KR101136407B1 - Material for substrate comprising inorganic filler having minus -coefficient of Thermal Expansion and Liquid Crystal Thermosetting Oligomer - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite material for a substrate, and more particularly, a liquid crystal thermosetting oligomer and a negative coefficient of thermal expansion having at least one soluble structural unit in a main chain and a thermosetting group at at least one of the ends of the main chain. The present invention relates to a substrate composite material including an inorganic filler having a CTE. The composite material according to the present invention can improve the mechanical, thermal and physical properties of the insulating layer of the printed circuit board by including an inorganic filler having a negative coefficient of thermal expansion.

Thermosetting, Main Chain, Coefficient of Thermal Expansion (CTE), Oligomer

Description

Material for substrate comprising inorganic filler having minus -coefficient of Thermal Expansion and Liquid Crystal Thermosetting Oligomer

The present invention provides a substrate comprising a thermosetting liquid crystal oligomer (Liquid Crystal Thermosetting Oligomer) having at least one soluble structural unit in the main chain, a thermosetting group at one or more of the ends of the main chain and an inorganic filler having a negative coefficient of thermal expansion It relates to a composite material.

BACKGROUND With the recent development of electronic devices, the weight reduction, miniaturization, and complexity of electronic devices are also progressing day by day. To meet these demands, boards and semiconductors, which are core components of electronic products, are also following this trend, and wiring of printed circuits of components is becoming more complicated and denser. In addition, the printed circuit board used for the connection between the active IC or the connection between the IC and the passive element serves to fix the IC so that the IC can operate properly according to the conditions of use. Due to the role of the substrate, it is necessary to maintain a very stable state electrically, mechanically and thermally. Among these, the dimensional deformation due to heat can be used for manufacturing substrates, mounting components such as ICs on substrates, and operating devices under certain conditions. I can make it. In particular, with the advent of low dielectric constant insulation layers, thinner and denser substrates have been accelerated and three-dimensional packaging technology is required, the use of insulating materials with low coefficient of thermal expansion (CTE) is not an option. It is an integral part and has become one of the important factors in determining reliability.

The printed circuit board consists of a circuit pattern composed of an insulating layer of the printed circuit board and copper (Cu), and the thermal expansion coefficient of copper is 17 ppm / ° C. Compared with copper, the CTE of the polymer constituting the insulating layer is very high. In order to overcome this difference, currently, the polymer is impregnated into the Woven Glass Fiber, or the CTE of the insulating layer is lowered by adding a large amount of various inorganic fillers having a lower CTE than the polymer. The fused silica had a CTE of about +5 ppm / ° C., and thus it was possible to lower the total CTE according to the mixing volume when mixed with an insulating polymer such as epoxy.

However, there is a need for an insulating polymer material having a thermal expansion coefficient such as CTE of a metal that ultimately serves as a circuit interconnect such as copper. However, the material obtained by controlling the type and amount of the epoxy polymer constituting the existing insulating layer, the size and amount of the inorganic filler is difficult to meet the above thermal and mechanical requirements.

Accordingly, in the present invention, as a result of repeated studies to solve the above problems, a substrate composite material including a thermosetting liquid crystal oligomer and an inorganic filler having a negative thermal expansion coefficient was completed.

Accordingly, an object of the present invention is to provide a composite material for a substrate having excellent mechanical, thermal and physical properties.

According to an aspect of the present invention, an inorganic filler having one or more soluble structural units in the main chain, a thermosetting liquid crystal oligomer having a thermosetting group at one or more of the ends of the main chain, and a negative coefficient of thermal expansion There is provided a composite material for a substrate comprising a.

In the substrate composite material, the soluble structural unit may include an aryl-amine group of C 4 to C 30 or an aryl-amide group of C 4 to C 30.

The soluble structural unit may also include a compound represented by the following formula (1):

Formula 1

Wherein Ar is a C4-C30 aryl group, X ¹ and Y ¹ are each independently selected from the group consisting of COO, O, CONR ", NR"'and CO, wherein said R "and R"' Each independently selected from the group consisting of a hydrogen atom, a C1-C20 alkyl group and a C6-C30 aryl group, at least ^one of X ¹ and Y ¹ is CONR "or NR"';

The soluble structural unit may also include one or more structural units selected from the compounds represented by the following formula (2):

Formula 2

In said formula, Ar is a C4-C30 aryl group.

In addition, Ar may be an aryl group or a substituent thereof selected from compounds represented by Formula 3 below:

Formula 3

On the other hand, the soluble structural unit may be included in more than 5 mol% 60 mol% based on the total of the total structural units.

In addition, the thermosetting liquid crystal oligomer may further include a structural unit represented by Formula 4 in the main chain:

Formula 4

Wherein Ar is a C4-C30 aryl group, X ² and Y ² are each independently selected from the group consisting of COO, O, CONR ", NR"'and CO, wherein said R "and R"' Each independently selected from the group consisting of a hydrogen atom, an alkyl group of C1 to C20 and an aryl group of C6 to C30.

The structural unit represented by Formula 4 may include one or two or more structural units selected from compounds represented by Formula 5 below:

Formula 5

In said formula, Ar is a C4-C30 aryl group.

In addition, Ar may be selected from compounds represented by Formula 3 below:

Formula 3

The thermosetting group may be a thermal crosslinkable reactor.

The thermosetting group is maleimide, maleimide, nedimide, phthalimide, acetylene, acetylene, propagyl ether, benzocyclobutene, sia Cyanate and substituents or derivatives thereof.

According to one embodiment, the thermosetting liquid crystal oligomer may be a compound represented by the following formula (6):

6

In the above formula, R ¹ is one or two or more structural units selected from compounds represented by the following formula (2); R ² is one or two or more structural units selected from compounds represented by Formula 5; Z ¹ and Z ² are the same or different from each other, and each hydrogen, halogen, hydroxy group, maleimide, nadimide, phthalimide, acetylene, propagyl ether , Benzocyclobutene, cyanate, and substituents or derivatives thereof; One or more of Z ¹ and Z ² is maleimide, nadimide, phthalimide, acetylene, propagyl ether, benzocyclobutene, cyanate (cyanate) and substituents or derivatives thereof; n and m are each independently an integer of 1-50; n / (n + m + 2) is greater than 5% and no greater than 60%:

Formula 2

In the above formula, Ar is a C4-C30 aryl group;

Formula 5

In the above formula, Ar is an aryl group of C4 ~ C30.

According to one preferred embodiment, the thermosetting liquid crystal oligomer may be a compound represented by the following formula (7) or (8):

Formula 7

Formula 8

Wherein Z ¹ and Z ² are the same or different from each other, and maleimide, nedimide, phthalimide, acetylene, propagyl ether, and benzocyclo It is selected from the group consisting of butene (benzocyclobutene), cyanate (cyanate) and substituents or derivatives thereof, m is an integer of 1-50, n is an integer of 1-50.

According to a preferred embodiment, the number average molecular weight of the thermosetting liquid crystal oligomer may be 500 ~ 15,000.

According to one embodiment, the inorganic filler is selected from the group consisting of eucryptite (LiAlSiO ₄ ), isotropic zirconium vanadate (ZrV ₂ O ₇ ) and isotropic zirconium tungstate (ZrW ₂ O ₈ ). It may be one or more.

In addition, the composite material may further include at least one inorganic filler selected from the group consisting of NaZr ₂ P ₃ O ₁₂ and Mg ₂ AL ₂ Si ₅ O ₁₈ .

In addition, the composite material may further include an inorganic filler having a coefficient of thermal expansion other than negative.

The eu cryptite may be a eu cryptite represented by the following formula (9).

Formula 9

xLiO ₂ -yAl ₂ O ₃ -zSiO ₂

In the above formula, x, y and z constitute a mixing molar ratio, x and y are each independently in the range of 0.9 to 1.1, and z is in the range of 1.9 to 2.1. In Chemical Formula 9, x = 1, y = 1, and z = 2.

According to one embodiment, the particle size of the filler may be 0.1 to 5㎛.

According to one embodiment, the thermal expansion coefficient of the filler may be in the range of -9 to -2 ppm / ℃. Synthesis temperature of the filler may be 1000 to 1400 ℃.

In an embodiment, the substrate composite material may further include an alkoxide metal compound having a reactor capable of covalent bonding with a thermosetting group of the thermosetting liquid crystal oligomer.

On the other hand, the reactor capable of covalent bonding with the thermosetting group may be selected from the group consisting of vinyl groups, acrylic groups, methacryl groups, mecapto groups and combinations thereof.

The metal of the alkoxide metal compound may be selected from the group consisting of Ti, Al, Ge, Co, Ca, Hf, Fe, Ni, Nb, Mo, La, Re, Sc, Si, Ta, W, Y, Zr and V. Can be.

The alkoxide metal compound may be at least one selected from the group consisting of the following compounds.

According to another aspect of the present invention, a film made of the composite material is provided.

According to another preferred aspect of the present invention, there is provided a prepreg made from the composite material.

The composite material according to the present invention can improve the mechanical, thermal and physical properties of the insulating layer of the circuit board by including an inorganic filler having a negative thermal expansion coefficient.

Hereinafter, the present invention will be described in more detail.

The composite material according to the present invention can secure a significantly lower CTE than an insulating material using a general-purpose epoxy, and in recent printed circuit board technologies requiring three-dimensional packing technology in accordance with the emergence of low dielectric constant and thinning of the substrate. In addition, it is possible to realize composites with strengths in the coefficient of thermal expansion (CTE).

According to a preferred aspect of the present invention, the inorganic filler having at least one soluble structural unit in the main chain, a thermosetting liquid crystal oligomer having a thermosetting group at one or more of the ends of the main chain and a negative coefficient of thermal expansion There is provided a composite material for a substrate comprising a).

In the present invention, a soluble LCT oligomer is used instead of a generally used epoxy resin. The LCT oligomer has a structure that realizes the characteristics of the liquid crystal and a soluble structure that can be dissolved in the solvent at the same time. In addition, a portion that may have a thermally cured structure is present at one or more of both ends. The structure of the liquid crystal oligomer is shown in FIG.

That is, the thermosetting liquid crystal oligomer includes at least one soluble structural unit in the main chain, and has a thermosetting group at at least one of both ends of the main chain. As used herein, "soluble" refers to a property that has good solubility in the solvent used in the composition.

The soluble structural unit inserted into the main chain of the thermosetting liquid crystal oligomer may be an aryl-amine group of C 4 to C 30 or an aryl-amide group of C 4 to C 30. The soluble structural unit may include a structural unit of Formula 1 below.

Formula 1

Wherein Ar is a C4-C30 aryl group, X ¹ and Y ¹ are each independently selected from the group consisting of COO, O, CONR ", NR"'and CO, wherein said R "and R"' Each independently selected from the group consisting of a hydrogen atom, an alkyl group of C1 to C20 and an aryl group of C6 to C30, and at least ^one of X ¹ and Y ¹ is CONR ″ or NR ″ ′.

Such soluble structural units include, but are not necessarily limited to, one or two or more structural units selected from compounds represented by Formula 2 below.

Formula 2

In said formula, Ar is a C4-C30 aryl group.

In each structural unit constituting the thermosetting liquid crystal oligomer, Ar is different from or identical to each other, and the aromatic ring of Ar may be substituted with an amide group, ester group, carboxyl group, alkoxy group, aryl group or fluoromethyl group.

Non-limiting examples of Ar may include a compound represented by the following formula (3).

Formula 3

The thermosetting liquid crystal oligomer may include a soluble structural unit in an amount of more than 5 mol% and 60 mol% or less with respect to the total of the entire structural units. When the content of the soluble structural unit is 5 mol% or less, the solubility improvement effect in the solvent may be insignificant. In contrast, when the content of the soluble structural unit exceeds 60 mol%, the hydrophilicity is increased and the hygroscopic resistance is lowered. This can happen. The content of the soluble structural unit in the thermosetting liquid crystal oligomer may include a desired level of the soluble structure in the thermosetting liquid crystal oligomer by controlling the monomer content added during the reaction. The content of the soluble structural unit can be adjusted by changing the size, mass, properties and chemical composition of the soluble structural unit.

The thermosetting liquid crystal oligomer may further include a structural unit represented by Formula 4 together with a soluble structural unit in a main chain.

Formula 4

In the above formula, Ar is a C4-C30 aryl group; X ² and Y ² are each independently selected from the group consisting of COO, O, CONR ″, NR ″ ′ and CO, wherein R ″ and R ″ ′ are each independently a hydrogen atom, an alkyl group of C 1 -C 20 and C 6 It is selected from the group which consists of -C30 aryl group.

Examples of the structural unit of Chemical Formula 4 may include one or two or more structural units selected from compounds represented by the following Chemical Formula 5.

Formula 5

In said formula, Ar is a C4-C30 aryl group.

When two or more structural units selected from the compounds represented by Formula 5 are included, Ar in each structural unit is the same as or different from each other, and the aromatic ring of Ar is an amide group, ester group, carboxyl group, alkoxy group, It may be substituted with an aryl group or a fluoromethyl group. Specifically, Ar may be selected from the following formula (3).

Formula 3

The thermosetting liquid crystal oligomer may have the same or different thermosetting groups introduced at one or more of both ends of the main chain. When the thermosetting group is subjected to high temperature curing when the composition for forming a substrate is used in the manufacture of a printed circuit board, these crosslinking functional groups crosslink with each other to form a stable structure in the form of a network, thereby improving mechanical properties of the printed circuit board.

The thermosetting group may be a thermal crosslinkable reactor. Examples of such thermosetting groups are maleimide, nadimide, phthalimide, acetylene, propagyl ether, benzocyclobutene, cyanate And compounds selected from the group consisting of substituents or derivatives thereof, but are not necessarily limited thereto. As used herein, the term "substituent" refers to a structure in which a portion of the terminal of the thermal crosslinking reactor is substituted with a substituent such as an alkyl group, a halogen atom, an aryl group, and the like. Substituted by alkyl groups, such as a methyl group, etc. are included. In addition, the term "derivative" herein refers to a structure in which a thermal crosslinkable reactor is bonded to an aromatic or heteroaromatic group, and the like, and for example, in the case of a maleimide reactor, a maleimide reactor is bonded to a benzene ring or naphthalene. .

Preferably, the thermosetting liquid crystal oligomer may have a structure of Formula 6 below.

6

In the above formula, R ¹ is one or two or more structural units selected from formula (2); R ² is one or two or more structural units selected from Formula 5;

Z ¹ and Z ² are the same or different from each other, and hydrogen, halogen, hydroxy group, maleimide, nadimide, phthalimide, acetylene and propagyl ether ), Benzocyclobutene, cyanate, and substituents or derivatives thereof;

n and m are each independently a positive integer, Preferably they are independently the integer of 1-50.

Formula 2

In the above formula, Ar is an aryl group of C4 ~ C30.

Formula 5

In the above formula, Ar is an aryl group of C4 ~ C30.

In addition, R ¹ and R ² in the above formula may be repeated in a block form or randomly. For example, Z ¹ R ¹ R ¹ R ¹ . R ² R ² R ² Z ² or Z ¹ R ¹ R ¹ R ² . R ² R ² Z ² or Z ¹ R ¹ R ² R ² R ² . R ¹ R ² Z ² or Z ¹ R ¹ R ² R ¹ R ² . R ² R ² Z ^{2 It} may be in the form of.

For example, the thermosetting liquid crystal oligomer may have a structure of Formula 7 or Formula 8.

Formula 7

Formula 8

Wherein Z ¹ and Z ² are the same as or different from each other, and maleimide, nadimide, phthalimide, acetylene, propagyl ether, and benzocyclo Benzocyclobutene, cyanate, and substituents or derivatives thereof; n and m are each independently a positive integer, Preferably they are each independently the integer of 1-50.

In addition, in the structure of Chemical Formulas 6 to 8, n / (n + m + 2) may be in a range of more than 5% and 60% or less.

The molecular weight of the thermosetting liquid crystal oligomer may be 500 to 15,000. When the molecular weight of the thermosetting liquid crystal oligomer is less than 500, the crosslinking density may be high, thereby causing brittle physical properties, and when the molecular weight is more than 15,000, the viscosity of the solution may be high to impair the glass fiber nonwoven fabric. .

The inorganic filler included in the composite material of the present invention is in the group consisting of anisotopic (eu) cryptite (LiAlSiO ₄ ), isotropic zirconium vanadate (ZrV ₂ O ₇ ) and zirconium tungstate (ZrW ₂ O ₈ ) It may be one or more selected.

CTE (100K ~ 400K) of eu krypite (LiAlSiO ₄ ) is -5.5ppm / ℃ or less (Fig. 2), CTE of zirconium vanadate (ZrV ₂ O ₇ ) is -10ppm / ℃ or less (Fig. 3), The CTE (100K-400K) of zirconium tungstate (ZrW ₂ O ₈ ) is -11 ppm / ° C. or less (FIG. 4).

The composite material may further include one or more inorganic fillers selected from the group consisting of NaZr ₂ P ₃ O ₁₂ and Mg ₂ AL ₂ Si ₅ O ₁₈ , which inorganic fillers have a CTE of almost zero. The material may further comprise an inorganic filler having a non-negative coefficient of thermal expansion.

Preferably cryptic (LiAlSiO ₄ ), zirconium vanadate (ZrV ₂ O ₇ ), zirconium tungstate (ZrW ₂ O ₈ ), or a mixed filler thereof with negative CTE, or zero or positive CTE The eggplant can add an inorganic filler and its mixed filler up to the inorganic filler dispersion threshold.

Preferably, the eu cryptite may be a eu cryptite represented by the following formula (9).

Formula 9

xLiO ₂ -yAl ₂ O ₃ -zSiO ₂

In the above formula, x, y and z constitute a mixing molar ratio, x and y are each independently in the range of 0.9 to 1.1, and z is in the range of 1.9 to 2.1. The eutectic inorganic filler is a crystallized glass composed of components of LiO ₂ , Al ₂ O ₃ , and SiO ₂ , and x, y in z, y, and z, respectively, representing a mixing molar ratio of the components, are each independently in the range of 0.9 to 1.1. And z ranges from 1.9 to 2.1. When x, y, and z have the above ranges, the LiAlSiO ₄ crystal structure having the lowest thermal expansion coefficient can be effectively synthesized as the crystal structure of the eutectic. However, if it is out of the above range, the crystal structure having other second phases such as LiAlO ₂ , Li ₂ SiO _3, etc. increases, and since they have a higher coefficient of thermal expansion than that of the LiAlSiO ₄ crystal structure, the coefficient of thermal expansion of the final eucryptite inorganic filler is eventually increased. It is not desirable because it results in increasing. Preferably fillers with x = 1, y = 1 and z = 2 can be used.

Such a cryptic inorganic filler can manufacture each oxide component by the general powder synthesis method. For example, LiO ₂ , Al ₂ O ₃ , and SiO ₂ may be synthesized by mixing each oxide component in the composition of the mixed molar ratio of Chemical Formula 1 and then performing heat treatment at a predetermined temperature. According to one embodiment, it is preferable to synthesize the single phase by mixing each oxide component and then heat treatment at 1000 to 1400 ℃. The higher the heat treatment temperature is LiAlSiO ₄ The purity of the crystal structure can be increased, and the crystal structure having other phases such as LiAlO ₂ , Li ₂ SiO _3, etc. can be reduced, so that a lower eucritite inorganic filler can be produced. However, when the heat treatment temperature is less than 1000 ℃ phase synthesis is not achieved because it does not have a negative CTE value, it is not preferable, if the heat treatment temperature exceeds 1400 ℃ part is difficult to form or crush the glass is not preferable. The eutectic inorganic fillers thus synthesized have a coefficient of thermal expansion in the range of -9 to -2 ppm / ° C.

In addition, the eu cryptite inorganic filler, when mixed with the thermosetting resin to lower the CTE of the substrate insulating material, it is preferable that the particle size ranges from 0.1 to 5㎛. If it is out of this range, since filler filler and board | substrate insulation tend to fall, it is not preferable.

In an embodiment, the substrate composite material may further include an alkoxide metal compound having a reactor capable of covalent bonding with a thermosetting group of the thermosetting liquid crystal oligomer.

Reactors capable of covalent bonding with the thermosetting group may be selected from the group consisting of vinyl groups, acrylic groups, methacryl groups, mecapto groups, and combinations thereof. This reactor is the main back-bone maleimide, Nedimide (Nadimide = Naphtalene acetaimide), Phthalimide, Acetylene, Propagyl ether, Benzocyclobutene ( By chemically reacting benzocyclobutene), cyanate and their substituents or derivatives, materials with excellent thermal, mechanical and electrical properties can be obtained.

According to one embodiment, the metal of the alkoxide metal compound is Ti, Al, Ge, Co, Ca, Hf, Fe, Ni, Nb, Mo, La, Re, Sc, Si, Ta, W, Y, Zr and V It may be selected from the group consisting of.

The alkoxide metal compound may be one or more selected from the group consisting of the following compounds, but is not particularly limited thereto.

Substrate composite materials according to embodiments of the present invention may further include one or more additives such as fillers, softeners, plasticizers, lubricants, antistatic agents, colorants, antioxidants, thermal stabilizers, light stabilizers and UV absorbers as needed. Examples of fillers include organic fillers such as epoxy resin powder, melamine resin powder, urea resin powder, benzoguanamine resin powder and styrene resin; And inorganic fillers such as silica, alumina, titanium oxide, zirconia, kaolin, calcium carbonate and calcium phosphate.

The composite material of the present invention may be manufactured in the form of prepreg by impregnating the glass fiber nonwoven fabric, and also may be manufactured as a buildup film itself and used as an insulating material of a substrate such as a printed circuit board.

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

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

Manufacturing example  1: liquid crystal Oligomer  synthesis

1-1. 4- Nedimide Benzoic Acid  synthesis

In a 1000 ml flask, 32.83 g (0.2 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride was added to 400 ml of glacial acetic acid and heated to 110 ° C to dissolve, followed by excess of 41.1 g of 4-aminobenzoic acid ( 0.3 mol) was added thereto. After the reaction, the reaction was stirred for 2 hours and then precipitated at room temperature. Precipitates were washed with glacial acetic acid and water, and then dried in a vacuum oven at 60 ℃ to prepare Nedimide benzoic acid. The yield was 95%.

1-2. Thermosetting liquid crystal Oligomer (LCT)  synthesis

10.789 g (0.065 mol) isophthalic acid, 47.948 g (0.254 mol) 6-hydroxy-2-naphthoic acid, 14.187 g (0.130 g) 4-aminophenol in a 500 ml flask equipped with a condenser and a mechanical stirrer mol), acetic anhydride 58.396g (9.5mol) was added, and gradually increased the temperature to 140 ℃ under a nitrogen atmosphere, the reaction was maintained for 3 hours while maintaining the temperature to complete the acetylation reaction. Subsequently, 36.79 g (0.130 mol) of the 4-neimidebenzoic acid obtained in Preparation Example 1-1 was added thereto, followed by removal of the reaction by-products acetic acid and unreacted acetic anhydride at 215 at a rate of 1 to 2 ° C. per minute. After the temperature was raised to 4 ° C, the reaction was carried out at that temperature for 4 hours to obtain a thermosetting liquid crystal oligomer represented by the following Chemical Formula 10 in which a nemidide group was introduced at one or more of both ends of the main chain.

Formula 10

Manufacturing example  2 : Euliptite  weapon Of filler  synthesis

LiO ₂ , Al ₂ O ₃ and SiO ₂ were mixed in a stoichiometric ratio of 1: 1: 2 as a starting material for the eutectic inorganic filler, and the heat treatment temperatures were 1000 ° C., 1100 ° C., 1200 ° C., It was synthesized into a single phase by heat treatment at 1300 ° C. for 2 hours.

The CTEs of the synthesized eu cryptite inorganic fillers are shown in Table 1 below.

One 2 3 4 Heat treatment temperature (℃) 1000 1100 1200 1300 CTE (Coefficient of Thermal Expansion) (ppm / ℃) -2.0 -3.1 -5.5 -8.7

When used as a filler in the insulating material of the printed circuit board, the eutectic ceramic filler used in the present invention enables the CTE of the insulating material to be effectively lowered without increasing the filling amount of the conventional filler. According to Table 1, it can be seen that the higher the synthesis temperature, the greater the negative value of the CTE absolute value.

Example  One: LCT + Cryptic  Using composite materials Prepreg  Produce

A composite material was prepared by mixing the LCT synthesized in Preparation Example 1 and the eutectic synthesized in Preparation Example 2.

LCT synthesized in Preparation Example 1 and the eutectic ceramic filler 4 (CTE = -8.7ppm / ° C) synthesized in Preparation Example 2 were mixed by adding 10% and 30% in weight ratio, respectively (Example 1), An insulating material for a printed circuit board was prepared. Prepreg (PPG) was formed by impregnating the prepared insulating material solution for a printed circuit board into glass fiber 1078 (manufactured by Taiwan-Wincom).

The linear thermal expansion coefficient of the composite material prepared in this manner is shown in Table 2 below, and a measurement graph is shown in FIG. 5.

Fiberglass 1078 (wt%) Euliptite Filler (ET08) (vol%) Prepreg
(xy-axis) a1, xy (50 ~ 100 ℃) 37 10 9.701 30 8.899 50 10 9.583 30 9.066

In FIG. 5, 37% of glass fiber 1078 used glass fiber 1078 of 37 wt% by weight of the LCT solution, and d1 and d2 are linear thermal expansion coefficient reproducibility measurements of the measured samples. 1078 50% (ET08 10vol%) used glass fiber 1078 in 50wt% by weight of LCT solution, again d1 and d2 are CTE reproducibility measurements for the measurement samples.

Comparative example  One: LCT neat  Solution Prepreg  Produce

Prepreg (PPG) was formed by impregnating glass fiber 1078 in the LCT neat solution.

Comparative example  2: Alkoxide Silane compounds  More composites and Prepreg  Produce

A reactor capable of covalent bonding with the thermosetting group of the thermosetting liquid crystal oligomer of LCT further comprises an alkoxide silane compound having a reactor selected from the group consisting of vinyl group, acrylic group, methacryl group, mecapto group and combinations thereof The prepreg was formed by impregnating the glass fiber 1078 in a solution for forming a substrate that does not include.

Table 3 below shows the linear coefficient of thermal expansion of the prepreg composite material made of the LCT neat solution of Comparative Example 1 and the material containing the LCT neat solution and the alkoxide silane compound.

SixO ₂ -x content
(wt%) Reaction condition Prepreg (xy-axis) a1, xy
(40 ~ 80 ℃) a2, xy
(220 ~ 240 ℃) 0 - 17.6 6.3 20 acidic 16.5 13.7 basic 14.9 12.3 30 acidic 15.3 12.3 basic 11.7 11.7

6 is a graph showing the data shown in Table 3 above. A graph showing the linear coefficient of thermal expansion including the prepreg prepared by the method of Comparative Example 1 and the LCT composite material (LCT + silane compound + glass fiber 1078) was measured. Shows an example containing 20% or 30% silane compound by weight of LCT)

Comparing Table 2 and Table 3, the CTEs of the prepreg composite material made of the LCT neat solution of Comparative Example 1 and the prepreg composite material made of the LCT neat solution and the silane compound of Comparative Example 2 were all tens of ppm / ° C. The CTEs of the prepreg composite including the LCT oligomer and the eutectic filler which are one embodiment of the present invention are all several ppm / ° C.

Based on this, when manufacturing a composite material for a substrate including an inorganic filler having a negative coefficient of thermal expansion, such as ukripite filler, to minimize the thermal expansion coefficient of the LCT polymer substrate that can be used for printed circuit board, It can be seen that a more secured composite material can be obtained.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims. It will be understood that the invention may be varied and varied without departing from the scope of the invention. Many embodiments other than the above-described embodiments are within the scope of the claims of the present invention.

1 is a diagram showing the structure of a liquid crystal oligomer.

Figure 2 is a graph showing the CTE of krypite.

3 is a graph showing the CTE of zirconium vanadate.

4 is a graph showing the CTE of zirconium tungstate.

5 is a graph showing a CTE of a prepreg composite material including an oligomer and a cryptite filler as an embodiment of the present invention.

Figure 6 is a graph showing the CTE of the prepreg composite material made of LCT neat solution and glass fiber of Comparative Examples 1 and 2 of the present invention and the prepreg composite material made of LCT neat solution and silane compound and glass fiber.

Claims (28)

It has one or more soluble structural units in the main chain, has a thermosetting liquid crystal oligomer (Liquid Crystal Thermosetting Oligomer) having a thermosetting group at one or more of the ends of the main chain and a negative coefficient of thermal expansion, and isotropic (LiAlSiO ₄ ), isotropic Zirconium vanadate (ZrV ₂ O ₇ ) and isotropic zirconium tungstate (ZrW ₂ O ₈ ) and at least one inorganic filler (filler) selected from the group consisting of vinyl, acrylic, methacryl, A composite material for a substrate comprising an alkoxide metal compound having a reactor capable of covalent bonding with a thermosetting group of the thermosetting liquid crystal oligomer selected from the group consisting of a mecapto group and a combination thereof. The method of claim 1, The soluble structural unit is a composite material for a substrate, characterized in that it comprises an aryl-amine group of C4 ~ C30 or aryl-amide group of C4 ~ C30. The method of claim 1, The soluble structural unit is a composite material for a substrate comprising a compound represented by the following formula (1): [Formula 1]

Wherein Ar is a C4-C30 aryl group, X ¹ and Y ¹ are each independently selected from the group consisting of COO, O, CONR ", NR"'and CO, wherein said R "and R"' Each independently selected from the group consisting of a hydrogen atom, an alkyl group of C1 to C20 and an aryl group of C6 to C30, and at least ^one of X ¹ and Y ¹ is CONR ″ or NR ″ ′; The method of claim 3, The soluble structural unit is a composition for forming a substrate, characterized in that it comprises one or more structural units selected from compounds represented by the following formula (2): [Formula 2]

In the formula, Ar is an aryl group of C4 ~ C30. The method according to claim 3 or 4, Ar is a composite material for a substrate, characterized in that the aryl group selected from the compound represented by the following formula (3) or substituents thereof. (3)

The method of claim 1, The soluble structural unit is a composite material for a substrate, characterized in that contained in more than 5 mol% 60 mol% based on the total of the total structural units. The method of claim 1, The thermosetting liquid crystal oligomer is a substrate composite material further comprises a structural unit represented by the following formula (4) in the main chain: [Formula 4]

Wherein Ar is a C4-C30 aryl group, X ² and Y ² are each independently selected from the group consisting of COO, O, CONR ", NR"'and CO, wherein said R "and R"' Each independently selected from the group consisting of a hydrogen atom, an alkyl group of C1 to C20 and an aryl group of C6 to C30. The method of claim 7, wherein The structural unit represented by the formula (4) is a composite material for a substrate comprising one or two or more structural units selected from compounds represented by the following formula (5): [Chemical Formula 5]

In the formula, Ar is an aryl group of C4 ~ C30. The composite material for a substrate according to claim 7 or 8, wherein Ar is selected from compounds represented by the following general formula (3). (3)

The method of claim 1, The thermosetting group is a composite material for a substrate, characterized in that the thermal crosslinkable reactor. The method of claim 1, The thermosetting group is maleimide, maleimide, phthalimide, acetylene, acetylene, propagyl ether, benzocyclobutene, benzocyclobutene, cyanate and these Substrate composite material, characterized in that selected from the group consisting of substituents or derivatives. The method of claim 1, The thermosetting liquid crystal oligomer is a composite material for a substrate, characterized in that the compound represented by the following formula (6): [Formula 6]

In the above formula, R ¹ is one or two or more structural units selected from compounds represented by the following formula (2); R ² is one or two or more structural units selected from compounds represented by Formula 5; Z ¹ and Z ² are the same or different from each other, and each hydrogen, halogen, hydroxy group, maleimide, nadimide, phthalimide, acetylene, propagyl ether , Benzocyclobutene, cyanate, and substituents or derivatives thereof; At least one of Z ¹ and Z ² is maleimide, nadimide, phthalimide, acetylene, propagyl ether, benzocyclobutene, sia Cyanate and substituents or derivatives thereof; n and m are each independently an integer of 1-50; n / (n + m + 2) is greater than 5% and no greater than 60%: [Formula 2] 　

In the above formula, Ar is a C4-C30 aryl group; [Chemical Formula 5]

In the above formula, Ar is an aryl group of C4 ~ C30. The method of claim 1, The thermosetting liquid crystal oligomer is a composite material for a substrate, characterized in that the compound represented by the following formula (7) or formula (8): [Formula 7]

[Formula 8]

Wherein Z ¹ and Z ² are the same or different from each other, and maleimide, nedimide, phthalimide, acetylene, propagyl ether, and benzocyclo Benzocyclobutene, cyanate, and substituents or derivatives thereof, m is an integer from 1 to 50, n is an integer from 1 to 50. The method of claim 1, The number average molecular weight of the said thermosetting liquid crystal oligomer is 500-15,000, The composite material for substrates characterized by the above-mentioned. delete The composite material for a substrate according to claim 1, wherein the eu cryptite is eu cryptite represented by the following formula (9): [Formula 9] xLiO ₂ -yAl ₂ O ₃ -zSiO ₂ In the above formula, x, y and z constitute a mixing molar ratio, x and y are each independently in the range of 0.9 to 1.1, and z is in the range of 1.9 to 2.1. The method of claim 16, X = 1, y = 1 and z = 2 in the formula (9). The method of claim 16, The particle size of the filler is a composite material for a substrate, characterized in that 0.1 to 5㎛. The method of claim 16, The thermal expansion coefficient of the filler is a composite material for a substrate, characterized in that the range of -9 to -2 ppm / ℃. The method of claim 16, The composite temperature of the filler is a composite material for a substrate, characterized in that the range of 1000 to 1400 ℃. delete delete The method of claim 1, The metal of the alkoxide metal compound is selected from the group consisting of Ti, Al, Ge, Co, Ca, Hf, Fe, Ni, Nb, Mo, La, Re, Sc, Si, Ta, W, Y, Zr and V A composite material for a substrate, characterized in that. The method of claim 1, The alkoxide metal compound is a substrate composite material, characterized in that at least one selected from the group consisting of the following compounds.

The composite material of claim 1, wherein the composite material further comprises at least one inorganic filler selected from the group consisting of NaZr ₂ P ₃ O ₁₂ and Mg ₂ AL ₂ Si ₅ O ₁₈ . The composite material for a substrate according to claim 1, wherein the composite material further comprises an inorganic filler having a coefficient of thermal expansion which is not negative. A film made of the composite material for a substrate of claim 1. A prepreg made of the composite material for a substrate of claim 1.

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