WO2008050768A1 - Composition de résist de brasage photodurcissable/thermodurcissable, et carte à circuits imprimés utilisant celle-ci - Google Patents

Composition de résist de brasage photodurcissable/thermodurcissable, et carte à circuits imprimés utilisant celle-ci Download PDF

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Publication number
WO2008050768A1
WO2008050768A1 PCT/JP2007/070654 JP2007070654W WO2008050768A1 WO 2008050768 A1 WO2008050768 A1 WO 2008050768A1 JP 2007070654 W JP2007070654 W JP 2007070654W WO 2008050768 A1 WO2008050768 A1 WO 2008050768A1
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WO
WIPO (PCT)
Prior art keywords
solder resist
parts
resist composition
aromatic ring
carboxyl group
Prior art date
Application number
PCT/JP2007/070654
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English (en)
Japanese (ja)
Inventor
Yoshikazu Daigo
Shigeru Ushiki
Original Assignee
Taiyo Ink Mfg. Co., Ltd.
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Filing date
Publication date
Application filed by Taiyo Ink Mfg. Co., Ltd. filed Critical Taiyo Ink Mfg. Co., Ltd.
Priority to JP2008519757A priority Critical patent/JP4538521B2/ja
Priority to CN2007800014375A priority patent/CN101356475B/zh
Publication of WO2008050768A1 publication Critical patent/WO2008050768A1/fr

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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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • 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
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/20—Details of printed circuits not provided for in H05K2201/01 - H05K2201/10
    • H05K2201/2054—Light-reflecting surface, e.g. conductors, substrates, coatings, dielectrics

Definitions

  • the present invention is suitable for use as a permanent mask of a printed wiring board. After exposure, an image is formed by developing with an alkaline aqueous solution, and then heat-cured to form a high-reflectance solder resist film.
  • the present invention relates to a photocurable / thermosetting solder resist composition that can be formed, and a printed wiring board obtained by forming a solder resist pattern on the surface of a printed wiring board on which a circuit is formed using the composition.
  • a printed wiring board is generally formed by removing unnecessary portions of a copper foil bonded to a laminated board by etching to form a circuit wiring. Electronic components are arranged at predetermined locations by soldering. Yes.
  • a solder resist film is used for manufacturing such a printed wiring board. That is, the solder resist film is used as a protective film for circuits when soldering electronic components.
  • the solder resist film prevents solder from adhering to unnecessary parts during soldering and prevents the circuit conductor from being exposed directly to air and reacting with oxygen and moisture. It also functions as a permanent protective film for circuit boards. Therefore, various properties such as adhesion, electrical insulation, solder heat resistance, solvent resistance, and chemical resistance are required.
  • the alkali developing type photoresist method has become the mainstream because of the photoresist method that can accurately form fine patterns, especially environmental considerations! /
  • Japanese Patent Publication No. 1 54390 and Japanese Patent Publication No. 7-17737 contain nopolak-type Epoch
  • a liquid resist ink composition which can be developed with an aqueous alkali solution based on a reaction product obtained by reacting an unsaturated resin with an unsaturated monocarboxylic acid and further adding a polybasic acid anhydride.
  • solder resist films have been formed on light emitting diodes (LEDs) that emit light at low power, such as backlights for liquid crystal displays of portable terminals, personal computers, televisions, etc., and light sources for lighting fixtures.
  • LEDs light emitting diodes
  • the solder resist film In order to efficiently use the light of the LED mounted directly on the printed wiring board, the solder resist film has a high reflectance as described above, and at the same time, the LED is used as a light source for the LED. It needs to be kept over the period of use.
  • a general solder resist composition includes a component having an aromatic ring as one means for improving heat resistance.
  • the aromatic ring has a property of gradually reacting with light or heat, and the solder resist film formed by such a sono-redder resist composition is gradually used during the LED mounting period. There is a problem that the reaction causes deterioration such as yellowing.
  • An object of the present invention is to provide a white photocurable / thermosetting solder resist composition capable of forming a highly reflective solder resist film that is less susceptible to light degradation and heat degradation, and the white An object of the present invention is to provide a printed wiring board having a solder resist film having a high reflectivity formed by using a photocurable / thermosetting solder resist composition.
  • (A) a carboxyl group-containing resin having no aromatic ring, (B) a photopolymerization initiator, (C) a hydrogenated epoxy compound, (D) Rutile titanium oxide, and (E) a white photo-curing / thermosetting solder resist characterized by containing a diluent A composition is provided.
  • a solder resist film is formed on the surface of a printed wiring board on which a circuit has been formed using the white photocurable / thermosetting solder resist composition according to the first aspect.
  • a printed wiring board obtained by forming is provided.
  • the white solder resist composition of the present invention comprises (A) a carboxyl group-containing resin having no aromatic ring, (B) a photopolymerization initiator, (C) a hydrogenated epoxy compound, (D) a rutile-type oxidation. Titanium, and (E) a diluent.
  • Carboxyl group-containing resin (A) includes an aromatic ring! /, A resin having a carboxy group, which itself has a photosensitive unsaturated double bond.
  • a resin having a carboxy group, which itself has a photosensitive unsaturated double bond can be used, and is not limited to a specific one.
  • those having no aromatic ring any of oligomers or polymers can be preferably used. That is,
  • An aliphatic unsaturated carboxylic acid and an aliphatic polymerizable monomer having 2 to 20 carbon atoms specifically, an aliphatic (meth) attalyloyl compound, an aliphatic butyl ether, a butyl ester of a fatty acid, etc.
  • a carboxyl group-containing (meth) acrylic copolymer resin produced from an aliphatic polymerizable monomer having 2 to 20 carbon atoms, and an oxysilane ring and an ethylenically unsaturated group in one molecule.
  • a photosensitive carboxyl group-containing resin obtained by reaction with 20 aliphatic polymerizable monomers;
  • An aliphatic polymerizable monomer having 4 to 20 carbon atoms each having one epoxy group and an unsaturated double bond in one molecule for example, glycidyl (meth) acrylate
  • unsaturated double Examples of the copolymer with an aliphatic polymerizable monomer having 2 to 20 carbon atoms having a bond specifically, an aliphatic (meth) attalyloyl compound, an aliphatic butyl ether, a fatty butyl ester, etc.
  • a photosensitivity obtained by reacting an aliphatic unsaturated monocarboxylic acid and reacting the resulting secondary hydroxyl group with a saturated or unsaturated aliphatic polybasic acid anhydride.
  • Photosensitive hydroxyl group and carboxyl group-containing resin obtained by reacting an aliphatic polymerizable monomer having 4 to 20 carbon atoms having a bond (for example, glycidyl (meth) acrylate).
  • aliphatic includes a compound containing a cyclo ring such as a cyclohexane ring or a cyclohexene ring in the molecule.
  • a photosensitive carboxyl group-containing resin obtained by a reaction between a resin and (b) an aliphatic polymerizable monomer having 4 to 20 carbon atoms having an oxysilane ring and an ethylenically unsaturated group in one molecule is preferable.
  • the carboxyl group-containing (meth) acrylic copolymer resin (a) produced from an aliphatic polymerizable monomer having 2 to 20 carbon atoms includes (meth) acrylic acid ester having 4 to 20 carbon atoms, and 1 It is obtained by co-polymerizing an aliphatic compound having one unsaturated group and at least one carboxyl group in the molecule.
  • Examples of the (meth) acrylic acid ester constituting the copolymer resin (a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) ) (Meth) acrylic acid alkyl esters such as acrylate, hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxy pill (meth) acrylate, hydroxybutyl (meth) acrylate , Force Prolataton Modified 2-Hydroxy Shetyl (Meth) acrylate (hydroxy) -containing (meth) acrylic esters, methoxy diethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxy diethylene glycol (meta ) Atarylate, methoxytri Examples include glycol-modified (meth)
  • an aliphatic compound having one unsaturated group and at least one carboxyl group in one molecule acrylic acid, methacrylic acid, or a modified chain in which the chain between the unsaturated group and the carboxylic acid is extended.
  • Unsaturated monocarboxylic acids such as / 3-carboxyethyl (meth) acrylate, 2-acids, unsaturated monocarboxylic acids having ester bonds due to rataton modification, etc., modified unsaturated monocarboxylic acids having ether bonds, Examples include those containing two or more carboxyl groups such as maleic acid in the molecule. These may be used alone or in combination of two or more.
  • Examples of aliphatic polymerizable monomers having 4 to 20 carbon atoms having an oxysilane ring and an ethylenically unsaturated group in one molecule include glycidyl (meth) acrylate and a-methyl darisidinole (meth) Atalylate, 3, 4-Epoxycyclohexylmethyl (meth) acrylate, 3, 4— Epoxy cyclohexylenoretinore (meth) acrylate, 3, 4-Epoxycyclohexenolevyl (meth) acrylate, 3, 4— The ability to mention epoxy cyclohexyl methyl amino acrylate etc.
  • the carboxyl group-containing resin (A) having no aromatic ring needs to have an acid value in the range of 50 to 200 mg KO H / g.
  • the acid value is less than 50 mgKOH / g, it is difficult to remove the unexposed area with a weak alkaline aqueous solution. If it exceeds 200 mgKOH / g, there are problems such as poor water resistance and electrical properties of the cured film.
  • the weight average molecular weight of the carboxyl group-containing resin (A) is preferably in the range of 5,000-100,000. If the weight average molecular weight is less than 5000, the dryness to touch tends to be extremely poor. On the other hand, if the weight average molecular weight exceeds 100,000, it is not preferable because developability and storage stability are remarkably deteriorated.
  • Examples of the photopolymerization initiator (B) used in the present invention include benzoin and benzoin Benzoin such as chinoleatenore, benzoinethinoleethenole, benzoinisopropinoleethenole, and benzoinanolenoquineateoles; acetophenone, 2,2-dimethoxy-2-phenyl dirucetophenone, 2,2-diethoxy-2-phenyl Acetophenone, 2, 2-diethoxy —2-phenylacetophenone, 1,1-dichloroacetophenone and other acetophenones; 2-methyl-1 [4 (methylthio) phenyl] -2-morpholinopropane 1-on, 2 — Benzyl-2 dimethylamino 1- (4 morpholinophenyl) -butanone 1, 2-— (dimethylamino)-2- [(4 methylphenyl) methyl] 1 [4 mono (4-morpholinyl) phen
  • the amount of the photopolymerization initiator (B) is preferably no aromatic ring! /, Preferably 1 to 30 parts by mass, more preferably 2 parts per 100 parts by mass of the carboxyl group-containing resin (A). ⁇ 25 parts by weight.
  • the blending amount of the photopolymerization initiator (B) is less than 1 part by mass, the photocurability is lowered, and pattern formation after exposure / development becomes difficult.
  • the amount exceeds 30 parts by mass the thick film curability is lowered and the cost is increased.
  • the hydrogenated epoxy compound (C) a compound having an aromatic ring is subjected to nuclear hydrogenation, and then the epoxidized compound and the aromatic ring of the aromatic epoxy compound are selectively subjected to nuclear hydrogenation. Any of the epoxy compounds obtained can be used.
  • hydrogenated bisphenol A type epoxy resin hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol S type epoxy resin, hydrogenated biphenol type epoxy resin, hydrogenated bixylenol type epoxy resin, hydrogenated phenol nopolac Type epoxy resin, hydrogenated cresol nopolac type epoxy resin, hydrogenated bisphenol A type nopolac type epoxy resin and other hydrogenated aromatic darisidyl ether compounds; hydrogenated terephthalic acid diglycidyl ester and other hydrogenated aromatic types Glycidyl ester compounds; hydrogenated N, N, ⁇ ', ⁇ , monotetraglycidyl metaxylene diamine, hydrogenated ⁇ , ⁇ -diglycidyl adiline and other hydrogenated aromatic glycidyl amine compounds Can be used.
  • hydrogenated bisphenol A type epoxy resin for example, trade name YX-8034 manufactured by Japan Epoxy Resin Co., Ltd. obtained by selectively nuclear hydrogenating the aromatic ring of bisphenol ⁇ type epoxy resin. It is more preferable to use from the viewpoint of electrical characteristics and heat resistance.
  • These hydrogenated epoxy compounds can be used alone or in combination of two or more.
  • the hydrogenation rate can be controlled, and the hydrogenation rate can be reduced. Crystallinity, heat resistance, heat degradation, etc. are different.
  • the average hydrogenation rate of the hydrogenated epoxy compound in the solder resist composition of the present invention is determined in consideration of suppressing deterioration of the solder resist film due to heat and maintaining good heat resistance. Specifically, the average hydrogenation rate is preferably 50 to 100%, more preferably 80 to 100%.
  • the amount of the hydrogenated epoxy compound (C) is preferably 5 to 70 parts by mass, more preferably 5 to 70 parts by mass with respect to 100 parts by mass of the carboxy group-containing resin (A) without having an aromatic ring! 60 parts by mass.
  • the blending amount of the hydrogenated epoxy compound (C) exceeds 70 parts by mass, the solubility of the unexposed part in the developer is lowered, and development residue tends to occur, making it difficult to use practically.
  • the amount is less than 5 parts by mass, the carboxyl group of the carboxyl group-containing resin (A) remains in an unreacted state, so that the cured coating has sufficient electrical properties, solder heat resistance, and chemical resistance. It tends to be difficult.
  • rutile titanium oxide (D) is used as the white pigment.
  • Anatase-type titanium oxide is often used because of its high whiteness compared to the rutile type.
  • anatase-type titanium oxide has photocatalytic activity, it may cause discoloration of the resin in the solder resist composition.
  • rutile type titanium oxide has a slightly lower whiteness than anatase type, but has almost no photoactivity, so that a stable solder resist film can be obtained.
  • rutile type titanium oxide (D) a known rutile type can be used as the rutile type titanium oxide (D).
  • TR-600, TR-700, TR-750, TR-840 manufactured by Fuji Titanium Industry Co., Ltd., R-550, R-580, R-630, R-820, manufactured by Ishihara Sangyo Co., Ltd. CR-50, CR-60, CR-90, KR-270, KR-310, KR-380 manufactured by Titanium Industry Co., Ltd. can be used.
  • the amount of the rutile-type titanium oxide (D) is preferably 50 to 300 parts by mass, more preferably 60 parts per 100 parts by mass of the carboxy group-containing resin (A) without having an aromatic ring! ⁇ 260 parts by mass. If the blending amount exceeds 300 parts by mass, the photocurability is lowered, and the curing depth is lowered, which is not preferable. On the other hand, if the amount is less than 50 parts by mass, it is impossible to obtain a solder resist film having a high reflectivity with a small hiding power.
  • the silica particles (F) when used in combination, a solder resist composition having a deeper curing depth can be obtained. This is probably because the refractive index of silica is relatively close to that of the carboxyl group-containing resin (A).
  • silica particles (F) can be used.
  • spherical silica Alignment-El, SO-E2, SO-E5, etc. manufactured by Admatechs
  • fine powdered silicon oxide fine powdered silicon oxide
  • amorphous silica crystalline silica
  • fused silica fused silica and the like
  • the compounding amount of the silica particles (F) is preferably 50 to 200 parts by mass with respect to 100 parts by mass of the carboxy group-containing resin (A) having no aromatic ring.
  • Examples of the diluent (E) used in the present invention include a photopolymerizable monomer and / or an organic solvent strength S.
  • Examples of the photopolymerizable monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl tert-oleate, 2-hydroxyethyl acrylate, and ethylene glycolate.
  • Mono- or diatalylates of glycols such as methoxytetraethylene glycol, polyethylene glycol, propylene glycol; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide; amino such as N, N-dimethylaminoethyl acrylate Alkyl acrylates; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or polyvalent acrylates of these ethylene oxide or propylene oxide adducts; Athenates such as phenoxy acrylate, bisphenol A diathalate and ethylene oxide or propylene oxide adducts of these phenols Examples thereof include talidates of glycidyl ethers such as glycerol serine glycidyl ether and trimethylolpropane triglycid
  • examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as tonolene, xylene and tetramethylbenzene; methyl cetosolve, ethinorecerosonolev, Butinorecero Sonoreb, Metinorecanorebitonore, Butinorecanolebitonore, Propylene Glyconore Monomethenoreatenore, Diethylene Glycolic Monoremonotinoreatenore, Dipropren Glico Reno Mononoreinore Glycol ethers such as tenole and triethyleneglycolenoethylenoate ether; esters such as ethyl acetate, butyl acetate, cellosolve acetate, diethyleneglycolenomonoethylenoate acetate, and esterified products of the above glycolen
  • ketones such as methyl
  • the diluent (E) as described above may be used alone or as a mixture of two or more.
  • Carboxy group-containing resin having no aromatic ring (A) It is preferable to use 20 to 300 parts by weight of diluent (E) with respect to 100 parts by weight of resin.
  • the purpose of use of the diluent is to increase the photopolymerizability of the photopolymerizable monomer by diluting the active energy ray curable resin that is easy to apply! This is because the organic solvent is formed into a film by drying. Therefore, depending on the diluent used, contact the photomask with the coating.
  • the contact method to be used is a non-contact type! /, Or a misalignment exposure method.
  • the white photocurable 'thermosetting solder resist composition of the present invention by containing an antioxidant and a hindered amine light stabilizer, thermal degradation and photodegradation can be further reduced. It can.
  • the antioxidant is not particularly limited. 1S is preferably a hindered phenol compound.
  • the hindered phenolic compounds are: Nocrack 200, Nocrack ⁇ —17, Nocrack SP, Nocrack SP—N, Nocrack NS—5, Nocrack NS—6, Nocrack NS—30, Nocrack 300, Nocrack NS-7, NOCRACK DAH (all of which are manufactured by Ouchi Shinsei Chemical Co., Ltd.); MARK AO-30, M ARK AO-40, MARK AO-50, MARK AO-60, MARK A0616, MA RK AO-635 , MARK AO—658, MARK AO—15, MARK AO—18, M ARK 328, MARK AO—37 (all manufactured by Adeka Gas Chemical Co., Ltd.); Irga Knox 245, Irganox 259, Irganox 565, Irganox 1010, Irganock Tas 1035, Inoreganox 1076, Inoreganox 1081, Inoreganox 1098, Inoreganox 1222, Inoreganox
  • the hindered amine light stabilizers include, for example, Tinuvin 622LD, Tinuvin 14 4; CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by Chinoku Specialty Chemicals); MARK LA-57, LA— 62, LA-67, LA-63, LA-68 (all manufactured by Adeka Gas Chemical Co., Ltd.); Sanonore LS-770, LS-765, LS-292, LS-2626 ,: LS-1114, LS- 744 (above! /, The deviation is made by Sankyo Life Tech Co., Ltd.).
  • the antioxidant and the light stabilizer preferably have no aromatic ring! /, And are added in an amount of 0 .;! To 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A).
  • a curing accelerator a thermal polymerization inhibitor, a thickener, an antifoaming agent, a leveling agent, a coupling agent, a flame retardant aid and the like can be used as necessary.
  • the white photocurable / thermosetting solder resist composition of the present invention can be provided in the form of a liquid or paste.
  • the white photocurable / thermosetting solder resist composition of the present invention may be diluted. And adjust to a viscosity suitable for the application method.
  • This is applied to a printed circuit board on which a circuit is formed by a method such as screen printing, curtain coating, spray coating, roll coating, etc., and is contained in the composition at a temperature of 70 to 90 ° C., for example.
  • a tack-free coating film can be formed by evaporating and drying the organic solvent.
  • the printed wiring board of the present invention can be obtained by selectively exposing with an active energy ray through a photomask and developing the unexposed portion with an alkaline aqueous solution to form a resist pattern.
  • the alkaline aqueous solution used here is generally 0.5 to 5% by mass of sodium carbonate aqueous solution, but other alkaline use liquids can also be used.
  • alkaline aqueous solutions include alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines.
  • a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a super-high pressure mercury lamp, a xenon lamp, a metal lamp, a ride lamp, or the like can be used.
  • a laser beam can be used as an actinic beam.
  • solder resist film In order to improve the heat resistance of the solder resist film thus obtained, it is desirable to secondarily cure the solder resist film with heat of 100 to 20 ° C, ultraviolet rays or far infrared rays.
  • solder resist film formed using the solder resist composition of the present invention has a high reflectivity, and has good adhesion, heat resistance, solvent resistance and electrical properties required for the solder resist. It was found to have Further, the solder resist film formed according to the present invention maintains a high reflectance even after the accelerated deterioration test.
  • Carboxyl group-containing copolymer resin was obtained by adding dropwise over 3 hours together with 21.4 g of dicarbonate (Nippon Yushi Co., Ltd. Parroyl TCP) and aging for 6 hours. The reaction was performed under a nitrogen atmosphere.
  • R820 Rutile titanium oxide manufactured by Ishihara Sangyo Co., Ltd.
  • KA-15 Anatase type titanium oxide manufactured by Titanium Industry Co., Ltd.
  • HBPA Maruzen Petrochemical Hydrogenated Bisphenol A Type Epoxy Resin HBPA—DGE
  • YX— 8300 Hydrogenated biphenyl type epoxy resin made by Japan Epoxy Resin
  • TEPIC-H Nissan Chemical Co., Ltd./3 body triglycidyl isocyanurate
  • TEPIC-S Nissan Chemical Co., Ltd. ⁇ - and 0-body mixed triglycidyl isocyanurate 82
  • INOREGACURE 907 manufactured by Ciba Specialty Chemicals
  • Solvent carbitol acetate.
  • Each sono-redder resist yarn composition is 100 mm XI 50 mm in size and a 1.6 mm thick FR-4 copper clad laminate is screen printed to a 100 mesh polyester to a film thickness of 40 m. It was printed with a solid plate using a bias plate and dried at 80 ° C for 30 minutes in a hot air circulation drying oven. Using an HMW-680GW manufactured by Oak Manufacturing Co., Ltd. for printed wiring boards, UV exposure is performed with a cumulative light intensity of 500 mj / cm 2 so that a 30 mm square negative pattern remains, and a 1% sodium carbonate aqueous solution at 30 ° C As a developer, development was carried out for 60 seconds with a developing machine for printed wiring boards, followed by thermosetting at 150 ° C. for 60 minutes in a hot-air circulating drying furnace to prepare test pieces for characteristic tests.
  • the obtained test piece was measured with a color difference meter CR-400 manufactured by Minolta.
  • the UV conveyor furnace (output 150W / cm metal halide lamp, cold mirror) was irradiated with 150j / cm 2 of light to cause accelerated light degradation. The results are shown in Table 2. [Table 2]
  • Y represents the reflectance of the XYZ color system
  • L * represents the lightness of the L * a * color system.
  • a * indicates the red direction
  • a * indicates the green direction
  • b * indicates the yellow direction
  • b * indicates the blue direction.
  • a E * ab indicates a color change. The smaller this value, the smaller the color change.
  • double circles show no discoloration
  • circles show almost no discoloration
  • triangles show slight discoloration
  • back marks show clear discoloration.
  • Comparative Example 4 contains anatase type titanium oxide instead of rutile type titanium oxide.
  • anatase-type titanium oxide has a high initial reflectivity, but after accelerated light degradation, both reflectivity Y and lightness L * are greatly reduced, and the color change AE * ab value is also large. Les. Also, discoloration is observed in visual evaluation.
  • rutile titanium oxide is superior as a component of a solder resist composition having a high reflectance than anatase titanium oxide!
  • test piece prepared in the same manner as (1) was measured with a Minolta color difference meter CR-400. Next, it was accelerated and deteriorated by heating at 150 ° C for 500 hours and 1000 hours in a hot-air circulating drying oven. The results are shown in Table 3.
  • Pencils from B to 9H which are sharpened so that the tip of the core is flattened, are pressed at an angle of about 45 ° to each test piece prepared in the same way as in (1), and the paint film does not peel off. The hardness of was recorded. The results are also shown in Table 4.
  • Specimens were prepared under the same conditions as in (1), except that the IPC B-25 test pattern comb-type electrode B coupon was used instead of the FR-4 copper-clad laminate. A bias of DC500V was applied to this test piece, and the insulation resistance value was measured. The results are also shown in Table 4.
  • a photocurable and thermosetting white solder resist composition capable of forming a solder resist film having a high reflectance can be obtained.
  • the solder resist film having a high reflectivity formed by the solder resist composition of the present invention can withstand long-term use in response to light degradation and thermal degradation.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Materials For Photolithography (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)

Abstract

L'invention concerne une composition de résist de brasage photodurcissable et thermodurcissable de couleur blanche, qui permet de former un film de résist de brasage hautement réfléchissant, qui n'est guère détérioré par la lumière ou la chaleur. L'invention concerne également une carte à circuits imprimés qui comprend un film de résist de brasage hautement réfléchissant formé à l'aide de la composition de résist de brasage photodurcissable et thermodurcissable de couleur blanche.
PCT/JP2007/070654 2006-10-24 2007-10-23 Composition de résist de brasage photodurcissable/thermodurcissable, et carte à circuits imprimés utilisant celle-ci WO2008050768A1 (fr)

Priority Applications (2)

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JP2008519757A JP4538521B2 (ja) 2006-10-24 2007-10-23 光硬化性・熱硬化性ソルダーレジスト組成物およびそれを用いたプリント配線板
CN2007800014375A CN101356475B (zh) 2006-10-24 2007-10-23 光固化性·热固化性阻焊剂组合物及使用其的印刷电路板

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JP2006-288942 2006-10-24
JP2006288942 2006-10-24

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JP2010169790A (ja) * 2009-01-21 2010-08-05 Tamura Seisakusho Co Ltd 感光性樹脂組成物、プリント配線板用のソルダーレジスト組成物およびプリント配線板
JP2010238785A (ja) * 2009-03-30 2010-10-21 Taiyo Ink Mfg Ltd 穴埋め用樹脂組成物及びこの樹脂組成物を充填したプリント配線板
JP2010266556A (ja) * 2009-05-13 2010-11-25 Tamura Seisakusho Co Ltd 感光性樹脂組成物、プリント配線板用のソルダーレジスト組成物およびプリント配線板
JP2011043806A (ja) * 2009-07-24 2011-03-03 Toyo Ink Mfg Co Ltd 感光性組成物
JP2011075679A (ja) * 2009-09-29 2011-04-14 Taiyo Holdings Co Ltd 絶縁性光硬化性熱硬化性樹脂組成物およびプリント配線板
KR101040781B1 (ko) * 2008-10-17 2011-06-13 다이요 홀딩스 가부시키가이샤 솔더 레지스트 조성물 및 이것을 이용하여 형성되는 인쇄 배선판
JP2011133670A (ja) * 2009-12-24 2011-07-07 Tamura Seisakusho Co Ltd スプレー塗装用白色ソルダーレジスト組成物
JP2011158628A (ja) * 2010-01-29 2011-08-18 Tamura Seisakusho Co Ltd 感光性樹脂組成物およびその硬化膜を用いたプリント配線板
WO2011125821A1 (fr) * 2010-03-31 2011-10-13 太陽ホールディングス株式会社 Composition de résine thermodurcissable et carte imprimée
KR101174978B1 (ko) 2009-03-23 2012-08-17 다이요 홀딩스 가부시키가이샤 경화성 수지 조성물, 그것을 사용한 드라이 필름 및 인쇄 배선판
JP2014067063A (ja) * 2013-12-17 2014-04-17 Goo Chemical Co Ltd 感光性樹脂組成物、ソルダーレジスト用組成物及びプリント配線板
JP2015165332A (ja) * 2015-05-29 2015-09-17 互応化学工業株式会社 感光性樹脂組成物、ソルダーレジスト用組成物及びプリント配線板
JP2015165331A (ja) * 2015-05-29 2015-09-17 互応化学工業株式会社 感光性樹脂組成物、ソルダーレジスト用組成物及びプリント配線板
JP2016035042A (ja) * 2014-07-31 2016-03-17 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板

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TWI571705B (zh) * 2016-01-15 2017-02-21 臺灣永光化學工業股份有限公司 負型白色感光性樹脂組成物及其用途
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JP2009302110A (ja) * 2008-06-10 2009-12-24 Mitsubishi Plastics Inc カバーレイフィルム
KR101040781B1 (ko) * 2008-10-17 2011-06-13 다이요 홀딩스 가부시키가이샤 솔더 레지스트 조성물 및 이것을 이용하여 형성되는 인쇄 배선판
JP2010169790A (ja) * 2009-01-21 2010-08-05 Tamura Seisakusho Co Ltd 感光性樹脂組成物、プリント配線板用のソルダーレジスト組成物およびプリント配線板
KR101174978B1 (ko) 2009-03-23 2012-08-17 다이요 홀딩스 가부시키가이샤 경화성 수지 조성물, 그것을 사용한 드라이 필름 및 인쇄 배선판
JP2010238785A (ja) * 2009-03-30 2010-10-21 Taiyo Ink Mfg Ltd 穴埋め用樹脂組成物及びこの樹脂組成物を充填したプリント配線板
JP2010266556A (ja) * 2009-05-13 2010-11-25 Tamura Seisakusho Co Ltd 感光性樹脂組成物、プリント配線板用のソルダーレジスト組成物およびプリント配線板
JP2011043806A (ja) * 2009-07-24 2011-03-03 Toyo Ink Mfg Co Ltd 感光性組成物
JP2011075679A (ja) * 2009-09-29 2011-04-14 Taiyo Holdings Co Ltd 絶縁性光硬化性熱硬化性樹脂組成物およびプリント配線板
JP2011133670A (ja) * 2009-12-24 2011-07-07 Tamura Seisakusho Co Ltd スプレー塗装用白色ソルダーレジスト組成物
JP2011158628A (ja) * 2010-01-29 2011-08-18 Tamura Seisakusho Co Ltd 感光性樹脂組成物およびその硬化膜を用いたプリント配線板
WO2011125821A1 (fr) * 2010-03-31 2011-10-13 太陽ホールディングス株式会社 Composition de résine thermodurcissable et carte imprimée
CN102834456A (zh) * 2010-03-31 2012-12-19 太阳控股株式会社 热固化性树脂组合物及印刷电路板
JP5542915B2 (ja) * 2010-03-31 2014-07-09 太陽ホールディングス株式会社 熱硬化性樹脂組成物及びプリント配線板
JP2014067063A (ja) * 2013-12-17 2014-04-17 Goo Chemical Co Ltd 感光性樹脂組成物、ソルダーレジスト用組成物及びプリント配線板
JP2016035042A (ja) * 2014-07-31 2016-03-17 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板
JP2015165332A (ja) * 2015-05-29 2015-09-17 互応化学工業株式会社 感光性樹脂組成物、ソルダーレジスト用組成物及びプリント配線板
JP2015165331A (ja) * 2015-05-29 2015-09-17 互応化学工業株式会社 感光性樹脂組成物、ソルダーレジスト用組成物及びプリント配線板

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JP4538521B2 (ja) 2010-09-08
KR20090068305A (ko) 2009-06-26
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