CN102722083B - Solder mask composition and printed circuit board (PCB) - Google Patents
Solder mask composition and printed circuit board (PCB) Download PDFInfo
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- CN102722083B CN102722083B CN201210191872.1A CN201210191872A CN102722083B CN 102722083 B CN102722083 B CN 102722083B CN 201210191872 A CN201210191872 A CN 201210191872A CN 102722083 B CN102722083 B CN 102722083B
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- mass parts
- solder mask
- mask composition
- photoepolymerizationinitiater initiater
- aromatic rings
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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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
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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
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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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3452—Solder masks
Abstract
The invention provides solder mask composition and printed circuit board (PCB), specifically, the invention provides can prevent from being caused by variable color deterioration the reduction of reflectivity, high reflectance and high-resolution solder mask composition, and the printed circuit board (PCB) using this solder mask composition to form soldering-resistance layer and obtain.The feature of solder mask composition of the present invention is, comprises: (A) do not have aromatic rings containing carboxy resin; (B) two acylphosphine oxide systems Photoepolymerizationinitiater initiater; (C) monoacylphosphine oxides system Photoepolymerizationinitiater initiater; (D) photopolymerization monomer; (E) Titanium Dioxide Rutile Top grade; And (G) organic solvent.
Description
The application is the divisional application of Chinese patent application 201010175136.8, and the applying date of original application 201010175136.8 is on May 14th, 2010, and its name is called " solder mask composition and printed circuit board (PCB) ".
Technical field
The present invention relates to the solder mask composition that can be formed and be suitable for soldering-resistance layer that use as the permanent mask of printed circuit board (PCB), high reflectance, and use this solder mask composition to form the printed circuit board (PCB) of soldering-resistant pattern on the surface of the printed circuit board (PCB) being formed with circuit.
Background technology
Printed circuit board (PCB) usually fits in not the needing part of Copper Foil on laminate by etching removing and is formed with wiring, is configured on the position of regulation by electronic unit by welding.In such printed circuit board (PCB), be used in base material is coated with and the soldering-resistance layer be solidified to form as the diaphragm of circuit during welding electronic unit.
When this soldering-resistance layer can prevent from welding, solder attachment is in unnecessary part, and circuit conductor can be prevented directly to be exposed to the deterioration caused by oxygen, hygroscopic water in air.In addition, soldering-resistance layer also has the function of the permanent diaphragm as circuit substrate.Therefore require that it has each characteristics such as adaptation, electrical insulating property, solder heat resistance, solvent resistance, chemical proofing.
In addition, for realizing densification, printed circuit board (PCB) is just steady towards the development of granular (becoming more meticulous), multiple stratification and single board, and its mounting means is also changing to surface mounting technique (SMT).For this reason, to the requirement of the becoming more meticulous of soldering-resistance layer, high resolving power, high precision, high reliability also in raising.
As the technology of pattern forming such soldering-resistance layer, the photoetching process that accurately can form fine pattern is used, and particularly for the consideration etc. to environment aspect, the photoetching process of alkali developable just becomes main flow.
Such as, patent documentation 1 and patent documentation 2 publicity are a kind of can with the solder mask composition of aqueous alkali development, this solder mask composition by reacted by phenolic resin varnish type epoxy resin and unsaturated monocarboxylic so that with multi-anhydride addition and the reaction product that obtains based on polymkeric substance.
On the other hand, in recent years, using the backlight of the liquid crystal display as portable terminal, PC, TV etc., the light source of ligthing paraphernalia etc., to be directly installed on the light emitting diode (LED) of low electric power luminescence and coating to be formed with purposes on the printed circuit board (PCB) of soldering-resistance layer in increase.
Therefore, in order to effectively utilize the light of LED, just needing soldering-resistance layer to be white printed circuit board (PCB), making this soldering-resistance layer have high reflectance.
But the composition of white solder masks self has high reflectivity, therefore just reflected by light when patterned exposure, light required when causing fully absorbing its solidification, differentiates rate variance, and result is difficult to the pattern sub-image forming fine.
In addition, for the printed circuit board (PCB) being directly provided with LED, the light and heat that LED sends can promote the deterioration of white solder masks, painted to cause the reduction of reflectivity.
prior art document
patent documentation
Patent documentation 1: Japanese Patent Publication 1-54390 publication
Patent documentation 2: Japanese Patent Publication 7-17737 publication
Summary of the invention
the problem that invention will solve
The object of the invention is to, be provided for being formed can effectively utilize the light of LED, high reflectance and the solder mask composition of high-resolution soldering-resistance layer and printed circuit board (PCB).
The present invention also aims to, the deterioration of the soldering-resistance layer caused by light and heat that can prevent from being sent by LED, painted solder mask composition and printed circuit board (PCB) are provided.
for the scheme of dealing with problems
Found that of the further investigation such as the present inventor, use can be developed by alkali, and the resin without aromatic rings as have Thermocurable containing carboxy resin, and use Titanium Dioxide Rutile Top grade as the Chinese white for realizing high reflectance, can suppress by light for a long time thus, deterioration caused by heat, also find by combinationally using two acylphosphine oxide system Photoepolymerizationinitiater initiater and monoacylphosphine oxides system Photoepolymerizationinitiater initiater as Photoepolymerizationinitiater initiater in addition, even if solder mask composition contains the high Titanium Dioxide Rutile Top grade of a large amount of reflectivity, also excellent in resolution can be formed, the pattern sub-image of fine.
That is, the feature of solder mask composition of the present invention is, contains: (A) do not have aromatic rings containing carboxy resin; (B) two acylphosphine oxide systems Photoepolymerizationinitiater initiater; (C) monoacylphosphine oxides system Photoepolymerizationinitiater initiater; (D) photopolymerization monomer; (E) Titanium Dioxide Rutile Top grade; And (G) organic solvent, also can contain (F) epoxy compound or (H) thioxanthones system photopolymerization sensitizer.
invention effect
According to the present invention, high reflectance can be formed and high-resolution soldering-resistance layer, it has the characteristic such as coating, photo-curable, developability, solder heat resistance, adaptation, electrical insulating property needed for developable solder flux, can suppress to change in time the reflectivity caused reduction and by deterioration cause painted.And solder mask composition of the present invention can also improve overall illumination when LED being mounted to printed circuit board (PCB).
Accompanying drawing explanation
Fig. 1 is the figure of the temperature representing the heating furnace used in the fast light resistance to thermochromism test of the test film of embodiment, comparative example.
Embodiment
Below, the present invention is described in further detail.
The feature of solder mask composition of the present invention is, contains: (A) do not have aromatic rings containing carboxy resin; (B) two acylphosphine oxide systems Photoepolymerizationinitiater initiater; (C) monoacylphosphine oxides system Photoepolymerizationinitiater initiater; (D) photopolymerization monomer; (E) Titanium Dioxide Rutile Top grade; And (G) organic solvent, also can contain (F) epoxy compound or (H) thioxanthones system photopolymerization sensitizer.
what do not have aromatic rings contains carboxy resin
As do not have aromatic rings containing carboxy resin (A), can use himself there is more than 1 photonasty unsaturated double-bond photosensitive containing carboxy resin, do not have photonasty unsaturated double-bond containing any one in the middle of carboxy resin, be not limited to predetermined substance.The resin (oligomer or polymkeric substance) without aromatic rings in the following resin enumerated can be used especially aptly.That is: what (1) was obtained by unsaturated carboxylic acid and the compound copolymerization with unsaturated double-bond contains carboxy resin; (2) the photosensitive carboxy resin that contains obtained containing the compound in carboxyl (methyl) acrylic copolymer resin and 1 molecule with oxirane ring and olefinic unsaturated group reacts is made; (3) multipolymer of the compound making to have in 1 molecule 1 epoxy radicals and 1 unsaturated double-bond and the compound with unsaturated double-bond, react with unsaturated monocarboxylic, what make the secondary hydroxyl that generated by this reaction and saturated or unsaturated multi-anhydride react and obtain photosensitively contains carboxy resin; (4) after hydroxyl polymer-containing and saturated or unsaturated multi-anhydride react, the compound in the carboxylic acid that generated by this reaction and 1 molecule with 1 epoxy radicals and 1 unsaturated double-bond is reacted and the resin of the photosensitive hydroxyl obtained and carboxyl.
Wherein, preferably the photosensitive of above-mentioned (2) contains carboxy resin, that is, (a) copolymerization system resin with carboxyl of obtaining containing the compound that carboxyl (methyl) acrylic copolymer resin and (b) 1 has oxirane ring and olefinic unsaturated group in molecule reacts.
(a) containing carboxyl (methyl) acrylic copolymer resin by obtaining by there is the compound copolymerization of 1 unsaturated group and at least 1 carboxyl in (methyl) acrylate and 1 molecule.As (methyl) acrylate forming copolymer resins (a), (methyl) methyl acrylate can be listed, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) amyl acrylate, (methyl) alkyl-acrylates such as (methyl) Hexyl 2-propenoate, (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) hydroxypropyl acrylate, (methyl) hy-droxybutyl, hydroxyl (methyl) esters of acrylic acids such as caprolactone modification (methyl) acrylic acid-2-hydroxyl ethyl ester, methoxyl diethylene glycol (methyl) acrylate, ethoxydiglycol (methyl) acrylate, different octyloxy diethylene glycol (methyl) acrylate, phenoxy group triethylene glycol (methyl) acrylate, methoxy triethylene (methyl) acrylate, glycol modification (methyl) esters of acrylic acids etc. such as methoxy poly (ethylene glycol) (methyl) acrylate.These one that can be used alone, also can be used in combination two or more.In addition, (methyl) acrylate is the term of general name acrylate and methacrylate in this manual, and all the other similar expression too.
In addition, as the compound in 1 molecule with 1 unsaturated group and at least 1 carboxyl, acrylic acid can be enumerated, methacrylic acid, modification unsaturated monocarboxylic, such as (methyl) senecioate-carboxyethyl of chain elongation, 2-acryloyl-oxyethyl succinic acid, 2-acryloyl-oxyethyl hexahydrophthalic acid between unsaturated group and carboxylic acid, be there is by lactone-modified grade the unsaturated monocarboxylic of ester bond, there is the modification unsaturated monocarboxylic of ehter bond, and in maleic acid equimolecular, comprise the compound etc. of more than 2 carboxyls.These one that can be used alone, also can be used in combination two or more.
There is in molecule as (b) 1 compound of oxirane ring and olefinic unsaturated group, as long as be the compound in 1 molecule with olefinic unsaturated group and oxirane ring, such as (methyl) glycidyl acrylate, (methyl) acrylic acid Alpha-Methyl ethylene oxidic ester, (methyl) acrylic acid 3 can be listed, 4-epoxycyclohexanecarboxylate, (methyl) acrylic acid 3,4-epoxycyclohexyl ethyl ester, (methyl) acrylic acid 3,4-epoxycyclohexyl butyl ester, 3,4-epoxycyclohexyl-methyl amino acrylates etc.Wherein, preferred (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate.The compound that these (b) 1 have oxirane ring and olefinic unsaturated group in molecule can be used alone one, also can be used in combination two or more.
The acid number containing carboxy resin (A) without aromatic rings needs within the scope of 50 ~ 200mgKOH/g.When acid number is lower than 50mgKOH/g, be difficult to the unexposed portion of the film removing solder mask composition in weak base aqueous solution.When acid number is more than 200mgKOH/g, the problem such as water tolerance, electric properties deteriorate of solidification tunicle can be produced.In addition, not there is the weight-average molecular weight containing carboxy resin (A) of aromatic rings preferably in the scope of 5000 ~ 100000.When weight-average molecular weight lower than 5000 time, the dry to touch of the film of solder mask composition has the tendency be significantly deteriorated.In addition, when weight-average molecular weight is more than 100000, the developability of solder mask composition can be produced, problem that bin stability significantly worsens, thus not preferred.
photoepolymerizationinitiater initiater
two acylphosphine oxide systems Photoepolymerizationinitiater initiater
As two acylphosphine oxide systems Photoepolymerizationinitiater initiater (B) used in the present invention, two-(2 can be listed, 6-dichloro-benzoyl base) phenyl phosphine oxide, two-(2, 6-dichloro-benzoyl base)-2, 5-3,5-dimethylphenyl phosphine oxide, two-(2, 6-dichloro-benzoyl base)-4-propylphenylphosphine oxide, two-(2, 6-dichloro-benzoyl base)-1-naphthyl phosphine oxide, two-(2, 6-Dimethoxybenzoyl) phenyl phosphine oxide, two-(2, 6-Dimethoxybenzoyl)-2, 4, 4-trimethylpentylphosphine oxide, two-(2, 6-Dimethoxybenzoyl)-2, 5-3,5-dimethylphenyl phosphine oxide, two-(2, 4, 6-trimethylbenzoyl) phenyl phosphine oxide, (2, 5, 6-trimethylbenzoyl)-2, 4, 4-trimethylpentylphosphine oxide etc.Wherein two-(2,4,6-trimethylbenzoyl) phenyl phosphine oxide (CibaJapanK.K. system, trade name: Irgacure819) easily obtains and practical.
monoacylphosphine oxides system Photoepolymerizationinitiater initiater
As monoacylphosphine oxides system Photoepolymerizationinitiater initiater (C) used in the present invention; can 2 be listed; 4; 6-trimethyl benzoyl diphenyl base phosphine oxide, 2; 6-Dimethoxybenzoyl diphenyl phosphine oxide, 2; 6-dichloro-benzoyl base diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl methyl-phosphonates, 2-methyl benzoyl diphenyl phosphine oxide, pivaloyl phenyl-phosphonic acid isopropyl ester etc.Wherein TMDPO (CibaJapanK.K. system, trade name: DarocurTPO) easily obtains and practical.
Solder mask composition of the present invention by combinationally using above-mentioned pair of acylphosphine oxide system Photoepolymerizationinitiater initiater (B) and aforementioned monoacylphosphine oxides system Photoepolymerizationinitiater initiater (C), and making the film of the high reflectance being combined with titanium dioxide also can absorb necessary light, can form the pattern of fine.In addition, inching can be carried out to the light absorption of film by changing its compounding ratio.That is, when the curability deficiency due to the deep of substrate surface side on the cross sectional shape of pattern causes easily occurring undercutting, the ratio of above-mentioned pair of acylphosphine oxide system Photoepolymerizationinitiater initiater (B) is increased.In addition, when surface cure deficiency causes the surface state after developing severe, the ratio of aforementioned monoacylphosphine oxides system Photoepolymerizationinitiater initiater (C) is increased.This pair of acylphosphine oxide system Photoepolymerizationinitiater initiater (B) is 90:10 ~ 1:99 with the compounding ratio of monoacylphosphine oxides system Photoepolymerizationinitiater initiater (C), is preferably 80:20 ~ 2:98.Outside this compounding ratio scope, the effect combinationally using these initiating agents tails off, and cannot absorb necessary light, therefore cause the pattern that cannot form fine.
Relative to 100 mass parts do not have aromatic rings containing carboxy resin (A); total use level of two acylphosphine oxide system Photoepolymerizationinitiater initiater (B) and monoacylphosphine oxides system Photoepolymerizationinitiater initiater (C) is preferably 1 ~ 30 mass parts, is more preferably 2 ~ 25 mass parts.When total use level of this pair of acylphosphine oxide system Photoepolymerizationinitiater initiater (B) and monoacylphosphine oxides system Photoepolymerizationinitiater initiater (C) is lower than 1 mass parts, photo-curable reduces, and is difficult to form pattern after exposure and development, therefore not preferred.On the other hand, when this use level is more than 30 mass parts, the painted change of the film brought by Photoepolymerizationinitiater initiater is large, and becomes the high reason of cost, therefore not preferred.
photopolymerization monomer
As the photopolymerization monomer used in the present invention (D), the hydroxyalkyl acrylates classes such as acrylic acid-2-hydroxyl ethyl ester, acrylic acid-2-hydroxy butyl ester can be listed; The mono acrylic ester of the glycol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol or diacrylate class; The acrylic amide such as N,N-DMAA, N hydroxymethyl acrylamide; The acrylate classes such as acrylic acid-N, N-dimethylamino ethyl ester; The multicomponent methacrylate class of the polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, trihydroxy ethyl isocyanurate or their oxirane or propylene oxide adduct; The esters of acrylic acid of the oxirane of phenoxy group acrylate, bisphenol a diacrylate and these phenols or propylene oxide adduct etc.; The esters of acrylic acid of the glycerin ether such as glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether; Melamine acrylate; And/or the methyl acrylic ester etc. corresponding with aforesaid propylene esters of gallic acid.
Relative to 100 mass parts do not have aromatic rings containing carboxy resin (A), the use level of these photopolymerization monomers (D) is preferably 10 ~ 100 mass parts, is more preferably 20 ~ 80 mass parts.When use level is more than 100 mass parts, the physical property as the soldering-resistance layer of cured coating film reduces, therefore not preferred.On the other hand, when this use level is lower than 10 mass parts, do not possess sufficient photo-curable, the pattern of fine cannot be obtained.
titanium Dioxide Rutile Top grade
The present invention uses Titanium Dioxide Rutile Top grade (E) as Chinese white.Usual titanium dioxide has Detitanium-ore-type and rutile-type.Because anatase-type titanium oxide has photocatalytic activity, the variable color of the resin in solder mask composition can be caused.And compared with anatase-type titanium oxide, Titanium Dioxide Rutile Top grade exists and absorbs near the border of ultraviolet range and visible region, though whiteness and the reflection differences in whole visible region, can obtain stable soldering-resistance layer because it does not have photolytic activity substantially.
As aforementioned Titanium Dioxide Rutile Top grade (E), known material can be used.Specifically, TIPAQUER-820 can be used, TIPAQUER-830, TIPAQUER-930, TIPAQUER-550, TIPAQUER-630, TIPAQUER-680, TIPAQUER-670, TIPAQUER-780, TIPAQUER-850, TIPAQUECR-50, TIPAQUECR-57, TIPAQUECR-80, TIPAQUECR-90, TIPAQUECR-93, TIPAQUECR-95, TIPAQUECR-97, TIPAQUECR-60, TIPAQUECR-63, TIPAQUECR-67, TIPAQUECR-58, TIPAQUECR-85, TIPAQUEUT771 (Ishihara Sangyo Kaisha, Ltd.'s system), Ti-PureR-100, Ti-PureR-101, Ti-PureR-102, Ti-PureR-103, Ti-PureR-104, Ti-PureR-105, Ti-PureR-108, Ti-PureR-900, Ti-PureR-902, Ti-PureR-960, Ti-PureR-706, Ti-PureR-931 (DuPontKabushikiKaisha system), TITONR-25, TITONR-21, TITONR-32, TITONR-7E, TITONR-5N, TITONR-61N, TITONR-62N, TITONR-42, TITONR-45M, TITONR-44, TITONR-49S, TITONGTR-100, TITONGTR-300, TITOND-918, TITONTCR-29, TITONTCR-52, TITONFTR-700 (Sakai Chemical Industry Co., Ltd.'s system) etc.
Relative to 100 mass parts do not have aromatic rings containing carboxy resin (A), the use level of such Titanium Dioxide Rutile Top grade (E) is preferably 50 ~ 450 mass parts, is more preferably 60 ~ 350 mass parts.When use level is more than 450 mass parts, photo-curable reduces, curing depth step-down, therefore not preferred.On the other hand, when this use level is lower than 50 mass parts, covering power diminishes, and cannot obtain the soldering-resistance layer of high reflectance.
epoxy compound
Then, as epoxy compound (F), such as bisphenol-s epoxy resin can be listed, o-phthalic acid diglycidyl ester resin, triglycidyl isocyanurate (TEPIC-H that such as Nissan Chemical (strain) manufactures (β body, its have 3 epoxy radicals in the same direction with the structure of s-triazine ring skeleton face phase bonding), TEPIC (potpourri of β body and α body, this α body have 1 epoxy radicals and other 2 epoxy radicals in different directions with the structure of s-triazine ring skeleton face phase bonding) etc.) and etc. hetero ring type epoxy resin, di-toluene phenol-type epoxy resin, biphenyl type epoxy resin, four glycidyl group xylenols ethane resin etc. is insoluble in the epoxy resin of thinning agent, bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol F type resin, brominated bisphenol a type epoxy resin, phenol novolak type or cresol novolak type epoxy resin, alicyclic epoxy resin, the phenolic resin varnish type epoxy resin of bisphenol-A, chelating type epoxy resin, glyoxal type epoxy resin, containing aminoepoxy resin, rubber modified epoxy resin, dicyclopentadiene phenol epoxy resin, silicone modified epoxy resin, 6-caprolactone modified epoxy etc. dissolves in the epoxy resin etc. of thinning agent.These epoxy resin can be used alone, and also use capable of being combined is two or more.
Relative to 100 mass parts do not have aromatic rings containing carboxy resin (A), the use level of such epoxy compound (F) is preferably 5 ~ 70 mass parts, is more preferably 5 ~ 60 mass parts.When the use level of epoxy compound (F) is more than 70 mass parts, the dissolubility of unexposed portion in developer solution reduces, easily produce development remains, and is difficult to use in practice.On the other hand, when this use level is lower than 5 mass parts, not there is remaining with unreacted state containing the carboxyl of carboxy resin (A) of aromatic rings, thus have be difficult to obtain sufficient cured coating film electrical characteristics, solder heat resistance, chemical proofing tendency.
Do not there is being reacted by ring-opening polymerization containing the carboxyl of carboxy resin (A) and the epoxy radicals of epoxy compound (F) of aromatic rings.Further, when using the epoxy resin of ease of solubility as other materials in organic solvent (G), solder mask composition, thermal capacitance time dry easily causes the crosslinked of carboxyl and epoxy radicals.For this reason, when this cross-linking reaction will be suppressed carry out drying for a long time, be used alone or use together with the epoxy resin of ease of solubility the epoxy resin of slightly solubility to be desirable.
organic solvent
(G) used in the present invention is to make solder mask composition be the state being easy to be coated with, and makes it the dry film that formed after being coated base material etc. and use.As such organic solvent (G), the ketone such as MEK, cyclohexanone can be listed; Toluene, dimethylbenzene, tetramethylbenzene etc. are aromatic hydrocarbon based; The glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, DPE, Triethylene glycol ethyl ether; The ester classes such as the carboxylate of ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetic acid esters and above-mentioned glycol ethers; The alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; The aliphatic hydrocarbon such as octane, decane; The petroleum solvents etc. such as sherwood oil, petroleum naphtha, non-hydrogenated petroleum naphtha, solvent naphtha.
Aforementioned organic solvents (G) can be used alone, and also can use two or more potpourris.Relative to 100 mass parts do not have aromatic rings containing carboxy resin (A), the use level of organic solvent (G) is preferably 20 ~ 300 mass parts.
thioxanthones system photopolymerization sensitizer
To for the purpose of the sensitivity of light during to improve exposure, the present invention coordinates thioxanthones system photopolymerization sensitizer (H) to be desirable.This is that the effect of thioxanthones system photopolymerization sensitizer (H) is very high due in the combination combinationally using above-mentioned pair of acylphosphine oxide system Photoepolymerizationinitiater initiater (B) and above-mentioned monoacylphosphine oxides system Photoepolymerizationinitiater initiater (C).As this thioxanthones system photopolymerization sensitizer (H), thioxanthones, 2-ethyl thioxanthones, ITX, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, 2,4-diisopropylthioxanthone etc. can be listed.
Relative to 100 mass parts do not have aromatic rings containing carboxy resin (A), the use level of such thioxanthones system photopolymerization sensitizer (H) is preferably 0.05 ~ 2 mass parts, is more preferably 0.1 ~ 1 mass parts.When this use level is lower than 0.05 mass parts, put forward highly sensitive effect few, during more than 2 mass parts, the painted change of the film brought by thioxanthones is large.
other compositions
stabilizing agent
And then solder mask composition of the present invention is by reducing light deterioration containing hindered amine system light stabilizer.
As hindered amine system light stabilizer, such as TINUVIN622LD, TINUVIN144 can be listed; CHIMASSORB944LD, CHIMASSORB119FL (being CibaJapanK.K. system above); MARKLA-57, LA-62, LA-67, LA-63, LA-68 (being Asahi Denka Co., Ltd.'s system above); SanolLS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (being SANKYOLIFETECHCO. above, LTD. system) etc.
Relative to 100 mass parts do not have aromatic rings containing carboxy resin (A), 0.1 ~ 10 mass parts is preferably added in aforementioned stable agent.
spreading agent
Solder mask composition of the present invention is by improving dispersiveness, the settleability of titanium dioxide containing spreading agent.As spreading agent, such as ANTI-TERRA-U can be listed, ANTI-TERRA-U100, ANTI-TERRA-204, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-185, DISPERBYK-184, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2009, DISPERBYK-2020, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, BYK-P104, BYK-P104S, BYK-P105, BYK-9076, BYK-9077, BYK-220S (Bi Ke chemistry (Japan) Co., Ltd. system), DISPARLON2150, DISPARLON1210, DISPARLONKS-860, DISPARLONKS-873N, DISPARLON7004, DISPARLON1830, DISPARLON1860, DISPARLON1850, DISPARLONDA-400N, DISPARLONPW-36, DISPARLONDA-703-50 (nanmu originally changes into Co., Ltd.'s system), FLOWLENG-450, FLOWLENG-600, FLOWLENG-820, FLOWLENG-700, FLOWLENDOPA-44, FLOWLENDOPA-17 (Kyoeisha Chemical Co., Ltd.'s system) etc.
For effectively realizing above-mentioned purpose, preferably, relative to 100 mass parts Titanium Dioxide Rutile Top grades (E), the content of spreading agent is 0.1 ~ 10 mass parts, is preferably 0.5 ~ 5 mass parts.
other adding ingredients
And then solder mask composition of the present invention can use curing accelerator, hot polymerization inhibitor, thickening agent, defoamer, levelling agent, coupling agent, flame retardant etc. as required.
method for making
Below, as an example of the use of solder mask composition, the manufacture of printed circuit board (PCB) is described.
First, as required solder mask composition of the present invention is diluted, be adjusted to the viscosity of fitting mutually with coating process.
Then, utilize the methods such as the painting of silk screen print method, curtain method, spraying process, rolling method to be coated on by the composition after adjustment viscosity to be formed on the printed circuit board (PCB) of circuit.Then, at the temperature of such as 70 ~ 90 DEG C, make organic solvent volatile dry contained in the composition after coating and form tack-free film.
Afterwards, utilize active energy beam optionally to expose this film by photomask, utilize aqueous alkali develop to unexposed portion and form corrosion-resisting pattern.Then this corrosion-resisting pattern is made at 100 ~ 200 DEG C, to carry out heat curing and form soldering-resistant pattern.
As the radiation source carrying out exposing, low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp or metal halide lamp etc. can be used.In addition, laser etc. also can be utilized as active ray.
As the aqueous alkali of developer solution, be generally the aqueous sodium carbonate of 0.5 ~ 5 quality %.Also other aqueous alkali can be used.As other aqueous alkali, the aqueous alkali of such as potassium hydroxide, NaOH, sal tartari, sodium phosphate, sodium silicate, ammonia, amine etc. can be listed.
Then, after formation soldering-resistant pattern, LED is installed and manufactures printed circuit board (PCB) of the present invention.Printed circuit board (PCB) of the present invention is like this solder resist containing the high titanium dioxide of reflectivity of the application of the invention and obtained, and it has high reflectance and has the pattern of fine.
embodiment
Below, illustrate that embodiment and comparative example are specifically described the present invention, but the present invention is not limited to following embodiment.
(A) not there is the synthesis containing carboxy resin of aromatic rings
synthesis example 1
In the 2 liters of removable flasks possessing stirring machine, thermometer, reflux condenser, tap funnel and nitrogen ingress pipe, add 900g as the diethylene glycol dimethyl ether of solvent and 21.4g as peroxidating (2 ethyl hexanoic acid) tert-butyl ester (Japan Oil Co's system, trade name: PERBUTYLO) of polymerization initiator, be heated to 90 DEG C.After heating, share and within 3 hours, drip 309.9g methacrylic acid, 116.4g methyl methacrylate, the lactone-modified HEMA of 109.8g (DaicelChemicalIndustries, Ltd. system, trade name: PLACCELFM1), 21.4g wherein as two (4-t-butylcyclohexyl) ester (Japan Oil Co's system, trade name: PERBUTYLTCP) of peroxy dicarbonate of polymerization initiator.And then make its slaking 6 hours, thus obtain containing carboxyl copolymer resins.In addition, above-mentioned reaction is carried out in a nitrogen atmosphere.
Then, 363.9g methacrylic acid 3 is added containing in carboxyl copolymer resins what obtain, 4-epoxy cyclohexyl (DaicelChemicalIndustries, Ltd. make, trade name: CyclomerA200), 3.6g as the dimethyl benzylamine of ring opening catalyst, 1.80g as the hydroquinone monomethyl ether of polymerization inhibitor, be heated to 100 DEG C, stir, carry out the opening of epoxy thus.After 16 hours, obtain the solution containing carboxy resin containing 53.8 quality % (nonvolatile component) without aromatic rings, the acid number of the solid constituent of wherein said resin is 108.9mgKOH/g, weight-average molecular weight is 25000.Below, this reaction solution is called A-1 varnish.
synthesis example 2
In the flask possessing thermometer, stirring machine, tap funnel and reflux condenser, add as the diethylene glycol monoethyl ether acetic acid esters of solvent, the azoisobutyronitrile as catalyzer, be heated to 80 DEG C in a nitrogen atmosphere, drip the monomer with the mixed in molar ratio methacrylic acid of 0.40:0.60 and methyl methacrylate with 2 hours.And then stirred 1 hour, be then warming up to 115 DEG C, make its inactivation and obtain resin solution.
After the cooling of this resin solution, use tetrabutyl ammonium bromide as catalyzer, under the condition of 95 ~ 105 DEG C, 30 hours, the mol ratio with 0.40 makes butyl glycidyl ether carry out addition reaction with the equivalent carboxyl of the resin obtained and cool.
And then under the condition of 95 ~ 105 DEG C, 8 hours, the mol ratio with 0.26 makes the OH base of the resin of tetrabydrophthalic anhydride and above-mentioned acquisition carry out addition reaction.Take out after it cooling, obtain the solution containing carboxy resin containing 50 quality % (nonvolatile component) without aromatic rings, the acid number of the solid constituent of wherein said resin is 78.1mgKOH/g, weight-average molecular weight is 35000.Below, this reaction solution is called A-2 varnish.
there is the synthesis containing carboxy resin of aromatic rings
relatively synthesis example 1
In the flask possessing thermometer, stirrer, tap funnel and reflux condenser, add 210g cresol novolak type epoxy resin (Dainippon Ink Chemicals EPICLONN-680, epoxide equivalent=210) and the 96.4g carbitol acetate as solvent, heating for dissolving.Then, 0.1g is added as the quinhydrones of polymerization inhibitor, 2.0g as the triphenylphosphine of catalysts.This potpourri is heated to 95 ~ 105 DEG C, and slowly instillation 72g acrylic acid, reacts about 16 hours until acid number reaches below 3.0mgKOH/g.After this reaction product is cooled to 80 ~ 90 DEG C, add 76.1g tetrabydrophthalic anhydride, react about 6 hours until according to the absorption peak (1780cm of infrared absorption analysis acid anhydrides
-1) disappear.In this reaction solution, add the aromatic series series solvent IPUZOL#150 that 96.4g Idemitsu Kosen Co., Ltd. manufactures, take out after dilution.The nonvolatile component of the carboxylic photosensitive polymer solution of such acquisition is 65 % by weight, and the acid number of solid constituent is 78mgKOH/g.Below, this reaction solution is called B-1 varnish.
the cooperation of embodiment 1 ~ 5 and comparative example 1 ~ 5:
Coordinate each composition according to table 1 and stir, carry out disperseing with 3 roller roller mills and obtain solder mask composition respectively.Numeral mass parts in table.
Table 1
Photoepolymerizationinitiater initiater A1: two-(2,4,6-trimethylbenzoyl) phenyl phosphine oxide Irgacure819 (CibaJapanK.K. system)
Photoepolymerizationinitiater initiater A2:2,4,6-trimethyl benzoyl diphenyl base phosphine oxide DarocurTPO (CibaJapanK.K. system)
Photoepolymerizationinitiater initiater B1:Irgacure907 (CibaJapanK.K. system)
Photopolymerization monomer: dipentaerythritol acrylate
Titanium dioxide A: Titanium Dioxide Rutile Top grade CR-95 (stone originates in industry Inc.)
Titanium dioxide B: anatase-type titanium oxide A-220 (stone originates in industry Inc.)
Epoxy compound: TEPIC-H (Nissan Chemical Inc.)
Thermosetting accelerator: dicyandiamide
Sensitizer: 2,4-diethyl thioxanthone KAYACUREDETX-S (Japanese chemical drug Inc. makes)
Solvent: carbitol acetate
Defoamer (silicone oil): KS-66 (Shin-EtsuChemicalCo., Ltd. system)
For each character of the soldering-resistance layer that investigation uses each solder mask composition to be formed, carry out following test and evaluation.
(1) resolution (cross sectional shape)
Utilize silk screen print method, on the FR-4 copper clad laminate that 100mm × 150mm size, 1.6mm are thick, use the full version (the whole face of substrate) of the version of 100 order polyester (cloth (bias) of tiltedly throwing the net system) to print each solder mask composition.Make its in heated air circulation type drying oven at 80 DEG C dry 10 minutes.And then respectively on above-mentioned dry coating, use the same method overlapping printing solder mask composition, in heated air circulation type drying oven at 80 DEG C dry 20 minutes.And then, with use in printed circuit board exposure machine HMW-680GW (ORCMANUFACTURINGCO., LTD. make), negative pattern is used to be of a size of the mask pattern of the wire of 250 μm, with the method that mask is mutually closely sealed with dried soldering-resistance layer, 450mJ/cm is used to embodiment 1,2 and 5 and comparative example 1 ~ 3 and 5
2accumulative light quantity, 900mJ/cm is used to embodiment 3 and 4, comparative example 4
2accumulative light quantity carry out ultraviolet exposure.Afterwards, using 30 DEG C, the aqueous sodium carbonate of 1% as developer solution, utilize use in printed circuit board developing machine to make it develop for 60 seconds.And then, it is carried out in heated air circulation type drying oven at 150 DEG C the heat curing of 60 minutes, obtained each test film.For the line of these test films, the upper surface utilizing measurement microscope to contact with mask and be contacted with the cross sectional shape of substrate surface of base material.Then, surface roughness meter is utilized to measure the thickness of each test film.In addition, the visual shape judging to observe is carried out to each test film.In this judgement, by cross sectional shape be substantially quadrilateral be designated as zero, by large to top bulging, undercutting, being designated as obviously in inverted trapezoidal ×.Result is as shown in table 2.Unit is μm.
Table 2
From table 2; in embodiment 1 ~ 5, comparative example; two acylphosphine oxide system Photoepolymerizationinitiater initiater (B) and monoacylphosphine oxides system Photoepolymerizationinitiater initiater (C) are combinationally used; from the cross sectional shape of line; the difference in size of upper surface and substrate surface is little; cross sectional shape is quadrilateral substantially, obtains excellent resolution.
(2) fast light resistance to thermochromism
For the solder mask composition of good embodiment 1 ~ 5 and comparative example 1 and 5 in resolution test, on the FR-4 copper clad laminate that 100mm × 150mm size, 1.6mm are thick, utilize silk screen print method, use the full version printed patterns (the whole face of substrate) of the version of 100 order polyester (tiltedly throwing the net fabric), make thickness reach 40 μm.Then, its in heated air circulation type drying oven at 80 DEG C dry 30 minutes are made.And then, with use in printed circuit board exposure machine HMW-680GW (ORCMANUFACTURINGCO., LTD. system), at 900mJ/cm
2accumulative light quantity under carry out ultraviolet exposure, make to leave the square negative pattern of 30mm.Afterwards, using 30 DEG C, the aqueous sodium carbonate of 1% as developer solution, utilize use in printed circuit board developing machine to make it develop for 60 seconds, then, utilize the heat curing that heated air circulation type drying oven carries out 60 minutes at 150 DEG C, each test film of obtained attribute testing.
The test film obtained is measured with color evaluating CR-400 (KonicaMinoltaSensing, Inc. system).And then, by each test film conveyor-type UV irradiating machine QRM-2082-E-01 (ORCMANUFACTURINGCO., LTD. system), at metal halide lamp, cold mirror, 120W/cm
2× 3 lamps, line speed 3m/ minute (the accumulative light quantity 3000mJ/cm near wavelength 350nm
2) condition under repeatedly irradiate UV50 time (computationally accumulative light quantity reach 150J/cm
2).Then, under the condition identical with initial value, measure the aberration of the postradiation each test film of UV, thus evaluate deterioration state.
Then, with parts installation conveyor type heating furnace, 2 times are heated repeatedly to each test film after Light Resistance Test.Under the condition identical with initial value, measure the aberration of each test film after heating, thus evaluate the deterioration state of each test film.In addition, also based on visual, these each test films are evaluated.The above results is shown in table 3.In addition, above-mentioned furnace temp as shown in Figure 1.
Table 3
In table 3, Y represents the reflectivity of XYZ colorimetric system, and L* represents the lightness of L*a*b* colorimetric system.Δ E*ab is, to each value of L*a*b* get the difference of the value after deterioration test and initial value square and the value that obtains of root that the summation of these squares is made even.A* represents that red direction ,-a* represent look direction, b* represents look direction ,-b* represents look direction, close to indicating chroma.Δ E*ab represents the change of color, and the change of this value little expression color is little.
After Light Resistance Test and after the heat test of carrying out afterwards, embodiment 1 ~ 5 variable color in Δ E*ab value and visual valuation is all few, and result is good.
(3) solder heat resistance
For embodiment 1 ~ 5, each test film that make same with (2) is coated with perfume (or spice) system solder flux, then makes it in the solder of 260 DEG C, flow for 10 seconds.Afterwards, with propylene glycol methyl ether acetate by it, after making it drying, adhesive strip is used to test, evaluation film.In this evaluation, by have be designated as zero, have be designated as ×.Result is as shown in table 4.
(4) solvent resistance
For embodiment 1 ~ 5, each test film that will make equally with (2) in propylene glycol methyl ether acetate 30 minutes, after making it drying, uses adhesive strip to test, and evaluates film.In this evaluation, by have be designated as zero, have be designated as ×.Result is as shown in table 4.
(5) degree test
For embodiment 1 ~ 5, the B to 9H polished by end is pressed onto on each test film made same with (2) with the degree of about 45 °, and note has generation film
Degree.Result is as shown in table 4.
(6) insulation resistance test
For embodiment 1 ~ 5, except using the type electrode B sample of IPCB-25 test pattern for except FR-4 copper clad laminate, all the other make test film under the condition same with (2).These test films are applied to the pressure of DC500V, measure insulating resistance value.To be more than 100G by value be designated as zero, less than being designated as of 100G ×.Result is as shown in table 4.
Table 4
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| (3) solder heat resistance | ○ | ○ | ○ | ○ | ○ |
| (4) solvent resistance | ○ | ○ | ○ | ○ | ○ |
| (5) degree test | 7H | 7H | 7H | 7H | 7H |
| (6) insulation resistance | ○ | ○ | ○ | ○ | ○ |
Obviously can be found out by table 4, in the embodiment 1 ~ 5 employing solder mask composition of the present invention, obtain good thermotolerance, solvent resistance, adaptation and the electrical insulating property needed for soldering-resistance layer.
Known as set forth in more detail above, even if coordinated titanium dioxide, solder mask composition of the present invention has also had good resolution.In addition, the soldering-resistance layer variable color under light, heat formed with solder mask composition of the present invention is few and have high reflectance.
Claims (6)
1. a solder mask composition, is characterized in that, comprises: (A) do not have aromatic rings containing carboxy resin; (B) two acylphosphine oxide systems Photoepolymerizationinitiater initiater; (C) monoacylphosphine oxides system Photoepolymerizationinitiater initiater; (D) photopolymerization monomer; (E) Titanium Dioxide Rutile Top grade; (G) organic solvent; (H) thioxanthones system photopolymerization sensitizer; And (I) dicyandiamide,
Relative to (A) described in 100 mass parts do not have aromatic rings containing carboxy resin, total use level of described (B) two acylphosphine oxide system's Photoepolymerizationinitiater initiater and described (C) monoacylphosphine oxides system Photoepolymerizationinitiater initiater is 1 ~ 30 mass parts;
Relative to (A) described in 100 mass parts do not have aromatic rings containing carboxy resin, the use level of described (D) photopolymerization monomer is 10 ~ 100 mass parts;
Relative to (A) described in 100 mass parts do not have aromatic rings containing carboxy resin, the use level of described (E) Titanium Dioxide Rutile Top grade is 50 ~ 450 mass parts;
Relative to (A) described in 100 mass parts do not have aromatic rings containing carboxy resin, the use level of described (G) organic solvent is 20 ~ 300 mass parts;
Relative to (A) described in 100 mass parts do not have aromatic rings containing carboxy resin, the use level of described (H) thioxanthones system photopolymerization sensitizer is 0.05 ~ 2 mass parts.
2. solder mask composition according to claim 1, it is characterized in that, described do not have serving as reasons the copolymerization system resin with carboxyl that (a) obtain containing the compound that carboxyl (methyl) acrylic copolymer resin and (b) 1 has oxirane ring and olefinic unsaturated group in molecule reacts containing carboxy resin (A) of aromatic rings.
3. solder mask composition according to claim 1 and 2, is characterized in that, the compounding ratio of described pair of acylphosphine oxide system Photoepolymerizationinitiater initiater (B) and monoacylphosphine oxides system Photoepolymerizationinitiater initiater (C) is 90:10 ~ 1:99.
4. solder mask composition according to claim 1 and 2, is characterized in that, also comprises (F) epoxy compound.
5. a printed circuit board (PCB), described printed circuit board (PCB) possesses the solder mask composition solidfied material described in claim 1 or 2.
6. printed circuit board (PCB) according to claim 5, is characterized in that, substrate for printed circuit board is provided with light emitting diode.
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| JP2010-032934 | 2010-02-17 | ||
| JP2010032934A JP4975834B2 (en) | 2010-02-17 | 2010-02-17 | Solder resist composition and printed wiring board |
| CN2010101751368A CN101980081A (en) | 2010-02-17 | 2010-05-14 | Solder resist composition and printed circuit board |
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| JP2011215384A (en) * | 2010-03-31 | 2011-10-27 | Taiyo Holdings Co Ltd | Solder resist composition and printed-circuit board |
| JP2011227308A (en) * | 2010-04-20 | 2011-11-10 | Taiyo Holdings Co Ltd | Solder resist composition and print circuit board |
| CN102944977B (en) * | 2012-11-28 | 2014-08-27 | 惠州市容大油墨有限公司 | Photosensitive solder resist composite, application thereof and printed circuit board (PCB) containing same |
| JP5688129B1 (en) * | 2013-09-30 | 2015-03-25 | 太陽インキ製造株式会社 | Curable composition for printed wiring board, cured coating film using the same, and printed wiring board |
| CN106028668A (en) * | 2016-05-05 | 2016-10-12 | 广合科技（广州）有限公司 | Printed circuit board preparing method preventing discoloration of solder resist layer |
| CN114442425A (en) * | 2020-10-30 | 2022-05-06 | 常州正洁智造科技有限公司 | Curable resin composition, solder resist film formed from the same, interlayer insulating material, and printed wiring board |
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| TW201129857A (en) | 2011-09-01 |
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