KR100813888B1 - Thermally curable resin composition having low dielectric constant and low dielectric loss in high frequency range - Google Patents

Abstract

A thermosetting resin composition is provided to ensure a low dielectric constant and low dielectric loss in fabricating a printed circuit board, and to impart transmission characteristics suitable for a high frequency range to a printed circuit board. A thermosetting resin composition having a low dielectric constant and low dielectric loss in a high frequency range comprises: a matrix resin formed of a solid phase single cycloolefin resin; an organic solvent for dissolving the matrix resin; a crosslinking agent used in an amount corresponding to a weight ratio of 1/20 to 1/3 based on the weight of the matrix resin. In the composition, the crosslinking agent modifies the properties of the matrix resin so as to realize improved dielectric properties in a high frequency range in a GHz scale.

Description

Highly low dielectric constant low loss thermosetting resin composition {Thermally Curable Resin Composition Having Low Dielectric Constant and Low Dielectric Loss in High Frequency Range}

1 is a schematic diagram showing a state of manufacturing a printed wiring board using a sheet, a film, or a prepreg containing a high frequency low dielectric constant low loss thermosetting resin composition according to the present invention.

The present invention relates to a thermosetting resin composition, and more particularly to a low dielectric constant low loss thermosetting resin composition having excellent electrical properties in the high frequency band. Moreover, this invention relates to the prepreg, laminated board, board for printed wirings, etc. which consist of the said low dielectric constant low loss thermosetting resin composition.

With the progress of advanced information society, it is necessary to process a large amount of information at high speed, and thus the frequency band of signals used in communication electronics has shifted from MHz to GHz to higher frequency ranges. As a result, the higher the frequency, the greater the transmission loss of the electrical signal. Therefore, there is a strong demand for the development of an electrically insulating material having a high frequency transmission characteristic in a high frequency band and a substrate using the same. In addition, in a device using a high frequency signal, signal delay in a printed wiring board becomes a problem. Since the delay of this signal is proportional to the square root of the dielectric constant of the insulating layer around the wiring, a material having a low dielectric constant is required to reduce the delay of the signal.

As the electrical insulating material for this property, a polymer insulating material is usually used. As specific polymer insulating materials, various resins such as polyolefin resins, epoxy resins, fluorine-based thermoplastic resins, polyimide resins, and bismarade triazine resins have been proposed.

Among various polymer insulating materials provided in the related art, epoxy resins have a high dielectric constant and have disadvantages in that electrical characteristics, in particular, dielectric properties in a high frequency region are bad. In addition, the fluorine-based thermoplastic resin represented by PTFE has good high frequency characteristics, but since it is a thermoplastic resin, its expansion and shrinkage during molding processing is large, and its workability is much inferior, so its use is limited to special applications. In addition, in the case of the thermoplastic resin, even when adhesiveness with the metal foil is secured when molding into a laminate, the reverse heat resistance is inferior. In the case of the polyol perrin-based resin, since it does not have a polar group, it has excellent electrical characteristics, particularly dielectric loss characteristics, but has a low heat resistance. In addition, when used as a laminate for wiring boards because of the large coefficient of linear expansion, there is a problem that the reliability of connection and through-hole plating are insufficient when mounting components. In addition, the bismaled triazine resin and the polyimide resin are in a state of low utility as a general purpose resin due to their high price.

The present invention has been made to solve the above problems, a resin comprising a cyclo-olefin polymer (COP); Crosslinking agents; And it aims at providing the high frequency low dielectric constant low loss thermosetting resin composition in which the initiator was contained.

Another object of the present invention is to prepare a prepreg, a laminate or a substrate for printed wiring using the thermosetting resin composition prepared according to the present invention comprising a cyclo olefin polymer (COP) having excellent electrical properties in the high frequency band. By doing so, the prepreg, the laminated board, the substrate for printed wiring, and the like have a smaller dielectric constant and dielectric loss than those of the conventional thermosetting resin composition.

That is, the present invention provides a low dielectric constant low loss thermosetting resin composition having a transmission characteristic suitable for a high frequency band, and comprises the thermosetting resin composition to provide a prepreg, a laminated plate or a substrate for printed wiring suitable for a high frequency band. It is for.

High frequency low dielectric constant low loss thermosetting resin composition according to the present invention for achieving the above object is a resin comprising a cyclo olefin polymer (COP); Crosslinking agents; And an initiator.

The prepreg which concerns on this invention is characterized by including the said high frequency low dielectric constant low loss thermosetting resin composition.

In addition, the laminate according to the present invention is characterized in that the prepreg is laminated several sheets.

Further, the printed wiring board according to the present invention is characterized in that the laminate is made by circuit processing.

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

The present invention provides a low loss curable resin composition with a low dielectric constant in a high frequency band, and provides a prepreg, a laminated board, and a substrate for printed wiring produced using the composition. To this end, in the present invention, since the dielectric loss is small and the insulation is good over a wide frequency range, a resin composition of cycloolefin polymer (COP) having excellent electrical properties in the high frequency range is utilized.

The cycloolefin polymer is a polymer having an alicyclic structure in the repeating unit, and the alicyclic structure may be either a main chain or a side chain. Cycloalkanes, cycloalkenes, etc. are mentioned as alicyclic structure. Resin of a cycloolefin polymer is well-known superposition | polymerization, such as a metathesis ring-opening polymerization or addition polymerization, of the monomer containing the monomer which has a norbornene ring structure, a monocyclic olefin, a cyclic conjugated diene, a vinyl aromatic compound, a vinyl alicyclic hydrocarbon compound, etc. It can superpose | polymerize by a method and can obtain by hydrogenating a carbon-carbon unsaturated bond as needed. The cycloolefin polymer of the present invention is not particularly limited, but is preferably a polymer of norbornene-based monomers such as substituted or unsubstituted norbornene, dicyclopentadiene, dihydrodicyclopentadiene. The norbornene-based monomer is a norbornene, methyl norbornene, dimethyl norbornene, ethyl norbornene, ethylidene norbornene, butyl norbornene, such as bicyclic norbornene, dicyclopentadiene, dihydrodicyclopentadiene, methyldicyne Tricyclic norbornenes such as clopentadiene and dimethyldicyclopentadiene, tetracyclic norbornenes such as tetracyclododecene, methyltetracyclododecene, dimethylcyclotetradodecene, tricyclopentadiene and tetracyclopentadiene Norbornene of 5 or more rings is mentioned. Among these, dicyclopentadiene, methyl tetracyclo dodecene, ethylidene norbornene, tricyclopentadiene, and tetracyclopentadiene are preferable, and dicyclopentadiene is especially preferable.

Although the tape film of a certain form can be produced only by the said cycloolefin polymer, since the intrinsic glass transition temperature (Tg) of cycloolefin polymer is 170 degrees C or less, it is difficult to use it as a board | substrate for printing. In particular, in the heat resistance test for the soldering process should be able to withstand 10 seconds or more at 288 ℃, it is used as a composite composition by blending with a certain amount of heat crosslinkable resin, that is, a crosslinking agent. The crosslinking agent is a thermal crosslinkable resin that crosslinks the components of the resin as described above, and is blended in the composition containing the resin to increase the adhesiveness, heat resistance, and chemical resistance with the metal foil. The crosslinking agent is not particularly limited, but is preferably a crosslinking agent based on N, N-M-PHENYLENEDIMALEIMIDE of formula (1). In addition, the crosslinking agent is preferably included in an amount corresponding to a weight ratio of 1/20 to 1/3 with respect to the mother resin. When the content of the crosslinking agent is out of the above range, the adhesiveness and electrical properties of the resin composition according to the present invention may be lowered.

[Formula 1: N, N ~ -M-PHENYLENEDIMALEIMIDE-based thermocrosslinkable resin]

Moreover, an initiator is contained in the low dielectric constant low loss thermosetting resin composition which concerns on this invention. The initiator acts as a catalyst for promoting thermosetting of the thermosetting resin composition according to the present invention. The initiator is a peroxide-based accelerator, in particular peroxy ester (dioxy) or dialkyl (dialkyl) is preferred. Is not particularly limited, the initiators are di-alkyl (dialkyl) system among the α, α 'bis - that the (t-butylperoxy) diisopropylbenzene (α, α'Bis (t -butylperoxy) diisopropyl benzene) are preferred . In addition, the initiator is preferably included in an amount corresponding to a weight ratio of 1/20 to 1/5 with respect to the crosslinking agent. The content range of the above-mentioned initiator is suitable for promoting the thermosetting of the thermosetting resin composition according to the present invention.

On the other hand, in the thermosetting resin composition according to the present invention, thermoplastic elastomers, crosslinked rubbers, oligomers, nucleating agents, antioxidants (if necessary) for the purpose of modifying the characteristics within a range that does not inhibit the achievement of the present invention. Additives such as anti-aging agents), heat stabilizers, light stabilizers, ultraviolet absorbers, lubricants, flame retardant aids, antistatic agents, antifog agents, fillers, softeners, plasticizers, colorants, and the like. These may be used independently, respectively and 2 or more types may be used together.

The method for producing the resin composition of the present invention is not particularly limited, and for example, each predetermined amount of the resin and the inorganic compound and each predetermined amount of one or two or more additives blended as necessary under normal temperature or heating. A direct kneading method of mixing and kneading directly and a method of mixing in a solvent and then removing the solvent; After preparing the master batch which mix | blended predetermined amount or more of the inorganic compound with the said resin or resin other than the said resin beforehand, 1 type (s) or 2 or more types of additives mix | blended as said master batch, the remainder of predetermined amount of resin, and if necessary And a master batch method of kneading each predetermined amount of the mixture at ordinary temperature or under heating or mixing in a solvent.

The thermosetting resin composition according to the present invention as described above comprises a cycloolefin resin composition having excellent electrical properties in the high frequency band, to prepare a prepreg, sheet, film, tape, laminate or substrate for printed wiring, etc. A high frequency low dielectric constant low loss thermosetting resin composition that can be used.

Although the use of the resin composition of this invention is not specifically limited, For example, the board | substrate material, sheet | seat, laminated board which form a core layer, a buildup layer, etc. of a multilayer board | substrate by melt | dissolving in a suitable solvent or shape | molding and processing into a film form, It is used suitably for copper foil with a resin, a copper clad laminated board, a tape for TAB, a printed board, a prepreg, a varnish, etc. Substrate materials, sheets, laminates, copper foils with resins, copper clad laminates, tapes for TAB, printed boards, prepregs, adhesive sheets and the like, which are formed using the resin composition of the present invention, are also one of the present inventions.

The prepreg of the present invention is characterized by including the above-mentioned high-frequency low dielectric constant low loss thermosetting resin composition alone or a fiber material. The prepreg is dissolved in an organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, and varnished by applying the thermosetting resin composition of the present invention to a fiber material, and impregnated with 80 to 200 It is prepared by drying in the range of ° C. Or it can also manufacture by semi-hardening the said resin composition to make it into a film form, and crimping | bonding it and a fiber material by hot press etc. It is preferable that the material used for a fiber material is heat resistant fiber, Specifically, carbon fiber, glass fiber, aramid fiber, aromatic polyester fiber, boron fiber, silica fiber, tetrafluorocarbon fiber, etc. are mentioned. These fiber materials may be used alone or in combination of two or more, but glass fibers, aramid fibers, aromatic polyester fibers or tetrafluorocarbon fibers are particularly preferable. These fibers may be long fibers or short fibers and may be used as woven or nonwoven fabrics. As a base material used for a prepreg, it is preferable in it being 30-500 micrometers in thickness, More preferably, it is 30-200 micrometers in thickness. If the thickness is too thin, the strength of the cloth becomes insufficient, and if the thickness is too thick, application and impregnation of the varnish of the resin composition becomes difficult.

The laminated board of this invention can be obtained by laminating | stacking two or more said prepregs. In addition, a metal clad laminate is manufactured by forming a metal layer made of metal foil or the like on one or both surfaces of the laminate. Although it does not restrict | limit especially as a metal layer to be used, Metal foil with a thickness of 5 micrometers-200 micrometers which consists of copper, a cuprous copper, aluminum, silver, iron, stainless, etc. is suitable. To produce a metal clad laminate in which metal foil is laminated on one or both sides of a laminate in which a low dielectric constant low loss thermosetting resin composition is filled in a fiber material, the thermosetting resin composition is filled by using a press machine, a vacuum press, or a thermal laminator. What is necessary is just to laminate | stack into a single piece by attaching metal foil to one side or both surfaces of the said laminated board, and heating and pressing.

The printed wiring board can be manufactured by carrying out the circuit process to a metal foil surface or a metal foil etching surface using a metal clad laminated board in this invention using a well-known method. 1 is a schematic diagram showing a state of manufacturing a printed wiring board using a sheet, a film, or a prepreg containing a low dielectric constant low loss thermosetting resin composition according to the present invention. As described above, using the thermosetting resin composition synthesized according to the present invention to produce a printed wiring board, first, the sheet, film or prepreg (1) molded using the resin composition according to the present invention The metal foil 2 is placed, and the metal plate 3 and the fusion pad are placed on both surfaces thereof, and then placed in the press 4 to be heated and pressurized. In addition, by pre-positioning the prepreg on both sides or one side by using such a double-sided or single-sided wiring board as an inner layer board, and performing a circuit processing or the like as described above by performing drilling, plating, etc. by a drill or the like for interlayer connection. The board | substrate for printed wirings can be manufactured.

The shaping | molding method of the board | substrate for printed wirings is not specifically limited to the said method, For example, extrusion molding method which melt-kneads with an extruder, and extrudes, and shape | molds into a film form using a T die or a circular die etc .; Casting molding method of dissolving or dispersing in a solvent such as an organic solvent and then casting and molding into a film; The dip molding method etc. which dip and shape | mold the cross-form nonwoven fabric base material which consists of inorganic materials, such as glass, or an organic polymer, and shape | mold in the varnish obtained by melt | dissolving or disperse | distributing in solvents, such as an organic solvent, are mentioned. Among them, an extrusion molding method is suitable for reducing the thickness of the multilayer substrate.

Said circuit processing can be performed by a well-known method. For example, it is possible to perform plating by forming a necessary through hole using a drill and conducting the conductive pattern. After forming the resist pattern, the plating of the unnecessary portion is removed by etching, and finally, the resist pattern is peeled off. In this way, a metal-clad laminated board is laminated | stacked on the surface of the printed wiring board obtained on the conditions similar to the above, and the same circuit processing is performed and it can be set as the board | substrate for multilayer printed wiring. In this case, it is not necessary to form the through holes, and the via holes may be formed or both may be formed. Such multilayering is carried out by stacking a predetermined number of sheets.

The substrate material, sheet, laminated board, copper foil with resin, copper clad laminate, TAB tape, printed wiring board, prepreg, adhesive sheet, and optical circuit forming material of the present invention are made of the resin composition of the present invention, thereby providing high temperature properties. Excellent dimensional stability, solvent resistance, moisture resistance and barrier properties can be obtained in high yield even when manufactured through many processes. In addition, in this specification, the sheet also includes the film-like sheet | seat which is not self-supporting. Moreover, in order to improve the slip characteristic of such a sheet | seat, the surface may be embossed.

Hereinafter, one preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings. The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example 1: Preparation of high-frequency low dielectric constant low loss thermosetting resin composition

First, the resin composition of the cycloolefin polymer (COP) was dissolved in an organic solvent in order to produce a tape in the required thickness and width. As the organic solvent used to dissolve the composition, a solvent having a low boiling point of 150 ° C. or less and a low volatility was used. Here, the blended composition used a ZEONEX480R ^TM product provided by ZEON.

Then, after mixing the cross-linking agent of N, N-M-PHENYLENEDIMALEIMIDE system, which is SR525 ^TM product provided by sartomer, to the composition dissolved in the above organic solvent in a weight ratio of 1/20 to 1/3, α, α '(Bis- t -butylperoxy) diisopropylbenzene (α, α'Bis ( t- butylperoxy) diisopropyl benzene) (Perbutyl P ^TM ) peroxide was added in an amount corresponding to the weight ratio of 1/20 to the crosslinking agent. I let you.

The high frequency dielectric properties of the thermosetting resin composition according to the present invention prepared using the cycloolefin resin composition according to the above method were measured by a dielectric constant meter and a dielectrometer provided by AET Japan, and are shown in Table 1 below.

Table 1: High Frequency Dielectric Properties of Thermosetting Resin Composition Comprising Cycloolefin Resin Composition

Imitation Crosslinking agent Initiator Crosslinker: Initiator permittivity Dielectric loss 1㎓ 9.4㎓ 1㎓ 9.4㎓ 95 5 PerbutylP ^TM  20: 1 2.46 2.43 0.0012 0.0019 90 10 2.48 2.46 0.0017 0.002 85 15 2.49 2.47 0.0021 0.004 80 20 2.55 2.52 0.0023 0.0042

The dielectric constant of the thermosetting resin composition according to the present invention prepared with the composition as shown in Table 1 all showed the characteristics of the low dielectric constant of 2.6 or less, all of the loss value was able to obtain a low loss value of less than 0.005.

In the case of LX67F ^TM substrate that is made including a conventional thermosetting resin composition, from Hitachi captive provide a printed wiring board, for the PCL-LD621 ^TM is a dielectric constant and loss of value of at least 3.4 is 0.0028, available from Cookson captured permittivity 3.4 The loss value is 0.007. Compared with these conventional products, the present invention is more suitable as a substrate material for the transmission line because the loss value is somewhat larger or smaller but relatively low in the case of permittivity.

 Table 2 below shows the heat resistance of the thermosetting resin composition according to the present invention prepared by using the cycloolefin resin composition according to the method described above by measuring the amount of the blended crosslinking agent.

[Table 2: Heat resistance test results according to the crosslinking agent content of the thermosetting resin composition comprising a cycloolefin resin composition]

Imitation Crosslinking agent Initiator Crosslinker: Initiator Experimental condition: 260 ℃, 10 seconds 100 Perbutyl P ^TM × 90 10 20: 1 ㅇ 80 20 20: 1 ㅇ

As shown in Table 2, the cycloolefin resin itself lacks heat resistance, but it can be seen that the heat resistance is improved by blending the heat crosslinkable resin. The heat resistance is a thermal property that must be satisfied in order to be used as the substrate composition for printing.

Example 2: Fabrication of Printed Wiring Boards

First, a sheet, a film, and a prepreg were manufactured using the thermosetting resin composition prepared according to Example 1, metal foils were disposed on and under the metal plate, and a metal plate and a fusion pad were disposed on both sides thereof, and then the press was pressed. The mixture was subjected to thermal pressurization. The temperature at this time was normally in the range of 100-300 degreeC in consideration of the reaction temperature of a peroxide and a crosslinking agent compound, and the softening point of a simulated property. In addition, the surface pressure applied in the press is preferably about 1 to 20 MPa.

On the other hand, while the invention has been shown and described in connection with specific preferred embodiments, the invention is variously modified and modified without departing from the technical features and fields of the invention provided by the claims below It will be apparent to those skilled in the art that such changes can be made.

According to the present invention as described above, a resin comprising a cyclo olefin polymer (COP); Crosslinking agents; And it can provide the thermosetting resin composition of the high frequency low dielectric constant low loss which contains the initiator.

The present invention is used to prepare a prepreg, a sheet, a film, a tape, a laminate, a circuit laminate, or a printed wiring board by including a cycloolefin resin having excellent electrical properties in the high frequency region, and according to the conventional resin composition There is an effect that the printed wiring board and the like can have a smaller dielectric constant and dielectric loss.

That is, the present invention has an effect of providing a thermosetting resin composition having a low loss in a low dielectric constant having suitable transmission characteristics in a high frequency band as a resin composition used to form a laminate for printed wiring and the laminate. According to the present invention, a prepreg, sheet, film, tape, laminate, circuit laminate or printed wiring board suitable for a high frequency band can be produced.

Claims (16)

A resin consisting of a solid monocycloolefin polymer, An organic solvent for dissolving the mother resin, Crosslinking agent in an amount corresponding to a weight ratio of 1/20 to 1/3 with respect to the mother resin, Initiator acting as a reaction catalyst of the crosslinking agent Including but not limited to, High-frequency low dielectric constant low loss thermosetting resin composition, characterized in that the crosslinking agent modifies the characteristics of the resin resin to exhibit improved dielectric properties in the high frequency region of the Ghz band. The high-frequency low dielectric constant low loss thermosetting resin composition according to claim 1, wherein the cycloolefin polymer is a homopolymer of a norbornene-based monomer. According to claim 1, wherein the cyclo olefin polymer is dicyclopentadiene, methyltetracyclododecene, ethylidene norbornene, tricyclopentadiene, tetracyclopentadiene polymer of at least one monomer selected from the group consisting of A high frequency low dielectric constant low loss thermosetting resin composition characterized by the above-mentioned. The thermosetting resin composition according to claim 1, wherein the organic solvent has a boiling point of 150 ° C. or less. The thermosetting resin composition according to claim 1, wherein the initiator is contained in an amount corresponding to a weight ratio of 1/20 to 1/5 with respect to the crosslinking agent. The high-frequency low dielectric constant low loss thermosetting resin composition according to claim 1, wherein the crosslinking agent is a heat crosslinkable resin and is a N, N-M-PHENYLENEDIMALEIMIDE-based crosslinking agent. The thermosetting resin composition of claim 1, wherein the initiator is a peroxy ester based initiator or a dialkyl based initiator. The method of claim 7, wherein the di-alkyl (dialkyl) based initiator is α, α 'bis - characterized in that the (t-butyl hydroperoxide during) diisopropylbenzene (α, α'Bis (t -butylperoxy) diisopropyl benzene) Thermosetting resin composition of high frequency low dielectric constant low loss. The thermosetting resin composition according to claim 1, wherein the dielectric constant is 3.0 or less in a high frequency band of 1 to 20 Hz after curing. The thermosetting resin composition according to claim 1, wherein the dielectric loss is 0.006 or less in a high frequency band of 1 to 20 Hz after curing. A prepreg prepared using the thermosetting resin composition according to any one of claims 1 to 10. The laminated board characterized by the several prepreg of Claim 11 laminated | stacked. A metal layer is formed on one side or both sides of the laminated sheet of Claim 12. The laminated sheet characterized by the above-mentioned. The laminate according to claim 13, wherein the metal layer has a thickness of 5 to 300 µm. The printed wiring board formed by circuit-processing the laminated board of Claim 13. Preparing a resin consisting of a solid monocycloolefin polymer, Dissolving the said resin using an organic solvent, Crosslinking the dissolved mother resin with a crosslinking agent for crosslinking the resin and an initiator in an amount corresponding to a weight ratio of 1/20 to 1/5 with respect to the crosslinking agent; Preparing a prepreg using the cross-linked resin; Stacking the prepregs; Disposing a metal foil at the top and bottom of the laminated prepreg; Thermally pressing the laminated prepreg and the metal foil in a range of 100 ° C. to 300 ° C. Method for producing a printed wiring board comprising a.

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