CN111315799B - Resin composition, use thereof, and method for producing resin composition - Google Patents
Resin composition, use thereof, and method for producing resin composition Download PDFInfo
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- CN111315799B CN111315799B CN201880072008.5A CN201880072008A CN111315799B CN 111315799 B CN111315799 B CN 111315799B CN 201880072008 A CN201880072008 A CN 201880072008A CN 111315799 B CN111315799 B CN 111315799B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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Abstract
The invention provides a resin composition with good solubility and storage stability for low-boiling point solvents such as methyl ethyl ketone, application thereof and a method for manufacturing the resin composition. A resin composition is produced by a melt-mixing step in which the content of a polymaleimide compound (A) in 100 parts by mass of a resin mixture containing a polymaleimide compound (A) represented by the formula (1) and a benzoxazine compound (B) is 30 to 95 parts by mass, and the resin mixture is melt-mixed.
Description
Technical Field
The present invention relates to a resin composition which is useful as a printed wiring board, an adhesive, a sealant, a coating material, a molded article, or the like, which are required to have high heat resistance in electronic and electric parts, is dissolved in a low boiling point solvent such as methyl ethyl ketone, and has good storage stability, and to an application thereof, and a method for producing the resin composition.
Background
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, and they are used depending on their applications and properties. Among them, polyimide resins are widely used for high heat resistance applications because of their excellent heat resistance and resistance to moist heat (heat resistance after moisture absorption), and modified polyimide resins having improved properties by combining with epoxy resins, aromatic diamines, or the like are also widely used.
In recent years, in the field of semiconductor substrates, a mounting method for directly mounting a semiconductor chip on a substrate has been widely used, and thus, as a material to be used, there is an increasing demand for high heat resistance that can withstand high-temperature processing in a mounting step and the like. In order to meet the demand for improvement in heat resistance, various heat-resistant resin materials have been studied for epoxy resins generally used.
Modified imide resins obtained by reacting polymaleimide with a specific phenol resin, a specific epoxy resin, and a specific compound have also been proposed (patent documents 1 and 2), but polyimide resins and modified polyimide resins have the following problems: the solubility in a low boiling point solvent (low boiling point organic solvent) generally used is poor, and the stability is poor because the resin component is precipitated from the varnish dissolved in the solvent.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2004-315705
Patent document 2: japanese patent laid-open No. 2003-73459
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above problems of the prior art, and an object of the present invention is to provide a resin composition having excellent solubility in a solvent having a low boiling point such as methyl ethyl ketone and excellent storage stability.
Means for solving the problems
[1] A resin composition produced by a melt-mixing step of melt-mixing a resin mixture containing 100 parts by mass of a resin mixture containing (A) a polymaleimide compound represented by the formula (1) and (B) a benzoxazine compound, wherein the resin mixture contains 30 to 95 parts by mass of the polymaleimide compound (A),
[ solution 1]
(in the formula (1), n 1 Is an integer of 0 to 10 inclusive, X1 is independently an alkylene group having 1 to 10 carbon atoms, a group represented by the following formula (2), or the formula "-SO 2 A group represented by- "or a group represented by-" -CO- ", an oxygen atom or a single bond, R 1 Each independently represents a hydrocarbon group having 1 to 6 carbon atoms, a is each independently an integer of 0 to 4, and b is each independently an integer of 0 to 3)
[ solution 2]
(in the formula (2), Y is a hydrocarbon group having an aromatic ring and having 6 to 30 carbon atoms, and n is 2 An integer of 1 to 3).
[2] The resin composition according to [1], wherein the resin mixture contains 10 to 100 parts by mass of the (B) benzoxazine compound per 100 parts by mass of the (A) polymaleimide compound.
[3]According to [2]]The resin composition, wherein n in the formula (1) 1 Has an average value of 0.01 to 5, X 1 is-CH 2 -, a is 0 and b is 0.
[4] The resin composition according to [1], [2] or [3], wherein the resin mixture further contains 5 to 100 parts by mass of (C) an epoxy resin per 100 parts by mass of the (A) polymaleimide compound.
[5] The resin composition according to [4], wherein the (C) epoxy resin comprises a compound represented by the formula (3),
[ solution 3]
[6] The resin composition according to any one of [1] to [5], wherein the content of the (A) polymaleimide compound 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 used for a printed wiring board.
[8] A varnish prepared by dissolving the resin composition according to any one of [1] to [7] in a solvent having a boiling point of 120 ℃ or lower and a dielectric constant of 10 to 30.
[9] An adhesive agent comprising the resin composition according to any one of [1] to [7 ].
[10] A sealing agent comprising the resin composition according to any one of [1] to [7 ].
[11] A coating material comprising 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 ].
[13] A method of manufacturing a resin composition, comprising: a melt-mixing step of melt-mixing the resin mixture according to any one of [1] to [7 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides a resin composition having excellent solubility in a solvent having a low boiling point and excellent storage stability by melt-mixing a resin mixture containing 30 to 95 parts by mass of a polymaleimide compound (A) and a benzoxazine compound (B) per 100 parts by mass of the resin mixture.
Detailed Description
(resin composition)
The resin composition of the present invention contains (A) a polymaleimide compound represented by formula (1) and (B) a benzoxazine compound, and is produced by a melt-mixing step of melt-mixing the resin mixture containing 30 to 95 parts by mass of the polymaleimide compound (A) to 100 parts by mass of the resin mixture. "30 to 95 parts by mass" means "30 to 95 parts by mass", and in the present invention, "to" means "to" ranges unless otherwise specified.
[ solution 4]
(in the formula (1), n 1 Is an integer of 0 to 10 inclusive, X 1 Independently represents an alkylene group having 1 to 10 carbon atoms, a group represented by the following formula (2), or the formula "— SO 2 A group represented by- "or a group represented by-" -CO- ", an oxygen atom or a single bond, R 1 Each independently represents a hydrocarbon group having 1 to 6 carbon atoms, a is each independently an integer of 0 to 4, and b is each independently an integer of 0 to 3)
[ solution 5]
(in the formula (2), Y represents a hydrocarbon having an aromatic ring and having 6 to 30 carbon atomsRadical, n 2 Is an integer of 1 to 3)
In the present invention, a substance before melt-mixing (a) the polymaleimide compound and (B) the benzoxazine compound is referred to as a "resin mixture", and a substance after melt-mixing is referred to as a "resin composition".
(A) Polymaleimide compounds
The resin composition of the present invention contains 30 to 95 parts by mass of the polymaleimide compound represented by formula (1) per 100 parts by mass of the resin mixture in the preceding stage of melt mixing. 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 still more preferably 50 to 80 parts by mass, from the viewpoint of obtaining a cured product having good solubility in a solvent having a low boiling point, stability in a dissolved state, and heat resistance.
The polymaleimide compound is preferably the following polymaleimide compounds: n in the formula (1) 1 Has an average value of 0.01 to 5, X 1 is-CH 2 -, a is 0 and b is 0. As the commercially available polymaleimide compounds, BMI-2000 and BMI-2300 (product name, manufactured by Daghi chemical industry, ltd.) are exemplified.
(B) Benzoxazine compounds
The resin composition of the present invention contains 10 to 100 parts by mass of a benzoxazine compound per 100 parts by mass of the polymaleimide compound (a) in a resin mixture at a preceding stage of melt mixing. From the viewpoint of solubility in a solvent having a low boiling point and stability of a dissolved state, the content of the benzoxazine compound is more preferably 15 parts by mass or more, and still more preferably 20 parts by mass or more, per 100 parts by mass of the polymaleimide compound. In addition, 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, with respect to 100 parts by mass of the polymaleimide compound, from the viewpoint of obtaining a cured product having good heat resistance.
The benzoxazine compound may have at least one benzoxazine ring in the molecule, and is preferably a dihydrobenzoxazine compound represented by the following general formula (4) or general formula (5), and more preferably a p-d type dihydrobenzoxazine represented by the following general formula (5).
[ solution 6]
[ solution 7]
(in the formulae (4) and (5), R 2 、R 3 Represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 3 carbon atoms)
These dihydrobenzoxazine compounds may 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. By further containing an epoxy resin in the resin mixture, the melt-mixing step required for obtaining a resin composition having good solubility in a low-boiling solvent can be performed at a low temperature. The content of the epoxy resin is preferably 5 to 100 parts by mass, more preferably 15 to 80 parts by mass, and still more preferably 30 to 60 parts by mass, relative to 100 parts by mass of the polymaleimide compound (a) in the resin mixture.
The epoxy resin may be a compound having an epoxy group, but is preferably a compound having three epoxy groups represented by formula (3). As a commercially available epoxy resin represented by formula (3), VG3101L (product name, a high heat-resistant trifunctional epoxy resin manufactured by printaceae (Printec) inc.).
[ solution 8]
As the epoxy resin 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 type epoxy resin, triphenol type epoxy resin, dicyclopentadiene type epoxy resin, and the like can be used.
The resin composition of the present invention and the resin mixture before melt-mixing may contain components other than the components (a), (B) and (C) in the range not to impair the object of the present invention.
In order to obtain a base material for a molded article by curing the resin composition of the present invention, an organic filler or an inorganic filler can be used. Examples of the filler include: oxides such as silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrite; hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and basic magnesium carbonate; carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, and hydrotalcite; sulfates such as calcium sulfate, barium sulfate, and gypsum fiber; silicates such as calcium silicate (wollastonite, xonotlite), talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, and silica-based spheres (balloon); nitrides such as aluminum nitride, boron nitride, and silicon nitride; carbon materials such as carbon black, graphite, carbon fiber, carbon spheres (carbon balls), and wood carbon powder; other various metal powders, potassium titanate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, ceramic powder, and the like.
The shape of the filler is preferably spherical or flake, and these may be used alone or in combination of two or more. Further, if necessary, a silane coupling agent having two or more different reactive groups (one of which is a reactive group that chemically reacts with an inorganic material and the other is a reactive group that chemically reacts with an organic material) in the molecule may be used in combination.
When an organic filler or an inorganic filler is used, the content thereof is preferably 5.0 to 250 parts by mass with respect to 100 parts by mass of the resin composition.
(D) Hardening accelerator
When the resin composition of the present invention is used, a hardening accelerator may be added. The time for adding the curing accelerator may be, for example, the time when the resin composition is used as a varnish prepared by dissolving the resin composition in a solvent, the time when the resin composition is prepreg, or the time when a substrate or a laminated plate is produced.
Examples of the hardening accelerator include: dicumyl peroxide, 4' -diaminodiphenylmethane, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptaimidazole and other imidazoles; amines such as triethanolamine, triethylenediamine, and N-methylmorpholine; organic phosphines such as triphenylphosphine and trimethylphenylphosphine; tetraphenylborons such as tetraphenylphosphonium tetraphenylboronate, triethylammonium tetraphenylboronate and the like; 1, 8-diazabicyclo (5.4.0) undec-7 ene-7 and derivatives thereof; and organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, tin oleate, manganese naphthenate, cobalt naphthenate, and cobalt octylate. These hardening accelerators may be used alone, or two or more kinds thereof may be used in combination, or an organic peroxide, an azo compound or the like may be used in combination as required.
The content of these hardening accelerators is preferably adjusted so as to obtain a gelation time required for a varnish or a prepreg obtained by dissolving the resin composition in a solvent, and may be generally used in a range of 0.01 to 5.00 parts by mass per 100 parts by mass of the total of the resin components.
(melt mixing step)
The resin composition can be obtained by a melt-mixing step of heating and mixing in a molten state a resin mixture containing (a) the polymaleimide compound represented by the formula (1) and (B) the benzoxazine compound. The melt-mixing step may use a usual mixing mechanism in a molten state. The mixing mechanism is preferably a kneader such as a kneader or a twin-screw extruder. The temperature during melt mixing may be set to a temperature of from 400 ℃ or lower at which the resin mixture is melted. More preferably 130 ℃ or more and 230 ℃ or less, and still more preferably 150 ℃ or more and 210 ℃ or less. The melt mixing step is usually carried out for about 0.1 to 10 minutes.
After the melt-mixing step, the resulting mixture is cooled by natural cooling or forced cooling to obtain the resin composition of the present invention.
The cooling method may be appropriately selected from known methods. For example, a method of natural cooling in an environment of 5 to 100 ℃ or a method of forced cooling using a refrigerant of-20 to 80 ℃ can be employed. Alternatively, a method of melting and mixing, placing in a thermostat at 30 to 300 ℃ and then cooling may be employed.
After cooling, the obtained resin composition is pulverized and stored in a dry state (dry), and can be used in a step after preparing a solid resin composition.
In the melt mixing step, a part of the polymaleimide compound (a) contained in the resin mixture is reacted with the benzoxazine compound (B), whereby a resin composition having good storage stability in a low-boiling solvent can be obtained. From the viewpoint of satisfactory solubility in a low-boiling solvent, the amount of the polymaleimide compound (also referred to as "residual maleimide compound" as appropriate) remaining in 100 parts by mass of the resin composition produced in the melt-mixing step is preferably 42 parts by mass or less, and more preferably 40 parts by mass or less.
In terms of improving the solubility of the modified resin composition after the melt-mixing step in the low-boiling solvent, the amount of the polymaleimide compound remaining as a residual maleimide compound in the resin composition after the melt-mixing step is preferably 30 to 60 parts by mass, more preferably 40 to 50 parts by mass, per 100 parts by mass of the polymaleimide compound in the resin mixture before the melt-mixing step.
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 like brominated epoxy resins and phosphorus compounds like condensed phosphoric esters, and inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, tin compounds and antimony compounds. These flame retardants may be used alone or in combination of two or more.
The flame retardant is desirably contained in an amount necessary for achieving sufficient flame retardancy (for example, acceptable V-0 in UL94 standard) without impairing the heat resistance and moist heat resistance of the resin composition. In the case of an organic flame retardant, it is generally preferable to use the organic flame retardant in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the total of the resin components including the organic flame retardant, and in the case of an inorganic flame retardant, it is preferable to use the inorganic flame retardant in the range of 10 to 300 parts by mass with respect to 100 parts by mass of the total of the resin components not including the inorganic flame retardant.
When the resin composition of the present invention is used, other additives may be added depending on the purpose. Examples of the other additives include synthetic rubbers such as various silicone oils, thermoplastic resins, acrylonitrile butadiene rubber (NBR), and leveling agents. The other additive is preferably used in an amount within a range where the content of the other additive is 0.0001 to 5 parts by mass in 100 parts by mass of the total of the other additive and the resin component.
(varnish)
The varnish of the resin composition of the present invention is obtained by dissolving the resin composition obtained by the above-mentioned production method in a solvent having a boiling point of 120 ℃ or lower and a dielectric constant of 10 to 30.
Examples of the solvent having a boiling point of 120 ℃ or lower and a dielectric constant of 10 to 30 include: ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ether solvents such as propylene glycol monomethyl ether, and alcohol solvents such as ethanol, 1-propanol, 2-propanol and 1-butanol. In view of handling properties and the like, ketone solvents are preferably used among the exemplified solvents. These solvents may be used alone or in combination of two or more. In addition, a solvent other than the above-exemplified solvents may be contained.
The content of the resin composition in 100 parts by mass of the varnish is usually 40 to 80 parts by mass, and preferably 50 to 70 parts by mass. The varnish may be obtained by dissolving the resin composition in a solvent. In the case of dissolving the compound under heating, a particularly long time is not required. The temperature is generally 50 to 200 ℃ and the time is generally 0.1 to 24 hours, although it depends on the boiling point of the solvent.
The prepreg can be produced by coating or impregnating the varnish on a substrate, followed by drying and removal of the solvent.
As the substrate, a known substrate usable in conventional prepregs such as glass nonwoven fabric, glass cloth, carbon fiber cloth, organic fiber cloth, and paper can be used.
The prepreg is produced by coating or impregnating the varnish on the substrate and then passing through a drying step, and the coating method, the impregnation method, and the drying method are not particularly limited, and conventionally known methods can be used. The drying conditions may be appropriately determined depending on the boiling point of the solvent used, and the high temperature is not preferable. It is desirable to dry the prepreg so that the amount of the solvent remaining in the prepreg is 3 mass% or less.
The resin composition of the present invention is suitable for printed wiring board applications, and the present invention can be carried out as a molded article obtained by curing the resin composition. Examples of the molded article include a cured product obtained by curing only a resin composition, a composite material obtained by compounding a resin composition with another raw material, and a laminate.
The composite material can be obtained by heating one prepreg under pressure by hot pressing or the like to harden it, or by laminating a plurality of prepregs and heating under pressure to integrate them. The heating and pressurizing conditions for producing the composite material are not particularly limited, and the heating temperature is 100 to 300 ℃, preferably 150 to 250 ℃, and the pressure is 10kg/cm 2 ～100kg/cm 2 The heating and pressurizing time is about 10 minutes to 300 minutes.
The laminate can be used for multilayer printed wiring board applications or the like by laminating and integrating a metal foil or a metal plate on one or both surfaces of the laminate. The laminate can be produced by laminating a metal foil or a metal plate on one or both surfaces of a prepreg and hot-pressing the laminate, or by laminating a metal foil or a metal plate on one or both surfaces of the outermost layer of a prepreg laminated with a plurality of prepregs and hot-pressing the laminate, thereby heat-curing the prepreg and integrating the prepreg.
As the metal foil or the metal plate, copper, aluminum, iron, stainless steel, or the like can be used. The conditions for heat curing are preferably the same as those for producing the composite material. Further, a multilayer board for a multilayer printed wiring board can be produced using the inner core material.
The present invention can also be implemented as an adhesive, a sealant and a coating material containing the resin composition.
Examples
The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The test methods and raw materials used in examples and comparative examples are as follows.
1. Test method
(1) Solubility in solvent
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, ultrasonic vibration was applied, and the dissolved state after 1 hour of dissolution was visually evaluated using the following criteria.
O: liquid transparent at room temperature
X: in a liquid or semi-liquid state in a turbid state at room temperature
(2) Gel time
Measured by a gel time measuring machine SG-70
(3) Glass transition Point (Tg)
The resin cured product obtained by curing the resin composition was cut (cut) into a predetermined size, and used as a sample for measuring the glass transition point. The glass transition temperature (. Degree. C.) of the sample was measured under the following conditions. Samples which develop outgassing upon hardening and for which the glass transition point (Tg) could not be determined and samples which were not determined are indicated.
Measurement machine: sample size of temopus (Themoplus) TMA8310 manufactured by ritaku company: width 5mm x length 5mm x height 4mm
Environment: n is a radical of hydrogen 2
Measuring temperature: 30-350 DEG C
Temperature rise rate: 10 ℃/min.
Measurement mode: compression
(4) Thermogravimetric change
The temperature at which the mass is reduced by 1% (Td (1%)) and the temperature at which the mass is reduced by 5% (Td (5%)) were measured by raising the temperature at a rate of 10 ℃ per minute from 30 ℃ based on Japanese Industrial Standards (JIS) K7120.
(5) Solubility in water
The solution obtained by dissolving the resin composition in methyl ethyl ketone was left at room temperature, and the dissolved state after a predetermined time (immediately after the dissolution and after 1 hour) was visually evaluated using the following criteria.
O: a liquid which is transparent after a prescribed time has elapsed
X: in a turbid liquid or semi-liquid state after each standing time
(6) Residual maleimide (content of maleimide compound in resin composition,%)
Measurement was carried out by using HLC-8320GPC manufactured by Tosoh corporation
(7) Molecular weight
Measurement was carried out by using HLC-8320GPC manufactured by Tosoh corporation
(8) Storage stability
The solution obtained by dissolving the resin composition in methyl ethyl ketone was left at room temperature, and the dissolved state after a predetermined period of time (2 days, 7 days) was visually observed to evaluate the storage stability of the solution (varnish).
O: no precipitation occurred after one week (7 days) from the time of preparation
And (delta): precipitation occurred after one week (7 days) from the time of preparation
X: precipitation occurred after two days from the preparation
2. Raw materials
(A) Polymaleimide compounds
BMI-1000 (product name, manufactured by Dahe chemical industry (stock), 4' -diphenylmethane bismaleimide)
BMI-2300 (trade name, dahe chemical industry (Strand) manufacture, polyphenylmethane polymaleimide)
(B) Benzoxazine compounds
BZO: (p-d type) benzoxazine (manufactured by Siguo Kangji)
(C) Epoxy resin
VG3101L (product name, manufactured by Printec (Printec), high heat resistant trifunctional epoxy resin, compound of formula (3))
(example 1-example 6, comparative example 1)
The raw materials having the compositions shown in table 1 were melt-mixed on a hot plate at a melting temperature of 230 ℃ for 90 seconds to produce resin compositions. The results of measuring the solubility and the gel time of each resin composition are shown in table 1. The contents of the components are shown in table 1 in parts by mass (the same applies to tables 2 and 3). The resin composition is heated at a curing temperature of 200 ℃ and 230 ℃ for 2 hours and cured to prepare a cured resin product. The results of measuring the glass transition point (Tg) and the thermogravimetric changes (Td (1%), td (5%)) of each cured resin are shown in table 1.
[ Table 1]
The results shown in Table 1 show the following.
A resin composition having good storage stability, which is soluble in Methyl Ethyl Ketone (MEK) and does not cause precipitation, can be obtained by melt-mixing a resin mixture containing a polymaleimide compound (BMI-2300) and Benzoxazine (BZO).
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 was used as the polymaleimide compound, the same solubility could be obtained even if an epoxy resin (VG 3101L) was further added.
The cured resin obtained by curing the resin compositions of examples 1 to 6 has high Tg and Td and good heat resistance.
(example 7-example 18)
The raw materials having the compositions shown in table 2 were melt-mixed on a hot plate at 185 ℃, 200 ℃, 220 ℃, 250 ℃ for 90 seconds to obtain resin compositions. The results of measuring residual maleimide, molecular weight and storage stability of the resin composition are shown in table 2.
Comparative example 2
The raw materials having the compositions shown in table 2 were mixed at room temperature without heating to obtain resin compositions. The results of measuring residual maleimide, molecular weight and storage stability of the resin composition are shown in table 2.
[ Table 2]
The results shown in Table 2 show the following.
The weight average molecular weight (Mw) of each of the resin compositions obtained in the formulations 1 (examples 7 to 10 and comparative example 2), 2 (examples 11 to 14) and 3 (examples 15 to 18) was about 600 to 670, and was not significantly different from each other.
The following tendency was confirmed in any of the formulations 1, 2 and 3: by increasing the melting temperature, the molecular weight of the resulting resin composition is slightly increased. In contrast, with either formulation, the residual maleimide in the resin composition is not changed by the melting temperature in the melt-mixing step.
Formulation 1, which contains both polymaleimide and benzoxazine components, has improved storage stability by increasing the temperature of the melt mixing step.
Formulations 2 and 3, in which an epoxy resin was added to the components of formulation 1, were able to obtain resin compositions having good storage stability even when the temperature in the melt-mixing step was lowered.
It is known that the storage stability of the resin composition obtained by the melt-mixing step is correlated with the amount (mass%) of residual maleimide contained in the resin composition.
By performing the melt-mixing step, the amount of residual maleimide in the resin composition becomes small, and the storage stability of the resin composition is improved.
Industrial applicability
The present invention is a resin composition having excellent solubility in a low-boiling solvent and excellent storage stability, and is useful as a raw material for adhesives, sealants, coatings and molded articles having excellent heat resistance.
Claims (8)
1. A resin composition characterized by: the resin composition is produced by a melt-mixing step of melt-mixing a resin mixture containing 100 parts by mass of a resin mixture containing (A) a polymaleimide compound represented by the formula (1), (B) a benzoxazine compound and (C) an epoxy resin, the resin mixture containing 50 to 80 parts by mass of the polymaleimide compound,
the content of the benzoxazine compound (B) is 10 to 50 parts by mass based on 100 parts by mass of the polymaleimide compound (A),
the resin mixture contains 5 to 100 parts by mass of the epoxy resin (C) per 100 parts by mass of the polymaleimide compound (A), the epoxy resin (C) being a compound represented by formula (3),
the content of the polymaleimide compound (A) in 100 parts by mass of the resin composition is 40 parts by mass or less,
in the formula (1), n 1 Has an average value of 0.01 to 5, X 1 is-CH 2 -，R 1 Each independently represents a hydrocarbon group having 1 to 6 carbon atoms, a represents 0, b represents 0,
2. the resin composition according to claim 1, which is used for a printed wiring board.
3. A varnish prepared by dissolving the resin composition according to claim 1 or 2 in a solvent having a boiling point of 120 ℃ or lower and a dielectric constant of 10 to 30.
4. An adhesive comprising the resin composition according to claim 1 or 2.
5. A sealant comprising the resin composition according to claim 1 or 2.
6. A coating material comprising the resin composition according to claim 1 or 2.
7. A molded article obtained by curing the resin composition according to claim 1 or 2.
8. A method for producing a resin composition, comprising: a melt-mixing step of melt-mixing the resin mixture according to claim 1 or 2.
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| JP2017-217211 | 2017-11-10 | ||
| JP2017217211 | 2017-11-10 | ||
| PCT/JP2018/033247 WO2019092968A1 (en) | 2017-11-10 | 2018-09-07 | Resin composition |
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| JP5848638B2 (en) * | 2012-03-07 | 2016-01-27 | 株式会社日本触媒 | Curable resin composition, method for producing the same, and electronic packaging material |
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| KR101668855B1 (en) * | 2013-09-30 | 2016-10-28 | 주식회사 엘지화학 | Thermosetting resin composition for semiconductor pakage and Prepreg and Metal Clad laminate using the same |
| JP2015101669A (en) * | 2013-11-26 | 2015-06-04 | 住友ベークライト株式会社 | Semiconductor sealing resin composition and semiconductor device |
| JP2016074871A (en) * | 2014-03-04 | 2016-05-12 | 四国化成工業株式会社 | Bismaleimide resin composition and use of the same |
| US10294324B2 (en) * | 2015-03-31 | 2019-05-21 | Namics Corporation | Resin composition, conductive resin composition, adhesive, conductive adhesive, paste for forming electrodes, and semiconductor device |
| JP6680523B2 (en) * | 2015-12-07 | 2020-04-15 | ソマール株式会社 | Powder paint |
| JP6614700B2 (en) * | 2016-03-18 | 2019-12-04 | 京セラ株式会社 | Molding material for sealing and electronic component device |
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| WO2019092968A1 (en) | 2019-05-16 |
| CN111315799A (en) | 2020-06-19 |
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