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
  • 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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • 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
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
• • 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
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • 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
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials

Definitions

• the present invention relates to a photosensitive resin composition using a bismaleimide compound, 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 reports that a resin film made of a resin composition containing a bismaleimide resin with a long-chain alkyl group as a non-epoxy material and a hardener has excellent low dielectric properties.
• Patent Documents 4 and 5 disclose polyimides made from dimer diamines and alicyclic diamines derived from aromatic tetracarboxylic acids and dimer acids, which are dimers of unsaturated fatty acids such as oleic acid.
• Patent Document 8 describes a resin composition containing a bismaleimide compound (curable resin) and a photoradical polymerization initiator (curing agent) as a photosensitive resin composition used for laminates and resin sheets.
• Cured products made from resin compositions using incompatible resins have poor heat resistance and can cause cracks, making them unsuitable for use in applications such as protective films, interlayer insulating films, insulating films for rewiring layers, and underfills that can be used on semiconductor elements and semiconductor substrates.
• the film described in Patent Document 3 is essentially a combination of a bismaleimide resin having a long-chain alkyl group and a hard low-molecular aromatic maleimide, but it has poor compatibility and is prone to uneven properties and curing. Furthermore, the polyimides described in Patent Documents 4 and 5 are difficult to use for single curing and have poor compatibility with other resins. Furthermore, since polyimides undergo ring-closing dehydration during curing, for example, when laminating a rewiring layer, voids may occur depending on the conditions of use, making it impossible to flatten the surface.
• 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 3, the maleimide compound is cured by additional heating before development, but because heating is involved, a high-definition resist pattern cannot be obtained.
• the present invention has been made in view of the above circumstances, and relates to a resin composition containing maleimide resins which are compatible even when the main skeletons are different from each other, and an object of the present invention is to provide a curable resin composition which exhibits excellent photocurability and heat resistance, and a cured product thereof.
• an object of the present invention is to provide a curable resin composition which exhibits excellent photocurability and heat resistance, and a cured product thereof.
• a resin composition comprising: 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; and a maleimide compound (B) containing a structure derived from a dimer diamine.
• a resin composition comprising: 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; and a maleimide compound (B) containing a structure derived from a dimer diamine.
• 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 maleimide compound (B) containing a structure derived from dimer diamine:
• R 5 independently represents a tetravalent organic group containing a cyclic structure derived from tetrabasic acid dianhydride (a-3).
• 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 4 is R 2 or R 4.
• 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):
• the curable resin composition has excellent solution stability and compatibility, significantly improving workability, and the cured product has excellent photocurability and heat resistance compared to the product cured alone.
• the resin composition of the present invention contains a bismaleimide compound (A) and a maleimide compound (B) containing a structure derived from dimer diamine (hereinafter also referred to as maleimide compound (B)).
• 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 the 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.
• 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 (3):
• 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 1 independently represents an integer of 1 to 4.
• R 5 is R 2 or R 4.
• n is 0 to 100
• m is 1 to 100.
• the order of the repeating units bracketed by n and m is not limited, and the bonding mode may be alternating, 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 (15) 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) preferably contains 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 (24):
• 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 content of the bismaleimide compound (A) is preferably 10% by weight or more and less than 95% by weight of the total amount of the curable resin composition, more preferably 40% by weight or more and less than 90% by weight, and even more preferably 50% by weight or more and less than 90% by weight. It is desirable that the content of the bismaleimide compound (A) is greater than that of the maleimide compound (B). When it is in the above range, the physical properties of the cured product tend to be good in heat resistance while maintaining good photocurability. Note that the total amount of the curable resin composition does not include the amount of solvent.
• 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 at 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 this makes it difficult for side reactions and high molecular weight compounds 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 maleimide compound (B) has a divalent hydrocarbon group (b) derived from a dimer acid and a cyclic imide bond.
• the maleimide compound (B) is a maleimide compound other than the bismaleimide compound (A). Specifically, it does not contain the structure of the above formula (3).
• Such a maleimide compound (B) can be obtained by reacting a diamine (b-1) derived from a dimer acid, a tetracarboxylic dianhydride (b-2), and maleic anhydride.
• the divalent hydrocarbon group (b) derived from the dimer acid refers to a divalent residue obtained by removing two carboxyl groups from the dicarboxylic acid contained in the dimer acid.
• such a divalent hydrocarbon group (b) derived from a dimer acid can be introduced into a maleimide resin by reacting a diamine (b-1), obtained by substituting two carboxyl groups of the dicarboxylic acid contained in the dimer acid with amino groups, with a tetracarboxylic dianhydride (b-2) and maleic anhydride, which will be described later, to form an imide bond.
• the dimer acid is preferably a dicarboxylic acid having 20 to 60 carbon atoms.
• Specific examples of the dimer acid include those obtained by dimerizing the unsaturated bonds of unsaturated carboxylic acids such as linoleic acid, oleic acid, and linolenic acid, followed by distillation purification.
• the above specific dimer acids mainly contain dicarboxylic acids having 36 carbon atoms, and usually contain tricarboxylic acids and monocarboxylic acids having 54 carbon atoms, each at a maximum of about 5% by mass.
• the diamine (b-1) derived from the dimer acid is a diamine obtained by substituting two carboxyl groups of each dicarboxylic acid contained in the dimer acid with amino groups, and is usually a mixture.
• dimer acid-derived diamines (b-1) include diamines such as [3,4-bis(1-aminoheptyl)6-hexyl-5-(1-octenyl)]cyclohexane, and diamines in which the unsaturated bonds are saturated by further hydrogenating these diamines.
• the divalent hydrocarbon group (b) derived from the dimer acid, which is introduced into the maleimide resin using the diamine (b-1) derived from such a dimer acid is preferably a residue obtained by removing two amino groups from the diamine (b-1) derived from the dimer acid.
• the maleimide compound (B) is obtained using the diamine (b-1) derived from the dimer acid, one type of diamine (b-1) derived from the dimer acid may be used alone, or two or more types of diamines having different compositions may be used in combination.
• a commercially available product such as "PRIAMINE 1074" (manufactured by Croda Japan Co., Ltd.) may be used.
• the tetracarboxylic dianhydride (b-2) has an alicyclic structure adjacent to the anhydride group, and is a tetracarboxylic dianhydride having a structure in which the portion adjacent to the imide ring becomes an alicyclic structure when the bismaleimide compound is formed after the reaction. If the portion adjacent to the imide ring becomes an alicyclic structure, the structure may also contain an aromatic ring.
• the maleimide compound (B) is preferably represented by the following formula (2):
• R5 and R6 are structures derived from the tetracarboxylic dianhydride (b-2).
• R 7 represents a divalent hydrocarbon group (b) derived from a dimer acid
• R 8 represents a divalent organic group (c) other than the divalent hydrocarbon group (b) derived from a dimer acid
• R 9 represents any one selected from the group consisting of the divalent hydrocarbon group (b) derived from a dimer acid and the divalent organic group (c) other than the divalent hydrocarbon group (b) derived from a dimer acid
• R 9 and R 10 each independently represent one or more organic groups selected from a tetravalent organic group having a monocyclic or condensed polycyclic alicyclic structure and having 4 to 40 carbon atoms (preferably having 6 to 40 carbon atoms), a tetravalent organic group having 8 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are linked to each other directly or via a crosslinked structure, and a tetravalent organic group having 8 to 40 carbon atoms and a semi-alicyclic structure having both
• the tetracarboxylic dianhydride (b-2) is preferably a tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the following formula (29).
• the tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the following formula (29) has an alicyclic structure adjacent to the anhydride group.
• Cy is a tetravalent organic group having 4 to 40 carbon atoms and containing a hydrocarbon ring, and the organic group may also contain an aromatic ring.
• the tetracarboxylic acid dianhydride (b-2) having an alicyclic structure represented by the above formula (29) can be specifically represented by the following formula (3-c).
• R 12 is a tetravalent organic group having 4 to 40 carbon atoms containing a hydrocarbon ring, and the organic group may also contain an aromatic ring.
• the tetracarboxylic dianhydride (b-2) may be a tetravalent organic group having 4 to 40 carbon atoms (preferably 6 to 40 carbon atoms) and a monocyclic or condensed polycyclic alicyclic structure, a tetravalent organic group having 8 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are linked to each other directly or via a crosslinked structure, or a tetravalent organic group having 8 to 40 carbon atoms and a semi-alicyclic structure having both an alicyclic structure and an aromatic ring.
• tetracarboxylic dianhydride (b-2) having an alicyclic structure examples include 1,2,3,4-cyclobutane tetracarboxylic dianhydride (CBDA), 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride (H-PMDA), 1,1'-bicyclohexane-3,3',4,4'-tetracarboxylic acid-3,4:3',4'-dianhydride (H-BPDA), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-
• the tetracarboxylic dianhydride (b-2) is preferably a tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the following formula (30):
• the tetracarboxylic dianhydride (b-2) is preferably a tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the following formula (27):
• the lower limit of the tetracarboxylic dianhydride (b-2) is preferably 40 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more.
• the upper limit may be 100 mol% or less.
• tetracarboxylic dianhydride (a-2) in the total amount of acid dianhydrides is less than 40 mol%, the light collection rate is low and small pattern openings tend not to be obtained, so the resolution of the obtained pattern may be reduced.
• acid dianhydrides containing an aromatic ring adjacent to an anhydride group other than the tetracarboxylic dianhydride include pyromellitic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl
• aromatic dianhydrides include aromatic tetracarboxylic dianhydrides such as bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, and 3,4,9,10-perylenetetracarboxylic dianhydride, as well as aromatic dianhydrides such as bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, or compounds in which the aromatic rings of these compounds are substituted with alkyl groups or halogen atoms, or
• the maleimide compound (B) may be a bismaleimide compound obtained by reacting the dimer acid-derived diamine (b-1), an organic diamine (b-3) other than the dimer acid-derived diamine (b-1), the tetracarboxylic dianhydride (b-2), and the maleic anhydride.
• the organic diamine (b-3) other than the dimer acid-derived diamine (b-1) it becomes possible to control the required physical properties as needed, such as further reducing the tensile modulus of the resulting cured product.
• organic diamine (b-3) other than the diamine (b-1) derived from the dimer acid refers to a diamine other than the diamine contained in the diamine (b-1) derived from the dimer acid.
• Such organic diamine (b-3) is not particularly limited, and examples thereof include aliphatic diamines such as 1,6-hexamethylenediamine; alicyclic diamines such as 1,4-diaminocyclohexane and 1,3-bis(aminomethyl)cyclohexane; aromatic diamines such as 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(aminomethyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, and 4,4'-diaminodiphenylmethane; 4,4'-diaminodiphenylsulfone;
• an aliphatic diamine having 6 to 12 carbon atoms such as 1,6-hexamethylenediamine; a diaminocyclohexane, such as 1,4-diaminocyclohexane; or an aromatic diamine having an aliphatic structure having 1 to 4 carbon atoms in the aromatic skeleton, such as 2,2-bis[4-(4-aminophenoxy)phenyl]propane.
• one of these organic diamines (b-3) may be used alone, or two or more of them may be used in combination.
• the method of reacting the diamine (b-1) derived from the dimer acid, the tetracarboxylic dianhydride (b-2) having an alicyclic structure, and the maleic anhydride, or the method of reacting the diamine (b-1) derived from the dimer acid, the organic diamine (b-3), the tetracarboxylic dianhydride (b-2) having an alicyclic structure, and the maleic anhydride, is not particularly limited, and any publicly known method can be used as appropriate.
• the diamine (b-1) derived from the dimer acid, the tetracarboxylic dianhydride (b-2), and, if necessary, the organic diamine (b-3) are stirred in a solvent such as toluene, xylene, tetralin, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, or a mixture thereof at room temperature (about 23°C) for 30 to 60 minutes to synthesize a polyamic acid, and then maleic anhydride is added to the obtained polyamic acid and stirred at room temperature (about 23°C) for 30 to 60 minutes to synthesize a polyamic acid having maleic acid added to both ends.
• a solvent such as toluene, xylene, tetralin, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, or a mixture thereof
• a catalyst such as pyridine or methanesulfonic acid may be further added.
• the mixing ratio of the raw materials in the reaction is 1:1, i.e., (total number of moles of all diamines contained in diamine (b-1) derived from dimer acid and organic diamine (b-3)): (total number of moles of tetracarboxylic dianhydride (b-2) having an alicyclic structure + 1/2 the number of moles of maleic anhydride).
• the flexibility derived from the dimer acid is expressed, and from the viewpoint that a cured product having a lower elastic modulus tends to be obtained, it is preferable that (number of moles of organic diamine (b-3))/(number of moles of all diamines contained in diamine (b-1) derived from dimer acid) is 1 or less, and more preferably 0.4 or less.
• the polymerization form of the amic acid unit consisting of the diamine (b-1) derived from a dimer acid and the tetracarboxylic dianhydride (b-2) having an alicyclic structure may be random polymerization or block polymerization.
• the maleimide compound (B) thus obtained is preferably a maleimide compound (B) represented by the following formula (2).
• R 7 represents a divalent hydrocarbon group (b) derived from a dimer acid
• R 8 represents a divalent organic group (c) other than the divalent hydrocarbon group (b) derived from a dimer acid
• R 9 represents any one selected from the group consisting of the divalent hydrocarbon group (b) derived from a dimer acid and the divalent organic group (c) other than the divalent hydrocarbon group (b) derived from a dimer acid
• R 9 and R 10 each independently represent one or more organic groups selected from a tetravalent organic group having a monocyclic or condensed polycyclic alicyclic structure and having 4 to 40 carbon atoms (preferably having 6 to 40 carbon atoms), a tetravalent organic group having 8 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are linked to each other directly or via a crosslinked structure, and a tetravalent organic group having 8 to 40 carbon atoms and a semi-alicyclic structure having both
• the divalent hydrocarbon group (b) derived from the dimer acid in the formula (28) is as described above.
• the divalent organic group (c) other than the divalent hydrocarbon group (b) derived from the dimer acid in the formula (2) refers to a divalent residue obtained by removing two amino groups from the organic diamine (b-3).
• the divalent hydrocarbon group (b) derived from the dimer acid and the divalent organic group (c) are not the same.
• the tetravalent organic group in the formula (2) refers to a tetravalent residue obtained by removing two groups represented by -CO-O-CO- from the tetracarboxylic dianhydride.
• m is the number of repeating units (hereinafter sometimes referred to as dimer acid-derived structures) containing a divalent hydrocarbon group (b) derived from the dimer acid, and represents an integer of 0 to 30. If the value of m exceeds the upper limit, the solubility in solvents decreases, and in particular the solubility in the developing solution during development described below tends to decrease. Moreover, from the viewpoint of obtaining favorable solubility in the developing solution during development, it is particularly preferable that the value of m is 0 to 10.
• n is the number of repeating units (hereinafter sometimes referred to as an organic diamine-derived structure) containing the divalent organic group (c) and represents an integer of 0 to 30. If the value of n exceeds the upper limit, the flexibility of the obtained cured product tends to deteriorate, resulting in a hard and brittle resin. In addition, it is particularly preferable that the value of n is 0 to 10, from the viewpoint that a cured product with a low elastic modulus tends to be obtained.
• the dimer acid derived structure and the organic diamine derived structure may be random or block.
• the n and m can be expressed by the mixed molar ratio of all diamines contained in the diamine (b-1) derived from the dimer acid, the organic diamine (b-3), the maleic anhydride and the tetracarboxylic dianhydride (b-2).
• (m+n):(m+n+2) is represented by (total number of moles of all diamines contained in diamine (b-1) derived from dimer acid and organic diamine (b-3)):(total number of moles of maleic anhydride and tetracarboxylic dianhydride (b-2))
• m:n is represented by (number of moles of all diamines contained in diamine (b-1) derived from dimer acid):(number of moles of organic diamine (b-3)
• 2:(m+n) is represented by (number of moles of maleic anhydride):(number of moles of tetracarboxylic dianhydride (b-2)).
• the sum of m and n in formula (28) (m+n) is preferably 2 to 30, from the viewpoint of tending to obtain a cured product with a lower elastic modulus.
• the ratio of m to n (n/m) is preferably 1 or less, and more preferably 0.4 or less, from the viewpoint of tending to obtain a cured product with a lower elastic modulus by expressing flexibility derived from the dimer acid.
• the maleimide compound (B) may be used alone or in combination of two or more.
• the content of the maleimide compound (B) is preferably 3% by weight or more and less than 60% by weight, more preferably 5% by weight or more and less than 50% by weight, and even more preferably 10% by weight or more and less than 40% by weight, of the total amount of the curable resin composition.
• the content of the bismaleimide compound (A) is desirably greater than that of the maleimide compound (B). When it is in the above range, the physical properties of the cured product tend to be good in heat resistance while maintaining good photocurability. Note that the total amount of the curable resin composition does not include the amount of solvent.
• the bismaleimide compound (A) and the maleimide compound (B) are characterized by their excellent compatibility.
• “compatible” means that when a curable resin composition is formed by uniformly mixing two or more resins, the haze of the solution is less than 50 in the case of a liquid, and when a cured product is formed, the glass transition temperature (Tg) of the curable resin composition is measured at only one point.
• Tg glass transition temperature
• the photopolymerization initiator (C) is not particularly limited, and a conventionally used one can be appropriately adopted.
• a photopolymerization initiator (C) 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 inventors infer 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 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 the bismaleimide compound (A) and the maleimide compound (B), as well as in other resins and compounds such as the photopolymerization initiator (C) and the compound (D) containing one or more carboxyl groups, and because they are easy to prepare varnishes 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), the compound (D) containing one or more carboxy groups, and, if necessary, a 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 filler is preferably insulating and does not inhibit the transparency to 405 nm wavelength (h-rays).
• the filler is not particularly limited, but examples thereof include silica (e.g., natural silica, fused silica, amorphous silica, hollow silica, etc.), aluminum compounds (e.g., boehmite, aluminum hydroxide, alumina, aluminum nitride, etc.), boron compounds (e.g., boron nitride, etc.), magnesium compounds (e.g., magnesium oxide, magnesium hydroxide, etc.), calcium compounds (e.g., calcium carbonate, etc.), molybdenum compounds (e.g., molybdenum oxide, zinc molybdate, etc.), barium compounds (e.g., barium sulfate, barium silicate, etc.), talc (e.g., natural talc, calcined talc, etc.), mica, glass (e.g.,
• silica boehmite, barium sulfate, silicone powder, fluororesin-based fillers, urethane resin-based fillers, (meth)acrylic resin-based fillers, polyethylene-based fillers, styrene-butadiene rubber, and silicone rubber.
• these fillers may be surface-treated with a silane coupling agent or the like, which will be described later.
• Silica is preferred, and fused silica is more preferred, from the viewpoint of improving the heat resistance of the cured product obtained by curing the resin composition of the present invention and obtaining good coating properties.
• Specific examples of silica include SFP-130MC manufactured by Denka Co., Ltd., and SC2050-MB, SC1050-MLE, YA010C-MFN, and YA050C-MJA manufactured by Admatechs Co., Ltd.
• the particle size of the filler is not particularly limited, but is usually 0.005 to 100 ⁇ m, and preferably 0.01 to 50 ⁇ m.
• the amount of the filler is not particularly limited, but from the viewpoint of improving the heat resistance of the cured product, it is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, and most preferably 300 parts by mass or less, per 100 parts by mass of the resin solids in the resin composition.
• the lower limit is not particularly limited, but from the viewpoint of obtaining the effect of improving various properties such as coating properties and heat resistance, it is usually 1 part by mass per 100 parts by mass of the resin solids in the resin composition.
• 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 resin sheet has a protective film
• 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 for 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 with an air pressure of 20 mmHg or less.
• the lamination process may be a batch process or a continuous process using rolls.
• the vacuum lamination method can be carried out using a commercially available vacuum laminator.
• An example of a commercially available vacuum laminator is the 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 for direct irradiation.
• 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 dose is approximately 10 to 1000 mJ/cm2.
• 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-line).
• an active energy ray having a wavelength of, for example, 365 nm (i-line) is used, the dose is approximately 10 to 10,000 mJ/cm2.
• 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-bake step is performed to form an insulating layer (cured product).
• the post-bake 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 formed from the resin composition can be used in electronic components such as semiconductor devices and multilayer wiring boards, and organic EL display devices. Specifically, it is suitably used for applications such as a passivation film for semiconductors, a surface protection film for semiconductor elements, an interlayer insulating film, an insulating film for a rewiring layer, an interlayer insulating film for multilayer wiring for high-density mounting, an interlayer insulating film for electronic components such as an inductor or a SAW filter, and an insulating film or flat layer for an organic electroluminescent device, but is not limited thereto, and can have various structures.
• the resin composition can also be used in the form of a dry film resist. That is, the resin composition 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 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 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 2 (A-2) 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 268 g toluene and 268 g N-methylpyrrolidone.
• 49.0 g (0.29 mol) isophorone diamine was added, followed by the slow addition of 42.6 g (0.44 mol) methanesulfonic acid to form the salt.
• 48.3 g (0.22 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 15.6 g (0.16 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 10 and Comparative Examples 1 to 6 The photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6 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 photosensitive resin composition obtained in each Example and Comparative Example was applied to a rolled copper foil (BHY-82F-HA-V2 (trade name), manufactured by JX Metals Corporation) having a thickness of 18 ⁇ m using an applicator, and then dried at a temperature of 80 ° C. for 30 minutes to form a film-like photosensitive resin composition on the copper foil.
• the coating thickness of the photosensitive resin composition was adjusted so that the film-like photosensitive resin composition after drying had a thickness of 20 ⁇ m.
• This film-like photosensitive resin composition was exposed to light at an exposure dose of 3000 mJ / cm 2 using a light source (Ultra-high pressure mercury lamp 500 W Multilight (trade name) manufactured by USHIO Corporation) capable of irradiating active energy rays including a wavelength of 405 nm (h-line), and then heated at a temperature of 250 ° C. for 60 minutes in a nitrogen atmosphere to cure, and the copper foil was removed by etching to obtain a cured film. Those that obtained a cured film were rated as having a good curability, and those that were impossible to remove the film in the etching process and difficult to obtain the physical properties of the cured film were rated as having a bad film-forming property.
• a light source Ultra-high pressure mercury lamp 500 W Multilight (trade name) manufactured by USHIO Corporation
• Glass transition temperature (Tg) evaluation The dynamic viscoelasticity of the cured bismaleimide product prepared as above was measured using a dynamic viscoelasticity measuring apparatus (DMA) (RSA-G2 manufactured by TA Instruments) (frequency 1 Hz, tensile mode, heating rate 5°C/min), and the glass transition temperature was determined from the maximum value of loss tangent (tan ⁇ ). Furthermore, the tan ⁇ peak waveform was examined from the viewpoint of compatibility, and the number of peaks was counted. The results are shown in Table 1.
• DMA dynamic viscoelasticity measuring apparatus
• RSA-G2 manufactured by TA Instruments
• Thermal decomposition resistance The cured film prepared as above was cut into 4 mm squares, 1.0 to 5.0 mg was weighed out and placed in a measuring pan, and the 5% weight loss rate (Td5) was measured under the conditions of an air flow rate of 100 mL/sec and a temperature rise rate of 10° C./min.
• the measuring device used was a TGA/DSC1 (manufactured by METTLER TOLEDO).
• the use of the photosensitive resin composition of the present invention provides good compatibility and photocurability, and has enabled the improvement of the heat resistance of flexible maleimide compounds, or the improvement of the photocurability of aromatic maleimide compounds.
• the present invention makes it possible to prepare a photocured film by light, and makes it possible to take advantage of both the flexibility and high photocurability of the flexible maleimide and the heat resistance of the aromatic maleimide. 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
  • 2023-03-30 JP JP2024551207A patent/JPWO2024079925A1/ja active Pending
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