WO2016157587A1 - 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 - Google Patents
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 Download PDFInfo
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- WO2016157587A1 WO2016157587A1 PCT/JP2015/080454 JP2015080454W WO2016157587A1 WO 2016157587 A1 WO2016157587 A1 WO 2016157587A1 JP 2015080454 W JP2015080454 W JP 2015080454W WO 2016157587 A1 WO2016157587 A1 WO 2016157587A1
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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- 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
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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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
Definitions
- the present invention relates to a curable resin composition (hereinafter, also simply referred to as “composition”), a dry film, a cured product, and a printed wiring board.
- composition a curable resin composition
- dry film a dry film
- present invention relates to a cured product and a printed wiring board.
- a printed wiring board is generally obtained by etching a copper foil bonded to a laminated board in accordance with circuit wiring, and electronic components are arranged at predetermined locations and soldered.
- the solder resist film is used as a protective film for a circuit when an electronic component is soldered to such a printed wiring board.
- This solder resist film prevents solder from adhering to unnecessary parts during soldering, and prevents the circuit conductor from being directly exposed to air and corroded by oxygen or moisture. Furthermore, it functions as a permanent protective film for the circuit board. Therefore, various properties such as adhesion, electrical insulation, solder heat resistance, solvent resistance, and chemical resistance are required.
- Patent Document 1 and Patent Document 2 development is possible with an aqueous alkali solution using a reaction product obtained by reacting a novolak type epoxy resin with an unsaturated monocarboxylic acid and further adding a polybasic acid anhydride as a base polymer.
- a liquid resist ink composition is disclosed.
- LEDs light-emitting diodes
- backlights for liquid crystal displays in portable terminals, personal computers, televisions, etc., and light sources for lighting fixtures have been applied to printed wiring boards coated with solder resist films.
- Applications for direct mounting are increasing.
- Patent Document 3 discloses a white curable solder resist composition containing a carboxyl group-containing resin having no aromatic ring and rutile titanium oxide. Yes.
- an object of the present invention is to provide a curable resin composition, a dry film, a cured product, and a printed wiring board having high reflectivity in addition to characteristics as a solder resist such as solder heat resistance.
- the inventor has used a whitening agent such as titanium oxide, a fluorescent whitening agent, and at least one selected from an isocyanate compound and a coupling agent in combination, and a curable resin composition.
- a whitening agent such as titanium oxide, a fluorescent whitening agent, and at least one selected from an isocyanate compound and a coupling agent in combination
- a curable resin composition In addition to the characteristics as a solder resist such as solder heat resistance, it has been found that it can achieve a high reflectance by using it in a product, and the present invention has been completed.
- the curable resin composition of the present invention is selected from (A) a curable resin, (B) a white colorant, (C) a fluorescent whitening agent, (D) an isocyanate compound and a coupling agent. And at least any one of the above.
- the dry film of the present invention is characterized by having a resin layer obtained by applying and drying the curable resin composition of the present invention on the film.
- the cured product of the present invention is obtained by curing a curable resin composition of the present invention or a resin layer obtained by applying and drying the curable resin composition of the present invention. It is what.
- the printed wiring board of the present invention is characterized by having the cured product of the present invention.
- the curable resin composition of the present invention is at least selected from (A) a curable resin, (B) a white colorant, (C) a fluorescent whitening agent, (D) an isocyanate compound and a coupling agent. It is characterized in that any one of them is contained. Thereby, in addition to the characteristics as a solder resist such as solder heat resistance, a curable resin composition having high reflectance can be obtained.
- (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
- the curable resin composition of the present invention contains (A) a curable resin.
- the (A) curable resin used in the present invention is (A-1) a thermosetting resin or (A-2) a photocurable resin, and may be a mixture thereof.
- thermosetting resin may be any resin that is cured by heating and exhibits electrical insulation, and examples thereof include epoxy compounds, oxetane compounds, melamine resins, and silicone resins.
- epoxy compounds oxetane compounds
- melamine resins melamine resins
- silicone resins silicone resins.
- an epoxy compound and an oxetane compound can be suitably used, and these may be used in combination.
- epoxy compound known and commonly used compounds having one or more epoxy groups can be used, and among them, compounds having two or more epoxy groups are preferable.
- monoepoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, glycidyl (meth) acrylate, bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin , Cycloaliphatic epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4′-diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol or propylene glycol Diglycidyl ether, sorbitol polyglycidyl ether, tris (2,3-epoxypropyl) isocyanurate, trigly
- oxetane compound containing an oxetane ring represented by include 3-ethyl-3-hydroxymethyloxetane (Toago Synthetic Co., Ltd., trade name OXT-101), 3-ethyl-3- (phenoxymethyl) oxetane (Toagosei Co., Ltd., trade name OXT-211), 3-ethyl-3- (2-ethylhexyl) Siloxymethyl) oxetane (trade name OXT-212, manufactured by Toagosei Co., Ltd.), 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene (trade name, manufactured by Toagosei Co., Ltd.) OXT-101, 3-ethyl-3- (phenoxymethyl) oxetane (Toagosei Co., Ltd., trade name OXT-211), 3-ethyl-3
- the photo-curable resin may be any resin that is cured by irradiation with active energy rays and exhibits electrical insulation properties.
- the photo-curable resin may be any resin that is cured by irradiation with active energy rays and exhibits electrical insulation properties.
- one or more ethylenic resins in the molecule A compound having an unsaturated bond is preferably used.
- photopolymerizable oligomers As the compound having an ethylenically unsaturated bond, known and commonly used photopolymerizable oligomers, photopolymerizable vinyl monomers, and the like are used.
- examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers.
- Examples of (meth) acrylate oligomers include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, epoxy (meth) acrylates such as bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meta ) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like.
- photopolymerizable vinyl monomer known and commonly used monomers, for example, styrene derivatives such as styrene, chlorostyrene and ⁇ -methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide (Meth) acrylamides such as rilamide and N-butoxymethylacrylamide; allyl compounds such as triallyl isocyan
- (A-3) carboxyl group-containing resin) In the case where the thermosetting reaction with the epoxy resin is promoted in the composition of the present invention, or when the composition of the present invention is an alkali development type photosensitive resin composition, (A) a curable resin, It is preferable to use a carboxyl group-containing resin.
- the carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group, and may or may not have an aromatic ring.
- a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
- an unsaturated carboxylic acid such as (meth) acrylic acid
- an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
- Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers
- a carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
- this carboxyl group-containing urethane resin has an aromatic ring, it is sufficient that at least one of diisocyanate, a carboxyl group-containing dialcohol compound and a diol compound has an aromatic
- Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems
- a terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
- Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin
- Photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its modified partial anhydride, carboxyl group-containing dialcohol compound and diol compound.
- this photosensitive carboxyl group-containing urethane resin has an aromatic ring
- at least one of diisocyanate, bifunctional epoxy resin (meth) acrylate or its partial acid anhydride modified product, carboxyl group-containing dialcohol compound and diol compound is aromatic. It only needs to have a ring.
- one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.
- the carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated When this photosensitive carboxyl group-containing urethane resin has an aromatic ring, a compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule may have an aromatic ring.
- a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride
- this photosensitive carboxyl group-containing resin has an aromatic ring, it is sufficient that at least one of a bifunctional epoxy resin and a dibasic acid anhydride has an aromatic ring.
- a carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
- this photosensitive carboxyl group-containing polyester resin has an aromatic ring, it is sufficient that at least one of a polyfunctional oxetane resin, dicarboxylic acid and dibasic acid anhydride has an aromatic ring.
- Reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with an unsaturated group-containing monocarboxylic acid.
- a carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.
- (11) Obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a reaction product obtained by reacting a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with an unsaturated group-containing monocarboxylic acid.
- a carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.
- 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, and (meth) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid.
- this photosensitive carboxyl group-containing polyester resin has an aromatic ring, an epoxy compound, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in a molecule, an unsaturated group-containing monocarboxylic acid and a polybasic It suffices that at least one of the acid anhydrides has an aromatic ring.
- One epoxy group and one or more (meth) acryloyl groups in the molecule such as glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate and the like in any one of the resins (1) to (12) above
- a photosensitive carboxyl group-containing resin obtained by adding a compound having a group.
- this photosensitive carboxyl group-containing urethane resin has an aromatic ring
- a compound having one epoxy group and one or more (meth) acryloyl groups in the molecule may have an aromatic ring.
- the carboxyl group-containing resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
- the carboxyl group-containing resin obtained by the copolymerization of (1) is preferable in that it is excellent in suppressing the decrease in reflectance due to heat and the color change. Moreover, it is preferable to use a carboxyl group-containing resin derived from styrene or a styrene derivative because a composition having excellent solder heat resistance can be obtained. Furthermore, it is preferable to use a non-photosensitive carboxyl group-containing resin because a composition having excellent solder heat resistance can be obtained.
- the acid value of the carboxyl group-containing resin is preferably in the range of 20 to 200 mgKOH / g, more preferably in the range of 40 to 180 mgKOH / g.
- it is in the range of 20 to 200 mg KOH / g, adhesion of the coating film is obtained, alkali development is facilitated, dissolution of the exposed area by the developer is suppressed, and the line does not fade more than necessary, and normal This is preferable because the resist pattern can be easily drawn.
- the weight average molecular weight of the carboxyl group-containing resin used in the present invention varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000. Within this range, tack-free performance is good, the moisture resistance of the coated film after exposure is good, and film loss is less likely to occur during development. Further, when the weight average molecular weight is within the above range, the resolution is improved, the developability is good, and the storage stability is improved. More preferably, it is 5,000 to 100,000.
- the weight average molecular weight can be measured by gel permeation chromatography.
- the equivalent of the epoxy group contained in an epoxy resin is 2 with respect to 1 equivalent of the carboxyl group contained in carboxyl group-containing resin.
- 0.0 or less is preferable because yellowing resistance is good, more preferably 1.5 or less, and even more preferably 1.0 or less. This is because if an epoxy group is contained, the color tends to change easily.
- the white colorant examples include titanium oxide, zinc oxide, potassium titanate, zirconium oxide, antimony oxide, lead white, zinc sulfide, lead titanate, and the like, since the effect of suppressing discoloration due to heat is high. It is preferable to use titanium oxide.
- the composition of the present invention can be white, and a high reflectance can be obtained.
- the titanium oxide may be a rutile type, anatase type, or ramsdellite type titanium oxide, and may be used alone or in combination of two or more.
- ramsdellite-type titanium oxide can be obtained by subjecting ramsdellite-type Li 0.5 TiO 2 to a lithium desorption treatment by chemical oxidation.
- rutile type titanium oxide when using rutile type titanium oxide, heat resistance can be further improved, discoloration caused by light irradiation is less likely to occur, and quality can be hardly deteriorated even under severe use environment. preferable.
- a rutile type titanium oxide surface-treated with aluminum oxide such as alumina or silica deterioration against light can be suppressed, and reflectance and heat resistance can be further improved.
- another surface treatment can be performed.
- the reflectance can be further improved by surface-treating with alumina and further surface-treating with zirconia.
- the content of rutile titanium oxide surface-treated from aluminum oxide in the total titanium oxide is preferably 10% by mass or more, more preferably 30% by mass. %, And the upper limit is 100% by mass or less. That is, the entire amount of titanium oxide may be rutile-type titanium oxide surface-treated with the aluminum oxide.
- the rutile titanium oxide surface-treated with the above aluminum oxide include, for example, CR-58 manufactured by Ishihara Sangyo Co., Ltd., which is rutile chlorine-based titanium oxide, and R manufactured by the company, which is rutile sulfuric acid-based titanium oxide. -630 or the like.
- rutile type titanium oxide surface-treated with silicon oxide it is also preferable to use rutile type titanium oxide surface-treated with silicon oxide, and in this case, the heat resistance can be further improved. Furthermore, it is also preferable to use rutile type titanium oxide surface-treated with both aluminum oxide and silicon oxide, such as CR-90 manufactured by Ishihara Sangyo Co., Ltd., which is rutile type chlorinated titanium oxide. It is done.
- anatase type titanium oxide has lower hardness than that of rutile type, when anatase type titanium oxide is used, it is better in terms of moldability of the composition.
- titanium oxide may contain sulfur
- the amount of sulfur is preferably 100 ppm or less, and more preferably 60 ppm or less. This is because when the sulfur amount is 100 ppm or less, discoloration of the peripheral portion due to the generated sulfur gas does not occur.
- the blending amount of the white colorant (B) is preferably 5 to 80 with respect to the solid content in the resin composition (in the case where the resin composition contains an organic solvent, the component excluding the organic solvent). It is in the range of mass%, more preferably in the range of 10 to 70 mass%.
- the (C) fluorescent whitening agent used in the present invention is one that can increase the whiteness of the cured product of the composition and make it appear as if it is not discolored.
- the (B) white colorant and the (C) fluorescent whitening agent can be used to achieve high reflectance in the cured coating film. It becomes possible.
- Fluorescent whitening agent absorbs light having a wavelength of 200 to 400 nm and emits light having a wavelength of 400 to 500 nm.
- fluorescent dyes include benzoxazoyl derivatives, coumarin derivatives, styrene biphenyl derivatives, pyrazolone derivatives, bis (triazinylamino) stilbene disulfonic acid derivatives, and the like. Of these, benzoxazoyl derivatives are preferred.
- a substituent which a benzoxazoyl derivative has butyl, octyl, naphthalene, thiophene, and stilbene are preferable.
- the blending amount of the (C) fluorescent whitening agent in the composition of the present invention is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7 parts by mass with respect to 100 parts by mass of the (A) curable resin. Part. (C) By making the compounding quantity of a fluorescent whitening agent into said range, a high reflectance can be achieved.
- the curable resin composition of the present invention contains at least one selected from (D) an isocyanate compound and a coupling agent.
- (D) By containing at least one selected from an isocyanate compound and a coupling agent, absorption by a 400-420 nm fluorescent whitening agent is further promoted, and the effect of the fluorescent whitening agent at 440-470 nm is achieved. That is, improvement in reflectance can be promoted.
- ((D-1) Isocyanate compound) (D-1)
- As the isocyanate compound known isocyanate compounds such as a monoisocyanate compound having one isocyanate group and a polyisocyanate having two or more isocyanate groups can be used. In the present invention, a blocked isocyanate compound is preferred from the viewpoint of improving workability because of excellent storage stability.
- polyisocyanate compound for example, aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate are used.
- aromatic polyisocyanate examples include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene. Mention may be made of diisocyanate, diphenylmethylene diisocyanate and 2,4-tolylene dimer.
- aliphatic polyisocyanate examples include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate.
- alicyclic polyisocyanate examples include bicycloheptane triisocyanate.
- the adduct body, burette body, and isocyanurate body of the isocyanate compound mentioned above can be mentioned.
- the blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.
- blocked isocyanate compound an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used.
- examples of the isocyanate compound that can react with the blocking agent include the polyisocyanate compounds described above.
- isocyanate blocking agent examples include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ⁇ -caprolactam, ⁇ -palerolactam, ⁇ -butyrolactam and ⁇ -propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, Alcohol blocking agents such as methyl acid and ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl e
- Amine-based blocking agents include imidazole-based blocking agents such as imidazole and 2-ethylimidazole; imine-based blocks such as methyleneimine and propyleneimine Agents; pyrazole block agents such as dimethylpyrazole; maleate ester block agents such as diethylmaleic acid.
- Examples of the blocked isocyanate compound include those commercially available, for example, Sumidur (registered trademark) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur (registered trademark) TPLS-2957, TPLS-2062, TPLS.
- Such isocyanate compounds can be used alone or in combination of two or more.
- a silane coupling agent a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, or the like
- a silane coupling agent can be suitably used.
- the silane coupling agent is composed of an organic substance (organic group) and silicon.
- organic group organic group
- silicon organic substance
- XnR ′ (n ⁇ 1) Si—R ′′ —Y vinyl group, epoxy group, A styryl group, a methacryloxy group, an acryloxy group, an amino group, a ureido group, a chloropropyl group, a mercapto group, a polysulfide group, an isocyanate group, etc.
- a silane coupling agent contains two or more silane coupling agents in the molecule. Since it has different reactive groups, it acts as an intermediary between organic and inorganic materials, which are usually very difficult to bond, and is used for improving the strength of composite materials, modifying resins, and modifying surfaces.
- silane coupling agent examples are as follows. N- ⁇ - (aminoethyl) - ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylphenyldiethoxysilane, 2-amino-1-methylethyltriethoxysilane, N-methyl- ⁇ -aminopropyltriethoxysilane, N-phenyl- ⁇ -aminopropyltriethoxysilane, N-butyl- ⁇ -aminopropylmethyldiethoxysilane, N- ⁇ - (aminoe
- silane coupling agents examples include KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM- 502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-9103, KBM-573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007 (all trade names; manufactured by Shin-Etsu Silicone Co., Ltd.) . These can be used alone or in combination of two or more.
- the total amount of (D-1) isocyanate compound and (D-2) coupling agent in the composition of the present invention is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of (A) curable resin. More preferably, it is 0.2 to 30 parts by mass. In the case of the (D-1) isocyanate compound, 0.2 to 20 parts by mass is more preferable, while in the case of the (D-2) coupling agent, 0.2 to 25 parts by mass is more preferable, and 0.2 to 15 parts by mass. Part by mass is particularly preferred.
- At least one of (E-1) curing agent and (E-2) curing catalyst In the composition of the present invention, when (A-1) a thermosetting resin is used, at least one of (E-1) curing agent and (E-2) curing catalyst should be added. Can do.
- Examples of the curing agent include polyfunctional phenol compounds, polycarboxylic acids and acid anhydrides thereof, aliphatic or aromatic primary or secondary amines, polyamide resins, polymercapto compounds, and the like.
- polyfunctional phenol compounds, polycarboxylic acids and acid anhydrides thereof are preferably used from the viewpoints of workability and insulation.
- any compound having two or more phenolic hydroxyl groups in one molecule may be used, and known ones can be used. Specific examples include phenol novolac resins, cresol novolac resins, bisphenol A, allylated bisphenol A, bisphenol F, bisphenol A novolac resins, vinyl phenol copolymer resins, and the like, which have high reactivity and increase heat resistance.
- a phenol novolac resin is particularly preferable because of its high effect.
- Such a polyfunctional phenol compound undergoes an addition reaction with at least one of an epoxy compound and an oxetane compound in the presence of a suitable curing catalyst.
- Polycarboxylic acids and acid anhydrides thereof are compounds having two or more carboxyl groups in one molecule and acid anhydrides thereof, such as (meth) acrylic acid copolymer and maleic anhydride copolymer. And condensates of dibasic acids.
- Examples of the commercially available products include Jonkrill (product group name) manufactured by BASF Japan, SMA resin (product group name) manufactured by Sartomer, and polyazeline acid anhydride manufactured by Shin Nippon Chemical Co., Ltd.
- the (E-2) curing catalyst does not use a compound that can be a curing catalyst in the reaction of at least one of an epoxy compound and an oxetane compound with the curing agent (E-1) or a curing agent. In some cases, it is a compound that becomes a polymerization catalyst.
- the curing catalyst include a tertiary amine, a tertiary amine salt, a quaternary onium salt, a tertiary phosphine, a crown ether complex, and a phosphonium ylide. Or two or more types can be used in combination.
- imidazoles such as trade names 2E4MZ, C11Z, C17Z and 2PZ
- AZINE compounds of imidazoles such as trade names 2MZ-A and 2E4MZ-A
- isocyanurates of imidazoles such as trade names 2MZ-OK and 2PZ-OK.
- Imidazole hydroxymethyl compounds such as trade names 2PHZ and 2P4MHZ (both trade names are manufactured by Shikoku Chemicals Co., Ltd.), dicyandiamide and derivatives thereof, melamine and derivatives thereof, diaminomaleonitrile and derivatives thereof, diethylenetriamine, triethylenetetramine, Amines such as tetraethylenepentamine, bis (hexamethylene) triamine, triethanolamine, diaminodiphenylmethane, organic acid dihydrazide, 1,8-diazabicyclo [5,4,0] undecene-7 (trade name D U, manufactured by San Apro Co., Ltd.), 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (trade name ATU, manufactured by Ajinomoto Co., Inc.), Alternatively, organic phosphine compounds such as triphenylphosphine, tricyclohexylphosphine,
- the blending amount of at least one of these (E-1) curing agent and (E-2) curing catalyst is sufficient in a usual ratio, and (A-1) relative to 100 parts by mass of the thermosetting resin.
- the amount is preferably 0.01 to 40 parts by mass, more preferably 0.05 to 30 parts by mass.
- the composition of the present invention preferably further contains (F) an antioxidant.
- an antioxidant By containing an antioxidant, it is possible to prevent the oxidative deterioration of the curable resin and the like and to suppress discoloration. In addition, the heat resistance is improved and the resolution (line width) is improved. The effect that the reproducibility is improved can also be obtained. That is, depending on the type of (B) white colorant, the resolution may be deteriorated by reflecting and absorbing light, but (B) white coloration can be achieved by adding (F) an antioxidant. Regardless of the type of agent, good resolution can be obtained.
- Antioxidants include radical scavengers that invalidate the generated radicals, and peroxide decomposers that decompose the generated peroxides into innocuous substances and prevent the generation of new radicals.
- 1 type may be used independently and may be used in combination of 2 or more type.
- antioxidants that act as radical scavengers include, for example, hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl.
- a phenol-based antioxidant from the viewpoint of further obtaining a discoloration suppressing effect, an improvement in heat resistance and a good resolution.
- the blending amount in the case of using an antioxidant is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass with respect to 100 parts by mass of (A) curable resin. .
- (F) By making the compounding quantity of antioxidant 0.01 mass part or more, the effect by addition of the above-mentioned antioxidant can be acquired reliably, on the other hand, by being 10 mass parts or less, Good alkali developability can be obtained without inhibiting the photoreaction, and good touch drying properties and coating film properties can be ensured.
- antioxidants particularly phenolic antioxidants, may exhibit further effects when used in combination with a heat stabilizer, and therefore the resin composition of the present invention has a heat resistant stability.
- An agent may be blended.
- heat stabilizer examples include phosphorus, hydroxylamine, and sulfur heat stabilizers.
- the said heat stabilizer may be used individually by 1 type, and may use 2 or more types together.
- the composition of the present invention may contain a photoexcitable inorganic filler.
- the photoexcitable inorganic filler include strontium aluminate and zinc sulfide. In particular, strontium aluminate can be suitably used.
- the photoexcitable inorganic filler improves the reflectance of a cured coating film, it is preferable that the surface treatment by an inorganic component or an acidic liquid is given.
- the inorganic component used for the surface treatment include silica (glass), alumina, zirconia and the like.
- a known method can be used and is not particularly limited.
- composition of the present invention may contain a photopolymerization initiator.
- a photopolymerization initiator when (A-2) a photocurable resin is used, it is preferable to add a photopolymerization initiator.
- acylphosphine oxide photopolymerization initiators such as bisacyl phosphine oxides and monoacyl phosphine oxides are preferred because they have less tack and are excellent in the effect of suppressing discoloration.
- the composition of the present invention may contain a reactive diluent solvent.
- the reactive dilution solvent is used to improve workability by adjusting the viscosity of the composition, to increase the crosslink density, to improve adhesion, and the like, and a photocurable monomer or the like can be used.
- a photocurable monomer the above-mentioned photopolymerizable vinyl monomer or the like can be used.
- the composition of the present invention may contain an organic solvent for the purpose of preparing the composition and adjusting the viscosity when applied to a substrate or a carrier 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 , Glycol ethers such as 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, butylcar
- composition of the present invention may be blended with other known and commonly used additives in the field of electronic materials.
- additives include thermal polymerization inhibitors, UV absorbers, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial and antifungal agents, antifoaming agents, leveling agents, fillers, thickeners, Adhesion imparting agent, thixotropic imparting agent, other colorant, photoinitiator aid, sensitizer, curing accelerator, mold release agent, surface treatment agent, dispersant, dispersion aid, surface modifier, stabilizer And phosphors.
- the curable resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more. In particular, when two or more components are used, the components (A) to (D) may be blended in the same formulation or in different formulations.
- the dry film of the present invention has a resin layer obtained by applying and drying the composition of the present invention on a carrier film.
- the composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, and a reverse coater.
- a transfer roll coater, a gravure coater, a spray coater, etc. the film is applied to a uniform thickness on the carrier film.
- the applied composition is usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to form a resin layer.
- the coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 10 to 150 ⁇ m, preferably 20 to 60 ⁇ m.
- a plastic film is used as the carrier film.
- a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used.
- the thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 ⁇ m.
- a peelable cover film is further laminated on the film surface for the purpose of preventing dust from adhering to the film surface.
- a peelable cover film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used.
- a cover film what is necessary is just a thing smaller than the adhesive force of a resin layer and a carrier film when peeling a cover film.
- a resin layer may be formed by applying and drying the composition of the present invention on the protective film, and a carrier film may be laminated on the surface. That is, as a film to which the composition of the present invention is applied when producing a dry film in the present invention, either a carrier film or a protective film may be used.
- the composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and the dip coating method, the flow coating method, the roll coating method, the bar coater method, the screen on the substrate.
- a tack-free resin layer is formed by volatile drying (temporary drying) of an organic solvent contained in the composition at a temperature of about 60 to 100 ° C. Can do.
- the layer of the composition of the present invention is brought into contact with the substrate by a laminator or the like. After bonding together, the resin layer can be formed by peeling off the carrier film.
- Examples of the base material include printed wiring boards and flexible printed wiring boards that have been previously formed with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy.
- PEN polyethylene naphthalate
- Volatile drying performed after the composition of the present invention is applied may be performed by using a hot-air circulating drying furnace, an IR furnace, a hot plate, a convection oven or the like (with a heat source of an air heating method using steam to direct hot air in the dryer. And a method of spraying on a support from a nozzle).
- composition of the present invention is cured with excellent characteristics such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics by, for example, heating to a temperature of about 100 to 180 ° C. and thermosetting.
- a film (cured product) can be formed.
- the exposed portion is cured by applying exposure (light irradiation) to the resin layer obtained after applying the composition of the present invention and evaporating and drying the solvent.
- exposure is selectively performed with an active energy ray through a photomask having a pattern formed by a contact method or a non-contact method, or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution ( For example, a resist pattern is formed by developing with a 0.3 to 3 mass% sodium carbonate aqueous solution.
- the exposure apparatus used for the active energy ray irradiation may be any apparatus that irradiates ultraviolet rays in the range of 350 to 450 nm, equipped with a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc.
- a direct drawing apparatus for example, a laser direct imaging apparatus that directly draws an image with a laser using 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 410 nm. Exposure for image formation depends thickness, etc., but generally 20 ⁇ 800mJ / cm 2, preferably be in the range of 20 ⁇ 600mJ / cm 2.
- the developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.
- the composition of the present invention is preferably used for forming a cured film on a printed wiring board, more preferably used for forming a permanent film, and more preferably a solder resist or a coverlay. Used to form. In addition, you may use the curable resin composition of this invention in order to form a solder dam. Further, the composition of the present invention is white, so that it can be used as a light source in a backlight of a liquid crystal display such as a lighting fixture, a portable terminal, a personal computer, and a television. EL) is suitably used for a reflector that reflects light emitted from EL.
- (A-1) a non-photosensitive carboxyl group-containing resin varnish A as a curable resin was obtained.
- This non-photosensitive carboxyl group-containing resin varnish A had a solid content acid value of 140 mgKOH / g and a solid content of 50% by mass.
- the thus obtained photosensitive carboxyl group-containing resin varnish B had a solid content concentration of 45.5% by mass and a solid acid value of 79.8 mgKOH / g. Moreover, the weight average molecular weight (Mw) of the solid content of the obtained photosensitive carboxyl group-containing resin varnish B was 15,000.
- each component was blended, premixed with a stirrer, dispersed with a three-roll mill, and kneaded to prepare compositions.
- Example 19 and Comparative Example 5 it prepared as A liquid (1 liquid) and B liquid (2 liquids).
- surface shows a mass part.
- Example 19 and Comparative Example 5 The compositions of the obtained Examples and Comparative Examples were evaluated according to the following.
- Example 19 and Comparative Example 5 the liquid A and the liquid B were sufficiently mixed at a ratio of 8: 2 when the substrate was manufactured. The results are also shown in the table below.
- composition described in Comparative Example 3 was applied on the entire surface of FR-4 material by screen printing, dried in a hot air circulation drying oven at 80 ° C. for 30 minutes, cooled to room temperature, and then a negative mask was applied at 600 mJ / cm 2. Then, after developing for 90 seconds under the condition of 0.2 MPa, the substrate was washed with water, and the substrate after development was cured by post-curing at 150 ° C. for 60 minutes to obtain a cured coating film. Thereafter, each composition described in Example 18 and Comparative Examples 3 and 4 was applied on the entire surface of the cured coating film by screen printing, dried in a hot air circulating drying oven at 80 ° C. for 30 minutes, and then released to room temperature. Chilled.
- This substrate was exposed through a negative mask at an exposure amount of 600 mJ / cm 2 , and developed and washed for 90 seconds under a spray pressure of 0.2 MPa using a 1 mass% sodium carbonate aqueous solution at 30 ° C., and the developed substrate Got. Further, the substrate was obtained by post-curing at 150 ° C. for 60 minutes and curing. With respect to the coating film surface of each obtained substrate, the reflectance at a wavelength of 450 nm was measured with a spectrocolorimeter (CM-2600d, manufactured by Konica Minolta Sensing Co., Ltd.). For the compositions of Examples 2 and 3 and Comparative Example 2, the reflectance in the wavelength range of 420 to 470 nm was measured in the same manner. The result is shown in the graph of FIG.
- This substrate was exposed through a negative mask at an exposure amount of 600 mJ / cm 2 , and developed and washed for 90 seconds under a spray pressure of 0.2 MPa using a 1 mass% sodium carbonate aqueous solution at 30 ° C., and the developed substrate Got. Further, the substrate was obtained by post-curing at 150 ° C. for 60 minutes and curing. A rosin-based flux was applied to each of the obtained substrates, immersed in a solder bath set at 260 ° C. in advance, and the flux was washed with denatured alcohol. Then, the resist layer was visually evaluated for swelling and peeling. The judgment criteria are as follows. ⁇ : No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more. X: The resist layer swells and peels off within 3 times for 10 seconds.
- Titanium oxide (silicone resin varnish) * 4) Titanium oxide (Typec CR-58, manufactured by Ishihara Sangyo Co., Ltd., rutile titanium oxide manufactured by the chlorine method) * 5) Titanium oxide (Taipeke R-820, manufactured by Ishihara Sangyo Co., Ltd., rutile titanium oxide manufactured by sulfuric acid method) * 6) Titanium oxide (TiONA 696, manufactured by CRISTAL, rutile titanium oxide manufactured by the chlorine method) * 7) NIKKAFLUOR SB conc.
- Block isocyanate compound (TRIXENE BI 7982, manufactured by Baxenden Chemicals Limited), solid Min: 70% by mass, liquid at normal temperature * 11) Block isocyanate compound (Duranate SBN-70D, manufactured by Asahi Kasei Chemicals Corporation), solid content: 70% by mass, liquid at normal temperature * 12) Silane coupling agent (KBM-402) , 3-glycidoxypropylmethyldimethoxysilane, manufactured by Shin-Etsu Silicone Co., Ltd.), liquid at normal temperature * 13) Silane coupling agent (KBM-5103, 3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone Co., Ltd.) Liquid at normal temperature * 14 IRGANOX 1010 (phenolic), BASF Japan K.K.
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Abstract
Description
本発明の硬化性樹脂組成物は、(A)硬化性樹脂と、(B)白色着色剤と、(C)蛍光増白剤と、(D)イソシアネート化合物およびカップリング剤のうちから選ばれる少なくともいずれか1種と、を含有する点に特徴を有する。これにより、はんだ耐熱性などのソルダーレジストとしての特性に加え、高い反射率をも兼ね備えた硬化性樹脂組成物を得ることができる。
本発明の硬化性樹脂組成物は、(A)硬化性樹脂を含有する。本発明において用いられる(A)硬化性樹脂は、(A-1)熱硬化性樹脂または(A-2)光硬化性樹脂であり、これらの混合物であってもよい。
(A-1)熱硬化性樹脂としては、加熱により硬化して電気絶縁性を示す樹脂であればよく、例えば、エポキシ化合物、オキセタン化合物、メラミン樹脂、シリコーン樹脂などが挙げられる。特に、本発明においては、エポキシ化合物およびオキセタン化合物を好適に用いることができ、これらは併用してもよい。
(式中、R1は、水素原子または炭素数1~6のアルキル基を示す)により表されるオキセタン環を含有するオキセタン化合物の具体例としては、3-エチル-3-ヒドロキシメチルオキセタン(東亞合成(株)製、商品名OXT-101)、3-エチル-3-(フェノキシメチル)オキセタン(東亞合成(株)製、商品名OXT-211)、3-エチル-3-(2-エチルヘキシロキシメチル)オキセタン(東亞合成(株)製、商品名OXT-212)、1,4-ビス{[(3-エチル-3-オキセタニル)メトキシ]メチル}ベンゼン(東亞合成(株)製、商品名OXT-121)、ビス(3-エチル-3-オキセタニルメチル)エーテル(東亞合成(株)製、商品名OXT-221)などが挙げられる。さらに、フェノールノボラックタイプのオキセタン化合物なども挙げられる。これらオキセタン化合物は、上記エポキシ化合物と併用してもよく、また、単独で使用してもよい。
次に、(A-2)光硬化性樹脂としては、活性エネルギー線照射により硬化して電気絶縁性を示す樹脂であればよく、特に、本発明においては、分子中に1個以上のエチレン性不飽和結合を有する化合物が好ましく用いられる。
また、本発明の組成物においてエポキシ樹脂との熱硬化反応を促進させる場合や、本発明の組成物をアルカリ現像型の感光性樹脂組成物とする場合には、(A)硬化性樹脂として、カルボキシル基含有樹脂を用いることが好ましい。カルボキシル基含有樹脂は、エチレン性不飽和基を有するカルボキシル基含有感光性樹脂であってもよく、また、芳香環を有しても有さなくてもよい。
(B)白色着色剤としては、酸化チタン、酸化亜鉛、チタン酸カリウム、酸化ジルコニウム、酸化アンチモン、鉛白、硫化亜鉛、チタン酸鉛等が挙げられるが、熱による変色の抑制効果が高いことから、酸化チタンを用いることが好ましい。(B)白色着色剤を含有させることで、本発明の組成物を白色とすることができ、高い反射率を得ることが可能となる。
本発明に用いる(C)蛍光増白剤とは、組成物の硬化物の白みを増して、変色していないように見せることができるものである。本発明においては、前述したように、硬化性樹脂組成物において、(B)白色着色剤とともに、(C)蛍光増白剤を用いることで、その硬化塗膜において高反射率を実現することが可能となる。
本発明の硬化性樹脂組成物は、(D)イソシアネート化合物およびカップリング剤のうちから選ばれる少なくともいずれか1種を含有する。(D)イソシアネート化合物およびカップリング剤のうちから選ばれる少なくともいずれか1種を含有することにより、400~420nmの蛍光増白剤による吸収をより促し、440~470nmでの蛍光増白剤の効果、すなわち、反射率の向上を促進することができる。
((D-1)イソシアネート化合物)
(D-1)イソシアネート化合物としては、イソシアネート基を1個有するモノイソシアネート化合物、イソシアネート基を2個以上有するポリイソシアネート等、公知のイソシアネート化合物を使用することができる。本発明においては、保存安定性に優れているため作業性が向上する観点から、ブロックイソシアネート化合物が好ましい。
(D-2)カップリング剤としては、シラン系カップリング剤やチタン系カップリング剤、ジルコニウム系カップリング剤、アルミニウム系カップリング剤などを用いることができる。特に、本発明においては、シラン系カップリング剤を好適に用いることができる。
N-γ-(アミノエチル)-γ-アミノプロピルトリエトキシシラン、N-γ-(アミノエチル)-γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルメチルジエトキシシラン、γ-アミノプロピルメチルジメトキシシラン、γ-アミノプロピルフェニルジエトキシシラン、2-アミノ-1-メチルエチルトリエトキシシラン、N-メチル-γ-アミノプロピルトリエトキシシラン、N-フェニル-γ-アミノプロピルトリエトキシシラン、N-ブチル-γ-アミノプロピルメチルジエトキシシラン、N-β-(アミノエチル)-γ-アミノプロピルトリエトキシシラン、N-β-(アミノエチル)-N-β-(アミノエチル)-γ-アミノプロピルトリメトキシシラン、γ-ウレイドプロピルトリエトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ-グリシドキシプロピルメチルジメトキシシラン(3-グリシドキシプロピルメチルジメトキシシラン)、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、γ-メルカプトプロピルトリメトキシシラン、γ-メルカプトプロピルメチルジメトキシシラン、γ-イソシアナートプロピルトリエトキシシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリス(2-メトキシエトキシ)シラン、メタクリロキシプロピルトリメトキシシラン、γ-ポリオキシエチレンプロピルトリメトキシシラン、3-アクリロキシプロピルトリメトキシシラン等を挙げることができ、中でも、3-グリシドキシプロピルメチルジメトキシシラン、3-アクリロキシプロピルトリメトキシシランが好ましい。
本発明の組成物において、(A-1)熱硬化性樹脂を用いる場合には、さらに、(E-1)硬化剤および(E-2)硬化触媒のうち少なくともいずれか1種を添加することができる。
本発明の組成物は、さらに、(F)酸化防止剤を含有することが好ましい。(F)酸化防止剤を含有させることで、硬化性樹脂等の酸化劣化を防止して、変色を抑制する効果が得られることに加えて、耐熱性が向上するとともに、解像性(線幅再現性)が良好になるとの効果も得ることができる。すなわち、(B)白色着色剤の種類によっては、光を反射し吸収することにより、解像性を悪化させる場合があるが、(F)酸化防止剤を含有させることで、(B)白色着色剤の種類によらず、良好な解像性を得ることができるものとなる。
<(A-1-1)硬化性樹脂(ワニスA)の合成>
攪拌機と冷却管を備えた2000mlのフラスコに、ジプロピレングリコールモノメチルエーテル431gを入れ、窒素気流下で90℃に加熱した。スチレン104.2g、メタクリル酸296.6g、ジメチル2,2’-アゾビス(2-メチルプロピオネート)(和光純薬工業(株)製:V-601)23.9gを混合溶解したものを、4時間かけてフラスコに滴下した。
このようにして、(A-1)硬化性樹脂としての、非感光性カルボキシル基含有樹脂ワニスAを得た。この非感光性カルボキシル基含有樹脂ワニスAは、固形分酸価が140mgKOH/g、固形分が50質量%であった。
温度計、撹拌機、滴下ロートおよび還流冷却器を備えたフラスコに、溶媒としてのジプロピレングリコールモノメチルエーテル325.0質量部を110℃まで加熱し、メタクリル酸174.0質量部、ε-カプロラクトン変性メタクリル酸(平均分子量314)174.0質量部、メタクリル酸メチル77.0質量部、ジプロピレングリコールモノメチルエーテル222.0質量部、および、重合触媒としてのt-ブチルパーオキシ2-エチルヘキサノエート(日油(株)製、パーブチルO)12.0質量部の混合物を、3時間かけて滴下し、さらに110℃で3時間攪拌し、重合触媒を失活させて、樹脂溶液を得た。この樹脂溶液を冷却後、(株)ダイセル製サイクロマーM100の289.0質量部、トリフェニルホスフィン3.0質量部およびハイドロキノンモノメチルエーテル1.3質量部を加え、100℃に昇温し、攪拌することによってエポキシ基の開環付加反応を行い、感光性カルボキシル基含有樹脂ワニスBを得た。
比較例3に記載する組成物をFR-4材にスクリーン印刷により全面塗布し、80℃の熱風循環式乾燥炉で30分乾燥させて、室温まで冷却後、600mJ/cm2でネガマスクを介して露光し、0.2MPaの条件で90秒現像後、水洗し、現像後の基板を150℃で60分ポストキュアをして硬化させ、硬化塗膜を得た。その後、実施例1~17、19および比較例1~2、5に記載する各組成物を上記硬化塗膜上にスクリーン印刷によりそれぞれ全面塗布し、150℃の熱風循環式乾燥炉で30分間硬化させて基板を得た。
また、比較例3に記載する組成物をFR-4材にスクリーン印刷により全面塗布し、80℃の熱風循環式乾燥炉で30分乾燥させて、室温まで冷却後、600mJ/cm2でネガマスクを介して露光し、0.2MPaの条件で90秒現像後、水洗し、現像後の基板を150℃で60分ポストキュアをして硬化させ、硬化塗膜を得た。その後、実施例18および比較例3、4に記載する各組成物を上記硬化塗膜上にスクリーン印刷によりそれぞれ全面塗布し、80℃の熱風循環式乾燥炉で30分間乾燥させて、室温まで放冷した。この基板を、露光量600mJ/cm2でネガマスクを介して露光し、30℃の1質量%炭酸ナトリウム水溶液を用いて、スプレー圧0.2MPaの条件で90秒間現像、水洗し、現像後の基板を得た。さらに、150℃で60分ポストキュアをして硬化させて基板を得た。
得られた各基板の塗膜表面について、分光測色計(CM-2600d、コニカミノルタセンシング(株)製)にて、波長450nmにおける反射率を測定した。
また、実施例2,3および比較例2の各組成物については、同様にして、波長420~470nmの範囲の反射率を測定した。その結果を、図1のグラフに示す。
実施例1~17、19および比較例1~2、5に記載する各組成物をFR-4材にスクリーン印刷により全面塗布し、150℃の熱風循環式乾燥炉で30分間硬化させて基板を得た。また、実施例18および比較例3、4に記載する各組成物をFR-4材にスクリーン印刷により全面塗布し、80℃の熱風循環式乾燥炉で30分間乾燥させて、室温まで放冷した。この基板を、露光量600mJ/cm2でネガマスクを介して露光し、30℃の1質量%炭酸ナトリウム水溶液を用いて、スプレー圧0.2MPaの条件で90秒間現像、水洗し、現像後の基板を得た。さらに、150℃で60分ポストキュアをして硬化させて基板を得た。得られた各基板にロジン系フラックスを塗布し、あらかじめ260℃に設定したはんだ槽に浸漬して、変性アルコールでフラックスを洗浄した後、目視によるレジスト層の膨れ・剥がれについて評価した。判定基準は以下のとおりである。
○:10秒間浸漬を3回以上繰り返しても剥がれが認められないもの。
×:10秒間浸漬を3回以内にレジスト層に膨れ、剥がれがあるもの。
各組成物を30g入りのプラスチック容器に適量入れ、10℃以下の条件下で180日間保管し、保管後の組成物の状態を目視にて評価した。実施例19および比較例5については、A液およびB液をそれぞれ30g入りのプラスチック容器に適量入れて、i)10℃以下の条件下で180日間、および、ii)30℃以下の条件下で180日間、それぞれ保管して、保管後のA液およびB液の状態を、それぞれ目視にて評価した。判定基準は以下の通りである。
○:ゲル化していない。
×:ゲル化した。
-:未評価
*2)非感光性カルボキシル基含有樹脂ワニス(表中の値は固形分の値)、ルミフロン200F、旭硝子(株)製(フッ素系樹脂ワニス)
*3)非感光性カルボキシル基含有樹脂ワニス(表中の値は固形分の値)、X-22-3701E、信越化学工業(株)製(シリコーン系樹脂ワニス)
*4)酸化チタン(タイペークCR-58、石原産業(株)製、塩素法で製造したルチル型酸化チタン)
*5)酸化チタン(タイペークR-820、石原産業(株)製、硫酸法で製造したルチル型酸化チタン)
*6)酸化チタン(TiONA 696、CRISTAL社製、塩素法で製造したルチル型酸化チタン)
*7)NIKKAFLUOR SB conc.、(株)日本化学工業所製
*8)LXS FBW MAN 01、ランクセス社製
*9)Tinopal OB CO、BASFジャパン社製
*10)ブロックイソシアネート化合物(TRIXENE BI 7982、Baxeneden Chemicals Limited社製)、固形分:70質量%、常温で液状
*11)ブロックイソシアネート化合物(デュラネートSBN-70D、旭化成ケミカルズ(株)製)、固形分:70質量%、常温で液状
*12)シランカップリング剤(KBM-402、3-グリシドキシプロピルメチルジメトキシシラン、信越シリコーン(株)製)、常温で液状
*13)シランカップリング剤(KBM-5103、3-アクリロキシプロピルトリメトキシシラン、信越シリコーン(株)製)、常温で液状
*14)IRGANOX1010(フェノール系)、BASFジャパン(株)製
*15)KS-66、信越シリコーン(株)製
*16)Disperbyk-111、ビックケミー・ジャパン(株)製
*17)TEPIC-HP、日産化学工業(株)製
*18)ジシアンジアミド(硬化触媒)
*19)メラミン-テトラヒドロフタル酸塩(硬化触媒)、日産化学工業(株)製
*20)アエロジルR-974、日本アエロジル(株)製
*21)LMP-100、富士タルク工業(株)製
*22)MFTG(トリプロピレングリコールモノメチルエーテル)、日本乳化剤(株)製
*23)DPM(ジプロピレングリコールモノメチルエーテル)
*24)メラミン(硬化触媒)
*25)DA-600(三洋化成社製)
*26)感光性カルボキル基含有樹脂ワニスB(表中の値は固形分の値)
*27)イルガキュアTPO(BASFジャパン社製)
Claims (4)
- (A)硬化性樹脂と、(B)白色着色剤と、(C)蛍光増白剤と、(D)イソシアネート化合物およびカップリング剤のうちから選ばれる少なくともいずれか1種と、を含有することを特徴とする硬化性樹脂組成物。
- フィルム上に、請求項1記載の硬化性樹脂組成物を塗布、乾燥して得られる樹脂層を有することを特徴とするドライフィルム。
- 請求項1記載の硬化性樹脂組成物、または、請求項1記載の硬化性樹脂組成物を塗布、乾燥して得られる樹脂層を、硬化させて得られることを特徴とする硬化物。
- 請求項3記載の硬化物を有することを特徴とするプリント配線板。
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JP2020160146A (ja) * | 2019-03-25 | 2020-10-01 | 株式会社タムラ製作所 | 感光性樹脂組成物 |
US20210283824A1 (en) * | 2016-10-14 | 2021-09-16 | Senoplast Klepsch & Co. Gmbh | Thermally deformable plate |
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CN111650811B (zh) * | 2020-06-18 | 2024-01-26 | 上海孚赛特新材料股份有限公司 | 一种白色感光膜及其制备方法和应用 |
CN111999982A (zh) * | 2020-09-09 | 2020-11-27 | 广州斯达利电子原料有限公司 | 一种led感光阻焊白油用光敏聚丙烯酸树脂及制备方法 |
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