TWI781304B - Resin compositions, varnishes, laminates, and printed wiring boards - Google Patents

Abstract

The present invention provides a resin composition, which has It has high heat resistance and low dielectric properties (low relative permittivity, low dielectric loss tangent), and is a cured product used as laminates, printed wiring boards, adhesives, sealants, coatings, and molded products.

The present invention is a resin composition comprising (A) polymaleimide compound, (B) benzoxazine, (C) epoxy resin, and (D) lavone resin. It is obtained by melting, and the content of the above-mentioned (A) polymaleimide compound in 100 parts by mass of the resin component of the above-mentioned resin mixture is 40 to 70 parts by mass.

Description

Resin composition, varnish, laminate, and printed wiring board

The present invention relates to an electronic and electrical component with high heat resistance and low dielectric properties (low relative permittivity, low dielectric loss tangent) and used as laminates, printed wiring boards, adhesives, sealants, coatings Resin compositions used in molded articles and the like, and methods for producing the same.

Heretofore, thermosetting resins such as epoxy resins, polyimide resins, unsaturated polyester resins, and phenol resins have been used as heat-resistant resins in the field of electronic materials. These thermosetting resins are used according to their uses and characteristics. Among them, polyimide resins are excellent in heat resistance and heat-and-moisture resistance (heat resistance after moisture absorption), and thus are widely used in applications requiring high heat resistance. In addition, modified polyimide resins in which performance is improved by combining other resins such as epoxy resins and aromatic diamines with polyimide resins are also used.

In recent years, in the field of semiconductor substrates, a mounting method of directly mounting a semiconductor chip on a substrate has been popularized. Therefore, materials used for semiconductors are required to have high heat resistance capable of withstanding high-temperature processing in mounting steps and the like. Epoxy resins are widely used as semiconductor materials, and studies have been conducted to meet the demand for improved heat resistance, and resins having excellent heat resistance have been proposed. For example, a modified polyimide resin composition is described in Patent Document 1. The modified polyimide resin composition is made of polymaleimide compound, phenol resin, bisphenol A type epoxy resin and Other epoxy resins are melted.

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2017-101152

Although the modified polyimide resin composition described in Patent Document 1 has the advantage of high heat resistance, it may not have sufficient low dielectric properties depending on the application. Therefore, an object of the present invention is to provide a resin composition having high heat resistance and low dielectric properties.

[1] A resin composition comprising (A) polymaleimide compound, (B) benzoxazine, (C) epoxy resin, and (D) coumarone resin The resin mixture is obtained by melting, and the content of the above-mentioned (A) polymaleimide compound in 100 parts by mass of the resin component of the above-mentioned resin mixture is 40 to 70 parts by mass.

[2] The resin composition according to [1], wherein the content of the (D) lavone resin in 100 parts by mass of the resin component of the resin mixture is 1 to 5 parts by mass.

[3] The resin composition according to [2], wherein the (D) lavone resin has a softening point of 100° C. or lower and a weight average molecular weight of 850 or lower.

[4] The resin composition as described in [2] or [3], wherein the above-mentioned resin mixture further contains (E) bisphenol A type cyanate, and the above-mentioned (E) in 100 parts by mass of the resin component of the above-mentioned resin mixture is ) The content of the bisphenol A type cyanate is 3 parts by mass to 7 parts by mass.

[5] The resin composition as described in [1], wherein the polymaleimide compound (A) is represented by the formula (1),

(In the above formula ( ₁ ), n1 is an integer of 0 to 10, X1 is each independently an alkylene group having a carbon number of ¹ to 10, a group represented by the following formula (2), "- A group represented by SO ₂ -", a group represented by "-CO-", an oxygen atom or a single bond, R ¹ are each independently a hydrocarbon group having 1 to 6 carbons, and a is each independently 0 to 4 The following integers, b are each independently an integer of 0 to 3, and the average value of the number _n of repeating units is 0.01 to 5)

(In the above formula (2), Y is a hydrocarbon group having an aromatic ring having a carbon number of 6 to 30, and n ₂ is an integer of 1 to 3).

[6] The resin composition according to [1], wherein the content of the (B) benzoxazine in 100 parts by mass of the resin component of the resin mixture is 10 to 30 parts by mass.

[7] The resin composition according to [1], wherein the (C) epoxy resin contains an α-naphthol-type epoxy resin, and the α-naphthol-type epoxy resin in 100 parts by mass of the resin component of the resin mixture is The content of the epoxy resin is 10 to 30 parts by mass.

[8] The resin composition according to any one of [1] to [7], which is composed of each component It is obtained by melting as follows: In 100 parts by mass of the above-mentioned (A) polymaleimide compound contained in the above-mentioned resin mixture, in the resin composition after the melt-mixing step, as a residual maleimide compound On the other hand, the remaining polymaleimide compound (A) is 30 to 60 parts by mass.

[9] The resin composition according to any one of [1] to [8], which is used for a printed wiring board.

[10] A varnish obtained by dissolving the resin composition described in any one of [1] to [8] in a solvent having a boiling point of 120° C. or lower and a relative dielectric constant of 10 to 30.

[11] A laminate manufactured using the resin composition described in any one of [1] to [8].

[12] A printed wiring board manufactured using the resin composition described in any one of [1] to [8].

[13] A molded article obtained by curing the resin composition described in any one of [1] to [8].

[14] A method for producing a resin composition, comprising a melt-mixing step of melt-mixing the resin mixture described in any one of [1] to [8].

By melting a resin mixture containing (A) polymaleimide compound, (B) benzoxazine, (C) epoxy resin, and (D) lavone resin, it is possible to provide a A cured resin composition with heat resistance and low dielectric properties (low relative permittivity, low dielectric loss tangent).

(resin composition)

The resin composition of the present invention is obtained by melting a resin mixture containing (A) polymaleimide compound, (B) benzoxazine, (C) epoxy resin, and (D) lavone resin Or, and the content of the above-mentioned (A) polymaleimide compound in 100 parts by mass of the resin component of the above-mentioned resin mixture is 40 parts by mass to 70 parts by mass. Hereinafter, each component (A)-(D) and other components which may be contained are demonstrated. In the present invention, the component before melt-mixing each component is called "resin mixture", and the component cooled after melt-mixing is called "resin composition".

(A) polymaleimide compound

The polymaleimide compound is a compound having two or more maleimide groups. From the viewpoint of high heat resistance and low dielectric properties of the cured product, a compound in which a maleimide group is bonded to an aromatic ring is preferable. Examples of such polymaleimide compounds include compounds represented by formula (1) shown in the section of means for solving the problems.

From the viewpoint of improving the solubility of the resin composition in a low-boiling solvent, the polymaleimide compound is preferably such that the average value of the number n of repeating units in formula ( ₁ ) is 0.01 or more and 5 or less . That is, the resin mixture is preferably such that the average value of the number of repeating units n1 _of the polymaleimide compound having the repeating unit (structural site) enclosed in parentheses in formula (1) becomes 0.01 or more and 5 The following ratios include. Thereby, the range of a melting temperature can be expanded, and the resin composition with favorable solubility in a low boiling point solvent can be obtained in this melting temperature range. In the present invention, "a polymaleimide compound having _an average value of n1 of 0.01 to 5" means a polymaleimide compound comprising one compound or a mixture of two or more compounds.

By using the (A) polymaleimide compound in which the average value of the number n of repeating units in the formula ( ₁ ) is 0.01 or more and 5 or less, it becomes in methyl ethyl ketone which is a low boiling point solvent A resin composition with good solubility. Therefore, a resin composition having good solubility in methyl ethyl ketone can be obtained without using a bisphenol A-type epoxy resin having the effect of increasing the temperature of the resin composition in a low-boiling point solvent. The role of solubility in .

The heat resistance of the cured product of the resin composition is improved by suppressing the content of the bisphenol A type epoxy resin in the resin component of the resin mixture. From the viewpoint of improving the heat resistance of the cured product of the resin composition, it is preferable that the resin mixture does not contain a bisphenol A type epoxy resin. Here, the term "not containing bisphenol A epoxy resin" means that bisphenol A epoxy resin is not contained substantially, that is, does not contain bisphenol A epoxy resin in an amount that would affect the properties of the resin mixture.

Since the resin mixture contains the polymaleimide compound at a high ratio of 40 to 70 parts by mass based on 100 parts by mass of the resin components of the resin mixture, it becomes a resin composition capable of forming a cured product having good heat resistance. From the viewpoint of both high heat resistance and low dielectric properties, the content of the polymaleimide compound in 100 parts by mass of the resin component of the resin mixture is more preferably 50 to 70 parts by mass, and more preferably 55 parts by mass. Parts by mass~65 parts by mass. Furthermore, in the present invention, the numerical range "A~B" means "more than A and less than B".

The polymaleimide compound represented by formula (1) is preferably a polymaleimide compound in which X ¹ is -CH ₂ -, a is 0, and b is 0. Examples of such commercially available polymaleimide compounds include BMI-2000 and BMI-2300 (product name, manufactured by Daiwa Chemical Industry Co., Ltd., phenylene maleimide).

(B) Benzoxazine compounds

As long as the benzoxazine compound is a compound having at least one benzoxazine ring in the molecule, it is preferably a dihydrobenzoxazine compound represented by the following general formula (3) or (4), Among them, p-d-type dihydrobenzoxazines represented by the following general formula (4) are more preferable.

(In formula (3) and formula (4), R ² and R ³ represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group with 1 to 3 carbons)

These dihydrobenzoxazine compounds can be used alone or in combination of two or more.

From the standpoint of high heat resistance and low dielectric properties of the cured product, and the solubility of the resin composition in a low-boiling solvent and the stability of the dissolved state, the benzoxazine in 100 parts by mass of the resin component of the resin mixture The content of the compound is preferably from 10 parts by mass to 30 parts by mass, more preferably from 12 parts by mass to 25 parts by mass, further preferably from 15 parts by mass to 22 parts by mass. In addition, from the viewpoint of solubility in a low boiling point solvent and stability of a dissolved state, the content of the benzoxazine compound is more preferably 15 parts by mass relative to 100 parts by mass of the polymaleimide compound (A). More than 20 parts by mass, more preferably more than 20 parts by mass. From the viewpoint of obtaining a hardened product with good heat resistance, benzoxazinated The content of the compound is more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, relative to 100 parts by mass of the (A) polymaleimide compound.

(C) epoxy resin

The epoxy resin should just be a compound having an epoxy group, but from the viewpoint of achieving both heat resistance and low dielectric properties of the cured product of the resin composition, biphenyl aralkyl type epoxy resins, including Naphthalene ring epoxy resins, compounds represented by formula (5) having three epoxy groups, and the like. As the epoxy resin containing a naphthalene ring, an α-naphthol type epoxy resin is preferable. As a commercially available epoxy resin containing a naphthalene ring, ESN-475V (product name, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., α-naphthol type epoxy resin) having two epoxy groups per naphthalene ring is exemplified. . Moreover, as a commercially available epoxy resin represented by Formula (5), VG3101L (product name, the product made by Printec Co., Ltd., a high heat-resistant trifunctional epoxy resin) is mentioned.

Examples of epoxy resins other than the above include bisphenol A epoxy resins, bisphenol E epoxy resins, bisphenol F epoxy resins, novolac epoxy resins, and cresol novolak epoxy resins. , bisphenol A novolac epoxy resin, bisphenol F novolak epoxy resin, triphenol-based epoxy resin, dicyclopentadiene epoxy resin Wait. These epoxy resins may be used alone or in combination of two or more.

From the viewpoint of high heat resistance and low dielectric properties of the cured product, the content of the epoxy resin in 100 parts by mass of the resin component of the resin mixture is preferably from 10 parts by mass to 30 parts by mass, more preferably from 12 parts by mass to 25 parts by mass, and more preferably 15 parts by mass to 22 parts by mass.

(D) Lavenderone resin

Laminone resin is a copolymer resin with lavone, indene and styrene as the main components. As a commercial item, G-90, V-120, L-5, L-20, H-100 (all are product names, manufactured by Nippon Chemical Co., Ltd.) etc. are mentioned. From the viewpoint of making a resin composition for realizing a cured product having low dielectric properties, a lavone resin having a softening point of 100° C. or lower and a weight average molecular weight of 850 or lower is preferable.

From the viewpoint of high heat resistance and low dielectric properties of the cured product, the content of the lavone resin in 100 parts by mass of the resin component of the resin mixture is preferably 0.1 to 5 parts by mass, more preferably 0.5 parts by mass ~4 parts by mass, and more preferably 1~3 parts by mass.

(E) Bisphenol A cyanate

Bisphenol A cyanate is a bisphenol A cyanate hardened by forming a triazine ring. By using bisphenol A type cyanate and (D) lavone resin together, the relative permittivity and dielectric loss tangent of the cured product obtained by hardening the resin composition can be further reduced. There are monomers and (homo)polymers (macromolecules) of bisphenol A cyanate, but from the viewpoint of obtaining a cured product with excellent low dielectric properties, bisphenol A cyanate monomer is preferred .

From the viewpoint of high heat resistance and low dielectric properties of the cured product, the content of (E) bisphenol A type cyanate in 100 parts by mass of the resin component of the resin mixture is preferable It is 1 mass part - 10 mass parts, More preferably, it is 3 mass parts - 8 mass parts, More preferably, it is 4 mass parts - 6 mass parts.

(F) hardening accelerator

When using the resin composition of this invention, you may add and use a hardening accelerator. The timing of adding the hardening accelerator includes when dissolving the resin composition in a solvent to obtain a varnish, when forming a prepreg, or when manufacturing a base material or a laminate.

Examples of hardening accelerators include dicumyl peroxide, 4,4'-diaminodiphenylmethane, 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-heptylimidazole Other imidazoles; triethanolamine, triethylenediamine, N-methylmorpholine and other amines; triphenylphosphine, tricresylphosphine and other organic phosphines; tetraphenylphosphonium tetraphenylborate, tetraphenylboronic acid Tetraphenylboron salts such as triethylammonium; 1,8-diazabicyclo(5,4,0)undecene-7 and its derivatives; lead naphthenate, lead stearate, naphthene Zinc acid, tin oleate, manganese naphthenate, cobalt naphthenate, cobalt octoate and other organic metal salts. These hardening accelerators may be used alone or in combination of two or more, and an organic peroxide, an azo compound, etc. may be used in combination if necessary.

The content of these hardening accelerators is preferably formulated in a range in which the desired gelation time is obtained in the varnish or the prepreg. Generally, it is used in the range of 0.01 to 5 parts by mass with respect to a total of 100 parts by mass of the resin components contained in the resin composition.

The resin composition and the resin mixture before melt mixing of the present invention may contain components other than the aforementioned (A) (B) (C) (D) (E) and (F). For example, an organic or inorganic filler can be used in order to obtain a base material for forming a molded article by curing the resin composition of the present invention. Examples of fillers include oxides such as silicon dioxide, diatomaceous earth, aluminum oxide, zinc chloride, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites; Calcium Hydroxide, Magnesium Hydroxide, Aluminum Hydroxide, Alkaline Magnesium carbonate and other hydroxides; calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, aluminum magnesium carbonate and other carbonates; calcium sulfate, barium sulfate, gypsum fiber and other sulfates; calcium silicate ( Wollastonite, xonotlite), talc, clay, mica, montmorillonite, bentonite, attapulgite, sepiolite, imogolite, sericite, glass fiber, glass beads, silicon Silicates such as soil-based balloons; nitrides such as aluminum nitride, boron nitride, and silicon nitride; carbons such as carbon black, graphite, carbon fiber, carbon balloons, and charcoal powder; other various metal powders, potassium titanate, titanic acid Lead zirconate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powder, slag fiber, ceramic powder, etc.

The shape of the filler is preferably spherical or scaly, and these fillers may be used alone or in combination of two or more. In addition, a silane coupling agent having two or more different reactive groups in the molecule (one of which is a reactive group for a chemical reaction with an inorganic material and the other is a reactive group for a chemical reaction with an organic material) can also be used in combination if necessary.

When using an organic or inorganic filler, the content of the filler is preferably 5.0 parts by mass to 250 parts by mass relative to 100 parts by mass of the resin component of the resin mixture.

In the resin composition, a flame retardant may be added as needed. Examples of flame retardants include organic flame retardants such as bromine compounds such as brominated epoxy resins and phosphorus compounds such as condensed phosphoric acid esters, inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, tin compounds, and antimony compounds. agent etc. These flame retardants may be used alone or in combination of two or more.

In addition, the content of the flame retardant is ideally required to achieve sufficient flame retardancy (for example, conforming to the V-0 condition in the UL94 standard) without impairing the heat resistance and moisture resistance of the cured product obtained by curing the resin composition. amount. In the case of organic flame retardants, In general, it is preferable to use in the range of 1 mass part to 20 mass parts with respect to a total of 100 mass parts of resin components including an organic flame retardant in the resin composition; in the case of an inorganic flame retardant, It is preferable to use in the range of 10 mass parts - 300 mass parts with respect to a total of 100 mass parts of resin components.

When using the resin composition of the present invention, other additives may be added depending on the purpose. Examples of other additives include various silicone oils, thermoplastic resins, synthetic rubbers such as nitrile-butadiene rubber (NBR), and leveling agents. The other additives are preferably used in a range of 0.0001 parts by mass to 5 parts by mass in a total of 100 parts by mass of the other additives in the resin composition and the resin component.

(melt mixing step)

The resin composition of the present invention is produced by a melt-mixing step, which contains (A) polymaleimide compound, (B) benzoxazine, (C) epoxy resin, and ( D) The resin mixture of lavone resin is heated and mixed in a molten state. A usual mixing device can be used in the melt mixing step. As the mixing device, a kneader, a twin-shaft kneader, and the like are preferable. The temperature at the time of melt mixing should just be more than the melting temperature of a resin mixture and 400 degreeC or less, More preferably, it is 130-230 degreeC, More preferably, it is 150-210 degreeC. The melt mixing step is usually performed for about 0.1 minutes to 10 minutes. As described above, in order to obtain a resin composition with good solubility in a low-boiling point solvent over a wide melting temperature range in the melt-mixing step, it is preferable to use the average of the number n of repeating units in formula ( ₁ ) (A) The polymaleimide compound whose value is 0.01-5.

The resin composition of the present invention is obtained by cooling by natural cooling or forced cooling after the melt-mixing step.

As a cooling method, it can select suitably from a well-known method, and can use it. For example, a method of natural cooling in an environment of 5°C to 100°C, or a method of forced cooling using a refrigerant of -20°C to 80°C can be used. In addition, after melting and mixing, it is also possible to adopt a method of placing in an environment of 30° C. to 300° C. in a thermostat, and then cooling.

After cooling, the obtained resin composition is pulverized and stored in a dry state (dry), so that it can be used in a subsequent step as a solid resin composition.

In the melt-mixing step, at least a part of (A) polymaleimide compound contained in the resin mixture is modified by reacting with other components in the resin mixture. Thereby, a resin composition with high heat resistance, low dielectric properties and good solubility in low boiling point solvents can be prepared.

From the viewpoint of making the solubility in low-boiling point solvents good, the polymaleimide compound (also appropriately referred to as "residual maleimide") remaining in the resin composition produced by the melt-mixing step The amine compound") is preferably 42 parts by mass or less, more preferably 40 parts by mass or less, in 100 parts by mass of the resin component.

From the viewpoint of improving the solubility of the modified resin composition after the melt-mixing step in a low-boiling-point solvent, it is preferably 100 parts by mass of the polymaleimide compound in the resin mixture before the melt-mixing step Among them, the polymaleimide compound remaining as a residual maleimide compound in the resin composition after the melt mixing step is 30 to 60 parts by mass, more preferably 40 to 50 parts by mass.

(varnish)

The varnish of the resin composition of the present invention is obtained by dissolving the resin composition obtained by the above-mentioned production method in a solvent having a boiling point of 120° C. or lower and a relative dielectric constant of 10 to 30.

Examples of solvents having a boiling point of 120°C or lower and a relative dielectric constant of 10 to 30 include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ether solvents such as propylene glycol monomethyl ether, ethanol , 1-propanol, 2-propanol, 1-butanol and other alcohol-based solvents. In consideration of handleability and the like, it is preferable to use a ketone-based solvent among the exemplified solvents. These solvents may be used alone or in combination of two or more. In addition, solvents other than the solvents exemplified above may be contained.

The content of the resin composition in 100 parts by mass of the varnish is usually 40 to 80 parts by mass, preferably 50 to 70 parts by mass. The varnish can be obtained by dissolving a resin composition in a solvent at normal temperature (room temperature) or under heating. When dissolving the above-mentioned resin composition under heating, although it also depends on the boiling point of the solvent, the general conditions for dissolution are a temperature of about 50°C to 200°C and a time of about 0.1 hour to 24 hours.

The prepreg can be produced by applying or impregnating the above-mentioned varnish to the substrate, followed by drying to remove the solvent.

As the base material, known base materials previously used for prepregs, such as glass nonwoven fabric, glass cloth, carbon fiber cloth, organic fiber cloth, and paper, can be used.

After coating or impregnating the above-mentioned varnish on the above-mentioned substrate, a prepreg is produced through a drying step. However, the coating method, impregnation method, and drying method are not particularly limited, and previously known methods can be used. Drying conditions are appropriately determined according to the boiling point of the solvent used, and the temperature is preferably not too high. Preferably, drying is performed so that the amount of the solvent remaining in 100% by mass of the prepreg becomes 3% by mass or less.

When preparing a prepreg, resins other than the above-mentioned resin composition may be added to the varnish. As said resin, polyphenylene ether resin etc. are mentioned. From the viewpoint of imparting high heat resistance, low relative permittivity, and low dielectric loss tangent to a cured product obtained by curing a prepreg, polyphenylene ether resin is preferred. From the same point of view, the preparation of prepreg The amount of the polyphenylene ether resin to be added when condensing is preferably 10 to 100 parts by mass, more preferably 10 to 50 parts by mass, with respect to 100 parts by mass of the resin component of the resin composition of the present invention, and further Preferably it is 20 to 40 parts by mass. As a commercially available polyphenylene ether resin, SA90, SA120, SA9000 (product name, SABIC JAPAN LLC make), etc. are mentioned.

The resin composition of the present invention is suitable for use in printed wiring boards, and the present invention can be implemented as a molded article obtained by curing the resin composition. Examples of molded products include cured products obtained by curing only the resin composition, composite materials and laminates obtained by compounding other raw materials.

Composite materials and laminates can be obtained by heating and hardening one sheet of prepreg under pressure with a hot press, or by laminating multiple sheets of prepreg and heating under pressure to integrate change. The heating and pressing conditions in the manufacture of composite materials are not particularly limited. The heating temperature is 100°C~300°C, preferably 150°C~250°C, the pressure is 10kg/cm ² ~100kg/cm ² , and the heating and pressing time is 10 Minutes ~ 300 minutes or so.

Metal foils or metal plates can be laminated and integrated on one side or both sides of the laminated material to form a laminated body that can be used for multilayer printed wiring boards and the like. Such a laminate can be produced by laminating metal foil or metal plate on one or both sides of a single prepreg and hot pressing, or laminating metal foil or metal plate on a multi-sheet prepreg. One or both sides of the outermost layer of the prepreg are hot-pressed to heat and harden the prepreg to achieve integration.

As the metal foil or metal plate, copper, aluminum, iron, stainless steel or the like can be used. For example, a laminate using copper as a metal foil is a copper clad laminate (CCL). The conditions during heating and hardening are preferably the same as those during the manufacture of composite materials. same. Moreover, it can also be set as the build-up board for multilayer printed wiring boards using an inner layer core material.

The present invention can also be implemented as an adhesive, sealant, and paint containing the above-mentioned resin composition.

[Example]

Hereinafter, although an Example is shown and this invention is demonstrated, this invention is not limited to these Examples. The test methods and raw materials used in Examples and Comparative Examples are as follows.

1. Test method

[solvent solubility]

Mix 60 parts by mass of the measurement sample (resin composition) and 40 parts by mass of methyl ethyl ketone (solvent) at room temperature, apply ultrasonic vibration for a predetermined time, and use the following criteria to visually observe the ultrasonic vibration. The dissolution state after sonic vibration was evaluated.

○: Becomes a transparent liquid within 1 hour (at room temperature)

△: Becomes a transparent liquid within 5 hours (at room temperature)

×: Liquid or semi-liquid state (at room temperature) that is still cloudy after 5 hours

[Glass transition point (Tg)]

[Thermal expansion coefficient: CTE (ppm/℃)]

The cured product obtained by curing the resin composition was cut into a predetermined size, and used as a sample for glass transition point measurement. The TMA (Thermomechanical Analysis) method was used under the following conditions to measure the glass transition point (temperature, °C) and coefficient of thermal expansion (CTE) of the sample.

A measuring machine: Thermo plus made by RIGAKU Corporation TMA8310

Sample size: width (length) 5mm × length (horizontal) 5mm × height 4mm

Gas atmosphere: Nitrogen (N ₂ )

Measuring temperature: 30℃~350℃

Heating rate: 10°C/min.

Measurement Mode: Compression

[Thermal weight change]

According to JIS K7120, the cured product is heated from 30°C at a rate of 10°C per minute, and the temperature at which the mass decreases by 1% (Td(1%)) and the temperature at which the mass decreases by 5% (Td(5%)) are measured.

[Relative permittivity (Dk), dielectric loss tangent (Df)]

Measurement was carried out at 1 GHz by the cavity resonator method.

2. Raw material

(A) polymaleimide compound

‧BMI-2300 (product name, manufactured by Daiwa Chemical Industry Co., Ltd., polyphenylmethane polymaleimide)

‧BMI-4000 (product name, manufactured by Daiwa Chemical Industry Co., Ltd., bisphenol A diphenyl ether bismaleimide)

(B) Benzoxazine compounds

‧BZO: (P-d type) benzoxazine (manufactured by Shikoku Chemical Co., Ltd.) (C) epoxy resin

‧VG3101L (product name, manufactured by Pulin Technology Co., Ltd., high heat-resistant trifunctional epoxy resin)

‧ESN-475V (product name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., α-naphthol aralkyl type epoxy resin represented by the following formula (6)

(D) Lavenderone resin

‧G-90 (product name, manufactured by Nippon Chemical Co., Ltd., solid at room temperature, softening point 90°C, weight average molecular weight 770)

‧H-100 (product name, manufactured by Nippon Chemical Co., Ltd., solid at room temperature, softening point 100°C, weight average molecular weight 710)

‧L-5 (product name, manufactured by Nippon Chemical Co., Ltd., liquid at room temperature, weight average molecular weight 160)

(E) Bisphenol A cyanate

‧Monomer: Monomer of bisphenol A cyanate (product name: Triazine, manufactured by Mitsubishi Gas Chemical Co., Ltd., CAS No.1156-51-0, 2,2-bis(4- cyanatophenyl)propane)

‧Polymer: (homo) polymer of bisphenol A type cyanate (product name: TA1500, manufactured by Mitsubishi Gas Chemical Co., Ltd., CAS No.1156-51-0, 25722-66-1, 2,2- Homopolymer of bis(4-cyanatophenyl)propane)

(other ingredients)

‧SA120: (product name, manufactured by SABIC Innovative Plastic, polyphenylene ether)

(Examples 1-5, Comparative Examples 1-4)

Using a biaxial mixing (kneading) machine, the ratio (parts by mass) shown in Table 1 The resin mixture is melt-mixed (melt-kneaded) to prepare a resin composition. The conditions of the melt-mixing step were set at a cylinder temperature of 270° C. and a resin composition temperature of 185° C. to 195° C. (the temperature at the outlet of the resin composition of the twin-screw mixer). Using the twin-shaft mixer used in this example, the following resin composition was successfully prepared under the above-mentioned conditions. The above-mentioned resin composition was obtained by mixing 100 parts by mass of (A) bismaleimide contained in the resin mixture. 30 to 60 parts by mass of the resin remain in the resin composition without polymerization, and the solubility in methyl ethyl ketone is high.

45 parts by mass of the resin composition prepared as described above and 55 parts by mass of the solvent were mixed under normal temperature conditions to prepare a varnish of the resin composition.

Examples 1 to 5 and Comparative Examples 1 to 2 are varnishes in which polyphenylene ether (SA120) is added in a ratio of 50 parts by mass to 100 parts by mass of the resin composition (resin component) in the varnish, and are formed in one layer A (1Ply) prepreg was prepared by impregnating glass cloth 2116. In Comparative Examples 3 and 4, a prepreg was prepared by directly impregnating the glass cloth 2116 with the varnish in one layer without adding polyphenylene ether to the varnish. The prepregs of each example and comparative example were cured under the conditions of pressing: 180°C × 30kg/cm ² × 1 hour, and main curing conditions: 230°C × 2 hours. Glass transition point (Tg), relative permittivity (Dk), and dielectric loss tangent (Df), and the measurement results are shown in Table 1.

From the results in Table 1, the following conclusions can be deduced.

By using a prepreg of a resin composition prepared by melting a resin mixture containing a lavone resin, a high heat resistance (Tg), a low relative dielectric constant (Dk) and a low The dielectric loss tangent (Df) of hardened products.

Compared with the lavone resin which is liquid at normal temperature, the lavone resin which is granular (solid) at normal temperature and has a weight average molecular weight of 800 or less is useful for obtaining a lower relative dielectric constant (Dk) and a higher It is more effective for hardened products with low dielectric loss tangent (Df).

To further reduce the relative permittivity (Dk) and dielectric loss tangent (Df) of the cured product, it is effective to use lavone resin and (E) bisphenol A type cyanate in combination.

Regarding (E) bisphenol A type cyanate, monomers are more effective in reducing the dielectric loss tangent of cured products than polymers.

Using a biaxial kneader, the resin mixtures of the ratios (parts by mass) shown in Table 2 and Table 3 were melt-mixed to prepare a resin composition. The resin composition was cured at 230°C for 4 hours, and the cured product was evaluated, and the evaluation result The results are shown in Table 2 and Table 3. The preparation conditions of the resin composition were the same as in Table 1.

As shown in Table 2, the relative dielectric constant and dielectric loss tangent can be reduced while maintaining the high heat resistance of the cured product by blending (D) lavone resin.

From the results in Table 3, the following conclusions can be deduced.

By using a compound represented by formula (1) in which the average value of n ₁ is 0.01 to 5, X ¹ is a group represented by -CH ₂ -, a is 0, and b is 0 polymaleimide The amine compound BMI-2300 becomes a resin composition with good solubility in methyl ethyl ketone.

By using a lavone resin with a softening point of 85°C to 105°C and a weight average molecular weight of 700 to 800, a relatively small amount of about 1 to 3 parts by mass can be formulated per 100 parts by mass of the resin component of the resin composition , Obtain a cured product with higher heat resistance (Tg), lower dielectric constant (Dk) and lower dielectric loss tangent (Df).

[industrial availability]

The present invention is a resin composition that becomes a hardened product having high heat resistance and low dielectric properties (low relative permittivity, low dielectric loss tangent), and the above-mentioned resin composition can be used as a Adhesives, sealants, coatings, moldings, laminates, and raw materials for printed wiring boards.

Claims (8)

A kind of resin composition, it is used for printed wiring board, and it is to contain (A) polymaleimide compound, (B) benzoxazine, (C) epoxy resin, (D) lavone resin, and (E) a resin mixture of bisphenol A type cyanate is melted, and the content of the (A) polymaleimide compound is 40 mass parts in 100 mass parts of resin components of the resin mixture Part～70 mass parts, the content of described (B) benzoxazine is 10 mass parts～30 mass parts, the content of described (C) epoxy resin is 10 mass parts～30 mass parts, described (D) The content of the lavone resin is 0.5 parts by mass to 4 parts by mass, and the content of the (E) bisphenol A type cyanate is 3 parts by mass to 7 parts by mass. The resin composition as described in item 1 of the scope of the patent application, wherein the softening point of the (D) lavone resin is below 100°C, and the weight average molecular weight is below 850. The resin composition as described in Item 1 of the scope of the patent application, wherein the (A) polymaleimide compound is represented by formula (1),

In the formula ( ₁ ), n1 is an integer of 0 to 10, and X1 is each independently an alkylene group having a carbon number of ¹ to 10, a group represented by the following formula (2), "- A group represented by SO ₂ -", a group represented by "-CO-", an oxygen atom or a single bond, R ¹ are each independently a hydrocarbon group having 1 to 6 carbons, and a is each independently 0 to 4 The following integers, b are independently an integer of not less than 0 and not more than 3, and the average value of the number _n of repeating units is not less than 0.01 and not more than 5;

In the formula (2), Y is a hydrocarbon group having an aromatic ring having 6 to 30 carbon atoms, and n ₂ is an integer of 1 to 3. The resin composition as described in item 1 of the scope of the patent application, wherein the (C) epoxy resin is an α-naphthol type epoxy resin. The resin composition described in Claim 1 of the patent application is obtained by melting each component in the following manner: 100 mass of the (A) polymaleimide compound contained in the resin mixture Parts, the (A) polymaleimide compound remaining as a residual maleimide compound in the resin composition after the melt-mixing step is 30 parts by mass to 60 parts by mass. A varnish comprising (A) polymaleimide compound, (B) benzoxazine, (C) epoxy resin, (D) lavone resin, and (E) bisphenol A type The resin composition obtained by melting the resin mixture of cyanate is dissolved in a solvent with a boiling point of 120° C. or lower and a dielectric constant of 10 to 30. In 100 parts by mass of the resin component of the resin mixture, the ( A) the content of polymaleimide compound is 40 mass parts～70 mass parts, the content of described (B) benzoxazine is 10 mass parts～30 mass parts, the content of described (C) epoxy resin 10 parts by mass to 30 parts by mass, The content of (D) lavone resin is 0.5 parts by mass to 4 parts by mass, and the content of (E) bisphenol A cyanate is 3 parts by mass to 7 parts by mass. A kind of laminated board, it is to use will contain (A) polymaleimide compound, (B) benzoxazine, (C) epoxy resin, (D) lavone resin, and (E) bisphenol A The resin composition obtained by melting the resin mixture of polycyanate is manufactured, and the content of the (A) polymaleimide compound is 40 parts by mass to 70 parts by mass in 100 parts by mass of the resin component of the resin mixture. parts by mass, the content of the (B) benzoxazine is 10 parts by mass to 30 parts by mass, the content of the (C) epoxy resin is 10 parts by mass to 30 parts by mass, and the content of the (D) lavone The content of the resin is 0.5 parts by mass to 4 parts by mass, and the content of the (E) bisphenol A type cyanate is 3 parts by mass to 7 parts by mass. A printed wiring board using a compound containing (A) polymaleimide compound, (B) benzoxazine, (C) epoxy resin, (D) lavone resin, and (E) bisphenol The resin composition obtained by melting the resin mixture of type A cyanate is produced, and in 100 parts by mass of the resin component of the resin mixture, the content of the (A) polymaleimide compound is 40 parts by mass~ 70 parts by mass, the content of the (B) benzoxazine is 10 parts by mass to 30 parts by mass, the content of the (C) epoxy resin is 10 parts by mass to 30 parts by mass, and the content of the (D) lavender The content of the ketone resin is 0.5 parts by mass to 4 parts by mass, and the content of the (E) bisphenol A type cyanate is 3 parts by mass to 7 parts by mass.