KR101539770B1 - Composition for forming Board and Printed Circuit Board using the same - Google Patents

Abstract

A composition for forming a substrate which can be used in the production of various printed circuit boards and a printed circuit board using the same are disclosed.

Thermosetting aromatic oligomers, soluble structural units, thermosetting groups, solvents, printed circuit boards

Description

TECHNICAL FIELD The present invention relates to a composition for forming a substrate and a printed circuit board using the composition.

Embodiments of the present invention relate to a composition for forming a substrate and a printed circuit board using the composition, and more particularly to a thermosetting aromatic oligomer having at least one soluble structural unit in its main chain and thermosetting groups at one or both ends of the main chain. And a printed circuit board using the same.

With the development of information and communication technology, computer and communication device have become integrated and become highly sophisticated communication and information society. Electronic devices such as mobile phones and personal computers have become smaller in size and higher in performance, and therefore, the printed circuit boards basically used for these devices have become more complicated due to multilayered structure, reduction of substrate thickness, downsizing of through-hole diameter, As the densification progresses, a substrate material of higher performance is required.

On the other hand, in electronic information apparatuses such as computers, a large amount of information is processed in a short time, so that a transmission loss is increased and a signal delay is increased as an operating frequency is increased. To solve this problem, A copper clad laminate having properties is required. In general, the signal delay in the printed circuit board increases in proportion to the square root of the relative dielectric constant of the insulator around the wiring, so that a resin composition having a low dielectric constant is required in a substrate requiring a high transmission rate.

However, in the case of the FR-4 class copper-clad laminate usually used at present, a relatively large dielectric constant of about 4.5-5.5 is exhibited, which causes a problem of increased transmission loss and signal delay. In addition, since such a substrate material is difficult to satisfy excellent mechanical properties, high heat resistance, low thermal expansion and low moisture absorption characteristics required in future packaging technologies, it is required to develop a new substrate material having characteristics required for a next generation substrate.

One embodiment is to provide a composition for forming a substrate that is easy to manufacture into a substrate because of its high solubility in a solvent.

Another embodiment is to provide a printed circuit board including a thermosetting aromatic oligomer, which is excellent in thermal characteristics such as heat resistance, resistance to water absorption and thermal expansion coefficient, and is easy to manufacture and low in manufacturing cost.

One aspect is a composition for forming a substrate comprising a solvent and a thermosetting aromatic oligomer, wherein the thermosetting aromatic oligomer has at least one soluble structural unit in the main chain and a thermosetting group at one or both ends of the main chain .

Wherein said soluble structural unit is a C ₄ -C ₃₀ aryl-amine group or a C ₄ -C ₃₀ aryl-amide group, said thermosetting group being selected from the group consisting of maleimide, nadimide, phthalimide phthalimide, acetylene, propagyl ether, benzocyclobutene, cyanate, and substituents or derivatives thereof.

Another embodiment relates to a composition for forming a substrate further comprising a toughening agent in addition to the thermosetting aromatic oligomer and the solvent.

Another embodiment relates to prepregs or printed circuit boards made by the compositions for forming a substrate.

The compositions for forming a substrate of the embodiments of the present invention have excellent thermal characteristics and improved solubility, thereby reducing manufacturing costs when used in the manufacture of various printed circuit boards.

Various embodiments of the present invention will now be described in more detail.

The composition for forming a substrate of various embodiments of the present invention comprises a solvent and a thermosetting aromatic oligomer, wherein the thermosetting aromatic oligomer comprises at least one soluble structural unit in the main chain, and at least one of the two ends of the main chain has a thermosetting group. As used herein, "solubility" means a solubility characteristic for the solvent used in the composition

Generally, even when the polymer resin is used by being melted or dissolved in a solvent, it is difficult to increase the solid content because the viscosity is very high. Particularly, when impregnated into glass fiber, impregnation is difficult due to high viscosity of the polymer composition, and when the solid content is low, the amount of impregnation is insufficient and the processing cost is increased due to problems such as reprocessing. On the other hand, the thermosetting aromatic oligomer has low viscosity, excellent properties such as dielectric constant, thermal expansion coefficient, and absorption resistance, and has excellent solubility in solvents, which can lower the manufacturing cost when applied to various substrate materials.

The soluble structural unit inserted into the main chain of the thermosetting aromatic oligomer may be a C ₄ -C ₃₀ aryl-amine group or a C ₄ -C ₃₀ aryl-amide group. The soluble structural unit may include a structural unit represented by the following general formula (1).

Wherein Ar is a C ₄ -C ₃₀ aryl group; X ¹ and Y ¹ are each independently selected from the group consisting of COO, O, CONR ", NR '" and CO, wherein R "and R'" each independently represent a hydrogen atom, It will be selected from the alkyl group, and the group consisting of an aryl group of C6 to C30 in the C20, the at least one of X ₁ and Y ₁ is CONR '', or NR '''.

Such a soluble structural unit includes one or two or more structural units selected from the following general formula (2), but is not limited thereto.

Wherein Ar is a C ₄ -C ₃₀ aryl group.

In the structural units constituting the thermosetting aromatic oligomer, Ar may be the same or different from each other, and the aromatic ring of Ar may be substituted with an amide group, an ester group, a carboxyl group, an alkoxy group, an aryl group or a fluoromethyl group.

Non-limiting examples of Ar may include those of formula (3).

But are not necessarily limited to these.

The thermosetting aromatic oligomer may contain a soluble structural unit in an amount of more than 5 mol% to 60 mol% or less based on the total amount of all structural units. When the content of the soluble structural unit is less than 5 mol%, the effect of improving the solubility 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 moisture absorption resistance is lowered Problems may arise. The content of the soluble structural unit in the thermosetting aromatic oligomer can be incorporated into the thermosetting aromatic oligomer at a desired level by adjusting the monomer content to be added during the reaction. The content of the soluble structural unit can be controlled by varying the size, mass, characteristic and chemical composition of the soluble structural unit.

The thermosetting aromatic oligomer may further include a structural unit represented by the following formula (4) together with a soluble structural unit in its main chain.

Wherein Ar is a C ₄ -C ₃₀ 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'" each independently represent a hydrogen atom, C20 alkyl group, and C6 to C30 aryl group.

Examples of the structural unit of the formula (4) may include one or two or more structural units selected from the following formula (5).

Wherein Ar is a C ₄ -C ₃₀ aryl group.

When two or more structural units selected from the above-mentioned general formula (3) are contained, Ar of each structural unit is the same or different from each other, and the aromatic ring of Ar is an aromatic group, an ester group, a carboxyl group, an alkoxy group, And may be substituted with a methyl group. Specifically, Ar may be selected from the following formula (3).

(3)

The thermosetting aromatic oligomer may have the same or different thermosetting groups introduced into at least one of both ends of the main chain. When the composition for forming a substrate is used in the production of a printed circuit board or the like, the crosslinked functional groups are crosslinked with each other to form a stable network structure, thereby improving the mechanical properties of the printed circuit board.

The thermosetting group may be a heat-crosslinkable reactor. Examples of such thermosetting groups include, but are not limited to, maleimide, nadimide, phthalimide, acetylene, propagyl ether, benzocyclobutene, cyanate, And substituents or derivatives thereof, but are not necessarily limited thereto. The term "substituent" as used herein means a structure in which a terminal portion of the thermocomposable reactor is substituted with a substituent such as an alkyl group, a halogen atom or an aryl group. For example, in the case of a maleimide reactor, And an alkyl group such as a methyl group. The term "derivative" as used herein means a structure in which an aromatic, heteroaromatic group or the like is bonded to a thermally curable reactor, for example, in the case of a maleimide reactor, a maleimide reactor is bonded to a benzene ring or naphthalene .

The thermosetting aromatic oligomer may have a structure represented by the following formula (6).

Wherein R < ¹ > is one or two or more structural units selected from the following formula (2); R ² is one or two or more structural units selected from the following general formula (5);

Z ¹ and Z ² are the same as or different from each other and each represent a hydrogen atom, a halogen atom, a hydroxy group, a maleimide group, a nadimide group, a phthalimide group, an acetylene group, a propagyl ether group ), Benzocyclobutene, cyanate and substituents or derivatives thereof, and at least one of Z ¹ and Z ² is selected from the group consisting of maleimide, nadimide, phthalate, Selected from the group consisting of phthalimide, acetylene, propagyl ether, benzocyclobutene, cyanate and substituents or derivatives thereof;

n and m are each independently a positive integer, preferably independently from 1 to 50.

(2)

In the above formula, Ar is a C ₄ -C ₃₀ aryl group.

[Chemical Formula 5]

In the above formula, Ar is a C ₄ -C ₃₀ aryl group.

For example, the thermosetting aromatic oligomer may have the following structure (7) or (8).

Wherein Z ¹ and Z ² are the same or different and are each independently selected from the group consisting of maleimide, nadimide, phthalimide, acetylene, propagyl ether, benzocyclobutene benzocyclobutene, cyanate, and substituents or derivatives thereof; n and m are each independently a positive integer, preferably independently from 1 to 50.

In the structures of Formulas 6 to 8, n / (n + m + 2) may range from more than 5% to less than 60%.

The molecular weight of the thermosetting aromatic oligomer may be from 500 to 15,000. If the molecular weight of the thermosetting aromatic oligomer is less than 500, crosslinking density may be increased and the physical properties may be brittle. If the molecular weight exceeds 15,000, the viscosity of the solution may be increased and the glass fiber may be deteriorated.

The method of preparing the thermosetting aromatic oligomer is not particularly limited and may be prepared by reacting compounds capable of producing aromatic oligomers containing soluble structural units through polymerization and compounds capable of introducing thermosetting groups.

The compounds capable of producing the aromatic oligomer containing the soluble structural unit are not particularly limited. At least one aromatic, aromatic heterocycle or aliphatic dicarboxylic acid; Aromatic, aromatic heterocycle or aliphatic diol; An aromatic, aromatic heterocyclic or aliphatic diamine; Aminophenol; Hydroxybenzoic acid; And aminobenzoic acid, and may be selected from the group consisting of aromatic, aromatic heterocyclic or aliphatic diols; Aminophenol; It is preferable to use at least one of aminobenzoic acid.

As an example, thermosetting aromatic oligomers can be prepared by solution polymerization or bulk polymerization. The melt polymerization and the bulk polymerization can be carried out in one reaction tank equipped with suitable stirring means

For example, isophthaloyl chloride, aminophenol, 2,6-dihydroxynaphthalene, and triethylamine are added to a reactor, The reaction was allowed to proceed at room temperature with stirring. After addition of a compound capable of adding a thermosetting group (for example, a compound capable of adding maleimide, nediimide, or acetylene or the like such as maleimido-benzoyl chloride) to a thermosetting aromatic oligomer Then, the thermosetting aromatic oligomer can be synthesized by separating and purifying it.

On the other hand, in the case of producing a thermosetting aromatic oligomer by bulk polymerization, it is preferable to add the isophthalic acid, aminophenol, 2-hydroxy-6-naphthoic acid and acetic anhydride to the reactor, The reaction is carried out for a predetermined time while refluxing. After removing the by-produced acetic acid and the anhydrous acetic acid flowing out, 4-hydroxybenzoic acid is further added, and the temperature is raised to 320 ° C to react. Thus, an aromatic oligomer having an alcohol group at one or both ends of the main chain is synthesized. When an aromatic oligomer having an alcohol group at both ends is obtained, the aromatic oligomer is dissolved in a solvent (for example, DMF) and then a compound capable of adding a thermosetting group is added and reacted. Group-added thermosetting aromatic oligomer can be obtained.

In the case of preparing a thermosetting aromatic oligomer by another bulk polymerization, the isophthalic acid, the aminophenol, the 2-hydroxy-6-naphthoic acid and the acetic anhydride are added to the reactor and the temperature is gradually increased to 150 ° C The reaction is carried out for a predetermined time while refluxing. Subsequently, the temperature was gradually raised to 230 deg. C, and the by-produced acetic acid and anhydrous acetic acid were removed to synthesize an oligomer. Ndimide benzoic acid was further added and the temperature was raised to 250 ° C to obtain a thermosetting aromatic oligomer.

The composition for forming a substrate according to an embodiment of the present invention can be applied to a solvent casting process, so that impregnation with glass fiber can be facilitated. The solvent in the composition for forming a substrate is not particularly limited, and a polar aprotic solvent may be used. Examples of the solvent include N, N-dimethylacetamide, N-methylpyrrolidone (NMP), N-methylcaprolactam, N, N-dimethylformamide, There may be used those selected from the group consisting of ethyl acetamide, N-methyl propionamide, dimethyl sulfoxide,? -Butyl lactone, dimethyl imidazolidinone, tetramethyl phosphoric amide and ethyl cellosolve acetate, Two or more types of mixed solvents may be used. The composition for forming a substrate may include 0.1 to 300 parts by weight of a thermosetting aromatic oligomer relative to 100 parts by weight of a solvent.

In another embodiment, the composition for forming a substrate may further comprise a toughening agent. When the thermosetting aromatic oligomer is mixed with a toughening agent, the flexibility of the composition can be improved. The toughening agent may be an aromatic polymer, and the number average molecular weight of the aromatic polymer may be about 2,000 to about 500,000. Examples of such aromatic polymers include aromatic polymers including one or two or more mesogen groups selected from the group consisting of ester, ester-amide, ester-imide, ester-ether and ester-carbonate in the main chain, . The mixing ratio of the thermosetting aromatic oligomer and the toughening agent may be 99.5: 0.5 to 35: 65 by weight.

The solid content in the composition may be 5 parts by weight or more and less than 100 parts by weight, preferably 5 parts by weight or more and 95 parts by weight or less, based on 100 parts by weight of the total composition. More preferably 30 parts by weight or more, and further, 50 parts by weight or more. Since the composition is excellent in the solubility of the thermosetting aromatic oligomer, the solid content may be high.

The composition for forming a substrate of embodiments of the present invention may further comprise one or more additives such as fillers, softeners, plasticizers, lubricants, antistatic agents, colorants, antioxidants, heat stabilizers, light stabilizers and UV absorbers . Examples of the filler 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 composition for forming a substrate has high adhesion strength to a copper foil and has excellent heat resistance, low expansion, and mechanical properties, and thus can be used as an excellent packaging material. The composition for forming a substrate may be formed into a substrate or may form a varnish for impregnation or coating. The composition is applicable to a printed board, each layer of a multilayer substrate, a copper-clad laminate (e.g., RCC, CCL), a film for TAB, but the use of the composition for forming a substrate is not limited thereto.

In order to use the composition as a substrate or the like, a composition comprising a thermosetting aromatic oligomer and a solvent or a composition comprising a toughening agent and a thermosetting aromatic oligomer and a solvent may be cast on a substrate to form a thin film, followed by curing at a high temperature . A composition in which flexibility is improved by adding a high molecular weight toughening agent to a thermosetting aromatic oligomer can provide a convenient advantage of handling in a copper foil laminating process.

A prepreg can be prepared using the composition for forming a substrate. The prepreg is prepared by impregnating the composition with a reinforcing material. Specifically, the composition for forming a substrate may be impregnated into a reinforcing material and cured to prepare a sheet. The reinforcing material is not particularly limited, and examples thereof include a woven glass cloth, a woven alumina glass fiber, a glass fiber nonwoven fabric, a cellulose nonwoven fabric, a woven carbon fiber, and a polymeric woven fabric. As a method for impregnating the reinforcing material with the composition for forming a substrate, dip coating, roll coating and the like can be used, and other conventional impregnation methods can be used.

A substrate can be produced using the composition for forming a substrate. The substrate is not particularly limited, and may be, for example, each layer of a multilayer substrate, a laminate in combination with a metal foil, a printing board, or the like. Also, the prepreg may be combined with a metal foil or the like.

The substrate may be in various forms and may be in the form of a film. The film can be produced by thinning the composition for forming a substrate. Examples of such a method include an extrusion molding method in which a composition for forming a substrate extruded from an extruder is formed into a film through a die; A cast molding method for casting a composition for forming a substrate into a film; And a dip molding method in which an inorganic substrate such as glass or a substrate in the form of a cloth is immersed in a varnish of the composition for forming a substrate, and then the substrate is molded into a film.

In addition to the film form, the substrate may be in the form of a laminate that is bonded to the metal foil. As the metal foil, a copper foil, an aluminum foil or the like is used. The thickness of the metal foil varies depending on the use, but it is suitably 5 to 100 mu m. The metal foil of the metal foil clad laminate can be fabricated as a printed circuit board by performing circuit processing. The metal foil clad laminate may also be laminated and processed on the surface of the print laminate to form a multilayer printed circuit board.

The laminate combined with the metal foil is manufactured by a method in which the composition for forming a substrate is applied on a metal foil (e.g., copper foil), cast on a metal foil (e.g., copper foil), removed from the solvent, and then subjected to heat treatment . The solvent removal is preferably carried out by evaporating the solvent. Examples of the method of evaporating the solvent include heating under reduced pressure, ventilation and the like.

Examples of the method of applying the composition for forming a substrate include, but are not necessarily limited to, a roller coating method, a dip coating method, a spray coating method, a spinner coating method, a curtain coating method, a slot coating method and a screen printing method. The composition for forming a substrate is preferably filtered using a filter or the like to remove fine foreign substances contained in the solution before being coated or cast on the copper foil.

The laminate to be bonded to the metal foil is not particularly limited, and examples thereof include resin coated copper (RCC) and copper clad laminate (CCL).

Another aspect relates to a thermosetting aromatic oligomer represented by the following formula (6).

[Chemical Formula 6]

Wherein R < ¹ > is one or two or more structural units selected from the following formula (2); R ² is one or two or more structural units selected from the following general formula (5); Z ¹ and Z ² are the same as or different from each other and each represent a hydrogen atom, a halogen atom, a hydroxy group, a maleimide group, a nadimide group, a phthalimide group, an acetylene group, a propagyl ether group ), Benzocyclobutene, cyanate and substituents or derivatives thereof, and at least one of Z ¹ and Z ² is selected from the group consisting of maleimide, nadimide, phthalate, Selected from the group consisting of phthalimide, acetylene, propagyl ether, benzocyclobutene, cyanate and substituents or derivatives thereof; n and m are each independently an integer of 1 to 50; n / (n + m + 2) is more than 5% and not more than 60%.

 (2)

In the above formula, Ar is a C ₄ -C ₃₀ aryl group.

[Chemical Formula 5]

In the above formula, Ar is a C ₄ -C ₃₀ aryl group.

In the formulas (2) and (5), Ar may be selected from the group consisting of the following formula (2).

(3)

In the above formula, R ¹ and R ² may be repeated in a block form or may be randomly repeated. 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 ¹ 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 ¹ may be in the form of R ² Z ^2.

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

Example

Production Example 1

1-1: Synthesis of 4-maleimido-benzoyl chloride

41.1 g (0.3 mol) of p-aminobenzoic acid and 300 ml of acetic acid were dissolved in a 250 ml flask, and 29.4 g (0.3 mol) of maleic anhydride was gradually added at 10 degrees to obtain a yellow precipitate. The precipitate was recrystallized from a DMF / ethanol (50:50 w / w) solution. The recrystallized intermediate was treated with sodium acetate and acetic anhydride at 85 DEG C for 15 minutes, then cooled to room temperature and precipitated in an ice bath to obtain a precipitate. The resulting precipitate was recrystallized from a solution of ethyl acetate / n-hexane (50:50, w / w) to give N- (p-carboxyphenyl) maleimide.

15 g (0.07 mol) of N- (p-carboxyphenyl) maleimide were added to 80 ml of benzene. To this was slowly added 21.83 g (0.172 mol) of oxalyl chloride and the temperature was raised to reflux for 2 hours. The unreacted oxalyl chloride was removed, cooled to room temperature, filtered, and washed with hexane to give 4-maleimido-benzoyl chloride.

1-2. Synthesis of thermosetting aromatic oligomer

After adding 100 ml of dimethylformamide to a 250 ml flask, 3.274 g (0.03 mol) of 4-aminophenol, 4.655 g (0.025 mol) of 4,4-dihydroxybiphenyl and 18 ml of triethylamine were added and dissolved , 10.151 g (0.05 mol) of isophthaloyl chloride was added while cooling in ice water. After reacting at room temperature for 60 hours, it was purified by using water and ethanol and dried.

After 1 g of the dried sample was dissolved in 9 g of NMP, 0.1 g of 4-maleimido-benzoyl chloride obtained in Preparation Example 1 and 10 ml of triethylamine were added, and the mixture was allowed to react at room temperature for 12 hours, A maleimide reactor was introduced to obtain a thermosetting aromatic oligomer having a structure represented by the following formula (9).

Wherein m is from 1 to 50 and n is from 1 to 50,

Production Example 2. Synthesis of thermosetting aromatic oligomer

Except that the addition amounts of 4-aminophenol and 4,4-dihydroxybiphenyl were changed to 3.820 g (0.035 mol) and 3.724 g (0.02 mol), respectively, to prepare a thermosetting aromatic oligomer Respectively.

Production Example 3. Synthesis of thermosetting aromatic oligomer

Except that the addition amounts of 4-aminophenol and 4,4-dihydroxybiphenyl were changed to 4.365 g (0.04 mol) and 2.793 g (0.015 mol), respectively, to obtain a thermosetting aromatic oligomer Were synthesized.

Production Example 4

4-1. 4-nedimide benzoic acid

In a 1000 ml flask, 32.83 g (0.2 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride was dissolved in 400 ml of glacial acetic acid and heated to 110 ° C., followed by the addition of an excess amount of 4-aminobenzoic acid Respectively. After the addition, the reaction was carried out with stirring for 2 hours, followed by precipitation at room temperature. The precipitate was washed with glacial acetic acid and water, respectively, and then dried in a vacuum oven at 60 DEG C to prepare 4-nedimide benzoic acid. The yield was 95%.

4-2. Synthesis of thermosetting aromatic oligomer

To a 500 ml flask equipped with a condenser and a mechanical stirrer were added 10.798 g (0.065 mol) of isophthalic acid, 47.948 g (0.254 mol) of 6-hydroxy-2-naphthoic acid and 14.187 g ) And acetic anhydride (58.396 g, 9.5 mol) were added. The temperature was gradually increased to 140 ° C under a nitrogen atmosphere, and the reaction was continued for 3 hours while maintaining the temperature. Then, 36.79 g (0.130 mol) of 4-nedimide benzoic acid obtained in Production Example 4-1 was added, and the reaction by-products, acetic acid and unreacted acetic anhydride were removed, After the temperature was elevated, the reaction was carried out at that temperature for 4 hours to obtain a thermosetting aromatic oligomer of the following formula (10) wherein a nodimide group was introduced into at least one of both ends of the main chain.

In order to investigate the introduction of a reactive functional group to the terminal of the thermosetting aromatic oligomer synthesized in Production Example 4-2, it was analyzed using NMR (Bruker NMR, DPX300). The solvent used was DMSO d6. As shown in FIG. 1, the peaks due to the nemedimide appeared in the range of 6.2 to 6.4, and it was confirmed that the nemedimide group was introduced at the terminal.

The reaction temperature of the thermosetting aromatic oligomer synthesized in Production Example 4-2 was measured using DSC (TA Instrument DSC 2010) and is shown in Fig. The rate of temperature rise was 20 degrees / min to 320 degrees. As can be seen in FIG. 2, the reaction peak due to the reactive functional group appears from 280 ° C. to 320 ° C., indicating that the reactive functional group has been successfully introduced to the terminal.

Production Example 5

In a 500 ml flask equipped with a condenser and a mechanical stirrer, 16.613 g (0.1 mol) of isophthalic acid, 51.75 And 64.572 g (0.633 mol) of acetic anhydride were added to the reaction mixture, and the temperature was gradually increased to 140 ° C under a nitrogen atmosphere. The mixture was reacted for 3 hours while maintaining the temperature, and the acetylation reaction was completed. Then, 28.3 g (0.1 mol) of 4-nedimide benzoic acid obtained in Production Example 4-1 was added, and acetic acid and unreacted acetic anhydride as reaction products were removed. After the temperature was raised, the reaction was carried out at that temperature for 4 hours to obtain a thermosetting aromatic oligomer having a nodimide group introduced into at least one of both ends of the main chain.

Production Example 6

To a 500 ml flask equipped with a condenser and a mechanical stirrer were added 19.936 g (0.12 mol) of isophthalic acid, 53.142 g (0.282 mol) of 6-hydroxy-2-naphthoic acid and 17.461 g ) And acetic anhydride (67.649 g, 0.663 mol) were slowly added to the mixture at 140 ° C under a nitrogen atmosphere, and the mixture was allowed to react at the temperature for 3 hours to complete the acetylation reaction. Then, 22.640 g (0.08 mol) of 4-nedimide benzoic acid obtained in Production Example 4-1 was added, and the reaction by-products, acetic acid and unreacted acetic anhydride were removed, After the temperature was raised, the reaction was carried out at that temperature for 4 hours to obtain a thermosetting aromatic oligomer having a nodimide group introduced into at least one of both ends of the main chain.

Production Example 7. Synthesis of aromatic polymer

(0.05 mol) of isophthalic acid, 18.8 g (0.1 mol) of 6-hydroxy-2-naphthoic acid and 5.5 g (0.05 mol) of 4-aminophenol were placed in a 500 ml flask equipped with a stirrer and a mechanical stirrer. , 32.7 (0.32 mol) of acetic anhydride were added, and the temperature was gradually increased to 150 ° C. under a nitrogen atmosphere. The reaction was continued for 4 hours while maintaining the temperature, and the acetylation reaction was completed. Then, while removing the acetic acid and the unreacted acetic anhydride, the temperature was raised to 300 ° C., and the reaction was carried out for 1 hour to synthesize an aromatic polymer (polyamide ester).

Example 1

The thermosetting aromatic oligomer prepared in Preparation Example 1-3 was added to NMP (N-methyl-2-pyrrolidone), and whether or not the thermosetting aromatic oligomer was dissolved in NMP at 160 ° C was visually observed and evaluated. In this case, the solubility was evaluated as 1 when the thermosetting aromatic oligomer was dissolved in 10 g of NMP, and when the solution was not dissolved at all, the evaluation was evaluated as X. When the solution was partially dissolved, the evaluation was evaluated as DELTA.

Production Example 1 Production Example 2 Production Example 3 Solubility ○ ○ ○

Example 2

Using GPC (GPCmax, VISCOTEK), the molecular weights of the thermosetting aromatic oligomers synthesized in Production Examples 4 to 6 were measured on the basis of polystyrene. The solvent used here was DMF, and the results are shown in Table 2 below.

The thermosetting aromatic oligomer synthesized in Production Example 4 was placed in NMP and dissolved at a solid content of 40 wt% while being heated to 60 캜 to obtain a brown solution. It was found that the thermosetting aromatic oligomer was sufficiently soluble up to 40 wt%, and the solubility was extremely excellent.

The viscosity of the thermosetting aromatic oligomer solution was measured at room temperature and found to be 1500 Cp.

M _n M _w PDI (M _w / M _n ) Production Example 4 3329 3902 1.17 Production Example 5 3671 4406 1.20 Production Example 6 4191 5232 1.25

Example 3-5

The thermosetting aromatic oligomer synthesized in Production Example 1-3 was added to NMP and dissolved at 100 ° C or higher to prepare a composition for forming a substrate. Glass fiber was placed on an electrolytic copper foil fixed on a glass plate, and impregnated into the glass fiber structure uniformly using the prepared composition. After elevating the temperature from room temperature to 300 DEG C to cure the impregnated specimen, the electrolytic copper foil was removed by adding 50 parts by weight of nitric acid solution to obtain a clean impregnated glass fiber specimen.

The glass transition temperature (Tg) and thermal expansion coefficient (CTE) of the glass fiber specimens obtained above were measured and shown in Table 3 below. The coefficient of thermal expansion (CTE) of the specimen was measured under nitrogen using TMA 2940 manufactured by TA Instruments (Thermomechanical Analyzer, TA Instruments TMA 2940), while increasing the temperature at a rate of 5 ° C / min.

Example 3 Example 4 Example 5 Thermosetting odorant oligomer Production Example 1
Production Example 2 Production Example 3 Glass transition temperature (캜) - - - Thermal Expansion Coefficient ( ppm / ° C) 3.635 2.861 5.205

As can be seen from the results of Table 3, the substrate prepared using the composition for forming a substrate containing the soluble structural unit had a very low coefficient of thermal expansion (CTE) and no glass transition temperature.

Examples 6-9

Except that the molar ratio of 4-aminophenol to 4,4-dihydroxybiphenyl was changed and the content of soluble structural unit (aminophenol group) was changed as shown in Table 4 below. A thermosetting aromatic oligomer was prepared in the same manner.

The composition for forming a substrate was prepared in the same manner as in Example 1 except that the thermosetting aromatic oligomer prepared above was used, and the solubility of the thermosetting aromatic oligomer was measured and shown in Table 4 below.

The glass transition temperature (Tg) and the thermal expansion coefficient (CTE) were measured in the same manner as in Example 3 except that the thermosetting aromatic oligomer prepared above was used in place of the thermosetting aromatic oligomer The results are shown together in Table 4 below.

Example 6 Example 7 Example 8 Example 9 Soluble structural unit content (mol%) 10 20 50 55 Glass transition temperature (캜) - - - -
Thermal Expansion Coefficient ( ppm / ° C) 3.112 3.655 6.721 9.322 Solubility △ △ ○ ○

As can be seen from the results of Table 4, the composition for forming a substrate of the embodiments of the present invention is excellent in thermal characteristics (thermal expansion coefficient, glass transition temperature) and solubility.

Example 10

3 g of the thermosetting aromatic oligomer obtained in Preparation Example 1 and 7 g of the polyamide-ester prepared in Preparation Example 5 were added to 40 g of NMP to prepare a mixed solution. The mixed solution was impregnated with 40x40x0.05 (mm) glass fiber, and the specimen was placed on the electrolytic copper foil and dried at a temperature of 300 ° C in a high-temperature furnace for two hours. The prepared specimen was treated with a nitric acid solution of 50 parts by weight to cleanly remove the copper foil to obtain a prepreg. The amount of the polymer impregnated into 1 part by weight of the glass fiber was 1 part by weight.

The prepreg thus prepared was measured for glass transition temperature and thermal expansion coefficient using a thermal analyzer (TMA: Thermomechanical Analyzer, TA Instruments TMA 2940). The results are shown in Table 6 below. The coefficient of thermal expansion (CTE) was measured under nitrogen, at which time the temperature was increased at a rate of 5 ° C / min.

Flexibility was measured for the prepreg obtained above, and the results are shown in Table 6 below. Flexibility was evaluated as x when the substrate was cracked when it was bent at 45 degrees, and when it was cracked when the substrate was warped by 90 degrees, and when it was not cracked when the substrate was warped by 90 degrees.

Examples 11-12

Prepregs were prepared in the same manner as in Example 10, except that each of the thermosetting aromatic oligomers prepared in Preparation Examples 2 and 3 was used in place of the thermosetting aromatic oligomer obtained in Preparation Example 1.

The thermal expansion coefficient was measured for the prepreg obtained in the same manner as in Example 10, and the results are shown in Table 5 below. Tg was measured for a part of the prepreg obtained in the same manner as in Example 10, and the results are also shown in Table 5 below.

Further, flexibility was measured for a part of the prepreg obtained above, and the results are shown in Table 5 below.

    division Example 10 Example 11 Example 12 Thermosetting aromatic oligomer  Production Example 1  Production Example 2  Production Example 3 Tg (占 폚) 244.37 281.80 281.75 CTE (ppm / ° C) 7.169 8.410 10.22 flexibility ○ △ △

As can be seen from the results of Table 5, the composition for forming a substrate of the embodiments of the present invention exhibits not only excellent thermal properties (glass transition temperature and thermal expansion coefficient) but also flexibility properties in preparing prepregs.

Example 13

A prepreg was produced in the same manner as in Example 10, except that each of the thermosetting aromatic oligomers prepared in Preparation Example 4 was used in place of the thermosetting aromatic oligomer obtained in Preparation Example 1.

As a result of measuring Tg in the same manner as in Example 10 for the prepregs obtained above, a glass transition temperature was observed at around 280 ° C.

The thermal expansion coefficient of the prepreg prepared using the thermosetting aromatic oligomer synthesized in Production Example 4 was measured in the same manner as in Example 10 and found to be 11 ppm / ° C.

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 and scope of the invention as set forth in the appended claims. Modifications and variations are intended to be included within the scope of the present invention.

1 is a graph showing NMR results of the thermosetting aromatic oligomer synthesized in Production Example 4-2.

2 is a graph showing the results of measurement of the reaction temperature of the thermosetting aromatic oligomer synthesized in Production Example 4-2 using DSC (TA Instrument DSC 2010).

Claims (27)

1. A composition for forming a substrate comprising a solvent and a thermosetting aromatic oligomer, wherein the thermosetting aromatic oligomer has at least one soluble structural unit represented by the following formula (1 ) and a mesogen structural unit represented by the following formula (4) A composition for forming a substrate having a thermosetting group, [Chemical Formula 1]

Wherein Ar is a C ₄ -C ₃₀ aryl group; X ¹ and Y ¹ are each independently selected from the group consisting of COO, O, CONR ", NR '" and CO, wherein R "and R'" each independently represent a hydrogen atom, will be selected from alkyl groups, and C6 to C30 aryl group consisting of C20, at least one of X ₁ and Y ₁ is CONR '', or NR ''',  [Chemical Formula 4]

Wherein Ar is a C ₄ -C ₃₀ 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'" each independently represent a hydrogen atom, C20 alkyl group, and a C6 to C30 aryl group, The thermosetting group may be selected from the group consisting of maleimide, nadimide, phthalimide, acetylene, propagyl ether, benzocyclobutene, and cyanate. ≪ / RTI > Wherein the soluble structural unit is contained in an amount of more than 5 mol% to 60 mol% or less based on the total amount of all the structural units . The composition of claim 1, wherein the soluble structural unit comprises a C ₄ -C ₃₀ aryl-amine group or a C ₄ -C ₃₀ aryl-amide group. delete The composition for forming a substrate according to claim 1, wherein the soluble structural unit comprises one or two or more structural units selected from the following structural formula (2). (2)

Wherein Ar is a C ₄ -C ₃₀ aryl group. The composition for forming a substrate according to claim 4, wherein Ar is an aryl group selected from the following general formula (3) or a substituent thereof. (3)

delete delete The composition for forming a substrate according to claim 1, wherein the structural unit of formula (4) comprises one or two or more structural units selected from the following formula (5). [Chemical Formula 5]

Wherein Ar is a C ₄ -C ₃₀ aryl group. 9. The composition for forming a substrate according to claim 8, wherein Ar is selected from the following formula (3). (3)

2. The composition of claim 1, wherein the thermosetting group is a heat-crosslinkable reactor. delete The composition for forming a substrate according to claim 1, wherein the thermosetting aromatic oligomer has a structure represented by the following formula (7) or (8): (7)

 [Chemical Formula 8]

Wherein Z ¹ and Z ² are the same or different and are each selected from the group consisting of maleimide, nadimide, phthalimide, acetylene, propagyl ether, Is selected from the group consisting of benzocyclobutene, cyanate and substituents or derivatives thereof, m is from 1 to 50, and n is from 1 to 50; The composition for forming a substrate according to claim 1, wherein the thermosetting aromatic oligomer has a number average molecular weight of 500 to 15,000. The composition for forming a substrate according to claim 1, wherein the solvent is a polar aprotic solvent. 15. The method of claim 14, wherein the polar aprotic solvent is selected from the group consisting of N, N-dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam, N, Ethylformamide, N, N-diethylacetamide, N-methylpropionamide, dimethylsulfoxide, gamma -butyllactone, dimethylimidazolidinone, tetramethylphosphoric amide and ethylcellosolve acetate, And a mixed solvent. The composition for forming a substrate according to claim 1, wherein the composition comprises 0.1 to 300 parts by weight of a thermosetting aromatic oligomer relative to 100 parts by weight of a solvent. 2. The composition of claim 1, wherein the composition further comprises a toughening agent. 18. The composition for forming a substrate according to claim 17, wherein the toughening agent is an aromatic polymer. The composition for forming a substrate according to claim 18, wherein the aromatic polymer has a number average molecular weight of 2,000 to 500,000. 19. The method of claim 18, wherein the aromatic polymer comprises at least one mesogen group selected from the group consisting of an ester, an ester-amide, an ester-imide, an ester-ether, and an ester-carbonate in the main chain / RTI > The composition for forming a substrate according to claim 17, wherein the mixing ratio of the thermosetting aromatic oligomer and the toughening agent is 99.5: 0.5 to 35: 65 by weight. The composition for forming a substrate according to claim 1, wherein the solid content in the composition is 5 to 95 parts by weight based on 100 parts by weight of the total composition. A prepreg produced from the composition for forming a substrate according to any one of claims 1, 2, 4, 5, 8 to 10, and 12 to 22. A substrate made from the composition for forming a substrate according to any one of claims 1, 2, 4, 5, 8 to 10, and 12 to 22.  25. The substrate of claim 24, wherein the substrate is a printed board or a copper clad laminate.  26. The substrate of claim 25, wherein the substrate is a CCL or a flexible CCL. A thermosetting aromatic oligomer represented by the following formula (6): [Chemical Formula 6]

Wherein R < ¹ > is one or two or more structural units selected from the following formula (2); R ² is one or two or more structural units selected from the following general formula (5); Z ¹ and Z ² are the same or different from each other and each represents a hydrogen atom, a halogen atom, a hydroxy group, a maleimide group, a nadimide group, a phthalimide group, an acetylene group, a propyl ether group, Benzocyclobutene, cyanate and substituents or derivatives thereof, and at least one of Z ¹ and Z ² is selected from the group consisting of maleimide, nadimide, phthalimide, selected from the group consisting of phthalimide, acetylene, propagyl ether, benzocyclobutene, and cyanate; n and m are each independently an integer of 1 to 50; (2)

In the above formula, Ar is a C ₄ -C ₃₀ aryl group. [Chemical Formula 5]

In the above formula, Ar is a C ₄ -C ₃₀ aryl group. Wherein the soluble structural unit of Formula 2 is contained in an amount of more than 5 mol% to 60 mol% or less based on the total amount of all the structural units .

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