JPWO2020161926A1 - Resin composition and its manufacturing method - Google Patents

Abstract

A resin composition obtained by melting a resin mixture containing (A) polymaleimide compound, (B) benzoxazine, (C) epoxy resin, and (D) kumaron resin, and the resin component of the resin mixture. A resin composition in which the content of the polymaleimide compound (A) is 40 to 70 parts by mass in 100 parts by mass, and has high heat resistance and low dielectric properties (low specific dielectric constant, low dielectric adjunct). It can also be used as an electronic / electrical component such as a laminated board, a printed wiring board, an adhesive, a sealing agent, a paint, and a molded product.

Description

The present invention relates to electronic and electrical components such as laminated boards, printed wiring boards, adhesives, sealants, paints and molded products having high heat resistance and low dielectric properties (low relative permittivity, low dielectric loss tangent). The present invention relates to a resin composition used as a material and a method for producing the same.

Conventionally, 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 properly according to their uses and characteristics. Among these, polyimide resin is widely used in applications requiring high heat resistance because it is excellent in heat resistance and moisture heat resistance (heat resistance after moisture absorption). Further, a modified polyimide resin whose performance has been improved by combining a polyimide resin with another resin such as an epoxy resin or an aromatic diamine is also used.

In recent years, in the field of semiconductor substrates, a mounting method in which a semiconductor chip is directly mounted on a substrate has become widespread. Therefore, the materials used for semiconductors are required to have high heat resistance that can withstand high temperature treatment 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 modified polyimide resin composition obtained by melting a polymaleimide compound, a phenol resin, a bisphenol A type epoxy resin, and another epoxy resin.

JP-A-2017-101152

Although the modified polyimide resin composition described in Patent Document 1 has a feature of high heat resistance, the low dielectric property may not be sufficient 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 obtained by melting a resin mixture containing (A) a polymaleimide compound, (B) benzoxazine, (C) an epoxy resin, and (D) kumaron resin, wherein the resin mixture is obtained. The resin composition in which the content of the polymaleimide compound (A) is 40 to 70 parts by mass in 100 parts by mass of the resin component of the above.

[2] The resin composition according to [1], wherein the content of the (D) kumaron 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) kumaron resin has a softening point of 100 ° C. or lower and a weight average molecular weight of 850 or less.

[4] The resin mixture further contains (E) bisphenol A type cyanate ester, and the content of the (E) bisphenol A type cyanate ester in 100 parts by mass of the resin component of the resin mixture is 3 to 3 to The resin composition according to [2] or [3], which is 7 parts by mass.

（前記式（１）において、ｎ_１は０以上１０以下の整数であり、Ｘ^１はそれぞれ独立に炭素数１以上１０以下のアルキレン基、下記式（２）で表される基、「−ＳＯ_２−」で表される基、「−ＣＯ−」で表される基、酸素原子または単結合であり、Ｒ^１はそれぞれ独立に炭素数１以上６以下の炭化水素基であり、ａはそれぞれ独立に０以上４以下の整数であり、ｂはそれぞれ独立に０以上３以下の整数であり、繰り返し単位の数ｎ_１の平均値が０．０１以上５以下である。）

（前記式（２）において、Ｙは芳香族環を有する炭素数６以上３０以下の炭化水素基であり、ｎ_２は１〜３の整数である。）[5] The resin composition according to [1], wherein the (A) polymaleimide compound is represented by the formula (1).

(In the above formula (1), n ₁ is an integer of 0 or more and 10 or less, and X ¹ is an alkylene group having 1 or more and 10 or less carbon atoms independently, a group represented by the following formula (2), "-SO". _{A group represented by "2-} ", a group represented by "-CO-", an oxygen atom or a single bond, R ¹ is an independently hydrocarbon group having 1 or more carbon atoms and 6 or less carbon atoms, and a is each. Independently, it is an integer of 0 or more and 4 or less, b is an integer of 0 or more and 3 or less independently, and _{the average value of the number n 1} of the repeating units is 0.01 or more and 5 or less.)

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

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

[8] Of the 100 parts by mass of the (A) polymaleimide compound contained in the resin mixture, 30 to the (A) polymaleimide compound remaining as a residual maleimide compound in the resin composition after the melt mixing step. The resin composition according to any one of [1] to [7], which is obtained by melting each component so as to have 60 parts by mass.

[9] The resin composition according to any one of [1] to [8] for a printed wiring board.
[10] A varnish in which the resin composition according to any one of [1] to [8] is dissolved in a solvent having a boiling point of 120 ° C. or lower and a relative permittivity of 10 to 30.
[11] A laminated board produced by using the resin composition according to any one of [1] to [8].
[12] A printed wiring board produced by using the resin composition according to any one of [1] to [8].
[13] A molded product obtained by curing the resin composition according to 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 according to any one of [1] to [8].

High heat resistance and low dielectric properties (low relative permittivity, low dielectric constant) by melting a resin mixture containing (A) polymaleimide compound, (B) benzoxazine, (C) epoxy resin, and (D) kumaron resin. It is possible to provide a resin composition which is a cured product having a dielectric loss tangent).

(Resin composition)
The resin composition of the present invention is a resin composition obtained by melting a resin mixture containing (A) a polymaleimide compound, (B) benzoxazine, (C) an epoxy resin, and (D) a kumaron resin. The content of the polymaleimide compound (A) in 100 parts by mass of the resin component of the resin mixture is 40 to 70 parts by mass. Hereinafter, each component (A) to (D) and other components that may be contained will be described. In the present invention, a mixture before melting and mixing of each component is referred to as a "resin mixture", and a mixture cooled after melting and mixing is referred to as a "resin composition".

(A) Polymaleimide Compound A 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, those in which a maleimide group is bonded to the aromatic ring are preferable. Examples of such a polymaleimide compound include those represented by the formula (1) shown in the section of means for solving the problem.

From the viewpoint of improving the solubility of the resin composition in a low boiling point solvent, the polymaleimide compound _{preferably has an average value of the number n 1} of the repeating units in the formula (1) of 0.01 or more and 5 or less. That is, the resin mixture contains a polymaleimide compound having a repeating unit (structural site) enclosed in parentheses in the formula (1) at a _{ratio such that the average value of the number n 1} of the repeating units is 0.01 or more and 5 or less. It is preferable to do so. Thereby, the range of the melting temperature at which a resin composition having good solubility in a low boiling point solvent can be obtained can be widened. In the present invention, the " _{polymaleimide compound having an average value of n 1} of 0.01 or more and 5 or less" means a polymaleimide compound composed of one kind of compound or a mixture of two or more kinds of compounds.

A resin composition having good solubility in methyl ethyl ketone, which is a low boiling point solvent, by using the polymaleimide compound (A) in which the average value _{of the number n 1} of the number of repeating units in the formula (1) is 0.01 or more and 5 or less. become. Therefore, a resin composition having good solubility in methyl ethyl ketone can be obtained without using a bisphenol A type epoxy resin having an action of improving the solubility of the resin composition in a low boiling solvent.

By suppressing the content of the bisphenol A type epoxy resin in the resin component of the resin mixture, the heat resistance of the cured product of the resin composition is improved. 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 the bisphenol A type epoxy resin. Here, the term "not containing bisphenol A type epoxy resin" means that it is substantially not contained, that is, it does not contain an amount of bisphenol A type epoxy resin that affects the properties of the resin mixture.

Since the resin mixture contains the polymaleimide compound in a high proportion of 40 to 70 parts by mass in 100 parts by mass of the resin component of the resin mixture, it is a resin composition capable of forming a cured product having good heat resistance. From the viewpoint of achieving 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, further preferably 55 to 65 parts by mass. In the present invention, the numerical range "A to B" means "A or more and B or less".

The polymaleimide compound represented by the 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 Kasei Kogyo Co., Ltd., phenylene maleimide).

（式（３）及び式（４）中、Ｒ^２、Ｒ^３は水素原子、炭素数１〜３の置換もしくは無置換の炭化水素基を表す。）
これらのジヒドロベンゾオキサジン化合物は単独でまたは二種以上を組み合わせて用いることができる。(B) Benzoxazine compound The benzoxazine compound may have at least one benzoxazine ring in the molecule, but the dihydrobenzoxazine compound represented by the following general formula (3) or (4) may be used. Of these, pd-type dihydrobenzoxazine represented by the following general formula (4) is more preferable.

(In formulas (3) and (4), R ² and R ³ represent hydrogen atoms and substituted or unsubstituted hydrocarbon groups having 1 to 3 carbon atoms.)
These dihydrobenzoxazine compounds can be used alone or in combination of two or more.

The content of the benzoxazine compound in 100 parts by mass of the resin component of the resin mixture is from the viewpoint of high heat resistance and low dielectric properties of the cured product, as well as solubility of the resin composition in a low boiling solvent and stability of the dissolved state. Therefore, 10 to 30 parts by mass is preferable, 12 to 25 parts by mass is more preferable, and 15 to 22 parts by mass is further preferable. Further, from the viewpoint of solubility in a low boiling point solvent and stability in a dissolved state, the content of the benzoxazine compound is more preferably 15 parts by mass or more, more preferably 20 parts by mass, based on 100 parts by mass of the (A) polymaleimide compound. More than a portion is more preferable. From the viewpoint of obtaining a cured product having 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, based on 100 parts by mass of the (A) polymaleimide compound.

(C) Epoxy resin The epoxy resin may be a compound having an epoxy group, but includes a biphenyl aralkyl type epoxy resin and a naphthalene ring from the viewpoint of achieving both heat resistance and low dielectric properties of the cured product of the resin composition. Epoxy resins, compounds having three epoxy groups represented by the formula (5), and the like are preferable. 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. Examples of the commercially available epoxy resin represented by the formula (5) include VG3101L (product name, manufactured by Printec Co., Ltd., highly heat-resistant trifunctional epoxy resin).

Examples of epoxy resins other than the above include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, and bisphenol F novolac type epoxy resin. , Triphenylol type epoxy resin, dicyclopentadiene type epoxy resin and the like. These epoxy resins can be used alone or in combination of two or more.

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

(D) Kumaron resin Kumaron resin is a copolymer resin containing Kumaron, inden and styrene as main components. Examples of commercially available products include G-90, V-120, L-5, L-20, and H-100 (all product names, manufactured by Nikko Kagaku Co., Ltd.). From the viewpoint of producing a resin composition that realizes a cured product having low dielectric properties, a kumaron resin having a softening point of 100 ° C. or lower and a weight average molecular weight of 850 or less is preferable.

The content of the kumaron 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 to 4 parts by mass, from the viewpoint of high heat resistance and low dielectric properties of the cured product. , 1 to 3 parts by mass is more preferable.

(E) Bisphenol A Cyanate Ester The bisphenol A cyanate ester is a bisphenol A cyanate ester that forms a triazine ring and is cured. By using the bisphenol A type cyanate ester and the (D) kumaron resin in combination, the relative permittivity and the dielectric loss tangent of the cured product obtained by curing the resin composition can be further reduced. The bisphenol A type cyanate ester includes a monomer and a (homo) polymer (polymer), and the monomer of the bisphenol A type cyanate ester is preferable from the viewpoint of obtaining a cured product having excellent low dielectric properties.

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

(F) Curing Accelerator When using the resin composition according to the present invention, a curing accelerator may be added and used. Examples of the timing for adding the curing accelerator include when the resin composition is made into a varnish dissolved in a solvent, when the resin composition is made into a prepreg, or when a base material or a laminated board is manufactured.

Examples of the curing accelerator include imidazoles such as dicumylperoxide, 4,4'-diaminodiphenylmethane, 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-heptaimidazole; triethanolamine, triethylenediamine, and the like. Amines such as N-methylmorpholin; organic phosphines such as triphenylphosphine and tritrylphosphine; tetraphenylborone salts such as tetraphenylphosphonium tetraphenylborate and triethylammonium tetraphenylborate; 1,8-diazabicyclo (5) , 4,0) Undecene-7 and derivatives thereof; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, tin oleate, manganese naphthenate, cobalt tefateate, cobalt octylate and the like can be mentioned. These curing accelerators may be used alone or in combination of two or more, and if necessary, an organic peroxide, an azo compound, or the like may be used in combination.

It is desirable that the content of these curing accelerators be blended in a varnish or prepreg within a range in which a desired gelation time can be obtained. 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 according to the present invention and the resin mixture before melt mixing may contain components other than the above (A), (B), (C), (D), (E) and (F). For example, an organic or inorganic filler can be used to cure the resin composition of the present invention to obtain a base material to be a molded product. Examples of fillers are oxides such as silica, diatomaceous earth, alumina, zinc chloride, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, 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, dosonite and hydrotalcite; sulfates such as calcium sulfate, barium sulfate and gypsum fiber; calcium silicate (Wollastonite, zonotrite), talc, clay, mica, montmorillonite, bentonite, active white clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica-based balun and other silicates; aluminum hydroxide, boron nitride, nitride Nitridees such as silicon; carbons such as carbon black, graphite, carbon fiber, carbon balun, charcoal powder; other various metal powders, potassium titanate, lead zirconate titanate, aluminum volate, molybdenum sulfide, silicon carbide, stainless steel fiber , Zinc borate, various magnetic powders, slag fibers, ceramic powders and the like.

The shape of the filler is preferably spherical or flaky, and these may be used alone or in combination of two or more. Also, if necessary, a silane coupling agent having two or more different reactive groups in the molecule (one is a reactive group that chemically reacts with an inorganic material and the other is a reactive group that chemically reacts with an organic material) is used in combination. You can also do it.

When an organic or inorganic filler is used, the content thereof 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 if necessary. Examples of the flame retardant include organic flame retardants such as brom compounds such as brominated epoxy resin and phosphorus compounds such as condensed phosphoric acid ester, and inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, tin compounds and antimony compounds. .. These flame retardants may be used alone or in combination of two or more.

The content of the flame retardant is an amount required to have sufficient flame retardancy (for example, passing the V-0 condition in the UL94 standard) without impairing the heat resistance and moisture heat resistance of the cured product obtained by curing the resin composition. Is desirable. In the case of an organic flame retardant, generally, in the range of 1 to 20 parts by mass with respect to a total of 100 parts by mass of the resin component including the organic flame retardant in the resin composition, in the case of an inorganic flame retardant, the resin component It is preferably used in the range of 10 to 300 parts by mass with respect to 100 parts by mass in total.

When using the resin composition according to the present invention, other additives can be added depending on the intended use. Examples of other additives include various silicone oils, thermoplastic resins, synthetic rubbers such as NBR, and leveling agents. The other additive is used in a blending amount range in which the content of the other additive in the total 100 parts by mass of the other additive and the resin component in the resin composition is 0.0001 to 5 parts by mass. Is preferable.

(Melting and mixing process)
The resin composition of the present invention is a melt mixture in which a resin mixture containing (A) polymaleimide compound, (B) benzoxazine, (C) epoxy resin, and (D) kumaron resin is heated and mixed in a molten state. Manufactured by the process. Ordinary mixing means can be used in the melt mixing step. As the mixing means, a kneader, a twin-screw kneader or the like is preferable. The temperature at the time of melting and mixing may be at least the temperature at which the resin mixture melts and 400 ° C. or lower, but is more preferably 130 ° C. to 230 ° C., still more preferably 150 ° C. to 210 ° C. The melting and mixing step is usually carried out for about 0.1 to 10 minutes. As described above, in order to obtain a resin composition having good solubility in a low boiling point solvent in a wide melting temperature range in the melting and mixing step, the average value _{of the number n 1 of the repeating units in the formula (1) is 0.01.} It is preferable to use the (A) polymaleimide compound having a temperature of 5 or more.

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 5 to 100 ° C. or a method of forced cooling using a refrigerant of -20 to 80 ° C. can be adopted. Further, a method of cooling after melting and mixing and placing the mixture in an environment of 30 to 300 ° C. in a constant temperature device may be adopted.

After cooling, the obtained resin composition can be pulverized and stored in a dry state (dry), and used as a solid resin composition in a later step.

In the melt mixing step, at least a part of the (A) polymaleimide compound contained in the resin mixture is modified by reacting with other components in the resin mixture. This makes it possible to prepare a resin composition having high heat resistance, low dielectric properties, and good solubility in a low boiling point solvent.

From the viewpoint of improving the solubility in a low boiling point solvent, the polymaleimide compound remaining in the resin composition produced by the melt mixing step (appropriately referred to as “residual maleimide compound”) is 100 parts by mass of the resin component. 42 parts by mass or less is preferable, and 40 parts by mass or less is more preferable.

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

(varnish)
The varnish of the resin composition according to 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 permittivity of 10 to 30.
Solvents having a boiling point of 120 ° C. or lower and a specific 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. , 1-Butanol and other alcoholic solvents can be mentioned. Considering operability and the like, a ketone solvent is preferably used among the exemplified solvents. These solvents may be used alone or in combination of two or more. Further, it may contain a solvent other than those exemplified above.

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 room temperature (room temperature) or under heating. When dissolving under heating, the temperature is about 50 to 200 ° C. and the time is about 0.1 to 24 hours, although it depends on the boiling point of the solvent.

The prepreg can be produced by applying or impregnating the base material with the varnish and then drying to remove the solvent.
As the base material, known base materials used for conventional prepregs such as glass non-woven fabric, glass cloth, carbon fiber cloth, organic fiber cloth, and paper can be used.

After applying or impregnating the varnish on the substrate, a prepreg is produced through a drying step, but the coating method, the impregnation method, and the drying method are not particularly limited, and conventionally known methods can be adopted. The drying conditions are appropriately determined depending on the boiling point of the solvent used, but a very high temperature is not preferable. It is desirable to dry the prepreg so that the amount of the solvent remaining in 100% by mass is 3% by mass or less.

When preparing the prepreg, a resin other than the resin composition described above may be added to the varnish. Examples of the resin include polyphenylene ether resin and the like. A polyphenylene ether resin is preferable from the viewpoint of imparting high heat resistance, low relative permittivity and low dielectric loss tangent to the cured product obtained by curing the prepreg. From the same viewpoint, the amount of the polyphenylene ether resin used when preparing the prepreg is preferably 10 to 100 parts by mass, 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. More preferably, 20 to 40 parts by mass is further preferable. Examples of commercially available polyphenylene ether resins include SA90, SA120, and SA9000 (product names, all manufactured by SABIC Japan LLC).

The resin composition of the present invention is suitable for a printed wiring board, and the present invention can be carried out as a molded product obtained by curing the resin composition. Examples of the molded product include a cured product obtained by curing only the resin composition, a composite material composited with other raw materials, and a laminate.

The composite material and the laminated body can be obtained by heating one prepreg with a hot press or the like to cure it, or by laminating a plurality of prepregs and heating them under pressure to integrate them. 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., the pressure is 10 to 100 kg / cm ² , and the heating is performed. The pressurization time is about 10 to 300 minutes.

A metal foil or a metal plate 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 a multilayer printed wiring board or the like. Such a laminate can be obtained by laminating a metal foil or a metal plate on one or both sides of one prepreg and heat-pressing it, or by heat-pressing, or by laminating a plurality of prepregs on one or both sides which is the outermost layer of the metal foil or the metal plate. Can be produced by laminating and heat-pressing the prepregs to heat-cure and integrate them.

As the metal foil or metal plate, copper, aluminum, iron, stainless steel or the like can be used. For example, a laminated plate 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 a composite material. Further, the inner layer core material may be used as a laminated board for a multilayer printed wiring board.
The present invention can also be carried out as an adhesive, a sealant and a paint containing the above-mentioned resin composition.

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

1. 1. Test method [solvent solubility]
60 parts by mass of the measurement sample (resin composition) and 40 parts by mass of methyl ethyl ketone (solvent) are mixed under room temperature conditions, and the dissolved state after applying ultrasonic vibration for a predetermined time is visually evaluated using the following criteria. bottom.
〇: Becomes a transparent liquid within 1 hour (room temperature)
Δ: Becomes a transparent liquid within 5 hours (room temperature)
X: Liquid or semi-liquid state (room temperature) in a turbid state even after 5 hours have passed

[Glass transition point (Tg)]
[Coefficient of thermal expansion: CTE (ppm / ° C)]
A cured product obtained by curing the resin composition was cut (cut out) to a predetermined size to prepare a sample for measuring the glass transition point. Under the following conditions, the glass transition point (temperature, ° C.) and coefficient of thermal expansion (CTE) of the sample were measured using the TMA (Thermomechanical Analysis) method.
Measuring equipment: Rigaku's Thermo plus TMA8310
Sample dimensions: width (length) 5 mm x length (width) 5 mm x height 4 mm
Atmosphere: N ₂
Measurement temperature: 30-350 ° C
Temperature rise rate: 10 ° C./min.
Measurement mode: compression

[Thermogravimetric change]
According to JIS K7120, the cured product is heated from 30 ° C. to 10 ° C. per minute to reduce the mass by 1% (Td (1%)) and 5% (Td (5%)). )) Was measured.

[Relative permittivity (Dk), dielectric loss tangent (Df)]
The measurement was performed under the condition of 1 GHz by the cavity resonator method.

2. Raw material (A) Polymaleimide compound, BMI-2300 (Product name, manufactured by Daiwa Kasei Kogyo Co., Ltd., polyphenylmethane polymaleimide)
・ BMI-4000 (Product name, manufactured by Daiwa Kasei Kogyo Co., Ltd., bisphenol A diphenyl ether bismaleimide)

(B) Benzodiazepine compound-BZO: (P-d type) benzoxazine (manufactured by Shikoku Chemicals Corporation)
(C) Epoxy resin, VG3101L (Product name, manufactured by Printec 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) Kumaron resin G-90 (product name, manufactured by Nikko Kagaku Co., Ltd., solid at room temperature, softening point 90 ° C., weight average molecular weight 770)
H-100 (Product name, manufactured by Nikko Kagaku Co., Ltd., solid at room temperature, softening point 100 ° C., weight average molecular weight 710)
・ L-5 (Product name, manufactured by Nikko Kagaku Co., Ltd., liquid at room temperature, weight average molecular weight 160)

(E) Bisphenol A type cyanate ester monomer: Bisphenol A type cyanate ester monomer (Product name: Triazine, manufactured by Mitsubishi Gas Chemical Company, Inc., CAS No. 1156-51-0, 2,2-bis (4-shi) Anatophenyl) Propane)
-Polymer: (homo) polymer of bisphenol A type cyanate ester (Product name: TA1500, manufactured by Mitsubishi Gas Chemical Company, Inc., CAS No. 1156-51-0, 25722-6
A homopolymer of 6-1 and 2,2-bis (4-cyanatophenyl) propane)
(Other ingredients)
-SA120: (Product name, manufactured by SABIC Innovative Plastics, polyphenylene ether)

(Examples 1 to 5, Comparative Examples 1 to 4)
A resin composition was prepared by melt-mixing (melt-kneading) the resin mixture having the ratio (parts by mass) shown in Table 1 using a twin-screw mixer (kneading). The conditions of the melt-mixing step were a barrel temperature of 270 ° C. and a resin composition temperature of 185 to 195 ° C. (the temperature at the outlet of the resin composition of the twin-screw mixer). In the twin-screw mixer used in this example, under the above conditions, 30 to 60 parts by mass of (A) bismaleimide contained in the resin mixture was left in the resin composition without being polymerized. A resin composition having high solubility in methyl ethyl ketone could be prepared.

45 parts by mass of the resin mixed 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.
In Examples 1 to 5 and Comparative Examples 1 to 2, the glass cloth 2116 was prepared by adding polyphenylene ether (SA120) at a ratio of 50 parts by mass to 100 parts by mass of the resin composition (resin component) in the varnish. A prepreg was prepared by impregnation with one layer (1Ply). In Comparative Examples 3 and 4, a prepreg was prepared by impregnating the glass cloth 2116 with a single layer as it was without adding polyphenylene ether to the varnish. The glass transition point (Tg) for each cured product obtained by curing the prepregs of each Example and Comparative Example under the conditions of pressing conditions: 180 ° C. × 30 kg / cm ² × 1 hour and main curing conditions: 230 ° C. × 2 hours. The results of measuring the relative permittivity (Dk) and the dielectric loss tangent (Df) are shown in Table 1.

From the results in Table 1, the following can be said.
A cured product having high heat resistance (Tg), low relative permittivity (Dk) and low dielectric loss tangent (Df) by prepreg using a resin composition prepared by melting a resin mixture containing kumaron resin. was gotten.
The kumaron resin has a lower relative permittivity (Dk) and a lower dielectric loss tangent (Df) when it is beaded (solid) at room temperature than when it is liquid at room temperature, and when the weight average molecular weight is 800 or less. It was effective for obtaining a cured product.
In order to further reduce the relative permittivity (Dk) and the dielectric loss tangent (Df) of the cured product, it was effective to use the kumaron resin and the (E) bisphenol A type cyanate ester in combination.
In the bisphenol A type cyanate ester, the monomer was more effective than the polymer in order to lower the dielectric loss tangent of the cured product.

表２に示すように、（Ｄ）クマロン樹脂を配合することにより、硬化物の高い耐熱性を維持したまま、比誘電率および誘電正接を低くすることができた。The resin mixture having the ratio (part by mass) shown in Tables 2 and 3 was melt-mixed using a twin-screw kneader to prepare a resin composition. Tables 2 and 3 show the results of evaluating the cured product prepared by curing the resin composition at 230 ° C. for 4 hours. The preparation conditions for the resin composition were the same as in Table 1.

As shown in Table 2, by blending the (D) kumaron resin, the relative permittivity and the dielectric loss tangent could be lowered while maintaining the high heat resistance of the cured product.

表３の結果から、以下のことがいえる。
式（１）で示される化合物のｎ_１の平均値が０．０１以上５以下であり、Ｘ^１が−ＣＨ_２−で表される基であり、ａが０であり、ｂが０であるポリマレイミド化合物ＢＭＩ−２３００を用いることにより、メチルエチルケトンに対する溶解性の良好な樹脂組成物となった。
軟化点８５〜１０５℃、重量平均分子量７００〜８００のクマロン樹脂を用いることにより、樹脂組成物の樹脂成分１００質量部中に１〜３質量部程度の少ない配合量で、高い耐熱性（Ｔｇ）と、低い誘電率（Ｄｋ）および低い誘電正接（Ｄｆ）とを備えた硬化物が得られた。

From the results in Table 3, the following can be said.
_{The average value of n 1} of the compound represented by the formula (1) is 0.01 or more and 5 or less, X ¹ is _{a group represented by −CH 2} −, a is 0, and b is 0. By using the polymaleimide compound BMI-2300, a resin composition having good solubility in methyl ethyl ketone was obtained.
By using a kumaron resin having a softening point of 85 to 105 ° C. and a weight average molecular weight of 700 to 800, high heat resistance (Tg) can be achieved with a small amount of about 1 to 3 parts by mass in 100 parts by mass of the resin component of the resin composition. A cured product having a low dielectric weight (Dk) and a low dielectric loss tangent (Df) was obtained.

The present invention is a resin composition that is a cured product having high heat resistance, high heat resistance, and low dielectric properties (low relative permittivity, low dielectric loss tangent), and the resin composition has heat resistance and low dielectric properties. It can be used as a raw material for excellent adhesives, sealants, paints, molded products, laminates and printed wiring substrates.

[1] A resin composition for a printed wiring substrate obtained by melting a resin mixture containing (A) a polymaleimide compound, (B) benzoxazine, (C) an epoxy resin, and (D) a kumaron resin. The resin composition, wherein the content of the polymaleimide compound (A) in 100 parts by mass of the resin component of the resin mixture is 40 to 70 parts by mass.

[9] A resin composition obtained by melting a resin mixture containing (A) a polymaleimide compound, (B) benzoxazine, (C) an epoxy resin, and (D) a kumaron resin, wherein the resin mixture is obtained. The resin composition having a content of the polymaleimide compound (A) in an amount of 40 to 70 parts by mass in 100 parts by mass of the resin component of the above was dissolved in a solvent having a boiling point of 120 ° C. or lower and a dielectric constant of 10 to 30. varnish.
[10] A resin composition obtained by melting a resin mixture containing (A) a polymaleimide compound, (B) benzoxazine, (C) an epoxy resin, and (D) kumaron resin, wherein the resin mixture is obtained. A laminated board produced by using a resin composition in which the content of the polymaleimide compound (A) is 40 to 70 parts by mass in 100 parts by mass of the resin component of.
[11] A resin composition obtained by melting a resin mixture containing (A) a polymaleimide compound, (B) benzoxazine, (C) an epoxy resin, and (D) a kumaron resin, wherein the resin mixture is obtained. A printed wiring substrate produced by using a resin composition in which the content of the polymaleimide compound (A) is 40 to 70 parts by mass in 100 parts by mass of the resin component of.

Examples of the curing accelerator, dicumyl peroxide, 4,4'-diaminodiphenylmethane, 2-methylimidazole, 2-ethyl-4-methylimidazole, imidazoles such as 2-heptene chill imidazole; triethanolamine, triethylenediamine , Amines such as N-methylmorpholin; organic phosphines such as triphenylphosphine and tritrylphosphine; tetraphenylborone salts such as tetraphenylphosphonium tetraphenylborate and triethylammonium tetraphenylborate; 1,8-diazabicyclo ( 5,4,0) undecene-7 and derivatives thereof; lead naphthenate, lead stearate, zinc naphthenate, tin oleate, manganese naphthenate, Na Putian cobalt, and the like organic metal salts such as cobalt octoate is .. These curing accelerators may be used alone or in combination of two or more, and if necessary, an organic peroxide, an azo compound, or the like may be used in combination.

[Glass transition point (Tg)]
[Thermal linear expansion coefficient: CTE (ppm / ℃)]
A cured product obtained by curing the resin composition was cut (cut out) to a predetermined size to prepare a sample for measuring the glass transition point. Under the following conditions, using TMA (Thermomechanical Analysis, thermomechanical analysis) the method, the glass transition point of the sample (temperature, ° C.) and thermal linear expansion rate (CTE) was measured.
Measuring equipment: Rigaku's Thermo plus TMA8310
Sample dimensions: width (length) 5 mm x length (width) 5 mm x height 4 mm
Atmosphere: N ₂
Measurement temperature: 30-350 ° C
Temperature rise rate: 10 ° C./min.
Measurement mode: compression

(Examples 1 to 5, Comparative Examples 1 to 4)
A resin composition was prepared by melt-mixing (melt-kneading) the resin mixture having the ratio (parts by mass) shown in Table 1 using a twin-screw mixer (kneading). The conditions of the melt mixing step were a barrel temperature of 270 ° C. and a resin composition temperature of 185 to 195 ° C. (the temperature at the outlet of the resin composition of the twin-screw mixer). In the twin-screw mixer used in this example, under the above conditions, 30 to 60 parts by mass of (A) bismaleimide contained in the resin mixture was left in the resin composition without being polymerized. A resin composition having high solubility in methyl ethyl ketone could be prepared.

And above way tree butter sets Narubutsu 45 parts by weight of solvent 55 parts by mass was prepared by mixing at ambient temperature conditions, to prepare a varnish of the resin composition.
In Examples 1 to 5 and Comparative Examples 1 to 2, the glass cloth 2116 was prepared by adding polyphenylene ether (SA120) at a ratio of 50 parts by mass to 100 parts by mass of the resin composition (resin component) in the varnish. A prepreg was prepared by impregnation with one layer (1Ply). In Comparative Examples 3 and 4, a prepreg was prepared by impregnating the glass cloth 2116 with a single layer as it was without adding polyphenylene ether to the varnish. The glass transition point (Tg) for each cured product obtained by curing the prepregs of each Example and Comparative Example under the conditions of pressing conditions: 180 ° C. × 30 kg / cm ² × 1 hour and main curing conditions: 230 ° C. × 2 hours. The results of measuring the relative permittivity (Dk) and the dielectric loss tangent (Df) are shown in Table 1.

表２に示すように、（Ｄ）クマロン樹脂を配合することにより、硬化物の高い耐熱性を維持したまま、比誘電率および誘電正接を低くすることができた。 Table 2, the resin mixture proportions (parts by weight) shown in Table 3, and melt mixed using a biaxial mixing kneader to prepare a resin composition. Tables 2 and 3 show the results of evaluating the cured product prepared by curing the resin composition at 230 ° C. for 4 hours. The preparation conditions for the resin composition were the same as in Table 1.

As shown in Table 2, by blending the (D) kumaron resin, the relative permittivity and the dielectric loss tangent could be lowered while maintaining the high heat resistance of the cured product.

The present invention, high heat resistance Contact and low dielectric properties (low dielectric constant, low dielectric loss tangent) is a resin composition comprising a cured product having a said resin composition has excellent heat resistance and low dielectric properties It can be used as a raw material for adhesives, sealants, paints, molded products, laminates and printed wiring substrates.

[1] A resin composition for a printed wiring substrate obtained by melting a resin mixture containing (A) a polymaleimide compound, (B) benzoxazine, (C) an epoxy resin, and (D) a kumaron resin. Te, the resin component 100 parts by weight of the resin mixture, wherein (a) the content of the polymaleimide compound is 40 to 70 parts by mass der is, the (D) coumarone resin, softening point be 100 ° C. or less , weight average molecular weight of Ru der 850 or less, the resin composition.

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

[3] The resin mixture further contains (E) bisphenol A type cyanate ester, and the content of the (E) bisphenol A type cyanate ester in 100 parts by mass of the resin component of the resin mixture is 3 to 3. The resin composition according to [2] , which is 7 parts by mass.

（前記式（１）において、ｎ₁は０以上１０以下の整数であり、Ｘ¹はそれぞれ独立に炭素数１以上１０以下のアルキレン基、下記式（２）で表される基、「−ＳＯ₂−」で表される基、「−ＣＯ−」で表される基、酸素原子または単結合であり、Ｒ¹はそれぞれ独立に炭素数１以上６以下の炭化水素基であり、ａはそれぞれ独立に０以上４以下の整数であり、ｂはそれぞれ独立に０以上３以下の整数であり、繰り返し単位の数ｎ₁の平均値が０．０１以上５以下である。）

（前記式（２）において、Ｙは芳香族環を有する炭素数６以上３０以下の炭化水素基であり、ｎ₂は１〜３の整数である。） [4] The resin composition according to [1], wherein the (A) polymaleimide compound is represented by the formula (1).

(In the above formula (1), n ₁ is an integer of 0 or more and 10 or less, and X ¹ is an alkylene group having 1 or more and 10 or less carbon atoms independently, a group represented by the following formula (2), "-SO". _{A group represented by "2-} ", a group represented by "-CO-", an oxygen atom or a single bond, R ¹ is an independently hydrocarbon group having 1 or more carbon atoms and 6 or less carbon atoms, and a is each. Independently, it is an integer of 0 or more and 4 or less, b is an integer of 0 or more and 3 or less independently, and _{the average value of the number n 1} of the repeating units is 0.01 or more and 5 or less.)

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

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

[7] Of the 100 parts by mass of the (A) polymaleimide compound contained in the resin mixture, 30 to the (A) polymaleimide compound remaining as a residual maleimide compound in the resin composition after the melt mixing step. The resin composition according to any one of [1] to [6] , which is obtained by melting each component so as to have 60 parts by mass.

[8] A resin composition obtained by melting a resin mixture containing (A) a polymaleimide compound, (B) benzoxazine, (C) an epoxy resin, and (D) a kumaron resin, wherein the resin mixture is obtained. in the resin component 100 parts by weight, the (a) content of the polymaleimide compound is 40 to 70 parts by mass der is, the (D) coumarone resin, a softening point is not more 100 ° C. or less, the weight average molecular weight 850 following der Ru resin composition having a boiling point of 120 ° C. or less and a dielectric constant was dissolved in 10 to 30 solvent varnish.
[9] A resin composition obtained by melting a resin mixture containing (A) polymaleimide compound, (B) benzoxazine, (C) epoxy resin, and (D) kumaron resin, which is the resin mixture. in the resin component 100 parts by weight, the (a) content of the polymaleimide compound is 40 to 70 parts by mass der is, the (D) coumarone resin, a softening point is not more 100 ° C. or less, the weight average molecular weight laminates manufactured using the 850 following der Ru resin composition.
[10] A resin composition obtained by melting a resin mixture containing (A) a polymaleimide compound, (B) benzoxazine, (C) an epoxy resin, and (D) a kumaron resin, wherein the resin mixture is obtained. in the resin component 100 parts by weight, the (a) content of the polymaleimide compound is 40 to 70 parts by mass der is, the (D) coumarone resin, a softening point is not more 100 ° C. or less, the weight average molecular weight printed circuit board manufactured by using a 850 or less der Ru resin composition.

Claims (14)

A resin composition obtained by melting a resin mixture containing (A) a polymaleimide compound, (B) benzoxazine, (C) an epoxy resin, and (D) a kumaron resin.
A resin composition in which the content of the polymaleimide compound (A) in 100 parts by mass of the resin component of the resin mixture is 40 to 70 parts by mass. The resin composition according to claim 1, wherein the content of the (D) kumaron resin in 100 parts by mass of the resin component of the resin mixture is 0.1 to 5 parts by mass. The resin composition according to claim 2, wherein the (D) kumaron resin has a softening point of 100 ° C. or lower and a weight average molecular weight of 850 or less. The resin mixture further contains (E) bisphenol A type cyanate ester.
The resin composition according to claim 2 or 3, wherein the content of the (E) bisphenol A type cyanate ester in 100 parts by mass of the resin component of the resin mixture is 3 to 7 parts by mass. The resin composition according to claim 1, wherein the (A) polymaleimide compound is represented by the formula (1).

(In the above formula (1), n ₁ is an integer of 0 or more and 10 or less, and X ¹ is an alkylene group having 1 or more and 10 or less carbon atoms independently, a group represented by the following formula (2), "-SO". _{A group represented by "2-} ", a group represented by "-CO-", an oxygen atom or a single bond, R ¹ is an independently hydrocarbon group having 1 or more carbon atoms and 6 or less carbon atoms, and a is each. Independently, it is an integer of 0 or more and 4 or less, b is an integer of 0 or more and 3 or less independently, and _{the average value of the number n 1} of the repeating units is 0.01 or more and 5 or less.)

(In the above formula (2), Y is a hydrocarbon group having an aromatic ring and having 6 to 30 carbon atoms, and n ₂ is an integer of 1 to 3). The resin composition according to claim 1, wherein the content of (B) benzoxazine in 100 parts by mass of the resin component of the resin mixture is 10 to 30 parts by mass. The (C) epoxy resin contains an α-naphthol type epoxy resin, and the epoxy resin (C) contains an α-naphthol type epoxy resin.
The resin composition according to claim 1, wherein the content of the α-naphthol type epoxy resin in 100 parts by mass of the resin component of the resin mixture is 10 to 30 parts by mass. Of the 100 parts by mass of the (A) polymaleimide compound contained in the resin mixture, 30 to 60 parts by mass of the (A) polymaleimide compound remaining as a residual maleimide compound in the resin composition after the melt mixing step. The resin composition according to any one of claims 1 to 7, which is obtained by melting each component so as to be. The resin composition according to any one of claims 1 to 8, which is used for a printed wiring board. A varnish in which the resin composition according to any one of claims 1 to 8 is dissolved in a solvent having a boiling point of 120 ° C. or lower and a dielectric constant of 10 to 30. A laminated board produced by using the resin composition according to any one of claims 1 to 8. A printed wiring board manufactured by using the resin composition according to any one of claims 1 to 8. A molded product obtained by curing the resin composition according to any one of claims 1 to 8. A method for producing a resin composition, which comprises a melt-mixing step of melt-mixing the resin mixture according to any one of claims 1 to 8.