KR20200078638A - Resin composition - Google Patents

Abstract

(상기 식 (1)에서, n₁은 0~10의 정수이고, X¹은 각각 독립적으로 탄소수 1 내지 10의 알킬렌기, 하기 식 (2)로 표시되는 기, 식 "-SO₂-"로 표시되는 기, "-CO-"로 표시되는 기, 산소 원자 또는 단일 결합이고, R¹은 각각 독립적으로 탄소수 1 내지 6의 탄화수소기이며, a는 각각 독립적으로 0~4의 정수이고, b는 각각 독립적으로 0~3의 정수이다.)

(상기 식 (2)에서, Y는 방향족 고리를 갖는 탄소수 6 내지 30의 탄화수소기이며, n₂는 1~3의 정수이다.)A resin composition having good solubility in a low boiling point solvent such as methyl ethyl ketone and storage stability is provided. The content of (A) polymaleimide compound in 100 parts by mass of the resin mixture containing (A) polymaleimide compound and (B) benzoxazine compound represented by formula (1) is 30 to 9 parts by mass, A resin composition prepared by a melt mixing process of melt-mixing the resin mixture.

(In the formula (1), n ₁ is an integer of 0 to 10, X ¹ are each independently an alkylene group having 1 to 10 carbon atoms, a group represented by the following formula (2), the formula "-SO ₂ -" The group represented, a group represented by "-CO-", an oxygen atom or a single bond, R ¹ are each independently a hydrocarbon group having 1 to 6 carbon atoms, a is each independently an integer of 0 to 4, and b is Each independently is an integer from 0 to 3.)

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

Description

Resin composition

The present invention has good storage stability that is soluble in low-boiling solvents such as methyl ethyl ketone, used in the form of printed wiring boards, adhesives, sealants, paints, and molded articles requiring high heat resistance in electrical and electronic parts. It relates to a resin composition.

Conventionally, as the heat-resistant resin in the field of electronic materials, thermosetting resins such as epoxy resins, polyimide resins, unsaturated polyester resins, and phenol resins are used, and are used according to their use and characteristics. Among them, polyimide resins are particularly widely used for high heat resistance applications because of their excellent heat resistance and heat resistance (heat resistance after moisture absorption), and also modified polyimide resins whose performance has been improved by combining epoxy resins and aromatic diamines. Is being used.

In recent years, in the field of semiconductor substrates, a mounting method for directly mounting a semiconductor chip on a substrate has been spreading, and as a material to be used, a demand for high heat resistance capable of withstanding high-temperature treatment in the mounting process is increasing. In order to meet the demand for improving the heat resistance, various epoxy-resistant resin materials have been studied.

Modified imide resins in which polymaleimide is reacted with a specific phenolic resin, a specific epoxy resin, and a specific compound have also been proposed (Patent Documents 1 and 2), and polyimide resins and modified polyimide resins are general-purpose low-boiling solvents (low-boiling organic solvents). There is a problem that the solubility to) is poor, and the resin component precipitates from the varnish dissolved in the solvent, resulting in poor stability.

Japanese Patent Publication No. 2004-315705 Japanese Patent Publication 2003-73459

The present invention aims to solve the problems of the prior art, and aims to provide a resin composition having good solubility and storage stability in a low boiling point solvent such as methyl ethyl ketone.

[1] In 100 parts by mass of the resin mixture containing the (A) polymaleimide compound and (B) the benzoxazine compound represented by the formula (1), the (A) polymaleimide compound contains 30 to 95 parts by mass A resin composition, characterized in that produced by a melt mixing process to melt-mix the resin mixture.

(In the formula (1), n ₁ is an integer of 0 to 10, X ¹ are each independently an alkylene group having 1 to 10 carbon atoms, a group represented by the following formula (2), the formula "-SO ₂ -" A group represented, a group represented by "-CO-", an oxygen atom or a single bond, R ¹ are each independently a hydrocarbon group having 1 to 6 carbon atoms, a is each independently an integer of 0 to 4, and b is Each independently is an integer from 0 to 3.)

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

[2] The resin composition according to [1], wherein the resin mixture contains 10 to 100 parts by mass of the benzoxazine compound (B) relative to 100 parts by mass of the polymaleimide compound (A).

[3] The resin composition according to [2], wherein the average value of n ₁ in the formula (1) is 0.01 or more and 5 or less, X ¹ is -CH ₂ -, a is 0, and b is 0.

[4] The resin mixture according to [1], [2] or [3], wherein the resin mixture further contains 5 to 100 parts by mass of the epoxy resin (C) relative to 100 parts by mass of the polymaleimide compound (A). Resin composition.

[5] The resin composition according to [4], wherein the epoxy resin (C) contains a compound represented by formula (3).

[6] The resin composition according to any one of [1] to [5], wherein the content of the polymaleimide compound (A) is 42 parts by mass or less in 100 parts by mass of the resin composition.

[7] The resin composition according to any one of [1] to [6], which is for a printed wiring board.

[8] A varnish in which the resin composition according to any one of [1] to [7] is dissolved in a solvent having a boiling point of 120°C or less and a dielectric constant of 10 to 30.

[9] An adhesive containing the resin composition of any one of [1] to [7].

[10] A sealing agent containing the resin composition of any one of [1] to [7].

[11] A paint containing the resin composition of any one of [1] to [7].

[12] A molded article obtained by curing the resin composition of any one of [1] to [7].

[13] A method for producing a resin composition comprising a melt mixing step of melt-mixing the resin mixture of any one of [1] to [7].

By melt-mixing the resin mixture containing (A) 30 to 95 parts by mass of the polymaleimide compound and (B) a benzoxazine compound in 100 parts by mass of the resin mixture, a resin composition having good solubility in a low boiling point solvent and storage stability is provided. can do.

(Resin composition)

The resin composition of the present invention contains (A) a polymaleimide compound represented by Formula (1) and (B) a benzoxazine compound, and the (A) polymaleimide compound is 30 to 100 parts by mass of the resin mixture. It is produced by a melt mixing process of melt-mixing the resin mixture containing 95 parts by mass. In addition, "30 to 95 parts by mass" means "30 parts by mass or more and 95 parts by mass or less", and unless otherwise specified, "~" in the present invention means a range of "above to less than".

In the formula (1), n ₁ is an integer of 0 to 10, X ¹ is each independently an alkylene group having 1 to 10 carbon atoms, a group represented by the following formula (2), represented by the formula "-SO ₂ -" Group, a group represented by "-CO-", an oxygen atom or a single bond, R ¹ are each independently a hydrocarbon group having 1 to 6 carbon atoms, a is independently an integer of 0 to 4, and b is each It is an integer of 0-3 independently.

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

In the present invention, the thing before melt-mixing (A) the polymaleimide compound and (B) the benzoxazine compound is called a "resin mixture", and the thing after melt-mixing is called a "resin composition".

(A) Polymaleimide compound

The resin composition of the present invention contains 30 to 95 parts by mass of the polymaleimide compound represented by formula (1) in 100 parts by mass of the resin mixture before melting and mixing. From the viewpoint of obtaining a cured product having good solubility in a low boiling point solvent, stability in a dissolved state, and heat resistance, the content of the polymaleimide compound in 100 parts by mass of the resin mixture is more preferably 40 to 83 parts by mass, and 50 to 80 parts by mass It is more desirable to deny it.

In the polymaleimide compound, in formula (1), the average value of n ₁ is 0.01 or more and 5 or less, X ¹ is -CH ₂ -, a is 0, and b is 0, or polymaleimide consisting of two or more types. Mid compounds are preferred. Examples of such commercially available polymaleimide compounds include BMI-2000 and BMI-2300 (product names, manufactured by Daiwa Chemical Industries, Ltd.).

(B) benzoxazine compound

The resin composition of this invention contains 10-100 mass parts of benzoxazine compounds with respect to 100 mass parts of (A) polymaleimide compounds in the resin mixture before melt-mixing. 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, and even more preferably 20 parts by mass or more with respect to 100 parts by mass of the polymaleimide compound. Further, 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 even more preferably 40 parts by mass or less with respect to 100 parts by mass of the polymaleimide compound.

The benzoxazine compound may be one having at least one benzoxazine ring in the molecule, but the dihydrobenzoxazine compound represented by the following general formula (4) or (5) is preferred, and among them, the following general formula (5) The pd-type dihydrobenzoxazine represented by is more preferable.

(In Formulas (4) and (5), R ² and R ³ represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 3 carbon atoms.)

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

(C) epoxy resin

The resin composition of the present invention may further contain an epoxy resin in the resin mixture before melt mixing. When the resin mixture further contains an epoxy resin, a melt mixing process required to obtain a resin composition having good solubility in a low boiling point solvent can be performed at a low temperature. The content of the epoxy resin with respect to 100 parts by mass of the (A) polymaleimide compound in the resin mixture is preferably 5 to 100 parts by mass, more preferably 15 to 80 parts by mass, and even more preferably 30 to 60 parts by mass.

The epoxy resin may be any compound having an epoxy group, but a compound having three epoxy groups represented by formula (3) is preferred. As a commercially available epoxy resin represented by Formula (3), VG3101L (product name, manufactured by PRIN TECH Co., Ltd., high heat-resistant trifunctional epoxy resin) can be mentioned.

As the epoxy resins other than the above, 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, bisphenol F novolac A type epoxy resin, a triphenylol type epoxy resin, and a dicyclopentadiene type epoxy resin can be used.

The resin composition according to the present invention and the resin mixture before melt-mixing may contain components other than the above (A), (B) and (C), without detracting from the object of the present invention.

Using the resin composition of the present invention, an organic or inorganic filler can be used to obtain a base material that is cured to form a molded article. 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; 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 fibers, 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 other various metal powders, potassium titanate, lead zirconate titanate, aluminorate, molybdenum sulfide, silicon carbide, stainless fiber, zinc borate, various magnetic powders, slag fibers, ceramic powder, and the like.

The shape of the filler is preferably spherical or scale (scales), and may be used alone or in combination of two or more. Further, if necessary, a silane coupling agent having two or more different reactors in the molecule (one is a chemical reaction with an inorganic material and the other is a chemical reaction with an organic material) may be used in combination.

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

(D) Curing accelerator

When using the resin composition according to the present invention, a curing accelerator may also be used. Examples of the time for adding the curing accelerator include when the resin composition is used as a varnish dissolved in a solvent, when prepregging, or when manufacturing a substrate or a laminate.

Examples of the curing accelerator include dicumyl peroxide, 4,4'-diaminodiphenylmethane, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptiimidazole, and the like. Polyazoles; Amines such as triethanolamine, triethylenediamine, and N-methylmorpholine; Organic phosphine such as triphenylphosphine and tritolylphosphine; Tetraphenyl boron salts such as tetraphenyl phosphonium tetraphenyl borate and triethylammonium tetraphenyl borate; 1,8-diazabicyclo(5,4,0)undecene-7 and derivatives thereof; And organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, tin oleate, manganese naphthenate, cobalt teptate, and cobalt octylate. These curing accelerators may be used alone or in combination of two or more, or may be used in combination with an organic peroxide or an azo compound, if necessary.

The content of the curing accelerator is preferably blended so that the desired gelation time of the varnish or prepreg in which the resin composition is dissolved in the solvent is obtained, but is generally used in a range of 0.01 to 5.00 parts by mass based on 100 parts by mass of the resin component. .

(Melting mixing process)

The resin composition can be obtained by a melt mixing step of heating and mixing a resin mixture containing a polymaleimide compound (A) and a benzoxazine compound represented by Formula (1) above. In the melt mixing process, conventional mixing means may be used in the molten state. As the mixing means, kneaders such as kneaders and twin-screw extruders are preferred. The temperature at the time of melt mixing may be 400° C. or less from the temperature at which the resin mixture melts, more preferably 130° C. or more and 230° C. or less, and more preferably 150° C. or more and 210° C. or less. The melt mixing process is usually carried out for 0.1 to 10 minutes.

After the melt mixing step, the obtained mixture is cooled by natural cooling or forced cooling to obtain the resin composition of the present invention.

As a cooling method, it can be carried out by appropriately selecting from a known method. 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. In addition, after melting and mixing, a method of cooling after being placed in an environment of 30 to 300° C. in a thermostat may be adopted.

After cooling, the obtained resin composition is crushed and stored in a dry (dry) state, and can be used in a post process as a solid resin composition.

In the melt mixing step, a part of the (A) polymaleimide compound contained in the resin mixture reacts with the (B) benzoxazine compound to obtain a resin composition having good storage stability that is dissolved in a low boiling point solvent. From the viewpoint of improving solubility in a low boiling point solvent, the polymaleimide compound (also referred to as "residual maleimide compound") remaining in 100 parts by mass of the resin composition prepared by the melt mixing step is 42 parts by mass or less. It 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 point solvent, it remains as a residual maleimide compound in the resin composition after the melt mixing step in 100 parts by mass of the polymaleimide compound in the resin mixture before the melt mixing step. It is preferable that the said polymaleimide compound is 30-60 mass parts, and it is more preferable that it is 40-50 mass parts.

A flame retardant can 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, 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 preferably an amount necessary to have sufficient flame retardancy (eg, passing V-0 conditions in UL94 standards) without impairing the heat and moisture resistance of the resin composition. In the case of an organic flame retardant, it is generally preferably used in a range of 1 to 20 parts by mass with respect to 100 parts by mass of the total resin component containing the organic flame retardant, and in the case of an inorganic flame retardant, it is It is preferably used in a range of 10 to 300 parts by mass relative to 100 parts by mass in total.

In using the resin composition according to the present invention, other additives may be added depending on the application. Examples of other additives include various silicone oils, thermoplastic resins, synthetic rubbers such as NBR, and leveling agents. It is preferable that other additives are used in the range of the blending amount in which the content of the other additives in the total 100 parts by mass of the other additives and the resin component is 0.0001 to 5 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-described preparation method in a solvent having a boiling point of 120°C or less and a dielectric constant of 10 to 30.

Examples of the solvent having a boiling point of 120°C or less and a dielectric constant of 10 to 30 include ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ether-based solvents such as propylene glycol monomethyl ether, ethanol, 1-propanol, and 2-propanol. And alcohol-based solvents such as 1-butanol. In consideration of operability and the like, a ketone-based solvent is preferably used among the exemplified solvents. These solvents may be used alone or in combination of two or more. Moreover, it may contain the solvent other than what was illustrated 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. When dissolved under heating, it does not require a particularly long time. Depending on the boiling point of the solvent, the general conditions for dissolving are about 50 to 200°C, and the time is about 0.1 to 24 hours.

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

As the base material, a known base material used in 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 to the substrate, a prepreg is prepared through a drying process. The coating method, impregnation method, and drying method are not particularly limited, and a conventionally known method can be adopted. The drying conditions are appropriately determined depending on the boiling point of the solvent used, but too high a temperature is not preferable. It is preferable to dry so that the amount of the solvent remaining in the prepreg is 3% by mass or less.

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

The composite material can be obtained by curing one prepreg by heating under pressure with a hot press or the like, or by laminating a plurality of prepregs and heating under pressure to integrate them. The heating and pressing conditions when manufacturing 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 pressing time is 10 to 300 Minutes.

A metal foil or a metal plate may be laminated and integrated on one side or both sides of the laminate to form a laminate usable for a multilayer printed wiring board and the like. Such a laminated plate is pre-preg by laminating a metal foil or a metal plate on one or both sides of one prepreg to heat press, or by laminating and heat-pressing a metal foil or metal plate on one or both surfaces of the multiple prepregs. It can be produced by heating and curing to integrate.

As the metal foil or metal plate, copper, aluminum, iron, stainless steel, or the like can be used. The conditions for heating and curing are preferably the same conditions as those for producing the composite material. In addition, an inner layer core material may be used to form a laminated board for a multilayer printed circuit board.

The present invention can also be carried out in the form of adhesives, encapsulants and paints containing the above-mentioned resin composition.

Example

Hereinafter, the present invention will be described 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

(1) Solvent solubility

60 parts by mass of the measurement sample (resin composition) and 40 parts by mass of methyl ethyl ketone (solvent) were mixed under room temperature conditions, and the dissolved state after dissolving for 1 hour by applying ultrasonic vibration was evaluated visually using the following criteria.

○: Transparent liquid at room temperature

×: Liquid or semi-liquid state that is cloudy at room temperature

(2) Gel time

Measured by gel time meter SG-70

(3) Glass transition point (Tg)

The cured resin cured product of the resin composition was cut (cut) to a predetermined size, and used as a sample for measuring the glass transition point. The glass transition temperature (°C) of the sample was measured under the following conditions. The outgas generated during curing indicates that the glass transition point (Tg) could not be measured and was not measured with "-".

Measuring equipment: ThemoplusTMA8310 from Rigak

Sample Dimension: Width 5mm × Length 5mm × Height 4mm

Atmosphere: N ₂

Measurement temperature: 30~350℃

Heating rate: 10℃/min.

Measurement mode: compression

(4) Thermal weight change

According to JIS K7120, the temperature was raised at a rate of 10°C per minute at 30°C, and the temperature at which the mass was reduced by 1% (Td(1%)) and the temperature at which the mass was reduced by 5% (Td(5%)) were measured.

(5) Solubility

The solution obtained by dissolving the resin composition in methyl ethyl ketone was left at room temperature, and the dissolution state after a predetermined period of time (right after dissolution and after 1 hour) was visually evaluated using the following criteria.

○: Transparent liquid after a certain period of time

×: liquid or semi-liquid state in turbidity after each standing time

(6) Residual maleimide (content of maleimide compound in resin composition, %)

Measured by HLC-8320GPC manufactured by Tosoh Corporation

(7) Molecular weight

Measured by HLC-8320GPC manufactured by Tosoh Corporation

(8) Preservation stability

The solution obtained by dissolving the resin composition in methyl ethyl ketone was left at room temperature, and the dissolution state after a predetermined period of time (2 days, 7 days) elapsed was visually checked to evaluate the storage stability of the solution (varnish).

○: Precipitation does not occur after a week (7 days) from the time of preparation.

△: Precipitation occurs a week (7 days) from the time of preparation.

×: precipitation occurs after 2 days from the time of preparation

2. Raw material

(A) Polymaleimide compound

BMI-1000 (Product name, manufactured by Daiwa Kasei Industrial Co., Ltd., 4,4'-diphenylmethane bismaleimide)

BMI-2300 (Product name, manufactured by Daiwa Kasei Industrial Co., Ltd., polyphenylmethane polymaleimide)

(B) benzoxazine compound

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

(C) epoxy resin

VG3101L (Product name, manufactured by PRINTECH Co., Ltd., high heat-resistant trifunctional epoxy resin, compound of formula (3))

(Examples 1 to 6 and Comparative Example 1)

The raw material of the composition shown in Table 1 was melt-mixed for 90 seconds at a melting temperature of 230° C. on a hot plate to prepare a resin composition. Table 1 shows the results of measuring solubility and gel time for each resin composition. In addition, Table 1 shows the content of each component in parts by mass (Table 2 and Table 3 are the same). The resin composition was cured by heating at a curing temperature of 200°C and 230°C for 2 hours to produce a cured resin. Table 1 shows the results of measuring the glass transition point (Tg) and thermal weight change (Td (1%), Td (5%)) for each resin cured product.

From the results shown in Table 1, the following were found.

By melt-mixing the resin mixture containing the polymaleimide compound (BMI-2300) and benzooxazine (BZO), a resin composition that is soluble in methyl ethyl ketone (MEK), does not precipitate, and has good storage stability was obtained.

The resin mixture obtained by melt-mixing the polymaleimide compound (BMI-1000) and benzoxazine (BZO) was not soluble in methyl ethyl ketone (MEK).

When BMI-2300 was used as the polymaleimide compound, the same solubility was obtained even when an additional epoxy resin (VG3101L) was added.

The resin cured products obtained by curing the resin compositions of Examples 1 to 6 had high Tg and Td and good heat resistance.

(Examples 7-18)

The raw materials of the composition shown in Table 2 were melt-mixed on a hot plate at 185°C, 200°C, 220°C and 250°C for 90 seconds to obtain a resin composition. Table 2 shows the results of measuring the residual maleimide, molecular weight, and storage stability for the resin composition.

(Comparative Example 2)

The raw material of the composition shown in Table 2 was mixed under room temperature without heating to obtain a resin composition. Table 2 shows the results of measuring the residual maleimide, molecular weight, and storage stability for the resin composition.

From the results shown in Table 2, the following items were found.

Prescription 1 (Examples 7 to 10, Comparative Example 2), Prescription 2 (Examples 11 to 14), and Prescription 3 (Examples 15 to 18), the weight average molecular weight (Mw) of the obtained resin composition is about 600 to 670 , Was not significantly different.

Both the prescription 1, the prescription 2, and the prescription 3 confirmed the tendency for the molecular weight of the obtained resin composition to become slightly large by raising the melting temperature. On the other hand, neither prescription changed the residual maleimide in the resin composition according to the melting temperature of the melt mixing process.

Prescription 1 consisting of two components, polymaleimide and benzoxazine, improved storage stability by increasing the temperature of the melt mixing process.

In the formulations 2 and 3 in which the epoxy resin was added to the components of the formulation 1, a resin composition having good storage stability was obtained even when the temperature of the melt mixing step was lowered.

It has been found that the storage stability of the resin composition obtained by the melt mixing process is related to the amount (% by mass) of the residual maleimide contained in the resin composition.

By performing the melt mixing step, the amount of residual maleimide in the resin composition is reduced, and the storage stability of the resin composition is improved.

The present invention is a resin composition excellent in solubility and storage stability in a low-boiling solvent, and can be used as a raw material for adhesives, sealants, paints and molded articles having good heat resistance.

Claims (13)

The resin containing 30 to 95 parts by mass of the (A) polymaleimide compound in 100 parts by mass of the resin mixture containing the (A) polymaleimide compound and (B) the benzoxazine compound represented by formula (1) A resin composition, characterized in that produced by a melt mixing process to melt-mix the mixture.
[Formula 1]

(In the formula (1), n ₁ is an integer of 0 to 10, X ¹ are each independently an alkylene group having 1 to 10 carbon atoms, a group represented by the following formula (2), the formula "-SO ₂ -" A group represented, a group represented by "-CO-", an oxygen atom or a single bond, R ¹ are each independently a hydrocarbon group having 1 to 6 carbon atoms, a is each independently an integer of 0 to 4, and b is Each independently is an integer from 0 to 3.)
[Formula 2]

(In the formula (2), Y is a hydrocarbon group having 6 to 30 carbon atoms having an aromatic ring, and n ₂ is an integer from 1 to 3.) According to claim 1,
The resin composition in which the resin mixture contains 10 to 100 parts by mass of the (B) benzoxazine compound relative to 100 parts by mass of the (A) polymaleimide compound. According to claim 2,
In the formula (1), the average value of n ₁ is 0.01 or more and 5 or less, X ¹ is -CH ₂ -, a is 0, and b is 0. The method according to claim 1, 2 or 3,
The said resin mixture further contains (C) 5-100 mass parts of epoxy resins with respect to (A) 100 mass parts of polymaleimide compounds. The method of claim 4,
The resin composition containing the compound represented by Formula (3) in the said (C) epoxy resin.
[Formula 3]

The method according to any one of claims 1 to 5,
The resin composition in which the content of the polymaleimide compound (A) is 42 parts by mass or less in 100 parts by mass of the resin composition. The method according to any one of claims 1 to 6,
Resin composition for printed wiring boards. A varnish in which the resin composition according to any one of claims 1 to 7 is dissolved in a solvent having a boiling point of 120°C or less and a dielectric constant of 10 to 30. Adhesive containing the resin composition of any one of Claims 1-7. A sealing agent containing the resin composition according to any one of claims 1 to 7. A paint containing the resin composition according to any one of claims 1 to 7. A molded article obtained by curing the resin composition according to any one of claims 1 to 7. A method for producing a resin composition comprising a melt mixing step of melt-mixing the resin mixture of any one of claims 1 to 7.