WO2020166212A1 - 硬化性樹脂組成物、硬化物、酸変性マレイミド樹脂および硬化剤 - Google Patents
硬化性樹脂組成物、硬化物、酸変性マレイミド樹脂および硬化剤 Download PDFInfo
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- WO2020166212A1 WO2020166212A1 PCT/JP2019/050507 JP2019050507W WO2020166212A1 WO 2020166212 A1 WO2020166212 A1 WO 2020166212A1 JP 2019050507 W JP2019050507 W JP 2019050507W WO 2020166212 A1 WO2020166212 A1 WO 2020166212A1
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- 0 C*(C(C)(C)C1C(*C(O)=O)C=CC(C)C11)C1=C Chemical compound C*(C(C)(C)C1C(*C(O)=O)C=CC(C)C11)C1=C 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4042—Imines; Imides
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
Definitions
- the present invention relates to an acid-modified maleimide resin, a curing agent, a curable resin composition containing the curing agent, in particular, a curable resin composition for forming a solder resist used for a printed wiring board, and a dry method using the same.
- the present invention relates to a film and a printed wiring board.
- the curable resin composition for resin insulating layers such as solder resists has improved performance and improved workability in response to the higher density of printed wiring boards that accompany lighter, thinner, shorter, and smaller electronic devices. Is required.
- electric control of automobiles, especially the drive section is progressing, and printed wiring boards are often mounted in places where the ambient temperature is high, such as the engine room and its surroundings. Automotive printed wiring boards are exposed to high temperatures of 80°C to 150°C for a long time depending on the mounting location, so they are excellent for high-performance solder resists used in in-vehicle printed wiring boards. Heat resistance is required.
- a material suitable for such a solder resist is a bismaleimide compound.
- Bismaleimide compound is a resin having excellent heat resistance, flame retardancy, dielectric properties, etc., but a known bismaleimide compound that does not show curing reactivity with an epoxy resin, when used in combination with a curable resin of epoxy curing type, There was a problem of insufficient heat resistance. Therefore, an amine-modified bismaleimide compound obtained by reacting an amino group of a monoamine compound such as aminophenol with an unsaturated N-substituted maleimide group of a bismaleimide compound may be used in combination with a curable resin of epoxy curing type. It has been proposed (for example, see Patent Document 1). However, since the compound has insufficient alkali developability, it is insufficient as a solder resist material, particularly as a solder resist material required for a recent printed wiring board having a miniaturized circuit.
- the problem to be solved by the present invention is to provide an acid-modified maleimide resin capable of obtaining a cured product having excellent alkali developability and heat resistance, a curable resin composition containing the resin, and a solder resist forming composition.
- Another object of the present invention is to provide a dry film and a printed wiring board using the curable resin composition.
- an acid-modified maleimide resin obtained by adding a fatty acid having a conjugated diene to an N-substituted maleimide group in a maleimide resin using a Diels-Alder reaction is used as a curing agent.
- a cured product having excellent heat resistance and good alkali developability was obtained, and the above problems were solved.
- the present invention provides an acid-modified maleimide resin (A) containing a structure (1) obtained by adding a fatty acid having a conjugated diene or its derivative (a1) to an N-substituted maleimide group, and a curable resin (B).
- A acid-modified maleimide resin
- B curable resin
- the present invention provides a curable resin composition containing the same, an application thereof, a cured product, and an acid-modified maleimide resin having a specific structure which can be suitably used as a curing agent.
- an acid-modified maleimide resin capable of obtaining a cured product having excellent heat resistance and alkali developability, a curable resin composition containing the compound, a solder resist forming composition, and the curable resin described above.
- a dry film and a printed wiring board using the composition can be provided.
- FIG. 3 is an FT-IR chart of the acid-modified maleimide resin obtained in Example 1 of the present invention. It is a GPC chart figure of the acid-modified maleimide resin obtained in Example 1 of this invention.
- the curable resin composition of the present invention comprises an acid-modified maleimide resin (A) containing a structure (1) formed by adding a fatty acid having a conjugated diene or its derivative (a1) to an N-substituted maleimide group, and a curable resin. It is characterized in that it contains a resin (B).
- the N-substituted maleimide group represents a so-called unsaturated N-substituted maleimide group of maleimide, that is, maleimide is preferably used as a raw material.
- maleimide examples include a bismaleimide compound having two maleimide groups in one molecule and a maleimide resin having three or more maleimide groups in one molecule.
- any compound can be used as long as it is a compound having at least two unsaturated N-substituted maleimide groups in its molecular structure, for example, the following formula (a1)
- R 1 is a divalent organic group having an aromatic ring or an aliphatic hydrocarbon
- the bismaleimide compound represented by can be illustrated as a preferable example.
- the R 1 is more preferably a divalent organic group having an aromatic ring from the viewpoint that the obtained cured product is more excellent in heat resistance.
- the divalent organic group having an aromatic ring or an aliphatic hydrocarbon represented by R 1 is an alkylene group, a cycloalkylene group, a monocyclic or polycyclic arylene group, or an atomic group in which these groups are divalent.
- a divalent group bonded by an alkylene group, a cycloalkylene group, an oxygen atom, a sulfur atom, a sulfone group, a sulfinyl group, a disulfide group, a carbonyl group, etc. is mentioned as a preferable structure.
- bismaleimide compound examples include N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'- [1,3-(2-methylphenylene)]bismaleimide, N,N′-[1,3-(4-methylphenylene)]bismaleimide, N,N′-(1,4-phenylene)bismaleimide, Bis(4-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bis(4-maleimidophenyl)ether , Bis(4-maleimidophenyl)sulfone, bis(4-maleimidophenyl)sulfide, bis(4-maleimidophenyl)ketone, bis(4-maleimidocyclohe
- bis(4-maleimidophenyl)methane bis(4-maleimidophenyl)sulfone, bis(4-maleimidophenyl)sulfide, bis(4-maleimidophenyl) ) Disulfide, N,N'-(1,3-phenylene)bismaleimide, and 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane are preferable, and bis(4-maleimidophenyl) is inexpensive.
- Methane and N,N'-(1,3-phenylene)bismaleimide are more preferable, and bis(4-maleimidophenyl)methane is particularly preferable from the viewpoint of solubility in a solvent.
- maleimide resin having three or more N-substituted maleimide groups in one molecule include those represented by any of the following structural formulas (a2) to (a4).
- R2 is independently a polymerizable unsaturated bond-containing group, an alkyl group, an alkoxy group, a halogen atom, an aryl group or an aralkyl group.
- R3 is a hydrogen atom, an alkyl group, a halogenated alkyl group, Any of halogen atoms, p is an integer of 0 or 1 to 4, q is an integer of 0 or 1 to 3.
- V is an alkylene group having 1 to 4 carbon atoms, an arylmethylene group, an alkylenearylenealkylene group.
- the resin represented by the structural formula (a2) from the viewpoint of easy control of the reaction when carrying out acid modification and from the viewpoint of being superior in heat resistance of the obtained cured product, and particularly It is more preferable to use a resin in which V is an alkylene group having 1 to 4 carbon atoms and p and q are 0.
- BMI series manufactured by Daiwa Kasei Co., Ltd. BMI-1000, 2000, 2300, 3000, 4000, 6000, 7000, 8000, TMH, etc.
- BMI, BMI-70, BMI-80 and the like manufactured by KI Kasei Co., Ltd. B1109, B4807, P0778, P0976 and the like manufactured by Tokyo Kasei Kogyo Co., Ltd.
- the fatty acid having a conjugated diene or a derivative thereof (a1) used in the present invention has a conjugated diene capable of a Diels-Alder reaction with the N-substituted maleimide group, and has a carboxy group or a derivative thereof.
- a conjugated diene capable of a Diels-Alder reaction with the N-substituted maleimide group
- carboxy group or a derivative thereof There is no particular limitation as long as it is a compound.
- Derivatives are those in which the carboxy group has a salt structure or a halide, which do not inhibit the Diels-Alder reaction, and which should be converted to the carboxy group after the addition reaction. Is possible. From the viewpoint of easy control of the reaction, it is preferable to use a fatty acid as a raw material.
- Examples of the fatty acid having the conjugated diene include sorbic acid, 2,4-decadienoic acid, 2,4-dodecadienoic acid, 10,12-octadecadienoic acid, 9-hydroxy-10,12-octadecadienoic acid, 13-hydroxy-9,11-octadecadienoic acid, 9,14-dihydroxy-10,12-octadecadienoic acid, 9,12,14-octadecatrienoic acid, 8,10,12-octadecatrienoic acid,
- Examples thereof include conjugated diene fatty acids obtained by selectively hydrogenating eleostearic acid and the like, or fatty acids having various alkyl groups, and may be used alone or in combination of two or more kinds.
- the Diels-Alder reaction is a known reaction and is not particularly limited in the present invention.
- the reaction temperature may be 20 to 150° C. and the reaction time may be 1 to 80 hours.
- an organic solvent can be used.
- the organic solvent that can be used include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as tetrahydrofuran.
- Solvents aromatic solvents such as toluene, xylene, mesitylene; S atom-containing solvents such as dimethyl sulfoxide; N atom-containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene Ethylene glycol dialkyl ethers such as glycol dibutyl ether; polyethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether; ethylene glycol monomethyl ether Ethylene glycol monoalkyl ether acetates such as acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate; diethylene glycol monomethyl
- organic solvents may be used alone or in combination of two or more.
- a solvent containing no alcoholic hydroxyl group is preferable from the viewpoint of suppressing side reactions.
- a ketone solvent such as cyclohexanone or methyl ethyl ketone, or an ester solvent is preferable.
- the amount of the organic solvent used is not particularly limited, but is usually 0.5 to 100 parts by mass based on 100 parts by mass of the total amount of the maleimide as a raw material and the fatty acid having a conjugated diene or its derivative (a1). %, preferably 0.5 to 70 parts by mass, more preferably 0.5 to 50 parts by mass.
- the acid-modified maleimide resin (A) of the present invention is obtained by the above-mentioned addition reaction and has the following structural formula (1) in the molecule.
- R is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms
- X is a direct bond or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms.
- R is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms
- X is a direct bond or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms.
- R 1 is a divalent organic group having an aromatic ring or an aliphatic hydrocarbon
- R is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms
- X is directly It is a bond or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms.
- R is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms
- X is a direct bond or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms
- s is an integer of 0 to 10
- t is an integer of 0 to 10
- s+t is 2 or more.
- the repeating structure may be random or block, and when s is 1 or more, it may be a structure in which the terminal is not acid-modified.
- the resin is Among these, the cured product obtained is a resin in which the addition ratio of the fatty acid having a conjugated diene or its derivative (a1) is 0.02 to 1 mol per mol of the N-substituted maleimide group. It is preferable from the viewpoint of heat resistance.
- the acid-modified maleimide resin (A) of the present invention thus obtained usually shows a colorless to brown solid resinous state or liquid state, and in some cases crystallizes.
- the hue of the acid-modified maleimide resin according to the present invention is poor, the hue may be improved by hydrogenating it in the presence of a hydrogenation catalyst.
- the hydrogenation catalyst used at that time is preferably one containing an iron group element such as nickel or a platinum group element such as palladium, rhodium or platinum as an active component, and more preferably a form in which the active component is held on a carrier. ..
- the carboxy group equivalent of the acid-modified maleimide resin in the present invention is not particularly limited, but when used as a curing agent described later, it is 200 to 10000 [g/eq] from the viewpoint of heat resistance of the obtained cured product. It is preferably in the range, and more preferably in the range of 350 to 2000 [g/eq] from the viewpoint of the alkali developability of the composition.
- the molecular weight of the acid-modified maleimide resin in the present invention is not particularly limited, but when used as a curing agent described later, from the viewpoint of shortening the molding time of the cured product and imparting an arbitrary shape.
- the weight average molecular weight is preferably 300 to 10,000, and more preferably 330 to 5,000. This weight average molecular weight is a polystyrene conversion value measured by the method described in the examples.
- the acid-modified maleimide resin can be used as a curing agent for a curable resin, and can be used, for example, with the following components.
- the curable resin (B) used in the present invention is not particularly limited as long as it is a resin curable by heating or active energy rays, and examples thereof include epoxy resins, melamine resins, benzoguanamine resins, and melamine. Derivatives, amino resins such as benzoguanamine derivatives, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional oxetane compounds, episulfide resins, bismaleimide, carbodiimide resins, known curable resins such as cyanate resins can be exemplified as preferable ones, Of these, epoxy resins are preferred.
- examples of the epoxy resin include novolac type epoxy resin, bisphenol A type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, and phenol aralkyl type epoxy resin.
- bisphenol A bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3',5,5'-tetramethyl-[ 1,1'-biphenyl]-4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde
- the composition ratio of the acid-modified maleimide resin (A) and the curable resin (B) is not particularly limited, but an epoxy resin having excellent heat resistance and moist heat resistance is used.
- the epoxy group of the curable resin (B) is preferably in the range of 1.0 to 2.0 equivalents relative to 1 equivalent of the carboxyl group of the acid-modified maleimide resin (A), and further alkali development is performed. From the viewpoint of sex, the range of 1.0 to 1.5 equivalents is more preferable.
- a known photopolymerization initiator (C) can be appropriately added to the curable resin composition of the present invention as needed.
- the photopolymerization initiator include an oxime ester photopolymerization initiator having an oxime ester group, an alkylphenone photopolymerization initiator, an ⁇ -aminoacetophenone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, and a titanocene photopolymerization initiator.
- One or more photopolymerization initiators selected from the group consisting of polymerization initiators can be preferably used.
- the compounding amount is excellent in photocurability and resolution, adhesiveness and PCT resistance are improved, and further chemical resistance such as electroless gold plating resistance is improved. Also, from the viewpoint that an excellent solder resist can be obtained, it is preferably 0.01 to 5% by mass, and more preferably 0.25 to 3% by mass of the entire composition.
- the compounding amount is preferably 0.2 to 30% by mass, and more preferably 2 to 20% by mass of the entire composition.
- the compounding amount thereof is preferably 0.1 to 25% by mass of the entire composition from the same point of view. It is more preferably 20% by mass.
- Irgacure 389 manufactured by BASF Japan can be preferably used as a photopolymerization initiator.
- the suitable amount of Irgacure 389 is 0.1 to 20% by mass, and more preferably 1 to 15% by mass, based on the entire composition.
- titanocene-based photopolymerization initiator such as Irgacure 784 can also be preferably used.
- the titanocene-based photopolymerization initiator is preferably added in an amount of 0.01 to 5% by mass, and more preferably 0.01 to 3% by mass, based on the entire composition.
- the photocurability and resolution are excellent, the adhesion and PCT resistance are improved, and the chemical resistance such as electroless gold plating resistance is also excellent. It can be a solder resist.
- a photoinitiator aid and a sensitizer can be used if necessary.
- the photoinitiator aid and sensitizer that can be preferably used in the curable resin composition include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. Can be mentioned.
- photoinitiator aids and sensitizers can be used alone or as a mixture of two or more kinds.
- the total amount of such photoinitiator aid and sensitizer is preferably 30 mass% or less of the total composition. If it exceeds 30 mass %, the deep-part curability tends to decrease due to the absorption of light.
- the diluent (D) can be appropriately added to the curable resin composition, if necessary.
- the diluent (D) it is preferable to add a compound having an ethylenically unsaturated group in the molecule.
- the compound having an ethylenically unsaturated group in the molecule can be photocured by irradiation with an active energy ray to insolubilize the resin composition of the present invention in an alkaline aqueous solution, or to help insolubilization.
- a conventionally known polyester (meth)acrylate, polyether (meth)acrylate, urethane (meth)acrylate, carbonate (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate can be used, Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; N,N-dimethylacrylamide , Acrylamides such as N-methylolacrylamide, N,N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythrito
- a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, an epoxy acrylate resin obtained by reacting acrylic acid, or a hydroxyl group of the epoxy acrylate resin, a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate.
- a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, an epoxy acrylate resin obtained by reacting acrylic acid, or a hydroxyl group of the epoxy acrylate resin, a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate.
- examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound, and an acid-modified epoxy acrylate resin obtained by similarly reacting an acid anhydride to contain a carboxylic acid group.
- Such an epoxy acrylate resin can improve the photocurability without
- the compounds having an ethylenically unsaturated group in the molecule as described above may be used alone or in combination of two or more.
- a compound having 4 to 6 ethylenically unsaturated groups in one molecule is preferable from the viewpoint of photoreactivity and resolution, and a compound having two ethylenically unsaturated groups in one molecule is used. It is preferable that the cured product has a low coefficient of linear thermal expansion and the occurrence of peeling during PCT is reduced.
- the amount of the diluent used in the curable resin composition of the present invention is such that photocurability is improved, pattern formation is improved by alkali development after irradiation with active energy rays, and solubility in a dilute alkaline aqueous solution is obtained. Is improved and the impact resistance of the coating film tends to be improved, so 2 to 50 mass% of the total composition is preferable.
- a hardening accelerator can be added to the curable resin composition of the present invention as needed.
- the curing accelerator include imidazoles such as 2-ethyl-4-methylimidazole and 1-methylimidazole, tertiary amines such as benzyldimethylamine and N,N-dimethylaniline, tetramethylammonium chloride and benzyltriethylammonium chloride.
- the compounding amount is preferably 0.01 to 8% by mass, more preferably 0.1 to 5% by mass.
- the amount of the curing accelerator is 0.01% by mass or more, a sufficient effect can be obtained, which is preferable.
- the compounding amount of the curing accelerator is 8% by mass or less, transparency and heat resistance of the obtained cured product can be maintained, which is preferable.
- An inorganic filler may be appropriately added to the curable resin composition of the present invention as needed.
- the inorganic filler is used for suppressing the curing shrinkage of the cured product of the curable resin composition and improving the properties such as adhesion and hardness.
- the inorganic filler for example, barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, nitriding Silicon, aluminum nitride, etc. can be mentioned.
- the average particle size of the inorganic filler is preferably 5 ⁇ m or less.
- the blending ratio is preferably 75% by mass or less of the total composition, and more preferably 0.1 to 60% by mass. When the blending ratio of the inorganic filler exceeds 75% by mass, the viscosity of the composition becomes high, the coatability may be lowered, and the cured product of the curable resin composition may become brittle.
- the curable resin composition of the present invention further, as an optional component, an organic solvent, an elastomer, a mercapto compound, a colorant, an antioxidant, an ultraviolet absorber, an adhesion promoter, a polymerization inhibitor, fine silica, organic bentonite, At least one of thickeners such as montmorillonite, silicone-based, fluorine-based, polymer-based defoaming agents and leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, rust preventives, Known additives such as flame retardants such as phosphinic acid salts, phosphoric acid ester derivatives, phosphorus compounds such as phosphazene compounds, and block copolymers may be added.
- an organic solvent can be used for the preparation of the above resin composition or for the adjustment of the viscosity for coating on the base material or the carrier film.
- the organic solvent for adjusting the viscosity for preparing such a resin composition or for applying it to a substrate or a carrier film include ketones, aromatic hydrocarbons, glycol ethers and glycol ether acetates. Examples thereof include esters, esters, alcohols, aliphatic hydrocarbons, petroleum-based solvents and the like.
- ketones such as methyl ethyl ketone and cyclohexanone
- aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene
- cellosolve methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol.
- Glycol ethers such as monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether Esters such as acetate and propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. A petroleum solvent etc. can be mentioned. One kind of such organic solvent may be used alone, or two or more kinds thereof may be used as a mixture.
- the dry film of the present invention has a curable resin layer formed by applying and drying the curable resin composition of the present invention.
- the dry film of the present invention can be used by laminating the curable resin layer so as to be in contact with the substrate.
- a curable resin composition is uniformly applied to a carrier film by an appropriate method such as a blade coater, a lip coater, a comma coater, or a film coater, and dried to form the curable resin layer described above.
- a cover film thereon.
- the cover film and the carrier film may be the same film material or different films.
- the film material for the carrier film and the cover film any of those known as those used for dry films can be used.
- thermoplastic film such as a polyester film such as polyethylene terephthalate having a thickness of 2 to 150 ⁇ m is used.
- cover film polyethylene film, polypropylene film or the like can be used, but it is preferable that the adhesive force with the curable resin layer is smaller than that of the carrier film.
- the thickness of the curable resin layer on the carrier film of the present invention is preferably 100 ⁇ m or less, more preferably 5 to 50 ⁇ m.
- the printed wiring board of the present invention is preferably produced using the curable resin layer of the present invention which constitutes the dry film of the present invention.
- a resin insulating layer by laminating a dry film including a curable resin layer and heating it to a temperature of, for example, about 140 to 180° C. to thermally cure it.
- a curable resin composition is directly applied to a substrate and dried to form a resin insulating layer by an appropriate method such as a blade coater, a lip coater, a comma coater, or a film coater.
- an appropriate method such as a blade coater, a lip coater, a comma coater, or a film coater.
- the resin insulating layer of the printed wiring board of the present invention can be patterned by irradiating a semiconductor laser such as a CO 2 laser or a UV-YAG laser. Moreover, a hole can be formed by a CO 2 laser, a UV-YAG laser, or a drill.
- a semiconductor laser such as a CO 2 laser or a UV-YAG laser.
- a hole can be formed by a CO 2 laser, a UV-YAG laser, or a drill.
- the resin insulation layer consists of multiple holes, even if the hole is a through hole that allows conduction with any layer of the resin insulation layer (through hole), it is a partial hole (conformal via) for the purpose of conduction between the circuit in the inner layer and the surface of the resin insulation layer. Either) can be opened.
- the residue (smear) existing on the inner wall and bottom of the hole is removed, and in order to develop the anchor effect with the conductor layer (the metal plating layer to be formed later), the surface has fine unevenness.
- a commercially available Desmear solution (roughening agent) or a solution containing an oxidizing agent such as permanganate, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, etc. for the purpose of forming a converted surface.
- a circuit is formed by a subtractive method or a semi-additive method on the hole from which the residue has been removed with a desmear solution or on the surface of the film roughened into fine irregularities.
- heat treatment at about 80 to 180° C. for about 10 to 60 minutes for the purpose of stress removal of metal and strength improvement ( Annealing treatment) may be performed.
- metal plating used here such as copper, tin, solder, nickel, and it is also possible to use a combination of multiple metals. Further, it is also possible to substitute metal sputtering or the like instead of the plating used here.
- the curable resin layer or the dry coating film formed on the substrate (substrate) may be used.
- the film is exposed by a contact type (or non-contact type) through a patterned photomask, selectively by an active energy ray or directly by a laser direct exposure machine.
- the exposed portion is cured.
- a direct drawing device for example, a laser direct imaging device that draws an image directly with a laser from CAD data from a computer
- an exposure device equipped with a metal halide lamp for example, a laser direct imaging device that draws an image directly with a laser from CAD data from a computer
- an exposure device equipped with a metal halide lamp for example, a metal halide lamp
- a (super) high-pressure mercury lamp It is possible to use an exposure machine equipped with an LED, an exposure machine equipped with an LED, and an exposure apparatus equipped with a mercury short arc lamp.
- the active energy ray it is preferable to use light having a maximum wavelength in the range of 350 to 410 nm. By setting the maximum wavelength within this range, radicals can be efficiently generated from the photopolymerization initiator.
- the exposure dose varies depending on the film thickness and the like, but can be generally in the range of 5 to 500 mJ/cm 2 , preferably 10 to 300 mJ/cm 2 .
- the direct drawing device for example, those manufactured by Nippon Orbotech Co., Ltd., Pentax Co., Ltd., Oak Co., Ltd., Dainippon Screen Co., Ltd., etc. can be used, and the maximum energy wavelength is 350 to 410 nm. Any device may be used as long as it is a device for irradiating.
- the unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.
- a dilute alkaline aqueous solution for example 0.
- a pattern is formed on the curable resin layer or the dried coating film.
- the developing method can be a dipping method, a shower method, a spray method, a brush method, or the like.
- an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines or the like can be used as the developing solution.
- the curable resin layer by heating the curable resin layer to a temperature of, for example, about 140 to 180° C. and thermally curing it, the carboxy group of the acid-modified maleimide resin (A) and the curable resin (B) react with each other, resulting in heat resistance. It is possible to form a resin insulating layer (pattern) having excellent characteristics such as chemical resistance, moisture absorption resistance, adhesion, and insulation reliability.
- the total thickness of the resin insulating layer in the printed wiring board of the present invention is preferably 100 ⁇ m or less, more preferably 5 to 50 ⁇ m.
- the resin insulation layer of the printed wiring board of the present invention is suitable as a permanent coating, and is particularly suitable as a solder resist or an interlayer insulation material.
- the laminated structure of the present invention has a base material and a plurality of resin insulating layers formed on the base material, and at least one of the plurality of resin insulating layers is formed from the curable resin composition of the present invention. Any insulating resin layer may be formed.
- the basic structure of the laminated structure of the present invention may be a general one, for example, an insulating resin layer (L1) provided in contact with the base material (S) and a surface layer, that is, an outermost layer. The thing which has a layer is mentioned. Another layer may be provided between the insulating resin layer (L1) and the surface layer.
- the insulating resin layer (L1) and the resin insulating layer (L2) may be alternate layers without providing another layer.
- insulating resin layer (L1)/resin insulating layer (L2)/insulating resin layer (L1)/resin insulating layer (L2) may be used.
- FT-IR measurement conditions Measuring instrument: FT/IR-4100 (JASCO Corporation) Sample preparation conditions: A solution was applied to a KBr plate and dried with warm air to obtain a measurement sample.
- Example 1 A flask equipped with a thermometer, a cooling tube, and a stirrer was charged with 30 parts of a maleimide compound (BMI-2300 manufactured by Daiwa Kasei), 5.7 parts of sorbic acid, and 35.7 parts of cyclohexanone while purging with a nitrogen gas, and at 60° C. Hold for 5 hours. After confirming disappearance of sorbic acid by GPC, it was taken out to obtain an acid-modified maleimide resin (A-1). The obtained resin had a solid content acid value of 77 mgKOH/g and a carboxy group equivalent of 729 g/eq.
- a maleimide compound BMI-2300 manufactured by Daiwa Kasei
- sorbic acid 5.7 parts of sorbic acid
- 35.7 parts of cyclohexanone cyclohexanone
- Example 2 A flask equipped with a thermometer, a cooling tube and a stirrer was charged with 30 parts of a maleimide compound (BMI-1000 manufactured by Daiwa Kasei), 5.7 parts of sorbic acid and 35.7 parts of cyclohexanone while purging with a nitrogen gas, and the mixture was heated at 60° C. Held for hours. After confirming disappearance of sorbic acid by GPC, it was taken out to obtain an acid-modified maleimide resin (A-1). The obtained resin had a solid content acid value of 77 mgKOH/g and a carboxy group equivalent of 729 g/eq.
- a maleimide compound BMI-1000 manufactured by Daiwa Kasei
- Comparative Example 1 In a 2 L reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet, 294.8 parts of ethyl diglycol acetate (hereinafter EDGAc), 196.5 parts of N,N-dimethylacetamide (hereinafter DMAc) and BMI were added. -1000 (manufactured by Daiwa Kasei Co., Ltd., 4,4'-diphenylmethane bismaleimide) (400.0 parts) and p-aminophenol (243.3 parts) were added, and the temperature was raised to 120°C over 150 minutes in a liquid nitrogen flow. ..
- EDGAc ethyl diglycol acetate
- DMAc N,N-dimethylacetamide
- BMI BMI
- Comparative example 2 In a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen inlet, 563 parts by mass of diethylene glycol monoethyl ether acetate (EDGAc), 4,4′-diphenylmethane bismaleimide (Daiwa Chemical Industry Co., Ltd., “BMI-1000”) 400 1 part by mass and 60.9 parts by mass of p-aminophenol were added, the temperature was raised to 120° C. over 150 minutes in a liquid nitrogen flow, and the reaction was carried out for 3 hours to obtain a resin solution (A′-) having a nonvolatile content of 45%. 2) was obtained.
- EDGAc diethylene glycol monoethyl ether acetate
- BMI-1000 4,4′-diphenylmethane bismaleimide
- Tg glass transition temperature
- the curable resin composition blended in the above proportion was applied onto a glass substrate with a 6 MIL applicator, and placed in a hot air dryer at 80°C for 30 minutes, 120°C. The mixture was heated at 30°C for 30 minutes and 200°C for 2 hours. After that, the cured film was isolated from the substrate and used as a test piece. The dynamic viscoelasticity of the measurement sample was measured under the following conditions, and the temperature of the maximum value of Tan ⁇ in the obtained spectrum was taken as the glass transition temperature (Tg). The obtained results are shown in Table 1 as "Tg (°C) of film".
- Alkali developable curable resin composition was coated on a tin plate so that the film thickness after drying was 25 to 35 ⁇ m. Next, this coated plate was dried in a drier at 80° C. for 30 minutes to prepare a test piece. This was immersed in an aqueous 1% potassium carbonate solution at 30° C. for 3 minutes and shaken, washed with tap water, and the residual state of the coating film was visually observed to evaluate the alkali developability. When the coating film was completely dissolved, " ⁇ " was given, and when a part of the coating film remained, it was given "X".
Abstract
Description
で表されるビスマレイミド化合物を好ましいものとして例示することができる。当該R1は、得られる硬化物においてより耐熱性に優れる点から、芳香環を有する二価の有機基であることがより好ましい。
で表される構造を有することが好ましく、特に、この構造を、1分子中に2個以上有するものであることが、得られる硬化物の耐熱性の観点からより好ましいものである。
で表される樹脂であることが好ましい。
で表される樹脂であることが好ましい。これらの中でも、特に共役ジエンを有する脂肪酸又はその誘導体(a1)の付加の割合が、N-置換マレイミド基1モルに対し、0.02~1モルである樹脂であることが、得られる硬化物の耐熱性の観点から好ましいものである。
測定機器:HLC8320GPC(東ソー株式会社製)
検出器:屈折率
溶媒:テトラヒドロフラン(THF)
カラム構成:TSKguardcolumn HxL-L,TSKgel-G4000HxL,G3000HxL,G2000HxL, G1000HxL
温度:40℃
流速:1.0ml/分
測定機器:FT/IR-4100(日本分光株式会社)
サンプル作成条件:KBr板に溶液を塗布し、温風乾燥したものを測定サンプルとした。
温度計、冷却管、撹拌器を取り付けたフラスコに窒素ガスパージを施しながら、マレイミド化合物(大和化成製BMI-2300)30部、ソルビン酸5.7部、シクロヘキサノン35.7部を仕込み、60℃で5時間保持した。GPCにてソルビン酸の消失を確認した後、取り出して酸変性マレイミド樹脂(A-1)を得た。得られた樹脂の固形分酸価は77mgKOH/g、カルボキシ基当量は729g/eqであった。
温度計、冷却管、撹拌器を取り付けたフラスコに窒素ガスパージを施しながら、マレイミド化合物(大和化成製BMI-1000)30部、ソルビン酸5.7部シクロヘキサノン35.7部を仕込み、60℃で5時間保持した。GPCにてソルビン酸の消失を確認した後、取り出して酸変性マレイミド樹脂(A-1)を得た。得られた樹脂の固形分酸価は77mgKOH/g、カルボキシ基当量は729g/eqであった。
温度計、攪拌機、還流冷却器および窒素導入口を備えた2Lの反応容器に、エチルジグリコールアセテート(以下EDGAc)294.8部、N,N-ジメチルアセトアミド(以下DMAc)196.5部、BMI-1000(大和化成工業社製、4,4’-ジフェニルメタンビスマレイミド)400.0部、p-アミノフェノール243.3部を入れ、液中窒素流下にて120℃まで150分間かけて昇温した。この反応容器に、リカシッドTH(新日本理化社製、1,2,3,6-テトラヒドロ無水フタル酸)339.3部を入れ、120℃にて反応を継続した。150℃昇温から4.5時間後、樹脂のFT-IRスペクトルに変化がなくなった事を確認した後、EDGAcを709.7部加え、140℃にて減圧操作を行い、DMAcを留去した。留出が終了した後、EDGAc196.5部を加え冷却し、不揮発分50%のイミド樹脂溶液(A’-1)を得た。
温度計、撹拌機、窒素導入口を備えた反応容器に、ジエチレングリコールモノエチルエーテルアセテート(EDGAc)563質量部、4,4’-ジフェニルメタンビスマレイミド(大和化成工業株式会社、「BMI-1000」)400質量部、p-アミノフェノール60.9質量部を入れ、液中窒素流通下にて120℃まで150分間かけて昇温し、3時間反応を行い、不揮発分45%の樹脂溶液(A’-2)を得た。
表1に示す組成割合で、最終的に不揮発分(N.V)が50質量%となるように、EDGAcを配合して、硬化性樹脂組成物を調製した。
上記の割合で配合した硬化性樹脂組成物を、ガラス基材の上に6MILのアプリケータで塗工し、熱風乾燥機に入れ、80℃30分、120℃30分、200℃2時間加熱した。その後基板から硬化フィルムを単離し、試験片とした。下記条件で、測定用試料の動的粘弾性を測定し、得られたスペクトルのTanδの最大値の温度をガラス転移温度(Tg)とした。得られた結果を表1に「フィルムのTg(℃)」として示した。
測定機器:レオバイブロンRSA-II(レオメトリック社製)
治具:引っ張り
チャック間:20mm
測定温度:25℃~400℃
測定周波数:1Hz
昇温速度:3℃/min
硬化性樹脂組成物を乾燥後の膜厚が25~35μmになるように、ブリキ基板上に塗装した。次いでこの塗装板を80℃の乾燥機で30分乾燥して試験片を作成した。これを、30℃の1%炭酸カリウム水溶液に3分間浸積振とうした後、水道水で洗浄し、塗膜の残存状況を目視観察してアルカリ現像性を評価した。塗膜が全て溶解した場合「○」、一部でも残存した場合「×」とした。
N-680:DIC株式会社、クレゾールノボラック型エポキシ樹脂、エポキシ当量212g/eq
2E4MZ:2-エチル-4-メチルイミダゾール
Claims (18)
- N-置換マレイミド基に共役ジエンを有する脂肪酸又はその誘導体(a1)を付加してなる構造(1)を含有する酸変性マレイミド樹脂(A)と、硬化性樹脂(B)を含むことを特徴とする硬化性樹脂組成物。
- 前記酸変性マレイミド樹脂(A)のカルボキシ基当量が200~10000〔g/eq〕の範囲である請求項1記載の硬化性樹脂組成物。
- 前記酸変性マレイミド樹脂(A)の重量平均分子量が300~10000の範囲である請求項1又は2記載の硬化性樹脂組成物。
- 前記酸変性マレイミド樹脂(A)が、1分子中に少なくとも2個の前記構造(1)を有するものである請求項1~3の何れか1項記載の硬化性樹脂組成物。
- 前記硬化性樹脂(B)がエポキシ樹脂である請求項1~7の何れか1項記載の硬化性樹脂組成物。
- さらに、光重合開始剤(C)を含む請求項1~8の何れか1項記載の硬化性樹脂組成物。
- さらに、希釈剤(D)を含む請求項1~8の何れか1項記載の硬化性樹脂組成物。
- 請求項1~10の何れか1項記載の硬化性樹脂組成物を硬化させてなる硬化物。
- 請求項1~10の何れか1項記載の硬化性樹脂組成物を含むソルダーレジスト形成用硬化性樹脂組成物。
- 請求項1~10の何れか1項記載の硬化性樹脂組成物を含む硬化性樹脂層を有するドライフィルム。
- 請求項1~10の何れか1項記載の硬化性樹脂組成物を含む硬化性樹脂層を熱硬化してなる樹脂絶縁層を有するプリント配線板。
- 基材と、該基材上に形成された複数の樹脂絶縁層とを有する積層構造体であって、前記複数の樹脂絶縁層のうちの少なくとも一層が、請求項1~10のいずれか1項に記載の硬化性樹脂組成物から形成された層であることを特徴とする積層構造体。
- 下記構造式(ii)又は(iii)
で表されることを特徴とする酸変性マレイミド樹脂。 - 前記構造式(iii)で表される酸変性マレイミド樹脂であって、共役ジエンを有する脂肪酸又はその誘導体(a1)の付加の割合が、N-置換マレイミド基1モルに対し、0.02~1モルである請求項16記載の酸変性マレイミド樹脂。
- 請求項16又は17記載の酸変性マレイミド樹脂からなる硬化剤。
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