CN116368196A - Curable resin composition and dry film - Google Patents

Curable resin composition and dry film Download PDF

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Publication number
CN116368196A
CN116368196A CN202180069607.3A CN202180069607A CN116368196A CN 116368196 A CN116368196 A CN 116368196A CN 202180069607 A CN202180069607 A CN 202180069607A CN 116368196 A CN116368196 A CN 116368196A
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Prior art keywords
curable resin
resin composition
film
resin
mass
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Inventor
德光香代子
松尾昭彦
栗田政寿
金子刚士
滝井庸二
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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Priority claimed from JP2021108031A external-priority patent/JP7130095B2/en
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Publication of CN116368196A publication Critical patent/CN116368196A/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
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C08L101/08—Carboxyl groups
    • 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
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • 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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  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

The invention provides a curable resin composition which has excellent cleaning and removing properties even when the composition is adhered to a compounding drum or equipment used in the process of producing a solder resist ink and dried. The curable resin composition of the present invention is a curable resin composition comprising (A) a curable resin, (B) a filler and (C) an organic solvent, wherein the dissolution start time of a completely dried coating film of 20mm in the longitudinal direction and 20mm in the transverse direction and 7 [ mu ] m in film thickness, which is formed using the curable resin composition, in propylene glycol monomethyl ether acetate as a cleaning solvent is within 20 seconds from the start of immersion in the cleaning solvent.

Description

Curable resin composition and dry film
Technical Field
The present invention relates to a curable resin composition. More specifically, the present invention relates to a curable resin composition having excellent cleaning and removing properties. The present invention also relates to a dry film using the curable resin composition.
Background
In general, a liquid type or dry film type solder resist is used as an insulating ink for the purpose of preventing solder from adhering to unnecessary parts and protecting circuits when soldering components on a printed wiring board of an electronic device. The curable resin composition used as a solder resist is composed of a curable resin as a main material, an organic solvent, a filler, and the like (for example, refer to patent document 1).
In addition, in the manufacturing process of the solder resist ink, compounding is performed in a vat of a large pot, pre-dispersion is performed by a mixer such as a dissolver, a planetary mixer, a butterfly mixer, etc., and uniform dispersion is performed by a kneader such as a three-roll mill, a bead mill, a blender, etc. Since it is an important problem to uniformly disperse powder in a liquid having a high viscosity using these mixers or kneaders, various devices have been developed and used (for example, refer to patent document 2).
Here, since the solder resist is patterned by chemical reaction, cleaning using equipment is important in order to prevent the mixed presence of compounds that cause characteristic changes (for example, refer to patent document 3). However, it is considered that the cleaning and removal of the solder resist ink after the curing reaction is more difficult than that of the general coating ink.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 1-141904.
Patent document 2: japanese patent laid-open No. 2014-147883.
Patent document 3: japanese patent application laid-open No. 2012-522068.
Disclosure of Invention
Problems to be solved by the invention
In order to reuse the mating bucket or equipment used in the manufacturing process of the solder resist ink, it is desirable to easily clean out the attached and dried solder resist ink. This is because the time taken for cleaning and removal can be a manufacturing cost for the solder resist ink. Accordingly, an object of the present invention is to provide a curable resin composition excellent in cleaning removability even when it is attached to a compounding drum or equipment used in the production process of a solder resist and dried. The present invention also provides a dry film using the curable resin composition.
Means for solving the problems
As a result of intensive studies, the present inventors have found that by adjusting the dissolution start time of a completely dried coating film of 20mm in the longitudinal direction and 20mm in the transverse direction and 7 μm in film thickness, which is formed using a curable resin composition, in a specific cleaning solvent, a curable resin composition excellent in cleaning removability can be obtained even when it is attached to a compounding drum or equipment used in the production process of a solder resist and dried, and completed the present invention.
Specifically, the curable resin composition of the present invention is a curable resin composition comprising (A) a curable resin, (B) a filler and (C) an organic solvent, and is characterized in that the dissolution start time of a completely dried coating film of 20mm in the longitudinal direction and 20mm in the transverse direction and 7 μm in film thickness, which is formed using the curable resin composition, in propylene glycol monomethyl ether acetate as a cleaning solvent is within 20 seconds from the start of immersion in the cleaning solvent.
In the embodiment of the present invention, it is preferable that the dissolution completion time of the completely dried coating film is within 40 seconds from the start of immersion in the cleaning solvent.
In the aspect of the present invention, the content of propylene glycol monomethyl ether acetate in the curable resin composition is preferably 20% by mass or more.
In the aspect of the present invention, the content of the filler (B) in the curable resin composition is preferably 45 mass% or less.
In the embodiment of the present invention, the (a) curable resin preferably contains a carboxyl group-containing resin.
In the embodiment of the present invention, the weight average molecular weight of the carboxyl group-containing resin is preferably 6000 or less.
In the embodiment of the present invention, the curable resin preferably contains two or more carboxyl group-containing resins.
In the aspect of the present invention, it is preferable to form a solder resist layer.
In the aspect of the present invention, it is preferable to form an interlayer insulating layer.
The dry film of another embodiment of the present invention comprises a first film and a resin layer comprising a dried film of a curable resin composition formed on the first film, wherein the curable resin composition comprises (A) a curable resin, (B) a filler and (C) an organic solvent, and the dissolution start time of a completely dried film of 20mm in the longitudinal direction, 20mm in the transverse direction, and 7 [ mu ] m in film thickness, obtained from the dry film, in propylene glycol monomethyl ether acetate as a cleaning solvent is within 20 seconds from the start of immersion in the cleaning solvent.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a curable resin composition excellent in cleaning removability even when it is attached to a compounding tank or equipment used in the production process of a solder resist ink and dried. Further, according to the present invention, a dry film using the curable resin composition can be provided.
Drawings
FIG. 1 is a schematic diagram of an apparatus for measuring the dissolution start time and dissolution completion time of a completely dried coating film in examples.
Detailed Description
[ curable resin composition ]
The curable resin composition of the present invention contains (A) a curable resin, (B) a filler, and (C) an organic solvent. The curable resin composition of the present invention may further contain a photopolymerization initiator, a colorant, a defoaming agent, a leveling agent, other components, and the like, as long as the following physical properties are satisfied. The curable resin may contain any one of a thermosetting resin, a carboxyl group-containing resin, and a photopolymerizable monomer, or may be a combination of a plurality of kinds. The curable resin composition of the present invention satisfies the following physical properties, and is excellent in cleaning removability even when it is attached to a compounding drum or equipment used in a process of producing a solder resist and dried. This is presumably because the cleaning removability (solubility in a cleaning solvent) of the dried composition (completely dried coating film) is mainly reflected in the dissolution start time in the cleaning solvent.
Physical Properties
The dissolution start time of the completely dried coating film of the curable resin composition of the present invention in propylene glycol monomethyl ether acetate as a cleaning solvent is 20 seconds or less, preferably 15 seconds or less, more preferably 10 seconds or less, still more preferably 9 seconds or less, and particularly preferably 8 seconds or less from the start of immersion in the cleaning solvent.
The dissolution completion time of the completely dried coating film is preferably 40 seconds or less, more preferably 30 seconds or less, further preferably 28 seconds or less, particularly preferably 26 seconds or less, and most preferably 25 seconds or less from the start of immersion in the cleaning solvent.
Regarding the formation of the completely dried coating film in the present invention, it is important that the solvent contained in the completely dried coating film is sufficiently volatilized. In the present specification, the term "completely dry coating film" refers to a case where the difference in volatility between a composition in a dry state prepared by heating a coating film having a film thickness of 7 μm immediately after formation by printing or the like at 80℃for 3 hours and a composition left to stand under normal temperature (25 ℃) conditions is 10% or less. As a method for obtaining the difference in volatility, the weight was measured using an electronic balance, and calculated by the following equation (1). That is, it is determined that the completely dried coating film is formed when the above conditions are satisfied.
[ number 1]
Figure BDA0004171376350000041
In the dissolution of the completely dried coating film in the cleaning solvent, the smooth surface becomes uneven, and the surface of the base material appears when the coating film is completely dissolved. In the present invention, since the purpose is to dissolve the most dry and difficult-to-clean coating film surface, the criterion of dissolution is determined according to the state of the coating film surface.
The components constituting the curable resin composition of the present invention will be described below.
[ (A) curable resin ]
Examples of the curable resin include a thermosetting resin contributing to a thermosetting reaction by heating, a photocurable resin contributing to a photo-curing reaction by light irradiation, and a photocurable thermosetting resin contributing to both reactions. The curable resin composition may contain only one of the thermosetting resin and the photocurable resin, or may contain both of them.
The content of the curable resin in the curable resin composition is preferably 20 to 80% by mass, more preferably 25 to 75% by mass, and even more preferably 50 to 70% by mass, in terms of solid content. By setting the content of the curable resin within the above range, a more excellent cured product can be obtained. Hereinafter, each curable resin will be described.
[ thermosetting resin ]
As the thermosetting resin, a known thermosetting resin can be arbitrarily used. The heat resistance of the cured coating film can be improved by containing the thermosetting resin in the curable resin composition. Examples of the thermosetting resin include known and commonly used thermosetting resins such as epoxy resins, isocyanate compounds, blocked isocyanate compounds, amino resins, polyfunctional oxetane compounds, benzoxazine resins, carbodiimide resins, cyclic carbonate compounds, and episulfide resins. Among them, the preferred thermosetting resin is an epoxy resin. The thermosetting resin can be used singly or in combination of two or more.
Examples of the epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol a type epoxy resin, brominated bisphenol a type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, and triphenylmethane type epoxy resin.
Examples of the commercially available epoxy resins include jER 828, 806, 807, YX8000, YX8034, 834, YD-128, YDF-170, ZX-1059, ST-3000, EPICLON 830, 835, 840, 850, N-730A, N-695, and RE-306, which are manufactured by Nippon Kagaku Co., ltd.
The isocyanate compound may be a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as 4,4' -diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, naphthalene-1, 5-diisocyanate, phthalene diisocyanate, m-xylylene diisocyanate and 2, 4-toluene dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; alicyclic polyisocyanates such as bicycloheptane triisocyanate; and adducts, biuret and isocyanurate of the above-listed isocyanate compounds, and the like.
As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Examples of the isocyanate compound capable of reacting with the isocyanate blocking agent include the polyisocyanate compound described above. Examples of the isocyanate blocking agent include a phenol blocking agent; a lactam-based capping agent; an active methylene-based capping agent; an alcohol-based capping agent; an oxime-based blocking agent; a thiol-based capping agent; an acid amide-based end-capping agent; an imide-based capping agent; an amine-based capping agent; imidazole-based capping agents; imine-based capping agents, and the like.
Examples of the amino resin include methylolmelamine compounds, methylolbenzoguanamine compounds, methylolglycourea compounds, and methylol urea compounds.
Examples of the polyfunctional oxetane compound include polyfunctional oxetanes such as bis [ (3-methyl-3-oxetylmethoxy) methyl ] ether, bis [ (3-ethyl-3-oxetylmethoxy) methyl ] ether, 1, 4-bis [ (3-methyl-3-oxetylmethoxy) methyl ] benzene, 1, 4-bis [ (3-ethyl-3-oxetylmethoxy) methyl ] benzene, (3-methyl-3-oxetanyl) methacrylate, (3-ethyl-3-oxetanyl) methacrylate, and an oligomer or copolymer thereof, and etherified compounds of oxetanes with resins having hydroxyl groups such as novolak resins, poly (p-hydroxystyrene), cado bisphenols (Cardo type bisphenol), calixarenes, resorcinol calixarenes, and silsesquioxane. In addition, copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate and the like are also exemplified.
When the composition contains a carboxyl group-containing resin described later, the number of functional groups of the thermosetting component to be reacted is preferably 0.5 to 2.5mol, more preferably 0.8 to 2.0mol, per 1mol of carboxyl group contained in the carboxyl group-containing resin.
As the thermosetting component, an alkali-soluble resin having an alkali-soluble group is preferably contained in terms of being able to impart alkali developability to the composition. Examples of the alkali-soluble resin include a carboxyl group-containing resin, a compound having two or more phenolic hydroxyl groups, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups. Among them, a carboxyl group-containing resin or a phenolic resin is preferable for improving adhesion to a substrate, and a carboxyl group-containing resin is more preferable for making development particularly excellent. The carboxyl group-containing resin will be described below.
As the carboxyl group-containing resin, various resins having a carboxyl group in a molecule, which are conventionally known, can be used. The carboxyl group-containing resin may or may not have an ethylenically unsaturated double bond in the molecule, but a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is particularly preferred from the viewpoint of photocurability or development resistance. In this case, the resin corresponds to a photocurable thermosetting resin. When the curable composition of the present invention contains a carboxyl group-containing resin, the composition can be used not only for alkali development but also for use without alkali development. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or derivatives thereof. In the case of using only a carboxyl group-containing resin having no ethylenically unsaturated double bond, in order to impart photocurability to the composition, it is necessary to use a photopolymerizable monomer which is a compound having a plurality of ethylenically unsaturated groups in the molecule, which will be described later. Specific examples of the carboxyl group-containing resin include the following compounds (optionally, oligomers and polymers).
(1) Carboxyl group-containing resins obtained by copolymerizing unsaturated carboxylic acids such as (meth) acrylic acid with unsaturated group-containing compounds such as styrene, α -methylstyrene, lower alkyl (meth) acrylates, isobutylene and the like (as lower alkyl (meth) acrylates, methyl (meth) acrylates and the like are exemplified).
(2) The carboxyl group-containing urethane resin is obtained by the polyaddition reaction of a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate with 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) A carboxyl group-containing photosensitive urethane resin obtained by polyaddition reaction of a diisocyanate with a (meth) acrylate or a partial anhydride modification thereof of a difunctional epoxy resin such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol type epoxy resin, a carboxyl group-containing diol compound and a diol compound.
(4) In the resin synthesis of (2) or (3), a compound having one hydroxyl group and one or more (meth) acryloyl groups in the molecule, such as hydroxyalkyl (meth) acrylate, is added to the carboxyl group-containing photosensitive urethane resin obtained by (meth) acrylating the terminal thereof.
(5) To the resin synthesis of the above (2) or (3), a compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, is added to obtain a carboxyl group-containing photosensitive urethane resin by (meth) acrylating the terminal thereof.
(6) A carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or more polyfunctional (solid) epoxy resin with (meth) acrylic acid to add a dibasic acid anhydride to a hydroxyl group present in a side chain.
(7) A carboxyl group-containing photosensitive resin obtained by reacting a (meth) acrylic acid with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl groups of a difunctional (solid) epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the generated hydroxyl groups.
(8) A carboxyl group-containing polyester resin obtained by reacting a difunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid, and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to the primary hydroxyl group thus formed.
(9) A carboxyl group-containing photosensitive resin is obtained by reacting an epoxy compound having a plurality of epoxy groups in 1 molecule with a compound having at least one alcoholic hydroxyl group and one 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 acid, and the like.
(10) A carboxyl group-containing photosensitive 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, reacting the resultant with an unsaturated group-containing monocarboxylic acid, and reacting the resultant with a polybasic acid anhydride.
(11) A carboxyl group-containing photosensitive 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, reacting the resultant with an unsaturated group-containing monocarboxylic acid, and reacting the resultant with a polybasic acid anhydride.
(12) A carboxyl group-containing photosensitive resin obtained by further adding 1 compound having one epoxy group and one or more (meth) acryloyl groups in a molecule to the resins of (1) to (11).
As the carboxyl group-containing resin, a carboxyl group-containing copolymer resin can be used. The carboxyl group-containing copolymer resin may be the resin of (1) or the copolymer resin of (12). Examples of the resin (12) include carboxyl group-containing photosensitive resins obtained by further adding (meth) acrylate having an alicyclic epoxy group such as glycidyl methacrylate or 3, 4-epoxycyclohexylmethyl (meth) acrylate to carboxyl group-containing resins obtained by copolymerizing (meth) acrylic acid and methyl (meth) acrylate.
In the present specification, (meth) acrylate is a term generically referring to acrylate, methacrylate, and a mixture thereof, and other similar expressions are also the same.
The carboxyl group-containing resin that can be used in the present invention is not limited to the above-listed resins. The above-mentioned carboxyl group-containing resins may be used singly or in combination.
In the present invention, in view of the developability when a weak base developer such as an aqueous sodium carbonate solution is used and the drawing property of a resist pattern, the acid value of the carboxyl group-containing resin is preferably in the range of 30 to 150mgKOH/g, more preferably in the range of 50 to 120 mgKOH/g. Although the higher the acid value of the carboxyl group-containing resin, the higher the developability, there are cases where the dissolution and peeling of the exposed portion and the unexposed portion with the developer are not distinguished due to the progress of dissolution of the exposed portion by the developer.
The weight average molecular weight of the carboxyl group-containing resin is preferably 6000 or less, and further preferably 2000 or more. By using a carboxyl group-containing resin having a weight average molecular weight of 6000 or less, the solubility of the completely dried coating film in a dissolution solvent can be improved and the cleaning removability can be improved. In addition, the use of a carboxyl group-containing resin having a weight average molecular weight of 2000 or more can improve sharpness or surface drying performance. The weight average molecular weight can be determined by Gel Permeation Chromatography (GPC).
The content of the carboxyl group-containing resin in the curable resin composition is preferably 20 to 80% by mass, more preferably 20 to 75% by mass, and even more preferably 20 to 50% by mass, in terms of solid content. By the content of 20 mass% or more, the strength of the cured coating film can be improved. In addition, the tackiness of the curable resin composition becomes appropriate and the workability improves by 80 mass% or less.
[ Photocurable resin ]
The photocurable resin is a compound having an ethylenically unsaturated group, and examples thereof include polymers, oligomers, monomers, and the like, and may be a mixture of these. By containing the photocurable resin, the strength of the cured film can be improved. The photocurable resin may be used singly or in combination of two or more.
As the compound having an ethylenically unsaturated group, a publicly known photopolymerizable oligomer, photopolymerizable monomer, or the like can be used. Among them, a photopolymerizable monomer is preferably used in order to further impart crosslinkability or curability to the cured coating film.
The photopolymerizable oligomer is an oligomer having an ethylenically unsaturated double bond. Examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers. Examples of the (meth) acrylate oligomer include epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, bisphenol epoxy (meth) acrylate, urethane (meth) acrylate, epoxyurethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene modified (meth) acrylate, and the like.
The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond. Examples of such photopolymerizable monomers include alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; mono-or di (meth) acrylic acid esters of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol and tris-hydroxyethyl isocyanurate, and polyvalent (meth) acrylates of ethylene oxide or propylene oxide adducts of these; (meth) acrylic esters of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A; (meth) acrylic esters of glycidyl ethers such as glycerol diglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; melamine (meth) acrylates. The photopolymerizable monomers may be used singly or in combination of two or more.
The content of the photocurable resin in the curable resin composition is preferably 3 to 20 mass%, more preferably 5 to 15 mass%, in terms of solid content. When the content of the photopolymerizable monomer is 3 mass% or more, the photocurability is good, and a pattern is easily formed in alkali development after irradiation with active energy rays. On the other hand, when 20 mass% or less, halation is less likely to occur and good sharpness is likely to be obtained.
[ (B) Filler ]
As the filler, a known filler can be arbitrarily used. Examples of the filler include silica such as amorphous silica, crystalline silica, fused silica, and spherical silica, talc, boehmite, hydrotalcite, slaked lime, calcium hydroxide, calcium carbonate, calcium sulfate, potassium carbonate, magnesium carbonate, clay, mica powder, alumina, aluminum hydroxide, barium sulfate, copper sulfide, alumina, zinc oxide, iron, zinc sulfide, zirconia, chromium oxide, cadmium sulfide, and copper oxide. Among them, silica and barium sulfate are preferable from the viewpoint of dispersibility. The filler may be used alone or in combination of two or more. By containing the filler, heat resistance can be improved and variation in coating can be reduced. In addition, from lower light From the viewpoint of polishing, siO can be used as 2 And Al 2 O 3 Aluminum silicate as a main component, and the like.
Whether or not the filler is subjected to surface treatment is not particularly limited, and surface treatment for improving dispersibility may be performed. By using the surface-treated filler, aggregation can be suppressed. The surface treatment method of the filler is not particularly limited, and a known and commonly used method may be used, but it is preferable to treat the surface of the inorganic filler by using a surface treatment agent having a curable reactive group, for example, a coupling agent having a curable reactive group as an organic group, or the like.
The average particle diameter of the filler is preferably 10 μm or less, but from the viewpoint of dispersibility, it is more preferably 0.1 to 5.0 μm, and still more preferably 0.2 to 3.0 μm. The average particle diameter of the filler is an average particle diameter (D) including not only the primary particle diameter but also the secondary particle diameter (agglomerate) 50 ) Is measured by a laser diffraction method 50 Is a value of (2). Examples of the measurement device by the laser diffraction method include Microtrac MT3300EXII manufactured by michaelbayer corporation (Microtrac Bell). The values of the particle diameters of the fillers are values obtained by measuring the fillers as described above before adjusting (pre-stirring and kneading) the curable resin composition.
According to the use scheme, the filler can be mixed with other components in a powder or solid state, or can be mixed with a solvent or a dispersing agent to form slurry and then mixed with other components. The content of the filler to be described later is a value in a powder or solid state.
The content of the filler in the curable resin composition is preferably 45 mass% or less, more preferably 40 mass% or less, further preferably 35 mass% or less, and further preferably 5 mass% or more, more preferably 10 mass% or more, further preferably 20 mass% or more. By setting the content of the filler in the above range, the cured product can be made high in strength and the cleaning removability of the completely dried coating film can be improved.
[ (C) organic solvent ]
The curable resin composition of the present invention may contain an organic solvent for the purpose of preparation of the composition, viscosity adjustment at the time of coating on a substrate or film, and the like. As the organic solvent, ketones such as methyl ethyl ketone and cyclohexanone can be used; 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 tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha and solvent naphtha. Among these, in the case where a porous material such as amorphous silica is used in the curable resin composition of the present invention, esters are preferable, and propylene glycol monomethyl ether acetate is more preferable, in terms of the fact that the silica surface is likely to absorb oil during curing or drying, and the glossiness of the formed cured coating film is lower. These organic solvents may be used singly or in combination of two or more.
The content of the organic solvent is not particularly limited, and can be appropriately set according to the target viscosity to facilitate the preparation of the curable resin composition.
In the present invention, the content of propylene glycol monomethyl ether acetate in the curable resin composition is preferably 20% by mass or more, more preferably 25% by mass or more, further preferably 30% by mass or more, and further preferably 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less. In the present invention, the content of propylene glycol monomethyl ether acetate in the curable resin composition is a value including not only the amount of propylene glycol monomethyl ether acetate blended as (C) an organic solvent but also the amount of propylene glycol monomethyl ether acetate in the liquid component used for the preparation of other components (the curable resin (a) and the filler (B) and the like). By setting the content of propylene glycol monomethyl ether acetate within the above range, the cleaning removability of the completely dried coating film can be improved.
The curable resin composition of the present invention may further contain any of the following components.
[ photopolymerization initiator ]
The photopolymerization initiator is used to react a carboxyl group-containing resin or a photopolymerizable monomer by exposure to light. As the photopolymerization initiator, any known photopolymerization initiator can be used. The photopolymerization initiator may be used alone or in combination of two or more.
Specific examples of the photopolymerization initiator include bisacylphosphinoxides such as 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-naphthylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) -2, 4-trimethylpentylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) -2, 5-dimethylphenylphosphine oxide, and bis- (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide; monoacylphosphine oxides such as 2, 6-dimethoxybenzoyl diphenylphosphine oxide, 2, 6-dichlorobenzoyl diphenylphosphine oxide, methyl 2,4, 6-trimethylbenzoyl phenylphosphonate, 2-methylbenzoyl diphenylphosphine oxide, isopropyl pivaloyl phenylphosphonate, and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide; hydroxyacetophenones such as phenyl (2, 4, 6-trimethylbenzoyl) phosphonic acid ethyl ester, 1-hydroxy-cyclohexylphenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one and the like; benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, and the like; benzoin alkyl ethers; benzophenone types such as benzophenone, p-methylbenzophenone, michler's ketone, methylbenzophenone, 4' -dichlorobenzophenone, and 4,4' -diethylaminobenzophenone; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl) -1- [4- (4-morpholino) phenyl ] -1-butanone, N-dimethylaminoacetophenone, and the like; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, 2-pentynthraquinone, and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoates such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate, and ethyl p-dimethylbenzoate; oxime esters such as 1, 2-octanedione, 1- [4- (phenylthio) phenyl ] -,2- (O-benzoyl oxime) ], 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethanone, and 1- (O-acetyl oxime); titanocenes such as bis (. Eta.5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl) -bis [2, 6-difluoro-3- (2- (1-pyrrol-1-yl) ethyl) phenyl ] titanium; phenyl disulfide 2-nitrofluorene, butanoin, anisoin diethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and the like.
Commercial products of the alkylbenzene photopolymerization initiator include Omnirad 907, 369E, 379, etc. manufactured by Ai Jianmeng resin company (IGM Resins). Further, as a commercial product of the acylphosphine oxide-based photopolymerization initiator, omnirad 819 manufactured by Ai Jianmeng resin company (IGM Resins) and the like are mentioned. As the oxime ester photopolymerization initiator, there may be mentioned commercially available products such as Irgacure OXE01, OXE02, N-1919, adeka Arkls NCI-831, NCI-831E, and TR-PBG-304, manufactured by Sesamara Strong electronics New Material Co., ltd.
In addition, examples thereof include carbazole oxime ester compounds described in Japanese patent application laid-open No. 2004-359639, japanese patent application laid-open No. 2005-097141, japanese patent application laid-open No. 2005-220097, japanese patent application laid-open No. 2006-160634, japanese patent application laid-open No. 2008-094770, japanese patent application laid-open No. 2008-509967, japanese patent application laid-open No. 2009-040762, and Japanese patent application laid-open No. 2011-80036.
The content of the photopolymerization initiator in the curable resin composition is preferably 0.1 to 10 mass%, more preferably 1 to 5 mass%, in terms of solid content. When the content of the photopolymerization initiator is 0.1 mass% or more, the photocurable property of the curable resin composition becomes good, and the coating film characteristics such as chemical resistance also become good. On the other hand, when the amount is 10 mass% or less, the light absorption on the surface of the resist film (cured coating film) is good, and the deep curability is not easily lowered.
A photoinitiating aid or sensitizer may be used in combination with the above photopolymerization initiator. Examples of the photoinitiating auxiliary or sensitizer include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. Particular preference is given to using thioxanthone compounds such as 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone and the like. By containing the thioxanthone compound, deep curability can be improved. These compounds can also be used as photopolymerization initiators in some cases, and are preferably used in combination with photopolymerization initiators. In addition, the photoinitiating auxiliary or sensitizer may be used singly or in combination of two or more.
Since these photopolymerization initiator, photoinitiation auxiliary agent, and sensitizer absorb a specific wavelength, there is a possibility that the sensitivity may be lowered and the photopolymerization initiator, photoinitiation auxiliary agent, and sensitizer may function as an ultraviolet absorber, as the case may be. However, these are not only used for the purpose of improving the sensitivity of the resin composition. By absorbing light of a specific wavelength as needed, it is possible to improve the photoreactivity of the surface, change the line shape and opening of the resist pattern into a vertical, tapered, inverted tapered shape, and improve the accuracy of the line width or opening diameter.
[ colorant ]
The curable resin composition of the present invention may contain a colorant. The colorant is not particularly limited, and known colorants such as red, blue, green and yellow may be used, and any of pigments, dyes and pigments may be used, but from the viewpoint of reducing environmental load and reducing influence on human body, a colorant containing no halogen is preferable.
Examples of the red colorant include monoazo-based, disazo-based, azo lake-based, benzimidazolone-based, perylene-based, diketopyrrolopyrrole-based, condensed azo-based, anthraquinone-based, and quinacridone-based colorants, and specifically, those having the following color index (c.i.; issued by the institute of dyeing (The Society of Dyers and Colourists)) number are given.
Examples of the monoazo-based red colorant include pigment red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, and the like. Examples of the bisazo-based red colorant include pigment red 37, 38, 41, and the like. Further, as the monoazo lake-based red colorant, pigment red 48: 1. 48: 2. 48: 3. 48: 4. 49: 1. 49: 2. 50: 1. 52: 1. 52: 2. 53: 1. 53: 2. 57: 1. 58: 4. 63: 1. 63: 2. 64: 1. 68, etc. Examples of the benzimidazolone-based red colorant include pigment red 171, 175, 176, 185, and 208. Examples of perylene red colorants include solvent red 135, 179, pigment red 123, 149, 166, 178, 179, 190, 194, 224, and the like. Examples of the diketopyrrolopyrrole-based red colorant include pigment red 254, 255, 264, 270, 272, and the like. Examples of the condensed azo-based red colorant include pigment red 220, 144, 166, 214, 220, 221, 242, and the like. Examples of the anthraquinone-based red colorant include pigment red 168, 177, 216, solvent red 149, 150, 52, 207, and the like. Examples of the quinacridone-based red colorant include pigment red 122, 202, 206, 207, 209, and the like.
Examples of the blue colorant include phthalocyanine-based and anthraquinone-based colorants, and examples of the Pigment-based colorant include compounds classified as pigments (Pigment), for example, pigment blue 15 and Pigment blue 15: 1. 15: 2. 15: 3. 15: 4. 15: 6. 16, 60. As the dye system, solvent blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70, and the like can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can be used.
Examples of the yellow colorant include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and anthraquinone-based, and examples of the anthraquinone-based yellow colorant include solvent yellow 163, pigment yellow 24, 108, 193, 147, 199, and 202. Examples of the isoindolinone yellow colorant include pigment yellow 110, 109, 139, 179, 185, and the like. Examples of the condensed azo-based yellow colorant include pigment yellow 93, 94, 95, 128, 155, 166, 180, and the like. Examples of the benzimidazolone yellow colorant include pigment yellow 120, 151, 154, 156, 175, 181, and the like. Examples of monoazo yellow colorants include pigment yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, and 62: 1. 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183, etc. Examples of the disazo yellow colorant include pigment yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, and the like.
In addition, coloring agents such as purple, orange, brown, black, white, etc. may be added. Specifically, pigment black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, pigment violet 19, 23, 29, 32, 36, 38, 42, solvent violet 13, 36, c.i. pigment orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, pigment brown 23, 25, carbon black, titanium oxide, and the like are exemplified.
The content of the colorant in the curable resin composition is preferably 0.1 to 2.0 mass%, more preferably 0.3 to 1.5 mass%, in terms of solid content.
[ other additive component ]
The curable resin composition of the present invention may further contain, if necessary, components such as at least one of photoinitiating auxiliaries, heat curing catalysts, cyanate ester compounds, elastomers, mercapto compounds, urethane catalysts, thixotropic agents, adhesion promoters, block copolymers, chain transfer agents, polymerization inhibitors, copper poison inhibitors, antioxidants, rust inhibitors, thickening agents such as microsilica, organobentonites and montmorillonite, antifoaming agents such as silicon-based, fluorine-based and polymer-based and leveling agents, silane coupling agents such as imidazole-based, thiazole-based and triazole-based, phosphonates, phosphate derivatives, phosphorus compounds such as phosphazene (phosphazene) compounds, and the like. These can be known materials in the field of electronic materials.
[ preparation method ]
In the preparation of the curable resin composition of the present invention, after weighing and blending the components, the components are pre-stirred by a stirrer. Then, the composition can be prepared by dispersing the components with a kneader and kneading the components as necessary.
Examples of the kneading machine include a bead mill, a ball mill, a sand mill, a three-roll mill, and a two-roll mill. The type of beads or the dispersion conditions of the particle size of the beads in the bead mill can be appropriately set according to the target viscosity, but examples of the type of beads include zirconia beads and alumina beads. The particle diameter of the beads may be, for example, in the range of 0.015 to 2.0 mm. Of these, the range of from 0.3 to 1.5mm is more preferable. Preferably, the bead packing ratio is 50 to 95% and the number of revolutions of the rotor is 800 to 1300rpm. In addition, as the target viscosity, the viscosity of the composition when put into a bead mill is preferably 200 dPa.s or less in terms of improving dispersibility or giving a cured coating film with a lower gloss. On the other hand, the lower limit is preferably 50 dPa.s or more. The viscosity in the present invention is according to JIS Z8803: 2011, a cone-rotor cone-plate viscometer (TVE-33H, manufactured by Tokyo industries Co., ltd.) was used at 50℃and 100rpm for 30 seconds.
On the other hand, dispersion conditions such as the rotation ratio of each roller of the three-roller mill can be appropriately set according to the target viscosity.
In order to further improve dispersibility, the raw material slurry may be formed into a slurry by a kneader such as a bead mill or a three-roll mill, weighed, and blended, and then pre-stirred by a stirrer. In the case of slurrying the raw materials, it is preferable to weigh and blend the wet dispersing agent such as the silane coupling agent and then mix the materials with a bead mill or the like. Then, each component containing the substance slurried with the above-mentioned mixer can be dispersed and kneaded with a bead mill or the like to prepare the composition.
[ use ]
The curable resin composition of the present invention is useful for forming a solder resist layer, a coverlay layer, an interlayer insulating layer, and the like as a pattern layer of a permanent film of a printed wiring board, and is particularly useful for forming a solder resist layer. Further, since the curable resin composition of the present invention can form a cured product excellent in film strength even in the case of a thin film, it can be suitably used for forming a pattern layer on a printed wiring board requiring thinning, for example, a package substrate (a printed wiring board used for semiconductor packaging). Further, the cured product obtained from the curable resin composition of the present invention is excellent in bendability, and therefore can be suitably used for a flexible printed wiring board.
The curable resin composition of the present invention can be used not only for the purpose of forming a pattern layer of a cured coating film but also for the purpose of not forming a pattern layer, for example, for molding (sealing) use.
[ Dry film ]
The curable resin composition of the present invention may be in the form of a dry film, and the dry film may include a first film and a resin layer formed of a dried film of the curable resin composition formed on the first film. The completely dried coating film of 20mm in the longitudinal direction and 20mm in the transverse direction and 7 μm in the film thickness obtained from the dry film of the present invention is characterized by satisfying the same physical properties as those described in the above [ physical properties ] of the above [ curable resin composition ].
The first film of the present invention is a film that is bonded to at least a resin layer formed on a substrate such as a base plate when integrally molded by heating or the like so as to contact the resin layer side constituted by the curable resin layer formed on the dry film. In dry film formation, the curable resin composition of the present invention is diluted with the above-mentioned organic solvent and adjusted to an appropriate viscosity, and the resulting film is coated on a first film to a uniform thickness by a corner-roll coater (comma coater), a blade coater, a lip coater, a bar coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, or the like, and usually dried at a temperature of 50 to 130 ℃ for 1 to 30 minutes to obtain a film. The thickness of the coating film is not particularly limited, but in general, the thickness after drying is appropriately selected to be in the range of 1 to 150. Mu.m, preferably in the range of 5 to 60. Mu.m.
The first film is not particularly limited as long as it is a known film, and for example, a polyester film such as polyethylene terephthalate or polyethylene naphthalate, a polyimide film, a polyamide imide film, a polypropylene film, a polystyrene film, or a film made of a thermoplastic resin can be suitably used. Among them, polyester films are preferable from the viewpoints of heat resistance, mechanical strength, handleability, and the like. In addition, a laminate of these films can also be used as the first film.
In addition, from the viewpoint of improving mechanical strength, the thermoplastic resin film is preferably a film extending in a uniaxial direction or a biaxial direction.
The thickness of the first film is not particularly limited, and can be, for example, 10 μm to 150 μm.
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 or the like from adhering to the surface of the resin layer. The second film in the present invention is a film that is peeled from the curable resin layer before lamination when laminated by heating or the like so as to contact the resin layer side constituted by the curable resin layer formed on the dry film on a substrate such as a substrate, for example, for integral molding. As the releasable second film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used, and when the second film is released, the adhesive force between the resin layer and the second film may be smaller than the adhesive force between the resin layer and the first film.
The thickness of the second film is not particularly limited, and may be, for example, 10 μm to 150 μm.
Examples
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples. In the following, "parts" and "%" are all based on mass unless otherwise specified.
(Synthesis of curable resin solution A-1 (containing carboxyl group))
To an autoclave equipped with a thermometer, a nitrogen introducing device, an alkylene oxide introducing device, and a stirring device, a novolak-type cresol resin (trade name "Shonol CRG951", OH equivalent: 119.4) 119.4g, potassium hydroxide 1.19g, and toluene 119.4g were added, and the inside of the system was replaced with nitrogen while stirring, and heated to a temperature. Then, 63.8g of propylene oxide is slowly added dropwise at 125-132 ℃ and 0-4.8 kg/cm 2 Is reacted for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56g of 89% phosphoric acid was added to neutralize potassium hydroxide, thereby obtaining a propylene oxide reaction solution of a novolak-type cresol resin having a hydroxyl value of 182.2g/eq, which was free from volatile matter of 62.1%. This is an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl groups.
Then, 293.0g of the obtained alkylene oxide reaction solution of novolak-type cresol resin, 43.2g of acrylic acid, 11.53g of methanesulfonic acid, 0.18g of methyl hydroquinone and 252.9g of toluene were added to a reactor equipped with a stirrer, a thermometer and an air-blowing tube, and air was blown at a rate of 10 ml/min, and reacted at 110℃for 12 hours while stirring. 12.6g of water were distilled off as an azeotropic mixture with toluene. Thereafter, the reaction solution obtained was cooled to room temperature, neutralized with 35.35g of 15% aqueous sodium hydroxide solution and washed with water. Thereafter, 118.1g of propylene glycol monomethyl ether acetate (hereinafter referred to as "PMA") was used in an evaporator to replace toluene and distilled off, whereby a novolak-type acrylic resin solution was obtained. Subsequently, 332.5g of the obtained novolak type acrylic resin solution and 1.22g of triphenylphosphine were added to a reactor equipped with a stirrer, a thermometer and an air-blowing tube, and air was blown at a rate of 10 ml/min, 60.8g of tetrahydrophthalic anhydride was slowly added while stirring, and the mixture was reacted at 95 to 101℃for 6 hours, thereby obtaining a curable resin solution A-1. The solid content of the obtained curable resin solution A-1 was 65%, the acid value of the solid matter was 88mgKOH/g, and the weight-average molecular weight was about 2500 (in terms of polystyrene).
(Synthesis of curable resin solution A-2)
456 parts of bisphenol A, 228 parts of water and 649 parts of 37% formalin were added to a flask equipped with a cooling tube and a stirrer, the temperature was kept at 40℃or lower, 228 parts of 25% aqueous sodium hydroxide solution was added, and the mixture was reacted at 50℃for 10 hours after the completion of the addition. After the reaction was completed, the mixture was cooled to 40℃and neutralized to pH 4 with 37.5% phosphoric acid aqueous solution while keeping the temperature below 40 ℃. After which it was allowed to stand and the aqueous layer was separated. After separation, 300 parts of methyl isobutyl ketone was added and dissolved uniformly, and then washed three times with 500 parts of distilled water, and water, solvent, etc. were removed under reduced pressure at a temperature of 50 ℃ or less. The obtained polyhydroxy methyl compound was dissolved in 550 parts of methanol, thereby obtaining 1230 parts of a methanol solution of the polyhydroxy methyl compound. When a part of the obtained methanol solution of the polyhydroxy methyl compound was dried at room temperature in a vacuum dryer, the solid content was 55.2%.
500 parts of the obtained methanol solution of the polyhydroxy compound, 440 parts of 2, 6-xylenol were added and uniformly dissolved at 50 ℃. After the uniform dissolution, methanol was removed at a temperature of 50 ℃ or lower under reduced pressure. Thereafter, 8 parts of oxalic acid was added and reacted at 100℃for 10 hours. After the completion of the reaction, the distilled portion was removed under reduced pressure of 50mmHg at 180℃to obtain 550 parts of novolak resin A. 130 parts of the above novolak resin A, 2.6 parts of a 50% aqueous sodium hydroxide solution, and 100 parts of toluene/methyl isobutyl ketone (mass ratio=2/1) were added to an autoclave equipped with a thermometer, a nitrogen introducing device, an alkylene oxide introducing device and a stirring device, and the mixture was stirred while being replaced with nitrogen, heated to a temperature of 8kg/cm at 150 DEG C 2 45 parts of ethylene oxide were gradually introduced and reacted. The reaction was continued for about 4 hours until the gauge pressure was 0.0kg/cm 2 After that, the mixture was cooled to room temperature. To the reaction solution was added and mixed 3.3 parts of 36% aqueous hydrochloric acid solution to neutralize sodium hydroxide. The resultant neutralization reaction was diluted with toluene and washed three times with water, and the solvent was removed by an evaporator, whereby an ethylene oxide adduct of novolak resin a having a hydroxyl value of 175g/eq. This is an average of 1 mole of ethylene oxide added to each equivalent of phenolic hydroxyl groups. The phenol thus obtained is then reacted with175 parts of ethylene oxide adduct of aldehyde varnish resin a, 75 parts of methacrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether and 130 parts of toluene were added to a reactor equipped with a stirrer, a thermometer and an air blowing pipe, and the mixture was stirred while blowing air and heated to 115 ℃, and water produced by the reaction was distilled off as an azeotropic mixture with toluene, and the mixture was further reacted for 4 hours and cooled to room temperature. The obtained reaction solution was washed with 5% aqueous NaCl solution, toluene was removed by distillation under reduced pressure, and PMA was added to obtain a curable resin solution A-2. The solid content of the obtained curable resin solution A-2 was 70%, and the weight-average molecular weight was about 5500 (in terms of polystyrene).
(Synthesis of curable resin solution A-3 (containing carboxyl group))
To a four-necked flask equipped with a stirrer and a reflux condenser, 220g of cresol novolak type epoxy resin (EPICLON N-695, epoxy equivalent: 220, manufactured by DIC Co., ltd.) and 214g of diethylene glycol monoethyl ether acetate (carbitol acetate) were added and dissolved by heating. Next, 0.1g of hydroquinone as a polymerization inhibitor and 2.0g of dimethylbenzylamine as a reaction catalyst were added. The mixture was heated to 95-105℃and 72g of acrylic acid was slowly added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90℃and 106g of tetrahydrophthalic anhydride was added thereto to react for 8 hours, followed by cooling and taking out. The resin solution of the curable resin solution A-3 thus obtained was obtained. The solid content of the obtained curable resin solution A-3 was 65%, the acid value of the solid content was 100mgKOH/g, and the weight-average molecular weight was about 8000 (in terms of polystyrene).
(Synthesis of curable resin solution A-4 (containing carboxyl group))
In a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 325.0 parts by mass of dipropylene glycol monomethyl ether as a solvent was heated to 110℃and a mixture of 174.0 parts by mass of methacrylic acid, 174.0 parts by mass of epsilon-caprolactone-modified methacrylic acid (average molecular weight 314), 77.0 parts by mass of methyl methacrylate, 222.0 parts by mass of dipropylene glycol monomethyl ether (DPM) and 12.0 parts by mass of t-butyl peroxy-2-ethylhexanoate (Perbutyl O, manufactured by Nikko Co., ltd.) as a polymerization catalyst was added dropwise over 3 hours, and further stirred at 110℃for 3 hours to deactivate the polymerization catalyst to obtain a resin solution. After this resin solution was cooled, 289.0 parts by mass of 3, 4-epoxycyclohexylmethyl methacrylate (Cyclomer M100, manufactured by Kagaku Co., ltd.), 3.0 parts by mass of triphenylphosphine and 1.3 parts by mass of hydroquinone monomethyl ether were added, and ring-opening addition reaction of an epoxy group was performed by heating to 100℃and stirring, to obtain a curable resin solution A-4. The solid content of the obtained curable resin solution A-4 was 46% by mass, the acid value of the solid content was 79.8mgKOH/g, and the weight-average molecular weight was about 18000 (equivalent to polystyrene).
(preparation of non-surface-treated silica slurry)
700g of spherical silica (manufactured by Adam, inc.) and 300g of PMA as a solvent were dispersed in a bead mill with zirconia beads of 0.7. Mu.m. This was repeated three times and filtered with a 3 μm filter to prepare a silica slurry having an average particle diameter of 0.7 μm. The solid content of the obtained silica slurry was 70 mass%.
(preparation of surface-treated silica slurry)
Using the silica slurry having an average particle diameter of 0.7 μm (solid content in PMA: 70% by mass), which was obtained as described above, a silane methacrylate (KBM-503, believed to be a product of the chemical industry, inc.) was added in an amount of 4% by mass to silica and treated with a bead mill for 10 minutes, thereby obtaining a silica slurry surface-treated with the silane methacrylate. The solid content of the obtained silica slurry was 70 mass%.
(preparation of barium sulfate slurry)
700g of barium sulfate (B-30 manufactured by Saka Kagaku Co., ltd.) having an average particle diameter of 0.3 μm, 295g of diethylene glycol monoethyl ether acetate (carbitol acetate) as a solvent, and 5g of a wetting dispersant were mixed and stirred, and dispersion treatment was performed with zirconia beads having an average particle diameter of 0.7 μm in a bead mill. This was repeated three times and filtered with a 3 μm filter to prepare a barium sulfate slurry having an average particle diameter of 0.3 μm. The solid content of the obtained barium sulfate slurry was 70 mass%.
Examples 1 to 6 and comparative examples 1 to 3
(preparation of curable resin composition)
The curable resin compositions were prepared by blending the components according to the blending shown in table 1 below and dispersing the components with a stirrer. The blending amount in the table represents parts by mass. The following evaluation was performed using the prepared curable resin composition.
TABLE 1
Figure BDA0004171376350000211
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The blending amount in table 1 represents parts by mass.
Details of the components in table 1 are as follows.
1: the above-mentioned synthetic curable resin solution A-1 (containing carboxyl groups). 2: the above-mentioned synthetic curable resin solution A-2.
3: the above-mentioned synthetic curable resin solution A-3 (containing carboxyl groups).
4: the above-mentioned synthetic curable resin solution A-4 (containing carboxyl groups).
And 5: carbitol acetate cutting product of epoxy resin (HP-7200L, manufactured by DIC Co., ltd.).
And 6: the synthetic non-surface treated silica slurry described above.
7: the synthetic surface-treated silica slurry described above.
8: the synthesized barium sulfate slurry is prepared.
※9：PMA。
10: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one (manufactured by Ai Jianmeng resin Co., ltd., OMNIRAD 907).
11: black colorant (MA-100, mitsubishi chemical Co., ltd.).
And (2) carrying out: white colorant (TIPAQUE CR-58 (yellow CR-58), manufactured by Shi Yuan Co., ltd.).
And (3) carrying out: acrylic leveling agent (BYK-350, manufactured by Pick chemical Japan).
And (2) carrying out the following steps: acrylic leveling agent (BYK-361N, manufactured by Pick chemical Japan).
15: polymerization inhibitor (QS-30, manufactured by Kawasaki chemical industry Co., ltd.).
The "PMA content in the curable resin composition" of 16 is a value including not only the amount of PMA blended as the organic solvent of (C) but also the amount of PMA in the liquid component used for the preparation of the curable resin of (a) and the filler (B).
Preparation of fully dried coating film (examples 1 to 6 and comparative examples 1 to 3) >
The curable resin compositions of examples 1 to 6 and comparative examples 1 to 3 were applied to a copper plate as a base material by screen printing, and left to dry at room temperature (25 ℃) for four months, thereby producing a coating film having a thickness of 7 μm in the longitudinal direction of 20 mm. Times.20 mm. Times.horizontal direction. Since the difference in volatility of the obtained coating film calculated from the above formula (1) is 10% or less, it is judged that a completely dried coating film is formed. The film thickness of the completely dried coating film was measured by a laser microscope (VR-3200, manufactured by Kagaku Co., ltd.).
Preparation of a completely dried coating film (example 7) >
The curable resin composition of example 6 was applied to a polyethylene terephthalate film as a first film by an applicator and dried at 80 ℃ for 10 minutes, thereby obtaining a dry film having a resin layer composed of a dried coating film of the curable resin composition. Thereafter, the first film was peeled off and left to stand at room temperature (25 ℃) for four months to dry, thereby producing a coating film having a thickness of 7 μm and a thickness of 20mm in the longitudinal direction and 20mm in the transverse direction. Since the difference in volatility of the obtained coating film calculated from the above formula (1) is 10% or less, it is judged that a completely dried coating film is formed. The film thickness of the completely dried coating film was measured by a laser microscope (VR-3200, manufactured by Kagaku Co., ltd.).
(dissolution start time and dissolution completion time)
The apparatus shown in fig. 1 was used for measurement of dissolution start time and dissolution completion time of the completely dried coating film. Specifically, 70ml of PMA as the cleaning solvent 5 and the stirrer 6 were added to a 100ml beaker 2, and placed in a water bath set at 25 ℃. The temperature of the cleaning solvent was stabilized by stirring the cleaning solvent with a stirrer 7 (made by Wawang, amaran, inc., M-3, 500 rpm). Next, the copper plate 1 coated with the completely dried coating film 3 prepared as described above was placed so that the immersion depth was 20mm from the water surface of the cleaning solvent, and was perpendicular to the water surface of the cleaning solvent. A laser (visible light semiconductor laser, wavelength 635nm, line width 2mm, light output 2.5mW or less) was horizontally incident on the completely dried coating film on the immersed copper plate using a laser ink line instrument (TJM design, inc.) and a part of the completely dried coating film was irradiated in the flow direction of the cleaning solvent. When a bright line on the copper plate of the substrate, which was generated by dissolving the completely dried coating film, was confirmed, a region of 2mm×1mm was set as a dissolution start time in the total irradiation portion (2 mm×20 mm) of the laser light 4. On the other hand, when a bright line on the copper plate of the substrate, which is generated by dissolving the completely dried coating film, was found to occupy a region of 2mm×19mm in the total irradiated portion (2 mm×20 mm) of the laser light, the completion time of the dissolution was regarded as the dissolution completion time. The glow wire may be confirmed at any position of the total irradiated portion of the laser light. The limit of measurement of the dissolution time was 120 seconds. Therefore, in the case where dissolution was not started or completed even after 120 seconds elapsed, it is indicated as x in table 2, respectively.
(confirmation of cleaning removability)
The surface of the completely dried coating film of the copper plate coated with the completely dried coating film prepared above was wiped with a clean cloth impregnated with PMA as a cleaning solvent, and visually evaluated according to the following criteria.
O: the completely dried coating film was completely removed from the copper plate.
Delta: a portion of the completely dried coating film was removed from the copper plate.
X: the completely dried coating film was not removed from the copper plate.
TABLE 2
Figure BDA0004171376350000241
As is clear from table 2, the curable resin compositions of examples 1 to 6 and the dry film of example 7 were excellent in cleaning removability of the completely dried film. On the other hand, regarding the completely dried coating films of comparative examples 1 to 3, it was found that the cleaning removability was poor, even though dissolution was not started and completed after 120 seconds from the start of immersion in PMA as a cleaning solvent.
Description of the reference numerals
1: copper plate.
2: a 100ml beaker.
3: the coating film was completely dried.
4: and (5) laser.
5: and (3) cleaning the solvent.
6: stirring.
7: a stirrer.

Claims (9)

1. A curable resin composition comprising (A) a curable resin, (B) a filler and (C) an organic solvent, characterized in that,
the dissolution start time of a completely dried coating film of 20mm in the longitudinal direction and 20mm in the transverse direction and having a film thickness of 7 μm, which is formed using the curable resin composition, in propylene glycol monomethyl ether acetate as a cleaning solvent is within 20 seconds from the start of immersion in the cleaning solvent.
2. The curable resin composition according to claim 1, wherein,
the dissolution completion time of the completely dried coating film is within 40 seconds from the start of immersion in the cleaning solvent.
3. The curable resin composition according to claim 1 or 2, wherein,
in the curable resin composition, the content of propylene glycol monomethyl ether acetate is 20% by mass or more.
4. The curable resin composition according to claim 1 to 3, wherein,
in the curable resin composition, the filler (B) is contained in an amount of 45 mass% or less.
5. The curable resin composition according to claim 1 to 4, wherein,
the curable resin (a) contains a carboxyl group-containing resin.
6. The curable resin composition according to claim 1 to 5, wherein,
the weight average molecular weight of the carboxyl group-containing resin is 6000 or less.
7. The curable resin composition according to claim 1 to 6, wherein,
the curable resin composition is used for forming a solder resist layer.
8. The curable resin composition according to claim 1 to 6, wherein,
the curable resin composition is used for forming an interlayer insulating layer.
9. A dry film comprising a first film and a resin layer comprising a dried film of a curable resin composition formed on the first film, characterized in that,
the curable resin composition contains (A) a curable resin, (B) a filler, and (C) an organic solvent,
the dissolution start time of the completely dried film of 20mm in the vertical direction, 20mm in the horizontal direction, and 7 μm in film thickness obtained from the dry film in propylene glycol monomethyl ether acetate as a cleaning solvent is within 20 seconds from the start of immersion in the cleaning solvent.
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