WO2009119821A1 - Curable resin composition, cured article thereof, and printed circuit board - Google Patents
Curable resin composition, cured article thereof, and printed circuit board Download PDFInfo
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- WO2009119821A1 WO2009119821A1 PCT/JP2009/056328 JP2009056328W WO2009119821A1 WO 2009119821 A1 WO2009119821 A1 WO 2009119821A1 JP 2009056328 W JP2009056328 W JP 2009056328W WO 2009119821 A1 WO2009119821 A1 WO 2009119821A1
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- resin composition
- curable resin
- manufactured
- pigment
- lactic acid
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Definitions
- the present invention relates to a curable resin composition, a cured product using the same, and a printed wiring board.
- a solder resist pattern for printed wiring boards is generally formed by applying and drying a curable resin composition on a circuit-formed substrate to form a dry coating film of the solder resist, and then exposing the photo tool to vacuum contact. Thereafter, it is formed by developing (see Patent Document 1).
- the dry coating is not sufficiently dry to the touch, it will be in close contact with the phototool during contact exposure, and after exposure, the phototool cannot be peeled off or the dry coating will peel off from the substrate. Occurs.
- An object of the present invention is to provide a curable resin composition capable of improving dryness to touch and coating properties after drying, a cured product using the same, and a printed wiring board.
- a curable resin composition of one embodiment of the present invention is a resin composition for a printed wiring board having a minute hole in a surface layer of a substrate, and includes a lactate ester, a carboxyl group-containing resin, and It is characterized by containing a photopolymerization initiator.
- the lactic acid ester is preferably an L-lactic acid ester derived from a natural product, so that the influence on the environment and the human body can be reduced from the environmental aspect of fossil fuel depletion and CO 2 emission reduction.
- the coating property and the coating property are improved.
- the present invention is effective when a minute hole is formed in the surface layer of the substrate.
- the cured product or printed wiring board of one embodiment of the present invention is a curable resin having a viscosity of 0.1 to 250 dPa ⁇ s diluted with a lactic acid ester on a substrate, in particular, a substrate in which minute holes are formed in the surface layer. It is characterized by having a pattern formed by exposing, developing, and curing a dry coating film formed by applying and drying the composition. Further, this exposure is preferably contact exposure.
- a minute hole means a hole (blind via, laser via) of ⁇ 20 ⁇ m to ⁇ 200 ⁇ m, and the depth direction is not particularly limited.
- the depth direction is applied in a wide range from a shallow hole having a depth of several ⁇ m to a hole having a depth of 100 ⁇ m.
- the present invention it is possible to improve the touch-drying property after drying and the coating property for minute holes. As a result, even if contact exposure is performed, peeling of the pattern from the substrate is suppressed, so that a higher definition pattern can be formed.
- the curable resin composition of the present embodiment is characterized by containing a lactic acid ester, a carboxyl group-containing resin, and a photopolymerization initiator.
- Such a configuration is less likely to cause repellency after coating and drying on a substrate with a minute hole when a lactic acid ester is used as a diluent in a curable resin composition such as an alkali development type solder resist. This is based on the new knowledge.
- the repellency phenomenon may occur when a curable resin composition 13 is applied and dried after forming a copper circuit 12 in which minute holes 12a are formed on a substrate 11.
- this is a phenomenon that the film thickness around the minute hole 12a of the copper circuit 12 becomes thin.
- the reason that the repellency phenomenon is reduced when a lactic acid ester is used as a diluent is considered to be related to the solubility of the lactic acid ester with the resin. That is, the lactic acid ester has a lower dilution efficiency than the other general-purpose solvents with respect to the resin component of the curable resin composition.
- the curable resin composition when the curable resin composition is diluted to a usable viscosity, the resin solid content relative to the solvent is relatively reduced. Accordingly, such a curable resin composition has a small resin solid content and is applied thickly on a minute hole and on a circuit to ensure an appropriate dry film thickness on the circuit.
- a lactic acid ester when used as a diluent, the repellency phenomenon is considered to be suppressed even when the dry coating film is a thin film as a result of increasing the coating thickness above the minute holes as compared with other general-purpose solvents.
- the curable resin composition containing the lactic acid ester of the present embodiment as shown in FIG. 3A, even if the coating thickness of the curable resin composition 13 on the minute hole 12a is increased, As shown in 3B, the thickness of the portion other than the minute holes 12a after drying and curing of the curable resin composition 13 can be reduced, and the repellency phenomenon can be suppressed.
- the viscosity of the curable resin composition of the present invention is preferably adjusted to 0.1 to 250 dPa ⁇ s with lactic acid ester. More effectively, it may be 0.5 to 50 dPa ⁇ s.
- dilution efficiency is poor when only lactic acid esters are diluted, it is possible to easily adjust the coating film thickness and the composition while suppressing the repellency phenomenon by using another general-purpose solvent in combination.
- the repellency phenomenon cannot be suppressed unless the coating thickness of the curable resin composition 13 is increased, but according to this embodiment, the film thickness is adjusted by adjusting the viscosity of the composition with lactic acid ester. Even if it is made thinner, the repellency phenomenon is suppressed, and the film thickness around the minute holes can be kept uniform.
- the lactic acid esters used in this way include not only lactic acid esters derived from fossil fuels but also lactic acid esters produced by fermentation from starch such as corn.
- a fossil fuel-derived lactic acid ester mixture of D-form and L-form which are optical isomers
- a fermented lactic ester derived from a natural product L-form
- L-form lactic acid ester L-lactic acid ester
- L-lactic acid ester has natural product-derived carbon, its use can reduce the impact on the environment and the human body from the environmental aspects of fossil fuel depletion and CO 2 emission reduction. .
- lactic acid ester in the present embodiment examples include methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, n-hexyl lactate, and cyclohexyl lactate.
- Benzyl lactate and the like preferably methyl lactate and ethyl lactate.
- These lactic acid ester compounds may be used alone or as a mixture of two or more, and either L-form or D-form may be used.
- the curable resin composition of this embodiment can contain various components such as a thermosetting component and a photosensitive component in addition to the lactic acid ester. As long as it can be used suitably for a printed wiring board, such as insulation and heat resistance, it is not limited to a specific structural component, and can be appropriately selected.
- thermosetting component e.g., a thermosetting component and / or a photosensitive component
- an alkali development type solder resist in addition to a lactic acid ester and a carboxyl group-containing resin, a photopolymerization initiator, a thermosetting component such as a compound having two or more ethylenically unsaturated groups in the molecule and an epoxy compound, Furthermore, a thermosetting catalyst, a filler, an organic solvent, etc. can be contained as needed. Since the curable resin composition of the present invention can be derived from natural products, the burden on the environment is small.
- cured material of a desired characteristic and a printed wiring board can be obtained by selecting suitably the kind of said each component, and using it as a curable resin composition which optimized the mixture ratio.
- the carboxyl group-containing resin various resin compounds having a carboxyl group in the molecule can be used, and alkali developability can be imparted.
- a carboxyl group-containing resin a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is more preferable from the viewpoint of photocurability and development resistance.
- the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof.
- (meth) acrylate is a general term for acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions.
- a carboxyl group-containing resin obtained by copolymerization of (meth) acrylic acid and an unsaturated group-containing material.
- a terminal (meth) acrylated carboxylic acid-containing urethane is added by adding a compound having one isocyanate group and one or more (meth) acryl groups in the molecule during the synthesis of the resin described in (2) or (3) above. resin.
- a photosensitive carboxyl group-containing resin obtained by reacting a bifunctional and polyfunctional (solid) epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group present in the side chain.
- a carboxylic acid-containing polyester resin obtained by reacting a difunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
- a photosensitive carboxyl group-containing resin obtained by adding a compound having one epoxy group and one or more (meth) acryl groups in one molecule to the resin described above.
- a lactic acid ester is also used for the synthesis of such a carboxyl group-containing resin.
- the backbone polymer has a number of free carboxyl groups in the side chain, so that development with a dilute alkaline aqueous solution is possible.
- the acid value of the carboxyl group-containing resin is preferably 40 to 200 mgKOH / g.
- the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult.
- the acid value exceeds 200 mgKOH / g dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary.
- the exposed portion and the unexposed portion may be dissolved and separated by the developer without distinction, and it becomes difficult to draw a normal resist pattern. More preferably, it is 45 to 120 mg KOH / g.
- the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000.
- the weight average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, and the film may be reduced during development, and the resolution may be greatly inferior.
- the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.
- the mixing ratio of such a carboxyl group-containing resin is preferably 20 to 60% by mass in the entire composition.
- the amount is less than the above range, the coating strength is lowered, which is not preferable.
- the amount is more than the above range, the viscosity becomes high or the coating property is lowered. More preferably, it is 30 to 50% by mass.
- Such carboxyl-containing resins can be used alone or in admixture of two or more.
- the photopolymerization initiator may be one or more selected from the group consisting of oxime ester photopolymerization initiators, ⁇ -aminoacetophenone photopolymerization initiators, and acylphosphine oxide photopolymerization initiators. Can be used.
- oxime ester photopolymerization initiator examples include commercially available products such as CGI-325, Irgacure OXE01, and Irgacure OXE02 manufactured by Ciba Specialty Chemicals, Inc. and N-1919 manufactured by ADEKA. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.
- Examples of ⁇ -aminoacetophenone photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethyl
- Examples include aminoacetophenone.
- Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.
- Acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2 4,4-trimethyl-pentylphosphine oxide and the like.
- Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.
- the blending ratio of such a photopolymerization initiator may be 0.01 to 30 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin described above. If it is less than 0.01 parts by mass, the photocurability on copper used for the printed wiring board is insufficient, and the coating film is peeled off or the coating film properties such as chemical resistance are deteriorated. . On the other hand, when it exceeds 30 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator becomes intense, and the deep curability tends to decrease. More preferably, it is 0.5 to 15 parts by mass.
- the blending ratio is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. More preferably, it is 0.01 to 5 parts by mass.
- a photopolymerization initiator other than the above-described compounds, a photoinitiator assistant, and a sensitizer can be used.
- examples include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, xanthone compounds, and tertiary amine compounds.
- benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
- acetophenone compound examples include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.
- anthraquinone compound examples include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.
- thioxanthone compound examples include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.
- ketal compound examples include acetophenone dimethyl ketal and benzyl dimethyl ketal.
- benzophenone compounds include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyl diphenyl sulfide. Etc.
- tertiary amine compound examples include ethanolamine compounds and compounds having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylaminobenzophenone ( Dialkylaminobenzophenones such as Hoabaya Chemical Co.
- 4,4′-dimethylaminobenzophenone Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.
- 4,4′-diethylaminobenzophenone Dialkylaminobenzophenones such as Hoabaya Chemical Co.
- EAB dialkylamino group-containing coumarins such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin) Compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylaminobenzoic acid (n- Toxi) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoic acid (Esolol manufactured by Van Dyk) 50
- thioxanthone compounds and tertiary amine compounds are particularly preferable.
- the inclusion of a thioxanthone compound is preferable in terms of deep curability, and among them, thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone are preferable.
- the mixing ratio of such a thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin.
- the mixing ratio of such a thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin.
- a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable.
- a dialkylaminobenzophenone compound 4,4'-diethylaminobenzophenone is preferable because of its low toxicity.
- the dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm is not colored because the maximum absorption wavelength is in the ultraviolet region, and uses not only a colorless and transparent photosensitive composition but also a colored pigment.
- a colored solder resist film reflecting the color can be provided.
- 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.
- the mixing ratio of such a tertiary amine compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
- proportion of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained.
- amount exceeds 20 parts by mass light absorption on the surface of the dried solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease.
- a ratio of 0.1 to 10 parts by mass is more preferable.
- photopolymerization initiators can be used alone or in admixture of two or more.
- a compound having two or more ethylenically unsaturated groups in the molecule is photocured by active energy ray irradiation to insolubilize or assist insolubilization of the carboxyl group-containing resin in an alkaline aqueous solution.
- examples of such compounds include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, and the like.
- Polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts or propylene oxide adducts; polyhydric acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane trig Ethers, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates.
- an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further, a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin.
- a polyfunctional epoxy resin such as a cresol novolac type epoxy resin
- a hydroxy acrylate such as pentaerythritol triacrylate
- a diisocyanate such as isophorone diisocyanate
- the blending ratio of the compound having two or more ethylenically unsaturated groups in the molecule is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
- the blending ratio is less than 5 parts by mass, the photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays.
- it exceeds 100 mass parts the solubility with respect to alkaline aqueous solution will fall, and a coating film will become weak.
- a ratio of 1 to 70 parts by mass is more preferable.
- thermosetting components such as epoxy compounds are used to impart heat resistance.
- thermosetting component having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.
- thermosetting component having two or more cyclic (thio) ether groups in the molecule is either one of the three-, four- or five-membered cyclic ether groups in the molecule, or the cyclic thioether group, or two kinds thereof.
- a compound having at least two epoxy groups in the molecule that is, a polyfunctional epoxy compound, a compound having at least two oxetanyl groups in the molecule, that is, a polyfunctional compound.
- examples include oxetane compounds, compounds having two or more thioether groups in the molecule, that is, episulfide resins.
- polyfunctional epoxy compound examples include Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, and Epicron 840, Epicron 850, Epicron 1050, and Epicron 2055 manufactured by Dainippon Ink & Chemicals, Inc. Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Toto Kasei Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R.
- Bisphenol A type epoxy resin such as 664 (all trade names); Epicoat YL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by Dainippon Ink & Chemicals, Epototo YDB-400, YDB- manufactured by Tohto Kasei Co., Ltd. 500, D.C. E. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R.
- Brominated epoxy resins such as 714 (all trade names); Epicoat 152 and Epicoat 154 manufactured by Japan Epoxy Resin Co., Ltd., D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by Dainippon Ink and Chemicals, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., Araldide ECN1235 manufactured by Ciba Specialty Chemicals, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumi-epoxy ESCN-195X, ESCN- manufactured by Sumitomo Chemical Co., Ltd.
- E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both are trade names); Epicron 830 manufactured by Dainippon Ink & Chemicals, Epicoat 807 manufactured by Japan Epoxy Resin, Epototo YDF-170 manufactured by Toto Kasei Co., Ltd., YDF -175, YDF-2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Specialty Chemicals Co., Ltd. (Etoto ST-2004, ST-2007, ST-3000 manufactured by Toto Kasei Co., Ltd.) Hydrogenated bisphenol A type epoxy resins such as Japan Epoxy Resin Co., Ltd.
- Epicoat 604 Toto Kasei Epototo YH-434, Ciba Specialty Chemicals Araldide MY720, Sumitomo Chemical Industries Sumitomo Epoxy ELM Glycidylamine type epoxy resins such as 120 (all trade names); Hydantoin type epoxy resins such as Araldide CY-350 (trade name) manufactured by Ciba Specialty Chemicals; Celoxide 2021 manufactured by Daicel Chemical Industries, Ciba Specialty Alicyclic epoxy resins such as Araldide CY175 and CY179 (both trade names) manufactured by Chemicals; YL-933 manufactured by Japan Epoxy Resin; E. N. , EPPN-501, EPPN-502, etc.
- Tetrahu Nylolethane type epoxy resin Tetrahu Nylolethane type epoxy resin
- heterocyclic epoxy resin such as Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries (all trade names)
- diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats
- Tetraglycidyl xylenoyl ethane resins such as ZX-1063 manufactured by Tohto Kasei
- naphthalenes such as ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750 and EXA-4700 manufactured by Dainippon Ink & Chemicals, Inc.
- These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.
- 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)
- polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolac resins, poly (P-hydroxystyrene), card
- Examples of the compound having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resins. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
- the blending ratio of the thermosetting component having two or more cyclic (thio) ether groups in the molecule is 0.6 to 2.5 equivalents relative to 1 equivalent of the carboxyl group of the carboxyl group-containing resin. It is preferable.
- the blending ratio of the thermosetting component having two or more cyclic (thio) ether groups in the molecule is less than 0.6, a carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation, etc. Will fall.
- the amount exceeds 2.5 equivalents the low molecular weight cyclic (thio) ether group remains in the dry coating film, thereby reducing the strength of the coating film. More preferably, it is 0.8 to 2.0 equivalents.
- thermosetting catalyst is preferably contained together with the above-described thermosetting component having two or more cyclic (thio) ether groups in the molecule.
- thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1-cyanoethyl-2.
- -Imidazole derivatives such as phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy- Amine compounds such as N, N-dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine and the like are also commercially available.
- things and Examples include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N, U-CAT3502T (both dimethylamine manufactured by San Apro) (Trade names of blocked isocyanate compounds), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof), and the like.
- thermosetting catalyst for an epoxy resin or an oxetane compound or any catalyst that promotes the reaction between an epoxy group and / or an oxetanyl group and a carboxyl group may be used. And it can use individually or in mixture of 2 or more types.
- S-triazine derivatives such as triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct You can also. These are preferably used in combination with the above-described thermosetting catalyst.
- thermosetting catalysts are sufficient in the usual quantitative ratio, for example, with respect to 100 parts by mass of the carboxyl group-containing resin or thermosetting component having two or more cyclic (thio) ether groups in the molecule. 0.1 to 20 parts by mass is preferable. More preferably, it is 0.5 to 15.0 parts by mass.
- Filler is used as necessary to increase the physical strength of the coating film.
- a filler an inorganic or organic filler can be used, and barium sulfate, spherical silica and talc are particularly preferably used.
- an interlayer insulation layer like a prepreg
- an insulating sheet, and copper foil with resin, a glass cloth, an inorganic, and an organic fiber nonwoven fabric can be used.
- metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers.
- the blending ratio of this filler is preferably 300 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin.
- the blending ratio of the filler exceeds 300 parts by mass, the viscosity of the photocurable resin composition is increased and the printability is lowered, or the cured product is brittle. More preferred is 0.1 to 300 parts by mass, and particularly preferred is 0.1 to 150 parts by mass.
- the organic solvent is an organic solvent other than a lactic acid ester, and is used for synthesis of a carboxyl group-containing resin, adjustment of a composition, or adjustment of viscosity for application to a substrate or a carrier film.
- organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like.
- ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, Esters such as propylene glycol butyl ether acetate; ethanol, propano Le, ethylene glycol, alcohols such as propylene glycol; octane,
- any known and commonly used colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc. ) Can be used.
- Blue colorants include phthalocyanine and anthraquinone, and pigments are compounds classified as Pigment. Specifically, the following color index (CI; issued by The Society of Dyers and Colorists) number Can be mentioned.
- Solvent Blue 35, Solvent Blue 45, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 101, Solvent Blue 104, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, etc. can be used. Besides these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
- green colorant include phthalocyanine, anthraquinone, and perylene. Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28 Etc. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
- yellow colorant examples include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone, and specific examples include the following.
- thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, thickeners such as finely divided silica, organic bentonite, montmorillonite, silicones, fluorines, polymers, etc.
- Additives such as an antifoaming agent and / or leveling agent, an adhesion-imparting agent such as imidazole, thiazole, and triazole, and a silane coupling agent can be blended.
- a photocurable composition containing a photosensitive component is applied on a substrate and photocured to form a cured product.
- Photocuring can be carried out by an ultraviolet exposure device or a laser light source, particularly laser light having a wavelength of 350 to 410 nm.
- the thermosetting resin composition and photocuring thermosetting composition containing a thermosetting component become a hardened
- a cured product and a printed wiring board are formed as follows.
- a curable resin composition adjusted to a viscosity suitable for the coating method with a lactic acid ester and other organic solvents is applied to a substrate including a circuit-formed substrate by a dip coating method, a flow coating method, a roll coating method. It is applied by a bar coater method, a spray coating method, a screen printing method, a curtain coating method 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, fluorine / polyethylene / PPO / cyanate ester, etc. are used as the base material.
- All grades (FR-4, etc.) of copper-clad laminates, other polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, etc. are used. Can do.
- a tack-free coating film is formed by volatile drying (temporary drying) of the organic solvent contained in the composition at a temperature of about 60 to 100 ° C.
- the composition may be applied onto a carrier film, dried, and wound up as a film and pasted onto a substrate.
- the contact pattern (or non-contact pattern) is selectively exposed through an active energy ray through a photomask on which a pattern has been formed or directly exposed by a laser direct exposure machine, and unexposed areas that have not been cured by light irradiation are diluted.
- a pattern is formed by developing with an alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution).
- a laser direct drawing device laser direct imaging device
- an exposure device equipped with a metal halide lamp an exposure device equipped with a (super) high-pressure mercury lamp
- an exposure device equipped with a mercury short arc lamp or A direct drawing apparatus using an ultraviolet lamp such as a (super) high pressure mercury lamp
- direct exposure is performed by a drawing apparatus
- either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used.
- the direct drawing apparatus for example, those manufactured by Nippon Orbotech, ORC, etc. can be used, and any apparatus may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .
- 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.
- an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines or the like can be used.
- Volatile drying is performed using a method using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, or the like equipped with a heat source of an air heating method using steam, and a counter current contact with hot air in the dryer It can carry out using the system sprayed on a support body.
- thermosetting component for example, by heating and curing at a temperature of about 140 to 180 ° C., the carboxyl group of the carboxyl group-containing resin and two or more in the molecule
- a thermosetting component having a cyclic ether group and / or a cyclic thioether group reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. Can do.
- thermosetting Even if it does not contain a thermosetting component, the ethylenically unsaturated bond remaining in an unreacted state at the time of exposure undergoes thermal radical polymerization even when it does not contain a thermosetting component, thereby improving the coating film properties.
- heat treatment thermosetting
- the obtained B-1 varnish was premixed with a stirrer using a diluting solvent (lactic acid ester and organic solvent) at a blending ratio as shown in Table 1 together with the components of the following blending examples, and then 3 It knead
- a diluting solvent lactic acid ester and organic solvent
- the degree of dispersion of the obtained photosensitive resin composition was evaluated by particle size measurement using a grindometer manufactured by Eriksen, it was 15 ⁇ m or less.
- the photocurable thermosetting resin composition of each Example and Comparative Example was a circuit pattern substrate having a copper thickness of 50 ⁇ m, buffed, washed with water, dried and then dried by spray coating or screen printing, and the film thickness was 25 ⁇ m. The whole surface is coated, dried in a hot air circulation drying oven at 80 ° C. for 30 minutes, and allowed to cool to room temperature. After allowing to cool, exposure was performed through a step tablet (Kodak No. 2) using an exposure apparatus (HMW680-GW20) manufactured by ORC, and development (30 ° C., 0.2 MPa, 1 mass% sodium carbonate aqueous solution) was performed in 60 seconds. When the pattern of the remaining step tablet was 7 steps, the optimum exposure amount was set.
- Example and Comparative Example The composition of each Example and Comparative Example was applied on the entire surface of a patterned copper foil substrate by spray coating or screen printing so that the film thickness was 25 ⁇ m after drying, and was heated in a hot air circulation drying oven at 60 ° C. for 30 minutes. Dry and allow to cool to room temperature.
- a negative film made of PET was applied to this substrate, and the film was pressure-bonded under reduced pressure for 1 minute with an exposure apparatus (HMW680-GW20) manufactured by ORC, and then the sticking state of the film when the negative film was peeled off was evaluated according to the following criteria. .
- ⁇ Cavity filling (for minute holes)> The composition of each Example and Comparative Example was applied to the entire surface of the substrate having fine holes adjusted to ⁇ 100 ⁇ m and depth of 50 ⁇ m after copper plating so that the film thickness was 25 ⁇ m after drying by spray coating or screen printing, and 80 ° C. Dry in a hot air circulating drying oven for 30 minutes and allow to cool to room temperature. After standing to cool, the number of solder resists on the hole was visually counted and evaluated according to the following criteria.
- Defect rate (%) number of repellency / total number of holes 1700 holes ⁇ : 3% or less ⁇ : 4% or more and 10% or less ⁇ : 10% or more ⁇ Deep part curability>
- a circuit pattern substrate having a line / space of 300/300 ⁇ m and a copper thickness of 50 ⁇ m was subjected to buffing, washing with water, drying, and then spray coating or screen printing, and then the film thickness was 25 ⁇ m. Then, the entire surface is coated, dried in a hot air circulating drying oven at 80 ° C. for 30 minutes, and allowed to cool to room temperature. After allowing to cool, exposure was performed using an exposure apparatus (HMW680-GW20) manufactured by ORC.
- HMW680-GW20 an exposure apparatus manufactured by ORC.
- the exposure pattern a pattern for drawing a 20/30/40/50/60/70/80/90/100 ⁇ m line in the space portion was used.
- the exposure amount was the exposure amount obtained by the optimum exposure amount evaluation.
- development was performed with a 1% by mass aqueous sodium carbonate solution at 30 ° C. to draw a pattern, and a cured coating film was obtained by heat curing at 150 ° C. for 60 minutes.
- the optical microscope which adjusted the minimum residual line of the cured coating film of the obtained photocurable thermosetting resin composition 200 times. Moreover, after cutting the center part of the line and performing mirror finish, the upper diameter, lower diameter, and film thickness of the minimum remaining line of the cured coating film were measured using an optical microscope adjusted to 1000 times. The evaluation criteria were such that the deeper part curability was better as the minimum remaining line was smaller and the lower diameter was closer to the design value.
- the photosensitive resin composition for solder resists of the examples is a composition excellent in dryness to touch, filling in minute holes, and deep curability.
- a curable resin composition that is excellent in dryness to touch, and further excellent in filling property and deep curability with respect to minute holes.
- a photocurable thermosetting resin composition suitable for use as a solder resist application, a cured product thereof, and a printed wiring board patterned using the same.
- the figure which shows a repelling phenomenon The figure which shows a repelling phenomenon.
- coating state The figure which shows the conventional dry state.
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Abstract
Description
40mgKOH/g未満であるとアルカリ現像が困難となり、一方、200mgKOH/gを超えると現像液による露光部の溶解が進むために、必要以上にラインが痩せたり、場合によっては、露光部と未露光部の区別なく現像液で溶解剥離してしまい、正常なレジストパターンの描画が困難となる。より好ましくは45~120mgKOH/gである。 The acid value of the carboxyl group-containing resin is preferably 40 to 200 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion may be dissolved and separated by the developer without distinction, and it becomes difficult to draw a normal resist pattern. More preferably, it is 45 to 120 mg KOH / g.
青色着色剤はフタロシアニン系、アントラキノン系があり、顔料系はピグメント(Pigment)に分類されている化合物、具体的には、下記のようなカラーインデックス(C.I.;The Society of Dyers and Colourists 社発行)番号が付されているものを挙げられる。 [Blue colorant]
Blue colorants include phthalocyanine and anthraquinone, and pigments are compounds classified as Pigment. Specifically, the following color index (CI; issued by The Society of Dyers and Colorists) number Can be mentioned.
染料系としては
Solvent Blue 35 、Solvent Blue 45、Solvent Blue 63、Solvent Blue 68、Solvent Blue 70 、Solvent Blue 83、Solvent Blue 87、Solvent Blue 94、Solvent Blue 97、Solvent Blue 101、Solvent Blue 104、Solvent Blue 122、Solvent Blue 136、Solvent Blue 67、Solvent Blue 70などを使用することができる。これら以外にも金属置換もしくは無置換のフタロシアニン化合物も使用することができる。 Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16,
As a dye system
Solvent Blue 35, Solvent Blue 45, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 101, Solvent Blue 104, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, etc. can be used. Besides these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
緑色着色剤としては同様にフタロシアニン系、アントラキノン系、ペリレン系があり、具体的には
Pigment Green 7、Pigment Green 36、Solvent Green 3、Solvent Green 5、Solvent Green 20、Solvent Green 28
などが挙げられる。これら以外にも金属置換もしくは無置換のフタロシアニン化合物なども使用することができる。 [Green colorant]
Similarly, green colorants include phthalocyanine, anthraquinone, and perylene.
Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5,
Etc. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
黄色着色剤としてはモノアゾ系、ジスアゾ系、縮合アゾ系、ベンズイミダゾロン系、イソインドリノン系、アントラキノン系などがあり、具体的には以下のものが挙げられる。 [Yellow colorant]
Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone, and specific examples include the following.
Solvent Yellow 163、Pigment Yellow 24、Pigment Yellow 108、Pigment Yellow 193、Pigment Yellow 147、Pigment Yellow 199、Pigment Yellow 202
(イソインドリノン系)
Pigment Yellow 110、Pigment Yellow 109、Pigment Yellow 139、Pigment Yellow 179、Pigment Yellow 185
(縮合アゾ系)
Pigment Yellow 93、Pigment Yellow 94、Pigment Yellow 95、Pigment Yellow 128
、Pigment Yellow 155、Pigment Yellow 166、Pigment Yellow 180
(ベンズイミダゾロン)
Pigment Yellow 120、Pigment Yellow 151、Pigment Yellow 154、Pigment Yellow 156、Pigment Yellow 175、Pigment Yellow 181
(モノアゾ)
PigmentYellow1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75,97,100,104,105,111,116,167,168,169,182,183,
(ジスアゾ)
PigmentYellow12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198
[赤色着色剤]
赤色着色剤としてはモノアゾ系、ジスアゾ系、アゾレーキ系、ベンズイミダゾロン系、ペリレン系、ジケトピロロピロール系、縮合アゾ系、アントラキノン系、キナクリドン系などがあり、具体的には以下のものが挙げられる。 (Anthraquinone)
Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202
(Isoindolinone series)
Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185
(Condensed azo)
Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128
, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180
(Benz imidazolone)
Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181
(Monoazo)
PigmentYellow1,2,3,4,5,6,9,10,12,61,62,62: 1,65,73,74,75,97,100,104,105,111,116,167,168,169,182,183,
(Disazo)
PigmentYellow12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198
[Red colorant]
Examples of red colorants include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Specific examples include the following: It is done.
PigmentRed1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147,151,170,184,187,188,193,210,245,253,258,266,267,268,269,
(ジスアゾ系)
Pigment Red 37,38,41
(モノアゾレーキ)
PigmentRed48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2,53:1,53:2,57:1,58:4,63:1,63:2,64:1,68
(ベンズイミダゾロン)
Pigment Red 171、Pigment Red 175、Pigment Red 176、Pigment Red 185、Pigment Red 208
(ぺリレン)
Solvent Red 135、Solvent Red 179、Pigment Red 123、Pigment Red 149、Pigment Red 166、Pigment Red 178、Pigment Red 179、Pigment Red 190、Pigment Red 194、Pigment Red 224
(ジケトピロロピロール系)
Pigment Red 254、Pigment Red 255、Pigment Red 264、Pigment Red 270、Pigment Red 272
(縮合アゾ)
Pigment Red 220、Pigment Red 144、Pigment Red 166、Pigment Red 214、Pigment Red 220、Pigment Red 221、Pigment Red 242
(アンスラキノン系)
Pigment Red 168、Pigment Red 177、Pigment Red 216、Solvent Red 149、Solvent Red 150、Solvent Red 52、Solvent Red 207
(キナクリドン系)
Pigment Red 122、Pigment Red 202、Pigment Red 206、Pigment Red 207、Pigment Red 209
その他色調を調整する目的で紫、オレンジ、茶色、黒などの着色剤を加えても良い。具体的には、Pigment Violet 19、23、29、32、36、38、42、Solvent Violet 13、36、C.I.ピグメントオレンジ1、C.I.ピグメントオレンジ5、C.I.ピグメントオレンジ13、C.I.ピグメントオレンジ14、C.I.ピグメントオレンジ16、C.I.ピグメントオレンジ17、C.I.ピグメントオレンジ24、C.I.ピグメントオレンジ34、C.I.ピグメントオレンジ36、C.I.ピグメントオレンジ38、C.I.ピグメントオレンジ40、C.I.ピグメントオレンジ43、C.I.ピグメントオレンジ46、C.I.ピグメントオレンジ49、C.I.ピグメントオレンジ51、C.I.ピグメントオレンジ61、C.I.ピグメントオレンジ63、C.I.ピグメントオレンジ64、C.I.ピグメントオレンジ71、C.I.ピグメントオレンジ73、C.I.ピグメントブラウン23、C.I.ピグメントブラウン25;C.I.ピグメントブラック1、C.I.ピグメントブラック7などが挙げられる。 (Monoazo)
PigmentRed1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147,151,170,184,187,188,193,210,245,253,258,266,267,268,269,
(Disazo series)
Pigment Red 37,38,41
(Monoazo lake)
PigmentRed48: 1,48: 2,48: 3,48: 4,49: 1,49: 2,50: 1,52: 1,52: 2,53: 1,53: 2,57: 1,58: 4,63: 1,63: 2,64: 1,68
(Benz imidazolone)
Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208
(Perylene)
Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224
(Diketopyrrolopyrrole)
Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272
(Condensed azo)
Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242
(Anthraquinone)
Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207
(Quinacridone series)
Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209
Other colorants such as purple, orange, brown, and black may be added for the purpose of adjusting the color tone. Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42,
攪拌機、温度計、環流冷却管、滴下ロートおよび窒素導入管を備えた2リットルのセパラブルフラスコに、クレゾールノボラック型エポキシ樹脂(日本化薬社製、EOCN-104S、軟化点92℃、エポキシ当量220)660g、カルビトールアセテート421.3g、およびソルベントナフサ180.6gを導入し、90℃に加熱・攪拌し、溶解した。 [Synthesis of Curable Resin Composition]
A 2 liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube was added to a cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy equivalent 220). ) 660 g, carbitol acetate 421.3 g, and solvent naphtha 180.6 g were introduced, heated and stirred at 90 ° C., and dissolved.
ワニス 154部(固形分100部)
Irg907(チバ・スペシヤリティケミカルズ社製) 12部
DETX (日本化薬社製) 0.5部
ジペンタエリスリトールヘキサアクリレート(DPHA/日本化薬社製) 20部
フェノールノボラック型エポキシ樹脂(ダウケミカル社製DEN-431) 15部
ビキシレノール型エポキシ樹脂(ジャパンエポキシレジン社製YX-4000)
25部
ジシアンジアミド 0.3部
メラミン 5部
硫酸バリウム (堺化学社製 硫酸バリウムB30) 100部
顔料1 C.I.PigmentBlue15:3 0.3部
顔料2 C.I.PigmentYellow147 0.8部
シリコーン系消泡剤 3部
Varnish 154 parts (
Irg907 (Ciba Specialty Chemicals) 12 parts DETX (Nippon Kayaku) 0.5 parts dipentaerythritol hexaacrylate (DPHA / Nippon Kayaku) 20 parts phenol novolac epoxy resin (Dow Chemical) DEN-431) 15 parts Bixylenol type epoxy resin (YX-4000 manufactured by Japan Epoxy Resin Co., Ltd.)
25 parts dicyandiamide 0.3 parts melamine 5 parts barium sulfate (barium sulfate B30 manufactured by Sakai Chemical Co., Ltd.) 100 parts Pigment 1 CI Pigment Blue 15: 3 0.3 part Pigment 2 CI Pigment Yellow 147 0.8 part 3 parts foam
*2:L-乳酸メチル(2-ヒドロキシメチルプロパン酸)武蔵野化学研究所社製発酵乳酸メチル(L体含有率99.6%)
*3:乳酸エチル(2-ヒドロキシエチルプロパン酸)
*4:PM(プロピレングリコールモノメチルエーテル)
*5:PMA(プロピレングリコールモノメチルエーテルアセテート)
なお、希釈溶剤の添加量は、図4に示す希釈粘度曲線からIWATA CUP 30秒時の希釈率を算出した。なお、
希釈率(%)=インキ全重量/100
時間(秒)=IWATA CUPによるインキの落下時間
インキ温度=21℃±2℃
とした。 * 1: Methyl lactate (2-hydroxymethylpropanoic acid)
* 2: L-methyl lactate (2-hydroxymethylpropanoic acid) Fermented methyl lactate manufactured by Musashino Chemical Laboratory (L-form content 99.6%)
* 3: Ethyl lactate (2-hydroxyethylpropanoic acid)
* 4: PM (propylene glycol monomethyl ether)
* 5: PMA (propylene glycol monomethyl ether acetate)
In addition, the addition amount of the dilution solvent computed the dilution rate at the time of IWATA CUP 30 second from the dilution viscosity curve shown in FIG. In addition,
Dilution rate (%) = total weight of ink / 100
Time (seconds) = ink drop time by IWATA CUP Ink temperature = 21 ° C ± 2 ° C
It was.
〈粘度の評価〉
各実施例および比較例の光硬化性熱硬化性樹脂組成物を、E型回転粘度計を用いて25℃で測定した回転数5rpm値を粘度とした。 [Performance evaluation]
<Evaluation of viscosity>
The rotation speed of 5 rpm measured at 25 ° C. using the E-type rotational viscometer for the photocurable thermosetting resin compositions of the examples and comparative examples was taken as the viscosity.
各実施例および比較例の光硬化性熱硬化性樹脂組成物を、銅厚50μmの回路パターン基板をバフロール研磨後、水洗し、乾燥してからスプレーコートまたはスクリーン印刷で乾燥後膜厚が25μmとなるよう全面塗布し、80℃の熱風循環式乾燥炉で30分間乾燥させ室温まで放冷する。放冷後、ORC社製露光装置(HMW680-GW20)を用いてステップタブレット(KodakNo2)を介して露光し、現像(30℃、0.2MPa、1質量%炭酸ナトリウム水溶液)を60秒で行った際残存するステップタブレットのパターンが7段の時を最適露光量とした。 <Evaluation of optimal exposure>
The photocurable thermosetting resin composition of each Example and Comparative Example was a circuit pattern substrate having a copper thickness of 50 μm, buffed, washed with water, dried and then dried by spray coating or screen printing, and the film thickness was 25 μm. The whole surface is coated, dried in a hot air circulation drying oven at 80 ° C. for 30 minutes, and allowed to cool to room temperature. After allowing to cool, exposure was performed through a step tablet (Kodak No. 2) using an exposure apparatus (HMW680-GW20) manufactured by ORC, and development (30 ° C., 0.2 MPa, 1 mass% sodium carbonate aqueous solution) was performed in 60 seconds. When the pattern of the remaining step tablet was 7 steps, the optimum exposure amount was set.
〈塗膜の色〉
各実施例および比較例のアルカリ現像型ソルダーレジストの硬化物の色を目視にて判断した。 [Characteristic evaluation]
<Color of coating film>
The color of the hardened | cured material of the alkali image development type solder resist of each Example and a comparative example was judged visually.
各実施例および比較例の組成物を、パターン形成された銅箔基板上にスプレーコートまたはスクリーン印刷で乾燥後膜厚が25μmとなるよう全面塗布し、60℃の熱風循環式乾燥炉で30分間乾燥させ室温まで放冷する。この基板にPET製ネガフィルムを当て、ORC社製露光装置(HMW680-GW20)で1分間減圧条件下圧着させ、その後、ネガフィルムを剥がしたときのフィルムの張り付き状態を、以下の基準で評価した。 <Finger dryness>
The composition of each Example and Comparative Example was applied on the entire surface of a patterned copper foil substrate by spray coating or screen printing so that the film thickness was 25 μm after drying, and was heated in a hot air circulation drying oven at 60 ° C. for 30 minutes. Dry and allow to cool to room temperature. A negative film made of PET was applied to this substrate, and the film was pressure-bonded under reduced pressure for 1 minute with an exposure apparatus (HMW680-GW20) manufactured by ORC, and then the sticking state of the film when the negative film was peeled off was evaluated according to the following criteria. .
各実施例および比較例の組成物を、銅めっき後φ100μm、深さ50μmに調整した微小な穴を有する基板にスプレーコートまたはスクリーン印刷で乾燥後膜厚が25μmとなるよう全面塗布し、80℃の熱風循環式乾燥炉で30分間乾燥させ室温まで放冷する。放冷後、穴上のソルダーレジストのハジキ数を目視にてカウントし、以下の基準で評価した。 <Cavity filling (for minute holes)>
The composition of each Example and Comparative Example was applied to the entire surface of the substrate having fine holes adjusted to φ100 μm and depth of 50 μm after copper plating so that the film thickness was 25 μm after drying by spray coating or screen printing, and 80 ° C. Dry in a hot air circulating drying oven for 30 minutes and allow to cool to room temperature. After standing to cool, the number of solder resists on the hole was visually counted and evaluated according to the following criteria.
○:3%以下
△:4%以上10%以下
×:10%以上
〈深部硬化性〉
各実施例および比較例の組成物を、ライン/スペースが300/300μm、銅厚50μmの回路パターン基板をバフロール研磨後、水洗し、乾燥してからスプレーコートまたはスクリーン印刷で乾燥後膜厚が25μmとなるよう全面塗布し、80℃の熱風循環式乾燥炉で30分間乾燥させ室温まで放冷する。放冷後、ORC社製露光装置(HMW680-GW20)を用いて露光した。露光パターンはスペース部に20/30/40/50/60/70/80/90/100μmのラインを描画させるパターンを使用した。露光量は、最適露光量評価によって得られた露光量とした。露光後、30℃の1質量%炭酸ナトリウム水溶液によって現像を行ってパターンを描き、150℃×60分の熱硬化をすることにより硬化塗膜を得た。 Defect rate (%) = number of repellency / total number of holes 1700 holes ○: 3% or less Δ: 4% or more and 10% or less ×: 10% or more <Deep part curability>
A circuit pattern substrate having a line / space of 300/300 μm and a copper thickness of 50 μm was subjected to buffing, washing with water, drying, and then spray coating or screen printing, and then the film thickness was 25 μm. Then, the entire surface is coated, dried in a hot air circulating drying oven at 80 ° C. for 30 minutes, and allowed to cool to room temperature. After allowing to cool, exposure was performed using an exposure apparatus (HMW680-GW20) manufactured by ORC. As the exposure pattern, a pattern for drawing a 20/30/40/50/60/70/80/90/100 μm line in the space portion was used. The exposure amount was the exposure amount obtained by the optimum exposure amount evaluation. After the exposure, development was performed with a 1% by mass aqueous sodium carbonate solution at 30 ° C. to draw a pattern, and a cured coating film was obtained by heat curing at 150 ° C. for 60 minutes.
12…銅回路
12a…微小な穴
13…硬化性樹脂組成物 DESCRIPTION OF
Claims (8)
- 基板の表層に微小な穴が形成されているプリント配線板に用いられる樹脂組成物であって、
乳酸エステルと、
カルボキシル基含有樹脂とを
含むことを特徴とする硬化性樹脂組成物。 A resin composition used for a printed wiring board in which minute holes are formed on the surface layer of a substrate,
Lactate ester,
A curable resin composition comprising a carboxyl group-containing resin. - 光重合開始剤を含むことを特徴とする請求項1に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, further comprising a photopolymerization initiator.
- 着色剤を含むことを特徴とする請求項1に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, further comprising a colorant.
- 前記乳酸エステルは、天然物由来のL-乳酸エステルであることを特徴とする請求項1に記載の硬化性樹脂組成物。 2. The curable resin composition according to claim 1, wherein the lactic acid ester is an L-lactic acid ester derived from a natural product.
- 粘度が0.1~250dPa・sであることを特徴とする請求項1に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, wherein the viscosity is 0.1 to 250 dPa · s.
- 基板の表層に微小な穴が形成されているプリント配線板を覆うソルダーレジストであることを特徴とする請求項1に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, wherein the curable resin composition is a solder resist that covers a printed wiring board in which minute holes are formed on the surface layer of the substrate.
- 乳酸エステルと、カルボキシル基含有樹脂とを含む硬化性樹脂組成物を、基材上に塗布し、乾燥して乾燥塗膜を形成し、この乾燥塗膜を硬化して形成されたことを特徴とする硬化物。 A curable resin composition containing a lactic acid ester and a carboxyl group-containing resin is applied onto a substrate, dried to form a dry coating film, and the dry coating film is cured to form. Cured product.
- 基板の表層に微小な穴が形成されているプリント配線板の基板上に、乳酸エステルと、カルボキシル基含有樹脂とを含む硬化性樹脂組成物を塗布し、乾燥して形成された乾燥塗膜を露光・現像、硬化することにより形成されたパターンを備えることを特徴とするプリント配線板。 A dried coating film formed by applying a curable resin composition containing a lactic acid ester and a carboxyl group-containing resin on a substrate of a printed wiring board in which minute holes are formed on the surface layer of the substrate, and drying the coating. A printed wiring board comprising a pattern formed by exposure, development and curing.
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JPWO2009119821A1 (en) | 2011-07-28 |
KR101612569B1 (en) | 2016-04-14 |
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JP5787516B2 (en) | 2015-09-30 |
CN101981131A (en) | 2011-02-23 |
CN101981131B (en) | 2014-01-01 |
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