Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/36—Amides or imides
  • C08F222/40—Imides, e.g. cyclic imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
  • C08F283/045—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides on to unsaturated polycarbonamides, polyesteramides or polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/68—Organic materials, e.g. photoresists
  • H10P14/683—Organic materials, e.g. photoresists carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W70/00—Package substrates; Interposers; Redistribution layers [RDL]
  • H10W70/60—Insulating or insulated package substrates; Interposers; Redistribution layers

Definitions

• the present invention relates to a photosensitive resin composition containing a bismaleimide compound and a compound having an ethylenically unsaturated group, or a cured product thereof, and a semiconductor device.
• Patent Document 1 polyimide resins and polybenzoxazole resins, which have excellent heat resistance and mechanical properties, have been widely used for surface protective films and interlayer insulating films of semiconductor elements.
• Patent Document 2 a method for forming through-holes and the like by etching using a positive photoresist containing these resins is known.
• this method has the problem of requiring complicated processes such as applying and peeling off the photoresist. Therefore, heat-resistant materials that have been given photosensitivity have been studied with the aim of streamlining the work process (Patent Document 2).
• Patent Document 3 and Patent Document 4 disclose polyimides made from aromatic tetracarboxylic acids and dimer diamines derived from dimer acids, which are dimers of unsaturated fatty acids such as oleic acid, and alicyclic diamines.
• Patent Document 5 also discloses a bismaleimide resin that has both a long-chain aliphatic chain portion and an alicyclic structure portion and has a glass transition point (Tg) of 100°C or higher.
• Patent Document 6 a bismaleimide compound is used as the curable resin, but since maleimide compounds usually have poor light transmittance, when a maleimide compound is included, light does not reach the photocuring initiator sufficiently, making it difficult for the photocuring initiator to generate radicals and resulting in very low reactivity. Therefore, in Patent Document 8, the maleimide compound is cured by additional heating at 100°C or higher before development.
• the present invention therefore aims to provide a resin composition containing a bismaleimide compound that has good compatibility, can be cured with light, and requires additional heating at a temperature of less than 100°C for a short heating time.
• a resin composition that is stable and has excellent compatibility even in a solution state improves workability during resin composition production and allows mixing with a variety of other materials, broadening the scope of material design.
• the present invention relates to the following [1] to [8].
• the resin composition comprises: a bismaleimide compound (A) having a cyclic imide bond, which is obtained by reacting an aromatic diamine (a-1) represented by the following formula (1), a tetrabasic acid dianhydride (a-3), and maleic anhydride; a resin or compound (B) having an ethylenically unsaturated group; and a photocuring initiator (C).
• A bismaleimide compound having a cyclic imide bond, which is obtained by reacting an aromatic diamine (a-1) represented by the following formula (1), a tetrabasic acid dianhydride (a-3), and maleic anhydride
• a resin or compound (B) having an ethylenically unsaturated group a photocuring initiator (C).
• Each R 1 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms.
• Each l independently represents an integer of 1 to 4.
• a resin composition comprising a bismaleimide compound (A) represented by the following formula (2) and a resin or compound (B) having an ethylenically unsaturated group:
• R 4 independently represents a tetravalent organic group containing a cyclic structure.
• R 3 independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms.
• R 2 independently represents a group represented by the following formula (3):
• Each R 6 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms.
• Each l independently represents an integer of 1 to 4.
• R 5 is R 2 or R 3.
• m is 1 to 100
• n is 0 to 100.
• the order of the repeating units bracketed by m and n is not limited, and the bonding pattern may be alternating, block, or random.
• Y is C(CF 3 ) 2 , SO 2 , CO, an oxygen atom, a direct bond, or a group represented by the following formula (13):
• a resin composition according to claim 1 further comprising a photocuring initiator (C).
• a cured product comprising the resin composition according to any one of claims 1 to 4.
• a semiconductor device comprising a surface protection film, an interlayer insulating film, or an insulating film of a rewiring layer, which comprises the bismaleimide compound-containing resin composition according to any one of claims 1 to 5.
• a dry film resist obtained by sandwiching the bismaleimide compound-containing resin composition according to any one of claims 1 to 6 between substrates.
• the present invention provides a resin composition capable of producing a resin sheet having good compatibility and photocurability, and a resin sheet, a multilayer printed wiring board, and a semiconductor device using the same.
• the present invention relates to a resin composition that contains a bismaleimide compound (A) having a cyclic imide bond obtained by reacting an aromatic diamine (a-1) represented by the above formula (1), a tetrabasic acid dianhydride (a-3), and maleic anhydride, a resin or compound (B) having an ethylenically unsaturated group, and a photocuring initiator (C).
• A bismaleimide compound having a cyclic imide bond obtained by reacting an aromatic diamine (a-1) represented by the above formula (1), a tetrabasic acid dianhydride (a-3), and maleic anhydride
• a resin or compound (B) having an ethylenically unsaturated group a photocuring initiator (C).
• the bismaleimide compound (A) is a compound having two maleimide groups, and has an aromatic diamine (a-1) represented by the following formula (1) and a cyclic imide bond.
• a bismaleimide compound (A) is obtained by reacting an aromatic diamine (a-1), a tetrabasic acid dianhydride (a-3), and maleic anhydride.
• a divalent organic diamine (a-2) having 6 to 200 carbon atoms other than the aromatic diamine (a-1) can be reacted.
• a bismaleimide compound (A) obtained by reacting an aromatic diamine (a-1), a tetrabasic acid dianhydride (a-3), maleic anhydride, and a divalent organic diamine (a-2) having 6 to 200 carbon atoms other than the aromatic diamine (a-1) is preferred.
• Each R 1 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms.
• Each l independently represents an integer of 1 to 4.
• the bismaleimide compound (A) is represented by the following general formula (2):
• R 4 independently represents a tetravalent organic group containing a cyclic structure.
• R 3 independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms.
• R 4 independently represents a group represented by the following formula (3):
• each R 6 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms.
• Each 1 independently represents an integer of 1 to 4.
• R 5 is R 2 or R 3.
• n is 1 to 100
• m is 0 to 100.
• the order of the repeating units bracketed by n and m is not limited, and the bonding pattern may be alternate, block, or random.
• It is a bismaleimide compound represented by the formula:
• each R 1 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms.
• the linear or branched alkyl group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, i-propyl, butyl, isobutyl, sec-butyl, and tert-butyl groups.
• alkyl groups having 1 to 4 carbon atoms are preferred, and methyl, ethyl, n-propyl, and i-propyl groups are more preferred, since they exhibit excellent adhesion to chips, substrates, and the like, as well as good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins.
• halogen atoms include fluorine, chlorine, bromine, and iodine atoms.
• the linear or branched alkoxy group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, 2-methylpropoxy, 1-methylpropoxy, and tert-butoxy.
• alkoxy groups having 1 to 4 carbon atoms are preferred, and methoxy, ethoxy, n-propoxy, and iso-propoxy groups are more preferred, because they exhibit excellent adhesion to chips, substrates, and the like, as well as good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins.
• R1 a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, a methoxy group, and an ethoxy group are preferable, a hydrogen atom, a methyl group, and a hydroxyl group are more preferable, and a hydrogen atom is even more preferable, because R1 exhibits good solubility in solvents, a low melting point, low water absorbency, and good compatibility with other resins in addition to excellent adhesion to chips, substrates, and the like.
• each 1 independently represents an integer of 1 to 4. Since 1 exhibits excellent adhesion to chips, substrates, and the like, as well as good solubility in solvents, a low melting point, low water absorption, and good compatibility with other resins, it is preferable that all R 1s are hydrogen atoms, and therefore 1 is preferably 4.
• aromatic diamine (a-1) represented by formula (1) examples include aromatic diamines such as metaxylenediamine (formula (14) below), paraxylenediamine (formula (15) below), and orthoxylenediamine (formula (16) below).
• aromatic diamine (MXDA: manufactured by Mitsubishi Gas Chemical Company, Inc.) is readily available.
• metaxylenediamine (formula (14) below) is preferred.
• the maleimide compound of this embodiment is not particularly limited as long as it exhibits the effects of the present invention, but in terms of good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins, the weight average molecular weight is preferably 100 to 100,000, and more preferably 500 to 30,000.
• the "weight average molecular weight” refers to the weight average molecular weight calculated using polystyrene standards as determined by gel permeation chromatography (GPC).
• maleimide compounds have poor light transmittance, so when a resin composition contains a maleimide compound, light does not reach the photocuring initiator dispersed in the resin composition sufficiently, and the photocuring initiator does not generate radicals easily. Therefore, the photoradical reaction of maleimide compounds generally does not proceed easily, and even if radical polymerization or dimerization reaction of maleimide alone proceeds, its reactivity is very low.
• the maleimide compound according to this embodiment has very good light transmittance because the maleimide group is bonded to the aromatic ring via a methylene group and has a short conjugation length, so that light reaches the photocuring initiator sufficiently and the photoradical reaction of maleimide occurs efficiently.
• the transmittance is 3% or more, which is very good light transmittance. Therefore, for example, when manufacturing a printed wiring board having a high-density, high-definition wiring pattern using a direct imaging exposure method, the photoradical reaction of maleimide occurs efficiently even when active energy rays having a wavelength of 405 nm (h-line) are used.
• a photocuring initiator that has an absorbance of 0.1 or more at a wavelength of 405 nm (h-rays) and exhibits excellent absorbency for light of a wavelength of 405 nm (h-rays) as the photocuring initiator described below.
• the maleimide compound of the present embodiment has excellent light transmittance. Therefore, even when light having a wavelength of 405 nm is used, the light sufficiently reaches the photocuring initiator, a radical reaction using radicals generated from the photocuring initiator proceeds, and photocuring is possible even in a resin composition containing a large amount of the maleimide compound. Furthermore, the cured product obtained by containing the resin composition of this embodiment has excellent photocurability, heat resistance and thermal stability, and can therefore be suitably used to form protective films and insulating layers.
• the divalent organic diamines (a-2) other than the aromatic diamines (a-1) used in the synthesis of the bismaleimide compound (A) are independently divalent hydrocarbon groups having 6 to 200 carbon atoms, preferably 8 to 100 carbon atoms, and more preferably 10 to 50 carbon atoms.
• the divalent hydrocarbon group is a branched divalent hydrocarbon group in which one or more hydrogen atoms are substituted with an alkyl or alkenyl group having 6 to 200 carbon atoms or more, preferably 8 to 100 carbon atoms, and more preferably 10 to 50 carbon atoms.
• the branched divalent hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated hydrocarbon group, and may have an alicyclic structure or an aromatic ring structure in the middle of the molecular chain.
• Specific examples of the branched divalent hydrocarbon group include a hydrocarbon group derived from a diamine at both ends, called a dimer diamine.
• dimer diamine is a compound in which two carboxyl groups of a dimer acid, which is a dimer of an unsaturated fatty acid such as oleic acid, are replaced with primary amino groups (see JP-A-9-12712, etc.).
• dimer diamines include PRIAMINE 1074 and PRIAMINE 1075 (both manufactured by Croda Japan Co., Ltd.), and Versamine 551 (manufactured by Cognis Japan Co., Ltd.). These may be used alone or in combination of two or more.
• PRIAMINE 1074 and PRIAMINE 1075 both manufactured by Croda Japan Co., Ltd.
• Versamine 551 manufactured by Cognis Japan Co., Ltd.
• the tetrabasic acid dianhydride (a-3) used in the synthesis of the bismaleimide compound (A) is not particularly limited as long as it has two acid anhydride groups in one molecule.
• Specific examples of the (a-3) component include pyromellitic anhydride, ethylene glycol bis(anhydrotrimellitate), glycerin bis(anhydrotrimellitate) monoacetate, 1,2,3,4-butane tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 5-(2,5-dioxotetrahydro
• dianhydride examples include 5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, 5,5'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, and 4,4'-bisphenol A dianhydride.
• 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, and 4,4'-bisphenol A dianhydride are preferred in terms of solvent solubility and adhesion to substrates. These may be used alone or in combination of two or more.
• the tetrabasic acid dianhydride (a-3) used in the synthesis of the bismaleimide compound (A) is preferably a compound selected from the group consisting of the following formulas (4) to (12) from the viewpoint of the solvent solubility of the final bismaleimide resin.
• Y represents C(CF 3 ) 2 , SO 2 , CO, an oxygen atom, a direct bond, or a divalent linking group represented by formula (13) above.
• the tetrabasic acid dianhydride (a-3) is preferably a tetrabasic acid dianhydride (a-3) represented by the following general formula (23):
• the tetrabasic acid dianhydride (a-3) is preferably a tetrabasic acid dianhydride (a-3) represented by the following general formula (24):
• the tetrabasic acid dianhydride (a-3) is preferably a tetrabasic acid dianhydride (a-3) represented by the following general formula (25):
• the tetrabasic acid dianhydride (a-3) is preferably a tetrabasic acid dianhydride (a-3) represented by the following general formula (26):
• the tetrabasic acid dianhydride (a-3) is preferably a tetrabasic acid dianhydride (a-3) represented by the following general formula (27):
• the bismaleimide compound (A) may be a bismaleimide compound obtained by reacting the aromatic diamine (a-1), an organic diamine (a-2) other than the aromatic diamine (a-1), the tetracarboxylic dianhydride (a-3), and the maleic anhydride.
• the organic diamine (a-2) other than the aromatic diamine (a-1) By copolymerizing the organic diamine (a-2) other than the aromatic diamine (a-1), it becomes possible to control the required physical properties as needed, such as further improving the photocurability and crack resistance of the obtained cured product.
• organic diamine (a-2) other than the aromatic diamine (a-1) refers to a diamine other than the diamine contained in the aromatic diamine (a-1).
• organic diamine (a-2) is not particularly limited, and examples thereof include aliphatic diamines such as 1,6-hexamethylenediamine; alicyclic diamines such as 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, isophoronediamine, and norbornenediamine; 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(aminomethyl)benzene, 1,3-bis(4- Examples of aromatic diamines include 4,4'-diaminodiphenylsulfone, 3,3'-diamino
• aliphatic diamines having 6 to 12 carbon atoms such as 1,6-hexamethylenediamine, and diaminocyclohexanes such as 1,3-bis(aminomethyl)cyclohexane, isophoronediamine, and norbornenediamine are more preferred.
• one of these organic diamines (a-2) may be used alone or two or more of them may be used in combination.
• the total content of the bismaleimide compound (A) is preferably 25 to 99 parts by mass, more preferably 30 to 97 parts by mass, and even more preferably 50 to 95 parts by mass per 100 parts by mass of the bismaleimide compound (A) and the resin or compound (B) in total, from the viewpoint of obtaining a cured product mainly composed of the bismaleimide compound and improving photocurability.
• the method for producing the bismaleimide compound (A) is not particularly limited, but the compound can be efficiently produced, for example, by the method described below.
• the basic flow is to synthesize an amic acid from a tetrabasic acid dianhydride and a diamine, go through step A where the amic acid is then subjected to ring-closing dehydration, then react with maleic anhydride to synthesize maleamic acid, and finally go through step B where the molecular chain terminals are blocked with maleimide groups by ring-closing dehydration to obtain a bismaleimide compound.
• each step can be broadly divided into two: amic acid or maleamic acid synthesis reaction and ring-closing dehydration reaction, which are described in detail below.
• step A a specific tetrabasic acid dianhydride is reacted with a specific diamine to synthesize an amic acid.
• This reaction generally proceeds in an organic solvent (e.g., a nonpolar solvent or a high-boiling point aprotic polar solvent) at room temperature (25° C.) to 100° C.
• the subsequent ring-closing dehydration reaction of the amic acid is carried out under conditions of 90 to 120° C., and then the water by-produced by the condensation reaction is removed from the system.
• an organic solvent e.g., a non-polar solvent, a high-boiling aprotic polar solvent, etc.
• an acid catalyst can be added.
• Examples of the organic solvent include toluene, xylene, anisole, biphenyl, naphthalene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc. These may be used alone or in combination of two or more.
• Examples of the acid catalyst include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc. These may be used alone or in combination of two or more.
• step B the diamine having amino groups at both ends obtained in step B is reacted with maleic anhydride at room temperature (25° C.) to 100° C. to synthesize maleamic acid, and finally, the molecular chain ends are blocked with maleimide groups by ring-closing dehydration while removing water by-produced in the system under conditions of 95 to 120° C., thereby obtaining the desired bismaleimide compound. It is preferable to carry out the blocking reaction of the molecular chain ends with maleimide groups at 120° C. or less, since side reactions and high molecular weight compounds are less likely to occur. According to such a production method, the bismaleimide compound obtained has a block copolymer structure, and therefore the compatibility of the synthesized resin can be made uniform and improved.
• the resin composition of the present embodiment contains a resin or compound (B) having an ethylenically unsaturated group (also referred to as “component (B)” or “resin or compound (B)”) in addition to the bismaleimide compound (A).
• component (B) also referred to as "component (B)” or “resin or compound (B)”
• resins or compounds (B) can be used alone or in appropriate mixtures of two or more types depending on the physical properties and applications of the resulting cured product.
• the compound having an ethylenically unsaturated group is not particularly limited as long as it has an ethylenically unsaturated group in one molecule.
• Specific examples of compounds having an ethylenically unsaturated group include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(
• adipic acid epoxy di(meth)acrylate bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide (meth)acrylate, bisphenol di(meth)acrylate, ⁇ -caprolactone modified hydroxypivalic acid neopen glycol di(meth)acrylate, ⁇ -caprolactone modified dipentaerythritol hexa(meth)acrylate, ⁇ -caprolactone modified dipentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane tri(meth)acrylate, and ethylene oxide adducts thereof; pentaerythritol tri(meth)acrylate, and ethylene oxide adducts thereof; pentaerythritol tetra(meth)acrylate, dipentaerythritol hex
• compounds having ethylenically unsaturated groups include urethane (meth)acrylates, which have both a (meth)acryloyl group and a urethane bond in the same molecule; polyester (meth)acrylates, which have both a (meth)acryloyl group and an ester bond in the same molecule; epoxy (meth)acrylates, which are derived from epoxy resins and also have a (meth)acryloyl group; and reactive oligomers, which use a combination of these bonds.
• urethane (meth)acrylates which have both a (meth)acryloyl group and a urethane bond in the same molecule
• polyester (meth)acrylates which have both a (meth)acryloyl group and an ester bond in the same molecule
• epoxy (meth)acrylates which are derived from epoxy resins and also have a (meth)acryloyl group
• reactive oligomers which use a combination of these bonds.
• Urethane (meth)acrylates include reaction products of hydroxyl-containing (meth)acrylate with polyisocyanate and other alcohols used as necessary.
• the hydroxyalkyl (meth)acrylates include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate;
• glycerin (meth)acrylates include glycerin mono(meth)acrylate and glycerin di(meth)acrylate; and urethane (meth)acrylates obtained by reacting sugar alcohol (meth)acrylates such as pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate with polyisocyanates such as toluene diisocyanate, hexamethylene
• polyester (meth)acrylates include monofunctional (poly)ester (meth)acrylates such as caprolactone-modified 2-hydroxyethyl (meth)acrylate, ethylene oxide and/or propylene oxide-modified phthalic acid (meth)acrylate, ethylene oxide-modified succinic acid (meth)acrylate, and caprolactone-modified tetrahydrofurfuryl (meth)acrylate; di(poly)ester (meth)acrylates such as hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, and epichlorohydrin-modified phthalic acid di(meth)acrylate; and mono-, di-, or tri(meth)acrylates of triols obtained by adding 1 mole or more of a cyclic lactone compound such as ⁇ -caprolactone, ⁇ -
• triols obtained by adding 1 mole or more of a cyclic lactone compound such as ⁇ -caprolactone, ⁇ -butyrolactone, or ⁇ -valerolactone to 1 mole of pentaerythritol, dimethylolpropane, trimethylolpropane, or tetramethylolpropane; mono- or poly(meth)acrylates of triols obtained by adding 1 mole or more of a cyclic lactone compound such as ⁇ -caprolactone, ⁇ -butyrolactone, or ⁇ -valerolactone to 1 mole of dipentaerythritol, or mono(meth)acrylates or poly(meth)acrylates of polyhydric alcohols such as triols, tetraols, pentaols, or hexaols.
• a cyclic lactone compound such as ⁇ -caprolactone, ⁇ -butyrolactone, or ⁇ -valerolact
• polyester polyols which are reaction products of diol components such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, (poly)butylene glycol, 3-methyl-1,5-pentanediol, and hexanediol with polybasic acids such as maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, and 5-sodium sulfoisophthalic acid, and their anhydrides; and polyfunctional (poly)ester (meth)acrylates such as (meth)acrylates of cyclic lactone-modified polyester diols consisting of diol components, polybasic acids, their anhydrides, and ⁇ -caprolactone, ⁇ -but
• Epoxy (meth)acrylates are carboxylate compounds of a compound having an epoxy group and (meth)acrylic acid. Examples include phenol novolac type epoxy (meth)acrylate, cresol novolac type epoxy (meth)acrylate, trishydroxyphenylmethane type epoxy (meth)acrylate, dicyclopentadiene phenol type epoxy (meth)acrylate, bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, biphenol type epoxy (meth)acrylate, bisphenol A novolac type epoxy (meth)acrylate, naphthalene skeleton-containing epoxy (meth)acrylate, glyoxal type epoxy (meth)acrylate, heterocyclic epoxy (meth)acrylate, and acid anhydride modified epoxy acrylates thereof.
• compounds having an ethylenically unsaturated group include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether; styrenes such as styrene, methylstyrene, ethylstyrene, and divinylbenzene; and compounds having a vinyl group such as triallyl isocyanurate, trimethallyl isocyanurate, and bisallylnadimide.
• KAYARAD registered trademark
• R-604 KAYARAD (registered trademark) R-684
• KAYARAD registered trademark
• HX-220 KAYARAD (registered trademark) HX-620
• KAYARAD registered trademark
• DPHA KAYARAD
• DPCA-60 KAYARAD (registered trademark)
• DPEA-12 KAYARAD (registered trademark) PET-30
• KAYARAD registered trademark
• ZXR-1801H trade name, manufactured by Nippon Kayaku Co., Ltd.
• ZXR-1806H trade name
• KAYARAD registered trademark
• ZXR-1810H trade name
• KAYARAD registered trademark
• ZXR-1889H trade name
• KAYARAD registered trademark
• ZCR-6001H KAYARAD (registered trademark)
• the total content of the resin or compound (B) is preferably 0.5 to 90 parts by mass, more preferably 1 to 84 parts by mass, and even more preferably 5 to 50 parts by mass per 100 parts by mass of the bismaleimide compound (A) and the resin or compound (B), from the viewpoint of obtaining a cured product mainly composed of the bismaleimide compound and improving photocurability.
• the photopolymerization initiator (C) of the present invention is not particularly limited, and a conventionally used one can be appropriately adopted.
• a photopolymerization initiator (C) of the present invention that efficiently generates radicals at an exposure wavelength of 310 to 436 nm (more preferably 365 nm) from the viewpoint of being able to form fine patterns using a reduction projection exposure machine (stepper; light source wavelength: 365 nm, 436 nm) that is standardly used in the manufacturing process of semiconductor protective films, etc.
• a reduction projection exposure machine stepper; light source wavelength: 365 nm, 436 nm
• maleimide groups generally do not undergo homopolymerization by radicals, but react with radicals generated mainly from the photopolymerization initiator to cause a dimerization reaction of the bismaleimide compound to proceed and form a crosslinked structure.
• the present inventors surmise that bismaleimide compounds appear to be less reactive than acrylic compounds and the like that are generally used as photopolymerizable compounds. Therefore, from the viewpoint of being able to generate radicals more efficiently and being highly reactive at an exposure wavelength of 310 to 436 nm (more preferably 365 nm), it is even more preferable for the photopolymerization initiator of the present invention to be a compound having an oxime structure or a thioxanthone structure.
• photopolymerization initiators examples include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] having an oxime structure (manufactured by BASF Japan, "IRGACURE OXE-01”), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (manufactured by BASF Japan, "IRGACURE OXE-02”), and 2,4-dimethylthioxanthone having a thioxanthone structure (manufactured by Nippon Kayaku Co., Ltd., "DETX-S").
• Such photopolymerization initiators with high radical generation capacity by light tend to be too reactive and difficult to control the reaction when used in the photopolymerization of ordinary acrylic compounds, etc., but can be used preferably in the present invention.
• the content of the photocuring initiator (C) is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, and even more preferably 0.3 to 10 parts by mass, per 100 parts by mass of the total of the bismaleimide compound (A) and the maleimide compound (B), from the viewpoint of obtaining a resin sheet that has better compatibility with the bismaleimide compound (A) and the maleimide compound (B), sufficiently progresses the photocuring thereof, sufficiently insolubilizes the exposed area in the developability with an organic solvent, and further suppresses cracking.
• the resin composition of the present embodiment may contain an organic solvent as necessary. By using an organic solvent, the viscosity during preparation of the resin composition can be adjusted.
• the type of organic solvent is not particularly limited as long as it can dissolve a part or all of the resin in the resin composition.
• organic solvents examples include halogen solvents such as dichloromethane, chloroform, dichloroethane, and chlorobenzene; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, dioxane, and acetonitrile; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; cellosolve solvents such as 2-ethoxyethanol and propylene glycol monomethyl ether; aliphatic alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; aromatic group-containing phenol solvents such as phenol and cresol; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl a
• cyclopentanone, propylene glycol monomethyl ether acetate, and dimethylacetamide are preferred because they can exhibit excellent solubility in other resins and compounds such as the bismaleimide compound (A), the maleimide compound (B), and the photopolymerization initiator (C), and because it is easy to prepare a varnish with good solubility.
• organic solvents can be used alone or in a suitable mixture of two or more.
• the resin composition of this embodiment is prepared by appropriately mixing the bismaleimide compound (A), the resin or compound (B), the photocuring initiator (C), and, if necessary, the filler, other resins, other compounds, and additives.
• the resin composition can be suitably used as a varnish when preparing the resin sheet of this embodiment described later.
• the organic solvent used to prepare the varnish is not particularly limited, and specific examples thereof are as described above.
• the resin composition can be produced, for example, by blending each of the above-mentioned components in a solvent in order and thoroughly stirring.
• the resin composition has excellent photocurability, and the cured product obtained from the resin composition has excellent heat resistance, thermal stability, and insulation reliability.
• the resin composition can be suitably used as a varnish when producing the resin sheet of this embodiment described below.
• the varnish can be obtained by a known method.
• the varnish can be obtained by adding 10 to 900 parts by mass of an organic solvent to 100 parts by mass of the components excluding the organic solvent in the resin composition of this embodiment, and carrying out the known mixing process (stirring, kneading, etc.) described above.
• the resin composition can be preferably used in applications requiring a resin composition with high insulation reliability.
• Applications include, for example, photosensitive films, photosensitive films with support, prepregs, resin sheets, circuit boards (for laminates, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, and component-embedding resins.
• the resin composition is excellent in photocurability, heat resistance, and thermal stability, and therefore can be suitably used as an insulating layer for multilayer printed wiring boards or as a solder resist.
• the cured product is obtained by curing the resin composition of the present embodiment.
• the resin composition is melted or dissolved in a solvent, poured into a mold, and cured under normal conditions using light.
• the light wavelength range is preferably 100 to 500 nm, which is a range where curing proceeds efficiently using a photopolymerization initiator or the like.
• the resin sheet of the present embodiment is a resin sheet with a support, which has a support and a resin layer disposed on one or both sides of the support, and the resin layer contains a resin composition.
• the resin sheet can be produced by applying the resin composition onto the support and drying it.
• the resin layer in the resin sheet has excellent heat resistance, thermal stability, and insulation reliability.
• resin films include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polyethylene naphthalate film, polyvinyl alcohol film, and triacetyl acetate film.
• PET film is preferable.
• the resin film is preferably coated with a release agent on its surface to facilitate peeling from the resin layer.
• the thickness of the resin film is preferably in the range of 5 to 100 ⁇ m, and more preferably in the range of 10 to 50 ⁇ m. If the thickness is less than 5 ⁇ m, the support tends to be easily torn when peeled off before development, and if the thickness exceeds 100 ⁇ m, the resolution tends to decrease when exposing from above the support.
• the resin film to have excellent transparency.
• the resin layer may be protected with a protective film.
• a protective film By protecting the resin layer side with a protective film, it is possible to prevent the adhesion of dirt and the like to the surface of the resin layer and scratches.
• the protective film a film made of the same material as the resin film can be used.
• the thickness of the protective film is preferably in the range of 1 to 50 ⁇ m, and more preferably in the range of 5 to 40 ⁇ m. If the thickness is less than 1 ⁇ m, the handleability of the protective film tends to decrease, and if it exceeds 50 ⁇ m, the cost efficiency tends to decrease. It is preferable that the adhesive strength between the resin layer and the protective film is smaller than the adhesive strength between the resin layer and the support.
• Examples of the method for producing the resin sheet of this embodiment include a method for producing a resin sheet by applying the resin composition of this embodiment to a support such as a PET film and drying it to remove the organic solvent.
• the coating method can be a known method using, for example, a roll coater, a comma coater, a gravure coater, a die coater, a bar coater, a lip coater, a knife coater, a squeeze coater, etc. Drying can be performed, for example, by a method of heating in a dryer at 60 to 200° C. for 1 to 60 minutes.
• the amount of organic solvent remaining in the resin layer is preferably 5% by mass or less relative to the total mass of the resin layer in order to prevent diffusion of the organic solvent in subsequent processes.
• the thickness of the resin layer is preferably 1 to 50 ⁇ m in order to improve handleability.
• the resin sheet can be preferably used for manufacturing insulating layers for multilayer printed wiring boards.
• the multilayer printed wiring board of the present embodiment has an insulating layer and a conductor layer formed on one or both sides of the insulating layer, and the insulating layer contains a resin composition.
• the insulating layer can be obtained, for example, by stacking one or more resin sheets and curing them.
• the number of insulating layers and conductor layers is not particularly limited, and the number of layers can be appropriately set according to the intended use.
• the order of the insulating layers and conductor layers is also not particularly limited.
• the conductor layer may be a metal foil used in various printed wiring board materials, for example, a metal foil such as copper and aluminum.
• the copper metal foil can be a copper foil such as rolled copper foil and electrolytic copper foil.
• the thickness of the conductor layer is usually 1 to 100 ⁇ m. Specifically, it can be manufactured by the following method.
• the resin layer side of the resin sheet is laminated on one or both sides of the circuit board using a vacuum laminator.
• circuit boards include glass epoxy boards, metal boards, ceramic boards, silicon boards, semiconductor sealing resin boards, polyester boards, polyimide boards, BT resin boards, and thermosetting polyphenylene ether boards.
• the circuit board refers to a board on which a patterned conductor layer (circuit) is formed on one or both sides of the board.
• a board in which one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits) is also included in the circuit board.
• the insulating layer laminated on this multilayer printed wiring board may be an insulating layer obtained by stacking and curing one or more resin sheets of the present embodiment, or may be an insulating layer obtained by stacking one or more resin sheets of the present embodiment and one or more known resin sheets different from the resin sheet of the present embodiment.
• the method of stacking the resin sheet of the present embodiment and the known resin sheet different from the resin sheet of the present embodiment is not particularly limited.
• the surface of the conductor layer may be roughened in advance by blackening and/or copper etching.
• the protective film is peeled off and then the resin sheet and the circuit board are preheated as necessary, and the resin layer of the resin sheet is pressure-bonded to the circuit board while being pressurized and heated.
• a method of laminating the resin layer of the resin sheet to the circuit board under reduced pressure by a vacuum lamination method is preferably used.
• the conditions of the lamination process are, for example, a pressure bonding temperature (lamination temperature) of 50 to 140°C, a pressure bonding pressure of 1 to 15 kgf/ cm2 , a pressure bonding time of 5 to 300 seconds, and lamination under reduced pressure of 20 mmHg or less.
• the lamination process may be a batch process or a continuous process using a roll.
• the vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a two-stage build-up laminator (product name) manufactured by Nikko Materials Co., Ltd.
• a predetermined portion of the resin layer is irradiated with active energy rays from a light source, thereby curing the resin layer in the irradiated portion.
• the irradiation may be performed through a mask pattern, or a direct writing method may be used in which the radiation is directly irradiated.
• active energy rays include ultraviolet rays, visible light rays, electron beams, and X-rays.
• the wavelength of the active energy rays is, for example, in the range of 200 to 600 nm. When ultraviolet rays are used, the amount of irradiation is approximately 10 to 1000 mJ/cm 2.
• a printed wiring board having a high-density and high-definition wiring formation is manufactured using a stepper exposure method, it is preferable to use an active energy ray having a wavelength of, for example, 365 nm (i-ray).
• an active energy ray having a wavelength of, for example, 365 nm (i-ray) is used, the amount of irradiation is approximately 10 to 10,000 mJ/cm 2.
• the exposure method through a mask pattern includes a contact exposure method in which the mask pattern is attached to the multilayer printed wiring board, and a non-contact exposure method in which the mask pattern is not attached to the multilayer printed wiring board and the exposure method uses parallel light, but either method may be used.
• the exposure may be performed from above the support, or after the support is peeled off.
• a development step may be included as necessary. That is, when there is no support on the resin layer, the pattern of the insulating layer can be formed by removing the non-photocured portion (unexposed portion) by wet development after the exposure step and developing the non-photocured portion (unexposed portion) and developing the non-photocured portion. When there is a support on the resin layer, the pattern of the insulating layer can be formed by removing the support after the exposure step and then removing the non-photocured portion (unexposed portion) by wet development and developing the non-photocured portion.
• the developer is not particularly limited as long as it selectively dissolves the unexposed parts.
• organic solvents such as cyclohexanone, cyclopentanone, and ⁇ -butyrolactone
• alkaline developers such as aqueous solutions of tetramethylammonium hydroxide, sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide can be used. These developers can be used alone or in a suitable mixture of two or more.
• the development method can be a known method such as dipping, paddle, spraying, oscillating immersion, brushing, scraping, etc. In forming a pattern, these development methods may be used in combination as necessary.
• a development method it is preferable to use a high-pressure spray, as this improves the resolution.
• the spray pressure is preferably 0.02 to 0.5 MPa.
• a post-baking step is performed to form an insulating layer (cured product).
• the post-baking step include an ultraviolet irradiation step using a high-pressure mercury lamp and a heating step using a clean oven, and these steps can be used in combination.
• the amount of irradiation can be adjusted as needed, and irradiation can be performed at an amount of irradiation of, for example, about 50 to 10,000 mJ/cm2.
• the heating conditions can be appropriately selected as needed, but are preferably selected in the range of 150 to 300°C for 20 to 180 minutes, and more preferably in the range of 200 to 300°C for 30 to 60 minutes.
• a conductor layer is formed on the surface of the insulating layer by dry plating.
• dry plating known methods such as vapor deposition, sputtering, and ion plating can be used.
• vapor deposition vacuum vapor deposition
• a multilayer printed wiring board is placed in a vacuum container, and a metal is heated and evaporated to form a metal film on the insulating layer.
• a multilayer printed wiring board is placed in a vacuum container, an inert gas such as argon is introduced, and a direct current voltage is applied to cause the ionized inert gas to collide with a target metal, and a metal film can be formed on the insulating layer by the metal that is knocked out.
• an inert gas such as argon
• a direct current voltage is applied to cause the ionized inert gas to collide with a target metal, and a metal film can be formed on the insulating layer by the metal that is knocked out.
• a conductor layer is formed by electroless plating or electrolytic plating.
• Subsequent pattern formation methods include, for example, subtractive and semi-additive methods.
• the encapsulating material of the present embodiment includes the resin composition of the present embodiment.
• the encapsulating material can be produced by a method that is generally known and is not particularly limited.
• the encapsulating material can be produced by mixing the resin composition of the present embodiment with various known additives or solvents that are generally used in encapsulating material applications using a known mixer.
• the maleimide compound of the present embodiment, various additives, and solvents can be added by a method that is generally known and is not particularly limited when mixed.
• the fiber-reinforced composite material of the present embodiment includes the resin composition of the present embodiment and reinforcing fibers.
• the reinforcing fibers generally known ones can be used, and are not particularly limited.
• glass fibers such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, and spherical glass; carbon fibers; aramid fibers; boron fibers; PBO fibers; high-strength polyethylene fibers; alumina fibers; and silicon carbide fibers.
• the form and arrangement of the reinforcing fibers are not particularly limited, and can be appropriately selected from woven fabrics, nonwoven fabrics, mats, knits, braided cords, unidirectional strands, rovings, and chopped fibers.
• a preform a laminate of woven fabric base fabrics made of reinforcing fibers, or a laminate of the laminated woven fabric base fabrics sewn together with a stitch thread, or a fiber structure such as a three-dimensional woven fabric or a braided fabric
• a preform a laminate of woven fabric base fabrics made of reinforcing fibers, or a laminate of the laminated woven fabric base fabrics sewn together with a stitch thread, or a fiber structure such as a three-dimensional woven fabric or a braided fabric
• These fiber-reinforced composite materials can be produced by any known method, and are not particularly limited. Examples include the liquid composite molding method, the resin film infusion method, the filament winding method, the hand lay-up method, and the pultrusion method.
• the resin transfer molding method which is one of the liquid composite molding methods, can be used for a variety of purposes because it allows materials other than the preform, such as metal plates, foam cores, and honeycomb cores, to be set in the mold beforehand. Therefore, it is preferably used when mass-producing composite materials with relatively complex shapes in a short period of time.
• the adhesive of the present embodiment includes the resin composition of the present embodiment.
• the method for producing the adhesive can be appropriately applied by a generally known method, and is not particularly limited.
• the adhesive can be produced by mixing the resin composition of the present embodiment with various known additives or solvents that are generally used in adhesive applications, using a known mixer.
• the method for adding the maleimide compound of the present embodiment, various additives, and solvents during mixing can be appropriately applied by a generally known method, and is not particularly limited.
• the heat-resistant resin coating film formed by the resin composition of the present invention can be used in electronic parts such as semiconductor devices and multilayer wiring boards, and organic EL display devices. Specifically, it is suitably used for applications such as passivation films for semiconductors, surface protective films for semiconductor elements, interlayer insulating films, insulating films for rewiring layers, interlayer insulating films for multilayer wiring for high-density mounting, interlayer insulating films for electronic parts such as inductors and SAW filters, and insulating films and flat layers for organic electroluminescent devices, but is not limited thereto, and can have various structures.
• the compound and composition of the present invention can also be used in the form of a dry film resist. That is, the compound and composition of the present invention can be applied to a base film using a roll coater, die coater, knife coater, bar coater, gravure coater, or the like, and then dried in a drying oven set at 45 to 140°C to remove a predetermined amount of solvent, and a cover film, or the like, can be laminated as necessary to form a dry film resist. In this case, the thickness of the resist on the base film is adjusted to 2 to 200 ⁇ m.
• the base film and cover film for example, films of polyester, polypropylene, polyethylene, TAC, polyimide, or the like are used.
• These films may be treated with a silicone-based release agent or a non-silicone-based release agent as necessary. If supplied as a dry film resist, it is possible to omit the steps of application to a support and drying, and the photosensitive resin composition of the present invention can be used more easily.
• the mixture was stirred for approximately 10 minutes to mix, and then 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (48.2 g, 0.11 mol) was slowly added to the stirred mixture.
• the mixture was heated to reflux for 6 hours to form the amine-terminated diimide. The theoretical amount of water produced from this condensation had been reached by this time.
• the reaction mixture was cooled below room temperature, and 25.5 g (0.26 mol) of maleic anhydride was added to the flask. The mixture was refluxed for an additional 8 hours, yielding the expected amount of water.
• Synthesis Example 2 (A-2) A 1 L round bottom flask equipped with a thermometer, reflux condenser, Dean Stark apparatus, powder inlet, nitrogen inlet, and stirrer was charged with 165 g toluene and 165 g N-methylpyrrolidone. Next, 26.6 g (0.20 mol) metaxylenediamine (Mitsubishi Gas Chemical Co., Ltd.) and 35.1 (0.06 mol) PRIAMINE 1075 (Croda Japan Co., Ltd.) were added, followed by the slow addition of 20.9 g (0.22 mol) methanesulfonic acid to form the salt.
• the mixture was stirred to mix for approximately 10 minutes, and then 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (48.2 g, 0.11 mol) was slowly added to the stirred mixture.
• the mixture was heated to reflux for 6 hours to form the amine-terminated diimide. The theoretical amount of water produced from this condensation had been reached by this time.
• the reaction mixture was cooled to below room temperature, and 25.5 g (0.26 mol) of maleic anhydride was added to the flask. The mixture was refluxed for an additional 8 hours, yielding the expected amount of water.
• Synthesis Example 3 (A-3) It was synthesized by a known method using the method described in Example 1 of Patent Document JP-A-2021-123672.
• a 1 L round bottom flask equipped with a thermometer, reflux condenser, Dean Stark apparatus, powder inlet, nitrogen inlet, and mechanical stirrer was charged with 165 g toluene and 165 g N-methylpyrrolidone.
• 37.25 g (0.219 mol) isophorone diamine was added, followed by the slow addition of 20.9 g (0.22 mol) methanesulfonic acid to form the salt.
• 38.47 g (0.11 mol) pyromellitic anhydride was slowly added to the stirred mixture.
• the mixture was heated to reflux for 6 hours to form the amine-terminated diimide. The theoretical amount of water produced from this condensation had been obtained by this time.
• the reaction mixture was cooled to below room temperature and 25.5 g (0.26 mol) maleic anhydride was added to the flask. The mixture was refluxed for an additional 8 hours to obtain the expected amount of water produced. After cooling to room temperature, the organic layer was washed with water (100 ml x 5 times) to remove salts and unreacted raw materials, and a varnish of a bismaleimide compound was obtained.
• Examples 1 to 7 and Comparative Examples 1 to 2 The photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2 were prepared by mixing the components (A) to (C) in the amounts (parts by mass) shown in Table 1 and 103 parts by mass of cyclopentanone as the organic solvent (G).
• the visual compatibility refers to a state in which the curable resin composition is visually observed after mixing and stirring the components (A) to (G).
• the compatibility is good, no precipitates are formed and the composition can be applied to a substrate, whereas when the compatibility is poor, precipitates are formed and the composition can be applied to a substrate with difficulty.
• ⁇ No precipitates
• ⁇ Precipitates present
• the present invention provides a composition in which the resins have good compatibility with each other, and allows curing with a relatively low exposure dose (1000 mJ/cm 2 or less) and additional heating at a low temperature in a short time. Therefore, the bismaleimide compound and photosensitive resin composition of the present invention are extremely useful as a surface protective film, an interlayer insulating film, an insulating film for a rewiring layer, and the like for semiconductor elements.

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• 2023
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