CN102844711A - Solder resist composition and printed-circuit board - Google Patents
Solder resist composition and printed-circuit board Download PDFInfo
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- CN102844711A CN102844711A CN201180017037XA CN201180017037A CN102844711A CN 102844711 A CN102844711 A CN 102844711A CN 201180017037X A CN201180017037X A CN 201180017037XA CN 201180017037 A CN201180017037 A CN 201180017037A CN 102844711 A CN102844711 A CN 102844711A
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- solder resist
- resist composition
- photoepolymerizationinitiater initiater
- circuit board
- melamine
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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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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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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
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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
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/20—Details of printed circuits not provided for in H05K2201/01 - H05K2201/10
- H05K2201/2054—Light-reflecting surface, e.g. conductors, substrates, coatings, dielectrics
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
Disclosed is a solder resist composition with high reflectivity and high resolution that includes (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) melamine or a derivative thereof, (D) a photopolymerizable monomer, (E) rutile titanium dioxide, (F) an epoxy compound, and (G) an organic solvent, and that prevents decreases in reflectivity that are attributable to discoloration and deterioration. Also disclosed is a printed circuit board obtained by forming a solder resist using the solder resist composition.
Description
Technical field
The present invention relates to form the solder resist composition of the solder mask that is suitable for the high reflectance that the permanent mask as printed circuit board (PCB) uses 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 has formed circuit.
Background technology
Printed circuit board (PCB) utilizes not the needing part of Copper Foil of fitting on the etching removal laminate usually and forms wiring, and electronic component is configured in the position of regulation through welding.In such printed circuit board (PCB),, use the solder mask that coating is solidified to form on base material as the diaphragm of circuit when the soldering of electronic components.
For this solder mask, it prevents on when welding, scolding tin was attached to unwanted part, and prevents that circuit conductor is directly exposed in the air and the deterioration that causes because of oxygen, moisture.And then solder mask also plays a role as the permanent diaphragm of circuit substrate.Therefore, it is required various characteristicses such as adaptation, electrical insulating property, anti-sweating heat performance, solvent resistance, chemical proofing.
In addition, printed circuit board (PCB) is miniaturization day by day (becoming more meticulous), multiple stratification and single board (one board) in order to realize densification, and packaged type is also just changing surface mounting technology (SMT) into.Therefore, for solder mask, become more meticulous, the requirement of high resolving power, high precision, high reliability also improving.
As the technology of the pattern of this formation solder mask, use can correctly form the photoetching process of fine pattern, and particularly from the consideration of environment aspect etc., the photoetching process of alkali developable is just becoming main flow.
For example; The solder resist composition that the enough aqueous alkalis of ability develop is disclosed in patent documentation 1 and the patent documentation 2; This solder resist composition is so that the reaction of phenolic resin varnish type epoxy resin and unsaturated monocarboxylic, so the addition multi-anhydride and reaction product as base polymer.
On the other hand; In recent years, will as the light source of Backlight For Liquid Crystal Display Panels such as portable terminal, computer, TV and ligthing paraphernalia etc., directly be encapsulated in the purposes that lining is formed with on the printed circuit board (PCB) of solder mask with the low luminous light emitting diode (LED) of electric power and increase gradually.
Therefore, in order effectively to utilize the light of LED, requiring solder mask is the printed circuit board (PCB) of white, so that solder mask has high reflectance.
But the printed circuit board (PCB) that has directly encapsulated LED is owing to the light and heat that sends from LED promotes the deterioration, painted of white solder mask to cause the reduction of reflectivity.Particularly in use, white solder mask long term exposure is in the light and heat that is sent by LED, so the deterioration of solder mask, painted and the reduction reflectivity that causes is remarkable.
The prior art document
Patent documentation
Patent documentation 1: Japan special fair 1-54390 number
Patent documentation 2: Japan special fair 7-17737 number
Summary of the invention
The problem that invention will solve
The objective of the invention is to, even providing a kind of is exposed in the light and heat that is sent by LED, particularly under the situation of long term exposure, also can prevent the deterioration of solder mask, painted solder resist composition and printed circuit board (PCB).
And then the objective of the invention is to, even a kind of volume titanium dioxide resolution also the solder resist composition and printed circuit board (PCB) of excellence, high reflectance of containing is provided.
The scheme that is used to deal with problems
The inventor etc. further investigate; The result finds; Through using Titanium Dioxide Rutile Top grade as the Chinese white that is used to realize high reflectance; And the compounding melamine, thereby, also can prevent the deterioration, painted of solder mask even be exposed in the light and heat that sends by LED, particularly under the situation of long term exposure.
In addition; Discoveries such as the inventor; Using two acylphosphine oxides through combination is that Photoepolymerizationinitiater initiater and monoacyl phosphine oxide are that Photoepolymerizationinitiater initiater is as Photoepolymerizationinitiater initiater; Even contain the solder resist composition of the high reflectance of volume titanium dioxide, also can form excellent in resolution, high meticulous pattern.
Promptly; Solder resist composition of the present invention is characterised in that, comprises (A) and contains carboxy resin, (B) Photoepolymerizationinitiater initiater, (C) melamine or derivatives thereof, (D) photopolymerization monomer, (E) Titanium Dioxide Rutile Top grade, (F) epoxy compound and (G) organic solvent.
In addition, solder resist composition of the present invention is characterised in that, also to use (B1) two acylphosphine oxides be Photoepolymerizationinitiater initiater and (B2) monoacyl phosphine oxide is that Photoepolymerizationinitiater initiater is as Photoepolymerizationinitiater initiater in combination.
The effect of invention
According to the present invention, have as characteristics such as the desired screening characteristics of developable solder flux, photo-curable, development property, anti-sweating heat performance, adaptation, electrical insulating properties, thereby and then can prevent the variable color that causes because of light, heat through the compounding melamine.In addition, through the compounding melamine, can improve acid resistance.
And then according to the present invention; Using (B1) two acylphosphine oxides through combination is that Photoepolymerizationinitiater initiater, (B2) monoacyl phosphine oxide are Photoepolymerizationinitiater initiater; Contain the volume titanium dioxide and reflectivity is high even can provide; Also can form excellent in resolution, and the solder resist composition of high meticulous pattern.
Embodiment
Below, further explain the present invention.
Solder resist composition of the present invention is characterised in that, comprises (A) and contains carboxy resin, (B) Photoepolymerizationinitiater initiater, (C) melamine or derivatives thereof, (D) photopolymerization monomer, (E) Titanium Dioxide Rutile Top grade, (F) epoxy compound, (G) organic solvent.In addition, solder resist composition of the present invention can also comprise (H) anti-oxidant.
(containing carboxy resin)
Contain not restriction of carboxy resin (A), especially preferably do not have the carboxy resin that contains of aromatic rings.At this moment, if having the resin of the carboxyl that does not contain aromatic rings, what then self have 1 above photonasty unsaturated double-bond photosensitively contains carboxy resin and does not have containing carboxy resin and all can using of photonasty unsaturated double-bond, has no particular limits.Especially the resin (oligomer or polymkeric substance all can) that does not have aromatic rings in the resin of enumerating below can using aptly.Promptly; (1) through unsaturated carboxylic acid and the copolymerization with compound of unsaturated double-bond obtain contain carboxy resin, (2) make contain photonasty that the compound reaction that has oxirane ring and ethene property unsaturated group in carboxyl (methyl) acrylic acid series copolymer resins and 1 molecule obtains contain carboxy resin, (3) make unsaturated monocarboxylic and, the compound of 1 epoxy radicals and unsaturated double-bond is arranged respectively and has the copolymer reaction of the compound of unsaturated double-bond in 1 molecule; After the photonasty that the secondary hydroxyl that generated by this reaction is obtained with the reaction of saturated or unsaturated multi-anhydride contains carboxy resin, (4) and makes hydroxyl polymer-containing and the reaction of saturated or unsaturated multi-anhydride, make by the compound that has 1 epoxy radicals and unsaturated double-bond in the carboxylic acid of this reaction generation and 1 molecule respectively and react and the photonasty hydroxyl that obtains and the resin of carboxyl.
Among these, the photonasty that is preferably above-mentioned (2) contain carboxy resin, to contain the copolymerization with carboxyl that the reaction that has the compound of oxirane ring and ethene property unsaturated group in carboxyl (methyl) acrylic acid series copolymer resins and (b) 1 molecule obtains through (a) be resin.
(a) containing carboxyl (methyl) acrylic acid series copolymer resins is through the compound copolymerization that has 1 unsaturated group and at least 1 carboxyl in (methyl) acrylic ester and 1 molecule is obtained.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 acid, methoxyl diethylene glycol (methyl) acrylic ester, ethoxy diethylene glycol (methyl) acrylic ester, iso-octyl oxygen base 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 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-hydroxy methacrylate, (methyl) acrylic acid hydroxy propyl ester, (methyl) acrylic acid hydroxyl butyl ester, caprolactone modification (methyl) acrylic acid 2-hydroxy methacrylate etc.These can use separately, also can mix more than 2 kinds and use.Need to prove that in this instructions, (methyl) acrylic ester is the term of general designation acrylic ester, methacrylate, and is also identical to other similar expression.
In addition; As the compound that has 1 unsaturated group and at least 1 carboxyl in 1 molecule, can enumerate out the modification unsaturated monocarboxylic that carried out chain elongation between acrylic acid, methacrylic acid, unsaturated group and the carboxylic acid, for example (methyl) propenoic acid beta-carboxyl ethyl ester, 2-acryloxy ethyl succinic acid, 2-acryloxy ethyl hexahydrophthalic acid, through interior material that comprises 2 above carboxyls in the unsaturated monocarboxylic of ester bond, modification unsaturated monocarboxylic and then the maleic acid equimolecular etc. that has such as ester modified with ehter bond.These can use separately, also can mix more than 2 kinds and use.
As the compound that has oxirane ring and ethene property unsaturated group in (b) 1 molecule; Get final product so long as have the compound of ethene property unsaturated group and oxirane ring in 1 molecule; For example can enumerate out (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 ethene property unsaturated group in these (b) 1 molecules can use separately, also can mix more than 2 kinds and use.
The acid number that contains carboxy resin (A) must be in the scope of 50 ~ 200mgKOH/g.During acid number deficiency 50mgKOH/g, be difficult to remove the unexposed portion of filming of solder resist composition with weak base aqueous solution.When acid number surpasses 200mgKOH/g, problems such as the water tolerance of solidifying tunicle, electrical characteristics difference are arranged.In addition, the weight-average molecular weight that contains carboxy resin (A) is preferably in 5000 ~ 100000 scope.During weight-average molecular weight less than 5000, the dry to touch property of filming of solder resist composition has the tendency of remarkable variation.In addition, weight-average molecular weight surpasses at 100000 o'clock, owing to can produce the development property of solder resist composition, the problem that storage-stable significantly worsens, so not preferred.
(Photoepolymerizationinitiater initiater)
Photoepolymerizationinitiater initiater has no particular limits, and preferred especially two acylphosphine oxides are that Photoepolymerizationinitiater initiater and monoacyl phosphine oxide are the combination of Photoepolymerizationinitiater initiater.
As being suitable for of the present invention pair of acylphosphine oxide is Photoepolymerizationinitiater initiater (B1), 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 (Ciba Japan Corporation makes two-(2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide, trade name; IRGACURE819) obtaining easily, is practical.
As being suitable for monoacyl phosphine oxide of the present invention is Photoepolymerizationinitiater initiater (B2); 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 hypophosphorous acid methyl esters, 2-methyl benzoyl diphenyl phosphine oxide, pivaloyl group phenyl hypophosphorous acid isopropyl ester etc.Wherein 2,4, (Ciba Japan Corporation makes 6-trimethylbenzoyl diphenyl phosphine oxide, trade name; DarocureTPO) obtaining easily, is practical.
In addition, in the solder resist composition of the present invention, in the scope of not damaging effect of the present invention, but compounding is that Photoepolymerizationinitiater initiater (B1), monoacyl phosphine oxide are the Photoepolymerizationinitiater initiater the Photoepolymerizationinitiater initiater (B2) except two acylphosphine oxides.
It is that Photoepolymerizationinitiater initiater (B1) and aforementioned monoacyl phosphine oxide are Photoepolymerizationinitiater initiater (B2) that solder resist composition of the present invention uses above-mentioned pair of acylphosphine oxide through combination, even compounding the filming of high reflectance of titanium dioxide also can absorb necessary light, can form the meticulous pattern of height.In addition through changing its compounding ratio, the inching of the light absorption that can film.That is, the curable in the deep of substrate surface side is not enough and when being easy to generate undercutting (undercut), be the ratio increase of Photoepolymerizationinitiater initiater (B1) with above-mentioned pair of acylphosphine oxide in the cross sectional shape of pattern.In addition, surface cure property is not enough, during the surface state difference after developing, and is that the ratio of Photoepolymerizationinitiater initiater (B2) increases with aforementioned monoacyl phosphine oxide.This pair acylphosphine oxide is a Photoepolymerizationinitiater initiater (B1) and the monoacyl phosphine oxide is that the compounding ratio of Photoepolymerizationinitiater initiater (B2) is 90:10 ~ 1:99, is preferably 80:20 ~ 2:98.Outside the scope of this compounding ratio,, can't absorb necessary light and can't form high meticulous pattern because the effect of using based on their combination reduces.This pair of acylphosphine oxide is that Photoepolymerizationinitiater initiater (B1) and monoacyl phosphine oxide are that total compounding amount of Photoepolymerizationinitiater initiater (B2) contains carboxy resin (A) with respect to 100 mass parts, is preferably 1 ~ 30 mass parts, 2 ~ 25 mass parts more preferably.This pair acylphosphine oxide is when to be Photoepolymerizationinitiater initiater (B1) with the monoacyl phosphine oxide be total compounding quantity not sufficient 1 mass parts of Photoepolymerizationinitiater initiater (B2), and photo-curable reduces, and the pattern behind the exposure imaging forms and becomes difficulty, so not preferred.On the other hand, when this compounding amount surpasses 30 mass parts, the painted increase of filming in Photoepolymerizationinitiater initiater source, and become the high reason of cost, so not preferred.
(melamine or derivatives thereof)
(C) the melamine or derivatives thereof adds in order to prevent variable color.About the preferred addition of melamine or derivatives thereof, be 0.5 ~ 15 quality %, 1 ~ 10 quality % more preferably with respect to the solid constituent that contains carboxy resin 100 quality %.When the compounding amount is very few, do not add the effect of melamine etc., on the contrary too much the time, have problems at storage stability, development property, the aspects such as water tolerance of filming.
In addition, solder mask of the present invention is through adding melamine in composition, thereby can improve the whiteness of filming.Here, the index of whiteness can represent that this numerical value is big more with the b* value of L*a*b* chromatmetry, and yellow is strong more.So, through adding melamine, make the b* value become very little, can make high the filming of whiteness.In addition, through adding melamine,, the xanthochromia of filming, the reduction of reflectivity are reduced even after shining UV to filming, applying the deterioration test of thermal process.
Melamine is 2,4, and 6-triamido-1,3,5-triazines is as its main application, as the raw material of melamine resin.Melamine is through obtaining melamine methylol with the formalin reaction, and through it being utilized the catalyzer heating, melamine methylol forms methene key, can make melamine resin.As the main method for making of melamine, the method that urea is reacted is arranged under the high pressure of ammonia.Melamine is made through this method for making in industry.In addition, as other method for makings of melamine, also can synthesize by lime nitrogen, dicyandiamide, cyanic acid.And then also can use melamine derivatives such as melamine methylol.About the preferred compounding amount of the melamine of solder resist composition of the present invention, be 0.5 ~ 15 quality %, 1 ~ 10 quality % more preferably with respect to the solid constituent that contains carboxy resin 100 quality %.This compounding amount is 0.5 quality % when following, the effect of not adding melamine, and in addition, this compounding amount is 15 quality % when above, storage stability, development property, the water tolerance of filming etc. have problems.
(photopolymerization monomer)
As being used for photopolymerization monomer of the present invention (D), can enumerate out acrylic acid hydroxyalkyl acrylate classes such as acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxyl butyl ester; The mono acrylic ester class 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-dimethylaminoethyl; The multicomponent methacrylate class of polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, three-hydroxyethyl 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 glycidol ether such as glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether; The melamine acrylic ester; And/or the methyl acrylic ester corresponding with the aforesaid propylene esters of gallic acid etc.
The compounding amount of these photopolymerization monomers (D) contains carboxy resin (A) with respect to 100 mass parts, is preferably 10 ~ 100 mass parts, 20 ~ 80 mass parts more preferably.When the compounding amount surpassed 100 mass parts, the rerum natura as solder mask of cured coating film reduced, so not preferred.On the other hand, do not have sufficient photo-curable during these compounding quantity not sufficient 10 mass parts, can't obtain high meticulous pattern.
(Titanium Dioxide Rutile Top grade)
Use Titanium Dioxide Rutile Top grade (E) as Chinese white among the present invention.Common titanium dioxide has Detitanium-ore-type and rutile-type.Anatase-type titanium oxide causes the variable color of the resin in the solder resist composition sometimes owing to have photocatalyst activity.Therewith relatively; Titanium Dioxide Rutile Top grade is compared with anatase-type titanium oxide; Boundary vicinity in ultraviolet range and visible region has absorption; Slightly poor aspect the whole reflectivity in whiteness and visible region, but, therefore can obtain stable soldering-resistance layer because it does not have photolytic activity basically.
As aforementioned Titanium Dioxide Rutile Top grade (E), can use known Titanium Dioxide Rutile Top grade.Particularly, can use TIPAQUE R-820, TIPAQUE R-830, TIPAQUE R-930, TIPAQUE R-550, TIPAQUE R-630, TIPAQUE R-680, TIPAQUE R-670, TIPAQUE R-680, TIPAQUE R-670, TIPAQUE R-780, TIPAQUE R-850, TIPAQUE CR-50, TIPAQUE CR-57, TIPAQUE CR-80, TIPAQUE CR-90, TIPAQUE CR-93, TIPAQUE CR-95, TIPAQUE CR-97, TIPAQUE CR-60, TIPAQUE CR-63, TIPAQUE CR-67, TIPAQUE CR-58, TIPAQUE CR-85, TIPAQUE UT771 (Ishihara Sangyo Kaisha, Ltd.'s manufacturing), 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 K.K manufacturing), 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 manufacturing) etc.
The compounding amount of this Titanium Dioxide Rutile Top grade (E) contains carboxy resin (A) with respect to 100 mass parts, is preferably 50 ~ 450 mass parts, 60 ~ 350 mass parts more preferably.When the compounding amount surpassed 450 mass parts, photo-curable reduced, and curing depth shoals, so not preferred.On the other hand, the solder resist that during these compounding quantity not sufficient 50 mass parts, covering power is little, can't obtain high reflectance.
(epoxy compound)
Secondly; As epoxy compound (F); For example can enumerate out bisphenol-s epoxy resin, diglycidyl phthalate resin, triglycidyl group isocyanuric acid ester (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 on the direction different with other 2 epoxy radicals with the structure of s-triazine ring skeleton face phase bonding) etc.) and etc. hetero ring type epoxy resin, di-cresols (bixylenol) type epoxy resin, biphenyl type epoxy resin, four glycidyl group xylenols ethane resin etc. to thinning agent be 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 slightly solubility phenolic resin varnish type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, to contain aminoepoxy resin, rubber modified epoxy resin, bicyclopentadiene phenol aldehyde type epoxy resin, modifying epoxy resin by organosilicon, 6-caprolactone modified epoxy etc. be epoxy resin of solubility etc. to thinning agent.These epoxy resin can use separately or make up more than 2 kinds and use.
The compounding amount of this epoxy compound (F) contains carboxy resin (A) with respect to 100 mass parts, is preferably 5 ~ 70 mass parts, 5 ~ 60 mass parts more preferably.When the compounding amount of epoxy compound (F) surpassed 70 mass parts, the dissolubility of the unexposed portion in the developer solution reduced, and it is residual to take place easily to develop, and is difficult in reality, use.On the other hand, during less than 5 mass parts, the carboxyl that contains carboxy resin (A) is residual with unreacted state, and therefore the tendency of the electrical characteristics that can't fully obtain cured coating film, anti-sweating heat performance, chemical proofing is arranged.
Containing the carboxyl of carboxy resin (A) and the epoxy radicals of epoxy compound (F) reacts through ring-opening polymerization.And the epoxy resin that uses ease of solubility is during as other materials in organic solvent (G), the solder resist composition, and the heat during because of drying promotes the crosslinked of carboxyl and epoxy radicals easily.Therefore, hope to suppress under cross-linking reaction, the situation, it is desirable to that epoxy resin with slightly solubility uses separately or together use with the epoxy resin of ease of solubility through longer drying time.
(organic solvent)
The organic solvent that uses among the present invention (G) is used to make the solder resist composition to become the state that is easy to be coated with, and its dry formation is filmed.As this organic solvent (G), can enumerate out ketones such as MEK, cyclohexanone; Toluene, xylene, durene 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 acetate (cellosolve acetate), 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, naphtha, hydrogenated naphtha, solvent naphtha etc.
Aforementioned organic solvent (G) can use separately or with the form of two or more potpourris.The compounding amount of organic solvent (G) contains carboxy resin (A) with respect to 100 mass parts, is preferably 20 ~ 300 mass parts.
(anti-oxidant)
About the anti-oxidant (H) that uses among the present invention,, also can be used for preventing the reduction, painted of the reflectivity of this solidfied material even the solidfied material long term exposure of solder resist at high temperature.As this anti-oxidant (H); N-octadecane base-3-(3 ' 5 '-two-tert-butyl group-4 '-hydroxy phenyl)-propionic ester, n-octadecane base-3-(3 '-methyl-the 5 '-tert-butyl group-4 '-hydroxy phenyl)-propionic ester, n-tetradecane base-3-(3 ' 5 '-two-tert-butyl group-4 '-hydroxy phenyl)-propionic ester, 1 are arranged; 6-hexanediol-two-(3-(3; 5-two-tert-butyl-hydroxy phenyl)-propionic ester), 1; 4-butylene glycol-two-(3-(3; 5-two-tert-butyl-hydroxy phenyl)-propionic ester), triethylene glycol-two-(3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl)-propionic ester), four-(methylene-3-(3 ', 5 '-two-tert-butyl group-4 '-hydroxy phenyl) propionic ester methane, 3, two (2-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl oxygen)-1,1-dimethyl ethyls) 2 of 9-; 4; 8,10-four oxaspiros (5,5) undecane, N; N '-two-3-(3 ' 5 '-two-tertiary butyl-4-hydroxy phenol) propiono hexamethylene diamine, N; N '-tetramethylene is two-3-(3 '-methyl-5 '-tertiary butyl-4-hydroxy phenol) propionyl diamines, N, and N '-two-(3-(3,5-two-tertiary butyl-4-hydroxy phenol) propionyl) hydrazine, N-salicyl-N '-salicylidene hydrazine, 3-(N-salicyl) amino-1; 2; 4-triazole, N, hindered phenol compound, two dodecyls-3 such as N '-two (2-(3-(3,5-two-butyl-4-hydroxy phenyl) propionyl oxygen) ethyl) oxanamide; 3 '-thiodipropionate, two myristyl-3; 3 '-thiodipropionate, two octadecyl-3,3 '-thiodipropionate, double tridecyl-3,3 '-thiodipropionate, pentaerythrite four (3-dodecyl thiopropionate), pentaerythrite four (3-myristyl thiopropionate), pentaerythrite four (3-tridecyl thiopropionate), dilauryl-3; 3-thiodipropionate, two myristyl-3; 3-thiodipropionate, distearyl-3, the zinc salt of 3-thiodipropionate, pentaerythrite four (3-lauryl thiodipropionate), 2-mercaptobenzimidazole, lauryl stearyl thiodipropionate, 2 mercaptomethyl benzimidazole, the zinc salt of 2-mercaptobenzimidazole, 2 mercaptomethyl benzimidazole, dibutyl sulfide are that ［ decyl gathers (oxygen ethylidene) phosphite ester, three (cyclohexyl phenyl) phosphite ester, thricyclohexyl phosphite ester, three (decyl) thiophosphite, three isodecyl thiophosphites, two (2-ethylhexyl) phosphite esters of phenyl, phenyl diiso decyl phosphite ester, myristyl and gathers phosphorous antioxidant, phenyl naphthyl amines, 4 such as (oxygen ethylidene) two (ethylphenyl) phosphite ester, phenyl dicyclohexyl phosphite ester, phenyl diisooctyl phosphite ester, phenyl two (tridecyl) phosphite ester, diphenyl cyclohexyl phosphite ester, diphenyl iso-octyl phosphite ester, diphenyl 2-ethylhexyl phosphite ester, diphenyl isodecyl phosphite ester, diphenyl cyclohexyl phenyl phosphite ester, diphenyl (tridecyl) thiophosphite, 4 '-dimethoxy diphenylamine, 4 for anti-oxidant, triphenyl phosphite ester, three (aminomethyl phenyl) phosphite ester, tri iso octyl phosphorite, phosphorous acid tridecane ester, three (2-ethylhexyl) phosphite ester, three (nonyl phenyl) phosphite ester, three (octyl phenyl) phosphite ester, three for sulphur such as carbaminates; 4 '-two (α; α-Er Jiajibianji) diphenylamine, two-tert-butyl diphenyl amine, N, N '-two (octyl phenyl) amine, 4-isopropoxy diphenylamine, N, (2-naphthyl)-aromatic amines such as p-phenylenediamine (PPD) are anti-oxidant etc. to N '-two.These also can select combination use more than a kind.Wherein hindered phenol compound reduces reflectivity and prevents painted effect height, is desirable therefore.As the trade name of the anti-oxidant of hindered phenol compound, can enumerate out NOCRAC 200, NOCRAC M-17, NOCRAC SP, NOCRAC SP-N, NOCRAC NS-5, NOCRAC NS-6, NOCRAC NS-30, NOCRAC 300, NOCRAC NS-7, NOCRAC DAH (more than be the emerging chemical industry of imperial palace (strain) manufacturing); MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO-15, MARK AO-18, MARK 328, MARK AO-37 (more than be (strain) ADEKA make); IRGANOX 245, IRGANOX 259, IRGANOX 565, IRGANOX1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1081, IRGANOX 1098, IRGANOX 1222, IRGANOX 1330, IRGANOX1425WL (more than be Ciba Japan Corporation. make).
The compounding amount of anti-oxidant (H) contains carboxy resin (A) with respect to 100 mass parts, is preferably 0.4 ~ 25 mass parts, 0.8 ~ 15 mass parts more preferably.When the compounding amount of anti-oxidant (H) contains carboxy resin (A) less than 0.4 mass parts with respect to 100 mass parts, because of the hot deterioration of solder mask causes variable color to prevent that effect is few.In addition, when the compounding amount of anti-oxidant (H) contains carboxy resin (A) above 25 mass parts with respect to 100 mass parts, the development property reduction that the application films, patterning goes wrong.
(thioxanthones is the photopolymerization sensitizer)
Among the present invention when improving exposure to the purpose of the sensitivity of light, it is desirable to the compounding thioxanthones is photopolymerization sensitizer (I).This is that thioxanthones is that the effect of photopolymerization sensitizer (I) is very high because using above-mentioned pair of acylphosphine oxide in combination is that Photoepolymerizationinitiater initiater (B1) is in the composition of Photoepolymerizationinitiater initiater (B2) with above-mentioned monoacyl phosphine oxide.As this thioxanthones is photopolymerization sensitizer (I), can enumerate out thioxanthones, 2-ethyl thioxanthones, 2-isopropyl thioxanthone, 2-clopenthixal ketone, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthones etc.
This thioxanthones is that the compounding amount of photopolymerization sensitizer (I) contains carboxy resin (A) with respect to 100 mass parts, is preferably 0.05 ~ 2 mass parts, 0.1 ~ 1 mass parts more preferably.During this compounding quantity not sufficient 0.05 mass parts, the effect that sensitivity improves is few, and is when above above 2 mass parts, big from the painted change of filming of thioxanthones.
(stabilizing agent)
And then, in the solder resist composition of the present invention, be light stabilizer through containing hindered amine, can reduce the light deterioration.
As hindered amine is light stabilizer, for example can enumerate out TINUVIN 622LD, TINUVIN 144; CHIMASSORB 944LD, CHIMASSORB 119FL (more than be Ciba Japan Corporation make); MARK LA-57, LA-62, LA-67, LA-63, LA-68 (more than be Asahi Denka Co., Ltd. make); SANOL LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (more than be Sankyo Lifetech Co., Ltd. makes) etc.
Above-mentioned light stabilizer contains carboxy resin (A) with respect to 100 mass parts, preferably adds 0.1 ~ 10 mass parts.
(spreading agent)
In the solder resist composition of the present invention,, can improve dispersiveness, the settleability of titanium dioxide through containing spreading agent.As spreading agent, for example can enumerate out ANTI-TERRA-U, 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 ((BYK-Chemie Japan K.K. manufacturing), DISPARLON 2150, DISPARLON 1210, DISPARLON KS-860, DISPARLONKS-873N, DISPARLON 7004, DISPARLON 1830, DISPARLON1860, DISPARLON 1850, DISPARLON DA-400N, DISPARLONPW-36, DISPARLON DA-703-50 (nanmu originally changes into Co., Ltd. and makes), FLOWLEN G-450, FLOWLEN G-600, FLOWLEN G-820, FLOWLEN G-700, FLOWLEN DOPA-44, FLOWLENDOPA-17 (Kyoeisha Chemical Co., Ltd.'s manufacturing).
About the content of spreading agent, in order to realize above-mentioned purpose effectively, preferably, with respect to 100 mass parts Titanium Dioxide Rutile Top grades (E), it is 0.1 ~ 10 mass parts, be preferably 0.5 ~ 5 mass parts.
(other adding ingredients)
And then, can use curing accelerator, hot polymerization inhibitor, thickening agent, foam-breaking agent, levelling agent, coupling agent, flame retardant etc. as required in the solder resist composition of the present invention.
(method for making)
An example of following use as the solder resist composition describes the manufacturing of printed circuit board (PCB).
At first, solder resist composition of the present invention is diluted as required be adjusted to the viscosity that is suitable for coating process.
Then, the adjusted composition of viscosity is coated on the printed circuit board (PCB) that has formed circuit through methods such as silk screen print method, heavy curtain rubbing method, spraying process, rolling methods.Then, for example under 70 ~ 90 ℃ temperature, make organic solvent volatile dry contained in the composition of coating, form not sticking filming.
Then, through negative mask, with active energy beam this is filmed and optionally to make public, with unexposed development, form corrosion-resisting pattern through aqueous alkali.Through being carried out heat curing under 100 ℃ ~ 200 ℃, this corrosion-resisting pattern forms soldering-resistant pattern then.
In addition, as the radiation source that is used to make 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 beam 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 alkalis, for example can enumerate out aqueous alkalis such as potassium hydroxide, NaOH, sal tartari, sodium phosphate, sodium silicate, ammonia, amine.
Then, form soldering-resistant pattern after, packaged LED and make printed circuit board (PCB) of the present invention.This printed circuit board (PCB) of the present invention uses and of the present inventionly contains the solder resist of the high titanium dioxide of reflectivity and make, and has high reflectance, high fine pattern.
Embodiment
Below embodiment is shown and comparative example specifies the present invention, but the present invention does not receive their any restriction.
(A) contain 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 as the 900g diethylene glycol dimethyl ether of solvent with as 21.4g peroxidating (2 ethyl hexanoic acid) tert-butyl ester (Japan Oil Co's system, the trade name of polymerization initiator; PERBUTYL O), be heated to 90 ℃.After the heating, (Daicel Corporation. made, trade name to wherein dripping 309.9g methacrylic acid, 116.4g methyl methacrylate and 109.8g lactone modified methacrylic acid 2-hydroxy methacrylate with 3 hours; Placcel FM1) and as two (4-tert-butylcyclohexyl) peroxy dicarbonates of the 21.4g of polymerization initiator (Japan Oil Co makes, trade name; PEROYL TCP).And then, obtain containing the carboxyl copolymer resins with its slaking of carrying out 6 hours.Wherein, these are reflected under the blanket of nitrogen and carry out.
Then, add 363.9g acrylic acid 3,4-epoxycyclohexyl methyl esters (Daicel Corporation. system, trade name in the carboxyl copolymer resins in containing of gained; Cyclomer-A200), as the 3.6g dimethyl benzyl amine of ring opening catalyst, as the 1.80g hydroquinone monomethyl ether of polymerization inhibitor, be heated to 100 ℃, thereby the opening of epoxy carried out in its stirring.After 16 hours, obtain comprising 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 this 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 ether acetate alone of solvent, as the azoisobutyronitrile of catalyzer; Under blanket of nitrogen, be heated to 80 ℃, with dripping in about 2 hours with methacrylic acid and methyl methacrylate monomer with the mixed in molar ratio of 0.40:0.60.And then after it is stirred 1 hour, temperature is risen to 115 ℃, make its inactivation obtain resin solution.
After the cooling of this resin solution, use TBAB as catalyzer, under 95 ~ 105 ℃, 30 hours condition, make butyl glycidyl ether carry out addition reaction with the carboxyl equivalent of gained resin and cool off with 0.40 mol ratio.
And then the OH base with respect to the resin of above-mentioned gained under 95 ~ 105 ℃, 8 hours condition, makes tetrabydrophthalic anhydride carry out addition reaction with 0.26 mol ratio.Its cooling back is taken out, obtain comprising the solution that contains carboxy resin that 50 quality % (non-volatile content) do not have aromatic rings, the acid number of the solid constituent of this resin is that 78.1mgKOH/g, weight-average molecular weight are 35000.Below, this reaction solution is called A-2 varnish.
Contain 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 (EPICLON N-680, epoxide equivalent=210 that Dainippon Ink Chemicals makes) and as the 96.4g carbitol acetate of solvent, heating makes its dissolving.Then, to its add 0.1g quinhydrones as polymerization inhibitor, as the 2.0g triphenylphosphine of catalysts.Heat this potpourri to 95 ~ 105 ℃, slowly drip 72g acrylic acid, it was reacted about 16 hours, become below the 3.0mgKOH/g until acid number.Cool off this reaction product to 80 ~ 90 ℃, add the 76.1g tetrabydrophthalic anhydride then, make its reaction 6 hours, until absorption peak (1780cm based on the acid anhydrides of infrared absorption analysis
-1) disappear.In this reaction solution, add the aromatic series series solvent Ipzole#150 that 96.4g Idemitsu Kosen Co., Ltd. makes, take out the dilution back.The nonvolatile component that contains carboxyl photosensitive polymer solution of as above operating gained is that the acid number of 65 weight %, solids is 78mgKOH/g.Below, this reaction solution is called B-1 varnish.
The prescription of embodiment 1 ~ 7 and comparative example 1 ~ 6:
According to each composition of table 1 compounding, stir and make its dispersion with 3 roll-type roller mills, make the solder resist composition respectively.Numeral mass parts in the table.
[table 1]
Melamine: the broken melamine of micro mist (the daily output chemistry is made)
Photoepolymerizationinitiater initiater A1: two-(2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide IRGACURE 819 (Ciba Japan Corporation manufacturings)
Photoepolymerizationinitiater initiater A2:2,4,6-trimethylbenzoyl diphenyl phosphine oxide DAROCUR TPO (Ciba Japan Corporation manufacturing)
Photoepolymerizationinitiater initiater B1:IRGACURE 907 (Ciba Japan Corporation manufacturing)
Photopolymerization monomer: dipentaerythritol acrylate
Titanium dioxide A: Titanium Dioxide Rutile Top grade CR-93 (the former industry manufactured of stone)
Titanium dioxide B: anatase-type titanium oxide A-220 (the former industry manufactured of stone)
Epoxy compound: TEPIC-H (daily output chemical company makes)
Heat curing promoter: dicyandiamide
Solvent: carbitol acetate
Foam-breaking agent (silicone oil): KS-66 (SHIN-ETSU HANTOTAI's chemistry is made)
In order to investigate the various character of the solder mask that uses each solder resist composition formation, carry out following test and evaluation.
(1) resolution (cross sectional shape)
On the FR-4 copper clad laminate of size 100mm * 150mm, thickness 1.6mm; Use the version of 100 order polyester (twill system) each solder resist composition through silk screen print method whole (the whole face of substrate) printing embodiment 1 ~ 7 and comparative example 1 ~ 6, with its with the heated air circulation type drying oven 80 ℃ of dryings 30 minutes down.Then it is used use in printed circuit board exposure machine HMW-680GW (Orc Manufacturing Co., Ltd. makes), uses negative-appearing image to be of a size of the mask pattern of lines 250 μ m, to embodiment 1 ~ 5 and 7, comparative example 1 ~ 4 and 6 with 450mJ/cm
2The accumulation light quantity, to embodiment 6, comparative example 5 with 900mJ/cm
2The accumulation light quantity so that mask carries out ultraviolet exposure with the method for having carried out dry solder mask driving fit.Then, under 30 ℃ with 1% aqueous sodium carbonate as developer solution, use the use in printed circuit board developing machine that they were developed for 60 seconds, then they are carried out heat curing in 60 minutes with the heated air circulation type drying oven under 150 ℃, make each test film.For the lines of each test film,, use the width (upper surface width) of the upper surface that measurement microscope contacts with mask and the width (substrate surface width) of the substrate surface that joins with base material as cross sectional shape.Calculate the difference of separately width and negative-appearing image size (250 μ m) this moment as the negative-appearing image difference in size.Then, use the thickness of fixed each test film of surfaceness instrumentation.In addition, judge through visual for the shape of viewed each test film.As decision method, with the shape in cross section be tetragonal test film basically as zero, will give prominence to, undercutting is big, obviously be down trapezoidal test film as *.The result is shown in table 2.Unit is μ m.
[table 2]
Having used two acylphosphine oxides for combination in embodiment 1 ~ 7 and the comparative example is that Photoepolymerizationinitiater initiater (B1) is the comparative example 1,2,6 of Photoepolymerizationinitiater initiater (B2) with the monoacyl phosphine oxide; In the cross sectional shape of its lines; The difference in size of upper surface and substrate surface is little; Cross sectional shape is a quadrilateral basically, has obtained excellent resolution.
(2) fast light heat-resisting discolouration
For the embodiment 1 ~ 7 good in the resolution test and the solder resist composition of comparative example 1,2,6; FR-4 copper clad laminate to size 100mm * 150mm, thickness 1.6mm; The plate that uses 100 order polyester (twill system) is through silk screen print method printed patterns on whole of substrate, and making thickness is 40 μ m.Then, under 80 ℃, make its dry 30 minutes with the heated air circulation type drying oven.And then use use in printed circuit board exposure machine HMW-680GW (the rc Manufacturing Co. of Co., Ltd. O, Ltd. system), with the mode of the square negative-appearing image pattern of residual 30mm, with 900mJ/cm
2The accumulation light quantity carry out ultraviolet exposure.Then, 30 ℃ down with 1% aqueous sodium carbonate as developer solution, through the use in printed circuit board developing machine they were developed for 60 seconds.Then carry out heat curing in 60 minutes with the heated air circulation type drying oven down, make each test film that attribute testing is used at 150 ℃.
The test film of measuring gained with color colour difference meter CR-400 (Konica Minolta Sensing, Inc. make) carries out each test as initial value with the test film separated into two parts.
(i) light fastness test of anti-encapsulation the (supposing component packages, the light fastness test that carries out then)
The conveyor type heating furnace that uses component packages to use is with twice of each test film repeated heating.Then, use conveyor-type UV irradiating machine QRM-2082-E-01 (the rc Manufacturing Co. of Co., Ltd. O, Ltd. system), with metal halide lamp, cold mirror, 120W/cm
2* 3 lamps, near transfer rate 3m/ minute (the accumulation light quantity 3000mJ/cm the wavelength 350nm
2) condition carry out 50 irradiation UV repeatedly (the accumulation light quantity be 150J/cm on calculating
2).Then,, measure aberration, estimate the deterioration state of each test film with the condition identical with initial value for postradiation each test film of UV.In addition, also each test film is estimated through visual.Its result is shown in table 3.
(ii) solder dipping test (suppose solder leveling (solder leveler), the insertion of through hole is encapsulated)
For this test,, can estimate the discolouration when having acid to exist under the high temperature through being coated with acid solder flux, being immersed in the solder bath.To the test film after the off-test of (i), the water soluble flux W-121 that coating MEC Company Ltd. makes flooded for 30 seconds in 260 ℃ solder bath.Also dry with 50 ℃ warm water washing then.After carrying out 3 these operations repeatedly,, under the condition identical, measure aberration, estimate the deterioration state of each test film with initial value for each test film.In addition, also each test film is estimated through visual.Its result is shown in table 3.
[table 3]
In the table 3, Y representes that reflectivity, the L* of XYZ colorimetric system represent the brightness of L*a*b* colorimetric system.△ E*ab for the difference of each value of L*a*b* being got deterioration test and initial value square and get the subduplicate result of its summation.A* represent red direction ,-a* represent green direction, b* represent yellow direction ,-b* representes blue direction, do not have colourity more near null representation more.△ E*ab representes change in color, and the more little expression change in color of this value is more little.With visual metewand be: zero: can't confirm, *: can see some variable colors, * *: can obviously find out variable color.
Even embodiment 1 ~ 7 is after carrying out 3 UV irradiations and solder bath immersion test, the value of △ E*ab and visual valuation do not have variable color basically yet, are good results.
(3) acid resistance
To in the aqueous sulfuric acid of 10 capacity %, flood 15 minutes under 25 ℃ with each test film that (1) likewise makes, wash and drying.The state of filming with visual valuation then.With the complete unconverted test film of filming as zero, film in visible breach, from the test film that floats of base material as *.Evaluation result is shown in table 4.Can know that the interpolation because of melamine improves acid resistance.
[table 4]
Table 4
(4) anti-sweating heat performance
For embodiment 1 ~ 7, coating rosin series solder flux flows (Flow) 10 seconds in 260 ℃ solder bath on each test film of likewise making with (2).Wash with propylene glycol monomethyl ether acetate then and drying after, utilize the bonding glass band to carry out disbonded test, peeling off of filming estimated.The test film that nothing is peeled off as zero, have the test film peeled off as *.The result is shown in table 5.
(5) solvent resistance
For embodiment 1 ~ 7, will in propylene glycol monomethyl ether acetate, flood 30 minutes and drying with each test film that (2) likewise make after, utilize the bonding glass band to carry out disbonded test, peeling off of filming estimated.The test film that nothing is peeled off as zero, have the test film peeled off as *.The result is shown in table 5.
(6) pencil hardness test
For embodiment 1 ~ 7, the pencil of the B to 9H that the core tip is polished is pressed onto on each test film of likewise making with (2) with about 45 ° angle, and record does not produce the hardness of the pencil of peeling off of filming.The result is shown in table 5.
(7) insulation resistance test
For embodiment 1 ~ 7,, use the condition identical to make test film with (2) except the comb-type electrode B sheet (coupon) that uses IPC B-25 test pattern replaces the FR-4 copper clad laminate.This test film is applied the bias voltage of DC500V, measure insulating resistance value.This value for more than the 100G Ω then be zero, not enough 100G Ω then for *.The result is shown in table 5.
[table 5]
Can know, use among the embodiment 1 ~ 7 of solder resist composition of the present invention to have the desired good thermotolerance of solder mask, solvent resistance, adaptation and electrical insulating property by table 5.
Like above detailed description, but even the solder resist composition compounding titanium dioxide of knowledge capital invention is also good based on the pattern voltinism of light, resolution is also excellent.In addition, use that solder mask that solder resist composition of the present invention forms is few because of the variable color of light, heating, high reflectance is excellent, also excellent to the patience of the variable color of acid, adaptation.
Claims (9)
1. solder resist composition; It is characterized in that, comprise (A) and contain carboxy resin, (B) Photoepolymerizationinitiater initiater, (C) melamine or derivatives thereof, (D) photopolymerization monomer, (E) Titanium Dioxide Rutile Top grade, (F) epoxy compound and (G) organic solvent.
2. solder resist composition; It is characterized in that; Comprise (A) and contain carboxy resin, (B) Photoepolymerizationinitiater initiater, (C) melamine or derivatives thereof, (D) photopolymerization monomer, (E) Titanium Dioxide Rutile Top grade, (F) epoxy compound and (G) organic solvent
It is that Photoepolymerizationinitiater initiater (B1) and monoacyl phosphine oxide are Photoepolymerizationinitiater initiater (B2) that said (B) Photoepolymerizationinitiater initiater comprises two acylphosphine oxides.
3. solder resist composition according to claim 1 and 2 is characterized in that, also comprising (I) thioxanthones is the photopolymerization sensitizer.
4. solder resist composition according to claim 1 and 2 is characterized in that, also comprises (H) anti-oxidant.
5. solder resist composition according to claim 1 and 2 is characterized in that, the said carboxy resin that contains is the carboxy resin that contains that (A) do not have aromatic rings.
6. printed circuit board (PCB), the base material that it possesses the solidfied material that forms the solder resist composition is characterized in that,
Said solidfied material comprises:
(A) reaction product of carboxyl and (F) epoxy radicals of epoxy compound, (B) Photoepolymerizationinitiater initiater, (C) melamine or derivatives thereof, (D) photopolymerization monomer and (E) Titanium Dioxide Rutile Top grade.
7. printed circuit board (PCB) according to claim 6 is characterized in that, (B) to comprise two acylphosphine oxides be that Photoepolymerizationinitiater initiater (B1) and monoacyl phosphine oxide are Photoepolymerizationinitiater initiater (B2) to Photoepolymerizationinitiater initiater.
8. according to claim 6 or 7 described printed circuit board (PCB)s, it is characterized in that it is the photopolymerization sensitizer that solidfied material also comprises (I) thioxanthones.
9. according to claim 6 or 7 described printed circuit board (PCB)s, it is characterized in that, be packaged with light emitting diode.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010083851A JP2011215384A (en) | 2010-03-31 | 2010-03-31 | Solder resist composition and printed-circuit board |
| JP2010-083851 | 2010-03-31 | ||
| JP2010-097254 | 2010-04-20 | ||
| JP2010097254A JP2011227308A (en) | 2010-04-20 | 2010-04-20 | Solder resist composition and print circuit board |
| PCT/JP2011/058178 WO2011125820A1 (en) | 2010-03-31 | 2011-03-31 | Solder resist composition and printed circuit board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102844711A true CN102844711A (en) | 2012-12-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180017037XA Pending CN102844711A (en) | 2010-03-31 | 2011-03-31 | Solder resist composition and printed-circuit board |
Country Status (3)
| Country | Link |
|---|---|
| KR (2) | KR101708987B1 (en) |
| CN (1) | CN102844711A (en) |
| WO (1) | WO2011125820A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102981366A (en) * | 2012-11-29 | 2013-03-20 | 惠州市容大油墨有限公司 | Solder-resistance composite and application to printed circuit board |
| JP6463079B2 (en) * | 2014-03-18 | 2019-01-30 | 太陽インキ製造株式会社 | Curable resin composition, dry film, cured product and printed wiring board |
| KR20150108744A (en) * | 2014-03-18 | 2015-09-30 | 다이요 잉키 세이조 가부시키가이샤 | Curable resin composition, dry film, cured product and printed wiring board |
| KR101898970B1 (en) * | 2014-12-10 | 2018-09-14 | 고오 가가쿠고교 가부시키가이샤 | Liquid solder resist composition and covered-printed wiring board |
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2011
- 2011-03-31 KR KR1020147027257A patent/KR101708987B1/en active IP Right Grant
- 2011-03-31 WO PCT/JP2011/058178 patent/WO2011125820A1/en active Application Filing
- 2011-03-31 KR KR1020127025360A patent/KR20120137391A/en active Application Filing
- 2011-03-31 CN CN201180017037XA patent/CN102844711A/en active Pending
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| CN101082773A (en) * | 2006-05-30 | 2007-12-05 | 太阳油墨制造株式会社 | Photo- and thermo-setting solder resist composition and printed wire board using same |
| CN101281367A (en) * | 2007-04-06 | 2008-10-08 | 太阳油墨制造株式会社 | Solder resist compound and cured product thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20140129329A (en) | 2014-11-06 |
| KR20120137391A (en) | 2012-12-20 |
| KR101708987B1 (en) | 2017-02-21 |
| WO2011125820A1 (en) | 2011-10-13 |
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