CN117642697A - Curable resin composition, laminate, cured product, and electronic component - Google Patents

Curable resin composition, laminate, cured product, and electronic component Download PDF

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Publication number
CN117642697A
CN117642697A CN202280048170.XA CN202280048170A CN117642697A CN 117642697 A CN117642697 A CN 117642697A CN 202280048170 A CN202280048170 A CN 202280048170A CN 117642697 A CN117642697 A CN 117642697A
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group
photopolymerization initiator
resin composition
curable resin
mass
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Inventor
工藤知哉
蒋铮
吕川
许红金
浦国斌
加藤贤治
刘洪兵
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Taiyo Ink Suzhou Co Ltd
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Taiyo Ink Suzhou Co Ltd
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Publication of CN117642697A publication Critical patent/CN117642697A/en
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    • 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • 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
    • 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
    • H05K3/287—Photosensitive compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided are a curable resin composition, a laminate, a cured product, and an electronic component, which have both surface curability and suppression of outgassing, and which have properties such as insulation reliability and solder heat resistance. The curable resin composition comprises (A) a carboxyl group-containing resin, (B) an inorganic filler, (C) a thermosetting resin, and (D) a photopolymerization initiator, wherein the (D) photopolymerization initiator comprises (D-a) an acylphosphine photopolymerization initiator and (D-B) a photopolymerization initiator having a specific structure, and the compounding amount of the (D-B) a photopolymerization initiator having a specific structure is 0.1 mass% or more and 10 mass% or less relative to the compounding amount of the (D-a) acylphosphine photopolymerization initiator.

Description

Curable resin composition, laminate, cured product, and electronic component Technical Field
The present invention relates to a curable resin composition, a laminate having the curable resin composition as a resin layer, a cured product formed from the laminate, and an electronic component having the cured product.
Background
In recent years, along with demands for miniaturization and higher performance, semiconductor chips mounted on electronic devices have been increasingly densified and functionalized, and printed circuit boards on which the semiconductor chips are mounted have also been demanded to be miniaturized and densified. As a result, recently, the insulation materials used for printed wiring boards are also required to be finer and higher in performance.
As such an insulating material, a photosensitive resin composition containing a compound having a carboxyl group and not having photosensitivity, an epoxy resin, and an oxime ester photopolymerization initiator, and the like as described in patent document 1 are currently used.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2012-098470
Disclosure of Invention
Problems to be solved by the invention
However, the photosensitive resin composition as in patent document 1 has insufficient surface curability after exposure, and there is a concern that sufficient performance cannot be exhibited due to surface scratches after pattern exposure until the heat curing treatment is performed. Depending on the type of photopolymerization initiator used, the exhaust gas is generated by heat treatment at high temperature, and the surrounding is polluted. Therefore, an insulating material is required which combines both surface curability and suppression of outgassing.
Further, for various characteristics such as insulation reliability and solder heat resistance, an insulating material satisfying a higher level of requirements than the conventional photosensitive resin composition is also required.
The invention provides a curable resin composition or a laminate which can obtain a cured product having both surface curability and exhaust gas suppression and having various characteristics such as insulation reliability and solder heat resistance.
As a result of intensive studies, the inventors have found that all of the above problems can be solved by simultaneously compounding an acylphosphine-based photopolymerization initiator and a photopolymerization initiator having a specific structure represented by the formula (1) as photopolymerization initiators in a cured resin composition, and have completed the present invention.
Namely, the present invention is as follows.
1. A curable resin composition comprising (A) a carboxyl group-containing resin, (B) an inorganic filler, (C) a thermosetting resin, and (D) a photopolymerization initiator,
as the photopolymerization initiator (D), there are included (D-a) an acylphosphine-based photopolymerization initiator and (D-b) a photopolymerization initiator represented by the formula (1),
the amount of the photopolymerization initiator represented by the formula (1) to be blended in the (D-b) is 0.1 mass% or more and 10 mass% or less relative to the amount of the (D-a) acylphosphine photopolymerization initiator to be blended.
Wherein R is 23 Represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group, and a naphthyl group; r is R 21 、R 22 Each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a phenyl group, a naphthyl group, an anthracenyl group, a pyridyl group, a benzofuranyl group, or a benzothienyl group;
ar represents a single bond, or an alkylene group having 1 to 10 carbon atoms, a vinylidene group, a phenylene group, a biphenylene group, a pyridylene group, a naphthylene group, an anthrylene group, a thienylene group, a furanylene group, a 2, 5-pyrrol-diyl group, a 4,4 '-stilbene-diyl group, or a 4,2' -stilbene-diyl group; n represents a number of 0 to 1.
2. The curable resin composition according to claim 1, wherein the amount of the inorganic filler (B) is 35 mass% or more and 55 mass% or less based on the total solid content of the curable resin composition.
3. The curable resin composition according to claim 1, wherein the inorganic filler (B) contains titanium oxide.
4. The curable resin composition according to 1, wherein the (D-a) acylphosphine photopolymerization initiator comprises 3 or more functional acylphosphine photopolymerization initiators.
5. The curable resin composition according to any one of 1 to 4, wherein the carboxyl group-containing resin (A) does not have a phenol skeleton.
6. A laminate comprising the curable resin composition according to any one of 1 to 5 as a resin layer.
7. A cured product obtained by curing the curable resin composition according to any one of 1 to 5 or by curing the resin layer of the laminate according to 6.
8. An electronic component having the cured product of claim 7.
Effects of the invention
The present invention provides a curable resin composition or laminate which can obtain a cured product having both surface curability and exhaust gas suppression and having properties such as insulation reliability and solder heat resistance.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
The present invention relates to a curable resin composition comprising (A) a carboxyl group-containing resin, (B) an inorganic filler, (C) a thermosetting resin, and (D) a photopolymerization initiator,
as the photopolymerization initiator (D), there are included (D-a) an acylphosphine-based photopolymerization initiator and (D-b) a photopolymerization initiator represented by the formula (1),
the amount of the photopolymerization initiator represented by the formula (1) to be compounded is 0.1 to 10 mass% inclusive, based on the amount of the (D-a) acylphosphine photopolymerization initiator to be compounded
Wherein R is 23 Represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group, and a naphthyl group; r is R 21 、R 22 Each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a phenyl group, a naphthyl group, an anthracenyl group, a pyridyl group, a benzofuranyl group, or a benzothienyl group;
ar represents a single bond, or an alkylene group having 1 to 10 carbon atoms, a vinylidene group, a phenylene group, a biphenylene group, a pyridylene group, a naphthylene group, an anthrylene group, a thienylene group, a furanylene group, a 2, 5-pyrrol-diyl group, a 4,4 '-stilbene-diyl group, or a 4,2' -stilbene-diyl group; n represents a number of 0 to 1.
The components of the curable resin composition of the present invention are described in detail below.
(A) Carboxyl group-containing resin
The carboxyl group-containing resin can have alkali developability by the carboxyl group contained therein. As the carboxyl group-containing resin (a), various conventionally known carboxyl group-containing resins having a carboxyl group in a molecule can be used. In view of curability and development resistance, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated bond in addition to a carboxyl group in the molecule is particularly preferable, and only a carboxyl group-containing resin having no ethylenically unsaturated bond may be used.
Specific examples of the carboxyl group-containing resin include the compounds (either oligomers or polymers) listed below. In the present specification, (meth) acrylate refers to a term generically referring to acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions.
(1) Carboxyl group-containing resins obtained by copolymerizing unsaturated carboxylic acids such as (meth) acrylic acid, and unsaturated group-containing compounds such as styrene, α -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
(2) A carboxyl group-containing polyurethane resin obtained by polyaddition reaction of a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, a carboxyl group-containing diol compound such as dimethylolpropionic acid or dimethylolbutyric acid, and a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(3) Polyurethane resins are obtained by polyaddition reaction of a diisocyanate compound such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, or aromatic diisocyanate, and a diol compound such as a polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol a alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, and a carboxyl group-containing polyurethane resin obtained by reacting the terminal of the polyurethane resin with an acid anhydride.
(4) A carboxyl group-containing polyurethane resin obtained by polyaddition reaction of a diisocyanate, a (meth) acrylate or a partial anhydride modification thereof of a 2-functional epoxy resin such as a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a bisxylenol epoxy resin, a bisphenol epoxy resin, a carboxyl group-containing diol compound, and a diol compound.
(5) A carboxyl group-containing urethane resin obtained by adding a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in the molecule, such as hydroxyalkyl (meth) acrylate, to the synthesis of the resin of the above (2) or (4) and subjecting the resultant resin to terminal (meth) acrylation.
(6) A carboxyl group-containing polyurethane resin obtained by adding a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in the molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, to the synthesis of the resin of the above (2) or (4), and subjecting the resultant resin to terminal (meth) acrylation.
(7) A carboxyl group-containing resin obtained by reacting a polyfunctional epoxy resin with (meth) acrylic acid, and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, or the like to a hydroxyl group present in a side chain.
(8) A carboxyl group-containing resin is obtained by reacting a (meth) acrylic acid with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl groups of a 2-functional epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the hydroxyl groups thus formed.
(9) A carboxyl group-containing polyester resin obtained by reacting a dicarboxylic acid with a polyfunctional oxetane resin and adding a dibasic acid anhydride to the primary hydroxyl group formed.
(10) A carboxyl group-containing resin is obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with an alkylene oxide such as ethylene oxide or propylene oxide to obtain a reaction product, reacting the reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the reaction product obtained thereby with a polybasic acid anhydride.
(11) A carboxyl group-containing resin is obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate to obtain a reaction product, reacting the reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the reaction product obtained thereby with a polybasic acid anhydride.
(12) A carboxyl group-containing resin obtained by reacting an epoxy compound having a plurality of epoxy groups in 1 molecule with a compound having at least 1 alcoholic hydroxyl group and 1 phenolic hydroxyl group in 1 molecule such as p-hydroxyphenylethanol, and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, and reacting the alcoholic hydroxyl group of the obtained reaction product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, and the like.
(13) A carboxyl group-containing resin having at least any one of an amide structure and an imide structure.
(14) The carboxyl group-containing resin described in (1) to (13) above, wherein a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in the molecule, such as glycidyl (meth) acrylate, α -methyl glycidyl (meth) acrylate, and 3, 4-epoxycyclohexylmethyl methacrylate, is further added to the carboxyl group-containing resin.
(A) The carboxyl group-containing resin is not particularly limited as long as it is a resin having a carboxyl group in the molecule, and is preferably not provided with a phenol skeleton from the viewpoint of further improvement in insulation reliability and reflectance. When the carboxyl group-containing resin does not contain a phenol skeleton, coloration due to thermal degradation is less likely to occur, and thus the reflectance tends to be improved.
The phenol skeleton means a skeleton derived from an aromatic compound having 1 or more hydroxyl groups directly bonded to an aromatic ring.
The carboxyl group-containing resin preferably contains at least 1 of the carboxyl group-containing resins described in (1), (7), (8), (10), (11) and (14). The carboxyl group-containing resin described in (1) above or (14) obtained by using (1) is particularly preferably contained from the viewpoint of facilitating reduction of chlorine concentration and further improvement of insulation reliability.
(A) The carboxyl group-containing resin may be used alone or in combination of 2 or more.
(A) The acid value of the carboxyl group-containing resin is preferably in the range of 20 to 120mgKOH/g, more preferably in the range of 30 to 100 mgKOH/g. By setting the acid value of the carboxyl group-containing resin (a) to the above range, good alkali development becomes possible, and a good pattern of a cured product can be formed.
(A) The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, and is usually preferably 2000 to 150000. When the weight average molecular weight is 2000 or more, the non-tackiness of the dried coating film, the moisture resistance of the exposed coating film, and the resolution are good. On the other hand, when the weight average molecular weight is 150000 or less, the developability and storage stability are good. More preferably 5000 to 100000.
(A) The amount of the carboxyl group-containing resin to be blended is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 12 to 60% by mass, relative to the total solid content of the curable resin composition.
(B) Inorganic filler
The curable resin composition of the present invention contains (B) an inorganic filler. (B) The inorganic filler may be used alone or in combination of 1 or more than 2.
(B) The blending amount of the inorganic filler is preferably in the range of 20 to 65% by mass, more preferably in the range of 25 to 60% by mass, and particularly preferably in the range of 35 to 55% by mass, relative to the total solid content of the curable resin composition. (B) When the blending amount of the inorganic filler is 35 mass% or more, a curable resin composition excellent in surface curability, reflectance, solder heat resistance, and insulation reliability tends to be obtained. (B) When the blending amount of the inorganic filler is 55 mass% or less, a curable resin composition having more excellent deaeration property and resolution tends to be obtained.
Examples of the inorganic filler (B) include titanium oxide, silica, barium sulfate, barium titanate, noorupo silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, silicon nitride, aluminum nitride, and the like. Among them, it is preferable to contain at least one of titanium oxide, silica, and barium sulfate, so that curing shrinkage of the curable resin composition can be suppressed, and properties such as adhesion, hardness, and reflectance can be improved. Among them, titanium oxide is particularly preferably contained at least from the viewpoint of reflectance.
As the titanium oxide that can be used in the curable resin composition of the present invention, titanium oxide produced by a sulfuric acid method or a chlorine method, rutile titanium oxide, anatase titanium oxide, or titanium oxide subjected to a surface treatment with a hydrated metal oxide or a surface treatment with an organic compound can be used. Titanium oxide is classified into rutile type and anatase type according to crystal structure. Among them, rutile titanium oxide is preferable. Anatase type titanium oxide is generally used because it has a higher whiteness than rutile type. However, anatase titanium oxide has photocatalytic activity, and thus may cause discoloration of the resin in the curable resin composition. On the other hand, rutile titanium oxide has little photoactivity although the whiteness is slightly inferior to that of anatase, and thus a stable cured product can be obtained.
(B) When the inorganic filler contains titanium oxide, the blending amount of titanium oxide is preferably 1% by mass or more and 50% by mass or less, more preferably 1.5% by mass or more and 30% by mass or less, particularly preferably 2% by mass or more and 25% by mass or less, relative to the total solid content of the curable resin composition, from the viewpoint of achieving the effect of improving reflectance by titanium oxide and improving surface curability.
(B) The average particle diameter of the inorganic filler is preferably 50 μm or less, more preferably 0.1 to 25 μm, and particularly preferably 0.2 to 10 μm. The average particle diameter herein means the average particle diameter of the inorganic filler or inorganic filler dispersion alone. In addition, a nanofiller having an average particle diameter of 100nm or less may be used in combination in a part thereof. Here, in the present specification, the average particle diameter of the inorganic filler is a volume average particle diameter (D50) including not only the particle diameter of the primary particles but also the particle diameter of the secondary particles (aggregates). The average particle diameter can be measured according to the average particle diameter using a measuring device based on a laser diffraction method such as Microtrac MT3300EXII manufactured by microtracbl corp. Or a measuring device based on a dynamic light scattering method such as Nanotrac Wave II UT151 manufactured by microtracbl corp. Or the like.
The inorganic filler (B) may be a surface-treated filler (surface-treated filler). (B) The surface treatment of the inorganic filler is not particularly limited, and a known and customary method such as a surface treatment with a coupling agent based on silane-based, titanate-based, aluminate-based, zirconium aluminate-based or the like, a surface treatment with alumina-based or the like, in which no organic group is introduced, may be used.
As the inorganic filler (B), commercially available ones can be used. As a commercial product of titanium oxide, for example, a commercially available rutile type titanium oxide can be used: taipaque R-820, taipaque R-830, taipaque R-930, taipaque R-550, taipaque R-630, taipaque R-680, taipaque R-670, taipaque R-780, taipaque R-850, taipaque CR-50, taipaque CR-57, taipaque CR-Super70, taipaque CR-80, taipaque CR-90, taipaque CR-93, taipaque CR-95, taipaque CR-97, taipaque CR-60, taipaque CR-63, taipaque CR-67, taipaque CR-58, taipaque CR-85, taipaque UT771 (manufactured by Shiformer Co., ltd.); ti-Pure R-100, ti-Pure R-101, ti-Pure R-102, ti-Pure R-103, ti-Pure R-104, ti-Pure R-105, ti-Pure R-108, ti-Pure R-900, ti-Pure R-902, ti-Pure R-960, ti-Pure R-706, ti-Pure R-931 (DuPont Co., ltd.); r-25, R-21, R-32, R-7E, R-5N, R-61N, R-62N, R-42, R-45M, R-44, R-49S, GTR-100, GTR-300, D-918, TCR-29, TCR-52, FTR-700 (manufactured by Kagaku Co., ltd.) and the like.
Among the above, taipaque CR-50, taipaque CR-57, taipaque CR-80, taipaque CR-90, taipaque CR-93, taipaque CR-95, taipaque CR-97, taipaque CR-60, taipaque CR-63, taipaque CR-67, taipaque CR-58, taipaque CR-85, taipaque UT771 (manufactured by Shiraw Co., ltd.) manufactured by chlorine method is preferably used; ti-Pure R-100, ti-Pure R-101, ti-Pure R-102, ti-Pure R-103, ti-Pure R-104, ti-Pure R-105, ti-Pure R-108, ti-Pure R-900, ti-Pure R-902, ti-Pure R-960, ti-Pure R-706, ti-Pure R-931 (DuPont Co., ltd.).
Further, as anatase titanium oxide, a known one can be used. As commercially available anatase titanium oxide, TITON A-110, TITON TCA-123E, TITON A-190, TITON A-197, TITON SA-1L (manufactured by Sasa chemical Co., ltd.); TA-100, TA-200, TA-300, TA-400, TA-500, TP-2 (Fushi titanium industries Co., ltd.); TITANIX JA-1, TITANIX JA-3, TITANIX JA-4, TITANIX JA-5, TITANIX JA-C (manufactured by Teika Co., ltd.); KA-10, KA-15, KA-20, KA-30 (titanium industry Co., ltd.); taipaque A-100, taipaque A-220, taipaque W-10 (manufactured by Shiraku Co., ltd.) and the like.
As commercial products of barium sulfate, there may be mentioned B-30, B-31, B-32, B-33, B-34, B-35T, etc. manufactured by Sakai chemical Co., ltd.
Examples of commercially available silica include Tokuyama Co., ltd. SE-40, lonsen MSV25G, lonsen MLV-2114, ADMATECHS SO-E5, ADMATECHS SO-E2, and the like.
(C) Thermosetting resin
The curable resin composition of the present invention comprises (C) a thermosetting resin. As the thermosetting resin (C), an epoxy resin, a blocked isocyanate compound, an amino resin, a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclic carbonate compound, an oxetane compound, an episulfide resin, a melamine derivative or the like can be used. (C) The thermosetting resin may be used alone or in combination of 1 or more than 2.
The thermosetting resin (C) is preferably an epoxy resin from the viewpoint of obtaining a curable resin composition excellent in surface curability, suppressing the occurrence of outgas, and also excellent in physical properties such as insulation reliability and solder heat resistance of a cured product. As the epoxy resin, for example, a known and customary epoxy resin such as bisphenol a type, bisphenol F type, aminophenol type, and phenol novolac type epoxy resin can be suitably used.
In the curable resin composition of the present invention, these epoxy resins may be used alone or in combination of 2 or more. In addition, a liquid epoxy resin may be used, or a solid epoxy resin may be used.
Examples of the commercial products of the thermosetting resin (C) include bisphenol A type epoxy resins such as joR 828, joR 834, joR 1001, joR 1004, EPICLON840, EPICLON850, EPICLON1050, EPICLON2055, epotote YD-011, YD-013, YD-127, YD-128, and NPEL-128E (all trade names) made by Nan Ya Plastics, made by Mitsubishi chemical Co., ltd; brominated epoxy resins such as jERYL903 manufactured by Mitsubishi chemical corporation, EPICLON152, EPICLON165, and Epotote YDB-400 and YDB-500 (all trade names) manufactured by Nitro chemical & materials corporation; novolak type epoxy resins such as jER152, jER154, epicolin N-730, epicolin N-770, epicolin N-865, epotot YDCN-701, YDCN-704, EPPN-201, EOCN-1025, EOCN-100, EOCN-104S, RE-306 (all trade names) manufactured by mitsubishi chemical corporation, and the like manufactured by japanese chemical & materials, respectively; bisphenol F-type epoxy resins such as EPICLON830 manufactured by DIC, jER807 manufactured by Mitsubishi chemical corporation, epotote YDF-170, YDF-175, YDF-2004 (all trade names) manufactured by Nitrose chemical & materials Co., ltd; hydrogenated bisphenol A type epoxy resins such as epoote ST-2004, ST-2007, ST-3000 (all trade names) manufactured by Nitro Chemie & Material Co., ltd; glycidyl amine type epoxy resins such as jor 604 manufactured by mitsubishi chemical Co., ltd., epotote YH-434 manufactured by Nitro iron chemical & materials Co., ltd., sumitomo epoxy ELM-120 (all trade names) manufactured by Sumitomo chemical Co., ltd.; daicel Chemical Industry alicyclic epoxy resins such as Celoxide2021 (trade name) manufactured by Ltd; trihydroxyphenyl methane type epoxy resins such as YL-933 manufactured by Mitsubishi chemical corporation, EPPN-501 manufactured by Japanese chemical corporation, and EPPN-502 (all trade names); examples of the epoxy resins include a bixylenol type or biphenol type epoxy resin, or a mixture thereof, such as YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Mitsubishi chemical corporation; bisphenol S-type epoxy resins such as EBPS-200 manufactured by Kagaku Co., ltd., EPX-30 manufactured by ADEKA manufactured by DIC Co., ltd., EXA-1514 (all trade names); bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by mitsubishi chemical corporation; tetraphenyl ethane type epoxy resins such as jER YL-931 (trade name) manufactured by mitsubishi chemical Co., ltd; heterocyclic epoxy resins such as TEPIC (trade name) manufactured by japanese chemical corporation; diglycidyl phthalate resins such as Blemmer DGT (trade name) manufactured by Japanese fat & oil Co., ltd; tetraglycidyl xylenol ethane (tetraglycidyl xylenoyl ethane) resins such as ZX-1063 (trade name) manufactured by Nitro iron chemical & materials Co., ltd; naphthalene group-containing epoxy resins such as ESN-190, ESN-360, HP-4032, EXA-4750, EXA-4700 (all trade names) manufactured by Nikka chemical & materials Co., ltd; epoxy resins having dicyclopentadiene skeleton such as HP-7200 and HP-7200H (both trade names) manufactured by DIC Co., ltd; glycidyl methacrylate copolymer epoxy resins such as CP-50S, CP-50M (all trade names) manufactured by Japanese fat and oil Co., ltd; and copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, etc., and these epoxy compounds may be used alone or in combination of 2 or more.
(C) The blending amount of the thermosetting resin is usually 1 to 50% by mass, more preferably 5 to 35% by mass, based on the total solid content of the curable resin composition.
(D) Photopolymerization initiator
The curable resin composition of the present invention comprises (D-a) an acylphosphine photopolymerization initiator and (D-b) a photopolymerization initiator represented by formula (1). By compounding (D-a) an acylphosphine photopolymerization initiator, a curable resin composition having excellent resolution, excellent weld heat resistance of a cured product thereof, and excellent exhaust gas resistance and insulation reliability can be obtained.
Examples of the (D-a) acylphosphine photopolymerization initiator include monoacylphosphine photopolymerization initiators and bisacylphosphine photopolymerization initiators. Specific examples thereof include bis- (2, 6-dichlorobenzoyl) phenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -2, 5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -1-naphtylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) -2, 4-trimethylpentylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) -2, 5-dimethylphenylphosphine oxide, bis- (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2, 6-dimethoxybenzoyl diphenylphosphine oxide, 2, 6-dichlorobenzoyl diphenylphosphine oxide, methyl 2,4, 6-trimethylbenzoyl phenylphosphinate, 2-methylbenzoyl diphenylphosphine oxide, pivaloylphenylphosphine isopropyl 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, and ethyl (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide.
The (D-a) acylphosphine photopolymerization initiator preferably includes a photopolymerization initiator having 3 or more acylphosphine skeletons (3-functional or more acylphosphine photopolymerization initiator) represented by the following formula (2).
In the method, in the process of the invention,
a independently of one another represents a single bond, O, S or NR 3 ；
G is a polyfunctional compound (core) G- (A-H) m+n Wherein a-H each represent an alcoholic hydroxyl group or an amino group or a thiol group;
m and n satisfy the number that m+n is between 3 and 10;
m is a number between 3 and 8;
R 1 r is R 2 Independently of one another C 1 -C 18 Alkyl, C of (2) 6 -C 12 Aryl and C of (2) 5 -C 12 Each of which may be uninterrupted or interrupted by: more than 1 oxygen and/or sulfur atom and/or more than 1 substituted or unsubstituted imino group, or R 1 R is R 2 Can be, independently of one another, a five-to six-membered heterocyclic radical containing oxygen and/or nitrogen and/or sulfur atoms, where R is as defined above 1 R is R 2 Each optionally being aryl, alkyl, aryloxy,Alkoxy, heteroatom and/or heterocyclic group substitution;
R 2 can be R 1 -(C＝O)-；
Y is O or S;
R 3 is hydrogen or C 1 ～C 4 Alkyl of (a);
wherein the photopolymerization initiator of formula (2) does not contain a photocurable ethylenically unsaturated group.
Preferably, in formula (2), m+n is a number between 3 and 8, more preferably a number between 3 and 6. For example, in the formula (2), m is a number between 3 and 6, more preferably a number between 3 and 5.
In the formula (2), when A is oxygen, G- (A-H) m+n Is a polyhydroxy (polyhydroxy) compound selected from the group consisting of monomeric polyols, oligomeric polyols, and polymeric polyols, and mixtures thereof. When A is sulfur, G- (A-H) m+n Is a polythiol compound. In the formula (I), when A is nitrogen, G- (A-H) m+n Is a linear or branched polyamine. When A is oxygen and/or nitrogen and/or sulfur, G- (A-H) m+n Are compounds containing different functional groups, for example compounds containing amino groups and hydroxyl groups. When A is a single bond, G-is G- (A-H) as exemplified above m+n Residues after removal of hydroxyl and/or amino and/or mercapto groups.
Preferred are G- (A-H) m+n Has a number average molecular weight of 1500 or less, more preferably 800 or less, still more preferably 500 or less.
When n is other than 0, the compound of formula (2) has an alcoholic hydroxyl group and/or an amino group and/or a mercapto group.
Representative 3-functional or more acylphosphine-based photopolymerization initiators included in formula (2) are shown in table 1. Among these, PI-3, PI-4, PI-10, PI-11, PI-12, PI-14, and PI-17 are particularly preferable. By including such an acylphosphine-based photopolymerization initiator having 3 or more functions, a cured product having suppressed outgassing and more excellent insulation reliability can be obtained.
Examples of the commercial products include Omnipol TP manufactured by IGM RESINS b.v., and these acylphosphine photopolymerization initiators may be used alone or in combination of 2 or more.
TABLE 1
A, b, c and d in table 1 are each independent numbers, and are appropriately selected so that the number average molecular weight of the 3-functional or higher acylphosphine-based photopolymerization initiator is a desired value.
Such a 3-functional or higher acylphosphine photopolymerization initiator can be produced by the method described in Japanese patent No. 6599446, for example.
The curable resin composition of the present invention further comprises (D-b) the photopolymerization initiator described in formula (1) as the photopolymerization initiator (D). By combining (D-a) an acylphosphine photopolymerization initiator and (D-b) a photopolymerization initiator described in formula (1), a curable resin composition excellent in surface curability, reflectance, solder heat resistance, and insulation reliability can be obtained.
Wherein R is 23 Represents a hydrogen atom, an alkyl group, an alkoxy groupA group, phenyl, naphthyl; r is R 21 、R 22 Each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a phenyl group, a naphthyl group, an anthracenyl group, a pyridyl group, a benzofuranyl group, or a benzothienyl group;
ar represents a single bond, or an alkylene group having 1 to 10 carbon atoms, a vinylidene group, a phenylene group, a biphenylene group, a pyridylene group, a naphthylene group, an anthrylene group, a thienylene group, a furanylene group, a 2, 5-pyrrol-diyl group, a 4,4 '-stilbene-diyl group, or a 4,2' -stilbene-diyl group; n represents a number of 0 to 1.
As R 23 The alkyl group is preferably an alkyl group having 1 to 17 carbon atoms.
As R 23 The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms.
R 23 The phenyl group may have a substituent, and examples of the substituent include: alkyl (preferably having 1 to 17 carbon atoms), alkoxy (preferably having 1 to 8 carbon atoms), amino, alkylamino (preferably having 1 to 8 carbon atoms) or dialkylamino (preferably having 1 to 8 carbon atoms).
R 23 The naphthyl group may have a substituent, and examples of the substituent include: and R is R 23 The phenyl groups shown may have the same substituents as described above.
As R 21 And R is 22 The alkyl group is preferably an alkyl group having 1 to 17 carbon atoms.
As R 21 And R is 22 The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms.
R 21 And R is 22 The phenyl group may have a substituent, and examples of the substituent include: alkyl (preferably having 1 to 17 carbon atoms), alkoxy (preferably having 1 to 8 carbon atoms), amino, alkylamino (preferably having 1 to 8 carbon atoms) or dialkylamino (preferably having 1 to 8 carbon atoms).
R 21 And R is 22 The naphthyl groups shown may have substituentsExamples of the substituent include: and R is R 21 And R is 22 The phenyl groups shown may have the same substituents as described above.
Further, in the formula (1), R is preferable 21 、R 23 Each independently is methyl or ethyl, R 22 Is methyl or phenyl, ar is a single bond, phenylene, naphthylene or thienyl, and n is 0.
As the compound represented by the formula (1), any one of the compounds represented by the following formula (2) or formula (3) is more preferable.
As a commercial product of the photopolymerization initiator described in the formula (1) of (D-b), TOE-04-A3 manufactured by Japanese chemical industry Co., ltd.
The photopolymerization initiator described in formula (1) of (D-b) may be used singly or in combination of 1 or 2 or more.
The amount of the photopolymerization initiator described in the formula (1) of (D-b) is in the range of 0.1 to 10% by mass relative to the amount of the (D-a) acylphosphine photopolymerization initiator. Preferably in the range of 0.2 to 8 mass%, more preferably in the range of 0.25 to 7.5 mass%. When (D-b)/(D-a) falls within the above range, the surface curability and resolution of the curable resin composition become good, and the reflectance, solder heat resistance and insulation reliability of the cured film are also improved.
The total blending ratio of the (D-a) acylphosphine photopolymerization initiator and the (D-b) photopolymerization initiator described in the formula (1) is preferably in the range of 0.5 to 30 mass%, more preferably in the range of 1 to 20 mass%, and particularly preferably in the range of 2 to 15 mass%, relative to the total solid content of the curable resin composition. When the blending amount is within the above range, the surface curability and resolution of the curable resin composition are improved, and the reflectance, solder heat resistance, and insulation reliability of the cured film are also improved.
The curable resin composition of the present invention may further comprise a photopolymerization initiator other than the (D-a) acylphosphine photopolymerization initiator and the (D-b) photopolymerization initiator represented by formula (1). As the other photopolymerization initiator. Examples include: known and used compounds such as benzophenone-based compounds, acetophenone-based compounds, aminoacetophenone-based compounds, benzoin ether-based compounds, benzil ketal-based compounds, oxime ether-based compounds, oxime ester-based compounds, hydroxyketone-based compounds, and titanocene-based compounds.
Examples of commercial products include IRGACURE OXE01 and IRGACURE OXE02 manufactured by BASF JAPAN LTD; IGM RESINS A. Omnirad907, omnirad369, omnirad379; n-1919 and NCI-831 manufactured by ADEKA CORPORATION; TR-PBG-304 manufactured by the company of new powerful electronic materials, inc.
(E) Polymerizable monomer
The curable resin composition of the present invention may further contain (E) a polymerizable monomer having an ethylenically unsaturated group in the molecule.
Examples of such polymerizable monomers include conventionally known polyester (meth) acrylates, polyether (meth) acrylates, carbonate (meth) acrylates, epoxy (meth) acrylates, and urethane (meth) acrylates, and 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; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, N-dimethylaminopropyl acrylamide, and the like; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol and tris-hydroxyethyl isocyanurate, and polyhydric acrylic esters such as an ethylene oxide adduct, propylene oxide adduct and epsilon-caprolactone adduct thereof; polyhydric acrylic esters such as phenoxy acrylic esters, bisphenol a diacrylate, and ethylene oxide adducts and propylene oxide adducts of these phenols; polyglycidyl ethers such as diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; examples of the urethane acrylate include, but are not limited to, acrylates and melamine acrylates obtained by directly acrylating a polyol such as a polyether polyol, a polycarbonate diol, a hydroxyl-terminated polybutadiene, or a polyester polyol, or by acrylating urethane with a diisocyanate, and at least 1 of various methacrylates corresponding to the above acrylates.
When the polymerizable monomer is contained, the amount of the polymerizable monomer to be blended is preferably in the range of 5 to 40 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A). When the amount of the photopolymerizable monomer to be blended is 5 parts by mass or more, the effect of imparting photocurability is excellent. On the other hand, when the amount is 40 parts by mass or less, the touch dryness of the coating film becomes good.
Additive agent
The curable resin composition of the present invention may further contain known additives such as coloring pigment, defoamer, surface tension adjuster, coupling agent, leveling agent, sensitizer, mold release agent, lubricant, plasticizer, antioxidant, ultraviolet absorber, flame retardant, polymerization inhibitor, thickener, adhesion promoter, and crosslinking agent, if necessary.
Organic solvents
In the curable resin composition of the present invention, an organic solvent may be used for the purpose of the synthesis of the carboxyl group-containing resin (a) and adjustment of the curable resin composition, or adjustment of the viscosity when applied to a substrate or a first film.
Examples of the solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, diethylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol ethyl ether 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 solvents such as petroleum ether, naphtha, hydrogenated naphtha and solvent naphtha. These organic solvents may be used alone or in the form of a mixture of 2 or more.
Laminate body
The curable resin composition of the present invention may be formed into a laminate comprising: a first film; and a resin layer formed on the first film and made of the curable resin composition. When laminating, the curable resin composition of the present invention is diluted with the above-mentioned organic solvent to an appropriate viscosity, and coated on the first film with a uniform thickness by using a corner-roll coater, doctor blade coater, lip coater, bar coater, extrusion coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc., and dried at a temperature of usually 50 to 130 ℃ for 1 to 30 minutes, whereby a resin layer can be obtained. The thickness of the coating film is not particularly limited, and is usually suitably selected so that the thickness of the dried resin layer is in the range of 1 to 150. Mu.m, preferably 10 to 60. Mu.m.
After forming the resin layer of the curable resin composition of the present invention on the first film, a releasable second film is preferably laminated on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer or the like. As the releasable second film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like may be used as long as the adhesive force between the resin layer and the second film is smaller than the adhesive force between the resin layer and the first film when the second film is released.
In the present invention, the curable resin composition of the present invention is applied to the second film and dried to form a resin layer, and the first film is laminated on the surface of the resin layer. That is, in the present invention, when a laminate is produced, either one of the first film and the second film may be used as a film to which the curable resin composition of the present invention is applied.
Cured product
The cured product of the present invention is obtained by curing the curable resin composition of the present invention or the resin layer of the laminate of the present invention, and has a combination of soldering heat resistance, exhaust gas resistance, and insulation reliability.
Printed circuit board with improved heat dissipation
The printed wiring board of the present invention has a cured product obtained from the curable resin composition of the present invention or the resin layer of the laminate. As a method for producing a printed wiring board of the present invention, for example, the curable resin composition of the present invention is prepared by adjusting the viscosity of the composition to a value suitable for the coating method, and then coating the composition on a substrate by a method such as dip coating, flow coating, roll coating, bar coating, screen printing, curtain coating, or the like, and then evaporating and drying (temporary drying) the organic solvent contained in the composition at a temperature of 60 to 100 ℃. In the case of the laminate, the resin layer is formed on the substrate by bonding the laminate to the substrate in such a manner that the resin layer contacts the substrate with a laminator or the like and then peeling the first film.
Examples of the base material include a printed wiring board and a flexible printed wiring board, which are formed by a circuit formed in advance of copper or the like: copper-clad laminate sheets of all grades (FR-4 etc.) of copper-clad laminate sheets for high frequency circuits, which are made of paper phenol resin, paper epoxy resin, glass cloth epoxy resin, glass polyimide resin, glass cloth/nonwoven fabric epoxy resin, glass cloth/paper epoxy resin, synthetic fiber epoxy resin, fluororesin/polyethylene/polyphenylene oxide resin, polyphenylene oxide/cyanate ester resin, etc.; and metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, and the like.
The volatilization drying performed after the application of the curable resin composition of the present invention can be performed as follows: the drying is performed by a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection type oven, or the like (a method of convecting hot air in a dryer using a device having a heat source of an air heating system using steam, and a system of blowing the hot air onto a support using a nozzle).
After forming a resin layer on a substrate, the resin layer is selectively exposed to active energy rays through a photomask having a predetermined pattern formed thereon, and the unexposed portion is developed with a dilute aqueous alkali solution (for example, 0.3 to 3% by weight aqueous sodium carbonate solution) to form a pattern of a cured product. Further, the cured product is irradiated with an active energy ray and then heat-cured (for example, 100 to 220 ℃), or the cured product is irradiated with an active energy ray after heat-curing, or is finally completely cured (main cured) by heat-curing alone, whereby a cured film excellent in various properties such as adhesion and hardness is formed.
As the exposure apparatus used for the active energy ray irradiation, an apparatus for irradiating ultraviolet rays, such as an LED light source lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, or a mercury short arc lamp, may be used, and a direct-imaging apparatus (for example, a laser direct imaging apparatus for directly drawing an image by a laser system using CAD data from a computer) may be used. The exposure wavelength of the direct imaging device is preferably in the range of 380 to 450 nm. The exposure amount for image formation varies depending on the film thickness, and may be generally 10 to 1500mJ/cm 2 Preferably, the ratio of the total length of the catalyst to the total length of the catalyst is 20 to 1000mJ/cm 2 Within a range of (2).
As the developing method, dipping, spraying, brushing, etc. can be used, and as the developing solution, an alkaline aqueous solution of potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. can be used.
The curable resin composition of the present invention is suitable for forming a cured film on an electronic component of an electronic device requiring miniaturization and high performance, particularly for forming a cured film on a printed wiring board requiring miniaturization and high density, more preferably for forming a permanent coating film, and further for forming a solder resist layer, an interlayer insulating layer, and a cover layer.
The present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the examples. In the following, "parts" and "%" are mass references unless otherwise specified.
< preparation of curable resin composition >
The components were mixed and stirred in the proportions shown in tables 2 to 3, and kneaded and dispersed by a three-roll kneader to obtain curable resin compositions of examples 1 to 110 and comparative examples 1 to 4. The blending amounts in tables 2 and 3 represent the blending amounts in terms of varnish.
TABLE 2
TABLE 3 Table 3
*1 (D-a) and (D-b) in total, and does not contain other photopolymerization initiator
*2 since the content of (D-a) is 0, the actual result of (D-b)/(D-a) is ≡
The detailed information of each component shown in tables 2 to 3 is as follows.
A-1 Synthesis example 1 carboxyl group-containing resin solution (solid content 39%)
A-2 Synthesis example 2 carboxyl group-containing resin solution (solid content 64%)
B-1 CR-97, shi Yuan Co., ltd., titanium oxide (solid content 100%)
B-2 SiO 2 (solid content 100%) SO-E2 manufactured by Admatechs Co., ltd
B-3 BaSO 4 (solid content 100%) BARIACE B-30 manufactured by Sakai chemical industry Co., ltd
C-1 NPEL-128E, bisphenol A type epoxy resin (solid content: 100%) manufactured by Nan Ya Plastics Co., ltd
Multifunctional epoxy resin (solid content: 75%) of phenol novolak type manufactured by C-2N-770-75 EA, DIC Co., ltd
D-1 Omnipol TP, 3-functional or more acyl phosphine oxide photopolymerization initiator (structure of PI-3 in Table 1 above), IGM RESINS B.V. Co., ltd. (solid content 100%)
D-2 Omnirad 819, bisacylphosphine oxide photopolymerization initiator, IGM RESINS B.V. (solid content: 100%)
Photopolymerization initiator (solid content: 100%) of formula (2) manufactured by D-3 TOE-04-A3, japanese chemical industry Co., ltd
D-4 Omnirad 369, alpha-aminobenzophenone photopolymerization initiator (solid content: 100%) manufactured by IGM RESINS B.V.)
Oxime ester photopolymerization initiator (solid content: 100%) produced by D-5 IRGACURE OXE02, BASF JAPAN LTD
Synthesis example 1 (Synthesis of carboxyl group-containing resin having no phenol skeleton)
In a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 900.0 parts of dipropylene glycol monomethyl ether as a solvent was heated to 110℃and a mixture of 174.0 parts of methacrylic acid, 174.0 parts of epsilon-caprolactone-modified methacrylic acid (average molecular weight 314), 77.0 parts of methyl methacrylate, 222.0 parts of dipropylene glycol monomethyl ether and 12.0 parts of tert-butyl peroxy 2-ethylhexanoate (Perbutyl O, manufactured by Japanese fat and oil Co., ltd.) as a polymerization catalyst was added dropwise over 3 hours, followed by stirring at 110℃for 3 hours to deactivate the polymerization catalyst, to obtain a resin solution.
After cooling the resin solution, 289.0 parts of Cyclomer A200 (3, 4-epoxycyclohexylmethyl methacrylate, 3.0 parts of triphenylphosphine and 1.3 parts of hydroquinone monomethyl ether, manufactured by Daicel corporation) were added thereto, and the mixture was heated to 100℃and stirred to carry out a ring-opening addition reaction of an epoxy group, thereby obtaining a carboxyl group-containing resin solution having no phenol skeleton.
The weight average molecular weight (Mw) of the resin solution thus obtained was 15000, the solid content was 39%, and the acid value of the solid was 79.8mgKOH/g.
Synthesis example 2 (Synthesis of carboxyl group-containing resin having phenol skeleton)
To 600g of diethylene glycol monoethyl ether acetate, 600g of an o-cresol novolak type epoxy resin [ DIC Co., ltd., EPICLON-695, a softening point of 95 ℃, an epoxy equivalent of 214, an average functional group number of 7.6 ] 1070g (glycidyl group number (total number of aromatic rings): 5.0 mol), 360g (5.0 mol) of acrylic acid, and 1.5g of hydroquinone were charged, and the mixture was heated and stirred to 100℃to uniformly dissolve the components.
Next, 4.3g of triphenylphosphine was charged, heated to 110℃and reacted for 2 hours, and then heated to 120℃to proceed the reaction for 12 hours. 415g of an aromatic hydrocarbon (Solvesso 150) and 456.0g (3.0 mol) of tetrahydrophthalic anhydride were charged into the obtained reaction solution, and the reaction was carried out at 110℃for 4 hours, followed by cooling to obtain a carboxyl group-containing resin solution having no phenol skeleton.
The solid content of the resin solution thus obtained was 64%, and the acid value of the solid content was 89mgKOH/g.
Fabrication of evaluation substrate
1. Evaluation substrate A production
The curable resin compositions of the examples and comparative examples were applied to the entire surface of a copper-clad laminate pretreated by polishing and grinding by screen printing, dried for 30 minutes at 80℃in a hot air circulation drying oven, and cooled to room temperature to form a resin layer having a thickness of 40. Mu.m. For the resin layer, a DI exposure machine (Ledia 6 manufactured by SCREEN Co.) equipped with an LED light source was used, the output of the light source was 100% at 385nm and 1000mJ/cm 2 The entire surface was exposed to light at 30℃in 1% by mass aqueous sodium carbonate, and developed under a spray pressure of 0.15MPa for 50 seconds. Then, the resin layer was cured for 60 minutes (post-curing) with a hot air circulation type drying oven adjusted to 150 ℃ to obtain an evaluation substrate a.
2. Evaluation substrate B production
The curable resin compositions of the examples and comparative examples were applied to the entire surface of an FR-4 substrate pretreated by polishing by screen printing, dried at 80℃for 30 minutes, and cooled to room temperature to form a resin layer having a thickness of 40. Mu.m. The upper surface (exposed surface) of the composition after drying was treated with a composition having a wire/space (L/S) of 30 μm/30 μm, 40 μm/40 μm, 50 μm/50 μm, 60 μm/60 μm, 70 μm/70 μm, 80 μm/80 μm, 90 μm/90 μm, 100 μm/F 100 μm, 200 μm/200 μm pattern negative film coverage, using an LED exposure machine (Ledia 6 manufactured by SCREEN Co.) was performed at a power of 385nm light source output of 100% and 1000mJ/cm 2 The resin layer is exposed to light through the negative film. Then, development was performed for 50 seconds using a 1 mass% aqueous sodium carbonate solution at 30℃under a spray pressure of 0.15 MPa. Then, the resin layer was cured for 60 minutes (post-curing) with a hot air circulation type drying oven adjusted to 150 ℃ to obtain an evaluation substrate B.
Characterization experiments
(1) Deaeration property
On one surface of a double-sided printed substrate having a linear pattern with a copper thickness of 105 μm and an L/S of 40 μm/300 μm and a circuit length of 2cm, polishing and grinding were performed as pretreatment, followed by washing with water and sufficiently drying the water.
Next, the curable resin compositions of the examples and comparative examples were applied to the whole surface of the dried double-sided printed board in a direction parallel to the pattern so that the film thickness after curing became 120 μm by screen printing. After standing at room temperature for 30 minutes, the substrate was dried at 80℃for 30 minutes in a hot air circulation type drying oven to prepare a defoamation evaluation substrate. The defoamability evaluation substrate was observed with a 20-fold optical microscope, and the number of bubbles between the circuits was counted, and the defoamability was evaluated as follows based on the number of bubbles.
And (3) the following materials: the number of bubbles of 100 μm or more is 5 or less
And (2) the following steps: more than 5 and less than 10 bubbles with the size of more than 100 μm
(2) Hardness of pencil after exposure
The curable resin compositions of the examples and comparative examples were applied to the entire surface of a copper-clad laminate pretreated by polishing and grinding by screen printing, dried for 30 minutes at 80℃in a hot air circulation drying oven, and cooled to room temperature to form a resin layer having a thickness of 40. Mu.m. For the resin layer, a DI exposure machine (Ledia 6 manufactured by SCREEN Co.) equipped with an LED light source was used, the output of the light source was 100% at 385nm and 1000mJ/cm 2 Is subjected to full-face exposure by using a 1 mass% aqueous solution of sodium carbonate at 30 ℃ to sprayDevelopment was carried out under a mist pressure of 0.15MPa for 50 seconds. The pencil hardness of the surface of the obtained resin layer was measured in accordance with JIS K5600-5-4. The evaluation criteria are as follows.
And (3) the following materials: pencil hardness of 4H or more
And (2) the following steps: pencil hardness of 2H or more and less than 4H
X: the hardness of the pencil is lower than 2H
The higher pencil hardness after pattern exposure means that the more excellent the surface curability of the curable resin composition
(3) Pencil hardness after heat curing
The pencil hardness of the cured product surface of the substrate A was evaluated by measurement according to JIS K5600-5-4. The evaluation criteria are as follows. The hardness of the pencil was 6H or more (shown as excellent in tables 2 and 3) for each of the cured products of examples and comparative examples.
(4) Resolution ratio
The minimum design line width remaining on the substrate was visually checked for the evaluation substrate B, and the resolution was evaluated according to the following criteria.
And (3) the following materials: residual line below 70 μm of minimum design line width
And (2) the following steps: residual line with minimum design line width of more than 70 μm and less than 90 μm
X: no line remains at all even in the case of a design line width exceeding 90 μm
(5) Reflectivity of
For the evaluation substrate A, the reflectance at 450nm of the obtained cured product was measured using a spectrophotometer CM-2600d manufactured by Konikokumi, inc., and evaluated according to the following criteria.
And (3) the following materials: reflectance of 75% or more
And (2) the following steps: the reflectivity is more than 70% and less than 75%
X: the reflectivity is less than 70%
(6) Solder heat resistance
For the evaluation substrate a, a rosin-based flux was applied to the surface of the cured product, and then immersed in a solder bath at 260 ℃ for 20 seconds. After dipping, naturally cooling the substrate to room temperature, and dipping the substrate into the solder tank again. After immersing several times, the appearance of the flux was visually observed after washing with denatured alcohol, and evaluated according to the following evaluation criteria.
And (3) the following materials: even if the dipping in the solder bath was performed 4 times or more, peeling of the cured product was not observed.
And (2) the following steps: even if the dipping in the solder bath was performed 2 times or more, peeling of the cured product was not observed, but when the dipping was performed 4 times or more, peeling of the resin layer was observed.
X: peeling of the cured product was observed when dipping in the solder bath was performed 2 times.
(7) Exhaust gas resistance
For the evaluation substrate A, a powder sample was collected from the formed solidified product, placed in a thermal desorption apparatus (TDU) manufactured by GESTEL Co., ltd.), and heated at a thermal extraction temperature of 260℃for 10 minutes, and the generated exhaust gas components were collected at-60℃with liquid nitrogen, respectively. The collected exhaust gas components were analyzed by separation using a gas chromatograph-mass spectrometer (6890N/5973N) manufactured by Agilent Technologies, and the exhaust gas amount of example 1 was defined as 100% by mass in terms of N-dodecane, and evaluated according to the following criteria.
And (3) the following materials: the exhaust gas component is 150 mass% or less
And (2) the following steps: the exhaust gas component exceeds 150 mass% and is 200 mass% or less
X: the exhaust gas component exceeds 200 mass%
(8) Insulation reliability
After the substrate on which the comb-shaped electrode of L/s=100 μm/100 μm was formed was subjected to a pretreatment by polishing and grinding, the curable resin compositions of the foregoing examples and comparative examples were applied over the entire surface by screen printing, and then dried at 80 ℃ for 30 minutes by a heated air circulation type drying oven to form a resin layer having a thickness of 40 μm. Then, the resin layer was cured by heating in a hot air circulating drying oven at 150℃for 60 minutes to prepare an insulation reliability evaluation substrate. The evaluation substrate was placed in a high-temperature and high-humidity tank at 85℃under an atmosphere of 85% humidity, and a voltage of 3.5V was applied thereto to conduct an in-tank insulation reliability test. The insulation resistance values in the tank of the cured product after various times were evaluated according to the following criteria.
And (3) the following materials: through 800 hours10 after the time 7 Omega or above
And (2) the following steps: an insulation resistance value of 10 after 500 hours 7 Omega or more, but the insulation resistance value is less than 10 when 800 hours pass 7 Ω
X: an insulation resistance value of less than 10 when 500 hours pass 7 Ω。
As can be seen from tables 2 and 3, the resolution, soldering heat resistance, exhaust gas resistance and insulation reliability of example 1 including both the photopolymerization initiator of (D-a) and the photopolymerization initiator of (D-b) were significantly improved as compared with comparative example 1 including only the photopolymerization initiator other than (D-a) and the photopolymerization initiator of (D-b). The pencil hardness, reflectance, soldering heat resistance and insulation reliability after exposure of the pattern of example 1, which contains both the photopolymerization initiator of (D-a) and the photopolymerization initiator of (D-b), were greatly improved as compared with comparative example 2, which contains only the photopolymerization initiator of (D-a). The pencil hardness, reflectance, soldering heat resistance and insulation reliability after exposure of example 10 containing both the photopolymerization initiator of (D-a) and the photopolymerization initiator of (D-b) were significantly improved as compared with comparative example 4 containing only the photopolymerization initiator of (D-a) and the photopolymerization initiator other than (D-b). The resolution, reflectance, soldering heat resistance and insulation reliability of example 9, in which (D-b)/(D-a) was 0.25 mass%, were greatly improved as compared with comparative example 3, in which (D-b)/(D-a) exceeded 10 mass%, though both the photopolymerization initiator of (D-a) and the photopolymerization initiator of (D-b) were contained.
Further, when the carboxyl group-containing resin (a) contains a carboxyl group-containing resin having no phenol skeleton, the reflectance and insulation reliability tend to be further improved (examples 1 and 10). When the blending amount of the inorganic filler is within a proper range, pencil hardness, reflectance, soldering heat resistance and insulation reliability after pattern exposure tend to be further improved (examples 1 to 3 and examples 4 and 5), or deaeration property and resolution tend to be further improved (examples 1 to 3 and examples 6 and 7). When titanium oxide is contained, the reflectance tends to be further improved (examples 1 and 8). When (D-a) contains an acylphosphine-based photopolymerization initiator having 3 or more functions, the defoaming property, resolution, exhaust gas resistance and insulation reliability tend to be further improved (examples 1 and 9).
From these results, it is clear that the curable resin composition of the present invention is excellent in resolution, deaeration and surface curability, and is suppressed in outgassing, and the cured product thereof is also excellent in insulation reliability, soldering heat resistance, and the like. The curable resin composition can efficiently produce an insulating material satisfying a higher level of requirements, and is highly suitable for electronic devices requiring miniaturization and high performance.

Claims (8)

  1. A curable resin composition comprising (A) a carboxyl group-containing resin, (B) an inorganic filler, (C) a thermosetting resin, and (D) a photopolymerization initiator,
    as the photopolymerization initiator (D), there are included (D-a) an acylphosphine-based photopolymerization initiator and (D-b) a photopolymerization initiator represented by the formula (1),
    the amount of the photopolymerization initiator represented by the formula (1) to be compounded is 0.1 to 10 mass% inclusive, based on the amount of the (D-a) acylphosphine photopolymerization initiator to be compounded
    Wherein R is 23 Represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group, and a naphthyl group; r is R 21 、R 22 Each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a phenyl group, a naphthyl group, an anthracenyl group, a pyridyl group, a benzofuranyl group, or a benzothienyl group;
    ar represents a single bond, or an alkylene group having 1 to 10 carbon atoms, a vinylidene group, a phenylene group, a biphenylene group, a pyridylene group, a naphthylene group, an anthrylene group, a thienylene group, a furanylene group, a 2, 5-pyrrol-diyl group, a 4,4 '-stilbene-diyl group, or a 4,2' -stilbene-diyl group; n represents a number of 0 to 1.
  2. The curable resin composition according to claim 1, wherein the inorganic filler (B) is blended in an amount of 35 mass% or more and 55 mass% or less with respect to the total solid component amount of the curable resin composition.
  3. The curable resin composition according to claim 1, wherein the inorganic filler (B) contains titanium oxide.
  4. The curable resin composition according to claim 1, wherein the (D-a) acylphosphine photopolymerization initiator comprises 3 or more functional acylphosphine photopolymerization initiators.
  5. The curable resin composition according to any one of claims 1 to 4, wherein the carboxyl group-containing resin (A) does not have a phenol skeleton.
  6. A laminate comprising the curable resin composition according to any one of claims 1 to 5 as a resin layer.
  7. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 5 or by curing the resin layer of the laminate according to claim 6.
  8. An electronic component having the cured product according to claim 7.
CN202280048170.XA 2021-09-30 2022-09-29 Curable resin composition, laminate, cured product, and electronic component Pending CN117642697A (en)

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