JP2002128977A - Curable polyvinyl benzyl ether resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition prepared by imparting a flexibility to a stage B cured product without deteriorating the excellent physical properties of polyvinyl benzyl ether compounds such as a good, constant dielectric property substantially independent of temperatures or moisture absorption within a wide frequency range and an excellent heat resistance, and to provide a composition imparted with a flexibility which shows an improved workability at stage B state, adhesion strengths and reliability (crack resistance) and has an excellent high-frequency dielectric property wherein an increase in the dielectric property is inhibited at frequencies ranging from 100 MHz to 10 GHz to improve the Q-VALUE. SOLUTION: The polyvinyl benzyl ether resin composition contains a polyvinyl benzyl ether compound and a styrene elastomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in physical properties of a polyvinyl benzyl ether compound, and more particularly, to high frequency characteristics, heat resistance, low dielectric constant, and low dielectric constant which are characteristics of a resin obtained from the polyvinyl benzyl ether compound. The present invention relates to a composition that satisfies resin properties required for electronic devices, electronic components, and circuit boards without losing characteristics such as tangent and low water absorption.

More specifically, 100 MHz to 10 GHz
In the frequency range of, the rise of the dielectric constant is suppressed, and Q-VA
The present invention relates to a composition capable of improving LUE and imparting flexibility.

[0003]

2. Description of the Related Art Conventionally, thermosetting resins have been used for bonding, casting,
Widely used for coating, impregnation, lamination, molding, etc. However, in recent years, it has been used in many different applications, and the required characteristics are becoming stricter year by year. In such a case, there are many cases where conventional resins cannot be used.

[0004] In particular, in the electric and electronic industries, such as electronic equipment, electronic components, and circuit boards, high frequency, high maturity resistance and high reliability are required. For example, in a printed wiring board, a low dielectric constant accompanying an increase in propagation speed (higher frequency),
In order to reduce the dielectric loss tangent, increase the heat resistance by using lead-less solder, and suppress the drift of characteristic impedance, it is required that the dielectric properties have little dependence on temperature and humidity.

[0005] Further, with the increase in the frequency of mobile phones, personal computers, and the like used in electronic parts, 100 MHz to 1 MHz is required.
In the frequency band of 0 GHz, low dielectric constant and low dielectric loss tangent are required. For the same reason as printed wiring boards, high heat resistance and suppression of characteristic impedance drift are required. Less dependence is required.

At present, phenol resins, epoxy resins, unsaturated polyester resins, vinyl ester resins, polyimide resins, polyphenylene oxide (polyphenylene ether) resins, bismaleimide triazine (cyanate ester) are mainly used in the market.
These resins include the following properties required for electronic components and wiring boards: (1) low dielectric loss tangent, low dielectric constant, (2) heat resistance, (3) low water absorption, (4)
It does not completely satisfy the temperature and humidity dependence of the dielectric properties.

In order to solve the above problems, for example, Japanese Patent Application Laid-Open No. 9-31006 discloses a polyvinyl resin which has good and constant dielectric properties in a wide frequency range, is less dependent on temperature and hygroscopicity, and has excellent heat resistance. Penzyl ether compounds have been proposed.

[0008] However, when considered for use in electronic parts, it is necessary to supply them in various forms. For example, in the case of a glass cloth-containing substrate, the glass cloth is coated, semi-cured to the B stage state, and heated and pressed as an interlayer adhesive layer to form a glass cloth-containing laminate, Is applied directly by a method such as doctor blade and semi-cured to the B stage and used as a build-up interlayer material.

[0009] In this case, if there is no flexibility in the B-stage state, cracks, deterioration in handling properties, and problems such as resin falling (powder falling) during cutting occur. Even when other electronic components are formed, cracks, cracks, and the like may occur due to their brittleness.

The polyvinyl pendyl ether compound disclosed in Japanese Patent Application Laid-Open No. 9-31006 is brittle in the semi-cured state of the B stage, and the above problem is highly likely to occur. In addition, since the polyvinyl penzyl ether compound is radical thermal dissociation polymerization, the reaction occurs steeply and the number of polar groups is small, so that it is difficult to secure the adhesion to the glass cloth and the pot foil.

[0011]

DISCLOSURE OF THE INVENTION The present invention relates to a polyvinyl penzyl ether compound which exhibits good and constant dielectric properties in a wide frequency range, is hardly dependent on temperature and hygroscopicity, and has excellent heat resistance. It is an object of the present invention to provide a resin composition in which flexibility is imparted to a B stage and a cured product without any loss.

Further, the workability in the B-stage state is improved,
Improves the adhesion strength, improves reliability (prevents cracks), and provides flexibility with excellent high-frequency dielectric properties that improve the Q-VALUE without increasing the dielectric constant in the frequency range of 100 MHz to 10 GHz. It is intended to provide an improved composition.

[0013]

That is, the above object is achieved by the following constitution of the present invention. (1) A polyvinyl benzyl ether resin composition containing a polyvinyl benzyl ether compound and a styrene-based elastomer. (2) The polyvinyl benzyl ether resin composition according to (1), wherein the styrene-based elastomer has a styrene: elastomer mass ratio of 50:50 to 80:20. (3) The styrene-based elastomer includes styrene,
Diblock or triblock copolymer with one or more selected from polybutadiene, polyisoprene, poly (ethylene / butylene), poly (ethylene / propylene), poly (vinyl / isopropylene), and polyethylene The polyvinyl benzyl ether resin composition according to (1) or (2) above. (4) The above-mentioned (1) to (5), wherein the styrene-based elastomer is contained in a mass ratio of polyvinyl benzyl ether compound: styrene-based elastomer of 95: 5 to 70:30.
The polyvinyl benzyl ether resin composition according to any one of (3). (5) The polyvinyl benzyl ether resin composition according to any one of (1) to (4), further crosslinked with a peroxide.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The polyvinyl benzyl ether resin composition of the present invention contains a polyvinyl benzyl ether compound and a styrene-based elastomer. By adding a styrene-based elastomer to the main component polyvinyl benzyl ether compound, flexibility can be imparted to the composition.

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

[0016]

Embedded image

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. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group, examples of the aralkyl group include a benzyl group, and examples of the aryl group include a phenyl group.

R ₃ represents a hydrogen atom or a vinylbenzyl group, and the hydrogen atom is derived from the starting compound when 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 preferable, 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.

A specific example of the compound represented by the formula (1) is R ₁
Are shown below, but are not limited thereto.

[0023]

Embedded image

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. For the details, reference can be made to the description in JP-A-9-31006.

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

The polymerization and curing of the polyvinyl benzyl ether compound can be performed by a known method. Curing is possible either in the presence or absence of a curing agent.

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.

For adjusting the curing, hydroquinone, benzoquinone, copper salt and the like may be added.

The polymerized or cured product of the polyvinyl benzyl ether compound itself has a low dielectric constant (2 GH) in a high frequency range.
relative dielectric constant ε at z = 2.6) and low dielectric loss tangent (2G
(Tan δ at Hz = 0.04), and has excellent insulation and heat resistance, a high glass transition temperature (Tg), a high decomposition onset temperature, and a low water absorption.

A polymerized or cured product (VB) of a polyvinyl benzyl ether compound, and commercially available FR-4 and FR-5
(Epoxy resin manufactured by Sumitomo Bakelite Co., Ltd.), BT resin (bismaleimide resin manufactured by Mitsubishi Gas Chemical Co., Ltd.), and polyphenylene oxide (PPO), water absorption (500 hours at 85 ° C./85% RH), differential scanning Table 1 shows the glass transition temperature by the calorimetric method (DSC method).

[0031]

[Table 1]

[Elastomer] The mature elastomer is a plastic material having the property of rubber, which does not require a vulcanization step. Among them, materials having good dielectric properties (low ε, high Q) include the following materials. (1) Butadiene (including oligomers), for example, syndiotactic 1,2-polybutadiene (2) Styrene-polyolefin copolymer Further, both (1) and (2) have a C = C double bond in the molecular structure. It is broadly divided into two types: unsweetened type, and saturated type with double bond hydrogenated.

Among them, styrene (rubber) is highly compatible with the polyvinyl benzyl ether compound and does not separate when blended in a solvent such as toluene.
The ratio is 50% or more by mass, more preferably 50 to 80.
%belongs to. When the styrene ratio is lower than 50%, separation becomes easy. On the other hand, if the styrene ratio exceeds 80%, the flexibility decreases.

The above-mentioned material is formed of a polystyrene block and a flexible polyolefin structure elastomer block, and is a block copolymer based on two types of diblock and triblock.

The polyolefin structure may be any of poly (polyethylene-propylene) poly (ethylene-butylene) (random copolymer) poly (ethylene-propylene-ethylene) (random copolymer) polybutadiene polyisoprene vinyl-polyisoprene.

The compounding ratio is 9% by weight of the polyvinyl benzyl ether compound and the styrene-polyolefin copolymer.
5: 5 to 70:30, particularly preferably 90:10 to 75:25. When the amount of the sterene-polyolefin copolymer is less than the above, the effect of modifying the polyvinyl benzyl ether compound is scarce and the brittle physical properties are not improved. Further, if it is more than that, the original physical properties of the polyvinyl benzyl ether compound cannot be exhibited, and the solid content concentration cannot be increased at the time of blending in a solvent, the solution viscosity increases, and problems such as an increase in water absorption occur. .

[Peroxide] A peroxide may be added to the polyvinyl benzyl ether compound + styrene elastomer. The peroxide acts as a cross-linking agent, and the free radicals of the peroxide deprive of the hydrogen, form C—C bonds between the molecules, and connect the molecular chains.

As a result, the cured product containing no peroxide has extremely poor solvent resistance (for example, toluene), whereas the addition of peroxide significantly improves the solvent resistance due to the above effect.

The amount of addition may be appropriately adjusted depending on the required curing conditions and the like, but is preferably 0.5 to the total amount of the resin.
-5 mass%, especially 0.5-2 mass%.

Specific examples of the peroxide include the following. There are ketone peroxide, diacyl peroxide, peroxyketal, peroxyester, hydroperoxide, peroxycarbonate, dialkyl peroxide and the like.

[Material Dispersion (Kneading Method)] As a method of kneading the polyvinyl benzyl ether compound and the styrene-based elastomer, known methods such as a kneader, a kneader, a ball mill, stirring, and a roll may be used as necessary.

Depending on the kneading and the form of the material, it may be considered that the material is dissolved in a solvent to form a paste. However, it is preferable that the solvent has a similar SP value for both materials. Specifically, toluene, xylene, methyl A solvent such as microhexane may be used.

[Form of Material] The material of the present invention is an electronic device,
It can be formed in the following forms for electronic components and circuit boards. Pellet (powder): molding material, powder paint Paste: adhesive material, casting material, insulating paint such as resist, varnish

Furthermore, various fillers can be kneaded to form a composite material according to the necessity of improving the electrical characteristics, mechanical and physical properties, and the material form.

Specifically, dielectric materials such as titanium oxide, magnetic materials such as ferrite and soft magnetic metals, silica, alumina, zirconia, potassium titanate whiskers, barium titanate whiskers, zinc oxide whiskers, glass fibers, glass beads , Carbon fiber, magnesium oxide (talc), etc., which may be used depending on the required characteristics.

Further, by impregnating a cloth material such as a glass cloth with the above paste, a prepreg, a laminated plate, and 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, polyethylene and the like.

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 equipment, electronic parts and circuit boards.

The above filler and cloth material are 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. Is also good.

When flame retardancy is required, a flame retardant may be added as required. The following are mentioned as a flame retardant.・ Chlorine flame retardant ・ Bromine flame retardant ・ Phosphorus flame retardant ・ Nitrous flame retardant ・ Metal salt flame retardant ・ Hydrated metal flame retardant ・ Fibrous flame retardant ・ Low melting point glass flame retardant ・ Silicone flame retardant

One or more of the above flame retardants (or a blend of two or more) may be used (polyvinyl benzyl ether compound + sterene elastomer): 95: 5 to 5: 5 depending on the required flame retardancy. It is advisable to add at a ratio of 50:50.

[0052]

EXAMPLES Example 1 As shown in Table 2, 95 g of a polyvinyl benzyl ether compound and 222.2 of toluene were used.
g, Septon 2104 (manufactured by Kuraray Co., Ltd.) was placed in a 500 ml container, and stirred for 2 hours with a shaker mill to prepare a blend.

The following Examples 2 to 9 and Comparative Example 1 shown in Table 2
7 were similarly blended and stirred to prepare a blend. The resin materials in Table 2 are as shown in Table 3.

[0054]

[Table 2]

[0055]

[Table 3]

In Tables 1 and 2, SEPS: styrene-ethylene-propylene-styrene triblock copolymer, SEBS: styrene-ethylene-butylene-styrene triblock copolymer SBS: styrene-butadiene-sterene triblock Copolymer SBS: hydrogenated styrene-butadiene-styrene triblock copolymer SEP: styrene-ethylene-propylene diblock copolymer.

[B Stage without Glass Cloth] The above compounded paste is treated with polyethylene terephthalate (PET).
The solution was flowed on a film and subjected to a solvent drying treatment at 110 ° C. for 2 hours. The obtained dried product was crushed in a mortar. This is placed in a mold (inner size 80 × 80 mm) preheated to 100 ° C.
g, heated at a pressure of 1.96 MPa for 2 minutes, pressed under pressure, and taken out. The dimensions were 80 × 80 × 1.2 mm.

[Cured Product without Glass Cloth] The above-prepared paste was flowed on a PET film and subjected to a solvent drying treatment at 110 ° C. for 2 hours. The obtained dried product was crushed in a mortar. This was preheated to 100 ° C.
0 × 80 mm), and 1 g at a pressure of 1.96 MPa.
After heating and pressing for 0 minutes and releasing the pressure, 180 ° C
/ 8 hours, then removed. Dimension is 80 × 80
× 1.2 mm.

[B Stage with Glass Cloth] The above-prepared paste was impregnated and coated on a glass cloth [Style 1080 (manufactured by Asahi Schabel)] and dried at 110 ° C. for 1 hour. The coating thickness was 100 μm.

[Cured product with glass cloth] The prepreg containing the glass cloth was cut into a 200 mm square, and electrolytic copper foil (18 µm) manufactured by Nikko Materials was vertically stacked on the upper and lower sides at 150 ° C / 60 minutes and + 195 ° C / 180. Min, 2.94
Press molding was performed at a MPa and a vacuum of 30 Torr or less.
The finished size was 200 × 200 × 0.13 mm.

[Evaluation method] (1) Compatibility of the composition The above composition was placed in a glass container and allowed to stand at room temperature for 48 hours, and then visually checked to see if it was separated, and the separation was confirmed. Is indicated by x, and those not confirmed are indicated by ○.

(2) Brittleness A measuring needle was pressed against each of the above cured products with a shore meter to apply weight, and the value of the memory of the shore meter when cracks were confirmed was read.

(3) Degree of Powderization The difficulty of pulverizing the dried resin composition into powder (granular) was classified into the following 1 to 4. 1: It easily breaks when hit with a mortar stick, and is easily pulverized. 2: It can be easily broken by tapping with a mortar stick. 3: Difficult to break when hit with a mortar stick, but cracks loosely and takes a little time to pulverize. 4: It does not break even if it is hit with a mortar stick, and the mass cannot be reduced.

(4) Permittivity and Q Evaluation was made by a perturbation method of measuring the permittivity and Q from the deviation of the resonance point when the test piece was placed in a predetermined resonance container. Conditions are: frequency: 2 GHz, test piece: 1.2 × 1.5
× 80 mm.

(5) Flexural strength and flexural modulus Test piece: 25 × 40 × 1.2 mm, JISC6481
It evaluated by the method based on. At this time, the distance between the fulcrums was 16 mm, and the load speed was 1 mm / min.

(6) Chemical Resistance Specimen: 25 × 40 × 1.2 mm. Changes in appearance after immersion in the following chemicals were visually observed. Those that did not exist were marked with ○. Toluene: Ultrasonic 15 minutes Clean through: 60 ° C / 8 minutes immersion Sodium hydroxide: 10% solution immersed for 30 minutes Potassium permanganate: 45 g / 1.80 ° C / 15 minutes immersion

(7) Electric corrosion test: Specimen: A bare copper wire having a diameter of 0.6 mm was wound around 10 × 30 × 1.2 mm, and 240 VDC was applied to the copper wire in an atmosphere of 40 ° C. and 98% RH. 1000 hours after the application, the presence or absence of disconnection or corrosion was visually observed.

(8) Adhesion of Copper Foil A test piece having a width of 10 mm and a length of 200 mm was used as a universal load tester:
Using AGS1000D (manufactured by Shimadzu), the peel strength of the copper foil was evaluated in accordance with JIS C6481.

(9) Interlayer adhesion Four layers of the above cured products were placed on each other at 150 ° C./60 min.
Press molding was performed for 180 minutes at 2.94 MPa and a degree of vacuum of 30 Torr or less to produce a test piece having a width of 10 mm and a length of 200 mm. Universal load tester: AGS1000D (SHIM
ADZU) and the force at the time of peeling the first layer was evaluated in accordance with JIS C6481.

Table 4 shows the results of the evaluation.

[0071]

[Table 4]

Results Compatibility of the polyvinyl benzyl ether compound in the toluene solution can be ensured when the stellene-based elastomer has a sterene ratio of 50% or more. By adding 5 to 30% of a styrene-based elastomer, the brittleness of the prepreg is improved. Also, powder drop is reduced.

The dielectric properties of the cured product are improved. 1 to dielectric constant
4% down, Q value up 10-25%. It can be seen that the flexural modulus of the cured product is reduced, and flexibility is imparted. The chemical resistance is not tolerated by the solvent, toluene, but is improved by the addition of peroxide. Flexibility can be imparted without reducing the corrosiveness of the material. As a result of the provision of the flexibility, the adhesion to the copper foil and the glass cloth was improved.

[0074]

As described above, according to the present invention, a polyvinyl pentyl ether compound which exhibits good and constant dielectric properties in a wide frequency range, is hardly dependent on temperature and hygroscopicity, and has excellent heat resistance. The present invention can provide a resin composition in which flexibility is imparted to the B stage and the cured product without impairing the physical properties.

Further, the workability in the B-stage state is improved,
Improves the adhesion strength, improves reliability (prevents cracks), and provides flexibility with excellent high-frequency dielectric properties that improve the Q-VALUE without increasing the dielectric constant in the frequency range of 100 MHz to 10 GHz. Compositions can be provided.

[Procedure amendment]

[Submission Date] September 25, 2001 (2001.9.2)
5)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

In this case, if there is no flexibility in the B-stage state, problems such as generation of cracks, lowering of handleability, and falling of resin (powdering) at the time of cutting occur. Even when other electronic components are formed, cracks, cracks, and the like may occur due to their brittleness.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction contents]

One or more of the above flame retardants (or a blend of two or more) may be used (polyvinyl pendant ether compound + sterene elastomer): 95: 5 to 50: depending on the required flame retardancy of the flame retardant It is advisable to add at a ratio of 50.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0066

[Correction method] Change

[Correction contents]

(6) Chemical Resistance Specimen: 25 × 40 × 1.2 mm. Changes in appearance after immersion in the following chemicals were visually observed. Those that did not exist were marked with ○. Toluene: Ultrasonic 15 minutes Clean-through: 60 ° C / 8 minutes immersion Sodium hydroxide: 10% solution immersion for 30 minutes Potassium permanganate: 45 g / l, 80 ° C / 15 minutes immersion

Claims (5)

[Claims] 1. A polyvinyl benzyl ether compound,
A polyvinyl benzyl ether resin composition containing a styrene-based elastomer. 2. The styrene elastomer has a styrene: elastomer mass ratio of 50:50 to 80:20.
The polyvinyl benzyl ether resin composition according to claim 1, which is 3. The styrene-based elastomer is styrene and one or more selected from polybutadiene, polyisoprene, poly (ethylene / butylene), poly (ethylene / propylene), poly (vinyl / isopropylene), and polyethylene. The polyvinyl benzyl ether resin composition according to claim 1 or 2, which is a diblock or triblock copolymer with two or more kinds. 4. The polyvinyl benzyl ether resin composition according to claim 1, wherein the styrene-based elastomer is contained in a mass ratio of polyvinyl benzyl ether compound: styrene-based elastomer of 95: 5 to 70:30. 5. The polyvinyl benzyl ether resin composition according to claim 1, which is further crosslinked with a peroxide.