WO2008059935A1 - Composition de résine photodurcissable/thermodurcissable, produit durci et planche de câblage imprimé - Google Patents

Composition de résine photodurcissable/thermodurcissable, produit durci et planche de câblage imprimé Download PDF

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Publication number
WO2008059935A1
WO2008059935A1 PCT/JP2007/072218 JP2007072218W WO2008059935A1 WO 2008059935 A1 WO2008059935 A1 WO 2008059935A1 JP 2007072218 W JP2007072218 W JP 2007072218W WO 2008059935 A1 WO2008059935 A1 WO 2008059935A1
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WIPO (PCT)
Prior art keywords
group
carbon atoms
resin composition
photocurable
thermosetting resin
Prior art date
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PCT/JP2007/072218
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English (en)
Japanese (ja)
Inventor
Nobuhito Itoh
Yoko Shibasaki
Kenji Kato
Masao Arima
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Taiyo Ink Mfg. Co., Ltd.
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Publication date
Priority claimed from PCT/JP2007/069219 external-priority patent/WO2008059670A1/fr
Application filed by Taiyo Ink Mfg. Co., Ltd. filed Critical Taiyo Ink Mfg. Co., Ltd.
Priority to KR1020087022256A priority Critical patent/KR101063643B1/ko
Priority to CN2007800089348A priority patent/CN101400706B/zh
Priority to JP2008525296A priority patent/JP4831786B2/ja
Priority to EP07831948A priority patent/EP2083019B1/fr
Priority to AT07831948T priority patent/ATE547435T1/de
Publication of WO2008059935A1 publication Critical patent/WO2008059935A1/fr
Priority to US12/195,793 priority patent/US8101336B2/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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

Definitions

  • the present invention particularly relates to a photocurable / thermosetting resin composition suitable for use in direct drawing with a laser beam as a solder resist application, a cured product, and a printed wiring pattern formed using the same. Regarding the board.
  • Patent Document 1 JP-A-2001-235858 and Patent Document 2: International Publication WO02 / 096969.
  • These technologies are capable of exhibiting sufficient photopolymerization capability even with only volatiles such as 350 to 370 nm.
  • the photopolymerization rate is very high, sufficient depth and surface hardenability cannot be obtained, and furthermore, the sensitivity decreases significantly due to deactivation of the photopolymerization initiator on the circuit after heat treatment. , Have a problem that peeling occurs on the copper circuit.
  • the present invention is capable of exhibiting a high photopolymerization ability with respect to ultraviolet light and laser light, and at the same time, sufficient deep-part curability is obtained, and further, photocuring / thermosetting resin having excellent thermal stability.
  • This composition is used for direct writing with laser light, especially for solder resist applications.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2006-010793 to Permission document 4: Japanese Patent Laid-Open No. 2006-071890.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2006-010793 to Permission document 4: Japanese Patent Laid-Open No. 2006-071890.
  • photopolymerization initiators other than oxime ester photopolymerization initiators such as phosphine oxide photopolymerization initiators together with oxime ester photopolymerization initiators.
  • the above-mentioned sulfur compound is added, and (-SH) Sulfur compound power having a mercapto group S, the mercapto group has poor reactivity at the copper interface and is stable. It was found that deactivation and delamination due to contact between the heat of the compound and copper were reduced, and the finished coating film had excellent adhesion and improved properties such as electroless gold plating.
  • the present invention has been made based on the above findings, and has the following configuration.
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or a phenyl group
  • R 2 represents an alkyl group having 1 to 7 carbon atoms or a phenyl group. Represents.
  • a photocurable thermosetting resin composition capable of alkali development comprising: (2) Photopolymerization initiator (C)
  • thermosetting resin composition which comprises one or a mixture selected from the group consisting of:
  • R 3 and R 4 each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group
  • R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R 5 and R 6 may be bonded to form a cyclic alkyl ether group.
  • thermosetting resin composition according to (1) which is a photopolymerization initiator represented by the following formula (V):
  • R is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentanol group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, or a C 2-12 alkyl group.
  • R and R are each independently a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group,
  • R represents a hydrogen atom, a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom).
  • the oxime ester photopolymerization initiator (B) is represented by the following general formula (VI)
  • thermosetting resin composition according to (1), further comprising (G) a thermosetting component.
  • thermosetting resin composition In the photocurable thermosetting resin composition according to the above (1), the absorbance of the dried coating film with respect to the light source is 0.4 to 25 per 111; Curing / thermosetting resin composition.
  • thermosetting dry film obtained by applying the photocurable 'thermosetting resin composition described in (1) above to a carrier film and drying.
  • thermosetting resin composition according to (1) (13) Printed wiring obtained by photocuring the photocurable thermosetting resin composition according to (1) above with a laser beam having a maximum wavelength of 350 to 410 nm, followed by thermosetting Board.
  • the present invention has the following effects by providing the above configuration.
  • the photocurable thermosetting resin composition of the present invention exhibits excellent photocurability with respect to a laser oscillation light source having a maximum wavelength of 350 nm to 420 nm.
  • One direct imaging system can be used, and there is no positional displacement due to the expansion and contraction of the photomask and glass substrate that has occurred in the conventional exposure method. Furthermore, there is no pattern loss due to foreign matter adhering to the photomask. High development is possible.
  • a photopolymerization initiator an oxime ester photopolymerization initiator and a phosphine oxide photopolymerization initiator are used in combination, and the sulfur compound according to the present invention is further blended to deepen the portion. It is excellent in curability and can have a cross-sectional shape as designed, and a solder resist with excellent surface curability, heat stability, and ball height can be obtained.
  • Fig. 1 is a schematic diagram of a cross-sectional shape of a resin composition obtained by exposure and development, and A to E show different evaluation shapes.
  • the carboxylic acid-containing resin (A) contained in the photocurable thermosetting resin composition of the present invention a known and commonly used resin compound containing a carboxyl group in the molecule can be used. Further, a carboxyl group-containing photosensitive resin ( ⁇ ′) force having an ethylenically unsaturated double bond in the molecule is more preferable from the viewpoint of development resistance. Specific examples include the resins listed below.
  • a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting the resulting hydroxyl group with a saturated or unsaturated polybasic acid anhydride
  • polybasic acid anhydride obtained by reacting a carboxylic acid-containing resin obtained by reacting a compound with a compound having one oxysilane ring and one or more ethylenically unsaturated groups in the molecule, etc.
  • carboxyl group-containing photosensitive resin obtained by reacting a carboxylic acid-containing resin obtained by reacting a compound with a compound having one oxysilane ring and one or more ethylenically unsaturated groups in the molecule, etc.
  • the carboxyl group-containing photosensitive resins (2) and (3) are preferable from the viewpoints of photocurability and baking properties.
  • (meth) atalylate is a general term for atalylate, metatalate, and a mixture thereof, and the same applies to other similar expressions.
  • the carboxylic acid-containing resin (A) as described above has a number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
  • the acid value of the carboxylic acid-containing resin (A) is in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. If the acid value of the carboxylic acid-containing resin is less than S40 mgKOH / g, alkali development becomes difficult.On the other hand, if it 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 a developer without distinction, and it becomes difficult to draw a normal resist pattern.
  • the weight-average molecular weight of the carboxylic acid-containing resin (A) varies depending on the resin skeleton, and generally ranges from 2,000 to 150,000, more preferably from 5,000 to 100,000. If 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, the film may be reduced during development, and the resolution may be greatly inferior. On the other hand, if the weight average molecular weight exceeds 150,000, the developability may be remarkably deteriorated and the storage stability may be inferior.
  • the amount of the carboxylic acid-containing resin (A) is preferably 10 to 80% by mass, more preferably 15 to 50% by mass, based on the total composition. If the blending amount is too small, the coating film strength decreases, which is not preferable. On the other hand, when the amount is too large, the viscosity becomes high, and the coating property and the like are deteriorated.
  • an oxime photopolymerization initiator having a functional group represented by the above general formula (I).
  • Examples of such compounds include 1,2-octanedione 1 [4- (phenylthio) 2- (O benzoyloxime)], ethanone 1 [9-ethyl 6- (2 methylbenzoyl) 9H, and rubazole.
  • the compounds represented by the above formulas (V) and (IV), ethanone 1 [9-ethyl 6- (2 methylbenzoyl) 9H force rubazol 3 yl] 1 (O-acetylyl), 2-(acetilo) Ximinomethyl) thixanthen 9-one is particularly preferred.
  • Examples of commercially available compounds include CGI 325, OXE 02, and OXE 01 manufactured by Ciba 'Specialty' Chemicals.
  • the amount of such oxime-based photopolymerization initiator (B) is preferably 0.0;! To 20 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing resin (A).
  • the ratio is preferably 0.0;! To 5 parts by mass. If the amount of the oxime-based photopolymerization initiator (B) is too small relative to 100 parts by mass of the carboxylic acid-containing resin (A), it is not preferable because sufficient photocurability cannot be obtained. On the other hand, if the amount is too large, the thick film curability is lowered and the cost of the product is increased.
  • the photocurable 'thermosetting resin composition of the present invention has, as a photopolymerization initiator, an aminoacetophenone photopolymerization initiator represented by the above general formula (III), the above general formula (IV) acylphosphine. It is preferable to use the phosphine oxide photopolymerization initiator (C) having a functional group having an oxide photopolymerization initiator in order to improve the thermal stability of the oxime ester photopolymerization initiator.
  • the photopolymerization initiator (C) other than the oxime ester photopolymerization initiator such as the phosphine oxide photopolymerization initiator 2, 4, 6 trimethylbenzoyldiphenylphosphine is used.
  • Acinolephosphine such as fin oxide, bis (2, 4, 6 trimethylbenzoyl) phenyl phosphine oxide, bis (2, 6 dimethoxybenzoinole) 1, 2, 4, 4 trimethyl monopentylphosphine oxide Oxide-based photopolymerization initiator and 2-methylolene 1
  • the blending amount of the photopolymerization initiator (C) other than the oxime ester photopolymerization initiator, such as the phosphine oxide photopolymerization initiator, is 100 parts by mass of the carboxylic acid-containing resin (A).
  • the ratio is 60 parts by mass or less, preferably 50 parts by mass or less.
  • the composition of the present invention can be used in combination with a known and commonly used photopolymerization initiator, photoinitiator assistant, and sensitizer, if necessary.
  • photopolymerization initiators other than the above-mentioned compounds, photopolymerization initiation assistants, and sensitizers can be used.
  • photopolymerization initiators other than the above-mentioned compounds, photopolymerization initiation assistants, and sensitizers can be used.
  • benzoin compounds, acetophenone compounds, And anthraquinone compounds, thixanthone compounds, ketal compounds, benzophenone compounds, xanthone compounds, and tertiary amine compounds for example, benzoin compounds, acetophenone compounds, And anthraquinone compounds, thixanthone compounds, ketal compounds, benzophenone compounds, xanthone compounds, and tertiary amine compounds.
  • benzoin compound examples include, for example, benzoin, benzoin methyl ethereol, benzoin ethinoreethenore, and benzoin isopropinoreethenore.
  • acetophenone compound examples include, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-1-2-phenylacetophenone, and 1,1-dichloroacetophenone.
  • anthraquinone compounds include, for example, 2 methylanthraquinone, and 2 [0050]
  • Specific examples of thixanthone compounds include, for example, 2,4 dimethylthioxanthone. 2, 4 Jetylthioxanthone, 2 Black mouth thixanthone, 2, 4 Diisopropyl thixanthone.
  • ketal compound examples include, for example, acetophenone dimethyl ketal and benzinoresimethinoreketanol.
  • benzophenone compound examples include, for example, benzophenone, 4 benzoyl diphenyl sulfide, 4 benzoyl rho 4'-methyldiphenyl sulfide, 4 benzoinoleure 4, Tildiphenylsulfide, 4 benzoyl 4 'propyldiphenylsulfide.
  • tertiary amine compound examples include, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4, 4'-dimethylaminobenzobenzoenone (Nisso-Cure I MABP manufactured by Nippon Soda Co., Ltd.), 4, 4 Dialkylaminobenzophenones such as' -jetylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), dialkyl such as 7- (jetylamino) -4 -methyl-2H—1-benzopiran 2one (7 (jetylamino) 4 methylcoumarin) Amino group-containing coumarin compounds, 4-dimethylaminobenzoic acid ethyl (Nippon Kayaku Co., Ltd., CACURE EPA), 2-dimethylaminobenzoic acid ethyl (International Bio Synthetics Quantacure DMB), 4-dimethylaminobenz
  • thixanthone compounds and tertiary amine compounds are preferred.
  • Thioxanthone compounds such as 2,4 dimethylenolechixanthone, 2,4 jetinolecidate xanthone, 2,4 dithioxanthone, 2,4-diisopropylthioxanthone, etc. are preferred because of their deep curability. Is preferred.
  • the mixing ratio of such a thixanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). If the compounding ratio of thixanthone compound is too high, the thick film curability will decrease and the product This leads to an increase in cost.
  • a compound having a dialkylaminobenzene structure is preferred, 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 preferred. Les.
  • a dialkylaminobenzophenone compound 4,4′-jetylaminobenzophenone has low toxicity and is preferable.
  • Dialkylamino group-containing coumarin compounds having a maximum absorption wavelength in the range of 350 to 410 nm have a maximum absorption wavelength in the ultraviolet region, so that not only a colorless and transparent photosensitive composition with little coloration but also a color pigment is used.
  • a colored solder resist film reflecting the color can be provided.
  • 7- (Jetylamino) -4-methyl 2H-1-benzopyran 2 -on is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.
  • the blending ratio of such a tertiary amine compound is preferably 0.;! To 20 parts by mass, more preferably 0. to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). ! ⁇ 10 parts by mass.
  • the compounding ratio of the tertiary amine compound is less than 0.1 part by mass, a sufficient sensitizing effect tends not to be obtained.
  • the amount exceeds 20 parts by mass light absorption on the surface of the dry calendar resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease.
  • photopolymerization initiator can be used alone or as a mixture of two or more.
  • the total amount of such photopolymerization initiator, photopolymerization initiation assistant, and sensitizer is within a range of 35 parts by mass or less with respect to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). Preferably it is. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.
  • the compound (D) having two or more ethylenically unsaturated groups in the molecule used in the photocurable / thermosetting resin composition of the present invention is photocured by irradiation with active energy rays,
  • the ethylenically unsaturated group-containing carboxylic acid-containing resin (A) is insolubilized or assists insolubilization in an alkaline aqueous solution.
  • Such compounds include ethylene glycol, meso Diacrylates of glycols such as toxitetraethylene glycolol, polyethylene glycolol, propylene glycol; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or these Polyvalent acrylates such as ethyloxide adducts or propylene oxide adducts; phenoxy acrylate, bisphenol A diatalylate, and ethylene oxide adducts or propylene oxide of these phenols
  • Examples include glycidyl ether polyvalent acrylates such as nurate; and melamine acrylate, and / or metatalates corresponding to the acrylate.
  • an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol nopolac-type epoxy resin, and further a hydroxy acrylate such as pentaerythritol triacrylate with a hydroxyl group of the epoxy acrylate resin.
  • rate and isophorone Epoki reacted a half urethane compound Jiisoshianeto such Jiisoshianeto urethane Atari rate such compound forces s, and the like.
  • Such an epoxy acrylate resin can improve photocurability without reducing touch dryness.
  • the compounding amount of the compound (D) having two or more ethylenically unsaturated groups in such a molecule is based on 100 parts by mass of the ethylenically unsaturated group-containing carboxylic acid-containing resin (A). 5 to; 100 parts by mass, more preferably;! To 70 parts by mass.
  • the blending amount 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, which is not preferable.
  • the amount exceeds 100 parts by mass the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.
  • R 3 represents an alkyl group, an aryl group or a substituted aryl group
  • R 4 represents a hydrogen atom or an alkyl group
  • R 3 and R 4 are bonded to each other to form oxygen
  • Non-metallic atom group necessary to form a 5- to 7-membered ring that may contain a heteroatom selected from sulfur and nitrogen atoms.
  • sulfur compounds are tautomers and exist as both SH and NH groups.
  • a carboxylic acid-containing resin is included, and it is presumed that the interaction stabilizes the NH group (base). Since the SH group is highly reactive to copper, the force that prevents development is possible. The NH group is inert to copper and does not impair the developability.
  • Examples of the sulfur compound (E) include mercaptobenzothiazole, 3 mercapto-4 methyl 4H—1, 2, 4-triazolene, 5-methyl-1,3,4-thiadiazole 2-thiol, 1 phenyl 5- Examples include mercapto 1H-tetrazole.
  • a known and commonly used inorganic or organic filler can be blended.
  • sodium sulfate and spherical silica are preferably used.
  • XP 0596, XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 104 5 all product grade names
  • NANOPOX trade name
  • XP 0516, XP 0525 from Hanse-Chemie XP 0314 product grade names
  • These may be used alone or in combination of two or more. These fillers suppress hardening shrinkage of the coating film and improve basic properties such as adhesion and hardness, as well as allow active energy rays to pass through the photocurable resin composition. It is used for the purpose of suppressing interference with light reflection and refraction.
  • the amount of these fillers to be added is 0.1% with respect to 100 parts by mass of the carboxylic acid-containing resin (A).
  • thermosetting component can be blended.
  • the thermosetting component used in the present invention include amino resins such as melamine resins and benzoquamine resins, block isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and episulfide resins.
  • a thermosetting resin can be used. Among these, heat having two or more cyclic ether groups and / or cyclic thioether groups in a molecule such as a polyfunctional epoxy compound (G-l), a polyfunctional oxetane compound (G-2), and episulfide resin.
  • a curable component hereinafter abbreviated as a cyclic (thio) ether compound is particularly preferred.
  • Examples of the polyfunctional epoxy compound (G-1) include Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, Epiclon 840, Epiclone 840, and Epiclone manufactured by Dainippon Ink & Chemicals, Japan Epoxy Resin. 850, Epiclon 1050, Epiclon 20 55, EPO made by Tohto Kasei Co., Ltd. YD— 011, YD— 013, YD— 127, YD— 128, DU 317, DER 331, DER 661, DER 664, Chinoku.
  • nopolac-type epoxy resins Nopolac-type epoxy resins
  • Epiclon 830 manufactured by Dainippon Ink & Chemicals
  • Epicoat 807 manufactured by Japan Epoxy Resin, manufactured by Toto Kasei Epototo YDF—170, YDF175, YDF—2004, Bisphenol F-type epoxy resin such as Araldide ⁇ ⁇ 30 6 manufactured by Chino 'Specialty' Chemicals (all trade names); Epototo S ⁇ 2004, ST— Hydrogenated bisphenolate type epoxy resin such as 2007, ST-3000 (trade name);
  • Epicoat 604 manufactured by Japan Epoxy Resin Co., Epotote YH 434 manufactured by Tohto Kasei Co., Ltd., Aralda manufactured by Chino 'Specialty' Chemicals MY720, Sumitomo Chemical Co., Ltd.
  • Heterocyclic epoxy resins such as T810, TEPIC manufactured by Nissan Chemical Industries (all trade names); diglycidyl phthalate resins such as Blemmer DGT manufactured by Nippon Oil &Fats; Tetraglycidylxylenoxy such as ⁇ 1063 manufactured by Tohto Kasei Co., Ltd. Luetan resin: Nippon Steel Chemical Co., Ltd. ESN-190, ⁇ SN-360, Dainippon Ink & Chemicals, Inc. HP-4032, EXA-4750, EXA-4700 Naphthalene group-containing epoxy resins such as Dainippon Ink & Chemicals, Inc.
  • Examples of the polyfunctional oxetane compound (G2) include bis [(3methyl-3-oxetaninoremethoxy) methinore] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4bis [ (3-Methyl-3-oxetanylmethoxy) methinole] benzene, 1,4bis [(3-Ethyl3-oxetanylmethoxy) methinole] benzene, (3-Methyl-3-oxetanyl) methyl acrylate, (3-Ethylate) Of 3-functional oxetanes such as (3-oxetanyl) methyl attalylate, (3-methyl-3-oxetanyl) methyl metatalylate, (3-ethyl-3-oxetanyl) methyl metatalylate and oligomers or copolymers thereof.
  • oxetane and nopolac resins poly (p-hydroxystyrene), hardened bisphenols, calixarenes, Box resorcin arenes, or the like ethers of a resin having a hydroxyl group such as Shirusesuki Okisan the like.
  • a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.
  • Examples of the compound having two or more cyclic thioether groups in the molecule include force S such as Bisphenol A-type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., Ltd.
  • force S such as Bisphenol A-type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., Ltd.
  • episulfide resin in which the oxygen atom of the epoxy group of the nopolac-type epoxy resin is replaced with a sulfur atom can be used by using the same synthesis method.
  • the amount of such a cyclic (thio) ether compound contains the ethylenically unsaturated group.
  • the cyclic (thio) ether group is in the range of 0.6 to 2.0 equivalents, preferably 0.8 to 1.5 equivalents with respect to 1 equivalent of the carboxyl group of the carboxylic acid-containing resin.
  • the carboxyl group remains, which is not preferable because the heat resistance, alkali resistance, electrical insulation and the like are lowered.
  • the above range is exceeded, the low molecular weight cyclic hydrocarbon ether group remains, which is not preferable because the strength of the coating film is lowered.
  • thermosetting component When the cyclic (thio) ether compound is used as the thermosetting component, it is preferable to contain a thermosetting catalyst.
  • thermosetting catalysts include imidazole, 2 methylenoremidazolene, 2 ethenoreidamidole, 2 ethenorei 4-methinoreidamidazonore, 2-phenylimidazole, 4 phenylimidazole.
  • thermal curing catalyst for epoxy resins and oxetane compounds that are not limited to these, or those that promote the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups may be used alone or in combination of two or more. Even if you use it, it does not turn.
  • These s-triazine derivatives can also be used, and preferably a compound that also functions as an adhesion-imparting agent is used in combination with the thermosetting catalyst.
  • the amount of the thermosetting catalyst to be blended is usually a normal quantitative ratio, and for example, it is preferably 0 with respect to 100 parts by mass of the ethylenically unsaturated group-containing carboxylic acid-containing resin (A) or thermosetting component. ! ⁇ 20 parts by mass, more preferably 0.5-15.0 parts by mass.
  • the photocurable / thermosetting resin composition of the present invention is applied for synthesis of the ethylenically unsaturated group-containing potent rubonic acid-containing resin (A), adjustment of the composition, or on a substrate or a carrier film.
  • An organic solvent can be used to adjust the viscosity.
  • organic solvents examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methylcetosolve, butylcetosolve, carbitol, methylcarbide Tonore, Butinorecanorebitonore, Propylene Glycole Monomethinoreatenore, Dipropylene Glyconore Monomethinoreatenore, Dipropylene Glycoleo Regina Pretenore, Triecirene Glyconore Monoceno Reteinore, etc.
  • ketones such as methyl ethyl ketone and cyclohexanone
  • aromatic hydrocarbons such as tolu
  • Dichloropropylene glycolate Dipropylene glycolenomethineate acetate, Propyleneglycolenomethineate acetate, Propylene glycolenoleatenoacetate, Propylene glycolenobutyinoate acetate
  • Glycol ether acetates such as: Ethyl acetate, butyl acetate and esters such as acetic acid ester of the above glycol ethers; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane
  • Petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.
  • Such an organic solvent is used alone or as a mixture of two or more.
  • the photo-curable 'thermosetting resin composition of the present invention further contains phthalocyanine as required.
  • the photocurable / thermosetting resin composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and is formed on the circuit-formed substrate by a dip coating method, a flow coating method, a mouth coating method, a bar coating method, or the like. It is applied by a method such as the one-tar method, screen printing method, curtain coating method, etc., and the organic solvent contained in the composition is evaporated and dried (temporary drying) at a temperature of about 60-100 ° C. A film can be formed.
  • a resin insulation layer can be formed by applying the composition described above onto a carrier finolene, and drying and winding the film as a film on a circuit-formed substrate.
  • the contact type (or non-contact type) is selectively exposed with active energy rays through a photomask with a pattern formed, and the unexposed part is diluted with a dilute alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution).
  • a dilute alkaline aqueous solution for example, 0.3 to 3% sodium carbonate aqueous solution.
  • a resist pattern is formed.
  • the carboxyl group of the ethylenically unsaturated group-containing carboxylic acid-containing resin (A) reacts with the thermosetting component (G).
  • a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics can be formed.
  • the substrates are laminated on a substrate using a hot roll laminator or the like (bonded so that the photosensitive resin composition layer and the substrate are in contact with each other).
  • a hot roll is made so that the photosensitive resin composition is in contact with the substrate. Paste using a laminator.
  • All grades (FR-4, etc.) of copper-clad laminates, other polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, etc. can be used.
  • Volatile drying performed after the photocurable / thermosetting resin composition of the present invention is applied may be a hot-air circulating drying oven, an IR oven, a hot plate, a competition oven, or the like (for an air heating method using steam). This method can be carried out by using a method equipped with a heat source to bring the hot air in the dryer into countercurrent contact and a method of spraying on a support from a nozzle.
  • the obtained coating film is exposed (irradiated with active energy rays).
  • the exposed portion (the portion irradiated by the activated energy line) is cured.
  • 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
  • a gas laser or a solid-state laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used.
  • the amount of exposure varies depending on the film thickness etc. Generally 5 to 200m
  • a direct drawing device for example, a device manufactured by Nippon Orbotech, manufactured by Pentax, manufactured by Hitachi Via Mechanitas, or manufactured by Ball Semiconductor Corporation can be used. Good. Also, a known ultraviolet exposure machine can be used.
  • the developing method may be a dating method, a shower method, a spray method, a brush method, or the like.
  • the developer may be potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, key. Alkaline aqueous solutions such as sodium acid, ammonia and amines can be used.
  • Examples 1 to 8 in Tables 1 and 2 are compositions of the present invention
  • Comparative Examples 1 and 4 do not contain a phosphine oxide photopolymerization initiator
  • Comparative Examples 2 and 5 are sulfur compounds.
  • Comparative Example 3 departs from the present invention in that the sulfur compound contains a sulfur compound different from the sulfur compound of the present invention.
  • the photo-curing / thermosetting resin compositions of Examples and Comparative Examples were screen printed using a circuit pattern board with 300/300 line / space and copper thickness of 35 m after buffing, washing with water and drying. And dry for 30 minutes in a hot air circulating drying oven at 80 ° C. After drying, exposure was performed using a direct drawing apparatus for each wavelength. The exposure pattern used was a pattern to draw 20/30/40/50/60/70/80/90/100 ⁇ m lines in the space. Active energy rays were irradiated so that the exposure amount was 40 mj / cm 2 on the photosensitive resin composition. 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.
  • the photocurable thermosetting resin compositions of the examples and comparative examples were obtained by polishing a circuit pattern substrate having a line / space of 300/300 and a copper thickness of 50 m, washing with water and drying. Apply by screen printing and dry for 30 minutes in a hot air circulation drying oven at 80 ° C. After drying, exposure was performed using a direct drawing apparatus for each wavelength.
  • the exposure pattern used was a pattern for drawing lines with a space of 20/30/40/50/60/70/80/90/100 ⁇ m.
  • the active energy line was irradiated so that the exposure amount was 40 mj / cm 2 on the photosensitive resin composition. After exposure, development was performed with an aqueous sodium carbonate solution to form a pattern.
  • E evaluation Surface layer thickening and undercut
  • a evaluation but also C evaluation and D evaluation are levels that can be used as solder resist.
  • C evaluation and D evaluation are levels that can be used as solder resist.
  • those with B evaluation have insufficient surface curability and inferior appearance and electrical characteristics, and those with E evaluation are at a level where the line and undercut parts peel off and cannot be used as a solder resist immediately. .
  • the photo-curable / thermosetting resin compositions of the above Examples and Comparative Examples were subjected to screen printing after the circuit pattern substrate having a line / space force of 3 ⁇ 400 / 300 and a copper thickness of 35 m was buffed, washed with water and dried. And dry for 60 minutes in a hot air circulating drying oven at 80 ° C. After drying, exposure was performed using a direct drawing apparatus for each wavelength. The exposure pattern used was an overall exposure pattern. The active energy line was irradiated so that the exposure amount was 40 mj / cm 2 on the photosensitive resin composition. After exposure, development (30 ° C, 0.2 MPa, 1% by weight aqueous sodium carbonate solution) was performed in 60 seconds to draw a pattern, and a cured coating film was obtained by heat curing at 150 ° C for 60 minutes.
  • the surface curability of the cured coating film thus obtained was evaluated for the glossiness at 60 ° using a gloss meter Micro Trigloss (manufactured by Big Gardner).
  • the evaluation criteria were a glossiness of 50 or higher after development as good and a glossiness of less than 50 as poor.
  • the evaluation results are shown in Tables 3 and 4.
  • an ultraviolet-visible spectrophotometer Ubest-V-570DS manufactured by JASCO Corporation
  • an integrating sphere device ISN-470 manufactured by JASCO Corporation
  • UV-visible spectrophotometer Ubest-V-570DS manufactured by JASCO Corporation
  • ISN-470 manufactured by JASCO Corporation an ultraviolet-visible spectrophotometer
  • the absorbance of the produced glass plate with the dried coating film was measured, and the absorbance of the dried film with the baseline force could be calculated, and the absorbances at the target wavelengths of 355 nm and 405 nm were obtained.
  • this operation is performed with the applicator changing the coating thickness in four stages, and graphs of the coating thickness and absorbance at 355 nm and 405 nm are created.
  • the absorbance of the dried coating film of 25 ⁇ was calculated and taken as the respective absorbance.
  • the evaluation results are shown in Tables 3 and 4.
  • compositions prepared in the blending examples described in the examples and comparative examples in the table below were applied to a copper clad laminate formed with a circuit pattern, dried at 80 ° C for 30 minutes, and then subjected to a high-pressure mercury lamp.
  • Exposed at 20mJ using ORRC EXP-2021 equipped with developed with sodium carbonate aqueous solution in the same way as the previous example to form a pattern, and after irradiation with UV light of lOOOmj / cm 2 with a high-pressure mercury lamp
  • a printed wiring board on which a solder resist was formed was obtained by thermosetting at 150 ° C. for 60 minutes.
  • the photocurable / thermosetting resin compositions of the examples according to the present invention can exhibit high photopolymerization ability with respect to ultraviolet light and laser light.
  • a composition with sufficient deep-curing properties and excellent surface curability and thermal stability, especially for solder resist applications that require electroless gold plating and for direct writing with laser light It is possible to provide a photocurable / thermosetting resin composition suitable for the present invention, and a printed wiring board patterned using the composition.
  • the photocurable thermosetting resin composition of the present invention can exhibit a high photopolymerization ability with respect to 350 to 410 nm laser light and is sufficient. It is a composition that provides deep curability, and has excellent surface curability and thermal stability, especially for solder resist applications that require electroless gold plating, and with a laser beam of 350 to 410 nm. It is possible to provide a photocurable / thermosetting resin composition suitable for use in direct drawing by the use of the resin, and a printed wiring board patterned using the composition.
  • Example 1 A test in which the photopolymerization initiator (C) was replaced with another type of photopolymerization initiator (C) was conducted on Example 1 in Table 1 relating to a solder resist compatible with a 355 nm laser.
  • the test was carried out using 6 chemical specialty chemicals). Same as Example 1 The same result was obtained. However, 40mj / cm 2 is not enough for the exposure amount when creating the substrate, and 50 mj / cm is necessary.
  • Example 1 the sulfur compound (D) was converted from mercaptobenzothiazole to 3 mercapto.
  • Example 1 the sulfur compound (D) was converted from mercaptobenzothiazole to 5-methyl-
  • Example 1 the sulfur compound (D) is converted from mercaptobenzothiazole to 1 phenol.
  • the photosensitive resin composition prepared in accordance with Example 1 was diluted with methyl ethyl ketone, applied onto a carrier film, dried by heating in a hot air dryer at 80 ° C for 30 minutes, and a thickness of 20 m. A photosensitive resin composition layer was formed. Further, a cover film was laminated thereon to obtain a dry film. After that, the cover film is peeled off, the film is heat-laminated on the patterned copper foil substrate, and then exposed in the same manner. After the exposure, the carrier film is peeled off and developed with a 1% aqueous sodium carbonate solution at 30 ° C for 60 seconds to form a film. Formed.
  • Example 1 The test substrate having the cured film thus obtained was subjected to an evaluation test of each characteristic by the test method and the evaluation method described above. The result was equivalent to Example 1.

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Abstract

L'invention concerne une composition de résine photodurcissable/thermodurcissable qui présente une excellente aptitude au durcissement en surface et une excellente aptitude au durcissement en profondeur. Cette composition de résine peut être dessinée par une lumière laser ayant une longueur d'onde de 350-410 nm, et est utilisable comme anti-soudure pour une imagerie directe au laser. Cette composition contient (A) une résine contenant un acide carboxylique, (B) un initiateur de photopolymérisation de type ester d'oxime, tel que la 2-(acétyloxyiminométhyl)thioxanthène-9-one, (C) un initiateur de photopolymérisation autre que (B), tel que l'oxyde de 2,4,6-triméthylbenzoyl-diphényl-phosphine, et (E) un composé du soufre, tel que le 2-mercaptobenzothiazole.
PCT/JP2007/072218 2006-11-15 2007-11-15 Composition de résine photodurcissable/thermodurcissable, produit durci et planche de câblage imprimé WO2008059935A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
KR1020087022256A KR101063643B1 (ko) 2006-11-15 2007-11-15 광경화성 수지 조성물, 경화물 및 인쇄 배선판
CN2007800089348A CN101400706B (zh) 2006-11-15 2007-11-15 光固化性热固化性树脂组合物、固化物以及印刷线路板
JP2008525296A JP4831786B2 (ja) 2006-11-15 2007-11-15 光硬化性・熱硬化性樹脂組成物、硬化物及びプリント配線板
EP07831948A EP2083019B1 (fr) 2006-11-15 2007-11-15 Composition de résine photodurcissable/thermodurcissable et film obtenu
AT07831948T ATE547435T1 (de) 2006-11-15 2007-11-15 Lichthärtbare/wärmehärtende harzzusammensetzung und daraus resultierender film
US12/195,793 US8101336B2 (en) 2006-11-15 2008-08-21 Photocurable and thermosetting resin composition, cured product thereof, and printed circuit board

Applications Claiming Priority (4)

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JP2006309105 2006-11-15
JP2006-309105 2006-11-15
PCT/JP2007/069219 WO2008059670A1 (fr) 2006-11-15 2007-10-01 Composition de résine photodurcissable/thermodurcissable, object durci et plaque de câblage imprimée
JPPCT/JP2007/069219 2007-10-01

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JP2010039475A (ja) * 2008-06-10 2010-02-18 Fujifilm Corp 紫外光レーザー露光用感光性樹脂組成物、パターン形成方法、その方法を用いて製造したカラーフィルタ、カラーフィルタの製造方法および液晶表示装置
JPWO2008140017A1 (ja) * 2007-05-11 2010-08-05 日立化成工業株式会社 感光性樹脂組成物、感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法
JP2010224267A (ja) * 2009-03-24 2010-10-07 Toyo Ink Mfg Co Ltd 青色着色組成物、カラーフィルタの製造方法およびカラーフィルタ
JP2011065088A (ja) * 2009-09-18 2011-03-31 Taiyo Holdings Co Ltd 感光性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP2014043523A (ja) * 2012-08-28 2014-03-13 Tamura Seisakusho Co Ltd 白色活性エネルギー線硬化性樹脂組成物
JP2014186266A (ja) * 2013-03-25 2014-10-02 Goo Chemical Co Ltd ソルダーレジスト用樹脂組成物及びプリント配線板
JP2018049220A (ja) * 2016-09-23 2018-03-29 株式会社タムラ製作所 感光性樹脂組成物

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JP2001235858A (ja) 1999-12-15 2001-08-31 Ciba Specialty Chem Holding Inc 感光性樹脂組成物
WO2002096969A1 (fr) 2001-05-25 2002-12-05 Taiyo Ink Manufacturing Co., Ltd. Composition de resine photo- et thermodurcissable
JP2006010793A (ja) 2004-06-23 2006-01-12 Jsr Corp 着色層形成用感放射線性組成物およびカラーフィルタ
JP2006071890A (ja) 2004-09-01 2006-03-16 Fuji Photo Film Co Ltd 染料含有ネガ型硬化性組成物、カラーフィルタおよびその製造方法
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JP2007033467A (ja) * 2005-06-22 2007-02-08 Tokyo Ohka Kogyo Co Ltd 感光性組成物およびブラックマトリクス
JP2007219362A (ja) * 2006-02-20 2007-08-30 Toyo Ink Mfg Co Ltd 重合性組成物およびそれを用いたネガ型レジストおよびそれを用いた画像パターン形成方法。

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JP2001235858A (ja) 1999-12-15 2001-08-31 Ciba Specialty Chem Holding Inc 感光性樹脂組成物
WO2002096969A1 (fr) 2001-05-25 2002-12-05 Taiyo Ink Manufacturing Co., Ltd. Composition de resine photo- et thermodurcissable
JP2006010793A (ja) 2004-06-23 2006-01-12 Jsr Corp 着色層形成用感放射線性組成物およびカラーフィルタ
JP2006071890A (ja) 2004-09-01 2006-03-16 Fuji Photo Film Co Ltd 染料含有ネガ型硬化性組成物、カラーフィルタおよびその製造方法
WO2006043638A1 (fr) * 2004-10-20 2006-04-27 Mitsubishi Chemical Corporation Composition photosensible, matériau de base de formation d’image, matériau de formation d’image, et procédé de formation d’image
JP2007033467A (ja) * 2005-06-22 2007-02-08 Tokyo Ohka Kogyo Co Ltd 感光性組成物およびブラックマトリクス
JP2007219362A (ja) * 2006-02-20 2007-08-30 Toyo Ink Mfg Co Ltd 重合性組成物およびそれを用いたネガ型レジストおよびそれを用いた画像パターン形成方法。

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2008140017A1 (ja) * 2007-05-11 2010-08-05 日立化成工業株式会社 感光性樹脂組成物、感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法
JP4985768B2 (ja) * 2007-05-11 2012-07-25 日立化成工業株式会社 感光性樹脂組成物、感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法
JP2010039475A (ja) * 2008-06-10 2010-02-18 Fujifilm Corp 紫外光レーザー露光用感光性樹脂組成物、パターン形成方法、その方法を用いて製造したカラーフィルタ、カラーフィルタの製造方法および液晶表示装置
JP2010224267A (ja) * 2009-03-24 2010-10-07 Toyo Ink Mfg Co Ltd 青色着色組成物、カラーフィルタの製造方法およびカラーフィルタ
JP2011065088A (ja) * 2009-09-18 2011-03-31 Taiyo Holdings Co Ltd 感光性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP2014043523A (ja) * 2012-08-28 2014-03-13 Tamura Seisakusho Co Ltd 白色活性エネルギー線硬化性樹脂組成物
JP2014186266A (ja) * 2013-03-25 2014-10-02 Goo Chemical Co Ltd ソルダーレジスト用樹脂組成物及びプリント配線板
JP2018049220A (ja) * 2016-09-23 2018-03-29 株式会社タムラ製作所 感光性樹脂組成物

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