metal foil, The metal foil is a substrate that is bonded to at least one surface of the cured resin.

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