JP2007002191A - Resin composition, and prepreg, substrate and conductive foil-clad substrate, using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition capable of providing a substrate suitable for high-frequency application, and having excellent heat resistance; and to provide the substrate obtained therefrom. <P>SOLUTION: The substrate 10 in a preferable embodiment has a resin layer 12 and a fiber base material 14 arranged in the resin layer 12. The resin layer 12 comprises a cured product of a resin composition, and the resin composition comprises a resin component containing a polyvinyl benzyl ether compound, and a phosphorus compound containing a reactive phosphorus compound including a benzene ring having a phosphorus atom and a vinyl group. The total content of the phosphorus atom contained in the phosphorus compound is ≥3.5 mass% and the content of the reactive phosphorus compound based on 100 pts.mass of the resin component is ≥20 pts.mass in the phosphorus compound and the resin component respectively in the resin composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin composition, a prepreg using the same, a substrate, and a substrate with a conductive foil.

  As a substrate used for a circuit board or the like mounted on an electronic device, a substrate obtained by impregnating a resin material into a fiber base material such as glass cloth or a nonwoven fabric and curing the resin material is used. Such a substrate is required to have excellent flame retardancy from the viewpoint of safety. Conventionally, as a method for imparting flame retardancy to a substrate, a material containing halogen having high flame retardancy has been used as a resin material.

However, a substrate using such a resin material is undesirable from an environmental point of view because it generates harmful gases during incineration. Therefore, as a method for improving flame retardancy without using halogen, use of a combination of a resin material not containing halogen and a phosphorus compound has been studied (for example, see Patent Document 1).
JP-A-1995-109416

  Incidentally, in recent years, it is required that a substrate has characteristics suitable for use in a high-frequency band in order to increase the speed and capacity of an electronic device. Specifically, in order to reduce a loss generated in the process of transmitting a high frequency signal in the circuit board, it is desirable that the board has a characteristic of a low dielectric constant and a low dielectric loss. However, as described above, when flame retardancy is improved by the addition of a phosphorus compound, the dielectric characteristics are likely to deteriorate, and it is difficult to reliably obtain a substrate excellent in high frequency response.

  Further, when obtaining sufficient flame retardancy, it is necessary to add a large amount of phosphorus compound, but as the amount of phosphorus compound added increases, the heat resistance of the resulting substrate decreases. However, the strength at high temperature tends to be insufficient.

  Therefore, the present invention has been made in view of such circumstances, and is suitable for high-frequency applications, and can obtain a substrate having excellent heat resistance, and a prepreg, a substrate, and a prepreg using the same. An object is to provide a substrate with a conductive foil.

  In order to achieve the above object, the resin composition of the present invention is a resin composition containing a resin component and a phosphorus compound, the resin component contains a polyvinyl benzyl ether compound, and the phosphorus compound contains a phosphorus atom and a plurality of phosphorus compounds. A resin containing at least a reactive phosphorus compound containing a benzene ring, wherein at least one of the benzene rings has a vinyl group, and at least one of the benzene rings is bonded to a phosphorus atom; The total content of phosphorus atoms contained in the phosphorus compound in the component and the phosphorus compound is 3.5% by mass or more, and the content of the reactive phosphorus compound with respect to 100 parts by mass of the resin component is 20 parts by mass or more. It is characterized by.

  Since the polyvinyl benzyl ether compound contained in the resin composition of the present invention as a resin component has a structure with a small polarity, the cured product has a characteristic of low dielectric constant and low dielectric loss tangent. It becomes. Moreover, the reactive phosphorus compound contained as the phosphorus compound can be copolymerized with the polyvinyl benzyl ether compound at the time of curing by the vinyl group bonded to the benzene ring. For this reason, in the substrate obtained by curing such a resin composition, the phosphorus compound is incorporated into the polymer of the polyvinyl benzyl ether compound, and the phosphorus compound is contained free as in the prior art. Compared to the above, excellent flame retardancy can be obtained while maintaining both dielectric properties and heat resistance. Based on the above factors, the substrate obtained from the resin composition of the present invention is suitable for high-frequency applications and can also exhibit excellent heat resistance. However, the action is not necessarily limited to these.

［式中、Ｒ^１１はメチル基又はエチル基であり、Ｒ^１２は、水素原子又は炭素数１〜１０の炭化水素基であり、ｎは、２〜６の整数である。］ Here, the vinyl benzyl compound is preferably a compound represented by the following general formula (1). Thereby, more excellent dielectric properties, heat resistance and flame retardancy can be obtained.

[Wherein, R ¹¹ represents a methyl group or an ethyl group, R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 to 6. ]

  In the resin composition of the present invention, the total content of phosphorus atoms contained in the phosphorus compound in the resin component and the phosphorus compound is more preferably 3.5% by mass or more and less than 5.5% by mass. When the phosphorus atom content is less than 3.5% by mass, it becomes difficult to obtain sufficient heat resistance. On the other hand, when it exceeds 5.5% by mass, the content of the resin component in the resin composition becomes relatively small, and the properties of the obtained substrate tend to deteriorate.

  Moreover, it is more preferable that the resin composition of the present invention further includes an inorganic filler having a tan δ of 0.003 or less in a frequency band of 2 GHz or more. As a result, a substrate with further improved strength can be obtained without deteriorating the dielectric characteristics.

  The prepreg of the present invention is obtained by using the resin composition of the present invention, and includes the resin composition of the present invention and a fiber substrate disposed in the resin composition. . The substrate of the present invention is preferably obtained from the prepreg, and includes a cured product of the resin composition of the present invention and a fiber base material arranged in the cured product. . Since the substrate having such a structure is mainly composed of the cured product of the resin composition of the present invention, as described above, it has excellent flame retardancy, low dielectric constant and low dielectric loss tangent, and excellent heat resistance. It will have.

  Furthermore, the present invention is provided with a conductive foil comprising a cured product of the resin composition of the present invention and a substrate including a fiber base material disposed in the cured product, and a conductive foil disposed on the surface of the substrate. Providing a substrate. Moreover, the board | substrate of this invention may be equipped with the board | substrate which consists of a hardened | cured material of the said resin composition of this invention, and the conductor foil distribute | arranged on the surface of this board | substrate. The substrate with conductor foil having such a configuration can form a circuit substrate by processing the conductor foil into a predetermined pattern. Moreover, it is also possible to laminate | stack further the board | substrate with a conductor foil which apply | coated the resin composition of this invention on such a circuit board as needed. The circuit board thus obtained has a substrate containing the cured product of the resin composition of the present invention, and is therefore suitable for high-frequency applications, and when it is mounted on an electronic device and exposed to a high temperature. Even so, excellent flame retardancy is exhibited and deformation or the like hardly occurs.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the resin composition which can obtain the board | substrate which is suitable for a high frequency use, and is excellent in heat resistance, and a prepreg using this, a board | substrate, and a board | substrate with conductor foil. .

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings as necessary.
[Resin composition]

  First, the resin composition according to a preferred embodiment will be described. The resin composition of the present embodiment contains at least a resin component and a phosphorus compound. Hereinafter, each component contained in the resin composition will be described.

［式中、Ｒ^１１はメチル基又はエチル基であり、Ｒ^１２は、水素原子又は炭素数１〜１０の炭化水素基であり、ｎは、２〜６の整数である。］ (Resin component)
The resin component in the resin composition contains at least a polyvinyl benzyl ether compound. The polyvinyl benzyl ether compound is a compound having a repeating unit in which a vinyl benzyl group is bonded to the side chain via an ether bond, and a compound represented by the following general formula (1) is preferable.

[Wherein, R ¹¹ represents a methyl group or an ethyl group, R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 to 6. ]

In the polyvinyl benzyl ether compound represented by the formula (1), examples of the hydrocarbon group represented by R ¹² include an alkyl group, an aralkyl group, and an aryl group which may have a substituent. Specifically, the alkyl group includes a methyl group, an ethyl group, a propyl group, and a butyl group, the aralkyl group includes a benzyl group, and the aryl group includes a phenyl group. In addition, as a polyvinyl benzyl compound, what has these structures may be included independently and you may include in combination of multiple types.

The polyvinyl benzyl ether compound having such a structure can be obtained, for example, by reacting a polyphenol compound represented by the following general formula (2) with vinyl benzyl halide. In the following formulae, R ¹¹ , R ¹² and n are as defined above.

  In the resin component of this embodiment, components other than the said polyvinyl benzyl ether compound may be contained. However, from the viewpoint of sufficiently obtaining the dielectric properties and heat resistance of the substrate obtained from the resin composition, the resin component preferably contains 50% by mass or more of a polyvinyl benzyl ether compound.

Examples of the components other than the polyvinyl benzyl ether compound include compounds obtained by reacting a polyphenol compound represented by the following general formula (3a) with vinyl benzyl halide. Moreover, the compound etc. which were obtained by making the polyvinyl phenol which has the structure represented by the following general formula (3b) or (3c), or its copolymer, and vinyl benzyl halide react can also be illustrated. In the following formulae, p and q are each an integer indicating the number of repetitions of the structure in parentheses, and are not particularly limited as long as they are numbers usually employed in these compounds.

  The resin component may further contain, for example, a monomer that can be copolymerized with the polyvinyl benzyl ether compound. Examples of such monomers include styrene, vinyl toluene, divinyl toluene, divinyl benzene, divinyl benzyl ether, allyl phenol, allyloxybenzene, diallyl phthalate, acrylic acid ester, methacrylic acid ester, vinyl pyrrolidone, and the like. The blending amount of these monomers is preferably 2 to 50% by mass with respect to the mass of the polyvinyl benzyl ether compound.

  Further, the resin component may contain a resin other than the polyvinyl benzyl ether compound. Examples of the resin include thermosetting resins such as vinyl ester resins, unsaturated polyester resins, maleimide resins, polyphenol polycyanate resins, vinyl benzyl compounds, and thermoplastic resins such as polyethersulfone, polyacetal, and dicyclopentadiene resins. It is done. The blending amount of these resins is preferably 5 to 30% by mass with respect to the mass of the polyvinyl benzyl ether compound.

(Phosphorus compound)
The resin composition of the present embodiment includes a phosphorus atom and a plurality of benzene rings as a phosphorus compound, at least one of the benzene rings has a vinyl group, and at least one of the benzene rings. One containing at least a reactive phosphorus compound bonded to a phosphorus atom.

  In the reactive phosphorus compound, it is preferable that the benzene ring having the vinyl group is directly bonded to the phosphorus atom. More preferably, the carbon atoms bonded to the phosphorus atom are all carbon atoms constituting an aromatic ring. That is, it is preferable that a linear hydrocarbon group is not bonded to the phosphorus atom. Thereby, the deterioration of the dielectric characteristics due to the addition of the reactive phosphorus compound can be further reduced. Among these, in the reactive phosphorus compound, it is more preferable that all the carbon atoms bonded to the phosphorus atom are constituent carbons of the benzene ring.

Specifically, such a reactive phosphorus compound is preferably p-styryldiphenylphosphine (DPPST) represented by the following general formula (4). DPPST is well incorporated into the polymerization structure of the polyvinyl benzyl ether compound when the resin composition is cured, and can improve the flame retardancy of the cured product while maintaining excellent heat resistance and mechanical strength. Moreover, DPPST is excellent also in the characteristic which maintains the dielectric property of a polyvinyl benzyl ether compound.

  The resin composition may further contain a phosphorus compound other than the reactive phosphorus compound described above as the phosphorus compound. However, from the viewpoint of sufficiently maintaining the dielectric properties, heat resistance and mechanical strength of the obtained substrate, it is preferable that the reactive phosphorus compound is contained in an amount of 20 parts by mass or more with respect to 100 parts by mass of the resin component, More preferably, 30 to 80 parts by mass is contained, and 40 to 60 parts by mass is more preferred.

［式中、Ｒ^５１は芳香環を有する２価の有機基又は炭素数２〜１４の２価の脂肪族炭化水素基を示し、Ｒ^５２、Ｒ^５３、Ｒ^５４及びＲ^５５は各々独立に水素原子又は炭素数１〜６のアルキル基を示し、ｋは１以上の整数を示し、ｍ^１、ｍ^２、ｍ^３及びｍ^４は各々独立に１〜３の整数を示す。］ As the phosphorus compound other than the reactive phosphorus compound, a phosphate ester is suitable. Thus, it is preferable that all the phosphorus compounds (reactive phosphorus compounds and other phosphorus compounds) contained in the resin composition are organic phosphorus compounds having an organic group in the molecule. Examples of the phosphoric acid ester that can be added to the resin composition include compounds represented by the following general formula (5) (for example, resorcinol bis (2,6-xylenyl phosphate)), hydroquinone-tetra (2,6-xy Renyl phosphate), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like.

[Wherein R ⁵¹ represents a divalent organic group having an aromatic ring or a divalent aliphatic hydrocarbon group having 2 to 14 carbon atoms, and R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ are each independently hydrogen. atom or an alkyl group having 1 to 6 carbon atoms, k represents an integer of 1 or ^{more, m 1, m 2, m} 3 and ^{m 4} each independently represents a 1-3 integer. ]

  The resin composition of the present embodiment contains the phosphorus compound as described above. In order to sufficiently obtain the effect of improving the flame retardancy due to the addition of such a phosphorus compound, the resin composition contains phosphorus atoms. The quantity meets the following conditions: That is, the total content of phosphorus atoms contained in the phosphorus compound in the resin component and the phosphorus compound is 3.5% by mass or more. Here, the total content of phosphorus atoms refers to the total mass of all phosphorus atoms contained in the phosphorus compound (including reactive phosphorus compounds and other phosphorus compounds) relative to the total mass of the resin component and the phosphorus compound. The ratio (mass%) shall be said. When the total content of such phosphorus atoms is less than 3.5% by mass, it becomes difficult to obtain sufficient flame retardancy.

  The upper limit of the total content of phosphorus atoms is preferably 5.5% by mass. When this upper limit exceeds 5.5 mass%, the compounding quantity of the phosphorus compound in a resin composition will become excess, and it exists in the tendency for the dielectric characteristics and heat resistance of the board | substrate obtained to fall. From the viewpoint of obtaining sufficient flame retardancy and maintaining excellent heat resistance and dielectric properties, the total content is preferably 3.5 to 5.5% by mass, and 4 to 4.5% by mass. Is more preferable.

(Other ingredients)
The resin composition of a preferred embodiment may contain components other than the resin component and the phosphorus compound described above according to desired properties. Examples of such other components include inorganic fillers. By further including an inorganic filler in the resin composition, the strength of the obtained substrate can be improved. Such an inorganic filler preferably has a tan δ (dielectric loss tangent) of 0.003 or less in a high-frequency band of 2 GHz or more from the viewpoint of preventing a decrease in dielectric properties of the substrate.

  Examples of such inorganic fillers include dielectric materials such as titanium oxide, silica, alumina, zirconia, potassium titanate, barium titanate, zinc oxide, glass fibers, glass beads, magnesium oxide (talc), and the like. Among these, silica having a low tan δ is preferable. Further, for the purpose of adjusting the relative dielectric constant, a low tan δ barium titanate compound may be contained as an inorganic filler.

  The blending amount of the inorganic filler is preferably 50% by volume or less with respect to the resin component, and more preferably 20 to 40% by volume, particularly when forming a substrate with a conductor foil as described later. When the blending amount of the inorganic filler is 20% by volume or more, an excellent strength improvement effect tends to be obtained. However, if it exceeds 50% by volume, it may be difficult to mold the resin composition and it may be difficult to produce the substrate.

  In the resin composition of the present embodiment, in addition to the inorganic filler, a curing agent that accelerates curing of the resin composition, a deterioration preventing agent, a flame retardant aid (nitrogen-based, silicone-based, metal hydroxide-based) Etc.), organic fillers, etc. may be contained in such a blending amount that does not deteriorate the properties such as dielectric properties, heat resistance and strength.

(Method for preparing resin composition)
The resin composition of this embodiment can be prepared by kneading each component mentioned above, for example. Kneading can be performed by a method such as a kneader, a kneader, a ball mill, a stirrer, or a roll. Depending on the material used, the resin component or phosphorus compound may be dissolved in a solvent before mixing the components. In this case, toluene, xylene, dioxane, tetrahydrofuran, methyl isobutyl ketone, methyl ethyl ketone, or the like can be used as the solvent.
[Substrate with conductive foil]

  Next, the board | substrate with a conductor foil using the resin composition mentioned above is demonstrated. FIG. 1 is a perspective view schematically showing a substrate with a conductive foil according to a preferred embodiment. As shown in FIG. 1, the board | substrate 10 with a conductor foil of this embodiment is equipped with the board | substrate 12 and the conductor foil layer 14 provided in both surfaces of this board | substrate 12. As shown in FIG.

  The board | substrate 12 contains the hardened | cured material of the resin composition of embodiment mentioned above. Moreover, this board | substrate 12 may contain further the fiber base material normally used as a reinforcing material of a board | substrate other than this hardened | cured material. That is, the board | substrate 12 may contain the hardened | cured material of the resin composition of embodiment mentioned above, and the fiber base material distribute | arranged in this hardened | cured material. As the fiber base material, fibers made of glass, aramid, quartz, liquid crystal polymer, or the like, or a woven fabric or a nonwoven fabric made of these fibers is preferable. Of these, glass cloth is preferable from the viewpoint of price and performance (strength and the like) as a fiber base material.

  Such a substrate 12 is preferably formed, for example, from a prepreg formed by impregnating a fiber base material with the resin composition of the present embodiment. The substrate 12 is obtained by curing the resin composition contained in the prepreg. When the prepreg is produced, the impregnation of the fiber base material with the resin composition is performed by dissolving or dispersing the fiber base material in the resin composition, or the resin component, the phosphorus compound, and other components in a solvent. It can be performed by dipping in a solution. Here, when the latter solution is used, a prepreg is obtained by heating the fiber base material after resin impregnation to remove the solvent and the like. The heating is preferably performed at a temperature at which the resin composition is not completely cured, and a part of the resin composition may be cured. The fiber substrate may be subjected to a surface treatment with a silane coupling agent or the like in order to improve the adhesiveness with the resin composition or its cured product.

  In such a substrate 12, the cured product of the resin composition mainly contains a polymer obtained by polymerizing the polyvinyl benzyl ether compound represented by the general formula (1) at the vinyl group. And the reactive phosphorus compound mentioned above is copolymerized in the vinyl group, and is in the state taken in into a part of this polymer.

  Examples of the conductive foil layer 14 include those made of a conductive material usually used for circuit materials such as circuit boards. For example, metal foils, such as gold | metal | money, silver, copper, aluminum, are mentioned, Especially, copper foil is preferable. The metal foil may be produced by any method of electrolysis and rolling.

  The substrate 10 with conductor foil having such a configuration is obtained by, for example, stacking the conductor foil to be the conductor foil layer 14 on both sides of the prepreg described above, and heating and pressing the obtained laminate by a vacuum press or the like. It can be manufactured by processing the conductive foil so as to have a desired pattern. By heating and pressurizing the laminate, the layers of the prepreg and the conductive foil are brought into close contact with each other, and the resin composition in the prepreg is cured to form the substrate 12. The heating and pressurization at this time are preferably performed under conditions of a temperature of 120 to 200 ° C. and a pressure of 0.5 to 4 MPa, and may be repeated a plurality of times within these conditions. The patterning of the conductor foil can be appropriately performed by a known patterning method such as a photolithography method.

  In the production of the substrate 10 with conductor foil, before laminating the conductor foil as described above, for example, only the substrate 12 is formed first by heating the prepreg and curing the resin composition, and thereafter The conductor foil layer 14 may be formed on the surface of the substrate 10. The heating for obtaining the substrate 12 can be performed preferably in the range of 100 to 220 ° C, more preferably 120 to 200 ° C. Such heating may be performed by applying pressure while heating by, for example, a vacuum press.

  Since the substrate 12 in the substrate 10 with a conductive foil having such a structure mainly contains the cured product of the resin composition of the present invention, it has excellent flame retardancy and has a low dielectric constant and a low dielectric loss tangent. In addition, heat resistance and mechanical strength are also excellent. For this reason, the circuit board obtained from the substrate 10 with the conductive foil can exhibit excellent flame retardancy even when mounted on an electronic device and exposed to high temperatures, is not easily deformed, and has a high frequency band. The signal can be transmitted with low loss.

  In addition, as a board | substrate with a conductor foil of this invention, you may have a structure other than the form mentioned above. For example, a board | substrate with conductor foil may be provided with the laminated substrate formed by laminating | stacking a plurality of the above-mentioned board | substrates as a board | substrate. FIG. 2 is a schematic cross-sectional view showing an example of a substrate with a conductive foil provided with a laminated substrate. As shown in the drawing, the substrate 40 with conductor foil is composed of a laminated substrate 25 composed of an arbitrary number of layers (here, three layers) of substrates 20, and a conductor foil 30 disposed on both surfaces of the laminated substrate 25. is there. The substrate 20 is the same as the substrate 12 of the above embodiment. Moreover, as the conductor foil 30, the thing similar to the conductor foil for forming the conductor foil layer 14 mentioned above is applicable. Such a substrate 40 with conductor foil can be used as a circuit board or the like mounted on an electronic device or the like by processing the conductor foil 30 into a predetermined circuit pattern or the like.

  Further, if the above-described substrate with copper foil is used as a core substrate, a multilayer substrate can be easily formed. That is, by alternately laminating insulating layers and conductive foil layers on the outer layer of the substrate with copper foil, a multilayer substrate having alternating conductive foil layers and insulating layers can be easily obtained. In the multilayer substrate having such a structure, the substrates 12 and 20 in the above embodiment may be used not only as a core substrate but also as an insulating layer (interlayer substrate) disposed between conductor foil layers.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.
[Production of substrate]

(Examples 1-6, Comparative Examples 1-6)
First, a polyvinylbenzyl ether compound (ARS-068, manufactured by Showa Polymer Co., Ltd.), p-styryldiphenylphosphine, which is a phosphorus compound, and other phosphorus compounds are dissolved in toluene, and then a desired additive is added to uniformly dissolve them. To obtain a resin composition solution. In addition, the kind and compounding quantity of each component used for the resin composition were as shown in Table 1 (Examples 1-6) and Table 2 (Comparative Examples 1-6).

  In Tables 1 and 2, VBE is a polyvinyl benzyl ether compound, DPPST is p-styryl diphenylphosphine (made by Hokuko Chemical Co., Ltd.), PX200 is resorcinol bis (2,6-xylenyl phosphate (made by Daihachi Chemical Co., Ltd.), MR -260 indicates diphenyl-2-methacryloyloxyethyl phosphate, and the phosphorus content indicates the content (% by weight) of all phosphorus atoms contained in the resin composition (total of each component in the table).

  Next, a glass cloth (E glass) was impregnated with the solution of each resin composition to form a prepreg. After forming a desired number of prepregs corresponding to each of the examples and comparative examples, each of the prepregs was stacked and subjected to a vacuum press, and a temperature profile of 120 ° C. for 30 minutes, 150 ° C. for 30 minutes, 180 ° C. for 6.5 hours, and a pressure of 3 MPa. Was pressed and cured to prepare a substrate (laminated substrate) having a thickness of 1.2 mm.

(Example 7)
Spherical silica (FB-3SDC: manufactured by Denki Kagaku Kogyo Co., Ltd.) as an inorganic filler was blended in the resin composition having the same composition as that used for forming the substrate of Example 4 so as to be 40% by volume. The resin composition after mixing the inorganic filler was formed into a film on a film by a casting method, dried at 120 ° C. for 1 hour to remove the solvent, and a coating film made of the resin composition was formed. Then, the obtained coating film was pressed with a metal mold and cured in a vacuum at 200 ° C. for 5 hours to produce a substrate having a thickness of 1.2 mm.

(Example 8)
40% by volume of ceramic powder (Ba ₂ Nd ₂ Ti ₄ O ₁₂ : manufactured by TDK, average particle diameter of 1.6 μm) as an inorganic filler is added to the resin composition having the same composition as that used for forming the substrate of Example 4. It mix | blended so that it might become. Using the resin composition after mixing the inorganic filler, a substrate having a thickness of 1.2 mm was produced in the same manner as in Examples 1-6.
[Characteristic evaluation]

  Using the substrates of Examples 1 to 8 and Comparative Examples 1 to 6, the dielectric properties, flame retardancy, heat resistance and solvent resistance of each substrate were evaluated according to the following methods. The results obtained are summarized in Table 3.

(Dielectric properties)
After the substrates of Examples 1 to 8 and Comparative Examples 1 to 6 were cut into a size of 90 mm × 1.5 mm × 0.8 mm to obtain a dielectric property measurement sample, the cavity resonator perturbation method (high-frequency dielectric property measurement apparatus, Hewlett) The dielectric constant (ε ′) and dielectric loss tangent (tan δ) of each sample were measured at a frequency of 2 GHz using Packard's 83620A and 8757D.

(Flame retardance evaluation)
The substrates of Examples 1 to 8 and Comparative Examples 1 to 6 were cut into a size of 127 mm × 12.7 mm × 0.8 mm (1/21 inch) to make a sample for combustion test, and then used for UL94 vertical test method. A flammability test was performed by a method based on the above, and whether each sample caused combustion was observed. In addition, about the sample in which combustion did not arise, the flame-retardant grade (V-0, V-1, and V-2) was also evaluated.

(Heat-resistant)
The substrates of Examples 1 to 8 and Comparative Examples 1 to 6 were cut into a size of 40 mm × 10 mm × 0.8 mm to make a sample for heat resistance test, and then the measurement temperature range from room temperature to 300 ° C. was increased using this sample. Measurement was performed with DMA (Dynamic Mechanical Analysis: viscoelasticity measuring device) under a temperature rate of 5 ° C./min, and the glass transition temperature (Tg) of each sample was measured. Tg was the peak of tan δ after measurement. It shows that the higher the Tg, the higher the heat distortion temperature and the better the heat resistance. Further, in Table 3, the case where there is no notation of Tg indicates that there was no clear peak and Tg could not be determined.

(Solvent resistance)
The board | substrate of Examples 1-8 and Comparative Examples 1-6 was immersed in toluene, and the process which applies an ultrasonic wave for 15 minutes was performed. Visually observe the appearance of the substrate after processing, and indicate that the appearance did not change compared to before processing as ○ with excellent solvent resistance, and the appearance changed with solvent resistance Inferior to x.

  From Table 3, the substrates of Examples 1 to 8 obtained using a resin composition containing DPPST as a phosphorus compound have a low dielectric constant and a low dielectric loss tangent, excellent dielectric properties, and excellent flame retardancy. It was confirmed that it had heat resistance and solvent resistance. On the other hand, the substrates of Comparative Examples 1 to 6 using a resin composition that does not contain DPPST as a phosphorus compound or the total content of phosphorus atoms is outside the scope of the present invention are particularly dielectric properties, It was confirmed that one of the properties of flame retardancy and heat resistance was inferior.

It is a perspective view which shows typically the board | substrate with a conductor foil which concerns on suitable embodiment. It is a schematic cross section which shows an example of a board | substrate with a conductor foil provided with a laminated substrate.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Substrate with conductor foil, 12 ... Substrate, 14 ... Conductor foil layer, 20 ... Substrate, 25 ... Laminated substrate, 30 ... Conductor foil, 40 ... Substrate with conductor foil

Claims (8)

A resin composition comprising a resin component and a phosphorus compound,
The resin component contains a polyvinyl benzyl ether compound,
The phosphorus compound includes a phosphorus atom and a plurality of benzene rings, at least one of the benzene rings has a vinyl group, and at least one of the benzene rings is bonded to the phosphorus atom. Containing reactive phosphorus compounds,
In the resin component and the phosphorus compound, the total content of phosphorus atoms contained in the phosphorus compound is 3.5% by mass or more,
Content of the said reactive phosphorus compound with respect to 100 mass parts of said resin components is 20 mass parts or more, The resin composition characterized by the above-mentioned. The resin composition according to claim 1, wherein the polyvinyl benzyl ether compound is a compound represented by the following general formula (1).

[Wherein, R ¹¹ represents a methyl group or an ethyl group, R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 to 6. ]   The total content of phosphorus atoms contained in the phosphorus compound in the resin component and the phosphorus compound is 3.5% by mass or more and less than 5.5% by mass. Resin composition.   The resin composition according to any one of claims 1 to 3, further comprising an inorganic filler having a tan δ of 0.003 or less in a frequency band of 2 GHz or more.   A prepreg comprising the resin composition according to any one of claims 1 to 4 and a fiber base material disposed in the resin composition.   The board | substrate characterized by including the hardened | cured material of the resin composition as described in any one of Claims 1-4, and the fiber base material distribute | arranged in this hardened | cured material.   A substrate comprising the cured product of the resin composition according to any one of claims 1 to 4 and a fiber base material disposed in the cured product, and a conductor foil disposed on a surface of the substrate. A board with a conductive foil, comprising: A substrate with a conductor foil, comprising: a substrate made of a cured product of the resin composition according to any one of claims 1 to 4; and a conductor foil disposed on a surface of the substrate.

Images