JP2004307867A - Curable and flame retarded polyvinyl benzyl ether resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable and flame retarded polyvinyl benzyl ether resin composition which can be flame retarded, when it is cured, while retaining its good dielectric properties. <P>SOLUTION: The curable and flame retarded polyvinyl benzyl ether resin composition comprises a polyvinyl benzyl ether compound and an additive-type flame retardant (in particular a brominated aromatic flame retardant) or both of an additive-type flame retardant and a retardant auxiliary. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a curable flame-retarded polyvinyl benzyl ether resin composition used for flame-retarding a cured product of a polyvinyl benzyl ether compound, and more specifically, features of a resin obtained from the polyvinyl benzyl ether compound. To achieve the flame retardancy required for electronic devices, electronic components, and circuit boards, without deteriorating features such as certain high-frequency characteristics, heat resistance, low dielectric constant, low dielectric loss tangent (high Q value), and low water absorption. It relates to a composition. More specifically, the present invention relates to a flame retardant composition capable of suppressing an increase in dielectric constant in a frequency range of 100 MHz to 10 GHz and improving a Q value.

  Conventionally, thermosetting resins have been widely used for bonding, casting, coating, impregnation, lamination, molding and the like. However, in recent years, it has been used in many different applications, and the required characteristics are becoming stricter year by year. In this case, there are many cases where conventional resins cannot be used. In particular, in the electric and electronic industry fields such as electronic devices, electronic components, and circuit boards, higher frequencies, higher heat resistance, and higher reliability are required.

  For example, in order to reduce the dielectric constant and dielectric loss tangent (high Q value) of printed wiring boards with higher propagation speed (higher frequency), to increase the heat resistance by using leadless solder, and to suppress the drift of characteristic impedance. It is required that the dielectric properties have little dependence on temperature and humidity. In addition, with the increase in the frequency of mobile phones and personal computers used in electronic components, low dielectric constant and low dielectric loss tangent (high Q value) are required in the frequency range of 100 MHz to 10 GHz. For the same reason as above, it is required that the dielectric properties have little dependence on temperature and humidity in order to increase the heat resistance and suppress the drift of the characteristic impedance.

At present, resins mainly used in the market include phenolic resins, epoxy resins, unsaturated polyester resins, vinyl ester resins, polyimide resins, polyphenylene oxide (ether) resins, bismaleimide triazine (cyanate ester) resins, and the like. However, these resins,
i) Low dielectric loss tangent, low dielectric constant
ii) Heat resistance
iii) Low water absorption
iv) It does not completely satisfy the temperature and humidity dependence of the dielectric properties.

  In order to solve the above-mentioned problem, Patent Document 1 discloses “Polyvinyl benzyl ether compound and a method for producing the same”. There has been proposed a polyvinyl benzyl ether compound which has a dielectric property that is hardly dependent on the heat resistance and further has excellent heat resistance.

  On the other hand, as an important property required for electronic devices, electronic components, and circuit boards, flame retardancy of resin is cited. For example, it is required to satisfy V-O in the UL94 flammability test of the flame retardancy test.

However, Patent Document 1 does not describe a flame retardant formulation of a polyvinyl benzyl ether compound, and the cured product of a polyvinyl benzyl ether compound is HB in a UL94 flammability test and is a flammable material. The fact is that it cannot be used.
JP-A-9-31006

  An object of the present invention is to provide a cured product having a good and constant property over a wide frequency range, exhibiting dielectric properties that are hardly dependent on temperature and hygroscopicity, and further exhibiting excellent physical properties of a polyvinyl benzyl ether compound having excellent heat resistance. To provide a curable flame-retarded polyvinyl benzyl ether resin composition that can be flame-retarded by using an addition-type flame retardant without inferring the reaction conditions and curing stress by using an addition-type flame retardant. It is. Another object of the present invention is to provide a curable flame-retarded polyvinyl benzyl ether resin composition having an excellent high-frequency dielectric property in which the dielectric constant does not increase in the frequency range of 100 MHz to 10 GHz and the Q value is improved.

The above problems can be solved by the present invention described below.
A curable flame-retarded polyvinyl benzyl ether resin composition containing a polyvinyl benzyl ether compound represented by the following formula (1) and an additive-type flame retardant, or both an additive-type flame retardant and a flame retardant auxiliary. hand,
The brominated flame retardant is decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromobisphenol A, tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A epoxy oligomer, ethylene-bis- ( From the group of tetrabromophthalimide), ethylene-bis- (pentabromodiphenyl), tris (tribromophenoxy) triazine, tris (tribromoneopentyl) phosphate, brominated polystyrene, octabromotrimethylphenylindane, and brominated polyphenylene oxide It is characterized in that it is at least one selected.

［式（１）中、Ｒ_１は メチル基またはエチル基を示し、Ｒ_２は 水素原子または炭素数１〜１０の炭化水素基を示し、Ｒ_３は 水素原子またはビニルベンジル基（ただし、水素原子とビニルベンジル基とのモル比は６０：４０〜０：１００）を示し、ｎは２〜４の整数である。］

[In the formula (1), R ₁ represents a methyl group or an ethyl group, R ₂ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₃ represents a hydrogen atom or a vinylbenzyl group (however, a hydrogen atom And the molar ratio of the vinylbenzyl group to 60:40 to 0: 100), and n is an integer of 2 to 4. ]

In the present invention, the polyvinyl benzyl ether compound preferably contains 5 to 70% by mass of a bromine-based flame retardant. When both the brominated flame retardant and the flame retardant auxiliary are used in combination, the bromine flame retardant and the flame retardant auxiliary are preferably contained in a mass percentage of 5 to 70% based on the polyvinyl benzyl ether compound. preferable.
In the present invention, the flame retardant aid is preferably at least one inorganic flame retardant selected from the group consisting of antimony trioxide, aluminum hydroxide, and magnesium hydroxide. It is preferable that the inorganic flame retardant has been surface-treated with a coupling agent.
The curable flame retarded polyvinyl benzyl ether resin composition of the present invention is used, for example, in a frequency range of 100 MHz to 10 GHz.

  According to the present invention, flame retardancy can be achieved while maintaining good dielectric properties when a cured product is obtained.

Hereinafter, the present invention will be described in detail.
The resin composition of the present invention is for flame-retarding a resin obtained by polymerizing or curing a polyvinyl benzyl ether compound, and comprises a polyvinyl benzyl ether compound, an addition type flame retardant, or a flame retardant auxiliary agent. And both are contained. Such an additive type flame retardant has a small influence on the curing conditions and does not need to take into account the reaction conditions and the like, so that it is easy to handle. Further, the degree of curing shrinkage does not vary depending on the conditions as compared with the case where a reactive flame retardant is used, so that the product has less variation.

As the polyvinyl benzyl ether compound used in the present invention, those represented by the formula (1) are preferable.

In the formula (1), R ₁ represents a methyl group or an ethyl group.

R ₂ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group represented by R ₂ is an alkyl group, an aralkyl group, an aryl group, and the like, each of which may have a substituent. The alkyl group is a methyl group, an ethyl group, a propyl group, a butyl group and the like, the aralkyl group is a benzyl group and the like, and the aryl group is a phenyl group and the like.

R ₃ represents a hydrogen atom or a vinylbenzyl group, and the hydrogen atom is derived from a starting compound for synthesizing the compound of the formula (1), and the molar ratio of the hydrogen atom to the vinylbenzyl group is 60:40 to 0: 100 is preferred, and more preferably 40:60 to 0: 100.

  n is a number from 2 to 4.

By setting the molar ratio of the hydrogen atom of R _{3 to} the vinylbenzyl group within the above range, the curing reaction can proceed sufficiently and sufficient dielectric properties can be obtained. On the other hand, when the number of unreacted substances in which R ₃ is a hydrogen atom increases, the curing reaction does not proceed sufficiently and sufficient dielectric properties cannot be obtained.

Specific examples of the compound represented by the formula (1) are shown below by combinations of R _{1 and the} like, but are not limited thereto.

The compound represented by the formula (1) is obtained by reacting a polyphenol in which R ₃ = H in the formula (1) with vinylbenzyl halide. The details can be referred to the description in Patent Document 1.

  The polyvinyl benzyl ether compounds of the present invention may be used alone or in combination of two or more.

  The polyvinyl benzyl ether compound of the present invention may be used by polymerizing it alone as a resin material, or may be used by being copolymerized with another monomer, and further, may be used in combination with another resin. .

  Examples of the copolymerizable monomer include styrene, vinyltoluene, divinylbenzene, divinylbenzyl ether, allylphenol, allyloxybenzene, diallylphthalate, acrylate, methacrylate, vinylpyrrolidone, and the like. The mixing ratio of these monomers is about 2 to 50% by mass percentage based on the polyvinyl benzyl ether compound.

  Examples of the resin that can be used in combination include, for example, a vinyl ester resin, an unsaturated polyester resin, a maleimide resin, a polycyanate resin of a polyphenol, an epoxy resin, a phenol resin, and a thermosetting resin such as a vinylbenzyl compound. There are thermoplastic resins such as polyetherimide, polyether sulfone, polyacetal, and dicyclopentadiene resin. The compounding ratio is about 5 to 90% by mass percentage with respect to the polyvinyl benzyl ether compound of the present invention. Among them, preferred is at least one selected from the group consisting of vinyl ester resins, unsaturated polyester resins, maleimide resins, polycyanate resins of polyphenols, epoxy resins and mixtures thereof.

  In the presence of a flame retardant, polymerization and curing of the polyvinyl benzyl ether compound itself or a curable resin composition containing this compound and another monomer or a thermosetting resin can be performed by a known method. Curing is possible either in the presence or absence of a curing agent. As the curing agent, a known radical polymerization initiator such as benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl perbenzoate and the like can be used. The amount used is 0 to 10 parts by mass based on 100 parts of the polyvinyl benzyl ether compound.

  The curing temperature varies depending on whether or not a curing agent is used and the type of the curing agent, but is in the range of 20 to 250 ° C, preferably 50 to 250 ° C for sufficient curing.

  In addition, hydroquinone, benzoquinone, a copper salt, or the like may be blended for adjusting the curing.

  The polymerized or cured product of the polyvinyl benzyl ether compound of the present invention (without addition of a flame retardant) has a low dielectric constant (relative permittivity ε at 2 GHz = about 2.6) and a low dielectric loss tangent (tan δ at 2 GHz) in a high frequency range. = About 0.04), is excellent in insulation and heat resistance, has a high glass transition temperature (Tg) and decomposition start temperature, and is a low water-absorbing polymer material.

  Polymerized or cured product (VB) of polyvinyl benzyl ether compound, commercially available FR-4, FR-5 (epoxy resin manufactured by Sumitomo Bakelite Co., Ltd.), BT resin (bismaleimide resin manufactured by Mitsubishi Gas Chemical), and polyphenylene For oxide (PPO), water absorption (85 hours at 85 ° C./85% RH), glass transition temperature by differential scanning calorimetry (DSC method) and decomposition by thermogravimetry and differential thermal analysis (TG / DTA method) The starting temperature is shown in Table 1.

The following are examples of the additive type flame retardant used in the present invention.
1) Halogen flame retardants
2) Phosphorus flame retardants
3) Nitrous flame retardant
4) Metal salt flame retardant
5) Hydrated metal flame retardant
6) Inorganic flame retardant Among them, the halogen-based flame retardant of 1) is preferable from the viewpoint of the dielectric properties, and the brominated aromatic flame retardant is more preferable in view of the heat resistance and the influence on the dielectric properties.

Representative brominated aromatic flame retardants include:
Decabromodiphenyl oxide,
Octabromodiphenyl oxide,
Tetrabromobisphenol A,
Bis (tribromophenoxy) ethane,
Tetrabromobisphenol A epoxy oligomer,
Ethylenebistetrabromophthalimide,
Ethylenebispentabromodiphenyl,
Tris (tribromophenoxy) triazine,
Tetrabromobisphenol A-bis (2,3-dibromopropyl ether),
Polydibromophenylene ether,
Brominated polystyrene,
Hexabromobenzene,
Tetrabromobisphenol S,
Octabromotrimethylphenylindane,
Brominated polyphenylene oxide,
And can be properly used depending on various required characteristics.

  Especially for heat resistance, reflow resistance at 260 ° C / 10 seconds at maximum several times (5-6 times), 260-350 ° C / several seconds (10- A solder dip test at a level of 3 seconds) is required, and a flame retardant that is difficult to decompose in this temperature range is required. The following flame retardants are preferred as satisfying this requirement.

Decabromodiphenyl oxide tetrabromobisphenol A epoxy oligomer ethylenebistetrabromophthalimide ethylenebispentabromodiphenyl tris (tribromophenoxy) triazine tribromoneopentyl alcohol brominated polystyrene octabromotrimethylphenylindane brominated polyphenylene oxide

  The blending ratio of such a brominated aromatic flame retardant may be appropriately selected according to the desired flame retardancy, but is preferably 5 to 70% by mass based on the polyvinyl benzyl ether compound. When the amount of the flame retardant is small, the flame retardant effect and the improvement of the dielectric properties are almost negligible, and when the amount is large, the excellent physical properties as a cured product of the polyvinyl benzyl ether compound are lowered (for example, the bending strength is lowered), and at the same time the paste is formed. With increasing viscosity, it becomes difficult to mix and paste.

  Taking a circuit board as a specific example, a compounding ratio of 20 to 50% by mass percentage is preferable in order to satisfy V-1 to V-0 of the UL94 flammability test of the flame retardancy test.

  If necessary, two or more kinds of the above-mentioned flame retardants may be blended and used.

  In the present invention, a flame retardant auxiliary may be used together with the flame retardant. Flame retardant aids are sometimes classified as flame retardants, but when used in combination with certain flame retardants, they exhibit a synergistic effect on the flame retardant effect of the flame retardant. As a flame retardant, when used in combination with a brominated aromatic flame retardant preferably used in the present invention, it is preferable to use one of the above-mentioned inorganic flame retardants as a flame retardant auxiliary. These inorganic flame retardant aids act as a dehydrating agent for the resin during combustion and contribute to the formation of a carbonized film. Specifically, aluminum hydroxide, magnesium hydroxide, silica, aluminum oxide, iron oxide, Metal oxides such as titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide, and tungsten oxide, aluminum, and iron Metal powders such as titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, cobalt, tin, antimony, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, carbonate Calcium and barium carbonate.

  Among them, antimony trioxide, aluminum hydroxide, and magnesium hydroxide have high synergistic effects when used in combination with a flame retardant and are suitable. Furthermore, antimony trioxide has a high melting point of 655 ° C and has excellent heat resistance as a material that clears heat resistance such as reflow and solder dip described earlier, and has a high flame-retardant synergistic effect with brominated aromatic compounds. It is particularly suitable for required properties such as properties.

  Further, if necessary, two or more kinds of the above-mentioned flame-retardant aids may be blended and used.

  The mixing ratio of the inorganic flame retardant aid to the total amount of the brominated aromatic flame retardant and the brominated aromatic flame retardant is preferably in the range of 5 to 70% by mass relative to the polyvinyl benzyl ether compound. It can be selected as appropriate according to the flammability. When the total amount is small, the flame retardant effect and the improvement of the dielectric properties are almost negligible, and when the total amount is large, the excellent physical properties as a cured product of the polyvinyl benzyl ether compound are reduced, and at the same time, it is difficult to mix and paste.

  As a specific example, in order to satisfy V-1 to V-0 of the UL94 flammability test of the flame retardancy test, a total mixing ratio of 20 to 40% by mass percentage is preferable.

  The mixing ratio of the inorganic flame retardant aid and the polyvinyl benzyl ether compound may be appropriately selected as necessary, and is not particularly limited. Can be selected from the range of 5/95 to 95/5 by mass.

  The flame retardant auxiliary may be subjected to a surface treatment in order to 1) improve the dispersibility and 2) improve the interface state with the polyvinyl benzyl ether compound.

  Specific examples include surface treatment with a silane compound (chlorosilane, alkoxysilane, organofunctional silane, silazane), titanate-based, aluminum-based coupling agent, or the like.

  The method of surface treatment includes a dry method, a wet method, an integral blend method, and the like. The method is selected as needed depending on required characteristics, steps, and equipment. Specifically, it can be performed according to a known method.

  By using the additive-type flame retardant and the flame-retardant auxiliary in combination, even if the compounding ratio of the polyvinylbenzyl compound in the composition of the present invention is increased as compared with the case of using the additive-type flame retardant alone, Levels can be kept equal.

  The composition of the present invention is used as a material for electronic devices, electronic components, and circuit boards. The molding material and the powder coating material are in the form of pellets (powder), such as an adhesive material, a casting material, and a resist. Various forms are possible as the insulating material, such as used in the form of a varnish or a paste.

  When such a material is obtained, a flame retardant (when a flame retardant aid is used, a flame retardant and a flame retardant aid) may be dispersed in the polyvinyl benzyl ether compound, and more specifically, by kneading. As for the method of kneading the polyvinyl benzyl ether compound and the flame retardant, a known method using a known machine such as a kneader, a kneader, a ball mill, a stirrer, or a roll may be used as needed.

  Further, at the time of kneading, or depending on the form of the material, it may be considered to dissolve in a solvent to form a paste, but toluene, o-xylene, m-xylene, p-xylene, dioxane, tetrahydrofuran, methyl isobutyl ketone, methyl ethyl ketone May be used.

  Further, various fillers can be kneaded to form a composite material according to the need for improving electrical characteristics, mechanical and physical properties, and material form. Specifically, dielectric materials such as titanium oxide, ferrite, magnetic materials such as soft magnetic metals, silica, alumina, zirconia, potassium titanate whiskers, barium titanate whiskers, zinc oxide whiskers, glass fibers, glass beads, carbon fibers, Magnesium oxide (talc) and the like can be mentioned, and they are used depending on the required characteristics.

  Further, a prepreg can be obtained by impregnating a cloth material such as a glass cloth with the above-mentioned paste, and further using this, a laminated plate or a laminated plate with a metal foil to which a metal such as copper is adhered can be obtained.

  Examples of the cloth material include glass, aramid, quartz, and polyethylene.

  Further, it is possible to produce a molded article of any shape by heating and curing in a mold, and it can be widely used as a material for electronic devices, electronic components, and circuit boards.

  The filler and the cloth material may be subjected to an insulating coating treatment or a surface treatment with a silane compound (chlorosilane, alkoxysilane, organic functional silane, silazane), a titanate-based or aluminum-based coupling agent, if necessary.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these.

(Example 1)
55 g of the polyvinyl benzyl ether compound and 45 g of toluene were stirred in the same vessel until completely dissolved to prepare a solution containing 55% solids by mass percentage.

  Using the above 55% solution and various addition type flame retardants and flame retardant auxiliaries, they are added so as to have a composition as shown in Table 2, and mixed and stirred until they are uniformly dispersed without aggregation. A slurry was prepared.

In the polyvinyl benzyl ether compound (VB), in the formula (1), R ₁ may be a methyl group, and R ₂ may be an alkyl group (an aralkyl group such as a benzyl group; And a molar ratio of the hydrogen atom of R ₃ to the vinylbenzyl group is hydrogen atom: vinylbenzyl group = 0: 100, and n = 3.

  Among them, the slurry for Sample No. 2 was prepared as follows.

Slurry for sample No. 2 55% (mass percentage) toluene solution of polyvinyl benzyl ether compound: 100 g
Cytex BT-93 (manufactured by Albemarle: additive type flame retardant ethylenebistetrabromophthalimide): 13.75 g
A glass cloth (1080 type, Asahi Shavel) was impregnated with the above slurry and subjected to a temporary curing treatment at 110 ° C. for 2 hours to obtain a prepreg containing a glass cloth. The thickness was 100 μm.

  Ten prepregs were stacked and heated at a temperature profile of 120 ° C. for 30 minutes, 150 ° C. for 30 minutes, 180 ° C. for 30 minutes, 200 ° C. for 30 minutes, and a pressure of 300 MPa, and pressure-cured to obtain a laminated board containing glass cloth. The thickness was 800 μm.

  Thus, samples as shown in Table 2 were obtained.

  Sample No. 1 is a sample of a laminated board containing a glass cloth not containing a flame retardant.

  The prepared sample was evaluated as follows. Each sample was cut into the described shape and evaluated. The results are shown in Tables 2 and 3. The dielectric constant and Q value are also shown in Tables 4 and 5 and FIGS.

i) UL94 flammability test The UL94 flammability test of UL-94HB and the UL94 flammability test of UL-94V-0, V-1, and V-2 were performed. The sample shape was 127 mm x 12.7 mm x 0.8 mm (1/32 inch).

ii) Dielectric constant and Q value Dielectric constant was determined at a measurement frequency of 2 GHz, 5 GHz and 10 GHz by a perturbation method, and a Q value was calculated. The sample shape was 90 mm × 1.5 mm × 0.8 mm.

iii) Volume resistivity Determined according to JIS C6481. The sample shape was such that the diameter of the electrode part was 50 mm and the thickness t was 0.8 mm.

iv) Water absorption (%)
The water absorption condition was set to 48 hours at 60 ° C. and 90% RH. The sample shape was 50 mm × 50 mm × 0.8 mm.

v) Linear expansion coefficient (material thickness direction)
Thermal analyzer: TMA-50 (SHIMADZU) was used and measured in air at room temperature (18 ° C.) to 250 ° C. at a heating rate of 10 ° C./min. The sample shape was 10 mm × 10 mm × 0.8 mm.

vi) Flexural strength A universal load tester: AGS1000D (SHIMADZU) was used and determined in accordance with JIS C 6481. The sample shape was 40 mm × 25 mm × 0.8 mm.

vii) Copper foil peel strength: Determined according to JIS C 6481 using a universal load tester: AGS1000D (SHIMADZU). The sample shape was 100 mm x 25 mm x 0.8 mm (the copper foil portion was 100 mm x 10 mm).

viii) Decomposition start temperature (℃)
Thermal analysis apparatus: DTG-50 (SHIMADZU) was used, and the temperature was measured in the air at room temperature (18 ° C.) to 800 ° C. at a heating rate of 20 ° C./min. The sample shape was 5 mm × 5 mm × 0.8 mm.

ix) Corrosion test (by impurity ions)
When 250 V (direct current) is applied to a copper wire (0.06 mm diameter) at 40 ° C. and 90% RH for 1000 hours, the presence or absence of copper wire breakage and corrosion is checked. When it was rejected. The sample shape was 30 mm × 10 mm × 0.8 mm.

  Tables 2 and 3 show that the addition of the additive type flame retardant improves the flame retardancy level. Samples No. 6 and No. 10 were the same HB as Comparative Sample No. 1, but the burning time was shortened, and it was found that the HB was clearly improved. Further, these samples have relatively small amounts of the flame retardant or the flame retardant auxiliary agent, and can be shifted to V-1 and V-0 by controlling the amount of these additives. In particular, when a brominated aromatic flame retardant, which is preferable in the present invention, is used, flame retardation can be achieved without lowering the dielectric properties. Other properties such as mechanical properties, heat resistance properties, and corrosiveness are also good.

  Further details will be described.

  Regarding the flame-retardant test, the flame retardance of brominated aromatic flame retardant was UL-94 V-1 by adding 20% (mass percentage) and V-0 by adding 30% (mass percentage) to thickness 1/32. It can be obtained in inches (0.8mm). In addition, the flame retardancy due to the combined use of a brominated aromatic flame retardant and the flame retardant assistant antimony trioxide is UL-94 V-1 with the addition of 20% (mass percentage) and V- with the addition of 23% (mass percentage). 0 can be obtained with a thickness of 1/32 inch (0.8 mm).

  Regarding the high frequency characteristics of the dielectric properties, the brominated aromatic flame retardant, the flame retardant prescription with the combined use of the brominated aromatic flame retardant and antimony trioxide are compared with the composition of the non-flame retarded polyvinyl benzyl ether compound alone. In the high frequency range where the Q value is 2 to 10 GHz, an improvement of 10 to 15% was observed (Table 5, FIG. 2). Also, it can be seen that the dielectric constant hardly increases even when compared with the composition of the polyvinyl benzyl ether compound which is not flame retarded (Table 4, FIG. 1). On the other hand, in the flame retardant formulation using another flame retardant, a phenomenon that the dielectric constant increases or the Q value decreases may be observed, which is not preferable as compared with the brominated aromatic flame retardant. For this reason, the formulation using the brominated aromatic flame retardant does not cause deterioration of the dielectric properties, but rather the Q value can improve the effect and can be made flame retardant, and is particularly excellent as a high frequency material. It is a prescription.

  Regarding heat resistance properties, the flame retardant formulation using a brominated aromatic flame retardant, or a combination of a brominated aromatic flame retardant and antimony trioxide has a decomposition onset temperature in comparison with the composition of a non-flame retarded polyvinyl benzyl ether compound alone. However, in actuality, it is necessary to start decomposition at a temperature lower than that of the base resin in order to effectively make the flame retardant, which is rather effective.

  However, compared to other flame retardants, it does not decompose to high temperatures, and also meets the heat resistance level required for electronic components and wiring boards (levels at 260-350 ° C for several seconds). The use of is advantageous.

  Regarding the mechanical properties, in the flame retardant formulation using a brominated aromatic flame retardant, the coefficient of linear expansion of the cured product varies depending on the blending amount, but can be reduced by 10 to 50%. This is a great advantage of extending the life in reliability, heat resistance tests, and the like.

  With regard to corrosiveness, brominated aromatic flame retardants can achieve flame retardancy without deteriorating the corrosiveness of the material.

4 is a graph showing frequency characteristics of a dielectric constant of a laminate obtained from the composition of the present invention. 4 is a graph showing the frequency characteristic of the Q value of a laminate obtained from the composition of the present invention.

Claims (6)

Curing containing a polyvinyl benzyl ether compound represented by the following formula (1) and a brominated flame retardant as an additive flame retardant, or both a brominated flame retardant and an additive flame retardant as an additive flame retardant A flame-retardant polyvinyl benzyl ether resin composition,
The brominated flame retardant is decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromobisphenol A, tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A epoxy oligomer, ethylene-bis- ( From the group of tetrabromophthalimide), ethylene-bis- (pentabromodiphenyl), tris (tribromophenoxy) triazine, tris (tribromoneopentyl) phosphate, brominated polystyrene, octabromotrimethylphenylindane, and brominated polyphenylene oxide A curable flame-retarded polyvinyl benzyl ether resin composition, which is at least one selected from the group consisting of:

[In the formula (1), R ₁ represents a methyl group or an ethyl group, R ₂ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₃ represents a hydrogen atom or a vinylbenzyl group (however, a hydrogen atom And the molar ratio of the vinylbenzyl group to 60:40 to 0: 100), and n is an integer of 2 to 4. ]   The curable flame-retarded polyvinyl benzyl ether resin composition according to claim 1, wherein the composition contains a brominated flame retardant in an amount of 5 to 70% by mass relative to the polyvinyl benzyl ether compound.   2. The method according to claim 1, comprising both a brominated flame retardant and a flame retardant auxiliary, and containing 5 to 70% by mass of the brominated flame retardant and the flame retardant auxiliary with respect to the polyvinyl benzyl ether compound. Curable flame retarded polyvinyl benzyl ether resin composition.   The curable flame retardant according to any one of claims 1 to 3, wherein the flame retardant aid is at least one inorganic flame retardant selected from the group consisting of antimony trioxide, aluminum hydroxide, and magnesium hydroxide. Flammable polyvinyl benzyl ether resin composition.   The curable flame retarded polyvinyl benzyl ether resin composition according to claim 4, wherein the inorganic flame retardant has been surface-treated with a coupling agent.   The curable flame retarded polyvinyl benzyl ether resin composition according to any one of claims 1 to 5, which is used in a frequency range of 100 MHz to 10 GHz.

Images