TW201918378A - Resin composition - Google Patents

Abstract

Provided is a resin composition having excellent preservation stability and solubility in a low-boiling point solvent such as methyl ethyl ketone. The resin composition is produced through a melt-mixing step of melt-mixing a resin mixture so that, in 100 parts by mass of the resin mixture containing (B) a benzo-oxazine compound and (A) a polymaleimide compound represented by formula (1), the content of (A) the polymaleimide compound is 30 to 95 parts by mass. (1) (In formula [1]: n1 represents an integer between 0 and 10; each X1 represents, independently, an alkylene group having a number of carbons ranging from 1 to 10, a group represented by formula [2], a group represented by the formula -SO2-, a group represented by -CO-, an oxygen atom, or a single bond; each R1 represents, independently, a hydrocarbon group having a number of carbons ranging from 1 to 6; each "a" represents, independently, an integer between 0 and 4; and each "b" represents, independently, an integer between 0 and 3.) (2) (In formula [2]: Y represents a hydrocarbon group having a number of carbons ranging from 6 to 30 and having an aromatic ring; and n2 represents an integer from 1 to 3.).

Description

Resin composition

The present invention relates to a resin composition which can be used as a printed wiring board, an adhesive, a sealant, a paint, a molded article, and the like which require high heat resistance in an electronic/electrical component, and is dissolved in a low methyl ethyl ketone or the like. It is in the boiling point solvent and has good storage stability.

Conventionally, as the heat resistant resin in the field of electronic materials, a thermosetting resin such as an epoxy resin, a polyimide resin, an unsaturated polyester resin, or a phenol resin can be used, and it can be used depending on the use and characteristics. Among them, in particular, the polyimide resin is excellent in heat resistance and moist heat resistance (heat resistance after moisture absorption), and thus can be widely used for high heat resistance, and is also widely used by using an epoxy resin or an aromatic diamine. A modified polyimine resin which achieves improved performance by a combination of the others.

In recent years, in the field of semiconductor substrates, a method of mounting a semiconductor wafer directly on a substrate has been popularized. Therefore, as a material to be used, there is a demand for high heat resistance which can withstand high-temperature treatment or the like in the mounting step. Various types of heat resistant resin materials have been studied in order to cope with the demand for improvement of these heat resistances.

A modified quinone imine resin obtained by reacting polymaleimide with a specific phenol resin, a specific epoxy resin, or a specific compound has also been proposed (Patent Document 1 and Patent Document 2), but polyimine The resin and the modified polyimine resin have problems in that the solubility in a low-boiling solvent (low-boiling organic solvent) which is usually used is poor, and the resin component is precipitated from a varnish dissolved in a solvent, and the stability is poor. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-315705 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-73459

[Problems to be Solved by the Invention] The present invention has been made to solve the problems of the prior art, and an object of the invention is to provide a resin having good solubility and storage stability for a solvent having a low boiling point such as methyl ethyl ketone. Composition. [Means for solving the problem]

[1] A resin composition characterized by comprising 100 kinds of resin mixture containing (A) polymaleimide compound represented by formula (1) and (B) benzoxazine compound a part of the mixture containing 30 parts by mass to 95 parts by mass of the resin mixture of the (A) polymaleimide compound melt-mixed by melt-mixing step, [Chemical Formula 1] In the above formula (1), n ₁ is an integer of 0 or more and 10 or less, and each of X _{1 is} independently an alkylene group having 1 or more and 10 or less carbon atoms, and a group represented by the following formula (2). The group represented by "-SO ₂ -" and the group represented by "-CO-", an oxygen atom or a single bond, and R ₁ are each independently a hydrocarbon group having 1 or more and 6 or less carbon atoms, and a is independently 0 or more. And an integer of 4 or less, and b is independently an integer of 0 or more and 3 or less) [Chemical 2] (In the formula (2), Y is a hydrocarbon group having an aromatic ring having 6 or more and 30 or less carbon atoms, and n ₂ is an integer of 1 to 3).

[2] The resin composition according to [1], wherein the resin mixture contains 10 parts by mass to 100 parts by mass of the (B) by mass of the (A) polymaleimide compound (B) a benzoxazine compound. [3] The resin composition according to [2], wherein the average value of n ₁ in the formula (1) is 0.01 or more and 3 or less, X ₁ is -CH ₂ -, a is 0, and b is 0. .

[4] The resin composition according to [1], wherein the resin mixture further contains 5 parts by mass based on 100 parts by mass of the (A) polymaleimide compound. ～100 parts by mass of (C) epoxy resin. [5] The resin composition according to [4], wherein the (C) epoxy resin is a compound represented by the formula (3), [Chem. 3] . [6] The resin composition according to any one of [1] to [5] wherein the content of the (A) polymaleimide compound in the resin composition is 42 parts by mass. The following.

[7] The resin composition according to any one of [1] to [6] which is used for a printed wiring board. [8] A varnish obtained by dissolving the resin composition according to any one of [1] to [7] in a solvent having a boiling point of 120 ° C or less and a dielectric constant of 10 to 30. [9] An adhesive composition according to any one of [1] to [7]. [10] A sealant comprising the resin composition according to any one of [1] to [7]. [11] A coating composition containing the resin composition according to any one of [1] to [7]. [12] A molded article obtained by curing the resin composition according to any one of [1] to [7]. [Effects of the Invention]

The present invention provides a method for melt-mixing a resin mixture containing (A) a polymaleimide compound in an amount of 30 parts by mass to 95 parts by mass per 100 parts by mass of the resin mixture, and (B) a benzoxazine compound. A resin composition having a low boiling point solvent and good storage stability.

(Resin Composition) The resin composition of the present invention contains the (A) polymaleimide compound represented by the formula (1) and (B) a benzoxazine compound, and is 100 parts by mass of the resin mixture. The melt-mixing step of melt-mixing the resin mixture containing 30 parts by mass to 95 parts by mass of the (A) polymaleimide compound is produced. In addition, "30 parts by mass or more and 95 parts by mass or less" means "30 parts by mass or more and 95 parts by mass or less", and "~" means "above to below" in the present invention unless otherwise specified. [Chemical 4] In the above formula (1), n ₁ is an integer of 0 or more and 10 or less, and each of X _{1 is} independently an alkylene group having 1 or more and 10 or less carbon atoms, and a group represented by the following formula (2). The group represented by "-SO ₂ -" and the group represented by "-CO-", an oxygen atom or a single bond, and R ₁ are each independently a hydrocarbon group having 1 or more and 6 or less carbon atoms, and a is independently 0 or more. And an integer of 4 or less, and b is independently an integer of 0 or more and 3 or less) [Chemical 5] (In the formula (2), Y is a hydrocarbon group having an aromatic ring having 6 or more and 30 or less carbon atoms, and n ₂ is an integer of 1 to 3)

(A) Polymaleimide compound The resin composition of the present invention contains 30 parts by mass to 95 parts by mass of the polymalaya represented by the formula (1) in 100 parts by mass of the resin mixture in the pre-melting stage. Amine compound. The content of the polymaleimide compound in 100 parts by mass of the resin mixture is more preferably 40 parts by mass from the viewpoint of obtaining a solubility in a solvent having a low boiling point, stability in a dissolved state, and a cured product having good heat resistance. ～83 parts by mass, and more preferably 50 parts by mass to 80 parts by mass.

The polymaleimide compound is preferably a polymaleimide compound: the average value of n ₁ in the formula (1) is 0.01 or more and 3 or less, X ₁ is -CH ₂ -, and a is 0, b. Is 0. Examples of the commercially available polymaleimide compound include BMI-2000 and BMI-2300 (product name, manufactured by Daiwa Kasei Kogyo Co., Ltd.).

(B) benzoxazine compound The resin composition of the present invention contains 10 parts by mass to 100 parts by mass per 100 parts by mass of the (A) polymaleimide compound in the resin mixture in the pre-melting phase. Benzooxazine compounds. The content of the benzoxazine compound is preferably 15 parts by mass or more, more preferably 15 parts by mass or more, based on 100 parts by mass of the polymaleimide compound, from the viewpoint of solubility in a solvent having a low boiling point and stability in a dissolved state. It is 20 parts by mass or more. In addition, the content of the benzoxazine compound is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less, based on 100 parts by mass of the polymaleimide compound, from the viewpoint of obtaining a cured product having a good heat resistance. .

The benzoxazine compound may be a compound having at least one benzoxazine ring in the molecule, and is preferably a dihydrobenzoxazine compound represented by the following formula (4) or (5). More preferably, it is a pd-type dihydrobenzoxazine represented by the following formula (5). [Chemical 6] [Chemistry 7] (In the formulae (4) and (5), R ² and R ^{3 each} represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 3 carbon atoms.) The dihydrobenzoxazine compounds may be used singly or in combination. Use two or more.

(C) Epoxy Resin The resin composition of the present invention may further contain an epoxy resin in the resin mixture before mixing and melting. By further containing an epoxy resin in the resin mixture, a melt-mixing step required to obtain a resin composition having good solubility in a low-boiling solvent can be carried out at a low temperature. The content of the epoxy resin is preferably from 5 parts by mass to 100 parts by mass, more preferably from 15 parts by mass to 80 parts by mass, based on 100 parts by mass of the (A) polymaleimide compound in the resin mixture. It is preferably 30 parts by mass to 60 parts by mass.

The epoxy resin may be a compound having an epoxy group, and is preferably a compound having three epoxy groups represented by the formula (3). The commercially available epoxy resin represented by the formula (3) includes VG3101L (product name, manufactured by Printec), and a highly heat-resistant trifunctional epoxy resin. [化8]

As the epoxy resin other than the above, a bisphenol A type epoxy resin, a bisphenol E type epoxy resin, a bisphenol F type epoxy resin, a novolac type epoxy resin, or a cresol novolak type epoxy resin can be used. , bisphenol A novolak type epoxy resin, bisphenol F novolak type resin, trisphenol type epoxy resin, dicyclopentadiene type epoxy resin, and the like.

The resin composition of the present invention and the resin mixture before melt-mixing may contain components other than the above (A), (B), and (C) within a range that does not impair the object of the present invention.

In order to obtain and cure the resin composition of the present invention to obtain a substrate as a molded article, an organic filler or an inorganic filler can be used. Examples of the filler include oxides such as cerium oxide, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, cerium oxide, and ferrite; and oxidizing Calcium hydroxide, magnesium hydroxide, aluminum hydroxide, alkaline magnesium carbonate, etc.; carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, soda-aluminum, hydrotalcite; calcium sulfate, barium sulfate, gypsum fiber Sulfate; calcium citrate (apatite, hard strontium), talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, fiberglass, glass beads And bismuth oxide such as bismuth dioxide ball; nitrides such as aluminum nitride, boron nitride, and tantalum nitride; carbon black, graphite, carbon fiber, carbon balloon, wood carbon powder, etc. Other various metal powders, potassium titanate, lead zirconate titanate, aluminum borate, molybdenum sulfide, tantalum carbide, stainless steel fiber, zinc borate, various magnetic powder, slag fiber, ceramic powder, etc.

The shape of the filler is preferably a spherical shape or a scale, and these may be used alone or in combination of two or more. Further, a decane coupling agent having two or more different reactive groups in the molecule, one of which is a reactive group which chemically reacts with an inorganic material and the other which is a reactive group which chemically reacts with an organic material, may also be used as needed.

In the case of using an organic filler or an inorganic filler, the content thereof is preferably 5.0 parts by mass to 250 parts by mass based on 100 parts by mass of the resin composition.

(D) Hardening accelerator When the resin composition of the present invention is used, a curing accelerator may be added. When it is used as a varnish obtained by dissolving a resin composition in a solvent, when it is used for prepreg, or when a substrate or a laminate is produced, it is used.

Examples of the curing accelerator include dicumyl peroxide, 4,4′-diaminodiphenylmethane, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptaimidazole, and the like. Imidazoles; amines such as triethanolamine, triethylenediamine, N-methylmorpholine; organophosphines such as triphenylphosphine and tricresylphosphine; tetraphenylphosphonium tetraphenylborate, triethylammonium tetra Tetraphenylborate such as phenylborate; 1,8-diazabicyclo (5.4.0) undecen-7 and its derivatives; lead naphthenate, lead stearate, zinc naphthenate, An organic metal salt such as tin oleate, manganese naphthenate, cobalt naphthenate or cobalt octoate. These hardening accelerators may be used singly or in combination of two or more kinds, and an organic peroxide or an azo compound may be used in combination as needed.

The content of the curing accelerator is preferably such that the gelation time required for obtaining the varnish or the prepreg in which the resin composition is dissolved in the solvent can be obtained, and usually 100% of the total of the resin components. The mass fraction is used in the range of 0.01 part by mass to 5.00 part by mass.

(Melting and mixing step) The resin composition can be heated and melted by a resin mixture containing the (A) polymaleimide compound represented by the above formula (1) and (B) benzoxazine compound. Obtained by performing a melt mixing step of mixing. The melt mixing step can use a conventional mixing mechanism in a molten state. As the mixing mechanism, a kneader such as a kneader or a twin-screw extruder is preferred. The temperature at the time of melt mixing is preferably a temperature at which the resin mixture is melted to 400 °C. The melt mixing step is usually carried out for about 0.1 minutes to 10 minutes. After the melt-mixing step, the obtained mixture is cooled by natural cooling or forced cooling to obtain a resin composition of the present invention.

As the cooling method, it can be suitably selected from a known method. For example, a method of naturally cooling in an environment of 5 ° C to 100 ° C or a method of forcibly cooling using a refrigerant of -20 ° C to 80 ° C can be employed. Further, it may be a method of cooling after being melted and mixed in an environment of 30 ° C to 300 ° C in a thermostat.

After cooling, the obtained resin composition is pulverized and stored in a dry state, and can be used in a step after forming a solid resin composition.

In the melt-mixing step, by reacting a part of the (A) polymaleimide compound contained in the resin mixture with the (B) benzoxazine compound, storage stability in a solvent having a low boiling point can be obtained. Resin composition. The polymaleimide compound remaining in 100 parts by mass of the resin composition produced by the melt-mixing step is also suitably referred to as "residual Malayan" from the viewpoint of improving the solubility in a low-boiling solvent. The amine compound ") is preferably 42 parts by mass or less, more preferably 40 parts by mass or less.

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

A flame retardant may be added to the resin composition as needed. Examples of the flame retardant include organic flame retardants such as a brominated epoxy resin-like bromine compound and a phosphatide-like phosphorus compound, and inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, a tin compound, and a ruthenium compound. . These flame retardants may be used singly or in combination of two or more.

The content of the flame retardant is desirably an amount required to not impair the heat resistance and heat and humidity resistance of the resin composition and to have sufficient flame retardancy (for example, the V-0 condition in the UL94 standard is acceptable). In the case of an organic flame retardant, it is usually preferably used in an amount of from 1 part by mass to 20 parts by mass based on 100 parts by mass of the total of the resin component containing the organic flame retardant, in the case of an inorganic flame retardant. It is preferably used in the range of 10 parts by mass to 300 parts by mass based on 100 parts by mass of the total of the resin components.

When the resin composition of the present invention is used, other additives may be added depending on the use. Examples of other additives include synthetic rubbers such as various eucalyptus oils, thermoplastic resins, and acrylonitrile butadiene rubber (NBR), and leveling agents. The other additive is preferably used in a range of from 0.0001 part by mass to 5 parts by mass based on 100 parts by mass of the total of the other additives and the resin component.

(Varnish) The varnish of the resin composition of the present invention is obtained by subjecting the resin composition obtained by the above production method to a solvent having a boiling point of 120 ° C or lower 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 a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone, an ether solvent such as propylene glycol monomethyl ether, or ethanol. An alcohol solvent such as 1-propanol, 2-propanol or 1-butanol. When operability or the like is considered, a ketone-based solvent can be preferably used among the solvents exemplified. These solvents may be used singly or in combination of two or more. Further, a solvent other than the above-exemplified ones may be contained.

The content of the resin composition in 100 parts by mass of the varnish is usually 40 parts by mass to 80 parts by mass, preferably 50 parts by mass to 70 parts by mass. The varnish can be obtained by dissolving the resin composition in a solvent. In the case where it is dissolved under heating, it does not require a particularly long time. Although it depends on the boiling point of the solvent, the general condition at the time of dissolution is about 50 to 200 ° C, and the time is about 0.1 to 24 hours.

The prepreg can be produced by coating or impregnating the varnish onto a substrate, followed by drying and removing the solvent. As the substrate, a known substrate which can be used in a conventional prepreg such as a glass nonwoven fabric, a glass cloth, a carbon fiber cloth, an organic fiber cloth, or paper can be used.

After the varnish is applied or impregnated on the substrate, the prepreg is produced through a drying step, and the coating method, the impregnation method, and the drying method are not particularly limited, and a conventionally known method can be employed. The drying conditions can be appropriately determined depending on the boiling point of the solvent to be used, and the high temperature is unsatisfactory. 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 use in a printed wiring board, and the present invention can be carried out as a molded article obtained by curing a resin composition. The molded article may be a cured product obtained by curing only the resin composition or a composite material or a laminate which is combined with other raw materials. The composite material can be obtained by heating or pressing a prepreg under pressure by heat pressing, or heating a plurality of prepreg layers under pressure to integrate them. Chemical. The heating and pressurizing conditions in the production of the composite material are not particularly limited, and the heating temperature is 100 ° C to 300 ° C, preferably 150 ° C to 250 ° C, and the pressure is 10 kg / cm ² to 100 kg / cm ² , heating and pressurizing time. It is about 10 minutes to 300 minutes.

A laminated body in which a metal foil or a metal plate is laminated on one side or both sides of a laminated material can be used for a multilayer printed wiring board use or the like. The laminated board can be manufactured by hot pressing a single-sided or two-area metal foil or a metal plate of a prepreg, or laminating a metal foil or a metal plate as a plurality of laminated layers. The outermost layer of the prepreg is subjected to hot pressing on one side or both sides, whereby the prepreg is heat-hardened and integrated.

As the metal foil or the metal plate, copper, aluminum, iron, stainless steel or the like can be used. The conditions for the heat curing are preferably the same as those for the case of producing a composite. Further, an inner layer core material can also be used to form a laminate for a multilayer printed wiring board.

The present invention can also be carried out as an adhesive, a sealant and a coating material containing the resin composition. [Examples]

The invention is illustrated by the following examples, but the invention is not limited by the examples. The test methods and raw materials used in the examples and comparative examples are as follows.

1. Test method (1) Solvent solubility: 60 parts by mass of a measurement sample (resin composition) and 40 parts by mass of methyl ethyl ketone (solvent) were mixed at room temperature to apply ultrasonic vibration, and the following criteria were used. The dissolution state after 1 hour of dissolution was evaluated by visual observation. ○: a liquid that is transparent at room temperature ×: a liquid or semi-liquid state that is turbid at room temperature

(2) Gel time was measured by gel time measuring machine SG-70

(3) Glass transition point (Tg) A resin cured product obtained by curing a resin composition was cut (cut) into a predetermined size and used as a sample for measurement of a glass transition point. The glass transition temperature (° C.) of the sample was measured using the following conditions. Those who are out of gas at the time of hardening and cannot measure the glass transition point (Tg) and those who are not measured are indicated by -. Measuring machine: Themoplus TMA8310 manufactured by Rigaku Corporation Sample size: width 5 mm × length 5 mm × height 4 mm Environment: N ₂ Measurement temperature: 30 ° C to 350 ° C Heating rate: 10 ° C / min. Mode: Compression

(4) The thermogravimetric change is based on Japanese Industrial Standards (JIS) K7120, and the temperature is increased from 30 ° C at a rate of 10 ° C per minute, and the temperature at which the mass is reduced by 1% (Td (1%)) and the reduction by 5% is measured. Temperature (Td (5%)). (5) Solubility The solution obtained by dissolving the resin composition in methyl ethyl ketone was allowed to stand at room temperature and visually evaluated after a predetermined period of time (after just after dissolution and after 1 hour) by using the following criteria. Dissolved state. ○: a liquid that is transparent after a predetermined period of time ×: a liquid or semi-liquid state that is turbid after each standing time

(6) Residue of maleic imine (content and % of residual maleimide compound in resin composition) was measured by HLC-8320GPC manufactured by Tosoh Corporation (7) Molecular weight using HLC-made by Tosoh Corporation 8320GPC was measured. (8) Storage stability The solution obtained by dissolving the resin composition in methyl ethyl ketone was allowed to stand at room temperature, and the dissolution state after a predetermined period of time (2 days, 7 days) was visually confirmed. The storage stability of the solution (varnish) was evaluated. ○: No precipitation occurred from the time of preparation until one week (7 days). Δ: Precipitation occurred from the time of preparation to one week (7 days). ×: Precipitation occurred from the time of preparation to two days after the preparation.

2. Raw material (A) Polymaleimide compound · BMI-1000 (product name, manufactured by Daiwa Chemical Industry Co., Ltd., 4,4'-diphenylmethane bismaleimide) · BMI-2300 ( The product name, manufactured by Daiwa Kasei Kogyo Co., Ltd., polyphenylmethane polymaleimide) is a polymaleimide compound in which the average value of n ₁ in the formula (1) is 0.01 or more and 3 or less, X ₁ is a group represented by -CH ₂ -, a is 0, and b is 0.

(B) benzoxazine compound · BZO: (p-d type) benzoxazine (manufactured by Shikoku Kasei Co., Ltd.)

(C) Epoxy resin · VG3101L (product name, manufactured by Printec), high heat-resistant trifunctional epoxy resin, compound of formula (3)

(Example 1-6, Comparative Example 1) The raw materials of the compositions shown in Table 1 were melt-mixed on a hot plate at a melting temperature of 230 ° C for 90 seconds to produce a resin composition. The results of measuring the solubility and the gel time of each resin composition are shown in Table 1. In addition, in Table 1, the content of each component is shown by mass parts (The same is the same in Table 2 and Table 3). The resin composition was heated at a curing temperature of 200 ° C and 230 ° C for 2 hours and cured to prepare a cured resin. The results of measuring the glass transition point (Tg) and the thermogravimetric change (Td (1%), Td (5%)) for each resin cured product are shown in Table 1.

[Table 1]

The results shown in Table 1 are as follows. By melt-mixing a resin mixture containing a polymaleimide compound (BMI-2300) and benzoxazine (BZO), it is obtainable to be soluble in methyl ethyl ketone (MEK), and A resin composition having good storage stability and precipitation is produced. The resin mixture in which the polymaleimide compound (BMI-1000) and benzoxazine (BZO) were melt-mixed was insoluble in methyl ethyl ketone (MEK). When BMI-2300 is used as the polymaleimide compound, the same solubility can be obtained even if an epoxy resin (VG3101L) is added. The cured resin obtained by curing the resin compositions of Examples 1 to 6 has high Tg and Td and is excellent in heat resistance.

(Example 7 - Example 18) The raw materials of the compositions shown in Table 2 were placed on a hot plate, and the melting temperature was set to 185 ° C, 200 ° C, 220 ° C, and 250 ° C, and melt-mixed for 90 seconds to obtain a resin composition. The results of measuring the residual maleimide, molecular weight, and storage stability of the resin composition are shown in Table 2.

(Comparative Example 2) The raw materials of the compositions shown in Table 2 were not heated and mixed at room temperature to obtain a resin composition. The results of measuring the residual maleimide, molecular weight, and storage stability of the resin composition are shown in Table 2.

[Table 2]

The results shown in Table 2 are as follows. Regarding Formulation 1 (Example 7 to Example 10, Comparative Example 2), Formulation 2 (Example 11 to Example 14), and Formulation 3 (Example 15 to Example 18), the obtained resin composition The weight average molecular weight (Mw) of the material is about 600 to 670, which is not significantly different. In any of Formulation 1, Formulation 2, and Formulation 3, it was confirmed that the molecular weight of the obtained resin composition was slightly increased by increasing the melting temperature. On the other hand, regarding any of the formulations, the residual maleimide in the resin composition does not change due to the melting temperature of the melt mixing step. Formulation 1 comprising the two components of polymaleimide and benzoxazine improves storage stability by increasing the temperature of the melt mixing step. In Formulation 2 and Formulation 3 in which an epoxy resin is added to the component of Formulation 1, even when the temperature of the melt-mixing step is lowered, a resin composition having good storage stability can be obtained. It is understood that the storage stability of the resin composition obtained by the melt mixing step is related to the amount (% by mass) of 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. [Industrial availability]

The present invention is a resin composition excellent in solubility in a low-boiling solvent and storage stability, and can be used as a raw material for a heat-resistant adhesive, a sealant, a paint, and a molded article.

no

no

Claims (12)

A resin composition containing 100 parts by mass of a resin mixture containing the (A) polymaleimide compound represented by the formula (1) and (B) a benzoxazine compound. 30 parts by mass to 95 parts by mass of the melt mixing step of melt-mixing the resin mixture of the (A) polymaleimide compound, In the above formula (1), n ₁ is an integer of 0 or more and 10 or less, and each of X _{1 is} independently an alkylene group having 1 or more and 10 or less carbon atoms, and a group represented by the following formula (2). a group represented by -SO ₂ -", a group represented by "-CO-", an oxygen atom or a single bond, and each of R _{1 is} independently a hydrocarbon group having 1 or more and 6 or less carbon atoms, and a is independently 0 or more. An integer of 4 or less, and b is independently an integer of 0 or more and 3 or less, In the formula (2), Y is a hydrocarbon group having an aromatic ring having 6 or more and 30 or less carbon atoms, and n ₂ is an integer of 1 to 3. The resin composition according to claim 1, wherein the resin mixture contains 10 parts by mass to 100 parts by mass of the (B) by mass of the (A) polymaleimide compound (B) a benzoxazine compound. The resin composition according to claim 2, wherein an average value of n ₁ in the formula (1) is 0.01 or more and 3 or less, X ₁ is -CH ₂ -, a is 0, and b is 0. . The resin composition according to the first aspect, the second or the third aspect, wherein the resin mixture further contains 5 parts by mass based on 100 parts by mass of the (A) polymaleimide compound. ～100 parts by mass of (C) epoxy resin. The resin composition according to claim 4, wherein the (C) epoxy resin is a compound represented by the formula (3), . The resin composition according to any one of the items 1 to 5, wherein the content of the (A) polymaleimide compound in the resin composition is 42 parts by mass. The following. The resin composition according to any one of claims 1 to 6, which is a printed wiring board use. A varnish obtained by dissolving the resin composition according to any one of items 1 to 7 in a solvent having a boiling point of 120 ° C or less and a dielectric constant of 10 to 30. An adhesive comprising the resin composition according to any one of claims 1 to 7. A sealant comprising the resin composition according to any one of claims 1 to 7. A coating material comprising 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 items 1 to 7 of the patent application.