KR20110097107A

KR20110097107A - Composition for forming substrate, and prepreg and substrate using the same

Info

Publication number: KR20110097107A
Application number: KR1020100016762A
Authority: KR
Inventors: 김진철; 유성현
Original assignee: 삼성전기주식회사
Priority date: 2010-02-24
Filing date: 2010-02-24
Publication date: 2011-08-31
Also published as: KR101156836B1

Abstract

The present invention relates to a composition for forming a substrate, and a prepreg and a substrate using the same, wherein the composition for forming a substrate includes (i) a thermosetting liquid crystal 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. An oligomer (Liquid Crystal Thermosetting Oligomer), (ii) a fluororesin powder, and (iii) a solvent.

Description

Composition for forming substrate, and prepreg and substrate using the same {Composition for forming substrate, and prepreg and substrate using the same}

The present invention relates to a composition for forming a substrate, and a prepreg and a substrate using the same.

As electronic devices become slimmer, the thickness of boards for component mounting is also decreasing. In contrast, the number of layers on the substrate is increasing. As a result, the thickness of the insulating material that is a component of the substrate is also reduced.

Each electronic device has a resistor that matches the resistance of each module or package. However, reducing the thickness of the insulating material of the substrate causes this resistance value to be lowered. To increase this lowered resistance, the width of the conductor must be reduced. However, reducing the width of the conductor can lead to an increase in the cost of manufacturing the substrate and making it impossible to manufacture. To solve this problem, it is most effective to lower the dielectric constant of the insulating material.

In this regard, Figure 1 shows a typical microstrip structure for circuit design. As shown in FIG. 1, the microstrip forms an electrode 20 for grounding on the entire lower surface, and clearly defines the height h and the dielectric constant ε _{r of the} intermediate insulator (dielectric) 10. It is the structure of the board | substrate which comprises a circuit, arrange | positioning the signal line 30 on the upper surface according to the height / dielectric constant. In order to match the impedance in the microstrip structure substrate, the height h and the dielectric constant epsilon _r of the intermediate insulator 10 must be clearly defined in addition to the width W and the height t of the signal line 30.

The impedance value Z ₀ may be defined as follows when W / h ≦ 1 (Equation 1) and when W / h ≧ 1 (Equation 2).

As can be seen from Figure 1 and the equations (1) and (2), by lowering the dielectric constant, the impedance can be increased, and thus it is possible to realize the lowering of the impedance due to the decrease in thickness without reducing the width of the circuit.

On the other hand, in order to lower the dielectric constant of the insulating material of the printed circuit board, PTFE, PPE, etc. are mainly used as the fluorine resin. However, PTFE resin substrates have a very low dielectric constant, but they are too hygroscopic and are not used as printed circuit boards for electronic devices. PPE resins have a large coefficient of thermal expansion and hardening shrinkage, and thus easily cause warpage and a large amount of drill wear. In addition, desmearability is not good. In addition, both have a disadvantage that the manufacturing cost is very high.

In addition, a PTFE resin and another resin may be mixed to form a composite using compression molding to be used as an insulating material. In addition, the composite is produced by lamination on a woven glass cloth. However, even in this case, there is a disadvantage that the manufacturing method is very expensive compared to the current substrate insulation.

In the present invention, as a result of extensive research to solve the above problems, low dielectric constant by dispersing the fluorine resin powder in the thermosetting liquid crystal (Liquid Crystal Thermosetting, LCT) oligomer using a solvent other than the conventional compression molding or lamination The insulating material composition for board | substrates which has a low thermal expansion characteristic was obtained, and this invention was completed based on this.

Accordingly, one aspect of the present invention is to provide a composition for forming a substrate having low dielectric constant and low thermal expansion characteristics.

Yet another aspect of the present invention is to provide a prepreg and a substrate using the composition for forming a substrate.

According to a preferred aspect of the present invention,

Forming a substrate comprising (i) a liquid crystal thermosetting oligomer having at least one soluble structural unit in the main chain and having a thermosetting group at at least one of the ends of the main chain, (ii) a fluororesin powder, and (iii) a solvent A composition for use is provided.

In the thermosetting liquid crystal oligomer, 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):

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 R "and R"' are Each independently selected from the group consisting of a hydrogen atom, a C1 to C20 alkyl group and a C6 to 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):

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

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

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:

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, a C1 to C20 alkyl group and a C6 to C30 aryl group.

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

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

Here, 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):

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 to 50; n / (n + m + 2) is greater than 5% and no greater than 60%:

Formula 2

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

Formula 5

In the above formula, Ar is a C4 to C30 aryl group.

According to one preferred embodiment, the thermosetting liquid crystal oligomer may be a compound represented by the following formula (7) or (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 number average molecular weight of the thermosetting liquid crystal oligomer may be 500 to 15,000.

The fluororesin is preferably PTFE (PolyTetraFluoro Ethylene), FEP (Fluorinated Ethylene Propylene), PFA (PerFluoro Alkoxy), ETFE (Ethylene-TetraFluoro Ethylene), PVDF (PolyVinyliDen Fluoride), ECTFE (Ethylene-Chloth-Ethoro-ChlothyleneFlutriF) PolyChloroTriFluoro Ethylene) and combinations thereof.

Preferably, the average particle diameter of the fluororesin powder may be 10 to 1000nm.

The content of the fluororesin powder in the composition is preferably 5 to 60% by weight.

On the other hand, the composition preferably comprises 0.1 to 300 parts by weight of the thermosetting liquid crystal oligomer with respect to 100 parts by weight of the solvent.

According to another preferred aspect of the present invention, a prepreg prepared from the composition for forming a substrate is provided.

According to another preferred aspect of the present invention, a substrate prepared from the composition for forming a substrate is provided.

The features and advantages of the present invention will become more apparent from the following detailed description based on the accompanying drawings.

Prior to this, the terms or words used in this specification and claims are not to be interpreted in a conventional and dictionary sense, and the inventors may appropriately define the concept of terms in order to best describe their own invention. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

According to the present invention, it is possible to provide an insulating material for a substrate having a uniform low dielectric constant by dispersing a fluororesin powder in a thermosetting liquid crystal (LCT) oligomer using a solvent other than conventional compression molding or lamination. . Accordingly, the composition for forming a substrate of the present invention does not have a local difference in dielectric constant, and may be used as a printed circuit board insulating material of a high speed circuit and a high frequency region.

In addition, the thermal and mechanical properties inherent in the thermosetting liquid crystal oligomer are maintained, so that the present invention can be applied to a substrate insulating material which exhibits a significantly lower coefficient of thermal expansion and lower dielectric constant than conventional epoxy materials.

1 is a view schematically showing a microstrip structure according to the prior art.
2 is a view for schematically explaining a manufacturing process of the prepreg using the composition for forming a substrate of the present invention.

The objects, specific advantages and novel features of the present invention will become more apparent from the following detailed description and the preferred embodiments associated with the accompanying drawings. In describing the present invention, when it is determined that the detailed description of the related known technology may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

The composition for forming a substrate of the present invention comprises (i) a thermosetting liquid crystal oligomer having at least one soluble structural unit in the main chain and having a thermosetting group at at least one of the ends of the main chain, (ii) a fluororesin powder, and ( iii) a solvent.

The thermosetting liquid crystal oligomer used in the present invention has a structure that realizes the characteristics of the liquid crystal and a soluble structure that can be dissolved in a solvent. In addition, a portion that may have a thermally cured structure is present at one or more of both ends.

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. By "soluble" herein is meant a property that has good solubility in the solvents used in the composition.

In general, the polymer resin is melted or dissolved in a solvent, so that the polymer resin has a very high viscosity, making it difficult to increase the solid content. In particular, when impregnated into a glass fiber nonwoven fabric has a high viscosity of the polymer composition is difficult to impregnate, when the solid content is low there is a problem that the processing cost increases due to insufficient impregnation amount, such as reprocessing. On the contrary, the thermosetting liquid crystal oligomer has a low viscosity and excellent properties such as dielectric constant, coefficient of thermal expansion, water absorption, and solubility in solvents, thereby lowering the manufacturing cost when applied to various substrate materials.

The soluble structural unit inserted into the main chain of the thermosetting liquid crystal oligomer may be an aryl-amine group of C4 to C30 or an aryl-amide group of C4-C30. 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 R "and R"' are 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"'.

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

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

Wherein Ar is a C4 to 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 to C 20 and C 6 It is selected from the group consisting of aryl groups of -C30.

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

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, for example, in the case of a maleimide reactor, at least one hydrogen in a double bond 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, heteroaromatic group, or the like. 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 each hydrogen, halogen, hydroxy group, maleimide, nadimide, phthalimide, acetylene, 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 a C4 to C30 aryl group.

Formula 5

In the above formula, Ar is a C4 to C30 aryl group.

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 thermosetting liquid crystal oligomer may have a molecular weight of 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 method of preparing the thermosetting liquid crystal oligomer is not particularly limited, and may be prepared by reacting compounds capable of preparing a liquid crystal oligomer including a soluble structural unit and a compound capable of introducing a thermosetting group through polymerization.

The compounds capable of producing the liquid crystal oligomer including the soluble structural unit are not particularly limited. For example, one or more aromatic, aromatic heterocycles or aliphatic dicarboxylic acids; Aromatic, aromatic heterocyclic or aliphatic diols; Aromatic, aromatic heterocyclic or aliphatic diamines; Amino phenol; Hydroxybenzoic acid; And aminobenzoic acid, and may be selected from the group consisting of aromatic, aromatic heterocyclic or aliphatic diols; Amino phenol; Preference is given to using at least one of aminobenzoic acids.

In one example, the thermosetting liquid crystal oligomer may be prepared by solution polymerization or bulk polymerization. Solution polymerization and bulk polymerization can be carried out in one reaction tank equipped with suitable agitation means.

For example, a solution polymerization method is described. First, isophthaloyl chloride, aminophenol, 2,6-dihydroxynaphthalene, and triethylamine are added to a reactor. After the reaction proceeds while stirring at room temperature. After a certain time, a compound capable of adding a thermosetting group (for example, a compound capable of adding maleimide, nemidimide, or acetylene, such as maleimido-benzoyl chloride) may be further added to react to obtain a thermosetting liquid crystal oligomer. Thereafter, the thermosetting liquid crystal oligomer may be synthesized by separating and purifying it.

On the other hand, when manufacturing a thermosetting liquid crystal oligomer by bulk polymerization, after gradually adding the isophthalic acid, aminophenol, 2-hydroxy-6-naphthoic acid, and acetic anhydride to the reactor and stirring, the temperature is gradually raised to 150 占 폚. The reaction is carried out for a certain time while refluxing. Subsequently, after removing the by-product acetic acid and acetic anhydride, 4-hydroxybenzoic acid is further added, and the reaction is performed by raising the temperature to 320 ° C. In this way, the liquid crystal oligomer which has an alcohol group in one or more of the both ends of a principal chain is synthesize | combined. When a liquid crystal oligomer having an alcohol group at both ends is obtained, the liquid crystal oligomer is dissolved in a solvent (such as DMF), and then reacted with the addition of a compound capable of adding a thermosetting group. Added thermosetting liquid crystal oligomers can be obtained.

In the case of producing a thermosetting liquid crystal oligomer by another bulk polymerization, isophthalic acid, aminophenol, 2-hydroxy-6-naphthoic acid and acetic anhydride are added to the reactor and then raised to 150 ° C. with stirring and then refluxed. React for hours. Subsequently, by-product acetic acid and acetic anhydride are removed while gradually raising the temperature to 230 ° C to synthesize the oligomer. Nedimide benzoic acid can be further added and heated up to 250 degreeC, and a thermosetting liquid crystal oligomer can be obtained.

The fluorine resin of the fluorine resin powder used in the present invention is PTFE (PolyTetraFluoro Ethylene), FEP (Fluorinated Ethylene Propylene), PFA (PerFluoro Alkoxy), ETFE (Ethylene-Tetra Fluoro Ethylene), PVDF (PolyVinyliDen Fluoride), ECTFE (Ethylene-Ethylene-Ethylene) One or more of ChlorotriFluoro Ethylene and PolyChloroTriFluoro Ethylene (PCTFE) may be selected.

The average particle diameter of the fluororesin powder is preferably 10 to 1000nm in terms of dispersibility.

The content of the fluororesin powder in the composition is preferably 5 to 60% by weight in terms of economical expression of the desired dielectric properties.

The solvent used in the composition for forming a substrate is not particularly limited, but a polar aprotic solvent is preferable. The solvent is, for example, N, N-dimethylacetamide, N-methylpyrrolidone (NMP), N-methylcaprolactone, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N-methylpropionamide, dimethyl sulfoxide, γ-butyllactone, dimethylimidazolidinone, tetramethylphosphoric amide and ethyl cellosolve acetate may be used. Alternatively, two or more kinds of mixed solvents among these may be used. The substrate-forming composition may include 0.1 to 300 parts by weight of the thermosetting liquid crystal oligomer based on 100 parts by weight of the solvent.

In addition, a small amount (about 5 to 30% by weight) of metal filler and / or ceramic filler may be further added to the composition for forming a substrate of the present invention in order to maximize the desired properties.

In addition, the composition for forming a substrate of the present invention may further include a toughening agent for improving flexibility. The toughening agent is an aromatic polymer, and the number average molecular weight of the aromatic polymer may be 2,000 to about 500,000. Examples of such aromatic polymers include, but are not limited to, aromatic polymers comprising at least one mesogenic group selected from the group consisting of esters, ester-amides, ester-imides, ester-ethers, and ester-carbonates in the backbone It is not limited to. The mixing ratio of the polymerization reactant and the toughening agent may be 99.5: 0.5 to 35:65 by weight.

The composition for forming a substrate of the present invention may include one or more additives such as insulating resins, organic-inorganic fillers, softeners, plasticizers, lubricants, antistatic agents, colorants, antioxidants, heat stabilizers, light stabilizers, and UV absorbers, if necessary. It may further include. Examples of organic-inorganic 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.

On the other hand, the composition for forming a substrate of the present invention can be applied to a solvent casting (solvent casting) process, it can be easily impregnated with glass fibers.

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

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

Hereinafter, with reference to FIG. 2, the prepreg manufacturing method using the composition for substrate formation of this invention is demonstrated, for example.

First, each raw material is supplied from the resin varnish supply part 11 and the fluororesin powder supply part 12 each containing a thermosetting liquid crystal oligomer (a), a solvent (b) and various additives (c), and mixed in the mixing part 13. Then, the mixed varnish 14 in which the fluororesin powder is dispersed is supplied to the impregnation part 16.

At the same time, the glass fiber nonwoven fabric is supplied from the glass fiber nonwoven fabric supply section 15 to the impregnation section 16 and impregnated with the mixed varnish.

Subsequently, the glass fiber nonwoven fabric impregnated with the mixed varnish is dried in the drying unit 17, and then a plurality of sheets are laminated to a desired thickness, if necessary, followed by heating and pressing to laminate and removing the solvent through complete drying and heat treatment. The final prepreg 18 is obtained.

In the case of using only conventional ceramic fillers, since the dielectric constant of the ceramic is 4 or more, it is impossible to simultaneously reduce the CTE while lowering the dielectric constant, but the prepreg of the present invention has a dielectric constant depending on the fluorine resin powder content. And CTE values can be simultaneously lowered to the desired level.

In addition, a 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.

The substrate may be in various forms and may be in the form of a film. The film may be prepared by thinning the composition for forming a substrate.

The substrate other than the film may be in the form of a laminate 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, what is 5-100 micrometers is used suitably. By performing a circuit process with respect to the metal foil of a metal foil clad laminated board, it can manufacture into a printed circuit board. The above-described metal foil-coated laminates may also be laminated and processed on the surface of a printed laminate to produce a multilayer printed circuit board.

The laminate combined with the metal foil is not particularly limited and includes, for example, resin coated copper (RCC) and copper clad laminate (CCL).

The substrate-forming composition may also be used as an excellent packaging material because of its high adhesive strength with copper foil, excellent heat resistance, low expansion, and mechanical properties. The composition for forming a substrate may be molded into a substrate or form a varnish for impregnation or coating. The composition can be applied to printed circuit boards, each layer of a multilayer substrate, copper foil laminates (eg, RCC, CCL), and films for TAB, but the use of the composition for forming a substrate is not limited thereto.

In order to use the composition as a material such as a substrate, it may be prepared by casting and curing on a substrate.

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.

Preparation Example 1

1-1. 4-nedimide Benzoic Acid synthesis

In a 1000 ml flask, 32.83 g (0.2 mol) of 5-norbornene-2,3-dicarboxylic anhydride was added to 400 ml of glacial acetic acid and heated to 110 ° C to dissolve, followed by 41.1 g of excess 4-aminobenzoic acid (0.3 mol). ) Was added. 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 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 4-nedimide benzoic acid obtained in Preparation Example 1-1 was added thereto, followed by removal of reaction byproducts acetic acid and unreacted acetic anhydride at 215 ° C at a rate of 1 to 2 ° C per minute. After the temperature was raised to 4 hours, the reaction was performed for 4 hours to obtain a thermosetting liquid crystal oligomer represented by Chemical Formula 9 having a nemidide group introduced into at least one of both terminals of the main chain.

Production Example 2

2-1. 4- Malamido - Benzoyl Chloride synthesis

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

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

2-2. Thermosetting liquid crystal Oligomer synthesis

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

After dissolving 1 g of the dried sample in 9 g of NMP, 0.1 g of 4-maleimido-benzoyl chloride obtained in Preparation Example 2-1 and 10 ml of treethylamine were added thereto, followed by reaction at room temperature for 12 hours, in which both ends of the main chain were reacted. The at least one maleimide reactor was introduced to obtain a thermosetting liquid crystal oligomer represented by the following Chemical Formula 10.

Example 1

After dissolving 40 parts by weight of the thermosetting liquid crystal oligomer obtained in Preparation Example 1 with respect to 100 parts by weight of N-methyl pyrrolidone solvent to obtain a resin varnish, 30% by weight of PTFE powder was dispersed in a resin equivalent thereto. Prepare the mixed varnish. The mixed varnish was impregnated into a glass fiber nonwoven fabric and then dried at a temperature of about 150 ° C. in an air atmosphere to prepare a prepreg according to the present invention. The prepreg obtained therefrom was finally cured at a temperature of about 200 ° C., and then the dielectric constant and the coefficient of thermal expansion were measured, and the results are shown in Table 1 below.

Example 2

After dissolving 40 parts by weight of the thermosetting liquid crystal oligomer obtained in Preparation Example 2 with respect to 100 parts by weight of a N-methyl pyrrolidone solvent to obtain a resin varnish, 15% by weight of PTFE powder was dispersed therein to prepare a mixed varnish. do. The mixed varnish was impregnated into a glass fiber nonwoven fabric and then dried at a temperature of about 150 ° C. in an air atmosphere to prepare a prepreg according to the present invention. The prepreg obtained therefrom was finally cured at a temperature of about 200 ° C., and then the dielectric constant and the coefficient of thermal expansion were measured, and the results are shown in Table 1 below.

Example 1 Example 2 permittivity 3.05 3.35 Coefficient of thermal expansion
(ppm / ℃) 14.7 15.5

As shown in Table 1, it can be seen that the prepreg according to the present invention simultaneously exhibits a low dielectric constant and a coefficient of thermal expansion. Therefore, the substrate-forming composition of the present invention is expected to exhibit excellent thermal, mechanical and electrical properties when used as a high-speed circuit and high-frequency printed circuit board insulating material.

Although the present invention has been described in detail through specific examples, this is for explaining the present invention in detail, and the composition for forming a substrate according to the present invention, and the prepreg and the substrate using the same are not limited thereto. It is apparent that modifications and improvements are possible by those skilled in the art within the scope of the idea.

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

11: Resin varnish supply part
12: fluorine resin powder supply unit
13: mixing section
14: mixed varnish
15 glass fiber nonwoven fabric supply part
16: impregnation
17: drying section
18: prepreg

Claims

(i) a liquid crystal thermosetting oligomer having at least one soluble structural unit in the main chain and having a thermosetting group at at least one of the ends of the main chain, (ii) a fluororesin powder, and (iii) a solvent. A composition for forming a substrate.

The method according to claim 1,
The soluble structural unit comprises a C4 to C30 aryl-amine group or a C4 to C30 aryl-amide group composition for forming a substrate.

The method according to claim 1,
The soluble structural unit is a composition for forming a substrate, characterized in that it comprises 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 R "and R"' are Each independently selected from the group consisting of a hydrogen atom, a C1 to C20 alkyl group and a C6 to C30 aryl group, at least ^one of X ¹ and Y ¹ is CONR ″ or NR ″ ′.

The method according to 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

Wherein Ar is an aryl group of C4 to C30.

The method according to claim 4,
Ar is a composition for forming a substrate, characterized in that the aryl group selected from the compound represented by the following formula (3) or substituents thereof:
Formula 3

The method according to claim 1,
The soluble structural unit is a composition for forming a substrate, characterized in that contained in more than 5 mol% 60 mol% based on the total of the total structural units.

The method according to claim 1,
The thermosetting liquid crystal oligomer composition for forming a substrate further comprising 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 according to claim 7,
The structural unit represented by the formula (4) is a composition for forming a substrate comprising one or two or more structural units selected from compounds represented by the following formula (5):
Formula 5

Wherein Ar is an aryl group of C4 to C30.

The composition for forming a substrate according to claim 8, wherein Ar is selected from compounds represented by the following Chemical Formula 3:
Formula 3

The method according to claim 1,
The thermosetting group is a composition for forming a substrate, characterized in that the thermal crosslinking reactor.

The method according to claim 1,
The thermosetting group may be maleimide, nedimide, phthalimide, acetylene, acetylene, propagyl ether, benzocyclobutene, cyanate and these Substrate composition for forming a substrate, characterized in that it is selected from the group consisting of substituents or derivatives.

The method according to claim 1,
The thermosetting liquid crystal oligomer is a composition for forming a substrate, characterized in that the compound represented by the 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 to 50; n / (n + m + 2) is greater than 5% and no greater than 60%:
Formula 2

In the above formula, Ar is a C4 to C30 aryl group;
Formula 5

In the above formula, Ar is a C4 to C30 aryl group.

The method according to claim 1,
The thermosetting liquid crystal oligomer is a composition for forming a substrate, characterized in that the compound represented by the formula (7) or formula (8):
Formula 7

8

The method according to claim 1,
The number average molecular weight of the said thermosetting liquid crystal oligomer is 500-15,000, The composition for substrate formation characterized by the above-mentioned.

The method according to claim 1,
The fluorine resin is PTFE (PolyTetraFluoro Ethylene), FEP (Fluorinated Ethylene Propylene), PFA (PerFluoro Alkoxy), ETFE (Ethylene-TetraFluoro Ethylene), PVDF (PolyVinyliDen Fluoride), ECTFE (Ethylene-ChlorotrifluoroFriloTriPoroTerofluorothylene) And a composition for forming a substrate, characterized in that selected from the group consisting of these.

The method according to claim 1,
The composition for forming a substrate, wherein the average particle diameter of the fluororesin powder is 10 to 1000 nm.

The method according to claim 1,
The content of the fluorine resin powder in the composition is a composition for forming a substrate, characterized in that 5 to 60% by weight.

The method according to claim 1,
The composition for forming a substrate, characterized in that it comprises 0.1 to 300 parts by weight of the thermosetting liquid crystal oligomer based on 100 parts by weight of the solvent.

Prepreg manufactured from the composition for substrate formation of Claim 1.

A substrate made from the composition for forming a substrate of claim 1.