CN102722083A - Solder resist composition and printed wiring board - Google Patents
Solder resist composition and printed wiring board Download PDFInfo
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- CN102722083A CN102722083A CN2012101918721A CN201210191872A CN102722083A CN 102722083 A CN102722083 A CN 102722083A CN 2012101918721 A CN2012101918721 A CN 2012101918721A CN 201210191872 A CN201210191872 A CN 201210191872A CN 102722083 A CN102722083 A CN 102722083A
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- solder resist
- resist composition
- photoepolymerizationinitiater initiater
- circuit board
- printed circuit
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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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- 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
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
A high reflective/high definition solder composition and a printed circuit board using thereof are provided secure the excellent patterning ability by light and resolving potency. A high reflective/high definition solder composition contains a carboxyl containing resin without an aromatic ring, bisacylphosphine oxide based photopolymerization initiator, a mono-acylphosphineoxide based photopolymerization initiator, a photo-polymerizable monomer, a rutile-type titanium oxide, and an organic solvent. The carboxyl containing resin without the aromatic ring is a copolymer resin having a carboxyl group obtained by reacting a (meth) acrylic copolymer resin containing the carboxyl group, and a compound with an ethylenically unsaturated group.
Description
The application is dividing an application of one 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 resist composition and printed circuit board (PCB) ".
Technical field
The present invention relates to form the solder resist composition that is suitable for as the permanent mask soldering-resistance layer that use, high reflectance of printed circuit board (PCB), and use this solder resist composition to form the printed circuit board (PCB) that soldering-resistant pattern forms on the surface of the printed circuit board (PCB) that is formed with circuit.
Background technology
Printed circuit board (PCB) is formed with wiring through the part that do not need that the Copper Foil that fits on the laminate is removed in etching usually, through welding electronic unit is configured on the position of regulation.In such printed circuit board (PCB), use on base material coating and the diaphragm of the soldering-resistance layer that the is solidified to form circuit during as the welding electronic unit.
Solder attachment was in unnecessary portions when this soldering-resistance layer can prevent to weld, and can prevent that circuit conductor directly is exposed in the air and by oxygen, the wet deterioration that causes of dividing.In addition, soldering-resistance layer also has the function as the permanent diaphragm of circuit substrate.Therefore require it to have each characteristic such as adaptation, electrical insulating property, solder heat resistance property, solvent resistance, chemical proofing.
In addition, for realizing densification, towards granular (becoming more meticulous), multiple stratification and single board development, its mounting means is also changing to surface mounting technique (SMT) printed circuit board (PCB) just steadily.For this reason, the requirement to the becoming more meticulous of soldering-resistance layer, high resolving power, high precision, high reliability is also improving.
As the technology of the pattern that forms such soldering-resistance layer, the photoetching process that can accurately form fine pattern is used, and particularly to the consideration of environment aspect etc., the photoetching process of alkali developable is just becoming main flow.
For example; Patent documentation 1 with patent documentation 2 publicities a kind of solder resist composition that can develop with aqueous alkali, this solder resist composition is a base polymer with the reaction product of being reacted by phenolic resin varnish type epoxy resin and unsaturated monocarboxylic and then obtain with the multi-anhydride addition.
On the other hand; In recent years, will increase as the purposes backlight liquid crystal display lamp of portable terminal, PC, TV etc., the light source of ligthing paraphernalia etc., that directly be installed on the printed circuit board (PCB) that is formed with soldering-resistance layer that is covered with the low luminous light emitting diode (LED) of electric power.
Therefore, in order effectively to utilize the light of LED, just needing soldering-resistance layer is the printed circuit board (PCB) of white, makes this soldering-resistance layer have high reflectance.
But the composition of white solder masks self has high reflectivity, therefore when patterned exposure just with the light reflection, required light when causing fully absorbing it and solidifying is differentiated rate variance, the result is difficult to form the meticulous pattern sub-image of height.
In addition, for the printed circuit board (PCB) that LED directly is installed, the light and heat that LED sends can promote the deterioration, painted of white solder masks, causes the reduction of reflectivity.
The prior art document
Patent documentation
Patent documentation 1: the special fair 1-54390 communique of Japan
Patent documentation 2: the special fair 7-17737 communique of Japan
Summary of the invention
The problem that invention will solve
The objective of the invention is to, be provided for forming solder resist composition and the printed circuit board (PCB) light that can effectively utilize LED, high reflectance and high-resolution soldering-resistance layer.
The present invention also aims to, the deterioration of the caused soldering-resistance layer of light and heat that can prevent to be sent by LED, painted solder resist composition and printed circuit board (PCB) are provided.
The scheme that is used to deal with problems
The result of further investigation such as the inventor finds; Use can alkali develop and also the resin that do not have an aromatic rings as the carboxy resin that contains with Thermocurable; And use Titanium Dioxide Rutile Top grade as the Chinese white that is used to realize high reflectance; But long term inhibition is by light, hot caused deterioration thus; Also find in addition through combination use two acylphosphine oxides be Photoepolymerizationinitiater initiater and monoacyl phosphine oxide be Photoepolymerizationinitiater initiater as Photoepolymerizationinitiater initiater, even if the solder resist composition contains the high Titanium Dioxide Rutile Top grade of a large amount of reflectivity, also can form excellent in resolution, the meticulous pattern sub-image of height.
That is, solder resist composition of the present invention is characterised in that, contains: the carboxy resin that contains that (A) does not have aromatic rings; (B) two acylphosphine oxides are Photoepolymerizationinitiater initiater; (C) the monoacyl phosphine oxide is a Photoepolymerizationinitiater initiater; (D) photopolymerization monomer; (E) Titanium Dioxide Rutile Top grade; And (G) organic solvent, also can contain (F) epoxy compound or (H) thioxanthones be the photopolymerization sensitizer.
The invention effect
According to the present invention; Can form high reflectance and high-resolution soldering-resistance layer; It has characteristics such as the required coating of developable solder flux, photo-curable, development property, solder heat resistance property, adaptation, electrical insulating property, can suppress to change in time the reflectivity that causes reduction and by deterioration cause painted.And solder resist composition of the present invention can also improve whole illumination when LED is mounted to printed circuit board (PCB).
Description of drawings
Fig. 1 is the figure that is illustrated in the temperature of employed heating furnace in the fast light heat-resisting discolouration test of test film of embodiment, comparative example.
Embodiment
Below, the present invention is further specified.
Solder resist composition of the present invention is characterised in that, contains: the carboxy resin that contains that (A) does not have aromatic rings; (B) two acylphosphine oxides are Photoepolymerizationinitiater initiater; (C) the monoacyl phosphine oxide is a Photoepolymerizationinitiater initiater; (D) photopolymerization monomer; (E) Titanium Dioxide Rutile Top grade; And (G) organic solvent, also can contain (F) epoxy compound or (H) thioxanthones be the photopolymerization sensitizer.
The carboxy resin that contains that does not have aromatic rings
Contain carboxy resin (A) as what do not have an aromatic rings, can use himself have 1 above photonasty unsaturated double-bond photosensitive to contain carboxy resin, not have in the middle of the carboxy resin any of containing of photonasty unsaturated double-bond, be not limited to predetermined substance.The resin that does not have aromatic rings in the resin of enumerating below can using aptly especially (oligomer or polymkeric substance all can).That is: (1) contains carboxy resin by what unsaturated carboxylic acid obtained with having the compound copolymerization of unsaturated double-bond; (2) make and contain the compound reaction that has oxirane ring and olefinic unsaturated group in carboxyl (methyl) acrylic acid series copolymer resins and 1 molecule and the photosensitive carboxy resin that contains that obtains; (3) make the compound that has 1 epoxy radicals and 1 unsaturated double-bond in 1 molecule and multipolymer with compound of unsaturated double-bond, with the unsaturated monocarboxylic reaction, the secondary hydroxyl that is generated by this reaction is reacted and the photosensitive carboxy resin that contains of acquisition with saturated or unsaturated multi-anhydride; (4) after the reaction of hydroxyl polymer-containing and saturated or unsaturated multi-anhydride, the compound that has 1 epoxy radicals and 1 unsaturated double-bond in the carboxylic acid that generated by this reaction and 1 molecule is reacted and the photosensitive hydroxyl of acquisition and the resin of carboxyl.
Wherein, the photosensitive carboxy resin that contains of preferably above-mentioned (2) promptly, (a) contains and has the compound reaction of oxirane ring and olefinic unsaturated group in carboxyl (methyl) acrylic acid series copolymer resins and (b) 1 molecule and the copolymerization with carboxyl of acquisition is a resin.
(a) carboxyl (methyl) the acrylic acid series copolymer resins that contains can be through being obtained by the compound copolymerization that has 1 unsaturated group and 1 carboxyl in (methyl) acrylic ester and 1 molecule at least.As (methyl) acrylic ester that constitutes copolymer resins (a), can enumerate out glycol modification (methyl) esters of acrylic acids such as hydroxyl (methyl) esters of acrylic acids such as (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, (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, methoxyl diethylene glycol (methyl) acrylic ester, ethoxy diethylene glycol (methyl) acrylic ester, different octyloxy diethylene glycol (methyl) acrylic ester, phenoxy group triethylene glycol (methyl) acrylic ester, methoxyl triethylene glycol (methyl) acrylic ester, methoxy poly (ethylene glycol) (methyl) acrylic ester etc.These can use a kind of separately, and it is two or more also can to mix use.In addition, (methyl) acrylic ester is the term of general name acrylic ester and methacrylate in this manual, and all the other similar expression too.
In addition; As the compound that has 1 unsaturated group and at least 1 carboxyl in 1 molecule; Can enumerate acrylic acid; Methacrylic acid, between unsaturated group and carboxylic acid chain elongation modification unsaturated monocarboxylic, for example (methyl) senecioate-carboxyl ethyl ester, 2-acryloxy ethyl succinic acid, 2-acryloxy ethyl hexahydrophthalic acid, have the unsaturated monocarboxylic of ester bond through interior ester modified grade; Modification unsaturated monocarboxylic with ehter bond, and comprise compound of 2 above carboxyls etc. in the maleic acid equimolecular.These can use a kind of separately, and it is two or more also can to mix use.
As the compound that has oxirane ring and olefinic unsaturated group in (b) 1 molecule; As long as be the compound that has olefinic unsaturated group and oxirane ring in 1 molecule; Can enumerate out for example (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, 3,4-epoxycyclohexyl methylamino acrylic ester etc.Wherein, preferred (methyl) acrylic acid 3,4-epoxycyclohexyl methyl esters.The compound that has oxirane ring and olefinic unsaturated group in these (b) 1 molecules can use a kind of separately, also can mix use two or more.
The acid number that contains carboxy resin (A) that does not have aromatic rings need be in 50～200mgKOH/g scope.When acid number is lower than 50mgKOH/g, be difficult in weak base aqueous solution, remove the unexposed portion of filming of solder resist composition.When acid number surpasses 200mgKOH/g, can produce problems such as the water tolerance of solidifying tunicle, electric properties deteriorate.In addition, the weight-average molecular weight that contains carboxy resin (A) that does not have aromatic rings is preferably in 5000～100000 scope.When weight-average molecular weight was lower than 5000, the dry to touch property of filming of solder resist composition had the tendency of remarkable variation.In addition, when weight-average molecular weight surpasses 100000, can produce the development property of solder resist composition, the problem that bin stability significantly worsens, so not preferred.
Photoepolymerizationinitiater initiater
Two acylphosphine oxides are Photoepolymerizationinitiater initiater
As the two acylphosphine oxides that use among the present invention is Photoepolymerizationinitiater initiater (B), can enumerate out two-(2,6-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-propyl group phenyl phosphine oxide, two-(2,6-dichloro-benzoyl base)-1-naphthyl phosphine oxide, two-(2; 6-dimethoxy benzoyl) phenyl phosphine oxide, two-(2,6-dimethoxy benzoyl)-2,4; 4-tri-methyl-amyl phosphine oxide, two-(2,6-dimethoxy benzoyl)-2,5-3,5-dimethylphenyl phosphine oxide, two-(2; 4, the 6-trimethylbenzoyl) phenyl phosphine oxide, (2,5; The 6-trimethylbenzoyl)-2,4,4-tri-methyl-amyl phosphine oxide etc.Wherein two-(2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide (Ciba Japan K.K. system, trade name: Irgacure 819) is prone to obtain and is practical.
The monoacyl phosphine oxide is a Photoepolymerizationinitiater initiater
As the monoacyl phosphine oxide that uses among the present invention is Photoepolymerizationinitiater initiater (C); Can enumerate out 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2; 6-dimethoxy benzoyl diphenyl phosphine oxide, 2; 6-dichloro-benzoyl base diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl-phosphonic acid methyl esters, 2-methyl benzoyl diphenyl phosphine oxide, pivaloyl phenyl-phosphonic acid isopropyl ester etc.Wherein 2,4,6-trimethylbenzoyl diphenyl phosphine oxide (Ciba Japan K.K. system, trade name: Darocur TPO) be prone to obtain and practical.
It is that Photoepolymerizationinitiater initiater (B) and aforementioned monoacyl phosphine oxide are Photoepolymerizationinitiater initiater (C) that solder resist composition of the present invention uses above-mentioned pair of acylphosphine oxide through combination, and makes filming of the high reflectance that is combined with titanium dioxide also can absorb necessary light, can form the meticulous pattern of height.In addition, cooperate ratio to carry out inching through changing it to the light absorption of filming.That is, when the curable deficiency on the cross sectional shape at pattern because the deep of substrate surface side causes being prone to undercutting, increase the above-mentioned pair of ratio that acylphosphine oxide is Photoepolymerizationinitiater initiater (B).In addition, when the surface state after surface cure property deficiency causes developing is abominable, the ratio that to increase aforementioned monoacyl phosphine oxide be Photoepolymerizationinitiater initiater (C).This pair acylphosphine oxide is a Photoepolymerizationinitiater initiater (B) with the monoacyl phosphine oxide is that the ratio that cooperates of Photoepolymerizationinitiater initiater (C) is 90:10～1:99, is preferably 80:20～2:98.Outside this cooperated ratio ranges, combination used the effect of these initiating agents to tail off, and can't absorb necessary light, therefore caused forming high meticulous pattern.
Do not contain carboxy resin (A) with respect to what 100 mass parts did not have an aromatic rings, two acylphosphine oxides are that Photoepolymerizationinitiater initiater (B) and monoacyl phosphine oxide are that total use level of Photoepolymerizationinitiater initiater (C) is preferably 1～30 mass parts, more preferably 2～25 mass parts.When this pair acylphosphine oxide is that Photoepolymerizationinitiater initiater (B) and monoacyl phosphine oxide are total use level of Photoepolymerizationinitiater initiater (C) when being lower than 1 mass parts, photo-curable reduces, exposure and develop after be difficult to form pattern, so not preferred.On the other hand, when this use level surpassed 30 mass parts, the painted change of filming that is brought by Photoepolymerizationinitiater initiater was big, and becomes the high reason of cost, so not preferred.
Photopolymerization monomer
As the photopolymerization monomer that uses among the present invention (D), can enumerate out acrylic acid-2-hydroxyl ethyl ester, acrylic acid-acrylic acid hydroxyalkyl acrylate classes such as 2-hydroxy butyl ester; The mono acrylic ester or the diacrylate class of glycol such as monoethylene glycol, methoxyl TEG, polyglycol, propylene glycol; N, acrylic amides such as N-DMAA, N hydroxymethyl acrylamide; Acrylic acid-N, acrylic-amino alkyl esters such as N-dimethylamino ethyl ester; The multicomponent methacrylate class of polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, trihydroxy ethyl isocyanuric acid ester or their oxirane or propylene oxide adduct; The esters of acrylic acid of the oxirane of phenoxy group acrylic ester, bisphenol a diacrylate and these phenols or propylene oxide adduct etc.; The esters of acrylic acid of glycerin ether such as glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether; The melamine acrylic ester; And/or with corresponding methyl acrylic ester of aforesaid propylene esters of gallic acid etc.
Do not contain carboxy resin (A) with respect to what 100 mass parts did not have an aromatic rings, the use level of these photopolymerization monomers (D) is preferably 10～100 mass parts, more preferably 20～80 mass parts.When use level surpasses 100 mass parts, reduce as the rerum natura of the soldering-resistance layer of cured coating film, so not preferred.On the other hand, when this use level is lower than 10 mass parts, do not possess sufficient photo-curable, can't obtain high meticulous pattern.
Titanium Dioxide Rutile Top grade
The present invention uses Titanium Dioxide Rutile Top grade (E) as Chinese white.Usually titanium dioxide has Detitanium-ore-type and rutile-type.Because anatase-type titanium oxide has photocatalytic activity, can cause the variable color of the resin in the solder resist composition.And compare with anatase-type titanium oxide; There is absorption in Titanium Dioxide Rutile Top grade at the boundary vicinity of ultraviolet range and visible region; Though whiteness and in the reflection differences of whole visible region, because it does not have photolytic activity basically and can obtain stable soldering-resistance layer.
As aforementioned Titanium Dioxide Rutile Top grade (E), can use known material.Specifically, can use TIPAQUE R-820, TIPAQUE R-830, TIPAQUE R-930, TIPAQUE R-550, TIPAQUE R-630, TIPAQUE R-680, TIPAQUER-670, TIPAQUE R-780, TIPAQUE R-850, TIPAQUE CR-50, TIPAQUE CR-57, TIPAQUE CR-80, TIPAQUE CR-90, TIPAQUECR-93, TIPAQUE CR-95, TIPAQUE CR-97, TIPAQUE CR-60, TIPAQUE CR-63, TIPAQUE CR-67, TIPAQUE CR-58, TIPAQUECR-85, TIPAQUE UT771 (Ishihara Sangyo Kaisha, Ltd.'s system), Ti-Pure R-100, Ti-Pure R-101, Ti-Pure R-102, Ti-Pure R-103, Ti-Pure R-104, Ti-Pure R-105, Ti-Pure R-108, Ti-Pure R-900, Ti-Pure R-902, Ti-Pure R-960, Ti-Pure R-706, Ti-Pure R-931 (Du Pont Kabushiki Kaisha system), TITON R-25, TITON R-21, TITON R-32, TITON R-7E, TITON R-5N, TITON R-61N, TITON R-62N, TITON R-42, TITON R-45M, TITON R-44, TITON R-49S, TITON GTR-100, TITON GTR-300, TITON D-918, TITON TCR-29, TITON TCR-52, TITON FTR-700 (Sakai Chemical Industry Co., Ltd.'s system) etc.
Do not contain carboxy resin (A) with respect to what 100 mass parts did not have an aromatic rings, the use level of such Titanium Dioxide Rutile Top grade (E) is preferably 50～450 mass parts, more preferably 60～350 mass parts.When use level surpassed 450 mass parts, photo-curable reduced, the curing depth step-down, so not preferred.On the other hand, when this use level was lower than 50 mass parts, covering power diminished, and can't obtain the soldering-resistance layer of high reflectance.
Epoxy compound
Then; As epoxy compound (F); Can enumerate out bisphenol-s epoxy resin for example, o-phthalic acid diglycidyl ester resin, triglycidyl isocyanurate (TEPIC-H (the β body made of daily output chemistry (strain) for example; It has 3 epoxy radicals on same direction with the s-triazine ring skeleton face structure of bonding mutually), 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 s-triazine ring skeleton face structure of bonding mutually) 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. be insoluble in epoxy resin, bisphenol A type epoxy resin, bisphenol-A epoxy resin, Bisphenol F type resin, brominated bisphenol a type epoxy resin, phenol phenolic varnish type or cresols phenolic resin varnish type epoxy resin, alicyclic epoxy resin, the bisphenol-A of thinning agent phenolic resin varnish type epoxy resin, chelating type epoxy resin, glyoxal type epoxy resin, contain aminoepoxy resin, rubber modified epoxy resin, dicyclopentadiene phenol epoxy resin, silicone modified epoxy, 6-caprolactone modified epoxy etc. and dissolve in epoxy resin of thinning agent etc.These epoxy resin can use separately, and use also capable of being combined is two or more.
Do not contain carboxy resin (A) with respect to what 100 mass parts did not have an aromatic rings, the use level of such epoxy compound (F) is preferably 5～70 mass parts, more preferably 5～60 mass parts.When the use level of epoxy compound (F) surpassed 70 mass parts, it is residual that the dissolubility of unexposed portion in developer solution reduces, is prone to produce development, is difficult in reality, use.On the other hand, when this use level was lower than 5 mass parts, the carboxyl that contains carboxy resin (A) that does not have aromatic rings was residual with unreacted state, thereby had the tendency of the electrical characteristics that are difficult to obtain sufficient cured coating film, solder heat resistance property, chemical proofing.
Not having the carboxyl that contains carboxy resin (A) of aromatic rings and the epoxy radicals of epoxy compound (F) reacts through ring-opening polymerization.And during as other materials in organic solvent (G), the solder resist composition, the thermal capacitance when dry is prone to cause the crosslinked of carboxyl and epoxy radicals at the epoxy resin that uses ease of solubility., carry out when for a long time dry will suppressing this cross-linking reaction, it is desirable using separately or using the epoxy resin of slightly solubility with the epoxy resin of ease of solubility for this reason.
Organic solvent
(G) used in the present invention is in order to make the solder resist composition be the state that is easy to be coated with, and with its coat make it behind the base material etc. dry form to film use.As such organic solvent (G), can enumerate out ketones such as MEK, cyclohexanone; Toluene, xylene, tetramethylbenzene etc. are aromatic hydrocarbon based; Glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, BC, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, DPG list ether, Triethylene glycol ethyl ether; The ester classes such as carboxylate of ethyl acetate, butyl acetate, cellosolve acetic acid esters, diethylene glycol monoethyl ether acetic acid esters and above-mentioned glycol ethers; Alcohols such as ethanol, propyl alcohol, monoethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, petroleum naphtha, hydrogenation petroleum naphtha, solvent naphtha etc.
Aforementioned organic solvent (G) can use separately, also can use two or more potpourris.Do not contain carboxy resin (A) with respect to what 100 mass parts did not have an aromatic rings, the use level of organic solvent (G) is preferably 20～300 mass parts.
Thioxanthones is the photopolymerization sensitizer
Sensitivity to light when making public to improve is purpose, and it is that photopolymerization sensitizer (H) is desirable that the present invention cooperates thioxanthones.This is that thioxanthones is that the effect of photopolymerization sensitizer (H) is very high because to use above-mentioned pair of acylphosphine oxide in combination be that Photoepolymerizationinitiater initiater (B) and above-mentioned monoacyl phosphine oxide are in the combination of Photoepolymerizationinitiater initiater (C).As this thioxanthones is photopolymerization sensitizer (H), can enumerate out thioxanthones, 2-ethyl thioxanthones, 2-isopropyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthones etc.
Do not contain carboxy resin (A) with respect to what 100 mass parts did not have an aromatic rings, such thioxanthones is that the use level of photopolymerization sensitizer (H) is preferably 0.05～2 mass parts, more preferably 0.1～1 mass parts.When this use level was lower than 0.05 mass parts, the effect that improves sensitivity was few, and when surpassing 2 mass parts, the painted change of filming that is brought by thioxanthones is big.
Other compositions
Stabilizing agent
And then solder resist composition of the present invention is that light stabilizer can reduce the light deterioration through containing hindered amine.
As hindered amine is light stabilizer, can enumerate out for example TINUVIN 622LD, TINUVIN 144; CHIMASSORB 944LD, CHIMASSORB 119FL (more than be Ciba Japan K.K. system); MARK LA-57, LA-62, LA-67, LA-63, LA-68 (more than be Asahi Denka Co., Ltd.'s system); Sanol LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (more than be SANKYOLIFETECH CO., the LTD. system) etc.
Do not contain carboxy resin (A) with respect to what 100 mass parts did not have an aromatic rings, 0.1～10 mass parts is preferably added in the aforementioned stable agent.
Spreading agent
Dispersiveness, settleability that solder resist composition of the present invention can improve titanium dioxide through containing spreading agent.As spreading agent, can enumerate out for example ANTI-TERRA-U, ANTI-TERRA-U 100, 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), DISPARLON 2150, DISPARLON 1210, DISPARLON KS-860, DISPARLON KS-873N, DISPARLON7004, DISPARLON 1830, DISPARLON 1860, DISPARLON 1850, DISPARLON DA-400N, DISPARLON PW-36, DISPARLON DA-703-50 (nanmu originally changes into Co., Ltd.'s system), FLOWLEN G-450, FLOWLEN G-600, FLOWLEN G-820, FLOWLEN G-700, FLOWLEN DOPA-44, FLOWLEN DOPA-17 (Kyoeisha Chemical Co., Ltd.'s system) etc.
For effectively realizing above-mentioned purpose, preferably, with respect 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 resist composition of the present invention can use curing accelerator, hot polymerization inhibitor, thickening agent, foam-breaking agent, levelling agent, coupling agent, flame retardant etc. as required.
Method for making
Below, as an example of the use of solder resist composition, the manufacturing of printed circuit board (PCB) is described.
At first, with solder resist composition dilution of the present invention, be adjusted to the viscosity of fitting mutually as required with coating process.
Then, utilizing silk screen print method, curtain to be coated with the composition that methods such as method, spraying process, rolling method will adjust after the viscosity is coated on the printed circuit board (PCB) that is formed with circuit.Then, under 70～90 ℃ temperature for example, make contained organic solvent volatile dry in the composition after the coating and form tack-free filming.
Afterwards, utilize active energy beam to this exposure of filming optionally, utilize aqueous alkali that unexposed is developed and form corrosion-resisting pattern through photomask.Make this corrosion-resisting pattern under 100～200 ℃, carry out heat curing then and form soldering-resistant pattern.
As the radiation source that makes public, 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, also laser capable of using etc. as active ray.
As the aqueous alkali of developer solution, be generally the aqueous sodium carbonate of 0.5～5 quality %.Also can use other aqueous alkali.As other aqueous alkali, can enumerate out the for example aqueous alkali of potassium hydroxide, NaOH, sal tartari, sodium phosphate, sodium silicate, ammonia, amine etc.
Then, after forming soldering-resistant pattern, LED is installed makes printed circuit board (PCB) of the present invention.The solder resist that contains the high titanium dioxide of reflectivity of printed circuit board (PCB) the application of the invention of the present invention like this makes, and it has high reflectance and has high meticulous pattern.
Embodiment
Below, embodiment is shown and comparative example specifies the present invention, but the present invention is not limited to following embodiment.
What (A) do not have an aromatic rings contains the synthetic of carboxy resin
Synthetic example 1
In possessing 2 liters of removable flasks of stirring machine, thermometer, reflux condenser, tap funnel and nitrogen ingress pipe; Add 900g as the diethylene glycol dimethyl ether of solvent and 21.4g peroxidating (2 ethyl hexanoic acid) tert-butyl ester (Japan Oil Co's system, trade name: PERBUTYL O), be heated to 90 ℃ as polymerization initiator.After the heating; PLACCEL FM1), 21.4g is as the peroxy dicarbonate of polymerization initiator two (4-tert-butyl group hexamethylene) ester (Japan Oil Co's system, trade names: PERBUTYL TCP) shared 3 hours to wherein dripping 309.9g methacrylic acid, 116.4g methyl methacrylate, 109.8g lactone modified methacrylic acid 2-hydroxyl ethyl ester (Daicel Chemical Industries, Ltd. system, trade name:.And then make its slaking 6 hours, thereby obtain to contain the carboxyl copolymer resins.In addition, above-mentioned being reflected under the nitrogen atmosphere carried out.
Then; The adding 363.9g methacrylic acid 3 in the carboxyl copolymer resins that contains that is obtaining; 4-epoxy cyclohexyl (Daicel Chemical Industries; Cyclomer A200), 3.6g is as the dimethyl benzylamine of ring opening catalyst, the 1.80g hydroquinone monomethyl ether as polymerization inhibitor, is heated to 100 ℃, stirs, and carries out the opening of epoxy thus Ltd. system, trade name:.After 16 hours, obtain to contain the solution that contains carboxy resin that 53.8 quality % (nonvolatile component) do not have aromatic rings, the acid number of the solid constituent of wherein said resin is that 108.9mgKOH/g, weight-average molecular weight are 25000.Below, this reaction solution is called A-1 varnish.
Synthetic example 2
In the flask that possesses thermometer, stirring machine, tap funnel and reflux condenser; Adding is as the diethylene glycol monoethyl ether acetic acid esters of solvent, as the azoisobutyronitrile of catalyzer; Under nitrogen atmosphere, be heated to 80 ℃, the monomer that forms with the mixed in molar ratio methacrylic acid and the methyl methacrylate that dripped in 2 hours with 0.40:0.60.And then it was stirred 1 hour, be warming up to 115 ℃ then, make its inactivation and obtain resin solution.
After this resin solution cooling, use TBAB as catalyzer, under 95～105 ℃, 30 hours condition, the mol ratio with 0.40 makes the butyl glycidyl ether and the equivalent carboxyl of the resin that is obtained carry out addition reaction and cooling.
And then under 95～105 ℃, 8 hours condition, the mol ratio with 0.26 makes the OH base of the resin of tetrabydrophthalic anhydride and above-mentioned acquisition carry out addition reaction.It cooling back is taken out, obtain to contain the solution that contains carboxy resin that 50 quality % (nonvolatile component) do not have aromatic rings, the acid number of the solid constituent of wherein said resin is that 78.1mgKOH/g, weight-average molecular weight are 35000.Below, this reaction solution is called A-2 varnish.
What have aromatic rings contains the synthetic of carboxy resin
Relatively more synthetic example 1
In the flask that possesses thermometer, stirrer, tap funnel and reflux condenser; Add 210g cresols phenolic resin varnish type epoxy resin (the system EPICLON N-680 of Dainippon Ink Chemicals, epoxide equivalent=210) and 96.4g carbitol acetic acid esters, heating for dissolving as solvent.Then, add 0.1g as the quinhydrones of polymerization inhibitor, 2.0g triphenylphosphine as catalysts.With this mixture heated to 95～105 ℃, slowly splash into 72g acrylic acid, react and reached below the 3.0mgKOH/g until acid number in about 16 hours.After this reaction product is cooled to 80～90 ℃, add the 76.1g tetrabydrophthalic anhydride, react about 6 hours until absorption peak (1780cm according to the 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. makes, take out the dilution back.The nonvolatile component of the carboxylic photosensitive polymer solution that obtains like this is 65 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:
Cooperate each composition and stir according to table 1, disperse and make the solder resist composition respectively with 3 roller roller mills.Numeral mass parts in the table.
Table 1
Photoepolymerizationinitiater initiater A1: two-(2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide Irgacure 819 (Ciba Japan K.K. system)
Photoepolymerizationinitiater initiater A2:2,4,6-trimethylbenzoyl diphenyl phosphine oxide Darocur TPO (Ciba Japan K.K. system)
Photoepolymerizationinitiater initiater B1:Irgacure 907 (Ciba Japan K.K. system)
Photopolymerization monomer: dipentaerythritol acrylate
Titanium dioxide A: Titanium Dioxide Rutile Top grade CR-95 (the former industry corporate system of stone)
Titanium dioxide B: anatase-type titanium oxide A-220 (the former industry corporate system of stone)
Epoxy compound: TEPIC-H (daily output chemical company system)
Heat curing promoter: dicyandiamide
Sensitizer: 2,4-diethyl thioxanthone KAYACURE DETX-S (Japanese chemical drug manufactured)
Solvent: carbitol acetic acid esters
Foam-breaking agent (silicone oil): KS-66 (Shin-Etsu Chemical Co., Ltd. system)
For investigating each character of the soldering-resistance layer that uses each solder resist composition formation, carry out following test and evaluation.
(1) resolution (cross sectional shape)
Utilize silk screen print method, on the FR-4 copper clad laminate big or small at 100mm * 150mm, that 1.6mm is thick, use the full version of version (the whole face of substrate) of 100 order polyester (cloth (bias) of tiltedly throwing the net system) to print each solder resist composition.Make it following dry 10 minutes at 80 ℃ in the heated air circulation type drying oven.And then on above-mentioned dry coating, the overlapping printing solder resist composition that uses the same method descended dry 20 minutes at 80 ℃ in the heated air circulation type drying oven respectively.And then; With use in printed circuit board exposure machine HMW-680GW (ORC MANUFACTURING CO.; LTD. make); Use negative pattern to be of a size of the mask pattern of the wire of 250 μ m, with mask and the dried soldering-resistance layer method of driving fit mutually, to embodiment 1,2 and 5 and comparative example 1～3 and 5 use 450mJ/cm
2The accumulative total light quantity, embodiment 3 and 4, comparative example 4 are used 900mJ/cm
2The accumulative total light quantity carry out ultraviolet exposure.Afterwards, as developer solution, utilize the use in printed circuit board developing machine that it was developed for 60 seconds with 30 ℃, 1% aqueous sodium carbonate.And then, with its heat curing of in the heated air circulation type drying oven, under 150 ℃, carrying out 60 minutes, make each test film.To the line of these test films, utilize measurement microscope upper surface that contacts with mask and the cross sectional shape that is contacted with the substrate surface of base material.Then, utilize the thickness of fixed each test film of surfaceness instrumentation.In addition, each test film is carried out the visual observed shape of judging.In this is judged, cross sectional shape is tetragonal basically is designated as zero, with top bulging, undercutting greatly, obviously be down trapezoidal being designated as *.The result is as shown in table 2.Unit is μ m.
Table 2
Visible by table 2; In embodiment 1～5, comparative example; It is that Photoepolymerizationinitiater initiater (B) and monoacyl phosphine oxide are Photoepolymerizationinitiater initiater (C) that two acylphosphine oxides have been used in combination, and from the cross sectional shape of line, the difference in size of upper surface and substrate surface is little; Cross sectional shape is quadrilateral basically, has obtained excellent resolution.
(2) fast light heat-resisting discolouration
For embodiment 1～5 good in resolution test, and the solder resist composition of comparative example 1 and 5; On the FR-4 copper clad laminate big or small at 100mm * 150mm, that 1.6mm is thick; Utilize silk screen print method; Use the full version of the version printed patterns (the whole face of substrate) of 100 order polyester (it is fabric tiltedly to throw the net), make thickness reach 40 μ m.Then, make it following dry 30 minutes at 80 ℃ in the heated air circulation type drying oven.And then, with use in printed circuit board exposure machine HMW-680GW (ORC MANUFACTURING CO., LTD. system), at 900mJ/cm
2The accumulative total light quantity under carry out ultraviolet exposure, make to stay the square negative pattern of 30mm.Afterwards, as developer solution, utilize the use in printed circuit board developing machine that it was developed for 60 seconds with 30 ℃, 1% aqueous sodium carbonate, then, the heat curing that utilizes the heated air circulation type drying oven under 150 ℃, to carry out 60 minutes makes each test film that attribute testing is used.
The test film that obtains is measured with color colour difference meter CR-400 (Konica MinoltaSensing, Inc. system).And then, with each test film with conveyor-type UV irradiating machine QRM-2082-E-01 (ORC MANUFACTURING CO., LTD. system), at metal halide lamp, cold mirror, 120W/cm
2* 3 lamps, near line speed 3m/ minute (the accumulative total light quantity 3000mJ/cm the wavelength 350nm
2) condition under shine UV50 time repeatedly (the accumulative total light quantity reach 150J/cm on calculating
2).Then, under the condition identical, measure the aberration of postradiation each test film of UV, thereby estimate deterioration state with initial value.
Then, install with conveyor type heating furnace each test film repeated heating after to fast light test 2 times with parts.Measuring the aberration of each test film after heating under the condition identical, thereby estimating the deterioration state of each test film with initial value.In addition, also these each test films are estimated based on visual.The above results is shown in table 3.In addition, above-mentioned furnace temp is as shown in Figure 1.
Table 3
In table 3, Y representes the reflectivity of XYZ colorimetric system, and L* representes the lightness of L*a*b* colorimetric system.Δ E*ab is, each value of L*a*b* is got value and initial value after the deterioration test difference square and with the make even value of root acquisition of the summation of these squares.A* represent red direction ,-a* represent look direction, b* represent the look direction ,-b* representes the look direction, near expression chroma arranged.Δ E*ab representes change in color, and it is little that this is worth little expression change in color.
Fast light test back and after after the heat test of carrying out, embodiment 1～5 in Δ E*ab value and visual valuation variable color all less, the result is good.
(3) solder heat resistance property
For embodiment 1～5, with (2) same each test film of making on coating perfume (or spice) be solder flux, it was flowed for 10 seconds in 260 ℃ scolder.Afterwards, with propylene glycol methyl ether acetate with it, make it drying after, use adhesive strip to make an experiment, estimate and to film.In this is estimated, will have be designated as zero, have be designated as *.The result is as shown in table 4.
(4) solvent resistance
For embodiment 1～5, will with (2) same each test film of making in propylene glycol methyl ether acetate 30 minutes, make it drying after, use adhesive strip to make an experiment, estimate and film.In this is estimated, will have be designated as zero, have be designated as *.The result is as shown in table 4.
(5) degree test
For embodiment 1～5, the degree of the B to 9H that end is polished with about 45 ° be pressed onto with (2) same each test film of making on, note has to produce films
Degree.The result is as shown in table 4.
(6) insulation resistance test
For embodiment 1～5, except that the type electrode B sample that uses IPC B-25 test pattern for the FR-4 copper clad laminate, all the other with (2) same condition under make test film.These test films are applied the pressure of DC500V, measure insulating resistance value.With value for more than the 100G be designated as zero, being designated as of not enough 100G *.The result is as shown in table 4.
Table 4
| |
Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| (3) solder heat resistance property | ○ | ○ | ○ | ○ | ○ |
| (4) solvent resistance | ○ | ○ | ○ | ○ | ○ |
| (5) degree test | 7H | 7H | 7H | 7H | 7H |
| (6) insulation resistance | ○ | ○ | ○ | ○ | ○ |
Can obviously find out by table 4, in the embodiment that has used solder resist composition of the present invention 1～5, obtain required good thermotolerance, solvent resistance, adaptation and the electrical insulating property of soldering-resistance layer.
Can know that like above detailed description even cooperated titanium dioxide, solder resist composition of the present invention also has good resolution.In addition, the soldering-resistance layer variable color under light, heat that forms with solder resist composition of the present invention is few and have a high reflectance.
Claims (10)
1. a solder resist composition is characterized in that, comprises: the carboxy resin that contains that (A) does not have aromatic rings; (B) two acylphosphine oxides are Photoepolymerizationinitiater initiater; (C) the monoacyl phosphine oxide is a Photoepolymerizationinitiater initiater; (D) photopolymerization monomer; (E) Titanium Dioxide Rutile Top grade; And (G) organic solvent.
2. solder resist composition according to claim 1; It is characterized in that, said do not have aromatic rings contain carboxy resin (A) serve as reasons (a) contain and have the compound reaction of oxirane ring and olefinic unsaturated group in carboxyl (methyl) acrylic acid series copolymer resins and (b) 1 molecule and the copolymerization with carboxyl of acquisition is a resin.
3. solder resist composition according to claim 1 and 2; It is characterized in that; The said pair of acylphosphine oxide is that Photoepolymerizationinitiater initiater (B) and monoacyl phosphine oxide are that the cooperation ratio of Photoepolymerizationinitiater initiater (C) is 90:10～1:99; And do not contain carboxy resin (A) with respect to what 100 mass parts did not have an aromatic rings, the said pair of acylphosphine oxide is that Photoepolymerizationinitiater initiater (B) and monoacyl phosphine oxide are that total use level of Photoepolymerizationinitiater initiater (C) is 1～30 mass parts.
4. according to each described solder resist composition of claim 1～3, it is characterized in that, also comprise (F) epoxy compound.
5. according to each described solder resist composition of claim 1～4, it is characterized in that also comprising (H) thioxanthones is the photopolymerization sensitizer.
6. printed circuit board (PCB), said printed circuit board (PCB) possess the base material that forms solder resist composition solidfied material, it is characterized in that said solidfied material comprises:
(A) do not have the carboxyl that contains carboxy resin of aromatic rings; (B) two acylphosphine oxides are Photoepolymerizationinitiater initiater; (C) the monoacyl phosphine oxide is a Photoepolymerizationinitiater initiater; (D) photopolymerization monomer; And (E) Titanium Dioxide Rutile Top grade.
7. printed circuit board (PCB) according to claim 6; It is characterized in that, said do not have aromatic rings contain carboxy resin (A) serve as reasons (a) contain and have the compound reaction of oxirane ring and olefinic unsaturated group in carboxyl (methyl) acrylic acid series copolymer resins and (b) 1 molecule and the copolymerization with carboxyl of acquisition is a resin.
8. according to claim 6 or 7 described printed circuit board (PCB)s, it is characterized in that solidfied material also comprises (F) epoxy compound.
9. according to each described printed circuit board (PCB) of claim 6～8, it is characterized in that also comprising (H) thioxanthones is the photopolymerization sensitizer.
10. according to each described printed circuit board (PCB) of claim 6～9, it is characterized in that, light emitting diode is installed on the substrate for printed circuit board.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010032934A JP4975834B2 (en) | 2010-02-17 | 2010-02-17 | Solder resist composition and printed wiring board |
| JP2010-032934 | 2010-02-17 | ||
| CN2010101751368A CN101980081A (en) | 2010-02-17 | 2010-05-14 | Solder resist composition and printed circuit board |
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| CN2010101751368A Division CN101980081A (en) | 2010-02-17 | 2010-05-14 | Solder resist composition and printed circuit board |
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| CN102722083B CN102722083B (en) | 2016-03-30 |
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| CN2010101751368A Pending CN101980081A (en) | 2010-02-17 | 2010-05-14 | Solder resist composition and printed circuit board |
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| JP2011227308A (en) * | 2010-04-20 | 2011-11-10 | Taiyo Holdings Co Ltd | Solder resist composition and print circuit board |
| JP2011215384A (en) * | 2010-03-31 | 2011-10-27 | Taiyo Holdings Co Ltd | Solder resist composition and printed-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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- 2010-05-13 KR KR1020100044824A patent/KR101718996B1/en active IP Right Grant
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| CN101980081A (en) | 2011-02-23 |
| TW201129857A (en) | 2011-09-01 |
| JP2011170049A (en) | 2011-09-01 |
| CN102722083B (en) | 2016-03-30 |
| TWI484290B (en) | 2015-05-11 |
| KR101718996B1 (en) | 2017-03-22 |
| KR20110095096A (en) | 2011-08-24 |
| JP4975834B2 (en) | 2012-07-11 |
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