KR100954996B1 - Resin Composition Having Low Dielectric Loss - Google Patents

Abstract

The present invention is a resin composition that can be suitably used to form a multilayer printed wiring board, and further improves crosslinkability, heat resistance, and flame retardancy, and has a low dielectric loss composite resin having good dielectric properties such as low dielectric loss having a transmission characteristic suitable for a high frequency band. Provided are compositions, which provide films, prepregs, laminates and the like made using the same.

Low dielectric loss, high frequency, composite resin composition, prepreg

Description

Resin Composition Having Low Dielectric Loss

The present invention relates to a low dielectric loss composite resin composition and a film, prepreg, printed wiring board manufactured using the same.

With the miniaturization of mobile communication devices, satellite broadcasting receivers, and computers, miniaturization, complexation, high functionality, and high precision have been progressed for electronic components used in them. To cope with the increase in speed is required. In addition, the frequency band of signals used in communication electronics is shifting from the MHz region to the GHz band. Since the electrical signal has a characteristic that the transmission loss increases as the frequency increases, development of an electrically insulating material having excellent high frequency transmission characteristics and a substrate using the same is essential.

BACKGROUND ART In general, polymer insulating materials are used as substrate materials such as printed circuit boards (PCBs). Here, various polymer insulating materials such as polyolefin resin, epoxy resin, fluorine-based thermoplastic resin, polyimide resin, bismaleimide triazine resin and the like have been proposed, and the laminates for printed circuit boards using these polymers are single or glass fibers, It is blended with a nonwoven fabric, an inorganic filler and the like and produced. A method of preparing a laminate by combining the above components includes a method of melting and pressing a polymer insulating material in an organic solvent to impregnate and dry a prepreg and a metal foil obtained by drying a glass cloth, and insulate the polymer from the organic solvent. In the case of a material, there is a method of melting and processing a melt injection method to produce a plate shape and then heating and pressing a metal foil such as copper foil and aluminum foil.

However, as various polymer insulating materials provided in the related art, in the case of epoxy resins, electrical characteristics, in particular, dielectric loss characteristics in the high frequency region have a disadvantage. On the other hand, the fluorine-based thermoplastic resin represented by PTFE has good high frequency characteristics, but since it is a thermoplastic resin, its use area is extremely limited because of its large expansion and contraction during molding and poor workability. Polyolefin-based thermoplastic resins generally have inferior lead heat resistance even when adhesion to metal foil is secured when formed into a laminate. In the case of polyolefin resins, since they do not have polar groups, they are excellent in electrical characteristics, particularly dielectric loss characteristics, but low heat resistance is a major disadvantage. In addition, since the coefficient of linear expansion is large, when used as a laminate for wiring boards, there is a problem in that connection reliability and plating reliability of through holes are insufficient when mounting components. Bismaleimide triazine resins and polyimide resins have low utility as general purpose resins due to their high price.

As a solution to this problem, it is possible to mix thermally crosslinkable components with thermoplastic resins such as polyphenylene oxide (PPO) and cycloolefin polymer resin, which have excellent dielectric properties at high frequencies, and thus have good dielectric properties, processability, and bonding properties in high frequency bands. Research is being conducted to develop compositions of substrate materials.

However, there has not yet been obtained a resin composition having a high heat resistance and flame retardancy that can be used as a substrate material. This is because the problem that the dielectric properties are poor when the heat resistance and flame retardancy is to be increased, in particular, a problem that the dielectric loss is increased, which is more problematic in the high frequency region.

The present invention is to solve the above problems, a resin composition that can be suitably used to form a multi-layer printed wiring board, while further improving crosslinking resistance, heat resistance, and flame retardancy, while having a low dielectric loss, especially having a transmission characteristic suitable for high frequency bands, etc. It provides a low dielectric loss composite resin composition having good dielectric properties, and provides a film, prepreg, laminate, and the like prepared using the same.

The present invention for achieving the above object,

Resin containing polyphenylene oxide; Crosslinking agents for imparting crosslinking properties to the mother resin; An initiator to initiate crosslinking of the crosslinking agent; And a flame retardant that does not participate in the crosslinking reaction because it does not react with the resin and the crosslinking agent, and provides a low dielectric loss composite resin composition including an organic flame retardant in which at least five or more hydrogens are substituted with bromine (Br).

In addition, it provides a low dielectric loss composite resin composition further comprises a flame retardant aid to increase the flame retardancy of the flame retardant.

In addition, the flame retardant aid provides a low dielectric loss composite resin composition, characterized in that the antimony oxide (Sb ₂ O ₃ ).

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In addition, the flame retardant is not dissolved and provides a low dielectric loss composite resin composition, characterized in that the dispersion is present in a solid state in the resin.

In addition, the resin provides a low dielectric loss composite resin composition, characterized in that the polyphenylene oxide and polystyrene is mixed in a weight ratio of 6: 4 to 8: 2 range.

In addition, the crosslinking agent is selected from among (meth) acrylate-based compounds, biallyl cyanurate, triallyl isocyanurate, and N, N'- m-phenylene dimaleimide having a bifunctional or higher functional group. It provides a dielectric loss composite resin composition.

In addition, the weight ratio of the crosslinking agent and the resin provides a low dielectric loss composite resin composition, characterized in that in the range of 5:95 ~ 30:70.

In addition, the initiator is an organic peroxide-based initiator, provides a low dielectric loss composite resin composition, characterized in that included in the weight ratio of 1/20 to 1/5 compared to the crosslinking agent.

The present invention also provides a hybrid composite film prepared by mixing the aforementioned low dielectric loss composite resin composition and an inorganic filler for improving the dielectric constant of the composite resin composition.

Thus, the present invention is a resin containing polyphenylene oxide; Crosslinking agents for imparting crosslinking properties to the mother resin; An initiator to initiate crosslinking of the crosslinking agent; And a flame retardant that does not react with the resin and the crosslinking agent and does not participate in a crosslinking reaction, wherein the low dielectric loss composite resin composition comprises an organic flame retardant in which at least five or more hydrogens are substituted with bromine (Br), and the composite resin composition. The inorganic filler is prepared by mixing the inorganic filler to improve the dielectric constant of the, the content of the inorganic filler is in the range of 25 to 30% by volume relative to the total volume of the low dielectric loss composite resin composition and the inorganic filler, the content of the flame retardant is low It may be a hybrid composite film, characterized in that 10% by weight relative to the weight of the dielectric loss composite resin composition.

The present invention also provides a prepreg, which is prepared using the low dielectric loss composite resin composition.

The present invention also provides a laminated plate in which a plurality of the above prepregs are laminated and a metal layer is formed on one surface or both surfaces.

The present invention also provides a substrate for printed wiring formed by circuit processing the laminate.

Hereinafter, the present invention will be described in more detail. The following description is a specific example of the present invention, but is not intended to limit the scope of the rights defined by the claims, even if there is an assertive, limited expression.

The present invention is to obtain a high heat resistance and flame retardancy that was not obtained in the case of a polyphenylene oxide-based resin composition, and in particular, while providing a low dielectric loss composite resin composition incorporating a highly reactive crosslinking component and a flame retardant, It is for providing a film, a prepreg, a laminated board, etc. which are made using.

First, the low dielectric loss composite resin composition according to the present invention will be described.

Low dielectric loss composite resin composition according to an embodiment of the present invention is a resin containing polyphenylene oxide, a crosslinking agent to impart crosslinking properties to the resin, an initiator to initiate the crosslinking of the crosslinking agent, and the resin and crosslinking agent A flame retardant that does not react with and does not participate in a crosslinking reaction, and includes an organic flame retardant in which at least five or more hydrogens are substituted with bromine (Br).

The composition is prepared by mixing a crosslinking agent capable of imparting crosslinking properties with a dielectric material having a low dielectric loss value, particularly in a high frequency band, and adding flame retardance to the crosslinking reaction with the resin and crosslinking agent. It is characterized by the use of an organic flame retardant in which at least five or more hydrogens are substituted with bromine (Br), which can obtain high heat resistance because it does not participate, and can obtain high heat resistance and dielectric properties that provide low dielectric loss.

The resin is preferably a thermoplastic resin, and in particular, a mixed polymer of polyphenylene oxide or polyphenylene oxide and polystyrene may be used. Since polyphenylene oxide itself is difficult to produce a film in the form of a tape, it is preferable to use a mixed polymer of polyphenylene oxide and polystyrene. It is preferable that the mixture of polyphenylene oxide and polystyrene is a weight ratio in the range of 6: 4 to 8: 2. When it is out of the said range, heat resistance will fall by an excess of polystyrene, or it becomes difficult to produce it into a tape-type film etc. by lack of polystyrene. The mixed polymer resin of polyphenylene oxide and polystyrene is preferably dissolved in a suitable organic solvent such as toluene and xylene in order to produce a film form.

As a crosslinking agent component which gives a crosslinking characteristic, the monomer or oligomer component more than the bifunctional group containing a vinyl group or an allyl group is preferable. Such a crosslinking agent is a crosslinkable resin that crosslinks the resin component as described above, and is blended into the composition in which the resin resin is melted to form a film and then subjected to a heat and pressure lamination step, thereby adhering to adhesion and heat resistance of the metal foil or the like. There is an effect of increasing the chemical properties. (Meth) acryl having a bifunctional group or more including trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tricyclo decane dimethanol diacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, and the like Lateral compounds, triallyl cyanurate and triallyl isocyanurate, N, N'- m-phenylenediimaleimide and the like can be used. Among these, it is most preferable to use especially N, N'- m-phenylene dimaleimide (m-PDMI). The crosslinking component is preferably mixed at a weight ratio of 5:95 to 30:70 with respect to the thermoplastic resin, and more preferably at a weight ratio of 10:90 to 20:80. If it is out of the above range it is difficult to expect the improvement of the crosslinkability, heat resistance, adhesiveness, etc. of the resin composition due to the lack of the crosslinking component, or the dielectric properties may be too bad due to the excessive crosslinking component.

On the other hand, an initiator may be used to initiate and promote crosslinking, and an organic peroxide-based initiator may be used as an example but not limited thereto. In particular, TBPB (tert-butyl peroxybenzoate), DCP (dicumyl peroxide), Di (2-tert-butylperoxyisopropyl) benzene, and the like are used, and the content thereof is in a weight ratio of 1/20 to 1/5 with respect to the crosslinking component. It is preferable to correspond.

Moreover, the resin composition of this invention contains a flame retardant, It is characterized by the above-mentioned. As a result of experiments using known flame retardants, it was found that the dielectric properties and heat resistance deteriorated according to the types of flame retardants, and the optimum flame retardant conditions did not participate in the crosslinking reaction of resin and crosslinking agent and did not affect the dielectric loss. It turned out that nothing was a priority. The flame retardant that satisfies these optimum conditions is preferably a brominated organic compound. Particularly, the use of an organic flame retardant in which at least five or more hydrogens are replaced with bromine (Br) can achieve high flame retardancy, heat resistance, and dielectric properties. An example is decabromo diphenyl ethane. The use of a reactive flame retardant inhibits the crosslinking reaction between the resin and the crosslinking agent, and as a result, a large number of uncrosslinked resin components may be generated, thereby reducing heat resistance. The content of the flame retardant is preferably used 10 to 20% by weight relative to the total resin composition. If it is less than the above range it is difficult to obtain the required flame retardancy and if it exceeds the above range heat resistance and dielectric properties may be a problem.

In addition, it is preferable to use the said flame retardant in the state disperse | distributed to the solid state without melt | dissolving in a solvent. By dispersing the flame retardant, it is present as a filler in the resin, thereby minimizing the influence on the crosslinking reaction. Since it does not inhibit a crosslinking reaction, it does not inhibit improving the crosslinking property and heat resistance of a resin composition.

A flame retardant aid may be further added to exhibit the flame retardancy of the flame retardant. For example, antimony oxide (Sb ₂ O ₃ ) may be used as the flame retardant aid to exhibit the flame retardancy of the bromine-based organic flame retardant. The amount of the flame retardant aid added is preferably 10 to 30% by weight based on 100 weight of the flame retardant.

In addition, polystyrene, poly (styrene-butadiene-styrene) copolymer, polybutadiene, poly (styrene-butadiene) copolymer, or the like may be added to the mother resin to enhance the flexibility and processability of the polymer film. The resin added in this way is preferably added in a weight ratio of 1/20 to 1/5 with respect to the mother resin.

Next, a high dielectric constant hybrid composite film may be manufactured using the low dielectric loss polymer material composition and an inorganic filler having a high dielectric constant for improving the dielectric constant of the composition. Since the base material has its own low dielectric loss characteristics, the composite fabricated using it has better dielectric properties in the high frequency band than the epoxy based filler composite material. As an inorganic filler, Ag, Al, Zn, Ni, Cu, etc., which exhibit high dielectric constant when placed in an electric field after forming a composite with ceramic materials such as titanium oxide, barium titanate, calcium titanate, and strontium titanate having their own high dielectric constant Metal materials, and materials such as carbon black and graphite may be used. The content of the inorganic filler is preferably 10 to 50% by volume, more preferably 25 to 30% by volume, when the total volume of the polymer composition and the inorganic filler is 100. When the inorganic filler is less than 10% by volume, there is little effect of increasing the dielectric constant, and when the inorganic filler is more than 50% by volume, the production of the film is difficult due to the excessive content of the inorganic filler, and the produced film is inflexible and may cause cracking or cracking. Easy handling makes handling difficult

In addition, it is possible to produce a film or prepreg using the low dielectric loss composite resin composition. First, the resin composition is dissolved in an organic solvent such as toluene, and uniformly mixed through ball milling to produce a varnish. When the produced varnish is put into a film coater, a thin film is coated on a carrier film and dried to obtain a molded product in the form of a film or sheet. Meanwhile, the produced varnish is impregnated into a glass fabric using an impregnation apparatus and dried to prepare a prepreg. It is preferable to use E-glass as the glass component constituting the glass fabric, and C-, D-, S2-glass, etc. may be used as necessary. Various kinds of glass fabrics such as # 7628, 2116, 1078, 1015, and 106 may be used as the type of glass fabric. The thickness thereof is preferably 200 μm or less, and more preferably 100 μm or less.

It is possible to manufacture a printed wiring board using a film or prepreg made of a low dielectric loss thermosetting composite resin composition according to the present invention. First, a plurality of films or prepregs molded using the composite resin composition according to the present invention are stacked, metal foils are disposed on and under the metal plates, and metal plates and fusion pads are disposed on both sides thereof, and then placed in a vacuum pressurized laminator and thermally pressurized. It is prepared by carrying out. The metal foil is then patterned into the desired shape to form a circuit. If necessary, a multilayer printed wiring board can be formed by repeating the lamination process.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the state which manufactures the board | substrate for printed wiring using the film or prepreg which concerns on an example of this 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.

By using the low dielectric loss composite resin composition of the present invention, a resin composition and a film, a prepreg, and a laminated substrate material having improved crosslinking, heat resistance, and flame retardancy can be obtained while maintaining low dielectric loss.

 Hereinafter, preferred embodiments of the present invention will be described in detail. The invention can be better understood by the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Experimental Example 1

1) material

  -Thermoplastic: Modified polyphenylene oxide (20% polystyrene blended) [by GE Plastics]

-Crosslinking agent: N, N'- m-phenylenediimaleimide [m-PDMI supplied by Sartomer]

  Thermal initiator: Di (2-tert-butylperoxyisopropyl) benzene [Perbutyl P, NOK provided]

2) film production

  The material was dissolved or dispersed in toluene solution and varnished to prepare a film using a film coater. The batch-specific resin composition is shown in Table 1.

3) Substrate Fabrication and Evaluation

Characteristics of the substrate material produced by pressure lamination of the produced film together with the copper foil was evaluated, which are shown in Table 1. The dielectric constant and quality coefficient were measured at 1 GHz using an AET dielectrometer. The inverse of the quality factor is the dielectric loss. The higher the quality factor, the lower the dielectric loss material. In addition, heat resistance and copper foil bonding strength (peel strength) are strengthened by a crosslinking component, thereby satisfying the general requirements required for a printed circuit board.

<Table 1>

Item One 2 3 4 PPO (g) Crosslinker (mPDMI) (g) Initiator (g) 47.5 2.5 0.125 45 5 0.25 28.3 5 0.25 20 5 0.25 PPO / Crosslinker Crosslinker / Initiator 95/5 20/1 90/10 20/1 85/15 20/1 80/20 20/1 Dielectric constant (@ 1 GHz) 2.48 2.52 2.60 2.61 Quality Factor (@ 1 GHz) 583 647 441 349 Peel Strength (kN / m) 0.6 1.4 1.4 1.2 Gel content (%) 65 89 99 99

Experimental Example 2

1) material

  -Thermoplastic: Modified polyphenylene oxide (20% polystyrene blended) [by GE Plastics]

-Crosslinking agent: N, N'- m-phenylenedimaleimide [m-PDMI supplied by Sartomer]

  Thermal initiator: Di (2-tert-butylperoxyisopropyl) benzene [Perbutyl P, NOK provided]

  Flame retardant: decabromodiphenylethane (Saytex8010)

Flame retardant: Sb ₂ O ₃ (high purity chemical reagent)

2) film production

  After the material was varnished by dissolving or dispersing it in a toluene solution, a film was prepared using a film coater. The batch-specific resin compositions are shown in Table 2.

3) Substrate Fabrication and Evaluation

The characteristics of the substrate material produced by pressure lamination of the produced film together with the copper foil were evaluated, which are shown in Table 2. The dielectric constant and quality coefficient were measured at 1 GHz using an AET dielectrometer. The inverse of the quality factor is the dielectric loss. The higher the quality factor, the lower the dielectric loss material. In addition, heat resistance, flame retardancy, and copper foil bonding strength (peel strength) are strengthened by a crosslinking component, thereby satisfying the general requirements required as a printed circuit board.

If the content of the flame retardant exceeds 20% by weight from the total weight of the low dielectric loss composite resin composition, the dielectric loss is rapidly increased to use less than 20% by weight, and the optimum value is about 10% by weight.

In particular, when comparing the item 4 of Experimental Example 1 and item 9 of Experimental Example 2, it is encouraging that the dielectric loss does not worsen even when the flame retardant is added.

<Table 2>

Item 5 6 7 8 9 PPO / crosslinking agent flame retardant (% by weight) flame retardant / Sb ₂ O ₃ crosslinker / initiator 90/10 5 5.16 20/1 90/10 10 5.16 20/1 90/10 20 5.16 20/1 85/15 10 5.16 20/1 80/20 10 5.16 20/1 Dielectric constant (@ 1 GHz) 2.52 2.56 2.58 2.56 2.62 Quality Factor (@ 1 GHz) 638 616 538 503 459 Peel Strength (kN / m) 1.2 1.2 1.2 1.2 1.0 Heat resistance (288 ℃, 10 seconds) Good Good Good Good Good Flame Retardant (UL-94) V-0 V-0 V-0 V-0 V-0

[Experimental Example 3]

1) material

  -Thermoplastic: Modified polyphenylene oxide (20% polystyrene blended) [by GE Plastics]

-Crosslinking agent: N, N'- m-phenylenediimaleimide [m-PDMI supplied by Sartomer]

  Thermal initiator: Di (2-tert-butylperoxyisopropyl) benzene [Perbutyl P, NOK provided]

  Flame retardant: decabromodiphenylethane (Saytex8010)

Flame retardant: Sb ₂ O ₃ (high purity chemical reagent)

-Inorganic filler: SrTiO ₃ powder (Ferro provided)

  -Additive: Polystyrene (PS) (GPPS-150, provided by Kumho Petrochemical)

2) film production

The material was dissolved or dispersed in toluene solution and varnished to prepare a film using a film coater. The batch-specific resin composition is shown in Table 3.

3) Substrate Fabrication and Evaluation

The characteristics of the substrate material produced by pressure lamination of the produced film together with the copper foil were evaluated, which are shown in Table 3. The dielectric constant and quality coefficient were measured at 1 GHz using an AET dielectrometer. The inverse of the quality factor is the dielectric loss. The higher the quality factor, the lower the dielectric loss material. It was observed that when the filler was added, sheet formation worsened when the flame retardant was added in excess (# 11, # 13). However, even if the flame retardant content is reduced (# 10, 12, 14, 15, 16), the flame retardancy of the substrate material is reinforced by the filler, so there is no problem in the use as the substrate material. In addition, heat resistance and copper foil bonding strength (peel strength) are strengthened by a crosslinking component, thereby satisfying the general requirements required for a printed circuit board. On the other hand, it was confirmed that heat resistance worsened when polystyrene was added (# 15).

<Table 3>

Item 10 11 12 13 14 15 16 PPO / crosslinking agent flame retardant (wt%) flame retardant / Sb ₂ O ₃ crosslinker / initiator SrTiO ₃ powder (vol.%) PPO / PS 90/10 10 5.16 20 25- 90/10 20 5.16 20 25- 90/10 10 5.16 20 25 20 90/10 20 5.16 20 25 20 90/10 10 5.16 20 30 10 90/10 10 5.16 20 30 6.67 85/15 10 5.16 20 30 10 Dielectric constant (@ 1 GHz) 6.2 Bad seat 6.42 Bad seat 8.04 7.24 10.1 Quality Factor (@ 1 GHz) 304 - 262 - 235 261 197 Peel Strength (kN / m) 0.8 - 0.8 - 0.7 0.7 0.7 Heat resistance (288 ℃, 10 seconds) Good - Good - Good Inadequate Good Flame Retardant (UL-94) V-0 - V-0 - V-0 V-0 V-0

As can be seen from the above results, the low dielectric loss composite resin composition according to the present invention can be seen that all excellent dielectric properties, heat resistance, flame retardancy, processability, bonding properties.

1 is a schematic diagram showing a state of manufacturing a printed wiring board using a film prepared using a low dielectric loss composite resin composition according to the present invention, prepreg.

Claims (14)

delete delete delete delete delete delete delete delete delete delete Resin containing polyphenylene oxide; Crosslinking agents for imparting crosslinking properties to the mother resin; An initiator to initiate crosslinking of the crosslinking agent; And a flame retardant which does not react with the resin and the crosslinking agent and does not participate in the crosslinking reaction, wherein the low dielectric loss composite resin composition comprises an organic flame retardant in which at least five or more hydrogens are substituted with bromine (Br); As prepared by mixing an inorganic filler to improve the dielectric constant of the composite resin composition, The content of the inorganic filler is in the range of 25 to 30% by volume relative to the total volume of the low dielectric loss composite resin composition and the inorganic filler, the content of the flame retardant is 10% by weight relative to the weight of the low dielectric loss composite resin composition. Hybrid composite film. delete delete delete

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