KR20210111316A - Resin composition, varnish, laminated board and printed circuit board - Google Patents

Abstract

A resin composition obtained by melting a resin mixture containing (A) a polymaleimide compound, (B) benzoxazine, (C) an epoxy resin, and (D) a coumarone resin, 100 parts by mass of a resin component of the resin mixture Among them, (A) is a resin composition in which the content of the polymaleimide compound is 40 to 70 parts by mass, and having high heat resistance and low dielectric properties (low dielectric constant, low dielectric loss tangent), laminated board, printed circuit board, adhesive, encapsulant , can be used as electronic/electrical parts such as paints and molded articles.

Description

Resin composition and its manufacturing method

The present invention relates to a resin composition used as a laminate, a printed circuit board, an adhesive, an encapsulant, a paint, a molded article, etc., having high heat resistance and low dielectric properties (low dielectric constant, low dielectric loss tangent) in electrical and electronic parts, and its manufacture it's about how

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 separately according to their use and characteristics. In particular, polyimide resins are widely used for applications requiring high heat resistance because they are excellent in heat resistance and heat resistance (heat resistance after moisture absorption). In addition, a modified polyimide resin whose performance is improved by combining another resin such as an epoxy resin or an aromatic diamine with a polyimide resin is also used.

In recent years, in the field of semiconductor substrates, a mounting method of directly mounting a semiconductor chip on a substrate has become popular. Accordingly, materials used for semiconductors are required to have high heat resistance capable of withstanding high-temperature treatment in a mounting process and the like. Epoxy resins are widely used as semiconductor materials, and studies have been made to respond to the demand for improvement in heat resistance, and resins excellent in heat resistance have been proposed. For example, Patent Document 1 describes a modified polyimide resin composition in which a polymaleimide compound, a phenol resin, a bisphenol A epoxy resin, and another epoxy resin are melted.

Patent Document 1: Japanese Patent Laid-Open No. 2017-101152

Although the modified polyimide resin composition described in Patent Document 1 has a characteristic of high heat resistance, the low dielectric properties may not be sufficient depending on the application. Accordingly, 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) a coumarone resin, the resin component of the resin mixture The content of the (A) polymaleimide compound in 100 parts by mass is 40 to 70 parts by mass, the resin composition.

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

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

[5] The resin composition according to [1], wherein the (A) polymaleimide compound is represented by the formula (1).

[Formula 1]

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

[Formula 2]

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

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

[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 parts by mass, [1] The resin composition described in.

[8] Among 100 parts by mass of the polymaleimide compound (A) contained in the resin mixture, 30 to 60 parts by mass of the polymaleimide compound (A) remaining as the remaining maleimide compound in the resin composition after the melt mixing step The resin composition according to any one of [1] to [7], obtained by dissolving each component as much as possible.

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

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

[11] A laminate produced by using the resin composition according to any one of [1] to [8].

[12] A printed circuit board manufactured using the resin composition according to any one of [1] to [8].

[13] A molded article 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].

By melting a resin mixture containing (A) a polymaleimide compound, (B) benzoxazine, (C) an epoxy resin, and (D) a coumarone resin, high heat resistance and low dielectric properties (low dielectric constant, low dielectric loss tangent) ) can be provided as a cured product having a resin composition.

(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 coumarone resin, the resin 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 mixture. Hereinafter, each component of (A)-(D) and other components which may be contained are demonstrated. In this invention, the thing before melt-mixing each component is called "resin mixture", and what cooled after melt-mixing is called "resin composition".

(A) polymaleimide compound

A polymaleimide compound is a compound which has two or more maleimide groups. From the viewpoint of high heat resistance and low dielectric properties of the cured product, it is preferable that a maleimide group is bonded to the aromatic ring. As such a polymaleimide compound, what is represented by Formula (1) shown in the term of the means for solving a subject is mentioned.

From the viewpoint of improving the solubility of the resin composition in the low boiling point solvent, the polymaleimide compound _{preferably has an average value of the number of repeating units (n 1} ) 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 moiety) enclosed in parentheses in Formula (1) in _{a ratio such that the average value of the number of repeating units (n 1} ) is 0.01 or more and 5 or less. desirable. Thereby, the range of melting temperature from which the resin composition with favorable solubility with respect to a low boiling point solvent can be obtained can be widened. In the present invention, "a _{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 compound or a mixture of two or more compounds.

_{By using the polymaleimide compound (A) having an average value of the number (n 1} ) of repeating units in the formula (1) of 0.01 or more and 5 or less, a resin composition with good solubility in methyl ethyl ketone as a low boiling point solvent. Accordingly, a resin composition having good solubility in methyl ethyl ketone is obtained without using a bisphenol A epoxy resin having an effect of improving the solubility of the resin composition in a low-boiling solvent.

By suppressing the content of the bisphenol A epoxy resin in the resin component of the resin mixture, the heat resistance of the cured product of the resin composition is improved. It is preferable that a resin mixture does not contain a bisphenol A epoxy resin from a viewpoint of making the heat resistance of the hardened|cured material of a resin composition favorable. Here, "not containing a bisphenol A epoxy resin" means not containing substantially, ie, not containing the bisphenol A epoxy resin of the quantity which affects the property of a resin mixture.

Since the resin mixture contains the polymaleimide compound in a high ratio of 40 to 70 parts by mass in 100 parts by mass of the resin component of the resin mixture, 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, and still more preferably 55 to 65 parts by mass. In addition, in the present invention, the numerical range 'A to B' means 'A or more and B or less'.

As for the polymaleimide compound represented by Formula (1), the polymaleimide compound whose X ¹ is -CH ₂ -, a is 0, and b is 0 is preferable. As such a commercially available polymaleimide compound, BMI-2000 and BMI-2300 (product name, Yamato Chemical Industry Co., Ltd. product, phenylene maleimide) are mentioned, for example.

(B) benzoxazine compounds

The benzoxazine compound may be one having at least one benzoxazine ring in the molecule, and a dihydrobenzoxazine compound represented by the following general formula (3) or (4) is preferable, and among them, the following general formula (4) The pd-type dihydrobenzoxazine represented by is more preferable.

[Formula 3]

[Formula 4]

(In Formulas (3) and (4), R ² , R ³ represents a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 3 carbon atoms.)

These dihydrobenzoxazine compounds can be used individually or in combination of 2 or more types.

The content of the benzoxazine compound in 100 parts by mass of the resin component of the resin mixture is preferably 10 to 30 parts by mass from the viewpoint of high heat resistance and low dielectric properties of the cured product, and solubility of the resin composition in a low boiling point solvent and stability of the dissolved state. and 12-25 mass parts is more preferable, and 15-22 mass parts is still more preferable. In addition, from the viewpoint of solubility in a low-boiling solvent and stability in a dissolved state, the content of the benzoxazine compound is more preferably 15 parts by mass or more, and more preferably 20 parts by mass or more, based on 100 parts by mass of the polymaleimide compound (A). more preferably. 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, and 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 from the viewpoint of achieving both heat resistance and low dielectric properties of the cured product of the resin composition, a biphenyl aralkyl type epoxy resin, an epoxy resin containing a naphthalene ring, and an epoxy group represented by Formula (5) A compound having three is preferable. As an epoxy resin containing a naphthalene ring, (alpha)-naphthol type epoxy resin is preferable. As a commercially available epoxy resin containing a naphthalene ring, ESN-475V (product name, Shin-Nippon Chemical Co., Ltd. product, (alpha)-naphthol type epoxy resin) in which each naphthalene ring has two epoxy groups is mentioned. Moreover, as a commercially available epoxy resin represented by Formula (5), VG3101L (a product name, the product made by PRINTEC Co., Ltd., high heat-resistant trifunctional epoxy resin) is mentioned.

[Formula 5]

Examples of the epoxy resin other than the above include bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy resin, bisphenol F novolac A type|mold epoxy resin, a triphenylol type|mold epoxy resin, a dicyclopentadiene type|mold epoxy resin, etc. are mentioned. These epoxy resins can be used 1 type or in combination of 2 or more types.

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, further 15 to 22 parts by mass from the viewpoint of high heat resistance and low dielectric properties of the cured product. desirable.

(D) coumarone resin

The coumarone resin is a copolymer resin containing coumarone, indene and styrene as main components. As a commercial item, G-90, V-120, L-5, L-20, H-100 (all are product names, Nitto Chemical Co., Ltd. product) etc. are mentioned. From the viewpoint of forming a resin composition realizing a cured product having low dielectric properties, a coumarone resin having a softening point of 100° C. or less and a weight average molecular weight of 850 or less is preferable.

The content of the coumarone 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, and further 1-3 parts by mass from the viewpoint of high heat resistance and low dielectric properties of the cured product. desirable.

(E) bisphenol A cyanate ester

Bisphenol A cyanate ester is a bisphenol A cyanate ester which forms and hardens|cures a triazine ring. By using the bisphenol A cyanate ester and (D) coumarone resin together, the dielectric constant and dielectric loss tangent of the cured product obtained by curing the resin composition can be further lowered. The bisphenol A cyanate ester includes a monomer and a (homo)polymer (polymer). From the viewpoint of obtaining a cured product having excellent low dielectric properties, a monomer of the bisphenol A cyanate ester is preferable.

The content of (E) bisphenol A cyanate ester in 100 parts by mass of the resin component of the resin mixture is preferably 1 to 10 parts by mass, more 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.

(F) curing accelerator

When using the resin composition according to the present invention, a curing accelerator may be added. As time to add a hardening accelerator, when a resin composition is made into the varnish which melt|dissolved in the solvent, the time of prepreg formation, the time of manufacturing a base material, a laminated board, etc. are mentioned.

Examples of the curing accelerator include imida such as dicumyl peroxide, 4,4'-diaminodiphenylmethane, 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-heptimidazole. zole; amines such as triethanolamine, triethylenediamine, and N-methylmorpholine; organic phosphines such as triphenylphosphine and tritolylphosphine; tetraphenyl boron salts such as tetraphenylphosphonium tetraphenylborate and triethylammonium tetraphenylborate; 1,8-diazabicyclo(5,4,0)undecene-7 and its derivatives; and organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, tin oleate, manganese naphthenate, cobalt tefthenate, and cobalt octylate. These hardening accelerators may be used individually or in combination of 2 or more types, and an organic peroxide, an azo compound, etc. can also be used together as needed.

The content of these curing accelerators is preferably blended in a varnish or prepreg within a range in which a desired gelation time is obtained. Generally, it is used in the range of 0.01-5 mass parts with respect to a total of 100 mass parts of resin components contained in a 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, in order to obtain the base material used as a molded article by hardening the resin composition of this invention, an organic or inorganic filler can be used. Examples of the filler include oxides such as silica, diatomaceous earth, alumina, zinc chloride, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites; hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, 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 fibers; silicates such as calcium silicate (wollastonite, zonotorite), talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, and silica-based balloons; nitrides such as aluminum nitride, boron nitride, and silicon nitride; carbons such as carbon black, graphite, carbon fiber, carbon balloon, and charcoal powder; and various other metal powders, potassium titanate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless fiber, zinc borate, various magnetic powders, slag fiber, ceramic powder, and the like.

As a shape of a filler, a spherical shape or a scale shape is preferable, and these may be used independently or 2 or more types may be used together. In addition, if necessary, a silane coupling agent having two or more different reactive groups in the molecule (one reactive with an inorganic material and the other reactive with an organic material) may be used in combination.

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

A flame retardant may be added to the resin composition as needed. Examples of the flame retardant 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. These flame retardants may be used independently or may use 2 or more types together.

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

In using the resin composition according to the present invention, other additives may be added according to the use. Examples of other additives include various silicone oils, thermoplastic resins, synthetic rubbers such as NBR, and leveling agents. It is preferable that the other additive is used in the range of the compounding quantity in which the content of the said other additive will be 0.0001-5 mass parts in a total of 100 mass parts of the other additive in a resin composition, and a resin component.

(melt mixing process)

The resin composition of the present invention is melt-mixed by heating a resin mixture containing (A) a polymaleimide compound, (B) benzoxazine, (C) an epoxy resin, and (D) a coumarone resin and mixing it in a molten state. manufactured by the process. A conventional mixing means may be used for the melt mixing process. As a mixing means, a kneader, a twin-screw kneader, etc. are preferable. What is necessary is just to set the temperature at the time of melt mixing to 400 degreeC or more above the temperature at which the resin mixture melts, 130 degreeC - 230 degreeC are more preferable, and 150 degreeC - 210 degreeC are still more preferable. The melt mixing process is usually performed 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 melt mixing process, _{the average value of the number of repeating units (n 1} ) in Formula (1) is 0.01 or more and 5 or less (A ), it is preferable to use a polymaleimide compound.

After the melt mixing step, natural cooling or forced cooling is performed to obtain the resin composition of the present invention.

As a cooling method, it can select suitably from a well-known method and can carry out. 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. may be adopted. In addition, a method of cooling after being placed under an environment of 30 to 300° C. in a thermostat after melt mixing may be adopted.

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

In the melt mixing step, at least a part of the (A) polymaleimide compound contained in the resin mixture reacts with other components in the resin mixture to thereby modify. Thereby, it is 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 the low-boiling solvent, the polymaleimide compound remaining in the resin composition produced by the melt-mixing step (appropriately, also referred to as 'remaining maleimide compound') is 42 parts by mass per 100 parts by mass of the resin component. A part or less is preferable, and 40 mass parts or less are more preferable.

From the viewpoint of improving the solubility of the modified resin composition in the low boiling point solvent after the melt mixing step, out of 100 parts by mass of the polymaleimide compound in the resin mixture before the melt mixing step, remaining as the remaining maleimide compound in the resin composition after the melt mixing step It is preferable that it is 30-60 mass parts, and, as for the polymaleimide compound to make, it is more preferable that it is 40-50 mass parts.

(varnish)

The varnish of the resin composition according to the present invention is obtained by dissolving the resin composition obtained by the above-described manufacturing method in a solvent having a boiling point of 120° C. or less and a relative permittivity of 10 to 30.

Examples of solvents having a boiling point of 120° C. or less and a relative permittivity of 10 to 30 include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ether solvents such as propylene glycol monomethyl ether, ethanol, 1-propanol, 2 - Alcoholic solvents, such as a propanol and 1-butanol, etc. are mentioned. In consideration of operability and the like, ketone-based solvents are preferably used among the exemplified solvents. These solvents may be used independently and may mix and use 2 or more types. Moreover, you may contain solvents other than what was illustrated above.

Content of the resin composition in 100 mass parts of varnishes is 40-80 mass parts normally, Preferably it is 50-70 mass parts. The varnish can be obtained by dissolving the resin composition in a solvent at room temperature (room temperature) or under heating. In the case of dissolving under heating, although it varies depending on the boiling point of the solvent, the general conditions for dissolving are about 50 to 200° C., and about 0.1 to 24 hours of time.

The prepreg may be prepared by applying or impregnating the varnish on a substrate, followed by drying to remove the solvent.

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

After the varnish is applied or impregnated on the substrate, a prepreg is manufactured through a drying process, but the application method, the impregnation method, and the drying method are not particularly limited, and a conventionally known method may be adopted. About drying conditions, although it determines suitably with the boiling point of the solvent to be used, too high temperature is unpreferable. It is preferable to dry so that the quantity of the solvent which remains in 100 mass % of prepreg may become 3 mass % or less.

When preparing a prepreg, you may add resin other than the resin composition mentioned above to a varnish. Polyphenylene ether resin etc. are mentioned as this resin. From the viewpoint of imparting high heat resistance, low dielectric constant, and low dielectric loss tangent to the cured product obtained by curing the prepreg, polyphenylene ether resin is preferable. From a similar viewpoint, the addition amount of the polyphenylene ether resin used when preparing the prepreg is preferably 10 to 100 parts by mass, more preferably 10 to 50 parts by mass, based on 100 parts by mass of the resin component of the resin composition of the present invention. , more preferably 20 to 40 parts by mass. As a commercially available polyphenylene ether resin, SA90, SA120, SA9000 (a product name, all are made by SABIC Japan Corporation), etc. are mentioned.

The resin composition of the present invention is suitable for a printed circuit board, and the present invention can be practiced as a molded article obtained by curing the resin composition. As a molded article, the hardened|cured material formed by hardening only the resin composition, the composite material composited with other raw materials, a laminated body, etc. are mentioned.

A composite material and a laminate can be obtained by heating and curing one prepreg under pressure using a hot press or the like, or by laminating a plurality of prepregs and heating them under pressure to integrate them. Heating and pressing conditions when manufacturing the composite material are not particularly limited, the heating temperature is 100 to 300 ℃, preferably 150 to 250 ℃, the pressure is 10 to 100kg / cm ² , the heating and pressing time is 10 to 300 about a minute

Metal foils or metal plates are laminated and integrated on one side or both sides of the laminate to obtain a laminate that can be used for multilayer printed circuit boards and the like. Such a laminate is obtained by laminating a metal foil or a metal plate on one side or both sides of one prepreg and hot pressing, or by laminating and hot pressing a metal foil or metal plate on one side or both sides to become the outermost layer of a plurality of laminated prepregs. It can be manufactured by heat-hardening and integrating.

Copper, aluminum, iron, stainless steel, etc. can be used as metal foil or a 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 those for manufacturing the composite material. Moreover, it can also be set as the laminated board for multilayer printed circuit boards using an inner-layer core material.

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

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

1. Test method

[Solvent Solubility]

60 parts by mass of the sample (resin composition) and 40 parts by mass of methyl ethyl ketone (solvent) were mixed under room temperature conditions, and the dissolved state after applying ultrasonic vibration for a predetermined time was visually evaluated using the following criteria.

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

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

×: turbid liquid or semi-liquid state even after 5 hours (room temperature)

[Glass Transition Point (Tg)]

[Coefficient of Thermal Expansion: CTE (ppm/℃)]

The cured product obtained by curing the resin composition was cut (cut out) to a predetermined size, and used as 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 a TMA (Thermomechanical Analysis) method.

Measuring device: Thermo plus TMA8310 manufactured by Rigaku

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

Atmosphere: N ₂

Measuring temperature: 30 to 350℃

Temperature increase rate: 10℃/min.

Measuring Mode: Compression

[Thermogravimetric change]

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

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

It was measured at 1 GHz condition by the cavity resonance technique.

2. Raw material

(A) polymaleimide compound

· BMI-2300 (product name, Yamato Chemical Industry Co., Ltd., polyphenylmethane polymaleimide)

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

(B) benzoxazine compounds

· BZO: (P-d type) benzoxazine (manufactured by Shikoku Chemical Co., Ltd.)

(C) Epoxy resin

· VG3101L (product name, made by PRINTEC Co., Ltd., high heat-resistant trifunctional epoxy resin)

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

[Formula 6]

(D) coumarone resin

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

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

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

(E) bisphenol A cyanate ester

· Monomer: bisphenol A-type cyanate ester monomer (product name: triazine, manufactured by Mitsubishi Gas Chemicals Co., Ltd., CAS No.1156-51-0, 2,2-bis(4-cyanatophenyl)propane)

Polymer: (homo)polymer of bisphenol A cyanate ester (product name: TA1500, manufactured by Mitsubishi Gas Chemical Co., Ltd., CAS No.1156-51-0, 25722-6

6-1, 2,2-bis(4-cyanatophenyl)propane homopolymer)

(other ingredients)

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

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

Using a twin-screw mixer (kneading), the resin mixture of the ratio (parts by mass) shown in Table 1 was melt-mixed (melt-kneaded) to prepare a resin composition. The conditions of the melt mixing step were a barrel temperature of 270°C and a resin composition temperature of 185 to 195°C (temperature at the outlet of the resin composition of the twin screw mixer). In the twin screw mixer used in this example, 30 to 60 parts by mass per 100 parts by mass of (A) bismaleimide contained in the resin mixture were left in the resin composition without polymerization under the above conditions, and the solubility in methyl ethyl ketone This high resin composition was able to be prepared.

45 parts by mass of the resin blend 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, polyphenylene ether (SA120) was added in a ratio of 50 parts by mass to 100 parts by mass of the resin composition (resin component) in the varnish, and glass fiber 2116 was impregnated in one layer. A prepreg was prepared by doing (1 Ply). In Comparative Examples 3 to 4, a prepreg was prepared by impregnating glass fiber 2116 as it is in one layer without adding polyphenylene ether to the varnish. The prepreg of each Example and the comparative example was pressed condition; 180℃ × 30kg/cm ² × 1 hour, main curing conditions; Table 1 shows the results of measuring the glass transition point (Tg), dielectric constant (Dk), and dielectric loss tangent (Df) for each cured product cured under the conditions of 230°C × 2 hours.

From the results in Table 1, the following can be said.

A cured product having high heat resistance (Tg), low dielectric constant (Dk) and low dielectric loss tangent (Df) was obtained by a prepreg using a resin composition prepared by melting a resin mixture containing a coumarone resin.

Coumarone resin is effective in obtaining a cured product having a low dielectric constant (Dk) and a low dielectric loss tangent (Df) that is in the form of beads (solid) at room temperature rather than liquid at room temperature, and has a weight average molecular weight of 800 or less. did.

In order to further lower the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product, it was effective to use coumarone resin and (E) bisphenol A cyanate ester together.

(E) In the case of bisphenol A cyanate ester, the monomer was more effective than the polymer in order to lower the dielectric loss tangent of the cured product.

The resin mixture of the ratio (mass part) shown in Table 2, Table 3 was melt-mixed using the twin screw kneader, and the resin composition was prepared. 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 conditions for preparing the resin composition were the same as in Table 1.

As shown in Table 2, by blending the (D) coumarone resin, the dielectric constant and dielectric loss tangent could be made low while maintaining high heat resistance of the cured product.

From the results of Table 3, the following can be said.

_{The average value of n 1} of the compound represented by 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 polymaleimide compound BMI-2300 By using it, it became the resin composition with favorable solubility with respect to methyl ethyl ketone.

By using a coumarone resin having a softening point of 85 to 105° C. and a weight average molecular weight of 700 to 800, about 1 to 3 parts by mass per 100 parts by mass of the resin component of the resin composition is a small compounding amount, and high heat resistance (Tg) and low dielectric constant (Dk) ) and a cured product having a low dielectric loss tangent (Df) was obtained.

The present invention is a resin composition that becomes a cured product having high heat resistance, high heat resistance and low dielectric properties (low dielectric constant, low dielectric loss tangent), and the resin composition is an adhesive, encapsulant, paint, and molded article having excellent heat resistance and low dielectric properties , can be used as a raw material for laminates and printed circuit boards.

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 coumarone 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, the resin composition. According to claim 1,
The content of the (D) coumarone resin in 100 parts by mass of the resin component of the resin mixture is 1 to 5 parts by mass, the resin composition. 3. The method of claim 2,
The (D) coumarone resin has a softening point of 100° C. or less, and a weight average molecular weight of 850 or less, a resin composition. 4. The method of claim 2 or 3,
The resin mixture further contains (E) bisphenol A cyanate ester,
The content of the (E) bisphenol A 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,
The resin composition in which the said (A) polymaleimide compound is represented by Formula (1).
[Formula 1]

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

(In the formula (2), Y is a hydrocarbon group having 6 or more and 30 or less carbon atoms having an aromatic ring, and n ₂ is an integer of 1 to 3.) According to claim 1,
The (B) benzoxazine content in 100 parts by mass of the resin component of the resin mixture is 10 to 30 parts by mass, the resin composition. According to claim 1,
The (C) epoxy resin contains α-naphthol type epoxy resin,
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, the resin composition. 8. The method according to any one of claims 1 to 7,
Among 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 the remaining maleimide compound in the resin composition after the melt mixing step, each A resin composition obtained by dissolving a component. 9. The method according to any one of claims 1 to 8,
A resin composition for a printed circuit board. A varnish obtained by dissolving the resin composition according to any one of claims 1 to 8 in a solvent having a boiling point of 120°C or less and a dielectric constant of 10 to 30. A laminate manufactured by using the resin composition according to any one of claims 1 to 8. A printed circuit board manufactured using the resin composition of any one of claims 1 to 8. A molded article formed by curing the resin composition according to any one of claims 1 to 8. The manufacturing method of the resin composition provided with the melt-mixing process of melt-mixing the said resin mixture in any one of Claims 1-8.