WO2023276379A1

WO2023276379A1 - Resin composition, varnish, laminated plate, printed wiring board, and molded product

Info

Publication number: WO2023276379A1
Application number: PCT/JP2022/015425
Authority: WO
Inventors: 達也川崎; 侑花仲澤; 健加藤; 珠奈松田
Original assignee: 株式会社プリンテック
Priority date: 2021-06-29
Filing date: 2022-03-29
Publication date: 2023-01-05
Also published as: KR20240026127A; CN117500880A; JPWO2023276379A1; TW202319481A

Abstract

Provided is a resin composition obtained by melting a resin mixture containing a bismaleimide compound (A), the composition forming a cured object to be used in electronic and electrical components as a laminated plate, printed wiring board, adhesive, sealant, coating material, molded product, or the like having high heat resistance and low dielectric properties (a low dielectric constant and low dielectric tangent). The bismaleimide compound (A) comprises an aliphatic bismaleimide compound represented by formula (1) and an aromatic bismaleimide compound represented by formula (2). (In formula (1), R1 is a C6-12 alkylene group.) (In formula (2), R2 is a C6-30 hydrocarbon group having an aromatic ring, each X1 is independently an oxygen atom or a single bond, R3 and R4 are C1-6 hydrocarbon groups, and a and b are each an integer of 0-3.)

Description

Resin compositions, varnishes, laminates, printed wiring boards and molded products

The present invention is a resin having low dielectric properties (low dielectric constant, low dielectric loss tangent), which is used as laminates, printed wiring boards, adhesives, sealants, paints, molded articles, etc. in electronic and electrical parts. Regarding the composition.

　Conventionally, thermosetting resins such as epoxy resins, polyimide resins, unsaturated polyester resins, and phenolic resins have been used as heat-resistant resins in the field of electronic materials. These thermosetting resins are used properly according to their uses and characteristics. Among these resins, polyimide resins are particularly excellent in heat resistance and moisture-heat resistance (heat resistance after moisture absorption), and are therefore widely used in applications requiring high heat resistance. Modified polyimide resins are also used, which are improved in performance by combining polyimide resins with other resins such as epoxy resins.

In the field of semiconductor substrates, mounting methods that directly mount semiconductor chips onto substrates are becoming more popular. For this reason, materials used for semiconductors are required to have high heat resistance to withstand high-temperature treatments in the mounting process. Epoxy resins are widely used as semiconductor materials, and studies have been made to meet the demand for improved heat resistance, and resins with excellent heat resistance have been proposed. For example, Patent Document 1 describes a resin composition obtained by melting a component containing a polymaleimide compound.

International publication WO2020/161926

2. Description of the Related Art In recent years, along with the improvement in performance, capacity, and speed of various electronic devices, the frequency of electrical signals is becoming higher. Increasing the frequency of electrical signals is advantageous for increasing the speed and capacity of communication, but there is a risk that signals will be attenuated due to increased dielectric loss and reliability will decrease. Therefore, there is a demand for further improvement in low dielectric properties as properties of resin compositions suitable for substrates compatible with high frequencies for next-generation communications.
Accordingly, an object of the present invention is to provide a resin composition containing a bismaleimide compound with further improved low dielectric properties. Another object of the present invention is to provide a resin composition containing a bismaleimide compound that has good solubility and curability in low boiling point solvents and is easy to handle.

The resin composition of the present invention is a resin composition obtained by melting a resin mixture containing (A) a bismaleimide compound, wherein the (A) bismaleimide compound is a fat represented by formula (1) A resin composition comprising a group bismaleimide compound and an aromatic bismaleimide compound represented by formula (2).

(In Formula (1), R ¹ is an alkylene group having 6 to 12 carbon atoms.)

(In Formula (2), R ² is a hydrocarbon group having 6 to 30 carbon atoms and having an aromatic ring, X ¹ is each independently an oxygen atom or a single bond, and R ³ and R ⁴ each have 1 carbon atom. is a hydrocarbon group of 6 or less, and a and b are integers of 0 or more and 3 or less.)

By containing the aliphatic bismaleimide compound and the aromatic bismaleimide compound in the resin composition, it is possible to improve the heat resistance of the cured product while maintaining low dielectric properties. Therefore, it is possible to provide a resin composition having excellent low dielectric properties (low dielectric constant, low dielectric loss tangent) while maintaining heat resistance, which generally has a trade-off relationship with low dielectric properties.

Graph showing GPC measurement results for the resin composition of Example 67 with a synthesis time of 2.5 minutes

<First Embodiment>
(resin composition)
The resin composition of the present embodiment contains (A) 30 to 65 parts by mass of a bismaleimide compound, (B) 5 to 25 parts by mass of a cumarone resin, and (C) an amine compound 1 in 100 parts by mass of the resin component of the resin mixture. It is a resin composition obtained by melting a resin mixture containing up to 30 parts by mass. The components (A) to (C) and other components that the resin composition may contain are described below. In the present invention, the numerical range "A to B" means "above A and below B". A mixture before melt-mixing each component is called a "resin mixture", and a mixture after cooling after melt-mixing is called a "resin composition".

(A) Bismaleimide compound The bismaleimide compound is a compound having two maleimide groups and contains an aliphatic bismaleimide compound represented by the formula (1) shown in the section of Means for Solving the Problems. there is By using the aliphatic bismaleimide compound, the low dielectric properties of the cured product of the resin composition are improved. In addition, a cured product having a low water absorption rate after being cured by hot pressing in an absolutely dry state is obtained. For this reason, the cured product can stably maintain the low dielectric properties immediately after production even after a long period of time has passed since the production.

In the aliphatic bismaleimide compound, R ¹ is preferably an alkylene group having 7 to 11 carbon atoms, and R ¹ is preferably an alkylene group having 9 carbon atoms, from the viewpoint of obtaining a cured product with low dielectric properties. more preferred. Moreover, an aliphatic bismaleimide compound having a melting point of 120° C. or less is preferable. Examples of such aliphatic bismaleimide compounds include 1,6-bismaleimide(2,2,4-trimethyl)hexane, hexamethylenediaminebismaleimide, N,N'-1,2-ethylenebismaleimide, N, N'-1,3-propylenebismaleimide, N,N'-1,4-tetramethylenebismaleimide and the like. Examples of commercially available aliphatic bismaleimide compounds include BMI-TMH (product name, manufactured by Daiwa Kasei Kogyo Co., Ltd.).

The bismaleimide compound further contains an aromatic bismaleimide compound represented by formula (2) shown in the section of Means for Solving the Problems. An aromatic bismaleimide compound having a melting point of 130° C. or higher is more preferable. By containing the aliphatic bismaleimide compound and the aromatic bismaleimide compound in the resin composition, it is possible to improve the heat resistance of the cured product while maintaining low dielectric properties. In addition, since solvent solubility and curability are improved, the resin composition can be easily brought into an appropriate B-stage state during prepreg formation and has excellent handleability.

Examples of the aromatic bismaleimide compound represented by formula (2) include 4,4′-diphenylmethanebismaleimide, bisphenol A diphenyletherbismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′- diphenylmethane bismaleimide and the like. Commercially available aromatic bismaleimide compounds include BMI-1000, BMI-4000, BMI-5000, and BMI-5100 (all product names, manufactured by Daiwa Kasei Kogyo Co., Ltd.).

In the aromatic bismaleimide compound represented by formula (2), R ² in formula (2) is preferably a group represented by formula (3) from the viewpoint of heat resistance of the cured product. Examples of such aromatic bismaleimide compounds include bisphenol A diphenyl ether bismaleimide.

From the viewpoint of improving the low dielectric properties and heat resistance of the cured product and improving the solubility in low boiling point solvents, the mass ratio of the content of the aliphatic bismaleimide compound to the content of the aromatic bismaleimide compound is The aliphatic bismaleimide compound: aromatic bismaleimide compound is preferably 3.0:7.0 to 7.0:3.0, more preferably 4.0:6.0 to 6.0:4.0, 4.5:5.5 to 5.5:4.5 are more preferred.

The content of the bismaleimide compound in 100 parts by mass of the resin component of the resin mixture is 30 to 65 parts by mass. The content of the bismaleimide compound in 100 parts by mass of the resin component is more preferably 40 to 62 parts by mass, more preferably 50 to 60 parts by mass, from the viewpoint of achieving both high heat resistance and low dielectric properties of the cured product. Two or more kinds of bismaleimide compounds are used in combination. Components (B) to (I) and other components described below can be used singly or in combination of two or more.

(B) Coumaron resin Coumaron resin is a copolymer resin composed mainly of coumarone, indene and styrene. Commercially available products include G-90, V-120, L-5, L-20, H-100 (all product names, manufactured by Nichinori Kagaku Co., Ltd.). A coumarone resin having a softening point of 100° C. or less is preferable from the viewpoint of low dielectric properties of the cured product. From the same point of view, the weight average molecular weight is preferably 850 or less, more preferably 800 or less. A coumarone resin that is beaded (solid) at ambient temperature is preferred over one that is liquid at ambient temperature.

The content of the coumarone resin in 100 parts by mass of the resin component of the resin mixture is preferably 5 to 25 parts by mass, more preferably 10 to 20 parts by mass, more preferably 13 to 18 parts by mass, from the viewpoint of high heat resistance and low dielectric properties of the cured product. Parts by mass are more preferred.

From the viewpoint of solubility in low-boiling solvents and stability in a dissolved state, the content of the coumarone resin is more preferably 15 parts by mass or more, more preferably 20 parts by mass or more, relative to 100 parts by mass of the bismaleimide compound (A). More preferred. From the viewpoint of obtaining a cured product with good heat resistance, the content of the coumarone resin is more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less with respect to 100 parts by mass of the bismaleimide compound.

(C) Amine compound The aliphatic bismaleimide compound represented by Formula (1) has a problem that once dissolved, it does not solidify and becomes liquid. In order to solve this handling problem, the resin composition of the present embodiment contains 1 to 30 parts by mass of an amine compound in 100 parts by mass of the resin component in addition to the aliphatic bismaleimide compound. The content of the amine compound is preferably 2 to 15 parts by mass, more preferably 3 to 8 parts by mass, from the viewpoints of curability of the resin composition and low dielectric properties and heat resistance of the cured product.

Examples of the amine compound include aromatic amines such as bisaniline and 1,3-bis(3-aminophenoxy)benzene, and bisaniline is preferable from the viewpoint of making a resin composition with good handling properties as a prepreg. Commercially available products include Bisaniline M and Bisaniline-P (manufactured by Mitsui Chemicals Fine Co., Ltd.); ODA, BODA, BAPP, HFBAPP, BAPB, TPE-M and TPE-Q (both manufactured by Seika Co., Ltd.); Kayabond C -200S (manufactured by Nippon Kayaku Co., Ltd.), BAN (manufactured by Nippon Kayaku Co., Ltd.), and the like.

Bisaniline is more preferably an aromatic amine represented by formula (4).

(In Formula (4), R ⁵ is a hydrocarbon group having 6 to 30 carbon atoms and having an aromatic ring, and each X ¹ is independently an oxygen atom or a single bond.)

Bisanilines represented by formula (4) include 4,4′-[dimethylmethylenebis(4,1-phenyleneoxy)]bisaniline and 4,4′-[biphenyl-4,4′-diylbis(oxy)]. bisaniline, bisaniline-M, bisaniline-P and the like. Bisaniline represented by formula (4) includes commercially available products such as Bisaniline M and Bisaniline-P (manufactured by Mitsui Chemicals Fine Co., Ltd.); BODA, BAPP and BAPB (manufactured by Seika Co., Ltd.).

(D) Benzoxazine compound The benzoxazine compound may have at least one or more benzoxazine rings in the molecule, but dihydrobenzoxazine compounds represented by the following general formula (5) or (6) A pd-type dihydrobenzoxazine represented by the following general formula (6) is preferred, and more preferred.

(In formulas (5) and (6), R ⁶ and R ⁷ represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 3 carbon atoms.)

The content of the benzoxazine compound in 100 parts by mass of the resin component of the resin mixture is 5 to 20 parts by mass from the viewpoint of the high heat resistance and low dielectric properties of the cured product and the solubility of the resin composition in low boiling point solvents. is preferred, 10 to 20 parts by weight is more preferred, and 15 to 20 parts by weight is even more preferred.

From the viewpoint of solubility in a low boiling point solvent and stability in a state of being dissolved in a low boiling point solvent, the content of the benzoxazine compound is more preferably 15 parts by mass or more, more preferably 20 parts by mass with respect to 100 parts by mass of the bismaleimide compound. The above is more preferable. From the viewpoint of obtaining a cured product with good heat resistance, the content of the benzoxazine compound is more preferably 50 parts by mass or less, still more preferably 40 parts by mass or less with respect to 100 parts by mass of the bismaleimide compound.

(E) Bisphenol A-type cyanate ester A bisphenol A-type cyanate ester is a bisphenol A-type cyanate ester (triazine) that forms a triazine ring and cures. Curability of the resin mixture is improved by containing the bisphenol A type cyanate ester. Bisphenol A-type cyanate esters include monomers and (homo)polymers (polymers), and bisphenol A-type cyanate ester monomers are preferred from the viewpoint of obtaining cured products with excellent low dielectric properties.

From the viewpoint of low dielectric properties of the cured product and prevention of component precipitation at the prepreg stage, the content of the bisphenol A-type cyanate ester in 100 parts by mass of the resin component of the resin mixture is preferably 0.1 to 3 parts by mass. 0.5 to 2 parts by weight is more preferred, and 0.7 to 1.3 parts by weight is even more preferred.

(F) Epoxy resin The resin composition may contain an epoxy resin, if necessary, for the purpose of complementing various properties such as flame retardancy. The inclusion of the epoxy resin may improve the interlaminar adhesion and insulating properties of a laminate obtained by stacking prepregs, which are sheets impregnated with a resin composition, on a base material and performing pressurization and heat treatment.

The epoxy resin may be a compound having an epoxy group, but from the viewpoint of achieving both heat resistance and low dielectric properties of the cured product, a biphenyl aralkyl type epoxy resin, an epoxy resin containing a naphthalene ring, and having three epoxy groups. Compounds and the like are preferred. As the epoxy resin containing a naphthalene ring, an α-naphthol type epoxy resin is preferable. Examples of commercially available epoxy resins containing naphthalene rings include ESN-475V (product name, α-naphthol type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) in which each naphthalene ring has two epoxy groups. Moreover, VG3101L (product name, manufactured by Printec Co., Ltd.) can be mentioned as a commercially available high heat-resistant trifunctional epoxy resin.

Epoxy resins other than the above include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin. , triphenylol-type epoxy resins, dicyclopentadiene-type epoxy resins, and the like.

However, the heat resistance of the cured product is improved by suppressing the content of the bisphenol A type epoxy resin in the resin component of the resin mixture. Therefore, from the viewpoint of improving the heat resistance of the cured product, it is preferable that the resin mixture does not contain a bisphenol A type epoxy resin. Here, "not containing a bisphenol A type epoxy resin" means substantially not containing it, that is, not containing an amount of a bisphenol A type epoxy resin that affects the properties of the resin mixture. For example, if the content of the bisphenol A type epoxy resin in 100 parts by mass of the resin component of the resin mixture is 1 part by mass or less, depending on the case, 0.3 parts by mass or less or 0.1 part by mass or less, a resin with low dielectric properties It has no effect on the properties of the mixture.

The content of the epoxy resin in 100 parts by mass of the resin component of the resin mixture is preferably 1 to 12 parts by mass, more preferably 2 to 10 parts by mass, and 3 to 8 parts by mass, from the viewpoint of high heat resistance and low dielectric properties of the cured product. Parts by mass are more preferred.

<Second embodiment>
(resin composition)
The resin composition of the present embodiment is a resin composition obtained by melting a resin mixture containing (A) a bismaleimide compound, wherein (A) the bismaleimide compound is and an aliphatic bismaleimide compound represented by formula (1) and an aromatic bismaleimide compound represented by formula (2). By containing the aliphatic bismaleimide compound and the aromatic bismaleimide compound, the resin composition can improve the heat resistance of the cured product while maintaining the low dielectric properties of the cured product. With respect to the bismaleimide compound, description of items common to the first embodiment will be omitted, and different items will be described below.

From the viewpoint of increasing the heat resistance of the cured product, the resin composition is such that the mass ratio of the content of the two types of bismaleimide compounds in the resin mixture is 25:55 as the aliphatic bismaleimide compound:aromatic bismaleimide compound. 45:35 is preferable, and 27:53 to 47:38 is more preferable.

(H) Triallyl isocyanurate The resin composition contains triallyl isocyanurate in the resin mixture from the viewpoint of increasing the solubility in low boiling point solvents. The content of triallyl isocyanurate in 100 parts by mass of the resin component of the resin mixture is preferably 16 to 26 parts by mass, more preferably 18 to 24 parts by mass. By containing triallyl isocyanurate, the resin composition can be prepared as a 60% by mass methyl ethyl ketone solution and has high solubility in a low boiling point solvent. Commercial products of triallyl isocyanurate include TAIC (trademark, manufactured by Mitsubishi Chemical Corporation).

The resin composition preferably further contains an amine compound and a carboxylic acid dianhydride from the viewpoint of making the state in the B-stage a solid rather than a viscous solid so that it is easy to handle.

(C) Amine Compound The same amine compound as in the first embodiment can be used as the amine compound. When the resin mixture contains triallyl isocyanurate, the content of the amine compound in 100 parts by mass of the resin component of the resin mixture is is preferably 8 to 20 parts by mass, more preferably 10 to 18 parts by mass, even more preferably 12 to 16 parts by mass.

(I) Carboxylic acid dianhydride Examples of tetracarboxylic acid dianhydride include BPADA, 6FDA, SFDA, BzDA: Enehyde (trademark, manufactured by ENEOS), TAHQ (see Examples for abbreviations), and the like. From the viewpoint of making a resin composition that becomes solid in the B stage and has high solubility in a low boiling point solvent, when the resin mixture contains triallyl isocyanurate, carboxylic acid dianhydride in 100 parts by mass of the resin component of the resin mixture The content is preferably 10 to 35 parts by mass, more preferably 15 to 30 parts by mass, even more preferably 20 to 27 parts by mass.

(G) Curing Accelerator When using the resin composition of the present invention described as the first and second embodiments, a curing accelerator may be added. Timing for adding the curing accelerator includes, for example, when the resin composition is dissolved in a solvent to form a varnish, when the varnish is prepregized, or when a substrate or laminate is produced. The following description is common to the resin compositions of the first and second embodiments.

Curing accelerators include, for example, imidazoles such as dicumyl peroxide, 4,4'-diaminodiphenylmethane, 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-heptylimidazole; triethanolamine, triethylenediamine, Amines such as N-methylmorpholine; Organic phosphines such as triphenylphosphine and tritolylphosphine; Tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triethylammonium tetraphenylborate; ,4,0) undecene-7 and its derivatives; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, tin oleate, manganese naphthenate, cobalt naphthenate and cobalt octylate. An organic peroxide, an azo compound, or the like can be used in combination as necessary.

The curing accelerator is blended in the varnish or prepreg at a content that gives the desired gelling time. For example, the curing accelerator is used in the range of 0.01 to 5 parts by mass with respect to the total 100 parts by mass of the resin components contained in the resin composition.

The resin composition and the resin mixture before melt mixing may contain components other than the above (A) to (I). For example, organic or inorganic fillers can be used to cure the resin composition to obtain a substrate for molding. Examples of fillers include oxides such as silica, diatomaceous earth, alumina, zinc chloride, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites; calcium hydroxide, magnesium hydroxide, hydroxide Hydroxides such as aluminum and basic magnesium carbonate; carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite and hydrotalcite; sulfates such as calcium sulfate, barium sulfate and gypsum fiber; calcium silicate (wollastonite, xonotlite), talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silicates such as silica-based balun; aluminum nitride, boron nitride, nitride Nitrides such as silicon; Carbons such as carbon black, graphite, carbon fiber, carbon balloons, and charcoal powder; Other metal powders, potassium titanate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber , zinc borate, various magnetic powders, slag fibers, and ceramic powders.

The shape of the filler is preferably spherical or scaly. If necessary, use a silane coupling agent with two or more different reactive groups in the molecule (one reactive group that chemically reacts with inorganic materials, the other that chemically reacts with organic materials). You may

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

A flame retardant can be added to the resin composition as needed. Flame retardants include organic flame retardants such as bromine compounds such as brominated epoxy resins and phosphorus compounds such as condensed phosphoric acid esters, and inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, tin compounds and antimony compounds. .

In addition, the flame retardant is a content that realizes sufficient flame retardancy (for example, passing the V-0 condition in UL94 standard) without impairing the heat resistance and moist heat resistance of the cured product obtained by curing the resin composition. . In the case of an organic flame retardant, for example, 1 to 20 parts by mass with respect to a total of 100 parts by mass of the resin components including the organic flame retardant in the resin composition. It is used in an amount of 10 to 300 parts by mass.

When using the resin composition, other additives can be added depending on the application. Examples of other additives include various silicone oils, thermoplastic resins, synthetic rubbers such as NBR, and leveling agents. Other additives are used, for example, in a content of 0.0001 to 5 parts by mass in a total of 100 parts by mass of the other additives and the resin component in the resin composition.

(Melting and mixing step)
The resin composition of the present invention is produced by a melt-mixing process in which a resin mixture is heated and mixed in a molten state. Usual mixing means can be used for the melt-mixing step. As a mixing means, a kneader, a twin-screw kneader, or the like is preferable. The temperature during melt-mixing may be the temperature at which the resin mixture melts or higher and 400°C or lower, preferably 130 to 230°C, more preferably 150 to 210°C, and even more preferably 170 to 190°C.

The melt-mixing step is preferably carried out under conditions such that the weight average molecular weight of the resin composition obtained by heating the resin mixture is 1,000 to 2,500, more preferably 1,200 to 1,800. The time for the melt-mixing step is, for example, about 0.1 to 10 minutes, and it is preferable to set conditions such as temperature in the melt-mixing step so as to be about 0.5 to 4 minutes.

After the melt mixing step, the resin composition of the present invention is obtained by cooling by natural cooling or forced cooling. The cooling method can be appropriately selected from known methods. For example, a method of natural cooling in an environment of 0 to 40° C. or a method of forced cooling using a refrigerant can be employed. Further, after melting and mixing, it may be placed in an environment of 30 to 300° C. in a constant temperature device and then cooled. After cooling, the resulting resin composition can be used in subsequent steps as a solid resin composition.

In the melt-mixing step, the aliphatic bismaleimide compound, the aromatic bismaleimide compound, and other components in the resin mixture react with each other, so that at least part of the bismaleimide compound is modified. As a result, a resin composition having high heat resistance, low dielectric properties, good solubility in low boiling point solvents, and good curability can be produced.

From the viewpoint of improving the solubility in low-boiling solvents, it is preferable that the resin composition produced by the melt-mixing process has a component with a molecular weight of 4,500 to 4,800. The ratio of the component having a molecular weight of 4500 to 4800 in 100% by mass of the resin composition is preferably 10 to 20% by mass, more preferably 12 to 18% by mass. The proportion of components with a molecular weight of 4500-4800 can be determined by gel permeation chromatography (GPC) measurement.

(varnish)
The resin composition varnish according to the present invention is obtained by dissolving the resin composition obtained by the above-described production method in a solvent having a boiling point of 120° C. or less and a dielectric constant of 10 to 30.
Examples of solvents having a boiling point of 120° C. or less and a 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 and 2-propanol. , and alcohol solvents such as 1-butanol. Among the exemplified solvents, a ketone solvent is preferably used in consideration of operability and the like. Solvents other than those 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 the resin composition in a solvent at normal temperature (room temperature) or under heating. When dissolving under heating, the conditions for dissolving are, for example, a temperature of about 50 to 200° C. and a time of about 0.1 to 24 hours, depending on the boiling point of the solvent.

A prepreg is produced by coating or impregnating a base material with the above varnish and then drying it to remove the solvent. As the substrate, known substrates used in conventional prepregs, such as glass nonwoven fabric, glass cloth, carbon fiber cloth, organic fiber cloth, and paper, can be used.

After coating or impregnating the base material with the varnish, the prepreg is manufactured through a drying process, but the coating method, impregnation method, and drying method are not particularly limited, and conventionally known methods can be adopted. The drying conditions are appropriately determined according to the boiling point of the solvent used, but too high a temperature is not preferable. It is desirable to dry so that the solvent remaining in 100 parts by mass of the prepreg is 3 parts by mass or less.

A filler other than the resin composition described above may be added to the varnish when producing the prepreg. Examples of fillers include silica particles, alumina particles, and polyphenylene ether resins. From the viewpoint of imparting high heat resistance, low dielectric constant and low dielectric loss tangent to the cured product, the amount of the filler used in preparing the prepreg is 10 to 100 parts per 100 parts by mass of the resin component of the resin composition. Parts by weight are preferred, 10 to 50 parts by weight are more preferred, and 20 to 40 parts by weight are even more preferred. Examples of commercially available silica particles and alumina particle fillers include the ADMAFINE series (product name, manufactured by Admatechs Co., Ltd.), and commercially available polyphenylene ether resins SA90, SA120, and SA9000 (product names, all manufactured by SABIC Japan LLC. ) and the like.

The resin composition of the present invention is suitable for printed wiring boards, and the present invention can be implemented as a molded product obtained by curing the resin composition. Examples of molded articles include cured products obtained by curing only the resin composition, composite materials combined with other raw materials, laminates, and the like.

The composite material and laminate can be obtained by heating and curing one sheet of prepreg under pressure using a hot press or the like, or by laminating a plurality of prepregs and heating and integrating them under pressure. The heating and pressurizing conditions for producing the composite material are not particularly limited, but the heating temperature is 100 to 300° C., preferably 150 to 250° C., more preferably 200 to 250° C., and the pressure is 10 to 100 kg/ cm ² , preferably 20 to 40 kg/cm, and heating/pressing time is 10 to 300 minutes, preferably 30 to 180 minutes.

A laminate that can be used for a multilayer printed wiring board may be obtained by laminating and integrating a metal foil or a metal plate on one or both sides of the laminate. Laminates are produced by laminating a metal foil or metal plate on one or both sides of a single prepreg, or by laminating a metal foil or metal plate on one or both sides of a plurality of laminated prepregs, which is the outermost layer, and then heating. The prepreg is heat-cured by pressing to be integrated.

Copper, aluminum, iron, stainless steel, etc. can be used as the metal foil or metal plate. For example, a laminate using copper as a metal foil is a copper clad laminate (CCL). The conditions for heat curing are preferably the same as the conditions for producing the composite material. Moreover, it is good also as a laminated board for multilayer printed wiring boards using an inner layer core material.
The present invention can also be implemented as adhesives, sealants and paints containing the resin composition described above.

The present invention will be described below with reference to examples, but the present invention is not limited by these examples. Test methods and raw materials used in Examples and Comparative Examples are as follows.

1. Test method [Solvent solubility (MEK solubility)]
60 parts by mass of a measurement sample (resin composition) and 40 parts by mass of methyl ethyl ketone (solvent) are mixed under conditions of 50° C. or less, and the dissolved state after applying ultrasonic vibration for a predetermined time is measured using the following criteria. It was evaluated visually.
◯: Brown transparent liquid at the time of applying ultrasonic vibration for 100 minutes, with no undissolved residue, separation, or turbidity.
x: Undissolved, separated or turbid after applying ultrasonic vibration for 100 minutes.

[Glass transition point (Tg)]
[Thermal expansion coefficient: CTE (ppm/°C)]
A cured product obtained by curing the resin composition was cut (cut out) into a predetermined size and used as a sample for measuring the glass transition point. The glass transition point (temperature, °C) and thermal expansion coefficient (CTE) of the samples were measured using DSC (differential scanning calorimeter) and TMA (thermomechanical analysis) methods under the following conditions.
(DSC)
Measuring instrument: Thermo plus EVO2 DSC8231 manufactured by Rigaku
Sample weight: 5mg
Atmosphere: _N2
Measurement temperature: 30 to 350°C
Temperature rising rate: 10°C/min.
Measurement mode: heat flux type (TMA)
Measuring equipment: Thermo plus TMA8310 manufactured by Rigaku
Sample dimensions: length (vertical) 19 mm x width (horizontal) 5 mm x thickness 0.1 mm
Atmosphere: _N2
Measurement temperature: 30 to 350°C
Temperature rising rate: 10°C/min.
Measurement mode: Tensile

[Dielectric constant (Dk), dielectric loss tangent (Df)]
Immediately after production and 24 hours after production, measurement was performed under 1 GHz or 10 GHz conditions by the cavity resonator method. The measurement by the cavity resonator method gave substantially the same results under the 1 GHz condition and the 10 GHz condition. As samples for measuring relative dielectric constant (Dk) and dielectric loss tangent (Df), A copper clad laminate (CCL) was manufactured using copper as the metal foil. The conditions of the hot press for heating and curing the prepreg for integration were a heating temperature of 230° C., a pressure of 20 kg/cm ² , and a heating and pressurizing time of 120 minutes.

For Examples 1 to 42 and Comparative Examples 1 to 4, relative permittivity (Dk) and dielectric loss tangent (Df) were measured as cured products.
In Examples 43-67 and Comparative Examples 5-7, the copper foil was removed from the CCL, cut into x: y: z = 80 mm × 20 mm × 0.1 mm using a mold, and the ends of the cut out members were sanded. An object to be measured was made smooth by removing burrs using paper or the like. The longitudinal direction of the cut member was x, the lateral direction was y, and the thickness direction was z. Measure the dimensions in the y and z directions at three locations with an interval of 20 mm in the x direction, calculate the average value, and use the values to three decimal places as the dimensions of the object to be measured in the y and z directions. did.

[Water absorption]
The cured products of Examples 66, 67 and Comparative Example 6 were 60 mm in width (vertical) × 60 mm in length (horizontal) × 1.2 mm in height, and the four sides were smoothed. Under the conditions, the weight was measured before and after storage for 48 hours, and the water absorption rate (%) under high temperature and high humidity conditions was evaluated.

[State of B stage (solidification)]
The resin composition was heated to 150 to 200° C., stirred for 3 to 5 minutes in that state, and then sufficiently cooled under room temperature conditions, and the state of the resin was evaluated according to the following criteria.
◯: The resin becomes powder or solid and can be easily recovered.
x: The resin becomes a viscous solid and is difficult to recover.

2. Raw material (A) Polymaleimide compound BMI-TMH (product name, manufactured by Daiwa Kasei Kogyo Co., Ltd., 1,6-bismaleimide-(2,2,4-trimethyl)hexane, melting point 73 to 110°C)
・ BMI-4000 (product name, manufactured by Daiwa Kasei Kogyo Co., Ltd., bisphenol A diphenyl ether bismaleimide, melting point 134 to 163 ° C.)
・BMI-2300 (product name, manufactured by Daiwa Kasei Kogyo Co., Ltd., polyphenylmethane polymaleimide, melting point 70 to 145 ° C.)

(B) coumarone resin G-90 (product name, manufactured by Nikko Chemical Co., Ltd., solid at room temperature, softening point 90°C, weight average molecular weight 770)
(C) Amine compound BAPP (product name, manufactured by Seika Co., Ltd., 2,2-bis[4-(4-aminophenoxy)phenyl]propane)
・ Bisaniline M (manufactured by Mitsui Chemicals Fine Co., Ltd.)
・ Kayabond C-200S (product name, manufactured by Nippon Kayaku Co., Ltd., 4,4'-methylenebis (2,6-dimethylamine))
・ ODA (product name, manufactured by Seika Co., Ltd., 4,4′-diaminodiphenyl ether)
・BAPB (product name, manufactured by Seika Co., Ltd., 4,4′-bis(4-aminophenoxy)biphenyl)
・APB-N (1,3-bis(3-aminophenoxy)benzene)
・BAN (product name, manufactured by Nippon Kayaku Co., Ltd.)

(D) benzoxazine compound BZO: (Pd type) benzoxazine (manufactured by Shikoku Kasei Co., Ltd.)

(E) Bisphenol A type cyanate ester/triazine (product name, manufactured by Mitsubishi Gas Chemical Co., Ltd., CAS No. 1156-51-0, bisphenol A type cyanate ester monomer, 2,2-bis(4-cyanatophenyl )propane)
(F) Epoxy resin ESN-475V (product name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., α-naphthol aralkyl epoxy resin)

(H) triallyl isocyanurate Tyke (product name, manufactured by Mitsubishi Chemical Corporation, CAS No. 1025-15-6)

(I) Tetracarboxylic dianhydride BPADA: 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic dianhydride 6FDA: 4,4'-(hexafluoroisopropylidene) diphthaltetra Carboxylic dianhydride SFDA: Spiro[fluorene-9,9'-xanthene]-2',3',6',7'-tetracarboxylic dianhydride 6FBPADA: 5,5'-(((Per Fluoropropane-2,2-diyl)bis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione)
・BzDA: Enehyde (trademark, manufactured by ENEOS)
・TAHQ: Bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene (CAS No. 2770-49-2)

(other ingredients: filler)
・ SC2500-SXJ: (product name, manufactured by Admatechs Co., Ltd., silica particles)

(Example, Comparative Example)
Using a twin-screw mixer (kneader), a resin composition was produced by melt-mixing (melt-kneading) resin mixtures in proportions (parts by mass) shown in Tables 1 to 8. The melt-mixing process was carried out under the condition that the temperature of the resin composition at the exit of the twin-screw mixer was 170°C ± 10°C.

45 parts by mass of the mixed resin composition produced as described above and 55 parts by mass of a solvent were mixed under normal temperature conditions to produce a varnish of the resin composition. Tetrahydrofuran was used as the solvent in Examples 1-22 and Comparative Examples 1-4, and methyl ethyl ketone was used as the solvent in Examples 23-67 and Comparative Examples 5-7.

In Examples 65 and 67, the glass cloth 2116 was impregnated with a filler (SC2500-SXJ) added and dispersed in a proportion of 100 parts by mass with respect to 100 parts by mass of the resin component in the resin composition in the varnish. (1 Ply) prepreg was produced. In other Examples 43 to 67 and Comparative Examples 5 to 7, prepregs were produced by impregnating the glass cloth 2116 in a single layer without adding polyphenylene ether to the varnish.

The prepreg of each example and comparative example was cured under press conditions: 180 ° C. x 30 kg/cm ² x 1 hour, main curing conditions: 230 ° C. x 2 hours. Tables 1 to 8 show the results of measuring dielectric constant (Dk) and dielectric loss tangent (Df). Examples 48 and 49 were not used for measurement because the resin had large scratches when the prepreg was manufactured.

As shown in Table 1, as (A) bismaleimide compounds, by melting a resin mixture containing two of an aliphatic bismaleimide compound of formula (1) and an aromatic bismaleimide compound of formula (2), these The Tg of the cured product was improved as compared with the case of using one of It is presumed that the improvement in Tg is due to the fact that the use of the two types of bismaleimide compounds increases the molecular density, resulting in a cured product with a strong and high-density molecular structure.

Cured products of resin compositions using the two types of bismaleimide compounds shown in Table 1 are excellent in heat resistance and low dielectric properties. However, although it dissolves in high boiling point solvents such as NMP (N-methyl-2-pyrrolidone), it has low solubility in low boiling point solvents such as methyl ethyl ketone.
As shown in Table 2, when the resin mixture contains 16 to 23 parts by mass of (H) triallyl isocyanurate in 100 parts by mass of the resin component, the cured product has excellent heat resistance and low dielectric properties. It was possible to obtain a resin composition that is soluble in a low-boiling-point solvent while maintaining the

From the results shown in Tables 2 and 3, in order to blend (H) triallyl isocyanurate and obtain a resin composition having high solubility in a low boiling point solvent, a predetermined ratio of the two types of bismaleimide compounds found to be within the range of That is, by setting the mass ratio in the resin mixture to 25:55 to 45:35 for the content of the aliphatic bismaleimide compound: the content of the aromatic bismaleimide compound, a resin with high solubility in a low boiling point solvent A composition was obtained.

As shown in Tables 2 and 3, by setting the mass ratio of the two types of bismaleimide compounds in the resin mixture to a predetermined range and blending (H) triallyl isocyanurate, solubility in low boiling point solvents A high resin composition was obtained. However, the resin composition was in a viscous solid form at the B stage and had poor handleability.
As shown in Tables 4 and 5, 8 to 20 parts by mass of (C) amine compound and 15 to 30 parts by mass of (I) carboxylic acid dianhydride are blended in 100 parts by mass of the resin component of the resin mixture. It was found that the resin composition becomes solid in the B stage and has excellent handleability. From the viewpoint of obtaining a resin composition highly soluble in a low boiling point solvent, (C) the amine compound is preferably one or more selected from the group consisting of APB-N, BAN, and BAPP, and (I) carboxylic Acid dianhydride is preferably one or more selected from the group consisting of BPDA, 6FDA and SFDA.

From the results shown in Table 6, the following can be said.
A cured product with low dielectric properties is produced from a prepreg using a resin composition obtained by melting a resin mixture containing components (A) to (C) in 100 parts by mass of the resin component of the resin mixture. could be manufactured.
By using the bisaniline represented by the formula (4) as the (C) amine compound, a resin composition having good handleability as a prepreg was obtained.
A resin composition obtained by melting a resin mixture containing (A) BMI-TMH and BMI-4000 as polymaleimide compounds and (C) BAPP as an amine compound has heat resistance (Tg (DSC)). and low dielectric properties (Df (after 24 hours)) were good.

From the results shown in Tables 7 and 8, the following can be said.
A cured product with a low CTE was obtained by setting the mass ratio of the contents of BMI-TMH and BMI-4000 to 3.0:7.0 to 7.0:3.0.
By setting the content of G-90 to 12 parts by mass or less in 100 parts by mass of the resin mixture, it was possible to increase the heat resistance (Tg) of the cured product.
A cured product having excellent heat resistance was obtained regardless of the triazine content. Since the resin mixture contained triazine, the viscosity (hardness) of the resin mixture was increased and the handleability was improved.
From the viewpoint of obtaining a cured product with excellent low dielectric properties, the triazine content in 100 parts by mass of the resin mixture is preferably 2.0 parts by mass or less, and more preferably 1.0 parts by mass or less.
Cured products with excellent heat resistance and low dielectric properties were obtained regardless of the epoxy content.
Example 67, in which SC2500-SXJ was dispersed as a filler, could achieve the best low dielectric properties. This is presumed to be due to the fact that dense molecular bonding was obtained as a result of the filler inhibiting and eliminating the molecular bonding due to aggregation.
By using BMI-TMH and BMI-4000 as bismaleimides, a cured product having a lower water absorption than Comparative Example 5 using BMI-2300 was obtained. Since the cured product obtained by curing the resin composition of the present invention has a low water absorption after curing by hot pressing, it is possible to stably maintain excellent low dielectric properties immediately after production.

[Examination of manufacturing conditions]
For the resin composition of Example 67, optimal production conditions were examined from the viewpoint of solvent solubility.
FIG. 1 shows the results of GPC of the resin composition with a synthesis time of 2.5 minutes.
Table 9 shows the effect of synthesis time on the properties of the resin composition.
[Synthesis conditions]
Resin temperature 170℃±10℃
[gel time]
Measurement of curing time on a hot plate at 171°C [peak area]
By GPC (gel permeation chromatography) measurement, the presence or absence of detection of a component with a molecular weight of 4500 to 4800 and, if detected, the ratio (%) of the peak area of the component with a molecular weight of 4500 to 4800 in the total peak area was determined.
[Weight average molecular weight]
The weight average molecular weight of the resin composition was determined by GPC measurement.
Solvent solubility was evaluated using the following criteria.
60 parts by mass of a measurement sample (resin composition) and 40 parts by mass of methyl ethyl ketone (solvent) are mixed under conditions of 50° C. or less, and the dissolved state after applying ultrasonic vibration for a predetermined time is measured using the following criteria. It was evaluated visually.
[MEK solubility (168 hours)]
An MEK solution of the resin was prepared by the method of solvent solubility (MEK solubility) described above, and the state of the measurement sample after standing for a predetermined time was visually evaluated using the following criteria.
◯: No precipitation of resin after standing at room temperature for 168 hours.
x: Precipitation of resin after standing for 168 hours at room temperature.

From the results shown in Table 9, the following can be said.
By lengthening the synthesis time, that is, the time for melt-mixing the resin mixture, the reaction progressed and the gel time was shortened.
The difference in synthesis time caused a difference in MEK solubility when left standing for a long time. A resin composition having good MEK solubility was obtained by setting the synthesis time to 2.5 minutes or longer.
Differences in synthesis time caused differences in the peak areas and weight average molecular weights of components with molecular weights of 4500 to 4800 measured by GPC. It can be said that it serves as an index.
A resin composition with good MEK solubility was obtained by setting the ratio of the component having a molecular weight of 4500 to 4800 corresponding to the peak marked with 1 in the graph of FIG. 1 to 10 to 20% of the total.
By setting the weight average molecular weight to 1100 to 2500, a resin composition having good MEK solubility was obtained.

[Solvent solubility]
The solubility in solvents other than MEK was evaluated for the resin composition of Example 67 (peak area: 12.3%, Mw = 1257) with a synthesis time of 2.5 minutes. As a result, PGM (propylene glycol monomethyl ether), PGM-Ac (propylene glycol monomethyl ether acetate), DMAc (dimethylacetamide), NMP (N-methylpyrrolidone), γ-butyrolactone, ethyl acetate, acetone, toluene, THF (tetrahydrofuran) ), cyclohexanone, DMF (dimethylformamide), methoxybenzene (anisole), 2-(2-butoxyethoxy)ethanol (ethylene glycol monoethyl ether) and 2-(2-ethoxyethoxy)ethyl acetate (ethyl carbitol acetate) When ultrasonic vibration was applied for 100 minutes, it was a brown transparent liquid with no undissolved residue, separation, or turbidity, and had good solubility.

The resin composition of the present invention has good solubility in solvents, low dielectric properties (low dielectric constant and low dielectric loss tangent), and high heat resistance. It can be used as a raw material for adhesives, sealants, paints, moldings, laminates and printed wiring boards that are excellent in heat resistance and low dielectric properties and suitable for various electronic devices.

Claims

(A) A resin composition obtained by melting a resin mixture containing a bismaleimide compound,
The (A) bismaleimide compound is
an aliphatic bismaleimide compound represented by formula (1);
and an aromatic bismaleimide compound represented by formula (2),
Resin composition.

(In Formula (1), R 1 is an alkylene group having 6 to 12 carbon atoms.)

(In Formula (2), R 2 is a hydrocarbon group having 6 to 30 carbon atoms and having an aromatic ring, X 1 is each independently an oxygen atom or a single bond, and R 3 and R 4 each have 1 carbon atom. is a hydrocarbon group of 6 or less, and a and b are each independently an integer of 0 or more and 3 or less.)
In the formula (1), R 1 is an alkylene group having 9 carbon atoms,
In the formula (2), R 2 is a group represented by the formula (3),
The resin composition according to claim 1.
the aliphatic bismaleimide compound is 1,6-bismaleimide(2,2,4-trimethyl)hexane,
The aromatic bismaleimide compound is bisphenol A diphenyl ether bismaleimide,
The resin composition according to claim 1.
The mass ratio of the content of the aliphatic bismaleimide compound to the content of the aromatic bismaleimide compound in the resin mixture, the aliphatic bismaleimide compound: the aromatic bismaleimide compound being 25:55 to 45: is 35;
The resin composition according to claim 3.
The resin mixture further contains (H) triallyl isocyanurate,
The content of the (H) triallyl isocyanurate in 100 parts by mass of the resin component is 16 to 23 parts by mass.
The resin composition according to claim 4.
The resin mixture further contains (C) an amine compound and (I) a carboxylic acid dianhydride,
The content of the (C) amine compound in 100 parts by mass of the resin component is 10 to 20 parts by mass,
In 100 parts by mass of the resin component, the content of the (I) carboxylic acid dianhydride is 15 to 30 parts by mass.
The resin composition according to claim 5.
The resin mixture further contains (B) a coumarone resin and (C) an amine compound,
In 100 parts by mass of the resin component of the resin mixture,
The content of the (A) bismaleimide compound is 30 to 65 parts by mass,
The content of the (B) coumarone resin is 5 to 25 parts by mass,
The content of the (C) amine compound is 1 to 30 parts by mass,
The resin composition according to claim 1.
The mass ratio of the content of the aliphatic bismaleimide compound to the content of the aromatic bismaleimide compound, the aliphatic bismaleimide compound: the aromatic bismaleimide compound is 3.0:7.0 to 7.0. : is 3.0;
The resin composition according to claim 7.
The (C) amine compound is bisaniline,
The resin composition according to claim 7.
The (C) amine compound is a bisaniline represented by formula (4),
The resin composition according to claim 7.

(In Formula (4), R 5 is a hydrocarbon group having 6 to 30 carbon atoms and having an aromatic ring, and each X 1 is independently an oxygen atom or a single bond.)
(C) the amine compound is bisaniline M, 4,4′-[dimethylmethylenebis(4,1-phenyleneoxy)]bisaniline or (4,4′-[biphenyl-4,4′-diylbis(oxy)]bisaniline ) is
The resin composition according to claim 7.
The resin mixture further contains (D) benzoxazine,
The content of the (D) benzoxazine in 100 parts by mass of the resin mixture is 5 to 20 parts by mass.
The resin composition according to claim 7.
The resin mixture further contains (E) a bisphenol A cyanate ester,
The content of (E) bisphenol A-type cyanate ester in 100 parts by mass of the resin mixture is 0.5 to 2 parts by mass,
The resin composition according to claim 12.
The resin mixture further contains (F) epoxy,
In 100 parts by mass of the resin mixture, the content of (F) the epoxy is 1 to 9 parts by mass.
The resin composition according to claim 13.
A weight average molecular weight of 1000 to 2500,
It has a component with a molecular weight of 4500 to 4800, and the proportion of the component is 10 to 20%.
The resin composition according to claim 7.
The resin composition according to claim 1, which is for printed wiring boards.
A varnish obtained by dissolving the resin composition according to claim 5 in a solvent having a boiling point of 120°C or less and a dielectric constant of 10 to 30.
A laminate manufactured using the resin composition according to claim 1.
A printed wiring board manufactured using the resin composition according to claim 1.
A molded article obtained by curing the resin composition according to claim 1.