WO2023100843A1 - Composition de résine durcissable, objet durci, carte de circuit imprimé et procédé de production de carte de circuit imprimé - Google Patents

Composition de résine durcissable, objet durci, carte de circuit imprimé et procédé de production de carte de circuit imprimé Download PDF

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Publication number
WO2023100843A1
WO2023100843A1 PCT/JP2022/043882 JP2022043882W WO2023100843A1 WO 2023100843 A1 WO2023100843 A1 WO 2023100843A1 JP 2022043882 W JP2022043882 W JP 2022043882W WO 2023100843 A1 WO2023100843 A1 WO 2023100843A1
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Prior art keywords
curable resin
resin composition
barium sulfate
printed wiring
solder resist
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PCT/JP2022/043882
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English (en)
Japanese (ja)
Inventor
義和 大胡
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太陽インキ製造株式会社
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Publication of WO2023100843A1 publication Critical patent/WO2023100843A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • 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
    • C08K3/24—Acids; Salts thereof
    • 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
    • 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

Definitions

  • the present invention relates to a curable resin composition, and more particularly to a curable resin composition that is suitable for forming solder resists. Furthermore, the present invention also relates to a printed wiring board using the curable resin composition and a method for producing the same.
  • solder bridging solder shorts
  • Patent Literature 1 proposes forming a solder resist having a matte surface by using a resin composition containing fine particles of aluminum silicate having a matting effect as a filler.
  • ultrafine anhydrous silica, talc, fused silica having a large particle size, clay, aluminum hydroxide, and the like as matting agents.
  • solder resists forming wiring boards are required to meet such needs.
  • Patent Document 2 a solder resist that has excellent heat resistance and moisture resistance, has a higher withstand voltage (insulation breakdown voltage) than conventional, and can be used stably for a long time even in a harsh environment is formed.
  • An electrically insulating resin composition has been proposed.
  • solder resists it has been difficult to achieve both the maintenance of low glossiness over time and the resulting solder adhesion resistance over time and the voltage resistance (dielectric breakdown voltage) at a high level. . Therefore, a solder resist that achieves both low glossiness over time and resistance to solder adhesion over time and voltage resistance at a high level, and a resin composition for forming such a solder resist. Providing it exists as a technical problem.
  • the present invention provides a solder resist that maintains low glossiness over time, which has been difficult to achieve in the past, and the resulting solder adhesion resistance over time, and voltage resistance at a high level.
  • An object of the present invention is to provide a curable resin composition that can be formed, a cured product thereof, and a printed wiring board comprising the cured product.
  • Another object of the present invention is to use the curable resin composition to provide a solder resist that achieves both low glossiness over time and solder adhesion resistance brought about by it and voltage resistance at a high level. It is an object of the present invention to provide a method for manufacturing a printed wiring board provided with.
  • the present inventors found that by adjusting the oil absorption of barium sulfate to 40 to 70 mL / 100 g in a curable resin composition containing a curable resin, barium sulfate, and a thermosetting catalyst, the above-mentioned I got the knowledge that the problem can be solved.
  • the present invention is based on such findings. That is, the gist of the present invention is as follows.
  • the curable resin according to [1] or [2], wherein the curable resin contains one or more thermosetting resins selected from the group consisting of epoxy compounds, polyfunctional oxetane compounds and oxazoline compounds. Composition.
  • a curable resin composition capable of forming a solder resist that maintains low glossiness over time and the resulting solder adhesion resistance over time and voltage resistance at a high level. product, a cured product thereof, and a printed wiring board comprising the cured product. Furthermore, using the curable resin composition, it is possible to provide a method for producing a printed wiring board having a solder resist that achieves both low gloss over time, solder adhesion resistance, and voltage resistance at a high level. can.
  • the curable resin composition of the present invention contains a curable resin, barium sulfate and a thermosetting catalyst as essential components.
  • the curable resin composition of the present invention is suitable for forming a solder resist in the manufacture of a printed wiring board, particularly a solder resist in a printed wiring board requiring high voltage and large current, especially a matte solder resist.
  • the curable resin composition of the present invention contains barium sulfate having an oil absorption of 40 to 70 mL / 100 g, so that the solder resist, which is a cured product of the curable resin composition, maintains low glossiness over time and it It is possible to provide the resistance to solder adhesion over time and the voltage resistance at a high level.
  • solder resists it has been difficult to maintain low glossiness over time, resulting in resistance to solder adhesion over time, and voltage resistance at a high level.
  • a component called a delustering agent as a filler into the resin composition for forming the solder resist.
  • silica or the like which is commonly used as a matting agent, is used, air bubbles adhere to those particles, air bubbles are present in the resin composition, and as a result in the solder resist formed by curing the resin composition. Air bubbles remain. Air bubbles adhering to silica or the like are difficult to separate and remove.
  • the curable resin composition of the present invention by using barium sulfate having a specific oil absorption as the matting agent, adhesion of air bubbles to the barium sulfate as the matting agent is suppressed, and the curable resin composition is improved. Residual air bubbles in the solder resist formed by curing are suppressed. As a result, it is believed that the solder resist can maintain low glossiness over time, resulting in resistance to solder adhesion over time, and withstand voltage at a high level.
  • the curable resin composition of the present invention has a 60° glossiness of a cured product (cured coating film) having a thickness of 25 ⁇ m, which is formed immediately after preparation, is preferably 20 or less, more preferably 15 or less, It is more preferably 10 or less.
  • the curable resin composition of the present invention even after being stored at 30 ° C. for 6 months after preparation, a cured product that maintains a low glossiness comparable to that of the curable resin composition immediately after preparation. can be formed. That is, the curable resin composition of the present invention is stored at 30 ° C. for 6 months after preparation. Below, more preferably 15 or less, still more preferably 10 or less.
  • the glossiness of the cured product of the curable resin composition was obtained by screen-printing the curable resin composition onto a copper plated FR-4 substrate with a thickness of 1.6 mm so that the film thickness after curing was 25 ⁇ m. and the cured product (cured coating film) of the curable resin composition formed by heating at 150 ° C for 30 minutes using a hot air circulation drying oven, BYK-Chemie gloss meter Micro Trigloss can be measured as the 60° specular reflectance measured using
  • a cured product (cured coating film) having a thickness of 50 ⁇ m has a withstand voltage value of preferably 5 kV (5 kV / 0.05 mm) or more, more preferably 5.5 kV (5.5 kV). /0.05 mm) or more, more preferably 6 kV (6 kV/0.05 mm) or more.
  • the withstand voltage value of the curable resin composition was measured using a withstand voltage tester TOS5101 manufactured by Kikusui Electronics Co., Ltd. for a substrate having a cured product (cured coating film) with a thickness of 50 ⁇ m. can be measured as the voltage value when the dielectric breakdown of the cured product occurs when the voltage is increased at 0.5 kV/sec in AC mode.
  • the curable resin composition of the present invention contains a curable resin.
  • the curable resin is not particularly limited as long as it is cured by the action of heat, light, or the like.
  • a thermosetting resin, a photocurable resin, or the like can be used as the curable resin.
  • the curable resin may be used singly or in combination of two or more.
  • a thermosetting resin or a photocurable resin may be used alone, or they may be used in combination.
  • thermosetting resin can be blended into the curable resin composition of the present invention as a curable resin. By adding a thermosetting resin, it is expected that the heat resistance of the curable resin composition is improved.
  • Thermosetting resins may be used singly or in combination of two or more. Any known thermosetting resin can be used.
  • known resins such as melamine resins, benzoguanamine resins, melamine derivatives, amino resins such as benzoguanamine derivatives, isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, epoxy compounds, oxetane compounds, oxazoline compounds, episulfide resins, bismaleimide, carbodiimide resins, etc.
  • a thermosetting resin can be used.
  • thermosetting resins may be monofunctional or polyfunctional.
  • thermosetting resins having a cyclic ether group or a cyclic thioether group in the molecule are preferably used.
  • examples of such thermosetting resins include epoxy compounds having an epoxy group in the molecule, oxetane compounds having an oxetanyl group in the molecule, oxazoline compounds having an oxazoline group in the molecule, and episulfide compounds having a thioether group in the molecule. Resin etc. are mentioned.
  • the thermosetting resin preferably contains one or more selected from the group consisting of epoxy compounds, polyfunctional oxetane compounds and oxazoline compounds, particularly preferably epoxy compounds.
  • Epoxidized vegetable oil bisphenol A type epoxy resin; hydroquinone type epoxy resin; bisphenol type epoxy resin; thioether type epoxy resin; brominated epoxy resin; Resin; bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; bisphenol A novolak epoxy resin; tetraphenylolethane epoxy resin; heterocyclic epoxy resin; diglycidyl phthalate resin; tetraglycidyl xylenoyl ethane resin; epoxy resin having a dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin; copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivative; It is not something that can be done.
  • These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or
  • oxetane compound a polyfunctional oxetane compound having two or more oxetanyl groups in one molecule is preferably used.
  • polyfunctional oxetane compounds include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1,4-bis[(3- methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3- Oxetanyl)methyl acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, and polyfunctional oxetanes such as their oligomers or
  • oxazoline compounds include possible compounds having two or more oxazoline groups in one molecule.
  • examples of such oxazoline compounds include oxazoline group-containing polymers such as polymers of oxazoline group-containing monomers and copolymers of oxazoline group-containing monomers and other monomers.
  • oxazoline group-containing monomers examples include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline, etc. is mentioned.
  • Examples of episulfide resins include compounds in which an oxygen atom constituting an epoxy group in any epoxy compound is substituted with a sulfur atom.
  • Epoxy compounds include those mentioned above.
  • a method for substituting an oxygen atom constituting an epoxy group in an epoxy compound with a sulfur atom a conventionally known method can be used.
  • Amino resins such as melamine derivatives and benzoguanamine derivatives include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds and methylol urea compounds.
  • a polyisocyanate compound can be blended as the isocyanate compound.
  • Polyisocyanate compounds include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and Aromatic polyisocyanates such as 2,4-tolylene dimer; Aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate) and isophorone diisocyanate; bicyclo alicyclic polyisocyanates such as heptane triisocyanate; and adducts, biurets and isocyanurates
  • an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used.
  • the isocyanate compound that can react with the isocyanate blocking agent include the aforementioned polyisocyanate compounds.
  • isocyanate blocking agents include phenolic blocking agents; lactam blocking agents; active methylene blocking agents; alcohol blocking agents; oxime blocking agents; mercaptan blocking agents; Amine-based blocking agents; imidazole-based blocking agents; imine-based blocking agents, and the like.
  • the amount of the thermosetting resin compounded in the curable resin composition is not particularly limited as long as the effect of the present invention is exhibited, for example, 3 to 50 in terms of solid content with respect to the total mass of the curable resin composition. % by mass or the like.
  • the curable resin composition of the present invention can contain a photocurable resin as a curable resin.
  • a photocurable resin a known and commonly used photocurable resin can be used. Among them, from the viewpoint of photocurability and development resistance, preferably a photocurable resin that can be cured by a radical addition polymerization reaction with an active energy ray, more preferably a photocurable resin having an ethylenically unsaturated group in the molecule.
  • a flexible resin is used.
  • the ethylenically unsaturated groups are preferably derived from acrylic acid, methacrylic acid, or derivatives thereof.
  • the photocurable resin may be used singly or in combination of two or more.
  • a carboxyl group-containing photosensitive resin which will be described later, is preferably used.
  • photocurable resin having an ethylenically unsaturated group in the molecule commonly known photopolymerizable oligomers, photopolymerizable monomers, and the like are used.
  • photopolymerizable oligomers include unsaturated polyester-based oligomers and (meth)acrylate-based oligomers.
  • (Meth)acrylate oligomers include epoxy (meth)acrylates such as phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, bisphenol type epoxy (meth)acrylate, urethane (meth)acrylate, epoxyurethane (meth)acrylate, ) acrylates, polyester (meth)acrylates, polyether (meth)acrylates, polybutadiene-modified (meth)acrylates, and the like.
  • epoxy (meth)acrylates such as phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, bisphenol type epoxy (meth)acrylate, urethane (meth)acrylate, epoxyurethane (meth)acrylate, ) acrylates, polyester (meth)acrylates, polyether (meth)acrylates, polybutadiene-modified (meth)acrylates, and the like.
  • the photopolymerizable monomer a monomer having an ethylenically unsaturated group is preferably used.
  • photopolymerizable monomers include commonly known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, epoxy (meth)acrylates, and the like.
  • alkyl acrylates such as 2-ethylhexyl acrylate and cyclohexyl acrylate
  • hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate
  • alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol.
  • acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, N,N-dimethylaminopropylacrylamide; N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl Aminoalkyl acrylates such as acrylates; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol and trishydroxyethyl isocyanurate, or their alkylene oxide adducts or ⁇ -caprolactone adducts, etc.
  • polyvalent acrylates phenols such as phenoxy acrylate and bisphenol A diacrylate or polyvalent acrylates such as alkylene oxide adducts thereof; glycidyls such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate Ether acrylates; not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadiene, and polyester polyols, or urethane acrylated via diisocyanate, and the above acrylates can be appropriately selected from at least one of the methacrylates corresponding to and used.
  • photopolymerizable monomer One type of the photopolymerizable monomer may be used alone, or two or more types may be used in combination. Photopolymerizable monomers can also be used as reactive diluents.
  • photopolymerizable monomer refers to a compound that is a monomer among photocurable resins.
  • the amount of the photocurable resin in the curable resin composition is not particularly limited as long as the effect of the present invention is exhibited, for example, 10 to 50 in terms of solid content with respect to the total mass of the curable resin composition % by mass or the like.
  • the curable resin may preferably contain a carboxyl group-containing resin in order to impart alkaline developability to the curable resin composition.
  • a carboxyl group-containing resin conventionally known various resins having a carboxyl group in the molecule can be used. Specific examples of carboxyl group-containing resins include the following compounds (both oligomers and polymers).
  • Carboxyl group-containing resins obtained by copolymerizing unsaturated carboxylic acids such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene, ⁇ -methylstyrene, lower alkyl (meth)acrylates, and isobutylene.
  • Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates; Polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, carboxyl group-containing urethane resins obtained by polyaddition reaction of diol compounds such as compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.
  • a diisocyanate 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 bixylenol type epoxy resin, or a biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin produced by a polyaddition reaction of a partial acid anhydride-modified reaction product with a monocarboxylic acid compound having an ethylenically unsaturated group such as meth)acrylic acid, a carboxyl group-containing dialcohol compound, and a diol compound.
  • a bifunctional 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 bixylenol type epoxy resin, or a biphenol type epoxy resin
  • a carboxyl group-containing photosensitive urethane resin produced by a polyaddition reaction of
  • one isocyanate group and one or more (meth)acryloyl groups are added in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.
  • a carboxyl group-containing photosensitive resin obtained by reacting (meth)acrylic acid with a polyfunctional (solid) epoxy resin having two or more functionalities and adding a dibasic acid anhydride to the hydroxyl groups present in the side chains.
  • Group-containing photosensitive resin A carboxyl obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the resulting hydroxyl group.
  • a bifunctional oxetane resin is reacted with a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid, and the resulting primary hydroxyl group is treated with a dibasic such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.
  • a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid
  • a dibasic such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.
  • Carboxyl group-containing polyester resin to which acid anhydride is added.
  • an epoxy compound having a plurality of epoxy groups in one molecule a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol;
  • Maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipine are reacted with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and the alcoholic hydroxyl group of the resulting reaction product is treated with A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid.
  • (11) Obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with a monocarboxylic acid containing an unsaturated group.
  • a carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.
  • a carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins (1) to (11).
  • (meth)acrylate is a generic term for acrylate, methacrylate and mixtures thereof, and the same applies to other similar expressions.
  • photosensitive resin a resin synthesized according to the procedure described in Examples described later can also be used.
  • the acid value of the carboxyl group-containing resin is suitably in the range of 30-150 mgKOH/g, more preferably in the range of 50-120 mgKOH/g.
  • the acid value of the carboxyl group-containing resin is 30 mgKOH/g or more, alkaline development can be performed appropriately. It is preferable because the exposed area and the unexposed area can be separated by dissolution and separation, and normal resist pattern drawing is facilitated.
  • the weight-average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, it is generally preferably in the range of 2,000 to 150,000, more preferably in the range of 5,000 to 100,000.
  • the weight-average molecular weight is 2,000 or more, the moisture resistance of the coating film after exposure is good, film reduction does not occur during development, and excellent resolution can be easily obtained.
  • the weight average molecular weight is 150,000 or less, good developability is likely to be obtained, and good storage stability is likely to be obtained.
  • Weight average molecular weight can be measured by gel permeation chromatography (GPC).
  • the curable resin composition of the present invention contains barium sulfate with an oil absorption of 40 to 70 mL/100 g.
  • the solder resist which is a cured product of the curable resin composition, maintains low glossiness over time and is thereby brought about. It is possible to provide a high level of resistance to solder adhesion over time and withstand voltage.
  • the oil absorption of barium sulfate is preferably 45-70 mL/100 g, more preferably 45-65 mL/100 g, and even more preferably 50-60 mL/100 g.
  • the oil absorption of barium sulfate can be measured according to the method defined by Japanese Industrial Standards (JIS K5101-13-1).
  • untreated barium sulfate may be used, or chemically and/or physically treated barium sulfate may be used.
  • treated barium sulfate for example, surface-treated barium sulfate can be used.
  • substances for surface-treating barium sulfate include inorganic substances such as silica and alumina. Among them, it is particularly preferable to use barium sulfate surface-treated with silica by multiple treatments (also referred to as “multi-treatment processing”).
  • the multi-treatment is a treatment in which a substance to be surface-treated (for example, silica, alumina, etc.) adheres to the surface of the barium sulfate to be surface-treated so that it exists very thickly.
  • a substance to be surface-treated for example, silica, alumina, etc.
  • Examples of commercial products of barium sulfate surface-treated with silica include PFS-701 manufactured by Ishihara Sangyo Co., Ltd., and the like.
  • Barium sulfate especially barium sulfate surface-treated with silica, has high matting performance compared to conventional matting agents, and by adding a small amount of barium sulfate surface-treated with silica to the curable resin composition, it is high. A matte effect can be obtained. Therefore, the inclusion of air bubbles in the curable resin composition, which is a problem when blending the matting agent, and the remaining air bubbles in the solder resist formed by curing the curable resin composition are suppressed, and as a result, , the decrease in voltage resistance of the solder resist can be suppressed. Furthermore, in general, when a matting agent is added to a resin composition, the viscosity of the resin composition increases.
  • barium sulfate By using the treated barium sulfate, an increase in the viscosity of the curable resin composition can be suppressed, and as a result, deterioration in printability of the curable resin composition onto the substrate can be suppressed. Furthermore, barium sulfate, especially barium sulfate surface-treated with silica, has high acid resistance (acid resistance). Therefore, by blending barium sulfate as a matting agent in the curable resin composition, the curable resin composition has high acid resistance, and as a result, it is highly resistant to tin plating etc. performed under strong acidity. (Tin plating resistance).
  • the amount of barium sulfate with an oil absorption of 40 to 70 mL/100 g is not particularly limited as long as the effect of the present invention is exhibited. , preferably 30 to 74% by mass, more preferably 40 to 70% by mass, and still more preferably 45 to 67% by mass in terms of solid content.
  • thermosetting catalyst The curable resin composition of the present invention contains a thermosetting catalyst.
  • thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl)-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzyl Amine compounds such as amines, 4-methoxy-N,N-dimethylbenzylamine and 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide;
  • commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2PHZ-PW, 2P4BHZ, and 2P4MHZ manufactured by Shikoku Kasei Co., Ltd. (all are trade names of imidazole compounds), manufactured by San-Apro Co., Ltd. U-CAT 3513N (trade name of dimethylamine compounds), DBU, DBN, U-CAT SA 102 (both of which are bicyclic amidine compounds and salts thereof).
  • thermosetting catalyst for an epoxy resin or an oxetane compound or any one that promotes the reaction between at least one of an epoxy group and an oxetanyl group and a carboxyl group.
  • a mixture of seeds or more may be used.
  • thermosetting catalyst 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as S-triazine/isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adducts can also be used, and these adhesion-imparting agents are preferred.
  • a compound that also functions is used in conjunction with a thermosetting catalyst.
  • One of the thermosetting catalysts may be used alone, or two or more thereof may be used in combination.
  • the content of the thermosetting catalyst is preferably 2 to 30 parts by mass, more preferably 5 to 25 parts by mass, based on 100 parts by mass of the thermosetting resin.
  • the curable resin composition of the present invention contains a photosensitive resin
  • the curable resin composition preferably contains a photopolymerization initiator. Any known photopolymerization initiator can be used.
  • a photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.
  • photopolymerization initiators 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-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide , bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2, bisacylphosphine oxides such as 4,6-trimethylbenzoyl)-phenylphosphine oxide; 2,6-dimeth
  • a photoinitiation aid or a sensitizer may be used in combination with the photopolymerization initiator described above.
  • photoinitiation aids or sensitizers include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds.
  • Thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone are particularly preferred.
  • Inclusion of a thioxanthone compound can improve deep-part curability.
  • These compounds can be used as a photopolymerization initiator in some cases, but are preferably used in combination with the photopolymerization initiator.
  • the photoinitiation aids or sensitizers may be used singly or in combination of two or more
  • photopolymerization initiators since these photopolymerization initiators, photoinitiator aids, and sensitizers absorb specific wavelengths, the sensitivity may be lowered in some cases, and they may function as ultraviolet absorbers. However, these are not used only for the purpose of improving the sensitivity of the curable resin composition. It absorbs light of a specific wavelength as needed to increase the photoreactivity of the surface, change the line shape and opening of the resist to vertical, tapered, and reverse tapered shapes, and improve the accuracy of the line width and opening diameter. can be improved.
  • the curable resin composition of the present invention may contain a filler other than barium sulfate as described above, if necessary, in order to increase the physical strength of the coating film, etc., as long as the effects of the present invention are not impaired. good.
  • fillers known inorganic or organic fillers can be used, and various types of silica (for example, finely divided silica, spherical silica, etc.), hydrotalcite and talc are particularly preferably used.
  • metal oxides and metal hydroxides such as aluminum hydroxide can be used as extender fillers in order to obtain a white appearance and flame retardancy.
  • the curable resin composition of the present invention can be blended with an organic solvent for the purpose of preparing the curable resin composition and adjusting the viscosity when applied to a substrate or film.
  • organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether; , dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, buty
  • Volatilization drying of organic solvents is carried out by using a hot air circulating drying furnace, IR furnace, hot plate, convection oven, etc. (equipped with a heat source that heats the air using steam), and a method in which the hot air in the dryer is brought into contact with the counter current and supported by a nozzle. method of spraying on the body) can be used.
  • the curable resin composition of the present invention may optionally further contain a coloring agent, an elastomer, a mercapto compound, a urethanization catalyst, a thixotropic agent, an adhesion promoter, a block copolymer, a chain transfer agent, a polymerization inhibitor, copper damage inhibitor, antioxidant, rust inhibitor, organic bentonite, thickener such as montmorillonite, at least one of silicone-based, fluorine-based, polymer-based defoaming agent and leveling agent, imidazole-based, Components such as a thiazole-based or triazole-based silane coupling agent, a phosphinate, a phosphoric acid ester derivative, a phosphorus compound such as a phosphazene compound, and other flame retardants can be blended.
  • a coloring agent an elastomer, a mercapto compound, a urethanization catalyst, a thixotropic agent, an adhesion
  • the curable resin composition of the present invention may be used as a dry film or as a liquid. Moreover, when it is used as a liquid, it may be one-liquid or two-liquid or more.
  • the cured product of the present invention is obtained by curing the curable resin composition of the present invention described above, and maintains low glossiness over time and the resulting solder adhesion resistance over time and resistance to It is compatible with voltage characteristics at a high level.
  • the cured product of the present invention is, for example, a solder resist having a thickness of 1 to 150 ⁇ m, especially a matte solder resist.
  • the printed wiring board of the present invention has a cured product obtained from the curable resin composition of the present invention described above.
  • the curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method using an organic solvent, and is coated on the substrate by a dip coating method, a flow After applying by a method such as coating method, roll coating method, bar coating method, screen printing method, curtain coating method, etc., the organic solvent contained in the composition is volatilized and dried (temporary drying) at a temperature of 60 to 100 ° C. to form a tack-free resin layer.
  • the substrate examples include printed wiring boards and flexible printed wiring boards on which circuits are formed in advance using copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy. , Synthetic fiber epoxy, fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, and other materials such as copper-clad laminates for high-frequency circuits, all grades (FR-4, etc.) of copper-clad laminates. Plates, metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates and the like can also be used.
  • PEN polyethylene naphthalate
  • Volatilization drying performed after applying the curable resin composition of the present invention can be performed using a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, etc.
  • a method of bringing hot air into countercurrent contact and a method of blowing hot air onto the support from a nozzle) can be used.
  • a resin layer on the substrate After forming a resin layer on the substrate, it is selectively exposed to active energy rays through a photomask having a predetermined pattern, and the unexposed area is treated with a dilute alkaline aqueous solution (eg, 0.3 to 3% by mass aqueous solution of sodium carbonate). to form a pattern of the cured product. Furthermore, after irradiating the cured product with active energy rays, heat curing (e.g., 100 to 220 ° C), or after heat curing, irradiating the active energy rays, or final final curing (main curing) only by heat curing. Forms a cured coating film with excellent properties such as toughness and hardness.
  • a dilute alkaline aqueous solution eg, 0.3 to 3% by mass aqueous solution of sodium carbonate
  • the exposure machine used for the active energy ray irradiation may be any device equipped with a high-pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, mercury short arc lamp, etc., and irradiating ultraviolet rays in the range of 350 to 450 nm.
  • a direct writing device eg, a laser direct imaging device that draws an image with a laser directly from CAD data from a computer
  • the lamp light source or laser light source of the direct drawing machine may have a maximum wavelength in the range of 350 to 450 nm.
  • the amount of exposure for image formation varies depending on the film thickness and the like, but can generally be in the range of 10-1000 mJ/cm 2 , preferably in the range of 20-800 mJ/cm 2 .
  • a developing method As a developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be used. , amines, etc. can be used.
  • a solution of a photocurable resin (an aromatic ring-containing carboxyl group-containing resin) used in this example was prepared according to the following procedure. 1070 g of ortho-cresol novolac type epoxy resin (EPICLON N-695, manufactured by DIC Corporation), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were added to 600 g of diethylene glycol monoethyl ether acetate and heated at 100°C. A solution was obtained by stirring until the mixture became uniform.
  • ortho-cresol novolac type epoxy resin EPICLON N-695, manufactured by DIC Corporation
  • Thermosetting resin phenol novolac epoxy resin (N-770, manufactured by DIC Corporation)
  • Photocurable resin (photosensitive resin) carboxyl group-containing resin solution having an aromatic ring prepared by the method described above, compounding amount is the value in terms of solid content
  • Photocurable resin (photopolymerizable monomer) dipentaerythritol hexa Acrylate (manufactured by Nippon Kayaku Co., Ltd.) Blue colorant: organic colorant phthalocyanine blue Yellow coloring agent: Organic coloring agent Chromophthalo Yellow Antifoaming agent: Polydimethylsiloxane (KS-66, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Photoinitiator 1 Bis ( ⁇ 5-2,4-cyclopentadien-1-yl) - bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium (Irgacure 784, BASF Japan Co., Ltd.) Photo
  • glossiness evaluation The glossiness of the cured product of each curable resin composition of Examples and Comparative Examples formed on each evaluation substrate was measured using a gloss meter Micro Trigloss manufactured by BYK-Chemie 60 ° specular reflection measured as a percentage. In addition, the evaluation of the glossiness is performed for each of the five evaluation substrates, and the second decimal place of the average value of the glossiness of the five evaluation substrates is rounded off to the first decimal place. expressed. Based on the numerical values obtained, glossiness was evaluated according to the following criteria. Table 1 shows the glossiness values and evaluation results. A: The glossiness is less than 10 and has an extremely low glossiness. ⁇ : The glossiness is 10 or more and less than 20, and has a sufficiently low glossiness. x: Glossiness is 20 or more and does not have low glossiness.
  • each curable resin composition of Examples and Comparative Examples was stored at 30 ° C. for 6 months after preparation, and then subjected to the same test for each evaluation substrate prepared, and the glossiness over time was measured according to the same criteria. evaluated.
  • Table 1 shows the values of the glossiness over time and the evaluation results.
  • solder adhesion resistance Using a flow soldering device on each evaluation board, without applying flux, in the atmosphere, the solder is flowed at a solder temperature of 260 ° C., a double wave, and a conveyor speed of 1.4 m / min, and then on each evaluation board. The adhesion state of solder on the surface of the cured product of the curable resin composition was visually observed, and solder adhesion resistance was evaluated according to the following criteria. Table 1 shows the evaluation results. In this evaluation, a copper circuit pattern board was used instead of the copper solid board in the production of the evaluation board, and the entire surface coating by screen printing in Examples 1 and 2 and Comparative Examples 1 and 2 was pattern printed.
  • evaluation substrates prepared in the same manner as in Examples 3 to 6 and Comparative Examples 3 to 6 were used, except that pattern exposure was used.
  • ⁇ No adhesion of solder was observed on the surface of the cured product, and the resistance to solder adhesion was good.
  • x Spike-like and web-like solder adhesion was observed, and the solder adhesion resistance was poor.
  • each curable resin composition of Examples and Comparative Examples was stored at 30 ° C. for 6 months after preparation, and then subjected to the same test for each evaluation board prepared. Evaluated according to criteria. Table 1 shows the evaluation results.
  • Each value of the dielectric breakdown voltage (kV / 0.05 mm) in Table 1 is the value of the dielectric breakdown voltage of each evaluation substrate having a cured coating film with a thickness of 25 ⁇ m (0.025 mm) to 0.05 mm. It is converted.
  • ⁇ Dielectric breakdown voltage is 5 kV/0.05 mm or more, and extremely high voltage resistance.
  • x The dielectric breakdown voltage is less than 5 kV/0.05 mm, and the withstand voltage is insufficient.
  • Each substrate for evaluation was tin-plated using a commercially available electroless tin-plating bath under conditions of 1 ⁇ 0.2 ⁇ m of tin. After visually observing the cured product of the curable resin composition on each substrate for evaluation after plating, the presence or absence of peeling of the cured product was confirmed by tape peeling, and the acid resistance was evaluated according to the following criteria. Table 1 shows the evaluation results. In this evaluation, a copper circuit pattern board was used instead of the copper solid board in the production of the evaluation board, and the entire surface coating by screen printing in Examples 1 and 2 and Comparative Examples 1 and 2 was pattern printed. Instead, evaluation substrates prepared in the same manner as in Examples 3 to 6 and Comparative Examples 3 to 6 were used, except that pattern exposure was used. ⁇ : Neither peeling nor whitening of the cured product was observed, and the acid resistance was sufficiently high. x: Peeling and whitening of the cured product are observed, and the acid resistance is insufficient.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

[Problème] Fournir une composition de résine durcissable permettant de former des réserves de soudure qui combinent une faible brillance durable et une liberté à long terme résultante de l'adhérence de soudure avec une tension de tenue à un niveau élevé. [Solution] Composition de résine durcissable comprenant une résine durcissable, du sulfate de baryum et un catalyseur de durcissement thermique, le sulfate de baryum ayant une absorption d'huile de 40 à 70 ml/100 g.
PCT/JP2022/043882 2021-11-30 2022-11-29 Composition de résine durcissable, objet durci, carte de circuit imprimé et procédé de production de carte de circuit imprimé WO2023100843A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017057356A (ja) * 2015-09-18 2017-03-23 関西ペイント株式会社 水性クリヤー塗料組成物
JP2020200449A (ja) * 2019-06-04 2020-12-17 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物、およびプリント配線板
CN113698669A (zh) * 2021-09-07 2021-11-26 河北辛集化工集团有限责任公司 白炭黑改性纳米硫酸钡及其制备方法和应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017057356A (ja) * 2015-09-18 2017-03-23 関西ペイント株式会社 水性クリヤー塗料組成物
JP2020200449A (ja) * 2019-06-04 2020-12-17 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物、およびプリント配線板
CN113698669A (zh) * 2021-09-07 2021-11-26 河北辛集化工集团有限责任公司 白炭黑改性纳米硫酸钡及其制备方法和应用

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