CN101356475B - Photocurable/thermocurable solder resist composition, and printed circuit board using the same - Google Patents
Photocurable/thermocurable solder resist composition, and printed circuit board using the same Download PDFInfo
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- CN101356475B CN101356475B CN2007800014375A CN200780001437A CN101356475B CN 101356475 B CN101356475 B CN 101356475B CN 2007800014375 A CN2007800014375 A CN 2007800014375A CN 200780001437 A CN200780001437 A CN 200780001437A CN 101356475 B CN101356475 B CN 101356475B
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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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- 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
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
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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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- 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
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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
- 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
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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
Disclosed is a white-colored photocurable and thermocurable solder resist composition which enables to form a highly reflective solder resist film that is hardly deteriorated by light or heat. Also disclosed is a printed circuit board having a highly reflective solder resist film formed by using the white-colored photocurable and thermocurable solder resist composition.
Description
Technical field
The present invention relates to Photosetting and thermosetting solder resist composition, it is suitable as the permanent mask of printed circuit board (PCB), after the exposure, thereby form image with the alkaline aqueous solution development, be heating and curing then, can form the soldering-resistance layer of high reflectance thus, and relate to printed circuit board (PCB), it obtains by using said composition to form the solder resist pattern in the printed circuit board surface that is formed with circuit.
Background technology
The no part that printed circuit board (PCB) normally will be bonded in the Copper Foil on the laminate by etching is removed and is formed wiring, and electronic unit is configured in the position of regulation by welding.In order to prepare such printed circuit board (PCB), use soldering-resistance layer.That is, soldering-resistance layer is used as the diaphragm of the circuit of welding during electronic unit.Soldering-resistance layer prevent welding time solder attachment to unnecessary portions, and prevent circuit conductor to be directly exposed in the air and react with oxygen, moisture.And then also the permanent diaphragm as circuit substrate works.Therefore, require various characteristicses such as adaptation, electrical insulating property, solder heat resistance, solvent resistance, chemical proofing.
In addition, printed circuit board (PCB) is sought miniaturization (becoming more meticulous), multiple stratification and a plateization in order to realize densification, and mounting means is also passed to surface mounting technique (SMT).Therefore, soldering-resistance layer also improve become more meticulous, the requirement of high resolving power, high precision, high reliability.
As the technology that forms such solder resist pattern, can correctly form the photoresist method of fine pattern, especially from the consideration of environment aspect etc., the photoresist method of alkali developable becomes main flow.
For example, the aqueous etching resisting ink composition that a kind of available alkaline aqueous solution develops is disclosed in Japanese special fair 1-54390 number and special fair 7-17737 number, said composition is to make phenolic resin varnish type epoxy resin and unsaturated monocarboxylic reaction, addition multi-anhydride again, with reaction products resulting as base polymer.
On the other hand, in recent years, the light source of Backlight For Liquid Crystal Display Panels such as portable terminal, PC, televisor and ligthing paraphernalia etc. has increased following purposes newly: be formed with the purposes of directly installing on the printed circuit board (PCB) of soldering-resistance layer with the luminous light emitting diode (LED) of low electric energy in lining.
Therefore, in order effectively to utilize the light of LED, require a kind of printed circuit board (PCB), it has soldering-resistance layer as described below, and this soldering-resistance layer is high reflectance and can improves all illumination when being installed to LED on the printed circuit board (PCB).
In order effectively to utilize the light that is directly installed on the LED on the printed circuit board (PCB), as mentioned above, when soldering-resistance layer is necessary for high reflectance, during using LED, keep this high reflectance as light source always.But common solder resist composition comprises the composition with aromatic rings as being used to improve a stable on heating method.At this, aromatic rings has because the character that light or heat can be reacted gradually has following problem by so formed soldering-resistance layer of solder resist composition: during installation LED, because aromatic rings reacts gradually, cause deteriorations such as flavescence.
Summary of the invention
The object of the present invention is to provide a kind of soldering-resistance layer that can form the high reflectance that is not subject to light deterioration and hot deterioration white Photosetting and thermosetting solder resist composition and a kind of printed circuit board (PCB) with soldering-resistance layer of the high reflectance that uses this white Photosetting and thermosetting solder resist composition and form is provided.
Further investigations such as the inventor, found that by use do not have aromatic rings contain carboxy resin, hydrogenation epoxy compound and as the Titanium Dioxide Rutile Top grade of Chinese white, the deterioration (flavescence) of soldering-resistance layer can be suppressed, high reflectance can be realized for a long time.
Promptly, the 1st side of the present invention can provide a kind of Photosetting and thermosetting solder resist composition of white, it is characterized in that what it comprised that (A) do not have an aromatic rings contains carboxy resin, (B) Photoepolymerizationinitiater initiater, (C) hydrogenation epoxy compound, (D) Titanium Dioxide Rutile Top grade and (E) thinning agent.
In addition, other sides of the present invention can provide a kind of printed circuit board (PCB), and the Photosetting and thermosetting solder resist composition of its white by using the 1st side forms soldering-resistance layer in the printed circuit board surface that is formed with circuit and obtains.
Embodiment
Below, further describe the present invention.
What the solder resist composition of white of the present invention comprised that (A) do not have an aromatic rings contains carboxy resin, (B) Photoepolymerizationinitiater initiater, (C) hydrogenation epoxy compound, (D) Titanium Dioxide Rutile Top grade and (E) thinning agent.
Contain carboxy resin (A) as what do not have an aromatic rings, so long as do not have the resin with carboxyl of aromatic rings, just can use in following any one: the photosensitive carboxy resin that contains that contains carboxy resin and do not have photosensitive unsaturated double-bond that himself has 1 above photonasty unsaturated double-bond.Be not limited to specific material.Especially the resin (can be in oligomer or the polymkeric substance any one) that does not have aromatic rings in the resin of enumerating below can suitably using.That is,
(1) copolymerization of the aliphatics polymerization monomer by aliphatics unsaturated carboxylic acid and carbon number 2～20 (particularly, can list the vinyl esters etc. of aliphatics (methyl) acryl compound, aliphatic ethylene base ether, fatty acid) and obtain contain carboxy resin,
(2) reaction of the aliphatics polymerization monomer that contains the carbon number 4～20 that has oxirane ring and ethylenically unsaturated group in carboxyl (methyl) acrylate based copolymerized resin and 1 molecule that is generated by aliphatics polymerization monomer by carbon number 2～20 obtain photosensitive contain carboxy resin,
(3) the aliphatics polymerization monomer that makes the carbon number 4～20 that has 1 epoxy radicals and unsaturated double-bond in 1 molecule respectively (for example; (methyl) glycidyl acrylate etc.) (particularly, can list the vinyl esters etc. of aliphatics (methyl) acryl compound, aliphatic ethylene base ether, fatty acid with aliphatics polymerization monomer with carbon number 2～20 of unsaturated double-bond.) multipolymer and aliphatics unsaturated monocarboxylic reaction, make institute generate secondary hydroxyl and saturated or unsaturated aliphatic multi-anhydride react and obtain photosensitive contain carboxy resin,
(4) make the polymkeric substance and the reaction of saturated or unsaturated aliphatic multi-anhydride of fatty family hydroxyl, the photosensitive hydroxyl that makes the aliphatics polymerization monomer that has the carbon number 4～20 of 1 epoxy radicals and unsaturated double-bond in the carboxylic acid that generated and 1 molecule respectively (for example, (methyl) glycidyl acrylate etc.) reaction then and obtain and the resin of carboxyl.
In addition, in this manual, so-called aliphatics comprises that also molecule contains the compound that cyclohexane ring, cyclohexene ring etc. contain cyclic rings.
In the middle of these, the photosensitive carboxy resin that contains of preferably above-mentioned (2), that is the photosensitive carboxy resin that contains that obtains of the reaction of the aliphatics polymerization monomer that contains the carbon number 4～20 that has oxirane ring and ethylenically unsaturated group in carboxyl (methyl) acrylate based copolymerized resin and (b) 1 molecule that is generated by aliphatics polymerization monomer, by (a) carbon number 2～20.
(a) the aliphatics polymerization monomer of carbon number 2～20 is generated contains carboxyl (methyl) acrylate based copolymerized resin, and the fatty compound copolymerization that has 1 unsaturated group and at least 1 carboxyl in (methyl) acrylate by making carbon number 4～20 and 1 molecule obtains.(methyl) acrylate as constituting copolymer resins (a) can list (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate; Hydroxyl (methyl) esters of acrylic acids such as (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxy butyl ester, caprolactone modification (methyl) acrylic acid 2-hydroxyl ethyl ester; Glycol modification (methyl) esters of acrylic acids such as methoxyl diethylene glycol (methyl) acrylate, ethoxy diethylene glycol (methyl) acrylate, different octyloxy diethylene glycol (methyl) acrylate, methoxyl triethylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate etc.These can use separately, also can mix more than 2 kinds and use.In addition, in this manual, (methyl) acrylate is meant the term of general designation acrylate and methacrylate, and other similar expression too.
In addition, as the fatty compound that has 1 unsaturated group and at least 1 carboxyl in 1 molecule, can list between acrylic acid, methacrylic acid, unsaturated group and the carboxylic acid by the modification unsaturated monocarboxylic of chain elongation, for example (methyl) propenoic acid beta-carboxyl ethyl ester, 2-acrylyl oxy-ethyl succinic acid, 2-acrylyl oxy-ethyl hexahydrophthalic acid, by comprising material of 2 above carboxyls etc. in interior unsaturated monocarboxylic with ester bond such as ester modified, the unsaturated monocarboxylic of modification and the maleic acid equimolecular with ehter bond.These can use separately, also can mix more than 2 kinds and use.
Aliphatics polymerization monomer as the carbon number 4～20 that has oxirane ring and ethylenically unsaturated group in (b) 1 molecule, for example can list, (methyl) glycidyl acrylate, (methyl) acrylic acid Alpha-Methyl ethylene oxidic ester, (methyl) acrylic acid 3,4-epoxycyclohexyl methyl esters, (methyl) acrylic acid 3,4-epoxycyclohexyl ethyl ester, (methyl) acrylic acid 3,4-epoxycyclohexyl butyl ester, acrylic acid 3,4-epoxycyclohexyl methylamino ester etc.Wherein, preferred (methyl) acrylic acid 3,4-epoxycyclohexyl methyl esters.The aliphatics polymerization monomer that has the carbon number 4～20 of oxirane ring and ethylenically unsaturated group in these (b) 1 molecules can use separately also can mix more than 2 kinds and use.
The carboxy resin (A) that contains that does not have aromatic rings needs the scope of its acid number at 50～200mgKOH/g.During acid number deficiency 50mgKOH/g, be difficult to remove the unexposed portion in weak alkaline aqueous solution.When surpassing 200mgKOH/g, the problems such as water tolerance, electrical characteristics difference of cured film are arranged.In addition, the weight-average molecular weight that contains carboxy resin (A) is preferably 5000～100000 scope.During weight-average molecular weight less than 5000, the tendency of the remarkable variation of dry to touch is arranged.In addition, weight-average molecular weight surpasses at 100000 o'clock, owing to produce the significantly problem of deterioration of development, storage stability, so not preferred.
As Photoepolymerizationinitiater initiater used in the present invention (B), for example can list benzoin and benzoin alkylether classes such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether; Acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1, acetophenones such as 1-dichloroacetophenone; 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-the aminoalkyl benzophenone class of 1-butanone etc.; Anthraquinone classes such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone; 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, thioxanthene ketones such as 4-diisopropyl thioxanthones; Ketal classes such as acetophenone dimethyl ketal, benzil dimethyl ketal; Benzophenones such as benzophenone; Perhaps xanthene ketone; (2,6-dimethoxy benzoyl)-2,4,4-amyl group phosphine oxide, two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxide, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, ethyl-2,4, phosphinoxidess such as 6-trimethylbenzoyl phenyl phosphites; Various peroxides, two luxuriant titanium series initiators etc., these can with N, N-dimethyl ethyl aminobenzoate, N, the photosensitizer that tertiary amines such as N-dimethylaminobenzoic acid isopentyl ester, amyl group-4-dimethylaminobenzoic acid ester, triethylamine, triethanolamine are such etc. is used in combination.These Photoepolymerizationinitiater initiaters can be used singly or in combination of two or more thereof.
The use level of Photoepolymerizationinitiater initiater (B) is preferably 1～30 mass parts, 2～25 mass parts more preferably with respect to the carboxy resin (A) that contains that 100 mass parts do not have aromatic rings.During use level less than 1 mass parts of Photoepolymerizationinitiater initiater (B), photo-curable reduces, and the pattern behind the exposure imaging forms and becomes difficulty, so not preferred.On the other hand, when surpassing 30 mass parts, the thick film curable reduces, and causes cost to improve, so not preferred.
Then, as hydrogenation epoxy compound (C), after to compound nuclear hydrogenation with aromatic rings epoxidised compound and to the aromatic rings of aromatic epoxy compound optionally nuclear hydrogenation and the epoxy compound that obtains can use.For example, can use the hydrogenated aromatic family glycidyl ether compounds such as phenolic resin varnish type epoxy resin of bisphenol-A epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin, A Hydrogenated Bisphenol A S type epoxy resin, hydrogenation united phenol-type epoxy resin, hydrogenation di-toluene phenol-type epoxy resin, hydrogenation phenol novolak type epoxy resin, hydrogenation cresols phenolic resin varnish type epoxy resin, hydrogenated bisphenol A type; Hydrogenated aromatic family epihydric alcohol ester compounds such as hydrogenation terephthalic acid diglycidyl ester; Hydrogenation N, N, N ', N '-four glycidyl group m-phenylene diamine, hydrogenation N, known substances such as hydrogenated aromatic family glycidyl amine compound such as N-diglycidylaniline.In the middle of these, from electrical characteristics, thermotolerance aspect, more preferably use the aromatic rings of bisphenol A type epoxy resin optionally nuclear hydrogenation and the bisphenol-A epoxy resin (for example, Japan Epoxy ResinsCo., the trade name YX-8034 that Ltd. produces etc.) that obtains.These hydrogenation epoxy compounds can use separately also can make up more than 2 kinds and use.
In addition, as mentioned above,,, change crystallinity, thermotolerance, hot deterioration etc. by hydrogenation ratio for optionally under the situation of the epoxy compound that obtains of nuclear hydrogenation, controlling hydrogenation ratio to the aromatic rings of aromatic epoxy compound.
The average hydrogenation ratio of the hydrogenation epoxy compound in the solder resist composition of the present invention can be considered to suppress the deterioration that the heat by soldering-resistance layer causes and keep good thermotolerance and determine.Particularly, average hydrogenation ratio is preferably 50～100%, more preferably 80～100%.
The use level of hydrogenation epoxy compound (C) is preferably 5～70 mass parts, 5～60 mass parts more preferably with respect to the carboxy resin (A) that contains that 100 mass parts do not have aromatic rings.When the use level of hydrogenation epoxy compound (C) surpassed 70 mass parts, the dissolubility of the unexposed portion in the developer solution reduced, and it is residual easily to take place to develop, and actual the use gone up difficulty.Therefore on the other hand, during less than 5 mass parts, the carboxyl that contains carboxy resin (A) is residual with unreacted state, has the tendency of the electrical characteristics that are difficult to fully obtain cured coating film, solder heat resistance, chemical proofing.
Do not have the carboxyl that contains carboxy resin (A) of aromatic rings and the epoxy radicals of hydrogenation epoxy compound (C) and pass through ring-opening polymerization.
In the present invention, one of feature is to use Titanium Dioxide Rutile Top grade (D) as Chinese white.Anatase-type titanium oxide is compared the whiteness height with rutile-type, therefore often use.But therefore anatase-type titanium oxide causes the variable color of the resin in the solder resist composition sometimes owing to have photocatalytic activity.Relative therewith, the whiteness of Titanium Dioxide Rutile Top grade is compared weaker with Detitanium-ore-type, but has photolytic activity hardly, therefore can obtain stable soldering-resistance layer.As Titanium Dioxide Rutile Top grade (D), can use the material of known rutile-type.Particularly, can use Fuji TitaniumIndustry Co., KR-270, the KR-310 that R-550, the R-580 that the former industry of TR-600, TR-700, TR-750, TR-840, stone (strain) that Ltd. makes is made, R-630, R-820, CR-50, CR-60, CR-90, チ タ Application industry (strain) are made, KR-380 etc.
The use level of Titanium Dioxide Rutile Top grade (D) is preferably 50～300 mass parts, 60～260 mass parts more preferably with respect to the carboxy resin (A) that contains that 100 mass parts do not have aromatic rings.When use level surpassed 300 mass parts, photo-curable reduced, and so the curing depth step-down is not preferred.On the other hand, during less than 50 mass parts, hidden power is little, can not obtain the soldering-resistance layer of high reflectance.
In addition, in the present invention, when being used in combination silica dioxide granule (F), can obtain having the solder resist composition of darker curing depth.This is considered to owing to the refractive index of silicon dioxide and contains carboxy resin (A) than approaching.
As such silica dioxide granule (F), can use known material.For example can list spherical silicon dioxide (ADMATECHS CO., Admafine SO-E1, the SO-E2 that LTD produces, SO-E5 etc.), micro mist shape monox, amorphous silica, crystalline silicon dioxide, fused silica etc.These silica dioxide granules can be used alone or in combination of two or more kinds.The use level of silica dioxide granule (F) is preferably 50～200 mass parts with respect to the carboxy resin (A) that contains that 100 mass parts do not have aromatic rings.
As thinning agent used in the present invention (E), can list photopolymerization monomer and/or organic solvent.As photopolymerization monomer, can list 2-Hydroxy ethyl acrylate, acrylic acid-acrylic acid hydroxy alkyl ester classes such as 2-hydroxyl butyl ester; The list or the diacrylate class of glycol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol; Acrylic amide such as N,N-DMAA, N hydroxymethyl acrylamide; N, amino alkyl acrylates classes such as N-dimethylaminoethyl acrylate; The multicomponent methacrylate class of polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or their ethylene oxide adduct or propylene oxide adduct etc.; The esters of acrylic acid of the ethylene oxide adduct of phenoxy group acrylate, bisphenol a diacrylate and these phenol or propylene oxide adduct etc.; The esters of acrylic acid of glycidol ethers such as glycerine diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether; And melamine acrylate; And/or the methyl acrylic ester corresponding with the aforesaid propylene esters of gallic acid etc.
On the other hand, as organic solvent, can list ketones such as MEK, cyclohexanone; Toluene, dimethylbenzene, tetramethylbenzene etc. are aromatic hydrocarbon based; Glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, the single ether of dipropylene glycol, Triethylene glycol ethyl ether; The ester classes such as carboxylate of ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetic acid esters and above-mentioned glycol ethers; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, naphtha, hydrotreated naphtha, solvent naphtha etc.
Above-mentioned thinning agent (E) can use separately or use with the form of potpourri more than 2 kinds.Do not contain carboxy resin (A) with respect to what 100 mass parts did not have an aromatic rings, preferably use the thinning agent (E) of 20～300 mass parts.The application target of aforementioned thinning agent is not only photopolymerization monomer and is made the state that is easy to be coated with, and is for active energy ray-curable resin dilution, strengthens optical polymerism, and on the other hand, organic solvent is for by making its dry film of making.Therefore, can be according to employed thinning agent, make the way of contact that the photomask contact films or any one Exposure mode in the noncontact mode.
In addition, in the Photosetting and thermosetting solder resist composition of white of the present invention, be light stabilizer by containing antioxidant and hindered amine, can further reduce hot deterioration and light deterioration.As antioxidant, be not particularly limited, be preferably the hindered phenol based compound.As the hindered phenol based compound, for example can list NOCRAC 200, NOCRAC M-17, NOCRAC SP, NOCRAC SP-N, NOCRAC NS-5, NOCRAC NS-6, NOCRAC NS-30, NOCRAC300, NOCRAC NS-7, NOCRAC DAH (more than be the emerging chemical industry of imperial palace (strain) manufacturing); MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO616, MARK AO-635, MARK AO-658, MARK AO-15, MARK AO-18, MARK 328, MARK A0-37 (more than be ADEKA ARGUS CHEMICAL CO., LTD. makes); Irganox245, Irganox 259, Irganox 565, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1081, Irganox 1098, Irganox 1222, Irganox1330, Irganox 1425WL (more than be Ciba Specialty Chemicals Inc. make) etc.
In addition, be light stabilizer as hindered amine, for example can enumerate TINUVIN622LD, TINUVIN 144; CHIMASSORB 944LD, CHIMASSORB119FL (more than be Ciba Specialty Chemicals Inc. make); MARKLA-57, LA-62, LA-67, LA-63, LA-68 (more than be ADEKA ARGUSCHEMICAL CO., LTD. makes); Sanol LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (more than be Sankyo Lifetech Co., Ltd. makes) etc.
Above-mentioned antioxidant and light stabilizer preferably add 0.1～10 mass parts with respect to the carboxy resin (A) that contains that 100 mass parts do not have an aromatic rings.
In addition, as required, can use curing accelerator, hot polymerization inhibitor, thickening agent, defoamer, levelling agent, coupling agent, flame retardant etc.
The Photosetting and thermosetting solder resist composition of white of the present invention can provide with form aqueous, pasty state.
As required, the dilution of the Photosetting and thermosetting solder resist composition of white of the present invention is adjusted into the viscosity that is suitable for coating process.Be coated with methods such as method, spraying process, rolling method by silk screen print method, curtain, it is applied on the printed circuit board (PCB) that is formed with circuit, make organic solvent volatile dry contained in the composition, can form tack-free filming in for example 70～90 ℃ temperature.Then, utilize active energy beam optionally to expose, unexposed development formed corrosion-resisting pattern, can obtain printed circuit board (PCB) of the present invention thus by alkaline aqueous solution by photomask.As at this employed alkaline aqueous solution, normally 0.5～5 quality % aqueous sodium carbonate can also use other alkaline aqueous solution.As other alkaline aqueous solutions, for example can list alkaline aqueous solutions such as potassium hydroxide, NaOH, sal tartari, sodium phosphate, sodium silicate, ammonia, amine.In addition, as the radiation source that is used to expose, can use low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp or metal halide lamp etc.In addition, laser beam etc. also can be used as active ray.
In order to improve the thermotolerance of the resulting soldering-resistance layer of such operation, it is desirable making the soldering-resistance layer regelate by 100～200 ℃ heat, ultraviolet ray or far infrared.
As can be known, use solder resist composition of the present invention and the soldering-resistance layer that forms has high reflectance and has the desired good adaptation of solder resist, thermotolerance, solvent resistance and electrical characteristics.In addition, behind activated deterioration test, also keep high reflectivity by the formed soldering-resistance layer of the present invention.
Embodiment
Below, by embodiment the present invention is described, but the present invention is not limited to this.
What do not have aromatic rings contains the synthetic of carboxy resin
In possessing 2 liters of removable flasks of stirrer, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe, add 900g as the diethylene glycol dimethyl ether of solvent and 21.4g as the peroxide-2-ethyl hexanoic acid tert-butyl (Japanese grease (strain) is made PERBUTYL O) of polymerization initiator, be heated to 90 ℃.After the adding, to it with 3 hours, drip 309.9g methacrylic acid, 116.4g methyl methacrylate and 109.8g lactone modified methacrylic acid 2-hydroxy methacrylate (DAICEL CHEMICAL INDUSTRIES together with 21.4g as peroxy dicarbonate-two (4-tert-butylcyclohexyl) ester of polymerization initiator (Japanese grease (strain) is made PEROYL TCP), LTD. make PLACCEL FM1), slaking is 6 hours again, obtains containing the carboxyl copolymer resins thus.In addition, be reflected under the nitrogen atmosphere and carry out.
Then, add 363.9g acrylic acid 3 to the resulting carboxyl copolymer resins that contains, 4-epoxycyclohexyl methacrylate (DAICEL CHEMICAL INDUSTRIES, LTD. produce Cyclomer A200), 3.6g is as the dimethyl benzyl amine of ring opening catalyst, the 1.80g hydroquinone monomethyl ether as polymerization inhibitor, be heated to 100 ℃, stir, thereby carry out the opening of epoxy.After 16 hours, obtain comprising the solution that contains carboxy resin that does not have aromatic rings of 53.8 quality % (nonvolatile component), the acid number of the solid constituent of this resin is that 108.9mgKOH/g, weight-average molecular weight are 25000.Below, claim that this reaction solution is an A-1 varnish.
Embodiment 1～3, comparative example 1～4
According to table 1 each components matching is stirred, disperse, obtain the solder resist composition respectively with 3 roll-type roller mills.Numeral mass parts in the table.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| A-1 varnish | 186 | 186 | 186 | 186 | 186 | 186 | 186 |
| R820 | 180 | 180 | 180 | 180 | 180 | 180 | |
| KA-15 | 180 | ||||||
| YX-8034 | 37 | 37 | |||||
| HBPA | 37 | ||||||
| YX-8300 | 37 | ||||||
| TEPIC-H | 19 | ||||||
| TEPIC-S | 19 | ||||||
| 828 | 37 | ||||||
| SO-E5 | 110 | 110 | 110 | 110 | 110 | 110 | 110 |
| Initiating agent | 19 | 19 | 19 | 19 | 19 | 19 | 19 |
| Sensitizer | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Monomer | 15 | 15 | 15 | 15 | 15 | 15 | 15 |
| KS-66 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| Solvent | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
R820: the former industry corporate system of stone is made Titanium Dioxide Rutile Top grade
KA-15: チ タ Application industrial group makes anatase-type titanium oxide
YX-8034:Japan Epoxy Resins Co., Ltd. makes bisphenol-A epoxy resin
HBPA: the kind petrochemistry of ball is made bisphenol-A epoxy resin HBPA-DGE
YX-8300:Japan Epoxy Resins Co., Ltd. makes the hydrogenation biphenyl type epoxy resin
TEPIC-H: daily output chemistry (strain) is made β body triglycidyl group isocyanuric acid ester
TEPIC-S: daily output chemistry (strain) is made α body and β body mixing triglycidyl group isocyanuric acid ester
828:Japan Epoxy Resins Co., Ltd. makes bisphenol A-type
SO-E5:ADMATECHS CO., LTD makes spherical silicon dioxide
Initiating agent: Ciba Specialty Chemicals Inc. makes Irgacur 907
Sensitizer: Japanese chemical drug is made DETX
Monomer: dipentaerythritol acrylate
KS-66: the シ リ コ of SHIN-ETSU HANTOTAI one Application is made silicone oil
Solvent: carbitol acetic acid esters.
In order to investigate each character of the soldering-resistance layer that uses each solder resist composition and form, the following test estimated.
(1) photostability
By silk screen print method, use the 100 order polyester fabric version of tiltedly throwing the net, the full version of each solder resist composition is printed onto on the FR-4 copper clad laminate of 100mm * 150mm size, 1.6mm thickness, so that thickness is 40 μ m.Following dry 30 minutes with the heated air circulation type drying oven at 80 ℃.Use use in printed circuit board exposure machine ORCMANUFACTURING CO., the HMW-680GW that LTD. makes uses 500mJ/cm
2The accumulation light quantity carry out ultraviolet exposure, so that the square negative pattern of residual 30mm, with 30 ℃, 1% aqueous sodium carbonate as developer solution, developed for 60 seconds by the use in printed circuit board developing machine, then with the heated air circulation type drying oven 150 ℃, carry out heat curing in 60 minutes, prepare the test film that attribute testing is used.
The color colour difference meter CR-400 that makes with Minolta measures resulting test film.Then, irradiation UV conveyor oven (power 150W/cm metal halide lamp Cold Mirrors) 150J/cm
2Light, quicken the light deterioration.The result is shown in the table 2.
Table 2
In table 2, Y represents the reflectivity of XYZ colorimetric system, L
*Expression L
*a
*b
*The brightness of colorimetric system.a
*The expression red is to ,-a
*Represent green direction, b
*Represent yellow direction ,-b
*Represent blue direction, approaching more zero represents not have chroma more.Δ E
*Ab represents change in color.The more little expression change in color of this value is more little.In the visual valuation project, " ◎ " represents imperceptible variable color, and " zero " expression does not almost have variable color, and " △ " represents variable color a little, and " * " expression has tangible variable color.
Comparative example 4 comprises anatase-type titanium oxide and replaces Titanium Dioxide Rutile Top grade.Anatase-type titanium oxide as shown in Table 2, initial reflectivity height, but after quickening the light deterioration, reflectivity Y and brightness L
*Reduce greatly together, as the Δ E of change color
*The ab value is also big.In addition, in visual valuation, also can see variable color.Hence one can see that, compares with anatase-type titanium oxide, and Titanium Dioxide Rutile Top grade is as the solder resist composition components excellence of high reflectance.
(2) thermotolerance
The color colour difference meter CR-400 that makes with Minolta measures and (1) same each test film for preparing.Then, in the heated air circulation type drying oven,, carry out accelerated deterioration 150 ℃ of heating 500 hours, 1000 hours.The result is shown in the table 3.
Table 3
As shown in Table 3, in using the embodiment 1～3 of composition of the present invention, behind the accelerated deterioration, reflectivity does not reduce yet, and the variation of brightness is also little, and as the Δ E of change color
*The value of ab is little.In addition, in visual valuation, there is not variable color fully or almost yet.
Comparative example 1～3 is to use the example of the epoxy compound beyond the hydrogenation epoxy compound.As shown in Table 3, the composition that in the solder resist composition, comprises the epoxy compound beyond the hydrogenation epoxy compound after quickening hot deterioration, reflectivity Y and brightness L
*Reduce widely together, and as the Δ E of change color
*The value of ab is also big.In addition, in visual valuation, can see variable color.Hence one can see that, uses hydrogenation epoxy compound epoxy compound in addition in the resin in the solder resist composition, because of thermal conductance causes the soldering-resistance layer deterioration.
(3) solvent resistance
To in propylene glycol methyl ether acetate, flood 30 minutes with each test film of (1) same preparation, make its drying after, utilize the viscose paper adhesive tape to carry out disbonded test, peeling off of filming and variable color are estimated.The result is shown in the table 4.At this, " zero " expression is not filmed peels off, variable color, and " * " expression has peeling off of filming, variable color.
(4) pencil hardness test
The B that the nib of pencil-lead is polished is to the pencil of 9H, with about 45 ° angle by give as security with each test film of (1) same preparation on, record does not produce the hardness of the pencil of peeling off of filming.The result illustrates in table 4 in the lump.
(5) insulation resistance test
Except the comb-type electrode B print that uses IPC B-25 test pattern replaces the FR-4 copper clad laminate, with (1) same condition under prepare test film.This test film is applied the bias voltage of DC 500V, measure insulating resistance value.The result illustrates in table 4 in the lump.
Table 4
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Solvent resistance | ○ | ?○ | ?○ | ○ | ?○ | ○ | ○ |
| Pencil hardness test | 7H | ?7H | ?7H | 7H | ?7H | 7H | 7H |
| Insulation resistance test (Ω) | 1×10 13More than | ?1×10 13More than | ?1×10 13More than | 1×10 13More than | ?5×10 12 | 1×10 12 | 1×10 13More than |
As shown in Table 4, use the embodiment 1～3 of solder resist composition of the present invention to have the desired good thermotolerance of soldering-resistance layer, solvent resistance, adaptation and electrical insulating property.
As above detailed description, can obtain to form the white solder resist composition of Photosetting and thermosetting of the soldering-resistance layer of high reflectance according to the present invention.Soldering-resistance layer by the formed high reflectance of solder resist composition of the present invention is not subject to light deterioration and hot deterioration, and withstand prolonged is used.
Claims (7)
1. Bai Se Photosetting and thermosetting solder resist composition, it is characterized in that, what it comprised that (A) do not have an aromatic rings contains carboxy resin, (B) Photoepolymerizationinitiater initiater, (C) hydrogenation epoxy compound, (D) Titanium Dioxide Rutile Top grade and (E) thinning agent, wherein
Aforementioned (A) do not have the scope of the acid number that contains carboxy resin of aromatic rings at 50～200mgKOH/g, and its weight-average molecular weight is in 5000～100000 scope,
Aforementioned (C) hydrogenation epoxy compound is more than one in hydrogenated aromatic family glycidyl ether compound, hydrogenated aromatic family epihydric alcohol ester compound, the hydrogenated aromatic family glycidyl amine compound, wherein the average hydrogenation ratio of (C) hydrogenation epoxy compound is 50～100%
The use level of aforementioned lights polymerization initiator (B) is 1～30 mass parts with respect to the aforementioned carboxy resin (A) that contains that does not have aromatic rings of 100 mass parts, the use level of aforementioned hydrogenation epoxy compound (C) is 5～70 mass parts with respect to the aforementioned carboxy resin (A) that contains that does not have aromatic rings of 100 mass parts, the use level of aforementioned Titanium Dioxide Rutile Top grade (D) is 50～300 mass parts with respect to the aforementioned carboxy resin (A) that contains that does not have aromatic rings of 100 mass parts, and the use level of aforementioned thinning agent (E) is 20～300 mass parts with respect to the aforementioned carboxy resin (A) that contains that does not have aromatic rings of 100 mass parts.
2. the Photosetting and thermosetting solder resist composition of white according to claim 1 is characterized in that, the aforementioned carboxy resin (A) that contains that does not have aromatic rings is to contain carboxy resin by what the aliphatics polymerization monomer of carbon number 2～20 generated.
3. the Photosetting and thermosetting solder resist composition of white according to claim 1, it is characterized in that, the aforementioned carboxy resin (A) that contains that does not have aromatic rings is that the copolymerization with carboxyl is a resin, and this copolymerization with carboxyl is that the reaction that resin passes through the aliphatics polymerization monomer that contains the carbon number 4～20 that has oxirane ring and ethylenically unsaturated group in carboxyl (methyl) acrylate based copolymerized resin and (b) 1 molecule that (a) generated by the aliphatics polymerization monomer of carbon number 2～20 obtains.
4. the Photosetting and thermosetting solder resist composition of white according to claim 1, it is characterized in that aforementioned hydrogenation epoxy compound (C) is to the aromatic rings of aromatic epoxy compound optionally nuclear hydrogenation and the bisphenol-A epoxy resin that obtains.
5. the Photosetting and thermosetting solder resist composition of white according to claim 1 is characterized in that, also comprises (F) silica dioxide granule.
6. the Photosetting and thermosetting solder resist composition of white according to claim 5 is characterized in that, the use level of aforementioned silica dioxide granule (F) is 50～200 mass parts with respect to the aforementioned carboxy resin (A) that contains that does not have aromatic rings of 100 mass parts.
7. printed circuit board (PCB), it forms soldering-resistance layer by the Photosetting and thermosetting solder resist composition that uses each described white of claim 1～6 in the printed circuit board surface that is formed with circuit and obtains.
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| PCT/JP2007/070654 WO2008050768A1 (en) | 2006-10-24 | 2007-10-23 | Photocurable/thermocurable solder resist composition, and printed circuit board using the same |
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| KR (1) | KR101002902B1 (en) |
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| JP5117416B2 (en) * | 2009-01-21 | 2013-01-16 | 株式会社タムラ製作所 | Photosensitive resin composition, solder resist composition for printed wiring board, and printed wiring board |
| JP5377021B2 (en) | 2009-03-23 | 2013-12-25 | 太陽ホールディングス株式会社 | Curable resin composition, dry film and printed wiring board using the same |
| JP5419514B2 (en) * | 2009-03-30 | 2014-02-19 | 太陽ホールディングス株式会社 | Hole filling resin composition and printed wiring board filled with this resin composition |
| JP5352340B2 (en) * | 2009-05-13 | 2013-11-27 | 株式会社タムラ製作所 | Photosensitive resin composition, solder resist composition for printed wiring board, and printed wiring board |
| JP5668348B2 (en) * | 2009-07-24 | 2015-02-12 | 東洋インキＳｃホールディングス株式会社 | Photosensitive composition |
| CN102483571B (en) * | 2009-09-10 | 2013-10-23 | 积水化学工业株式会社 | Photosensitive composition and printed wiring board |
| JP5618516B2 (en) * | 2009-09-29 | 2014-11-05 | 太陽ホールディングス株式会社 | Insulating photocurable thermosetting resin composition and printed wiring board |
| JP5147820B2 (en) * | 2009-12-24 | 2013-02-20 | 株式会社タムラ製作所 | White solder resist composition for spray painting |
| JP5325805B2 (en) * | 2010-01-29 | 2013-10-23 | 株式会社タムラ製作所 | Photosensitive resin composition and printed wiring board using cured film thereof |
| JP4975834B2 (en) * | 2010-02-17 | 2012-07-11 | 太陽ホールディングス株式会社 | Solder resist composition and printed wiring board |
| JP2011170050A (en) * | 2010-02-17 | 2011-09-01 | Taiyo Holdings Co Ltd | Solder resist composition and printed circuit board |
| WO2011125821A1 (en) * | 2010-03-31 | 2011-10-13 | 太陽ホールディングス株式会社 | Thermosetting resin composition and printed wiring board |
| JP2011216687A (en) * | 2010-03-31 | 2011-10-27 | Taiyo Holdings Co Ltd | White coating layer, method of forming the same, and printed circuit board |
| KR101250736B1 (en) * | 2011-02-14 | 2013-04-03 | 세키스이가가쿠 고교가부시키가이샤 | First liquid and second liquid of two-liquid mixing type, and method for manufacturing printed wiring board |
| WO2012141124A1 (en) * | 2011-04-13 | 2012-10-18 | 太陽インキ製造株式会社 | Curable resin composition, cured product thereof and printed circuit board using same |
| KR101456133B1 (en) * | 2012-11-01 | 2014-11-03 | 주식회사 케이씨씨 | Photosensitive composition having good light absorbance and suitable for forming fine pattern |
| JP5878913B2 (en) * | 2013-12-17 | 2016-03-08 | 互応化学工業株式会社 | Photosensitive resin composition, composition for solder resist, printed wiring board, and method for producing photosensitive resin composition |
| JP2016035042A (en) * | 2014-07-31 | 2016-03-17 | 太陽インキ製造株式会社 | Curable resin composition, dry film, cured product, and printed wiring board |
| WO2016092595A1 (en) * | 2014-12-10 | 2016-06-16 | 互応化学工業株式会社 | Liquid solder resist composition and coated printed wiring board |
| JP6055028B2 (en) * | 2015-05-29 | 2016-12-27 | 互応化学工業株式会社 | Photosensitive resin composition, solder resist composition and printed wiring board |
| JP6055029B2 (en) * | 2015-05-29 | 2016-12-27 | 互応化学工業株式会社 | Photosensitive resin composition, solder resist composition and printed wiring board |
| TWI571705B (en) * | 2016-01-15 | 2017-02-21 | 臺灣永光化學工業股份有限公司 | Negative white photosensitive resin composition and use thereof |
| CN107203095B (en) * | 2017-07-19 | 2020-08-18 | 江苏广信感光新材料股份有限公司 | White alkali-soluble photosensitive composition and preparation method and application thereof |
| KR102293308B1 (en) | 2021-01-15 | 2021-08-23 | 한국전기연구원 | Photo solder resists based on organo-siloxane binder and their manufacturing method |
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