CN102385244B - Black curable resin composition - Google Patents
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- CN102385244B CN102385244B CN201110163251.8A CN201110163251A CN102385244B CN 102385244 B CN102385244 B CN 102385244B CN 201110163251 A CN201110163251 A CN 201110163251A CN 102385244 B CN102385244 B CN 102385244B
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Abstract
The invention aims to provide a black curable resin composition that is excellent in resolution characteristics and easy for adjustment to a black color, and allows color tone variation after heat treatment to be prevented. The black curable resin composition includes: a photosensitive carboxylic resin (A); a photopolymerization initiator (B); a diluent (C); an epoxy compound (D); and a black colorant (E). The black curable resin composition is characterized in that the black colorant (E) includes a carbon black-based black colorant (E-1) and a perylene-based black colorant (E-2), and contains 53 mass% or more of the perylene-based black colorant (E-2).
Description
Technical field
The present invention relates to the black curable resin composition with excellent resolution, such as, relate to following black curable resin composition, when its solder resist as printed circuit board (PCB) uses, close spacing (fine pitch) and the miniaturization of electrode can be corresponded to, and the excellent hue of black, even if also can tonal variation be prevented after heat treatment.
Background technology
Printed circuit board (PCB), for forming conductor circuit figure on substrate, the pad of this pattern carries electronic unit by soldering, and the circuit part not comprising this pad is covered by the solder resist film as permanent protective film.Thus, on a printed circuit during soldering electronic unit, prevent scolding tin to be attached to unwanted part, prevent circuit conductor to be directly exposed to air simultaneously and be corroded because of oxidation or humidity.
In addition, in recent years, along with technical progress, improve further in the requirement of electronics field to miniaturization, lighting, thereupon, in order to configure the electronic unit of more miniaturization to high-density, require the close spacing of the conductor circuit figure of printed circuit board (PCB), miniaturization, high precision.Corresponding to this, also require that solder resist film has all characteristics such as more high performance resolution, dimensional accuracy, thermotolerance, as one of above-mentioned solder resist film, have the solder resist film of black.
As the material forming black solder resist film, the colorant proposing the resin be matched with containing carboxyl is the solder mask composition (patent documentation 1) of more than a kind colorant beyond black colorant and black colorant.But the black solder mask composition of patent documentation 1 has black, so light absorption increases during exposure, particularly light is difficult to the deep arriving solder resist film.Therefore, there is the problem that resolution or residual lines (line) are wanting in, namely the photocuring in solder resist film deep is insufficient, after development, the size in solder resist film deep reduce too much and cured coating film from printed circuit board (PCB) stripping etc.
For this reason, propose by being set as that blackened black solder mask composition is carried out in any one combination be selected from following combination by being matched with containing the colorant in the resin of carboxyl, described in be combined as: yellow colorants and violet colorant; Yellow colorants, blue colorant and red stain; Green colourant and violet colorant; And green colourant and red stain (patent documentation 2).But in patent documentation 2, owing to making it blackened with the colorant beyond black colorant, so the operation being adjusted to black is difficult, loaded down with trivial details, and in order to improve degree of blackness, the containing ratio of colorant improves, and still there is the problem that exploring performance is insufficient.
[prior art document]
[patent documentation]
[patent documentation 1] JP 2008-257045
[patent documentation 2] JP 2010-91876
Summary of the invention
In view of the foregoing, the object of the present invention is to provide and a kind ofly there is excellent resolution and be easily adjusted to black, the black curable resin composition of the tonal variation after thermal treatment can be prevented.
The solution of the present invention is a kind of black curable resin composition, it contains (A) photoresist containing carboxyl, (B) Photoepolymerizationinitiater initiater, (C) thinning agent, (D) epoxy compound and (E) black colorant, described (E) black colorant contains (E-1) carbon black system black colorant and (E-2) perylene system black colorant, described (the E-2) perylene system content of black colorant in described (E) black colorant is more than 53 quality %.
In such scheme, carbon black system black colorant is coordinated Yu the perylene system mixing ratio of black colorant in whole black colorant is set as more than 53 quality % by perylene system black colorant in the colorant of black curable resin composition, arriving the film deep of black curable resin composition thus in order to carry out photocuring for the light that exposes, all fully carrying out photocuring from the surface element of film to deep.Carbon black system black colorant reduces the lightness of black curable resin composition, supplements and improves degree of blackness.
The solution of the present invention is a kind of black curable resin composition, it is characterized in that, described (E-2) perylene system black colorant is more than 3% to the light transmission rate that wavelength is 300 ~ 400nm.In such scheme, owing to coordinating the transmitance of the light of wavelength 300 ~ 400nm to be 3% with upper perylene system black colorant, so the ultraviolet light of photocuring institute light requirement positively arrives the deep of the black curable resin composition coated on substrate.
The solution of the present invention is a kind of black curable resin composition, it is characterized in that, described (E-2) perylene system black colorant is the transmitance of the light of 400 ~ 700nm to wavelength is less than 20%.The solution of the present invention is a kind of black curable resin composition, it is characterized in that, described (E-2) perylene system black colorant infrared absorption spectrum measure in being less than 1669 ~ 1671cm
-1between, 1548 ~ 1550cm
-1between, 1498 ~ 1500cm
-1between, 1402 ~ 1404cm
-1between, 1283 ~ 1285cm
-1between, 822 ~ 824cm
-1between, 763 ~ 765cm
-1between, 739 ~ 741cm
-1between absorption position there is infrared ray absorbing peak.
The solution of the present invention is a kind of black curable resin composition, it is characterized in that, also containing (F) blue colorant.Except above-mentioned each black colorant, by coordinating blue colorant further, the lightness (L* value) that reduction measures with colour difference meter, adjusts chromaticity index (chromaticity) (a* value) near side direction 0 simultaneously.In addition, the solution of the present invention is a kind of black curable resin composition, it is characterized in that, described (F) blue colorant is phthalocyanine system blue colorant.
The solution of the present invention is a kind of black curable resin composition, it is characterized in that, also containing (G) yellow colorants.Except above-mentioned each black colorant, also coordinate yellow colorants further, thus the L* value that measures with colour difference meter of reduction, simultaneously by chromaticity index (b* value) from minus value side to adjustment near 0.In addition, the solution of the present invention is a kind of black curable resin composition, it is characterized in that, described (G) yellow colorants is anthraquinone system yellow colorants.
The solution of the present invention makes above-mentioned black curable resin composition solidify the solidfied material obtained.In addition, the solution of the present invention is a kind of solidfied material, it is characterized in that, L* value be less than 25, a* value and b* value all-2 ~ 2 scope.The solution of the present invention is a kind of solidfied material, it is characterized in that, when thickness is 20 μm, wavelength is the transmitance of the light of 400nm is more than 7.0%.In addition, the solution of the present invention is a kind of printed circuit board (PCB), it is characterized in that, the above-mentioned black curable resin composition of its coating obtains as solder resist.
According to the solution of the present invention, by the mixing ratio of perylene system black colorant joined together in black colorant total amount is set as more than 53 quality %, the film deep of black curable resin composition is arrived for the light that exposes, so all can abundant photocuring from the surface element of film to deep for carrying out photocuring.Thus, because photocuring fully proceeds to the deep of film, even if so be coated on the substrates such as the printed circuit board (PCB) of the circuit diagram with close spacing, also can prevent from causing film to come off because deep photocuring is not enough or defect etc., resolution improves.In addition, because photocuring fully proceeds to the deep of film, so can prevent the width dimensions in development Post RDBMS film deep from reducing.Therefore, the width dimensions in cured coating film deep is close to the width dimensions of cured coating film skin section, and the dimensional accuracy of cured coating film improves.
According to the solution of the present invention, because the transmitance of the light coordinating wavelength 300 ~ 400nm is perylene system black colorant Shang 3% Yi, so positively prevent the film caused because film deep photocuring is not enough from coming off or defect etc., resolution and dimensional accuracy improve further.
According to the solution of the present invention, blue colorant can also be coordinated as required, the L* value measured with colour difference meter can be reduced thus, a* value can be worth neighbouring adjustment from the occasion of side direction 0 simultaneously, so easily adjust concentration and the color state of black.
According to the solution of the present invention, by coordinating yellow colorants further, can reduce the L* value measured with colour difference meter, b* value can adjust near 0 value from minus value side by while, so easily adjust concentration and the color state of black.
Embodiment
Then, each composition of black curable resin composition of the present invention is described.Black curable resin composition of the present invention contains (A) carboxylic photoresist, (B) Photoepolymerizationinitiater initiater, (C) thinning agent, (D) epoxy compound and (E) black colorant, described (E) black colorant contains (E-1) carbon black system black colorant and (E-2) perylene system black colorant, in described (E) black colorant, described (content of E-2) perylene system black colorant is more than 53 quality %.
(A) carboxylic photoresist
Carboxylic photoresist is not particularly limited, and can use the photosensitive carboxylic resin with more than 1 photonasty unsaturated double-bond, the carboxylic resin without photonasty unsaturated double-bond any one.As the example of composition (A), following modified by polyacid (methyl) acrylic acid epoxy ester can be enumerated, it is the epoxy reaction at least partially making to have in the free-radical polymerised unsaturated monocarboxylics such as acrylic or methacrylic acid and molecule the polyfunctional epoxy resin of more than 2 epoxy radicals, obtain (methyl) acrylic acid epoxy ester, make the hydroxyl reaction of polyprotonic acid or its acid anhydrides and generation and obtain.
As long as described multi-functional epoxy resin 2 official can above epoxy resin, can use arbitrarily, epoxide equivalent is not particularly limited, and usually uses epoxide equivalent to be less than 1000, is preferably the epoxy resin of 100 ~ 500.Multi-functional epoxy resin can enumerate such as biphenyl type epoxy resin, naphthalene type epoxy resin, bicyclopentane diene type epoxy resin, the rubber modified epoxy resins such as silicone modified epoxy resin, 6-caprolactone modified epoxy, bisphenol A-type, bisphenol-f type, the phenolic resin varnish type epoxy resins such as bisphenol-A D type, the cresol novolak type epoxy resins such as ortho cresol novolak type, bisphenol A novolac type epoxy resin, annular aliphatic polyfunctional epoxy resin, glycidyl ester type polyfunctional epoxy resin, glycidyl amine type polyfunctional epoxy resin, hetero ring type polyfunctional epoxy resin, bis-phenol modified novolac type epoxy resin, multifunctional modified novolac type epoxy resin, phenols and the condensation product type epoxy resin etc. of aromatic aldehyde with phenolic hydroxyl group.In addition, the epoxy resin importing the halogen atoms such as Br, Cl and obtain can be also used in above-mentioned resin.In above-mentioned epoxy resin, from the viewpoint of film flexibility, the rubber modified epoxy resins such as preferred silicone modified epoxy resin.Above-mentioned epoxy resin can be used alone, and can also mix two or more and use.
The free-radical polymerised unsaturated monocarboxylic used is not particularly limited, such as can enumerate acrylic acid, methacrylic acid, crotonic acid, cinnamic acid etc., any one of preferred acrylic acid and methacrylic acid is (hereinafter sometimes referred to (methyl) acrylic acid.), particularly preferably acrylic acid.The material that (methyl) acrylic acid is obtained by reacting is (methyl) acrylic acid epoxy ester.The reaction method of epoxy resin and free-radical polymerised unsaturated monocarboxylic is not particularly limited, such as, epoxy resin and acrylic acid can be heated to react in suitable thinning agent.
Polyprotonic acid or multi-anhydride and the hydroxyl reaction generated in the reaction of described epoxy resin and free-radical polymerised unsaturated monocarboxylic, make carboxyl free on resin strip.As the polyprotonic acid used or its acid anhydrides, be not particularly limited, any one of saturated, unsaturated carboxylic acid or acid anhydrides can be used.Polyprotonic acid can enumerate such as succinic acid, maleic acid, hexane diacid, citric acid, phthalic acid, four hydrogen phthalates, 3-methyl four hydrogen phthalate, 4-methyl four hydrogen phthalate, 3-ethyl four hydrogen phthalate, 4-ethyl four hydrogen phthalate, hexahydrobenzene dioctyl phthalate, 3-methyl hexahydrobenzene dioctyl phthalate, 4-methyl hexahydrobenzene dioctyl phthalate, 3-ethyl hexahydrobenzene dioctyl phthalate, 4-ethyl hexahydrobenzene dioctyl phthalate, methyl four hydrogen phthalate, methyl hexahydrobenzene dioctyl phthalate, interior methine four hydrogen phthalate, methine four hydrogen phthalate in methyl, trimesic acid, trimellitic acid and diglycolic acid etc., as multi-anhydride, the acid anhydrides of above-mentioned acid can be enumerated.Above-claimed cpd can be used alone, and also can mix two or more and use.
In the present invention, above-mentioned modified by polyacid unsaturated monocarboxylic epoxy resin also can be used as photoresist, but by the carboxyl reaction that the glycidyl compound and above-mentioned modified by polyacid unsaturated monocarboxylic epoxy resin that make to have more than 1 free-radical polymerised unsaturated group and epoxy radicals have, free-radical polymerised unsaturated group can be imported further, obtain the photoresist that photonasty improves further.
This improves in photosensitive photoresist, free-radical polymerised unsaturated group utilizes the reaction of last glycidyl compound and is bonded to the side chain of the macromolecular scaffold of the photoresist of its precursor, so photopolymerization reaction is high, excellent sensitometric characteristic can be had.As the compound with more than 1 free-radical polymerised unsaturated group and epoxy radicals, such as, can enumerate glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, pentaerythritol triacrylate list glycidyl ether etc.It should be noted that can have multiple glycidyl in 1 molecule.The above-mentioned compound with more than 1 free-radical polymerised unsaturated group and epoxy radicals can be used alone, and also can mix two or more and use.
From the viewpoint of certain alkali development, the lower limit of the acid number of the photoresist containing carboxyl is 30mgKOH/g, is preferably 40mgKOH/g.On the other hand, from the viewpoint preventing exposure portion from being dissolved by alkaline developer, the higher limit of acid number is 200mgKOH/g, from the viewpoint of the moisture-proof and electric properties deteriorate that prevent solidfied material, is preferably 150mgKOH/g.
In addition, from the obdurability of solidfied material and the viewpoint of dry to touch, the lower limit of the weight-average molecular weight of the photoresist containing carboxyl is 3000, is preferably 5000.On the other hand, from the viewpoint with the intermiscibility of the thinning agent as composition (C) etc. and alkali-developable smoothly, the higher limit of weight-average molecular weight is 200000, is preferably 50000.
As in the material that the photoresist containing carboxyl is commercially available, such as ZFR-1124, FLX-2089 (above is Japanese chemical drug (strain) system), CYCLOMER P (ACA) Z-250 (Daicel chemical industry (strain) system), Ripoxy SP-4621 (Showa macromolecule (strain) system) etc. can be enumerated.Above-mentioned resin can be used alone, and also can mix two or more and use.
(B) Photoepolymerizationinitiater initiater
As long as the normally used material of Photoepolymerizationinitiater initiater, is not particularly limited, such as, can enumerate oxime series initiators, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino benzoylformaldoxime, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-(4-(methylsulfany) phenyl)-2-morpholinyl-propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-2-(hydroxyl-2-propyl group) ketone, benzophenone, to phenyl benzophenone, 4,4 '-diethylamino benzophenone, dichloro benzophenone, 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 2-amino anthraquinones, 2-methyl thioxanthones, 2-ethyl thioxanthones, CTX, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, ESCAROL 507 ethyl ester etc.Above-mentioned substance can be used alone, and also can mix two or more and use.Contain the photoresist of carboxyl relative to 100 mass parts, the use level of Photoepolymerizationinitiater initiater is 5 ~ 20 mass parts, is preferably 8 ~ 15 mass parts.
(C) thinning agent
Thinning agent is such as the photopolymerization monomer as reactive diluent, for making the photocuring of the photoresist containing carboxyl fully carry out, obtains the solidfied material with acid resistance, thermotolerance, alkali resistance etc.As photopolymerization monomer, such as, can enumerate BDO two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, neopentyl glycol hexane diacid two (methyl) acrylate, 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate, dicyclopentenyl two (methyl) acrylate, caprolactone modification dicyclopentenyl two (methyl) acrylate, ethylene-oxide-modified di(2-ethylhexyl)phosphate (methyl) acrylate, allylation cyclohexyl two (methyl) acrylate, isocyanuric acid ester two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, dipentaerythritol three (methyl) acrylate, propionic acid modification dipentaerythritol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, three (acryloyl-oxyethyl) isocyanuric acid ester, propionic acid modification dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate isoreactivity thinning agent.Above-mentioned substance can be used alone, and also can mix two or more and use.Contain the photoresist of carboxyl relative to 100 mass parts, the use level of above-mentioned reactive diluent is 2.0 ~ 40 mass parts, is preferably 10 ~ 25 mass parts.
In addition, as thinning agent, in order to regulate viscosity or the drying property of black solidification compound, above-mentioned reactive diluent can be replaced, or be used as the organic solvent of non-reactive diluent together with above-mentioned reactive diluent.As organic solvent, such as, can enumerate the ketone such as methyl ethyl ketone, cyclohexanone; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; The alcohols such as methyl alcohol, isopropyl alcohol, cyclohexanol; The ester ring type such as cyclohexane, methylcyclohexane hydro carbons; The petroleum such as sherwood oil, naphtha solvent based; The cellosolve such as cellosolve, butyl cellosolve class; The carbitol such as carbitol, butyl carbitol class; The acetate esters etc. such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, acetate of butyl carbitol.Contain the photoresist of carboxyl relative to 100 weight portions, use level time is with an organic solvent preferably 40 ~ 500 weight portions.
(D) epoxy compound
Epoxy compound, for improving the cross-linking density of solidfied material, obtains the cured coating film with sufficient physical strength.Epoxy compound such as has epoxy resin.As epoxy resin, such as, can enumerate bisphenol A type epoxy resin, phenolic resin varnish type epoxy resin (phenolic resin varnish type epoxy resin, o-cresol phenolic resin varnish, p-tert-butylphenol Novolac type etc.), the bisphenol-f type that chloropropylene oxide and Bisphenol F or bisphenol S are obtained by reacting or bisphenol-s epoxy resin and there is the alicyclic epoxy resin of 7-oxa-bicyclo[4.1.0 base, epoxy tristane base, cyclopentane epoxide base etc.; Three (2,3-epoxypropyl) isocyanuric acid ester, triglycidyl group three (2-hydroxyethyl) isocyanuric acid ester etc. have triglycidyl group isocyanuric acid ester, dicyclopentadiene-type epoxy resin, the diamantane type epoxy resin of triazine ring.Above-claimed cpd can be used alone, and also can mix two or more and use.After solidification, obtain the viewpoint of the sufficient film of physical strength, contain the photoresist of carboxyl relative to 100 mass parts, the use level of epoxy compound is 10 ~ 50 mass parts, is preferably 20 ~ 30 mass parts.
(E) black colorant
In the present invention, as black colorant, coordinate (E-1) carbon black system black colorant and (E-2) perylene system black colorant.
(E-1) carbon black system black colorant
Carbon black system black colorant is given solidfied material and is covered power and pitch-dark property.Carbon black system black colorant can enumerate carbon black.The kind of carbon black is not particularly limited, such as, can enumerate furnace black, channel black, alkynes black etc.In addition, the pigment of carbon black system such as can enumerate the pigment of the color index numberings such as C.I. pigment black 6,7,9,18.Above-mentioned pigment can be used alone, and also can mix two or more and use.
(E-2) perylene system black colorant
Perylene system black colorant is given the solidfied material formed by black curable resin composition of the present invention and is covered power and degree of blackness, gives the permeability of black curable resin composition ultraviolet light simultaneously.The kind of perylene system black colorant is not particularly limited, but the viewpoint of photo-curable from film deep, the transmitance of the light of optimal wavelength 300 ~ 400nm is perylene system black colorant Shang 3% Yi.From the color state easily adjusting black, namely reduce the tones such as red tone contained in black and give pitch-dark property, and suppress the heat-resisting metachroic viewpoint of scolding tin, more preferably, except having the light transmission rate of above-mentioned light, the transmitance of the light of wavelength 400 ~ 700nm is perylene system black colorant Xia 20% Yi.And then, from the viewpoint of more easily giving pitch-dark property, particularly preferably except the light transmission rate of the light of above-mentioned wavelength 300 ~ 400nm and wavelength 400 ~ 700nm, at least at 1669 ~ 1671cm
-1between, 1548 ~ 1550cm
-1between, 1498 ~ 1500cm
-1between, 1402 ~ 1404cm
-1between, 1283 ~ 1285cm
-1between, 822 ~ 824cm
-1between, 763 ~ 765cm
-1between and 739 ~ 741cm
-1between absorption position there is infrared ray absorbing Feng perylene system black colorant.
Transmitance as the light of wavelength 300 ~ 400nm is perylene system black colorant Shang 3% Yi, such as, can enumerate " the Paliogen Black S 0084 ", " Lumogen Black FK 4280 ", " Lumogen Black FK 4281 " etc. of BASF (BASF Aktiengesellschaft) Inc..Wherein, the transmitance of the light of wavelength 300 ~ 400nm is more than 3% and the transmitance of the light of wavelength 400 ~ 700nm is that perylene system black colorant can enumerate " Lumogen Black FK 4280 ", " Lumogen Black FK4281 " Xia 20% Yi.It should be noted that, " Paliogen Black S 0084 " transmitance to the light of the short wavelength side of wavelength ratio 680nm is less than 20%, but is that the transmitance of the light of more than 680nm is more than 20% to wavelength." Lumogen Black FK 4280 " is the transmitance of the light of 300 ~ 750nm to wavelength is less than 20%." Lumogen Black FK 4281 " is the transmitance of the light of 300 ~ 900nm to wavelength is less than 20%.
Wherein, except the light transmission rate of the light of above-mentioned wavelength 300 ~ 400nm and wavelength 400 ~ 700nm, also at least at 1669 ~ 1671cm
-1between, 1548 ~ 1550cm
-1between, 1498 ~ 1500cm
-1between, 1402 ~ 1404cm
-1between, 1283 ~ 1285cm
-1between, 822 ~ 824cm
-1between, 763 ~ 765cm
-1between and 739 ~ 741cm
-1between absorption position there is infrared ray absorbing Feng perylene system black colorant can enumerate " Lumogen Black FK 4281 ".It should be noted that, " LumogenBlack FK 4280 " does not have infrared ray absorbing peak, at least 1542 ~ 1544cm in above-mentioned each absorption position
-1between, 1502 ~ 1504cm
-1between, 1284 ~ 1286cm
-1between and 748 ~ 750cm
-1between absorption position there is infrared ray absorbing peak.Shang Shu perylene system black colorant can be used alone, and also can mix two or more and use.
In addition, except above-mentioned each black colorant, the known black colorants such as nigrosine, titanium are black, azo black, graphite system can be coordinated as required further.
Cover the viewpoint of power and degree of blackness from imparting solidfied material, contain the photoresist of carboxyl relative to 100 mass parts, the lower limit of the use level of black colorant is 0.1 mass parts, from the viewpoint of the outward appearance as black, is preferably 0.2 mass parts.From the viewpoint of lines forming fine cured coating film, the photoresist of carboxyl is contained relative to 100 mass parts, the higher limit of the use level of black colorant is 20 mass parts, from the viewpoint of the resolution and dimensional accuracy that obtain solidfied material, is preferably 10 mass parts.The content that Guan Yu perylene system black colorant is shared in black colorant total amount in addition, from the viewpoint of the permeability of ultraviolet light, its lower limit is 53 quality %, from the viewpoint of the photo-curable in film deep, be preferably 60 quality %, from the viewpoint of resolution, be particularly preferably 65 mass parts.The content that Guan Yu perylene system black colorant is shared in black colorant total amount on the other hand, from making a* value close to 0 to give the viewpoint of pitch-dark property, its higher limit is 90 quality %, from reducing L* value, namely obtaining the viewpoint of degree of blackness, be preferably 85 quality %, as the viewpoint of the outward appearance of black, be particularly preferably 80 quality %.
(F) blue colorant
For the solidfied material formed by black curable resin composition of the present invention, coordinate the object of blue colorant to be L* value that reduction colour difference meter obtains is to improve degree of blackness, and from being worth on the occasion of side direction 0, direction is close gives pitch-dark property to the a* value simultaneously making to utilize colour difference meter to obtain.Coordinate carbon black system black colorant Yu perylene system black colorant time, there is red tone in the tone of solidfied material sometimes, has positive a* value.It can thus be appreciated that by adding blue colorant, the a* value of solidfied material is close to 0 value, and red tone is suppressed, thus solidfied material has pitch-dark property.
The kind of blue colorant is not particularly limited, and can enumerate phthalocyanine system, anthraquinone system, dioxazine series pigments.As the concrete example of blue colorant, the pigment of the color index such as Pigment Blue 15, Pigment Blue15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue15:6, Pigment Blue 16, Pigment Blue 60 numbering can be enumerated.Wherein, from the viewpoint of the concentration and color state, the easily pitch-dark property of extraction that easily adjust black, preferred phthalocyanine system.Above-mentioned colorant can be used alone, and also can mix two or more and use.
The use level of blue colorant can make the a* value of solidfied material to 0 value direction close to suppressing the scope of red tone to be selected.If the a* value of the solidfied material of specific thickness is near 0 value (such as, the scope of-2 ~ 2), then blue colorant can not be added, even if near being worth 0, in order to make it closer to 0 value to draw pitch-dark property, the blue colorant of ormal weight can be added.When adjusting the color state of the concentration of black and tone redly, such as from the viewpoint suppressing the red tone of solidfied material to draw pitch-dark property, relative to 100 mass parts black colorants, the lower limit of use level is preferably 5 mass parts, from the viewpoint of degree of blackness, be particularly preferably 10 mass parts.In addition, from the view point of making the a* value of solidfied material close to 0 value, relative to 100 mass parts black colorants, its higher limit is preferably 50 mass parts, from the viewpoint of resolution, is particularly preferably 30 mass parts.
(G) yellow colorants
For the solidfied material formed by black curable resin composition of the present invention, coordinate the object of yellow colorants to be L* value that reduction colour difference meter obtains is to improve degree of blackness, and the b* value simultaneously making to utilize colour difference meter to obtain is close from minus value side to 0 value direction gives pitch-dark property.Coordinate carbon black system black colorant Yu perylene system black colorant time, there is violet hue in the tone of solidfied material sometimes, has negative b* value.It can thus be appreciated that by adding yellow colorants, the b* value of solidfied material is worth close to 0, and violet hue is suppressed, solidfied material thus there is pitch-dark property.
The kind of yellow colorants is not particularly limited, and can enumerate anthraquinone system, monoazo system, bisdiazo system, condensation azo system, benzimidazolone system, isoindolinone system etc.As the concrete example of yellow colorants, Solvent Yellow 163 can be enumerated, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, PigmentYellow 202 (being anthraquinone system above); Pigment Yellow 1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75,97,100,104,105,111,116,167,168,169,182,183 (being monoazo system above); Pigment Yellow 12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198 (being bisdiazo system above); Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow155, Pigment Yellow 166, Pigment Yellow 180 (above is condensation azo system); PigmentYellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181 (being benzimidazolone system above); The pigment of the color index numbering of PigmentYellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185 (being isoindolinone system above) etc.Wherein, from the concentration and the color state that easily adjust black, the viewpoint of pitch-dark property is easily drawn, preferred anthraquinone system.Above-mentioned yellow colorants can be used alone, and also can mix two or more and use.
The use level of yellow colorants can make the b* value of solidfied material close to 0 value direction to suppress suitably to select in the scope of violet hue.If the b* value of the solidfied material of specific thickness 0 value near (such as, the scope of-2 ~ 2), then can not add yellow colorants, even if near 0 value, in order to make it closer to 0 value to draw pitch-dark property, the yellow colorants of ormal weight can be added.When adjusting concentration and the purpuric color state of band of black, such as from the viewpoint suppressing the violet hue of solidfied material to draw pitch-dark property, relative to 100 mass parts black colorants, the lower limit of use level is preferably 5 mass parts, from the viewpoint of degree of blackness, be particularly preferably 10 mass parts.In addition, from the viewpoint of making the b* value of solidfied material close to 0 value, relative to 100 mass parts black colorants, its higher limit is preferably 50 mass parts, from the viewpoint of resolution, is particularly preferably 30 mass parts.
About the tone of the solidfied material of black curable resin composition of the present invention, from the viewpoint of degree of blackness, the L* value measured with colour difference meter is preferably less than 30, is particularly preferably less than 25.In addition, from the viewpoint of pitch-dark property, with colour difference meter measure a* value and b* value all preferred-3 ~ 3, particularly preferably in-2 ~ 2.In addition, from the viewpoint of the photo-curable in film deep, the transmitance of thickness to be the solidfied material of 20 μm to wavelength the be light of 400nm is preferably more than 7%, is particularly preferably more than 8%.Therefore, for black curable resin composition of the present invention, consider the L* value of above-mentioned solidfied material, a* value, b* value, transmitance, coordinate the colorant of mentioned component (A) ~ (D) or following any composition and mentioned component (E) ~ (G) with suitable mixing ratio.
In black curable resin composition of the present invention, in addition to the above ingredients, can suitably coordinate various adding ingredient as required, such as defoamer, various adjuvant, extender pigment, thickening agent etc.
Defoamer can use known material, such as, can enumerate silicone-based, hydrocarbon system, acrylic acid series etc.Adjuvant can enumerate such as silane system, titanate esters system, alumina series etc. are called the spreading agent of coupling agent, boron trifluoride-amine complex, dicyandiamide (DICY) and derivant thereof, organic hydrazides, diaminomaleonitrile (DAMN) and derivant thereof, melamine and derivant thereof, guanidine and derivant thereof, the potentiality hardening agent such as amine acid imide (AI) and polyamine, the slaine of the diacetone such as zinc acetylacetonate and chromium acetylacetonate, enamine, tin octoate, season sulfonium salt, triphenylphosphine, imidazoles, the curing accelerators such as imidazole salts and triethanolamine sequestrant.Extender pigment is the material of the physical strength for improving solidfied material, such as, can enumerate silicon dioxide, barium sulphate, aluminium oxide, aluminium hydroxide, talcum, mica etc.In addition, thickening agent can enumerate organobentonite etc.
The manufacture method of the black curable resin composition of the invention described above is not defined in specific method, such as, ratio can coordinate after above-mentioned each composition according to the rules, at room temperature utilize three-roll grinder to make it mix dispersion to manufacture.
Then, the coating method of the black curable resin composition of the invention described above is described.Herein, be described for the situation that black curable resin composition of the present invention is coated on printed circuit board (PCB) as solder resist.
Use the flowing of silk screen print method, rolling method, stick coating method, spraying process, curtain-type rubbing method, gravure coating process etc., the black curable resin composition of the present invention manufactured as mentioned above is such as coated into desired thickness on the printed circuit board (PCB) with the circuit pattern that etching Copper Foil is formed, volatilize to make the solvent in black curable resin composition, carry out heating about 15 ~ 60 minutes predrying at the temperature of about 60 ~ 80 DEG C, form the film of dry to touch.Then, the minus film had the pattern being set as light transmission beyond the pad of described circuit diagram is made to be close contact on the black curable resin composition of coating, irradiation ultraviolet radiation from it.Then, with the non-exposed areas that dilute alkaline aqueous solution removing is corresponding with described pad, film is developed thus.Developing method uses spray-on process, elution method etc., as dilute alkaline aqueous solution used, is generally the aqueous sodium carbonate of 0.5 ~ 5%, but also can uses other alkali.Then, the post-curing (post cure) of 20 ~ 80 minutes is carried out with the warm braw circulating drying machines etc. of 130 ~ 170 DEG C, make its heat curing, thus the cured coating film of the black curable resin composition as target can be formed on a printed circuit.
With the soldering electronic unit on the printed circuit board (PCB) covered by the cured coating film obtained as mentioned above such as jet solder method, reflux scolding tin method, form circuit unit thus.
Black curable resin composition of the present invention, except being used as solder resist coating on a printed circuit, can also being used for street lamp backlight, paying attention to back plate surface used for solar batteries attractive in appearance, the back plate surface etc. of LED with suitable coating method.
[embodiment]
, embodiments of the invention are described below, as long as but the present invention is no more than its purport, be just not limited to example below.
Embodiment 1 ~ 13, comparative example 1 ~ 5
Coordinate each composition shown in following table 1 according to the mixing ratio shown in following table 1, after stirring machine premixed, use three-roll grinder at room temperature to make it mix dispersion, the black curable resin composition that modulation embodiment 1 ~ 13, comparative example 1 ~ 5 use.Then, on substrate, apply the black curable resin composition modulated and obtain with following test film production process, make test film.The use level of each composition shown in following table 1 unless otherwise specified, represents mass parts.
[table 1]
In addition, the details of each composition in table 1 is as described below.
(A) carboxylic photoresist
Ripoxy SP-4621: Showa macromolecule (strain) system, modified by polyacid cresol novolak type acrylic acid epoxy ester resin
(B) Photoepolymerizationinitiater initiater
IRGACURE 907: Ciba (strain) system, 2-methyl isophthalic acid-[4-(methylsulfany) phenyl]-2-morpholinopropane-1-ketone
IRGACURE 369: Ciba (strain) system, 2-benzyl 2-dimethylamino-1-(4-morphlinophenyl)-butanone-1
(C) thinning agent
EDGAC: Sanyo changes into (strain) system, diethylene glycol monoethyl ether acetate
(D) epoxy compound
EPCRON 860: large Japanese ink chemical industry (strain) system, bisphenol A type epoxy resin
(E) black colorant
Carbon black: electrochemically industry (strain) system, " Denka Black "
LUMOGEN BLACK FK4281: BASF AG's system
LUMOGEN BLACK FK4280: BASF AG's system
Paliogen Black S 0084: BASF AG's system
(F) blue colorant
Direct indigo plant (Lionol blue) FG-7351: Japan's ink liquid manufacture (strain) system, phthualocyanine pigment
(G) yellow colorants
Cromophtal yellow-AGR: Ciba (strain) system, anthraquione pigmentss
In addition, DICY-7 is the curing accelerator that japan epoxy resin (strain) is made.
Test film production process
After surface treatment is carried out in glass epoxy substrate (FR-4) the polishing grinding forming circuit diagram, after black curable resin composition with silk screen print method respectively coating Examples 1 ~ 13 and comparative example 1 ~ 5, at 80 DEG C, carry out 20 minutes predrying with BOX stove.After predrying, film is used exposure device (ORC A.B. HMW-680GW) with 500mJ/cm
2after exposure, with 30 DEG C, after the aqueous sodium carbonate of 1% development, at 150 DEG C, carry out the solidification of 60 minutes with BOX stove, glass epoxy substrate formed the cured coating film of black curable resin composition, make test film.The thickness of cured coating film is 20 μm.
Evaluate
(1) resolution
The residual lines that visual inspection confirms the exposure portion formed by the photomask (live width 30 ~ 130 μm) of regulation and the spacing (space) come off, and evaluate.
(2) undercut (under cut)
It is the substrate of the lines of the photomask formation cured coating film of 100 μm for use width, cut off substrate and observe lines from section, measure the width (x) of lines face side and the width (y) of bottom side (side, deep), evaluate undercut by (x-y)/2.
(3) L* value, a* value, b* value
Measure with colour difference meter SE2000 (Japanese electric look industry (strain)).
(4) transmitance
For the glass epoxy substrate forming cured coating film, measure the transmitance that wavelength is the light of 400nm, use the transmitance of the light that the wavelength of the glass epoxy substrate monomer measured in addition is 400nm as baseline, measure the transmitance of cured coating film.UV spectrophotometer U-3310 (Hitachi's high-tech (HI-Technology) (strain)) is used in the mensuration of transmitance.
(5) the heat-resisting rear variable color of scolding tin
After test film was flooded for 20 seconds in the solder bath of 260 DEG C, by the state of visual inspection cured coating film, evaluate the degree of variable color.
The resolution of embodiment 1 ~ 13, comparative example 1 ~ 5, undercut, L* value, a* value, b* value, transmitance, the heat-resisting metachroic result of scolding tin are shown in table 2.
[table 2]
From embodiment 1 ~ 13 and the comparative example 1 ~ 4 of table 2, use carbon black system black colorant Yu the black colorant of the mixing ratio of potpourri Qie perylene system black colorant of perylene system black colorant more than 52 quality % time, wavelength is that the transmitance of the light of 400nm improves, and can obtain having excellent resolution and the solidfied material of low undercut.And then, a* value can be suppressed near 0 value (such as, the scope of-2 ~ 2), even if or not near 0 value, it also can be suppressed to depart from more greatly 0 value.Thus, black curable resin composition of the present invention due to the thickness of cured coating film be 20 μm time, wavelength is the transmitance of the light of 400nm is more than 7.5%, so till photocuring can proceed to film deep.In addition, till photocuring can proceed to film deep, so have the resolution of less than 70 μm, therefore also can the circuit diagram of corresponding close spacing.Also owing to undercut can be suppressed below 26 μm, even so the circuit diagram of close spacing, also can prevent lines stripping or defect etc., line size precision improves.And owing to a* value can be suppressed for lower, so easily adjust black state, namely easily reduce the color state such as red tone in black or violet hue, draw pitch-dark property.
In addition, by embodiment 2, 8 is known with embodiment 10, compared with being the transmitance of the light of 680 ~ 700nm " Paliogen Black S 0084 " (embodiment 10) more than 20% with wavelength, wavelength is the transmitance of the light of 300 ~ 400nm is more than 3%, and the transmitance that wavelength is the light of 400 ~ 700nm is that L* value suppresses for lower by perylene system black colorant " Lumogen Black FK 4281 " (embodiment 2) and " LumogenBlack FK 4280 " (embodiment 8) Xia 20% Yi, and a* value and b* value can be made closer near 0 value, so more easily raising degree of blackness suppresses the color state of red tone or violet hue etc. simultaneously, draw pitch-dark property.
In addition, from embodiment 2,8, compared with " Lumogen Black FK 4280 " (embodiment 8), 1669 ~ 1671cm
-1between, 1548 ~ 1550cm
-1between, 1498 ~ 1500cm
-1between, 1402 ~ 1404cm
-1between, 1283 ~ 1285cm
-1between, 822 ~ 824cm
-1between, 763 ~ 765cm
-1between, 739 ~ 741cm
-1between absorption position there is infrared ray absorbing Feng perylene system black colorant " Lumogen Black FK 4281 " (embodiment 2) L* value suppressed lower, also make a* value and b* value closer near 0 value, so be easier to draw pitch-dark property.
In addition, use wavelength to be that the transmitance of the light of 300 ~ 400nm is more than 3% and the transmitance that wavelength is the light of 400 ~ 700nm is perylene system's black colorant Xia 20% Yi time, the heat-resisting rear variable color of scolding tin can be suppressed.
In addition, from embodiment 1 ~ 9, relative to 100 mass parts black colorants, coordinate 9 ~ 19 mass parts blue colorant, the following yellow colorants of 30 mass parts, a* value and b* value all can be set in the scope of-2 ~ 2, suppress the color state such as the red tone in black, can give solidfied material pitch-dark property.
From comparative example 5, when the use level of black colorant to be set as relative to the carboxylic photoresist of 100 mass parts be more than 21.8 mass parts, the lines of residual solidfied material, resolution is deteriorated.
Utilizability in industry
Black curable resin composition of the present invention has excellent resolution, and is easily adjusted to black, can prevent the tonal variation after thermal treatment, so such as high in the field value of solder resist.
Claims (19)
1. a black curable resin composition, it contains (A) carboxylic photoresist, (B) Photoepolymerizationinitiater initiater, (C) thinning agent, (D) epoxy compound and (E) black colorant, it is characterized in that
Described (E) black colorant contains (E-1) carbon black system black colorant and (E-2) perylene system black colorant, it is described that (the E-2) perylene system content of black colorant in described (E) black colorant is more than 53 quality %, relative to (A) photoresist containing carboxyl described in 100 mass parts, the use level of described (E) black colorant is less than or equal to 20 mass parts.
2. black curable resin composition as claimed in claim 1, it is characterized in that, described (E-2) perylene system black colorant is the transmitance of the light of 300 ~ 400nm to wavelength is more than 3%.
3. black curable resin composition as claimed in claim 1 or 2, it is characterized in that, described (E-2) perylene system black colorant is the transmitance of the light of 400 ~ 700nm to wavelength is less than 20%.
4. black curable resin composition as claimed in claim 1 or 2, is characterized in that, described (E-2) perylene system black colorant in infrared absorption spectrum measures, at least at 1669 ~ 1671cm
-1between, 1548 ~ 1550cm
-1between, 1498 ~ 1500cm
-1between, 1402 ~ 1404cm
-1between, 1283 ~ 1285cm
-1between, 822 ~ 824cm
-1between, 763 ~ 765cm
-1between, 739 ~ 741cm
-1between absorption position there is infrared ray absorbing peak.
5. black curable resin composition as claimed in claim 3, is characterized in that, described (E-2) perylene system black colorant in infrared absorption spectrum measures, at least at 1669 ~ 1671cm
-1between, 1548 ~ 1550cm
-1between, 1498 ~ 1500cm
-1between, 1402 ~ 1404cm
-1between, 1283 ~ 1285cm
-1between, 822 ~ 824cm
-1between, 763 ~ 765cm
-1between, 739 ~ 741cm
-1between absorption position there is infrared ray absorbing peak.
6. the black curable resin composition as described in claim 1,2 or 5, is characterized in that, it is also containing (F) blue colorant.
7. black curable resin composition as claimed in claim 3, is characterized in that, it is also containing (F) blue colorant.
8. black curable resin composition as claimed in claim 4, is characterized in that, it is also containing (F) blue colorant.
9. black curable resin composition as claimed in claim 6, it is characterized in that, described (F) blue colorant is the blue colorant of phthalocyanine system.
10. black curable resin composition as claimed in claim 7 or 8, it is characterized in that, described (F) blue colorant is the blue colorant of phthalocyanine system.
11. black curable resin compositions as claimed in claim 6, is characterized in that, also containing (G) yellow colorants.
12. black curable resin compositions according to any one of claim 7 ~ 9, is characterized in that, also containing (G) yellow colorants.
13. black curable resin compositions as claimed in claim 10, is characterized in that, also containing (G) yellow colorants.
14. black curable resin compositions as described in claim 11 or 13, it is characterized in that, described (G) yellow colorants is the yellow colorants of anthraquinone system.
15. black curable resin compositions as claimed in claim 12, is characterized in that, described (G) yellow colorants is the yellow colorants of anthraquinone system.
16. 1 kinds of solidfied materials, it makes the solidification of the black curable resin composition according to any one of claim 1 ~ 15 obtain.
17. solidfied materials as claimed in claim 16, is characterized in that, L* value be less than 25, a* value and b* value all-2 ~ 2 scope.
18. solidfied materials as described in claim 16 or 17, it is characterized in that, when thickness is 20 μm, wavelength is the transmitance of the light of 400nm is more than 7.0%.
19. 1 kinds of printed circuit board (PCB)s, is characterized in that, the black curable resin composition of its coating according to any one of claim 1 ~ 15 obtains as solder resist.
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| JP2010134361A JP5007453B2 (en) | 2010-06-11 | 2010-06-11 | Black curable resin composition |
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| JP5916373B2 (en) * | 2011-12-22 | 2016-05-11 | 東京応化工業株式会社 | Photosensitive resin composition for black column spacer, black column spacer, display device, and method for forming black column spacer |
| WO2013171888A1 (en) * | 2012-05-17 | 2013-11-21 | 太陽インキ製造株式会社 | Alkali-development-type thermoset resin composition and printed circuit board |
| JP5766671B2 (en) * | 2012-09-05 | 2015-08-19 | 株式会社タムラ製作所 | Black curable resin composition and printed wiring board using the same |
| JP5695622B2 (en) * | 2012-09-24 | 2015-04-08 | 株式会社タムラ製作所 | Black curable resin composition |
| JP5564144B1 (en) * | 2013-01-15 | 2014-07-30 | 太陽インキ製造株式会社 | Curable resin composition, dry film and cured product thereof, and printed wiring board using them |
| KR101658374B1 (en) * | 2013-01-25 | 2016-09-22 | 롬엔드하스전자재료코리아유한회사 | Colored photosensitive resin composition with dual property for column spacer and black matrix |
| JP2015069181A (en) * | 2013-09-30 | 2015-04-13 | Jsr株式会社 | Radiation-sensitive resin composition, cured film, method for forming the same and display element |
| KR102419975B1 (en) * | 2014-09-30 | 2022-07-13 | 다이니폰 인사츠 가부시키가이샤 | Infrared-light-transmitting ink of dark color, and infrared-light-transmitting sheet obtained using same |
| JP6610069B2 (en) * | 2015-08-06 | 2019-11-27 | 住友ベークライト株式会社 | Resin composition for solder resist, resin film with carrier, wiring board, electronic device, and method of manufacturing electronic device |
| US10983436B2 (en) * | 2016-03-18 | 2021-04-20 | Toray Industries, Inc. | Negative-type photosensitive resin composition, cured film, display device provided with cured film, and production method therefor |
| JP6985715B2 (en) * | 2016-06-15 | 2021-12-22 | 山陽色素株式会社 | Black pigment composition and black coating film forming composition containing the same |
| JP6374595B1 (en) * | 2017-09-26 | 2018-08-15 | 東京応化工業株式会社 | Photosensitive resin composition, cured film, display device, and pattern forming method |
| CN112711175A (en) * | 2021-01-28 | 2021-04-27 | 杭州福斯特应用材料股份有限公司 | Black curable resin composition |
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| JP5007453B2 (en) | 2012-08-22 |
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